WO2022230988A1

WO2022230988A1 - Ammonia-mixed fuel, production device for ammonia-mixed fuel, production method for ammonia-mixed fuel, supply device for ammonia-mixed fuel, combustion device for ammonia-mixed fuel, power generation equipment using ammonia-mixed fuel, and transport device using ammonia-mixed fuel

Info

Publication number: WO2022230988A1
Application number: PCT/JP2022/019333
Authority: WO
Inventors: 直樹八田; 大樹谷本; 聡一郎櫻井; 哲郎村山
Original assignee: 株式会社三井Ｅ＆Ｓマシナリー
Priority date: 2021-04-30
Filing date: 2022-04-28
Publication date: 2022-11-03
Also published as: KR20230159607A; JP2022171351A

Abstract

This ammonia-mixed fuel contains: liquid ammonia; and a liquid combustion improver that improves combustion of the ammonia. The combustion improver is at least one of (a) liquefied petroleum gas, naphtha, gasoline, kerosene, and diesel oil, (b) a material hydrocarbon that is at least one hydrocarbon species contained as a component in at least one of the liquefied petroleum gas, the naphtha, the gasoline, the kerosene, and the diesel oil, and (c) a material alcohol that is an alcohol having three or less carbon atoms. The ammonia-mixed fuel is in a vapor-liquid equilibrium state, and at least a portion of the liquid phase part of the ammonia-mixed fuel is in a solution state in which the ammonia and the combustion improver are mutually dissolved, or in an emulsion state of the ammonia and the combustion improver.

Description

Ammonia mixed fuel, ammonia mixed fuel manufacturing apparatus, ammonia mixed fuel manufacturing method, ammonia mixed fuel supply apparatus, ammonia mixed fuel combustion apparatus, power generation facility using ammonia mixed fuel, and transportation using ammonia mixed fuel machine

The present invention provides an ammonia mixed fuel, an ammonia mixed fuel manufacturing apparatus, an ammonia mixed fuel manufacturing method, an ammonia mixed fuel supply apparatus, an ammonia mixed fuel combustion apparatus, a power generation facility using an ammonia mixed fuel, and an ammonia mixed fuel. related to transport equipment using

Due to recent greenhouse gas (hereinafter referred to as GHG) emission regulations, GHG emissions have been reduced from conventionally widely used fossil fuels (e.g., gasoline, kerosene, light oil, heavy oil, coal, etc.) that generate carbon dioxide when burned. There is a need to switch to other fuels that can be controlled. In contrast, ammonia does not contain carbon, so no carbon dioxide is produced during combustion. For this reason, in recent years, ammonia has been viewed as a promising alternative fuel for complying with GHG regulations.
However, since ammonia has a very high ignition temperature and a very slow burning rate compared to conventional fossil fuels, it is difficult to stably burn ammonia alone.
For this reason, there is known a technique of adding light oil or other liquid hydrocarbon fuel, or gas fuel such as methane or hydrogen to ammonia as a combustion improver for assisting the combustion of ammonia.

For example, in a combustion device simulating a two-stroke diesel engine that can periodically pressurize and compress the gas mixture in the combustion chamber, pressurized liquefied ammonia and a small amount of light oil as a pilot fuel are mixed with air. It has been reported that direct injection into the combustion chamber into which is introduced enables diffusion combustion required for diesel engine operation (Non-Patent Document 1).
According to Non-Patent Document 1 above, in direct injection combustion of liquefied ammonia, liquefied ammonia is injected into a diesel engine and vaporized in the same way as conventional hydrocarbon-based volatile fuels, and light oil of pilot fuel is used. It is said that ammonia is heated by self-igniting combustion after volatilization, ignites ammonia, and undergoes diffusion combustion.

In addition, in Non-Patent Document 2, hydrogen as a combustion improver corresponding to 30% on a calorific value basis for pre-vaporized ammonia corresponding to 70% of the total on a calorific value basis, and a hydrogen volume ratio of 1/3 It is reported that by pre-mixing nitrogen and a predetermined amount of air and injecting it into the combustion device of a four-stroke engine for spark ignition, the engine can be operated by burning with an unburned rate of 2%. . The reason why nitrogen is added to the fuel gas here is that it is produced on the spot by catalytically decomposing a part of ammonia (reaction formula: NH ₃ →3/2H ₂ +1/2N ₂ ) at the time of practical use. This is because it is assumed that hydrogen is used as a combustion improver, and nitrogen, which is produced as a by-product at that time, is also added to the fuel gas.

In addition, in Non-Patent Document 3, in order to increase the combustion speed and stabilize the combustion, for pre-vaporized ammonia, hydrogen or methane, and a premixed gas mixed with a predetermined amount of air Evaluation of laminar combustion speed etc. , and evaluations of turbulent combustion behavior, etc., assuming application to gas turbines, etc. have been reported. In the same literature, under atmospheric pressure, the laminar burning velocity of ammonia, which is as low as about 7 cm/s at 25°C, is reduced by mixing with methane (laminar burning velocity about 37 cm/s) and hydrogen (about 220 cm/s). It has been confirmed that

On the other hand, in recent years, from an environmental point of view, such as the prevention of ozone depletion and global warming due to refrigerants used in refrigerators and air conditioners, liquefied ammonia and , liquefied propane, and other component hydrocarbon species of liquefied petroleum gas have received attention. In addition, assuming the use of these mixed systems for the expansion of refrigerant functions, the phase equilibrium between the liquid phase and the gas phase of these mixtures is also being studied. For example, the results of evaluating the equilibrium relationship between the liquid phase and the gas phase in a two-component system of liquefied ammonia, liquefied propane, liquefied propylene, liquefied n-butane, or liquefied 1-butene have been reported (non-patent literature 4, 5).
According to Non-Patent Documents 4 and 5 above, for a mixture of liquefied ammonia and each hydrocarbon species of the liquefied petroleum gas component, in a temperature range of about -10 to 20 ° C., the liquid separated into two phases. A heterogeneous azeotropic vapor-liquid-liquid equilibrium relationship (VLLE) is observed between the phase and the gas phase, and the composition range in which the liquid phase is compatible expands with increasing temperature. Approximate calculation of the liquid equilibrium relationship, etc. are shown. Furthermore, propylene and 1-butene become completely miscible with liquefied ammonia at any liquid phase composition (mixing ratio) when the temperature rises above a certain temperature, and between the homogeneous liquid phase and the gas phase, It has also been shown that a homogeneous azeotropic vapor-liquid equilibrium relationship (VLE) holds.

Among the above reports, Non-Patent Document 1 states that liquefied ammonia can be ignited using light oil as a pilot fuel, but at the same time, poor ignitability and low flame propagation speed are also recognized. It is suggested that it is not easy to uniformly and stably completely burn the entire amount of ammonia supplied as fuel with a small amount of pilot fuel diesel oil. _In addition, since ammonia contains nitrogen elements, nitrogen oxides ₍ NOx ) may be generated in large amounts.
In addition, it is conceivable to improve the combustibility of liquefied ammonia by mixing liquefied ammonia with a liquid hydrocarbon fuel such as light oil used as a pilot fuel in Non-Patent Document 1. , gas oil and other liquid non-polar hydrocarbons are hardly compatible in the liquid phase, so it is difficult to uniformly and stably mix and burn them.

In addition, using the fact that any substances are homogeneously mixed in the gas phase regardless of their polarity, Non-Patent Documents 2 and 3 use hydrogen or methane gas as a combustion improver for pre-vaporized ammonia. Combustion is improved by premixing. However, these combustion improvers have significant drawbacks in terms of storage and transportation. Ammonia itself is easily liquefied by cooling to about −33° C. under atmospheric pressure and pressurizing to about 0.8 MPa at normal temperature (25° C.), and can be easily stored and transported as liquefied ammonia. However, the hydrogen and methane described above cannot be liquefied under atmospheric pressure unless they are cooled to extremely low temperatures of about -253°C and -162°C, respectively. The energy required for cooling is also very large. Furthermore, even in a liquefied state, hydrogen has a volumetric energy density of only about 29% that of gasoline or light oil, which is 26% lower than that of liquefied ammonia. Also, near room temperature, none of them are liquefied (become supercritical) by pressurization, and their volumetric energy densities in the compressed state are even lower than in the liquefied state. Furthermore, the solubility of non-polar methane and hydrogen gas in liquefied ammonia is low, and it is practically impossible to dissolve the amount required for supporting combustion in liquefied ammonia. Therefore, when hydrogen or methane is used as a combustion improver, expensive and large-scale facilities are required for storing and transporting them, in addition to facilities for liquefied ammonia.
In Non-Patent Document 2, it is assumed that hydrogen as a combustion improver is obtained by catalytic decomposition of ammonia, and in this case, it is not necessary to store and transport hydrogen itself. However, in the preceding stage of ammonia combustion, it is necessary to sequentially produce a predetermined amount of hydrogen as a combustion improver from ammonia partially branched from the supply route to combustion, and if some problem such as a failure occurs in that process is forced to stop the entire system. Therefore, this is unlikely to be a robust process.

On the other hand, Non-Patent Documents 4 and 5 show that liquefied ammonia and liquefied petroleum gas components such as liquefied propane are at least partially dissolved based on their gas-liquid equilibrium relationship. It is noted that these substances and their mixtures can be used as "refrigerants" that do not accelerate ozone depletion and global warming even if they themselves are released into the atmosphere. However, these documents do not assume that they can be used as a "fuel" that does not easily generate GHG such as _CO2 even when burned. In addition, the possibility of mixing and dispersing the mixed liquid phase of liquefied ammonia and liquefied petroleum gas components under conditions where phase separation occurs, the requirements for mixing them when used as fuel, and the above-mentioned liquefied petroleum It does not describe or suggest the types of combustion improvers that can be used other than gas components.

Therefore, the present invention stably mixes and disperses a combustion improver with high combustibility, storability, and transportability with respect to liquefied ammonia, thereby suppressing emissions of GHG, NOx, etc., and liquefied ammonia efficiently. To provide an ammonia mixed fuel that can be combusted well, to provide an apparatus for producing this ammonia mixed fuel, a method for producing an ammonia mixed fuel, and a supply apparatus for an ammonia mixed fuel, and to provide a combustion using this ammonia mixed fuel. An object of the present invention is to provide an apparatus, power generation equipment using this ammonia mixed fuel, and transportation equipment using this ammonia mixed fuel.

One aspect of the present invention is
An ammonia mixed fuel,
Ammonia in a liquefied state;
and a combustion improver that assists combustion of the ammonia,
The combustion improver is
(a) liquefied petroleum gas, naphtha, gasoline, kerosene, and diesel;
(b) a feedstock hydrocarbon which is at least one hydrocarbon species contained as a component in any one of the liquefied petroleum gas, the naphtha, the gasoline, the kerosene, and the light oil; and (c) carbon Raw material alcohol that is alcohol of number 3 or less,
is at least one of
The ammonia mixed fuel is in a gas-liquid equilibrium state, and at least a part of the liquid phase portion of the ammonia mixed fuel is in a solution state in which the ammonia and the combustion improver are mutually dissolved, or the ammonia and the combustion improver are dissolved. characterized by being in an emulsion state of

Another aspect of the present invention is a production apparatus for producing an ammonia mixed fuel,
an ammonia storage closed container for storing ammonia in a liquefied state;
(a) liquefied petroleum gas, naphtha, gasoline, kerosene, and light oil; and (c) a raw material alcohol, which is an alcohol having 3 or less carbon atoms. A closed container for storing a combustion improver,
A dissolved solution state or an emulsified mixture is obtained by stirring and mixing the above and the combustion improver with a stirrer, and the mixture obtained by stirring and mixing with the stirrer can maintain a vapor-liquid equilibrium state. A closed mixing container configured to
an ammonia introduction line provided with an ammonia fixed quantity introduction mechanism configured to connect the ammonia storage closed container and the mixing closed container and introduce a predetermined amount of the ammonia into the mixing closed container;
Combustion improver metered introduction configured to connect the combustion improver storage closed container and the mixing closed container, and to introduce a predetermined amount of the combustion improver from the combustion improver storage closed container into the mixing closed container. A combustion improver introduction line provided with a mechanism;
and at least one liquid phase discharge line configured to discharge the mixture obtained by stirring and mixing the agitator in the closed mixing vessel as an ammonia mixed fuel from the closed mixing vessel. and

Another embodiment of the present invention is an ammonia mixed fuel supply device,
a device for producing the ammonia mixed fuel;
an ammonia-mixed fuel supply line for supplying the ammonia-mixed fuel discharged from the mixing closed container to a combustor configured to burn the ammonia-mixed fuel.
In this embodiment, the supply device may include a plurality of combustors. In this case, the supply device preferably includes a plurality of ammonia mixed fuel supply lines so that the ammonia mixed fuel is supplied to each of the combustors.

Another aspect of the present invention is an ammonia mixed fuel combustion apparatus,
a combustor configured to burn the ammonia mixed fuel;
an ammonia mixed fuel supply device configured to supply the ammonia mixed fuel to the combustor;
a combustion gas discharge line configured to discharge combustion gas generated by combustion of the ammonia-mixed fuel in the combustor into the atmosphere.

Another aspect of the present invention is a power generation facility that generates power in any one of land, water, and air space,
The power generation equipment is equipped with at least one of the ammonia-mixed fuel combustion device provided with an internal combustion engine and the ammonia-mixed fuel combustion device provided with an external combustion engine,
a generator configured to generate power using mechanical power extracted using the energy of the combustion gas of the ammonia mixed fuel;
a power output end configured to output power generated by the generator;
a control mechanism configured to control the amount of power at the power output.

Another aspect of the present invention is a transportation device configured to move or transport goods in any one of land area, water area, and air area,
At least one of the ammonia-mixed fuel combustion device provided with an internal combustion engine and the ammonia-mixed fuel combustion device provided with an external combustion engine is installed,
The mechanical power extracted by at least one of the internal combustion engine and the external combustion engine from the energy of the combustion gas of the ammonia-mixed fuel is used as at least part of the power for propulsion of the transportation equipment. and a power conversion transmission mechanism.

Another aspect of the present invention is a transportation device configured to move or transport goods in any one of land, water, and air space,
The power generation equipment is mounted,
Using the energy of the combustion gas of the ammonia-mixed fuel, the electric power output from the power generation facility is used for at least one of the following: propulsion of the transportation equipment, operation control of the transportation equipment, and maintenance and management of the transportation equipment. at least one of an electric propulsion mechanism and a power supply mechanism configured to use at least a portion of the power requirements in the

Another aspect of the present invention is a method for producing an ammonia mixed fuel, comprising:
(1) ammonia in a liquid state;
(a) liquefied petroleum gas, naphtha, gasoline, kerosene, and diesel oil;
(b) a feedstock hydrocarbon which is at least one hydrocarbon species contained as a component in any one of the liquefied petroleum gas, the naphtha, the gasoline, the kerosene, and the light oil; and
(c) a raw material alcohol that is an alcohol having 3 or less carbon atoms;
and a liquid-state combustion improver that assists combustion of the ammonia, which is at least one of
(2) The ammonia and the combustion improver are stirred and mixed while maintaining a gas-liquid equilibrium state with the liquid phase remaining in the closed container for mixing, thereby obtaining the liquid phase portion of the ammonia and the combustion improver. At least a part of is in a solution state in which the ammonia and the combustion improver are mutually dissolved, or a mixture in which the ammonia and the combustion improver are in an emulsion state,
(3) The mixture is discharged as an ammonia-mixed fuel from the closed container for mixing.

According to the ammonia mixed fuel, the ammonia mixed fuel manufacturing apparatus, the ammonia mixed fuel manufacturing method, the ammonia mixed fuel supply apparatus, and the combustion apparatus using the ammonia mixed fuel described above, the combustibility and storage of liquefied ammonia It is possible to uniformly and stably mix and disperse the combustion improver with high ductility and transportability, thereby making it possible to efficiently burn liquefied ammonia while suppressing emissions of GHG, NOx, and the like. Therefore, the above-described ammonia mixed fuel and the like can be suitably used for power generation equipment, transportation equipment, and the like.

(a) and (b) are diagrams illustrating an example of properties of an ammonia mixed fuel (a gas-liquid-liquid equilibrium state and an emulsified state at a predetermined temperature) of one embodiment. It is a figure showing an example of composition of a manufacture device of ammonia mixed fuel of one embodiment. 3(a) and 3(b) are diagrams showing an example of modification of the main part of the ammonia-mixed fuel manufacturing apparatus of the embodiment of FIG. 2. FIG. FIG. 4 is a diagram showing an example of the configuration of an ammonia-mixed fuel manufacturing apparatus according to another embodiment; FIG. 4 is a diagram showing an example of the configuration of an ammonia-mixed fuel manufacturing apparatus according to another embodiment; FIG. 4 is a diagram showing an example of the configuration of an ammonia-mixed fuel manufacturing apparatus according to another embodiment; FIG. 4 is a diagram showing an example of the configuration of an ammonia-mixed fuel manufacturing apparatus according to another embodiment; FIG. 4 is a diagram showing an example of the configuration of an ammonia-mixed fuel manufacturing apparatus according to another embodiment; FIG. 4 is a diagram showing an example of the configuration of an ammonia-mixed fuel manufacturing apparatus according to another embodiment; FIG. 4 is a diagram showing an example of the configuration of an ammonia-mixed fuel manufacturing apparatus according to another embodiment; FIG. 4 is a diagram showing an example of the configuration of an ammonia-mixed fuel manufacturing apparatus according to another embodiment; 1 is a block diagram of an example of a main part of an ammonia-mixed fuel manufacturing apparatus according to an embodiment; FIG. 1(a) and 1(b) are block diagrams illustrating an example of the configuration of an ammonia-mixed fuel supply device according to an embodiment; FIG. FIG. 4 is a block diagram showing an example of the configuration of an ammonia-mixed fuel supply device according to another embodiment; 1 is a block diagram illustrating an example of a configuration of an ammonia-mixed fuel combustion apparatus according to an embodiment; FIG.

Hereinafter, the ammonia mixed fuel of the embodiment, the ammonia mixed fuel manufacturing apparatus, the ammonia mixed fuel manufacturing method, the ammonia mixed fuel supply apparatus, the ammonia mixed fuel combustion apparatus, the power generation equipment using the ammonia mixed fuel, and the ammonia mixture Transportation equipment using fuel will be described in detail.

(ammonia mixed fuel)
The ammonia mixed fuel of the embodiment is a fuel containing ammonia in a liquefied state (liquefied ammonia) and a combustion improver.
Liquefied ammonia is difficult to ignite and has a low burning rate. Therefore, a combustion improver is used to facilitate ignition of ammonia and improve the burning rate.
As a combustion improver,
(a) liquefied petroleum gas, naphtha, gasoline, kerosene, and diesel;
(b) a feedstock that is at least one hydrocarbon (hereinafter also referred to as component hydrocarbon) species contained as a component in any one of the liquefied petroleum gas, the naphtha, the gasoline, the kerosene, and the diesel oil; and (c) a raw material alcohol that is an alcohol having 3 or less carbon atoms,
At least one of is used.

Here, liquefied petroleum gas (LPG) is generally obtained as a fraction that is easily liquefied at around normal temperature (25 ° C.) from by-product gas such as oil fields, natural gas fields, or oil refineries, by compression equipment or cooling vessels. It is a thing. Liquefied petroleum gas contains chain hydrocarbons with 3 and 4 carbon atoms as components. Liquefied petroleum gas can be easily stored and transported after being liquefied, and the gas after vaporization is used as a portable fuel, a propulsion fuel for vehicles equipped with a gas engine, and the like.
Naphtha corresponds to a fraction with a boiling point range of about 30 to 200° C. among the products obtained by distilling and separating crude oil by an atmospheric distillation apparatus, and its components are chain-like with about 5 to 12 carbon atoms. and aromatic hydrocarbons such as alicyclic hydrocarbons (naphthenes) and benzene. Naphtha is mainly used as a raw material for gasoline, which will be described later, as well as a raw material for the petrochemical industry. Naphtha and its component hydrocarbon species can also be used as fuels.
Gasoline is a hydrocarbon fuel obtained mainly by refining and reforming the light fraction of naphtha. Like naphtha, gasoline is a mixture of hydrocarbons having about 5 to 11 carbon atoms, and has a boiling point of about 30°C to 220°C. ℃ range, the flash point is -40 ℃ or less petroleum products. Compared to naphtha, gasoline contains mainly aromatic hydrocarbons such as toluene and branched hydrocarbons generated by reforming, which improves the octane number. , is widely used as a propellant for mobile vehicles.
Kerosene is a petroleum product mainly composed of chain hydrocarbon components with about 8 to 15 carbon atoms, corresponding to fractions with boiling points in the range of about 150 to 280°C. Products based on kerosene that have undergone predetermined refinement or addition of anti-freezing components are used as heating fuel (kerosene), aircraft jet engine fuel, rocket fuel, etc. In this specification, kerosene shall also include these products.
Gas oil is a petroleum product with a boiling point in the range of about 180° C. to 350° C., and mainly consists of chain hydrocarbons with about 10 to 22 carbon atoms. Light oil is widely used as a fuel that burns particularly well in diesel engines, for thermal power generation, and for the propulsion of large land vehicles, railroads, and ships.

The feedstock hydrocarbons contained in the liquefied petroleum gas, naphtha, gasoline, kerosene, and light oil are generally linear, branched, or alicyclic saturated hydrocarbons having 3 to 20 carbon atoms, and/or alkenes, Mainly unsaturated hydrocarbons such as aromatics. Specific components of liquefied petroleum gas include propane, propylene, n-butane, isobutane, 1-butene, cis-2-butene, trans-2-butene, and isobutene. Naphtha is composed of linear and branched saturated hydrocarbons such as n-pentane, isopentane, neopentane, n-hexane, n-octane, n-decane, linear and branched hydrocarbons such as 1-pentene, 1-hexene, isopentene, etc. It includes unsaturated hydrocarbons, alicyclic hydrocarbons such as cyclohexane and cycloheptane, and isomers thereof. Gasoline contains mainly branched saturated or unsaturated hydrocarbons and aromatic hydrocarbons such as toluene produced by reforming naphtha, with straight-chain saturated hydrocarbon components removed to improve the octane number. The main components of kerosene and light oil are straight-chain saturated hydrocarbons with a larger molecular weight than the component hydrocarbon species in gasoline. It mainly contains a series of linear saturated hydrocarbon species centered around 15-16 n-pentadecanes and n-hexadecanes.
The above-mentioned liquefied petroleum gas, naphtha, gasoline, kerosene, light oil, and the above-mentioned raw material hydrocarbons are generally obtained from fossil fuels mined in nature or from fossil fuels through separation, refining, reforming, etc. However, as long as the chemical structure is generally common, it may be a bio-derived harvested product or its modified product, or a synthetic product having roughly the same components, as will be described later.

All of liquefied petroleum gas, naphtha, gasoline, kerosene, light oil, and the above raw material hydrocarbons, which are components thereof, can compensate for the difficulty of igniting ammonia as combustion improvers. The ignition point of ammonia is about 650° C., which is much higher than that of methane (about 540° C.), which is known as a hydrocarbon with a particularly high ignition point, and is difficult to ignite. On the other hand, for example, although there are some differences depending on the measurer, liquefied petroleum gas (ignition point about 400 ° C), naphtha (about 230 to 290 ° C), gasoline (about 300 ° C), kerosene (about 220 ° C) , light oil (approximately 250°C), propane (approximately 430°C) and n-butane (approximately 365°C), a component of liquefied petroleum gas, cyclohexane (approximately 245°C), a component of naphtha, naphtha and gasoline n-Hexane (approximately 220°C) and toluene (approximately 480°C), n-decane (approximately 210°C), a component of kerosene, n-hexadecane (approximately 200°C), a component of light oil Both have low ignition points, compensating for the difficulty of igniting ammonia. Also, liquefied petroleum gas, naphtha, gasoline, kerosene, diesel, and their constituent hydrocarbon species generally have higher burning rates than ammonia (e.g., these The laminar burning velocity of is equal to or higher than that of methane, and both are about 5 to 7 times the laminar burning velocity of ammonia, which is about 7 cm/s). From the above, the low combustibility of ammonia can be compensated for by adding these liquefied petroleum gas, naphtha, gasoline, kerosene, light oil, and the above-mentioned feedstock hydrocarbons as combustion improvers.

In addition, the raw material alcohol includes methanol, ethanol, n-propanol, and isopropanol. These raw material alcohols also have lower ignition points than ammonia (the ignition points of methanol, ethanol, n-propanol, and isopropanol are about 385° C., about 384° C., about 370° C., and about 450° C., respectively), In addition, since both of them have a high burning rate (approximately 6 to 7 times that of ammonia in terms of laminar flow burning rate), they can also be used as a combustion improver. In addition, these raw material alcohols, like ammonia, do not produce so-called soot when burned, so the inside of the combustor (including sliding parts such as reciprocating engines) and the inside of the flue during combustion are clean. It also has the advantage of being easy to maintain.

The ammonia-mixed fuel, which is a mixture of liquefied ammonia and such a combustion improver, is in a solution state in which at least part of the liquid phase portion is a solution in which ammonia and the combustion improver are mutually dissolved, according to the following embodiments of the present invention. Alternatively, it can be in an emulsion state of ammonia and a combustion improver.
For example, when mixing liquefied ammonia with liquefied petroleum gas in a liquid state or a hydrocarbon species of its components as a combustion improver in a closed space, liquefaction of ammonia and each hydrocarbon species of components or a mixture thereof Between petroleum gas and petroleum gas, as will be described later, there is a thermodynamic gas-liquid equilibrium relationship (phase equilibrium between gas-liquid two phases or gas-liquid three phases of gas phase and liquid phase (two-phase separation or mutual solution) relationship) holds. Based on this relationship, the simple mixing of these with liquefied ammonia, to varying degrees depending on the constituent hydrocarbon species, will result in both being at least partially compatible and thermodynamically stable. If the temperature is further increased, the proportion of these combustion improvers that are compatible with ammonia can be increased and even completely miscible. Further, by further adding a suitable surfactant (an example of which will be shown later), at least a part of the remaining part of these combustion improvers that could not be dissolved by simple mixing at a given temperature can be dissolved at that temperature. In, it is possible to homogenize as an emulsion state.
Also, when naphtha, gasoline, kerosene, light oil, and these component hydrocarbon species are used as combustion improvers containing hydrocarbon species having 5 or more carbon atoms, the thermodynamic vapor-liquid equilibrium relationship (phase equilibrium relationship between gas-liquid two phases or gas-liquid three phases of gas phase and liquid phase (two-phase separation or mutual solution)) is established, and ammonia is dissolved under gas-liquid equilibrium conditions in a closed space be able to. For example, naphthas, which are rich in branched chain hydrocarbon species, alicyclic hydrocarbon species and aromatic hydrocarbons such as benzene, which are more dispersible than straight chain hydrocarbon species, have relatively high compatibility with ammonia. . In addition to branched chain hydrocarbon species, gasoline containing a large amount of non-polar or low-polar aromatic hydrocarbon species with a large induced dipole has high compatibility with liquefied ammonia (Examples described later 14). For example, benzene, and toluene, o, m, p-xylene, etc., which are aromatic hydrocarbon species contained in large amounts in commercial gasoline, are mixed at around room temperature (25 ° C.) in the same manner as the above-mentioned methanol. completely miscible with liquefied ammonia.
At least a portion of the liquefied petroleum gas and its component hydrocarbon species can be further solubilized as an emulsion by adding a suitable surfactant as described below. As a result, the combustibility of the mixed fuel as a whole is more uniformly improved.
When ammonia and these combustion improvers are in a solution or emulsion state, a situation is created in which the vaporized ammonia is mixed in the very vicinity of these combustion improvers that have been vaporized during combustion and ignited, and the vaporized ammonia is induced. Good, simultaneous and uniform combustion can be achieved as a whole, as a result of the targeted ignition and improved burning velocity.
In addition, the raw material alcohol having 3 or less carbon atoms is a liquid having a polarity similar to that of liquefied ammonia at around room temperature (25° C.) under atmospheric pressure, and is compatible with each other due to the effect of hydrogen bonding between molecules. It is compatible with liquefied ammonia over a wide range of compositions due to its high toughness. Furthermore, in the mixture of liquefied ammonia and the raw material alcohol, hydrogen bonding occurs between the molecules of the two to suppress the vaporization of ammonia. Lower than the saturated vapor pressure. This is necessary for the pressure resistance of the storage container when storing the solution of liquefied ammonia and the raw material alcohol at around room temperature (25 ° C.) and for cooling when cooling and liquefying at around atmospheric pressure. This means that the energy can be greatly reduced compared to ammonia alone, which is a great advantage in terms of storage and transportation. That is, it is excellent in storability and transportability.
Further, during combustion, the ammonia and the raw material alcohol are in a solution state, and as in the case of mixing with the hydrocarbon species, an extremely homogeneous mixed gas of these is generated after vaporization, and the ammonia Since the raw material alcohol dissolved in NH3 acts as a combustion improver, the ignition point is lowered and the ignitability is improved compared to when ammonia is used alone. However, among these raw material alcohols, ethanol is known to gradually react with ammonia in a solution and decompose, increasing the risk of fire and the like. Therefore, it is preferable that the ammonia-mixed fuel containing ethanol is not stored for a long period of time after production and is quickly burned and consumed as a fuel, unless an additive or the like is added to suppress such reactions.

The mass ratio of ammonia to the combustion improver is appropriately determined according to the application and purpose of the mixed fuel. For example, hydrocarbon fuels such as liquefied petroleum gas, naphtha, gasoline, kerosene, diesel oil, and some of these component hydrocarbon species are replaced with liquefied ammonia (for example, the ammonia content is about 1% by mass or more, 20% by mass %), the mass of these combustion improvers is relatively greater than the mass of ammonia if the aim is to suppress the production of CO ₂ that occurs during combustion. In such a composition ratio, most of the liquefied ammonia and the combustion improver can be compatible with each other in a closed space with a temperature range of up to about 50°C, which is close to normal temperature (25°C), or a suitable Emulsification can be achieved by adding a surfactant. A mixed fuel with such a mass ratio can achieve a certain level of GHG emission control while continuing to use combustors, burners, internal or external combustion engines, and other existing combustion equipment that are compatible with hydrocarbon fuels. It is advantageous when doing
Conversely, it is also possible to make a mixed fuel containing liquefied ammonia as a main component and containing relatively small amounts of the above-mentioned hydrocarbon fuel, these component hydrocarbon species, and the raw material alcohol as a combustion improver (for example, ammonia when the content is about 80% by mass or more and 99% by mass or less). Even at such a mass ratio, in a temperature range up to about 50°C, which is close to normal temperature (25°C), most of the liquefied ammonia and the combustion improver can be compatible with each other with respect to the total volume, or It can be emulsified by adding a suitable surfactant. When using such a mixed fuel mainly composed of liquefied ammonia, GHG emissions can be suppressed to a greater extent.

In addition, when the combustion improver is liquefied petroleum gas, naphtha, gasoline and its component hydrocarbon species, or a raw material alcohol having 3 or less carbon atoms, the mixed dispersibility with liquefied ammonia is high, so the ammonia content is Even with a mixed fuel of about 20 to 80% by mass, which is between the two cases where the mass ratio is shown, by stirring in a temperature range from about normal temperature (25 ° C.) to about 50 ° C., The majority of the total volume can be made compatible, or it can be emulsified by adding a suitable surfactant as described below. On the other hand, when the combustion improver is kerosene, light oil, or a component hydrocarbon species thereof, the mixed dispersibility with liquefied ammonia is low in the temperature range from about normal temperature (25°C) to about 50°C. At a mixing ratio where the content is about 20 to 80% by mass and the mass ratio with the combustion improver is competitive, even if a suitable surfactant described later is used, it is difficult to uniformly disperse the whole as an emulsion. , the required amount of addition is significantly increased (for example, an equivalent amount of about 10% by mass or more is required). It also becomes difficult to sufficiently disperse a large amount of surfactant. Therefore, in such a mixed composition, in fact, it is difficult to avoid a portion that undergoes liquid phase separation (for this reason, the added amount of either liquefied ammonia or the combustion improver is the upper limit amount that can be solubilized or emulsified. are dealt with by, for example, limiting them to within However, if a suitable surfactant, which will be described later, is used, even if the liquid phase is separated by adding a maximum of about 5% by mass, the combustion improver ( kerosene, light oil, and their component hydrocarbon species) can be emulsified and dispersed up to about 10% by mass, so the combustibility of such an ammonia-side phase in which the combustion improver is dispersed is greater than that of liquefied ammonia. Better than alone. In addition, since the other phase of the separated liquid phase is mainly composed of the combustion improver, its combustibility is high. As will be described later, if kerosene and its component hydrocarbon species are heated to about 50 to 100° C., and if light oil and its component hydrocarbon species are heated to about 80 to 130° C., surface activity Even if the agent is not added, it can be compatible with liquefied ammonia in a wide range of mixing ratios (at about 130° C. or higher, the mixture becomes subcritical or supercritical and compatible).
In the above combustion improver for the ammonia mixed fuel, even when both the raw material hydrocarbon and the raw material alcohol are contained, the mass ratio of each is appropriately determined according to the application and purpose of the mixed fuel.

In the ammonia mixed fuel, the proportion of the portion in the mixed solution state or emulsion state to the total amount is preferably as large as possible. As a result, the overall combustibility of the ammonia-mixed fuel can be improved more uniformly. In addition, when such an ammonia mixed fuel is sent through a piping system, if the liquid phase is separated into two phases, each phase will be divided into layers in the vertical direction in the piping system due to the difference in the specific gravity of each phase. Either of the phases tends to stay in the stagnation point in the system, and as a result, a situation may occur in which the composition of the ammonia-mixed fuel deviates at the liquid feed outlet. However, the larger the ratio of the portion in the mixed solution state or emulsion state to the total amount, the easier it is to prevent such a situation in which the composition deviates.
In particular, the liquefied petroleum gas, naphtha, gasoline, and their component hydrocarbon species, and the raw material alcohol, in which the combustion improver added to ammonia can be compatible to a considerable extent due to an equilibrium relationship without the addition of a surfactant. In some cases, as long as the temperature at the time of dissolution is maintained and the gas-liquid equilibrium state is maintained, the part that has once dissolved will remain in a thermodynamically stable solution state and will continue to be compatible permanently as it is (however, , as described above, when the combustion improver contains ethanol, the reaction with ammonia proceeds gradually).
In addition, the longer the time in which the emulsion state formed after mixing and dispersing is stably maintained, the better. The stable maintenance time is about 5 minutes, preferably several days, and more preferably about 1 month or more as a guide in terms of storage and use as a fuel. In particular, when a mixed fuel in an emulsion state is prepared by adding a sufficient amount of a suitable surfactant, which will be described later, and stirring at an appropriate temperature, the emulsion once formed maintains the temperature at the time of dissolution. As long as the gas-liquid equilibrium state is maintained, the dispersed state can be maintained for a long period of time, from one day to several days to about one month or more, because it maintains a thermodynamically metastable state.
If the ammonia mixed fuel is in a non-equilibrium transitional emulsion state and phase separation occurs during storage, the ammonia mixed fuel should be stirred and mixed again to form an emulsion before it is supplied to the combustor. It is good to restore the state. At that time, if necessary, the temperature is appropriately adjusted as described later. This can restore the combustion advantages of the ammonia-blended fuel.
Furthermore, the ammonia mixed fuel is such that the entire liquid phase portion of the ammonia mixed fuel is in a solution state in which the ammonia and the combustion improver are mutually dissolved, or in an emulsion state of the ammonia and the combustion improver. It is preferable to keep at a predetermined temperature according to the liquid phase composition.
As will be described later, the ammonia mixed fuel is maintained at a proper composition and a proper temperature range according to the composition and temperature of its constituent components, or a sufficient amount of a suitable surfactant described later is added. by at least one of mixing and dispersing the ammonia and the combustion improver so that the entire liquid phase portion of the ammonia mixed fuel is in a solution state in which the ammonia and the combustion improver are mutually dissolved, or the ammonia and the combustion improver are dissolved. It is also possible to make it into an emulsion state. The entire liquid phase portion of the ammonia mixed fuel maintains a solution state in which ammonia and the combustion improver are mutually dissolved, or an emulsion state of ammonia and the combustion improver, thereby improving the combustibility of the entire ammonia mixed fuel. , can be improved uniformly and to the highest degree.

In particular, for ammonia (which does not contain carbon at all), liquefied petroleum gas, and raw material alcohols with 3 or less carbon atoms, _CO2 emissions per calorific value are lower than those of gasoline and kerosene, which have been widely used as fossil fuels. , light oil, heavy oil, coal, etc., so the ammonia mixed fuel, which is a mixture of these as a combustion improver, is itself a very effective fuel in reducing greenhouse gas (GHG) emissions such as _CO2 . .
In addition, the aforementioned liquefied petroleum gas, naphtha, gasoline, kerosene, light oil, hydrocarbon species having structures equivalent to those of raw material hydrocarbons of these components, and raw material alcohols with 3 or less carbon atoms excluding ethanol are _CO2 separated and collected from industrial exhaust gases and the atmosphere by using renewable energy such as light, wind power, hydraulic power, and geothermal power, electric power obtained from nuclear power, and hydrogen obtained by electrolysis of water using such electric power. In some cases, it is produced by chemical synthesis via CO, methane, etc. synthesized by reducing . Unlike fossil fuels, these raw material hydrocarbons and the above-mentioned raw material alcohols, which are produced based on renewable energy, are burned and the exhaust gas is released into the atmosphere, CO ₂ emissions are assumed to be substantially reduced.
In addition, many of the hydrocarbon species with structures equivalent to these and raw material alcohols having 3 or less carbon atoms, including methanol and ethanol, can be synthesized from raw materials such as metabolites of plants and microorganisms that perform photosynthesis. Are known. When such products based on photosynthesis, metabolites, etc. are used as combustion improvers, the carbon contained is derived from atmospheric _CO2 , so combustion must not substantially increase atmospheric _CO2 . be regarded. Therefore, the use of the above-mentioned renewable energy-based combustion improver and the ammonia mixed fuel mixed with the photosynthesis-based bio-based combustion improver can greatly suppress global warming.

From the viewpoint of storing and transporting the ammonia-mixed fuel so that the fuel can be stably supplied in a liquefied state, it is preferable that it be isolated and stored in a closed environment where gas-liquid equilibrium is maintained.

In one embodiment, the ammonia mixed fuel contains at least one of the liquefied petroleum gas, the raw material hydrocarbon, and the raw material alcohol as a combustion improver, and the raw material hydrocarbon is the liquefied petroleum gas. At least one hydrocarbon species contained as a component, and the starting alcohol is preferably methanol. That is, the ammonia mixed fuel preferably contains at least one of liquefied petroleum gas, at least one hydrocarbon contained as a component in liquefied petroleum gas, and methanol as a combustion improver.
Liquefied petroleum gas and the hydrocarbon species contained as its constituents produce less _CO2 per calorific value during combustion than gasoline, kerosene, light oil, or heavy oil, which have traditionally been widely used as liquid fuels. is preferable in terms of less occurrence of
As described above, the liquefied petroleum gas and the hydrocarbon species contained as its constituents have a saturated vapor pressure relatively close to that of ammonia in the liquid state at the same temperature, and a lower molecular weight hydrocarbon such as methane. It is easy to ignite due to its low ignition temperature compared to , and has a burning rate equal to or higher than that of methane, which is about 5 to 6 times that of ammonia, and is advantageous as a combustion improver for ammonia.
Therefore, when liquefied petroleum gas or its component hydrocarbon species and ammonia are in a solution state or an emulsion state, they are mixed very uniformly and vaporize substantially simultaneously and uniformly during combustion. It is easy to obtain a situation in which the gases are heated simultaneously and uniformly. Thus, vaporized ammonia mixed in close proximity to the gas of liquefied petroleum gas or its constituent hydrocarbon species, such as liquefied petroleum gas or its constituent hydrocarbon species, such as propane, ignites in the combustor after vaporization. is heated and ignited, and overall a particularly good, simultaneous and homogeneous combustion can be achieved.

Among the liquid fossil fuels that have been widely used as fuels, kerosene, light oil, and the hydrocarbon species of these components, excluding gasoline, are non-polar linear saturated hydrocarbons having about 8 or more carbon atoms. Mainly hydrogen. In general, a mixture of non-polar straight-chain saturated hydrocarbon species having about 8 or more carbon atoms and liquefied ammonia has a temperature range from about normal temperature (25 ° C.) to about 50 ° C. under the vapor-liquid equilibrium conditions. However, it is difficult to mix with each other and separates into two phases. In order to make them compatible without adding a surfactant, which will be described later, a higher temperature than liquefied petroleum gas and its component hydrocarbon species (e.g., about 50 to 100 ° C. for kerosene and its component hydrocarbon species) degree, about 80 to 130 ° C for gas oil and its component hydrocarbon species). about 3 to 4 MPa or more), a high pressure resistance is required for production equipment during production and storage of the mixed fuel. For this reason, in order to burn such non-polar straight-chain saturated hydrocarbons having about 8 or more carbon atoms and liquefied ammonia in a stable and precisely mixed state, it is necessary to add a predetermined surfactant as described later. Emulsification by mixing is generally required.
On the other hand, eight types of hydrocarbons with 3 and 4 carbon atoms (propane, propylene, n-butane, isobutane, 1-butene, cis-2-butene, trans-2-butene, and For isobutene), although both are non-polar, the surfactant is added under gas-liquid equilibrium conditions in a closed space with a predetermined temperature of about 40 ° C. or less and a saturated vapor pressure of about 2 MPa or less. Even if it is not added, it is uniformly compatible with highly polar liquid ammonia in almost all composition ranges. The compatibility of such ammonia and low-molecular-weight hydrocarbons and the related equilibrium relationship between gas-liquid phases are partly shown in Non-Patent Documents 4 and 5 concerning mixed properties of ammonia and low-molecular-weight hydrocarbons as refrigerants. ing. Hereinafter, based on the data described in Non-Patent Documents 4 and 5, the case where propane and n-butane, which are the main components of liquefied petroleum gas, are used as the combustion improver will be taken as an example. A situation in which a compatible solution state is obtained and a situation in which an emulsion state is obtained will be described.

1 (a) and (b) illustrate the relationship between the vapor-liquid-liquid equilibrium (VLLE) of the ammonia-propane system and the ammonia-n-butane system, respectively, described in Non-Patent Documents 4 and 5 ( In FIGS. 1(a) and 1(b), the ammonia concentrations (x, y) in the liquid phase and gas phase are converted from the mole fraction representation used in Non-Patent Documents 4 and 5 to mass % representation. are).
In FIG. 1(a), the relationship between the gas-liquid composition and the saturated vapor pressure in the gas-liquid-liquid equilibrium (VLLE) of the heterogeneous azeotropic ammonia-propane system at 20 ° C. (upper) and 0 ° C. (lower) relationship is shown. The solid line in the figure (the locus of PABQ at 20°C and P'A'B'Q' at 0°C) indicates the relationship (liquidus line) between the liquid phase composition (x) and the saturated vapor pressure (p). The lower dashed line (the locus of POQ at 20°C and P'O'Q' at 0°C) is the relationship between the gas phase composition (y) and the saturated vapor pressure (p) in equilibrium with the liquid phase (gas phase line ). At 20° C., from point P where the gas-liquid phase composition x, y = 0, which indicates the gas-liquid equilibrium of pure propane, the concentration of ammonia in the liquid phase rises to point A (ammonia concentration x _A = 16.2% by mass), ammonia continues to uniformly dissolve in the liquid phase mainly composed of propane, and the saturated vapor pressure increases while maintaining the liquid single-phase state.
When the ammonia concentration in the liquid phase reaches the point A where the saturated concentration x _A is reached (at this time, the gas phase reaches the point O where the saturated vapor pressure is maximized (azeotropic point: gas phase ammonia concentration y _O = 31.2 mass %, the saturated vapor pressure p _O =1.64 MPa) was reached), the concentration of ammonia in the propane-based liquid phase did not increase any further, and a phase-separated ammonia-based separate phase from the propane-based liquid phase A liquid phase appears. In this phase-separated liquid phase mainly composed of ammonia, propane is saturated and dissolved (ammonia concentration in the phase x _B =86.5% by mass, propane concentration (saturation) 1−x _B =13.5 mass%). Between the liquid phase composition x _A and x _B (on the line segment AB of the liquidus line), the propane-based liquid phase with the ammonia concentration x _A and the ammonia-based liquid phase with the ammonia concentration x _B undergo phase separation. In the meantime, the gas phase is maintained in an azeotropic state ₍ point _O ) of ammonia concentration y 0 and saturated vapor pressure p 0 , which are in equilibrium with this. In addition, at point C (ammonia concentration x _C ) on line segment AB in the region where the liquid phase separates into two phases, a propane-based phase with ammonia concentration x _A and an ammonia-based phase with ammonia concentration x _B , The respective mass ratios are represented by (x _B −x _C ):(x _C −x _A ) according to the “lever principle”.
When the concentration of ammonia in the liquid phase increases beyond x _B (point B on the liquidus line), the propane-based phase disappears, and the liquid phase becomes the ammonia-based monolith with dissolved propane. When there is only one phase and the concentration of ammonia in the phase is further increased, the single phase remains at the point Q in the figure, which indicates the vapor-liquid equilibrium of pure ammonia, via the trajectory of BQ on the liquidus line. The vapor phase composition and saturated vapor pressure in equilibrium with this draw a locus of OQ on the vapor phase line, and the saturated vapor pressure decreases to the Q point as the vapor phase ammonia concentration increases. Since the above behavior is based on a thermodynamic equilibrium relationship, the behavior is the same even if the operation is performed in the direction of decreasing the ammonia concentration from the Q point indicating the vapor-liquid equilibrium of pure ammonia.

From the above, at 20 ° C., the liquid phase mainly composed of _propane contains ammonia through the trajectory of PA in FIG. ) can be thermodynamically stably dissolved without phase separation. In addition, in the liquid phase mainly composed of ammonia, propane is phase-separated up to its saturation concentration 1-x _B (= 13.5% by mass) through the locus of QB in the figure. can be thermodynamically stably dissolved. Assuming a mixed fuel at 20°C in which liquefied propane is dissolved as a combustion improver in liquefied ammonia, the liquid phase mainly composed of propane among the above two liquid phases has an amount of liquefied propane as a combustion improver that is equal to that of liquefied ammonia. It corresponds to the case where it is remarkably large compared to . Part of the liquefied propane (here, 16.2% by mass or less) is replaced with ammonia, and if this is taken out as a mixed fuel and subjected to combustion, it becomes a single-phase compatible mixed fuel that burns uniformly as a whole. In addition, due to the replacement, the production of CO ₂ can be suppressed as compared with the combustion of liquefied propane alone. Of the two liquid phases, the liquid phase mainly composed of ammonia corresponds to the case where the amount of liquefied propane as the combustion improver is smaller than that of liquefied ammonia. Part of the liquefied ammonia (here, 13.5% by mass or less) is replaced with propane, and if this is taken out as a mixed fuel and subjected to combustion, it becomes a single-phase compatible mixed fuel that burns uniformly as a whole. Moreover, due to the replacement, the combustibility can be improved as compared with the combustion of liquefied ammonia alone.
In addition, in the gas-liquid-liquid equilibrium relationship at 20 ° _C. in FIG. A phase mainly composed of ammonia (ammonia concentration x _A =16.2% by mass), and a lower layer becomes a phase mainly composed of ammonia (ammonia concentration x _B =86.5% by mass)). At this time, as shown in the figure, when point C is close to point B, from the above-mentioned "lever principle", the mass of the liquid phase mainly composed of propane is It is relatively small compared to the mass of the main liquid phase. When this entire amount is taken out as a mixed fuel and subjected to combustion, due to phase separation, the uniformity of combustion as a mixed fuel is inferior to that of the above-mentioned single-phase compatible mixed fuel, but a small amount of phase separation Since the liquid phase mainly composed of propane is also highly combustible, it can be combusted well as a whole. On the other hand, even when point C is close to point A, if the entire amount is taken out as a mixed fuel and subjected to combustion, the uniformity of combustion as a mixed fuel is lower than in the case of the above single-phase compatible mixed fuel. However, the liquid phase mainly composed of ammonia with a small amount of phase separation also has propane saturated and dissolved at a concentration of 1-x _B (= 13.5% by mass), so a combustion-supporting effect is imparted. It can burn well. Further, as will be described later, if the upper and/or lower layers separated into two phases can be separately taken out as a mixed fuel, and each layer can be separately burned, each layer itself is a single-phase mixed fuel. Therefore, each shows uniform and good combustibility.

In the gas-liquid equilibrium relationship of the ammonia-propane system at 0 ° C. shown in the lower part of FIG. It is represented by the locus of 'O'Q'. At 0°C, the two-phase separation region in the liquid phase (between A'B' on the liquidus line) expands compared to the time of 20°C described above, and the single-phase region on both sides (P'A' on the liquidus line) expands. and B'Q') are reduced, and the saturated vapor pressure, including the azeotropic vapor pressure p _O' (= 0.66 MPa) at the azeotropic point O', is generally compared to that at 20 ° C. declining. The shrinking of the single-phase regions (between P'A' and B'Q' on the liquidus line) indicates that the compatibility between liquefied ammonia and liquefied propane decreases with decreasing temperature. Therefore, when this system is used as a single-phase compatible mixed fuel at 0°C, the liquid phase mainly composed of propane contains ammonia up to a concentration x _A' (= 6.7% by mass), and ammonia It is possible to dissolve propane up to a concentration of 1-x _B' (=6.5% by mass) in the liquid phase mainly composed of , but the solubility of each is lower than at 20°C.
FIG. 1(b) shows the relationship between the gas-liquid composition and the saturated vapor pressure in the vapor-liquid-liquid equilibrium (VLLE) of the ammonia-n-butane system at 0.degree. For comparison with the ammonia-propane system, the symbols (P', A', B', Q', O', etc.) in FIG. 1(a) correspond to the ammonia-propane system at 0 ° C. It is common with the symbol to In the gas-liquid equilibrium relationship of the ammonia-n-butane system at 0 ° C. in FIG. A phase line (trajectory of P'O'Q') is recognized, and qualitatively, it is common to the vapor-liquid equilibrium of the ammonia-propane system in FIG. 1(a). That is, when this system is used as a single-phase compatible mixed fuel at 0 ° C., ammonia is added to the concentration x _A' (= 5.2% by mass) in the liquid phase mainly composed of n-butane, and It is possible to dissolve n-butane up to a concentration of 1−x _B′ (=2.7 mass %) in the liquid phase mainly composed of ammonia. Also, reflecting the lower volatility of n-butane compared to propane, the saturated vapor pressure, including the azeotropic vapor pressure p _O' (=0.53 MPa) at the azeotropic point O', is generally low in comparison. Although there are differences as described above, even in the vapor-liquid equilibrium relationship of the ammonia-n-butane system, in terms of the temperature and composition region where the liquid phase separates into two phases, the vapor-liquid equilibrium relationship of the ammonia-propane system and qualitatively common.

In general, not only the propane and n-butane described above, but also each component hydrocarbon species of liquefied petroleum gas other than them is qualitatively similar in a heterogeneous azeotropic gas in a predetermined temperature range. Figure 2 shows the liquid-liquid equilibrium (VLLE) relationship. In both cases, as the relative temperature rises, for example, the point A-B (or point A'-B') on the liquidus line shown in FIG. The separation area is reduced and the compatibility is increased. Furthermore, above each predetermined temperature (critical solution temperature), the A point (or A' point) and B point (or A' point) are the azeotropic point O (or O' point) With convergence, the two-phase separation region in the liquid phase disappears. That is, it is known that each component hydrocarbon species of liquefied petroleum gas becomes completely miscible with liquefied ammonia in the liquid phase at any composition ratio above the critical solution temperature. ing.
Among the component hydrocarbon species of liquefied petroleum gas, when compared at the same temperature, those with 3 carbon atoms (propane, propylene) and those with double bonds (propylene, various butenes) are relatively Compatibility with liquid ammonia is higher than that of component hydrocarbons outside the category of For example, the above critical solution temperature is about 33° C. for propane, which is a saturated straight-chain hydrocarbon having 3 carbon atoms, and about 38° C. for n-butane, which is a straight-chain saturated hydrocarbon having 4 carbon atoms. In the temperature range of , it has been confirmed that both are miscible with ammonia in the liquid phase at any composition ratio. In addition, in Non-Patent Documents 4 and 5, at 0 ° C. for propylene, which is an unsaturated straight-chain hydrocarbon having 3 carbon atoms, and at 10 ° C. for 1-butene, which is an unsaturated straight-chain hydrocarbon having 4 carbon atoms, regardless of the composition. Liquid-phase miscibility with ammonia has also been reported (although it is not specified whether these temperatures are critical solution temperatures). In the temperature range above the critical solution temperature of each component hydrocarbon species of these liquefied petroleum gases, homogeneous azeotropic gas-liquid An equilibrium (VLE) relationship holds.
Further, for example, in the liquid phase composition (ammonia concentration x _C ) at point C in the gas-liquid-liquid equilibrium relationship of the ammonia-propane system at 20 ° C. in FIG. Phase separation occurs. However, even in the liquid phase composition at point C, a predetermined temperature that is higher than 20 ° C. and lower than the critical solution temperature (about 33 ° C.) at which ammonia and propane are completely compatible is always exist. For example, in the case of the liquid phase ammonia concentration x _C ≈ 77% by mass, which corresponds to the position of the composition x _C at point C in the equilibrium relationship between ammonia and propane at 20 ° C. in Fig. 1 (a) (at this time , the average composition of the total liquid phase and gas phase, that is, the concentration of ammonia in the feed composition is about 75% by mass, which corresponds to the conditions of Example 1 described later). (That is, at 23 ° C., point B and point C overlap, and the ammonia concentration x _B corresponding to point B, which is the saturated state of propane, is about 77% by mass. It will be described later. See Example 1). Such behavior is similarly observed for all component hydrocarbon species of liquefied petroleum gas other than propane. That is, in a mixed fuel of liquefied petroleum gas or a component hydrocarbon species of liquefied petroleum gas and ammonia, the temperature of the mixed fuel is maintained above the above-mentioned temperature according to the liquid phase composition of the mixed fuel. Thus, the entire liquid phase portion of the mixed fuel can be in a solution state in which ammonia and the combustion improver are mutually dissolved (see Example 2 described later (when the combustion improver is n-butane)). . As a result, when the entire amount is taken out as a mixed fuel and used for combustion, the effect of the combustion improver can be maximized and the mixed fuel can be burned extremely uniformly.

In the above mixed system of liquefied ammonia and liquefied petroleum gas component hydrocarbon species, the vapor-liquid equilibrium and the saturated vapor pressure in vapor-liquid equilibrium are respectively Generally higher than the saturated vapor pressure alone.
In addition, the component hydrocarbon species of liquefied petroleum gas other than propane, and the single-phase compatible mixed fuel of liquefied petroleum gas, which is a mixture thereof, and liquefied ammonia, can also be liquefied in the same manner as in the case of propane described above. The component hydrocarbon species of liquefied petroleum gas dissolved in ammonia forms a uniform mixed gas with ammonia after vaporization, and in that state acts as a combustion improver, so compared to liquefied ammonia alone, the ignition point is lower and ignitability. is improved and the burning velocity is also increased, resulting in improved combustibility. On the other hand, even if the mixture composition and temperature conditions are such that phase separation occurs due to immiscibility with ammonia, the liquefied petroleum gas component as a combustion improver is saturated and dissolved in the liquid phase mainly composed of ammonia generated by phase separation. In addition, the liquid phase mainly composed of the component hydrocarbon species of the other liquefied petroleum gas also has good combustibility as a whole because the component hydrocarbon species themselves have good combustibility. can. Furthermore, if the phase-separated phases are taken out separately as a mixed fuel and burned separately, each becomes a uniform single phase, exhibiting good combustibility.

Methanol, like liquefied petroleum gas or its components, can also be used as a GHG-reducing fuel. Since methanol has a low ignition point of about 385° C., it is easily ignited, and its laminar combustion velocity is about 45 cm/s, which is 6 to 7 times higher than that of ammonia. In addition, compared with heavy oil, light oil, kerosene, and gasoline, which have conventionally been widely used as liquid fuels, less CO ₂ is generated per calorific value during combustion. Furthermore, methanol is uniformly mixed (completely dissolved) in a liquid state with liquefied ammonia without the addition of a surfactant at least in the temperature range of about 0 to 40 ° C., so liquefied petroleum The vaporized ammonia, which, like the gas or its main component, is mixed very closely with the ignited methanol after vaporization, is heated and ignited, and overall a particularly good, simultaneous and homogeneous combustion can be achieved. Methanol, like ammonia, does not generate soot during combustion, and has the advantage of easily maintaining the cleanliness of the inside of the combustor and the inside of the flue. Unlike the mixed system of liquefied ammonia and liquefied petroleum gas or its component hydrocarbon species, the mixture of liquefied ammonia and methanol is a non-azeotropic gas-liquid system in which the liquid phase is completely miscible regardless of the liquid phase composition. indicates equilibrium. Therefore, if the mixed fuel is taken out as a mixed fuel and subjected to combustion at any composition ratio, uniform and good combustion becomes possible. Furthermore, in a solution of liquefied ammonia and methanol, since hydrogen bonding occurs between the molecules of the two and vaporization of ammonia is suppressed, the saturated vapor pressure of these mixed solutions is the saturated vapor pressure of ammonia alone at the same temperature (See Example 13 below). When storing a mixed fuel of liquefied ammonia and methanol, the pressure resistance of the storage container when storing at room temperature (25°C), and the energy required for cooling when storing in a liquefied state near atmospheric pressure. can be greatly reduced compared to ammonia alone, which is a great advantage in terms of storage and transportation.

In addition, ammonia, liquefied petroleum gas or its constituent hydrocarbon species, and methanol, which are raw materials for ammonia mixed fuel, are also excellent in terms of raw material procurement.
That is, ammonia has been produced from methane, which is the main component of natural gas, as a raw material, and has been synthesized worldwide in large quantities by the Haber-Bosch process. For this reason, large-scale ammonia synthesis plants are often built near natural gas fields around the world. Extraction of natural gas with a high methane content, which is used as a raw material for ammonia, involves separating hydrocarbons with higher boiling points from raw gas extracted from gas fields by pressurizing or cooling to liquefy them. It is mainly performed by In addition to liquefied petroleum gas, naphtha components are generally included in this high boiling point component. They are separated from each other in the same natural gas refining plant and each becomes a product. Therefore, in many cases, liquefied petroleum gas is also produced in the vicinity of an ammonia production plant that uses natural gas as a raw material. Therefore, when an ammonia mixed fuel is additionally produced in an ammonia production plant, liquefied petroleum gas and hydrocarbons such as propane and n-butane, which are components thereof, are used as combustion improvers added to the ammonia mixed fuel. is advantageous in procuring raw materials for manufacturing.

Similarly, methanol is also mass-produced using methane, which is the main component in natural gas, as a raw material. The initial steps in the synthesis of methanol from methane are the desulfurization step and the steam reforming step (CH4+ _2H2O →4H2 ₊ _CO2 and CH4 ₊ _H2O → _3H2 ₊ CO), which is the natural It is the same as the initial process of ammonia production by Haber-Bosch process from gas raw material. For this reason, the co-production of ammonia and methanol in the same production plant will reduce _CO2 emissions to the environment by effectively using carbon in natural gas (carbon, which is a component element in natural gas that is eliminated in ammonia production, can be replaced by methanol). (used in manufacturing) and improved efficiency through common processes. In fact, large-scale manufacturing plants co-producing both have also been constructed in recent years. Therefore, in an ammonia production plant using natural gas as a raw material, methanol can also be advantageously co-produced. Therefore, when an ammonia mixed fuel is additionally produced in an ammonia production plant, methanol is also advantageous as a combustion improver contained in the ammonia mixed fuel in raw material procurement in terms of production.

Furthermore, if it is assumed that ammonia will be mass-transported from the mass-manufacturing base to a remote mass-consumption demand area by transport equipment, it will be easy to use the fuel for the transport equipment at the mass-manufacturing base of ammonia. And it is preferable from the viewpoint of efficiency and cost that it can be procured at a low cost. As described above, liquefied petroleum gas and its constituent hydrocarbon species, as well as methanol, can be advantageously procured at sites for mass production of ammonia, and thus ammonia mixed fuels containing these can be used to drive transportation equipment that transports ammonia in bulk. It can be advantageously used as a fuel. Furthermore, by utilizing the similarity in the saturation vapor pressure and liquefying temperature of liquefied petroleum gas and liquefied ammonia, it is possible to share pressure-resistant or cooling tanks to store them, so currently, the liquefied ammonia is operated worldwide. About 20% of the liquefied petroleum gas carriers in Japan are designed to carry liquefied ammonia as well. For this reason, the fact that the liquefied ammonia, liquefied petroleum gas, and its constituent hydrocarbons can be used together as fuel for the engines, gas turbines, steam turbines, and other propulsion systems used to propel these transport ships is also a major contributor to facility consolidation. In addition to being able to do so, it is of great significance in terms of the suppression of GHG emissions from the propulsion internal/external combustion engines of the transport ship.

(Surfactant and emulsification by surfactant)
In one embodiment, in the ammonia mixed fuel containing the non-polar raw material hydrocarbon that is difficult to mix with liquefied ammonia as a combustion improver, a surfactant is added to make the liquid ammonia and the combustion improver into an emulsion state. is preferably included. Emulsification with a surfactant can be suitably applied regardless of whether the raw material hydrocarbon contained in the ammonia-mixed fuel is liquefied petroleum gas, naphtha, gasoline, light oil, or component hydrocarbon species thereof. In particular, when the raw material hydrocarbon is kerosene, light oil, or any of these component hydrocarbon species, it is compatible with ammonia in the temperature range from about normal temperature (25 ° C.) to about 50 ° C. Therefore, it is necessary to emulsify by adding a surfactant. Due to the emulsification caused by the addition of a surfactant, at least a part of the phase-separated portion that could not be dissolved due to the vapor-liquid equilibrium at that temperature in the liquid phase of the ammonia mixed fuel is maintained at that temperature. , and can also be dispersed in the liquid phase.
For example, in the case of an ammonia mixed fuel in which propane, which is a component hydrocarbon species of liquefied petroleum gas, is used as a combustion improver, the vapor-liquid equilibrium relationship of the ammonia-propane system at 20 ° C. shown in FIG. Even in the liquid phase composition near point _C in FIG. can be emulsified to For example, the upper liquid phase mainly composed of propane (ammonia concentration x _A = 16.2 mass%, mass ratio to the whole (x _B - x _C ) / (x _B - x _A ) ≈ 0.14) will be described later. By adding about 1% by mass of a mixed surfactant common to that used in Example 3 and emulsifying it, the other lower liquid phase mainly composed of ammonia (ammonia concentration x _B = 86.5 %, can be evenly distributed in the mass fraction of the total (x _C −x _A )/(x _B −x _A )≈0.86). This uniform emulsion state is maintained even when cooled down to about 17°C (upper layer appears separated below 17°C). The above-described emulsification can be similarly realized for other component hydrocarbon species of liquefied petroleum gas in addition to n-butane.
The above-described emulsification increases the solubility of the combustion improver (liquefied petroleum gas and its component hydrocarbon species) in ammonia at a predetermined temperature, so that the above-mentioned combustion support effect during combustion of the mixed fuel is further enhanced. In addition, since the temperature required for solubilization can be reduced, the rise in the saturated vapor pressure of the ammonia mixed fuel can also be suppressed. Therefore, by emulsification by adding a surfactant, the required pressure resistance of the storage container during storage at around room temperature (25° C.) can be reduced.

The amount of surfactant to be added is adjusted according to the molecular weight, compounding composition, characteristics and performance of the surfactant, which will be described later. It can be appropriately determined based on the volume fraction (approximately mass fraction is also possible) of the droplets dispersed and suspended in the medium. For example, liquefied ammonia becomes fine droplets (when the combustion improver is liquefied petroleum gas or its component hydrocarbon species, part of the combustion improver is dissolved in the liquid phase mainly composed of the liquefied ammonia), When dispersed or suspended in a liquid phase mainly composed of fuel (hereinafter, this state is referred to as "a/o (ammonia in oil) emulsion"), depending on the volume fraction of liquefied ammonia in the ammonia mixed fuel Then, the amount of surfactant to be added is determined. Conversely, the combustion improver becomes fine droplets (when the combustion improver is liquefied petroleum gas or its component hydrocarbon species, part of the liquefied ammonia is dissolved in the liquid phase mainly containing the combustion improver), When dispersed or suspended in a liquid phase mainly composed of ammonia (this state is hereinafter referred to as "o/a (oil in ammonia) emulsion"), the volume fraction of the combustion improver in the mixed fuel (approximately The amount of surfactant to be added is determined according to the mass fraction of The emulsion formed by the mixed surfactant used in Example 3 described above corresponds to this o/a emulsion. In general, the larger the volume fraction (approximately mass fraction) of the liquefied ammonia or combustion improver dispersed or suspended in the form of fine droplets in the mixed fuel, the larger the amount of surfactant added. Needed. The required amount of surfactant varies depending on the type of surfactant, but suitable surfactants described later (high-performance mixed surfactants in which nonionic and ionic surfactants are mixed) When using , as a guideline, the mass fraction of about 1/10 of the numerical value of the volume fraction (approximately mass fraction) in the mixed fuel of the liquefied ammonia or the combustion improver to be dispersed or suspended Surfactants are preferred for stable emulsion formation. Normally, about 0.1 to 10% by mass is added to the ammonia mixed fuel.
In addition, when such nonionic and ionic mixed surfactants are used together, the polar ammonia and the non-polar raw material hydrocarbon are added to the a / o emulsion and the o / a emulsion. Either state is possible. Furthermore, it is also possible to appropriately select a surfactant that is particularly suitable for each formation so as to preferentially form any one of them, or to adjust the composition by blending or the like. In general, when the volume of the separated liquid phase mainly composed of liquefied ammonia is smaller than the volume of the separated liquid phase mainly composed of raw hydrocarbons, it is better to form an a/o emulsion. is advantageous in terms of saving and uniformly dispersing the emulsion throughout, and for this reason, a surfactant that facilitates the formation of an a/o emulsion is selected or formulated. Conversely, surfactants that are more likely to form o/a emulsions are selected or formulated. However, it may be possible to adapt to both a/o emulsification and o/a emulsification by selecting or formulating the same surfactant.

A preferred surfactant in the ammonia mixed fuel of one embodiment above is a mixed system comprising at least one nonionic surfactant (A) and at least one ionic surfactant (B) is a surfactant. However, "ionic" and "nonionic" here are distinguished by whether or not they have the property of being ionized in the environment of the liquid ammonia mixed fuel. The general terms "ionic" and "nonionic" are differentiated mainly in terms of whether or not they ionize as hydrated ions in the presence of water. However, since the ammonia mixed fuel in the present invention contains substantially no water, can "ionic" and "nonionic" ionize in the ammonia mixed fuel mainly as ions solvated by ammonia? or not. In addition, in the process of ionization, H ⁺ and anionic/cationic species, etc. are transferred and received between ionic and nonionic surfactant molecules and between these surfactant molecules and ammonia molecules. The above "ionic" and "nonionic" are distinguished by the presence or absence of ionization including such a series of processes.
In general, a surfactant has two parts that exhibit affinity for each of the two phases that undergo liquid-phase separation. It has the property of being arranged two-dimensionally at the interface. In order for such a surfactant to exhibit the effect of emulsification, when either phase of the two separated liquid phases is divided into a large number of fine droplets by stirring and dispersed in the other phase , while surfactant molecules are arranged two-dimensionally on the surface interface of all the microdroplets in the above manner, the microdroplets continue to be covered (formation of so-called "micelles"), and the microdroplets It is necessary to combine the two elements of generating a stable electrostatic repulsive force between the microdroplets (micelles) so as to prevent the (micelles) from recontacting and remelting. .

For the formation of emulsions between water and common liquefied petroleum gas, naphtha, gasoline, kerosene, gas oil and their component hydrocarbon species, either nonionic or ionic, alone There are many surfactants that can form emulsions. However, when emulsifying an ammonia-mixed fuel containing liquefied ammonia and the raw material hydrocarbon, the present inventor independently tried typical commercially available nonionic and ionic surfactants. The effect of emulsion formation was poor in both cases, and the emulsion was divided into two layers as in the case of no addition. This is because the polarity of ammonia is not as high as that of water, and the difference in polarity with the raw material hydrocarbon is smaller than in the case of an aqueous system. It is presumed that it is difficult for a single surfactant to achieve both of the above-mentioned two factors of covering droplets (forming micelles) and providing sufficient electrostatic repulsion between micelles.
However, as will be described later, the present inventor uses several kinds of nonionic surfactants and several kinds of ionic surfactants mixed in an appropriate amount ratio. As a result, an ammonia mixed fuel containing liquefied ammonia and the raw material hydrocarbons (liquefied petroleum gas, naphtha, gasoline, kerosene, light oil, and component hydrocarbon species thereof) can be stably and satisfactorily emulsified. Found it. Here, the nonionic surfactant mainly contributes to the stable formation of an extremely thin film (micelle interface film) covering the microdroplets while being two-dimensionally arranged on the surface layer interface of the microdroplets. On the other hand, the ionic surfactant mainly participates in the formation of the film by the nonionic surfactant, and is constantly ionized by itself to form the surface layer interface of the microdroplet (micelle). It provides stable electrostatic repulsion and contributes to preventing re-contact and re-fusion of fine droplets. In this way, when suitable nonionic and ionic surfactants are mixed and used, the synergistic effect of the respective contributions described above enables good emulsification of the ammonia mixed fuel.
However, even a nonionic surfactant suitable for film formation at the micelle interface or an ionic surfactant suitable for ionization repulsion cannot form a stable emulsion by itself. That is, with only the former, the electrostatic repulsion between the formed micelles is insufficient, and transient contacts and fusions of the micelles are repeated, eventually resulting in reseparation into two phases. Moreover, since the film-forming property at the two-phase interface is insufficient only with the latter, it is difficult to form the micelle itself.
In addition, in the category of "mixing of nonionic surfactant (A) and ionic surfactant (B)" in the above "suitable surfactant", simple physical mixing of each surfactant In addition, it is intended to include an embodiment using a surfactant having both nonionic and ionic polar sites in one surfactant molecule. Such surfactants also include copolymers in which the above-mentioned ionic and two types of ionic polar sites are polymerized. As the molecular structure, for example, a structure in which the partial structure of the preferred nonionic surfactant described above and the partial structure of the preferred ionic surfactant described above are provided in series in the main chain, or the preferred and the partial structure of the preferred ionic surfactant described above are provided in parallel as side chains. In these, the quantitative ratio of the partial structure portion of the nonionic surfactant and the partial structure portion of the ionic surfactant is a mere physical It is determined according to the respective quantitative ratios which are suitable for mixing.

Among the suitable mixed surfactants described above, particularly suitable surfactants specifically have the following aspects. Namely
(A) In the molecular structure, a primary or secondary amino group [—NH ₂ or >NH], a polyoxyalkyleneamino group [>N(C _a H _2a O) _c —H, or —N ((C _b H _2b O) _d —H)((C _b H _2b O) _e —H)] (a and b are 2 or 3, c is an integer of 1 to 8, and d and e are 0 such that d+e=1 to 8 or positive integer), amide group [-C(=O)NH ₂ ], polyoxyalkyleneamide group [-C(=O)N((C _f H _2f O) _g -H) ((C _f H _2f O) _h —H)] (f is 2 or 3, g and h are 0 or positive integers such that g+h=1 to 8), and a polyoxyalkylene group [—O(C _i H _2i O ) _j —H] (i is 2 or 3 and j is an integer of 1 to 8), and has at least one group as a nonionic polar moiety, and an alkyl group [C _k H _2k+1 -] (k is an integer of 7 to 18), and alkenyl group [C _l H _2l-1 -] (l is an integer of 7 to 18) as a nonpolar site. at least one nonionic surfactant having a group;
(B) In the molecular structure, a quaternary methylammonium group, a quaternary methylalkanolammonium group, or a quaternary alkanolammonium group [—N ⁺ (CH ₃ ) _p (C _m H _2m OH) _qX ⁻ , or >N ⁺ (CH ₃ ) _r (C _n H _2n OH) _s ·X′ ⁻ ] (m and n are 2 or 3, p and q are 0 or positive integers satisfying p+q=3, r and s are r+s=2 0 or a positive integer, X and X′ are Cl, Br and I), and a carboxyl group [—C(=O)OH], any of the ionic polar having at least one group as a site, and an alkyl group [C _t H _2t+1 -] (t is an integer of 7 to 18) and an alkenyl group [C _u H _2u-1 -] (u is an integer of 7 to 18 is an integer) and at least one ionic surfactant having at least one non-polar site.

In the above, (A) is a nonionic surfactant as a main component constituting a particularly suitable surfactant in an ammonia mixed fuel containing the non-polar raw material hydrocarbon as a combustion improver, and ( B) is an ionic surfactant as a secondary component which constitutes a particularly preferred surfactant. As described above, the nonionic surfactant (A) mainly contributes to the formation of a thin film in which its molecules are arranged two-dimensionally at the interface between the two separated liquid phases, and the micelle covered with the film. However, the ionic surfactant (B) is mainly ionized in the membrane and contributes to electrostatic repulsion between the micelles.
Among the above, the molecule of the nonionic surfactant (A) has a primary or secondary amino group [—NH ₂ , or >NH], a polyoxyalkyleneamino group [>N(C _a H _2a O) _c —H, or —N((C _b H _2b O) _d —H) ((C _b H _2b O) _e —H )] (a and b are 2 or 3, c is an integer of 1 to 8, d and e are 0 or positive integers such that d + e = 1 to 8), an amide group [-C(=O)NH ₂ ], and a polyoxyalkyleneamide group [-C(=O)N((C _f H _2f O) _g -H) ((C _f H _2f O) _h -H)] (f is 2 or 3, g and h is 0 or a positive integer such that g + h = 1 to 8), or a polyoxyalkylene group [-O(C _i H _2i O) _j -H] ( i is 2 or 3 and j is an integer of 1 to 8), it has a high affinity based on hydrogen bonding with respect to liquefied ammonia or a liquid phase mainly composed of liquefied ammonia. These nonionic surfactants (A), including the case where the polar part is an amino group, hardly participate in ionization themselves in ammonia mixed fuels containing no water (this classified as “nonionic”). In addition, the nonionic surfactant (A) contains a nonpolar long-chain alkyl group [C _k H _2k+1 -] or a long-chain alkenyl group [C _l H _2l-1 -] (k and l are 7 to 18). integer), it has a high affinity for the raw material hydrocarbon or the liquid phase mainly composed of the raw material hydrocarbon. Moreover, among commercially available surfactants, there are cases where they dissolve in either liquefied ammonia or the liquid phase consisting mainly of liquefied ammonia, or the raw material hydrocarbon or the liquid phase consisting mainly of the raw material hydrocarbon. In contrast, the above nonionic surfactant (A), probably due to its affinity balance, has low solubility in both liquid phases and does not dissolve in either of the two phases. It also has the feature of being easily migrated to the interface.

As the nonionic surfactant (A), when an emulsion is formed between liquefied ammonia or a liquid phase mainly composed of liquefied ammonia and a raw material hydrocarbon or a liquid phase mainly composed of raw material hydrocarbon is a long-chain alkylamine [property formula: C _k H _2k+1 _{NH 2} _] ( k is an integer from 7 to 18) showed the highest effect. Such long-chain alkylamines migrate to the interface of both phases to form films well, and as a result, tend to form micelles. Such a long-chain alkylamine nonionic surfactant (A) can be used satisfactorily in forming both the a/o emulsion and the o/a emulsion. In particular, it seems to tend to form the latter, and for this reason, it is particularly effective in emulsifying a mixed fuel containing a large amount of liquefied ammonia and a relatively small amount of raw material hydrocarbons.
Further, in the nonionic surfactant (A), an emulsion is formed between liquefied ammonia or a liquid phase mainly composed of liquefied ammonia and a raw material hydrocarbon or a liquid phase mainly composed of raw material hydrocarbon. In the case of using
A long-chain alkylpolyoxyalkyleneamine having one long-chain alkyl group and a polyoxyalkyleneamino group [rheometric formula: C _k H _2k+1 N((C _b H _2b O) _d -H) ((C _b H _2b O) _e —H)] (b is 2 or 3, d and e are 0 or positive integers such that d+e=1 to 8, k is an integer of 7 to 18),
a long-chain alkylamide having one long-chain alkyl group and an amide group [rheometric formula: C _k H _2k+1 -C(=O)NH ₂ ] (k is an integer of 7 to 18),
A long-chain alkylpolyoxyalkyleneamide having one long-chain alkyl group and a polyoxyalkyleneamide group [rheometric formula: C _k H _2k+1 -C(=O)N((C _f H _2f O) _g - H) ((C _f H _2f O) _h −H)] (f is 2 or 3, g and h are 0 or positive integers such that g+h=1 to 8, k is an integer of 7 to 18), and
A polyalkoxyethylene long-chain alkyl ether having one long-chain alkyl group and a polyoxyalkylene group [rhetic formula: C _k H _2k+1 O(C _i H _2i O) _j -H] (i is 2 or 3, j is an integer of 1 to 8, and k is an integer of 7 to 18).
Also, among the above, long-chain alkyl (and long-chain alkenyl) polyoxyalkyleneamines, long-chain alkyl (and long-chain alkenyl) polyoxyalkyleneamides having a polyoxyalkylene group (polyether) partial structure, and Polyalkoxyethylene long-chain alkyl (or long-chain alkenyl) ethers may be particularly effective in forming emulsions where, in addition to liquefied ammonia and feedstock hydrocarbons, a feedstock alcohol is also included.

On the other hand, as the ionic surfactant (B), when an emulsion is formed between liquefied ammonia or a liquid phase mainly composed of liquefied ammonia and a raw material hydrocarbon or a liquid phase mainly composed of raw material hydrocarbon In the trial of the present inventor, a quaternary long-chain alkyltrimethylammonium [ratic formula: C _k H _2k+1 N ⁺ (CH ₃ ) ₃・X ⁻ ] (k is an integer from 7 to 18) showed the highest effect. The quaternary long-chain alkyltrimethylammonium participates in the film formation at the interface by the nonionic surfactant (A), and is ionized at the boundary with the liquid phase mainly composed of liquefied ammonia. Good fusion prevention. Such a quaternary long-chain alkyltrimethylammonium ionic surfactant (B) can be used satisfactorily in forming both the a/o emulsion and the o/a emulsion. Similar to the long-chain alkylamines described above in nonionic surfactants (A), there appears to be a particular tendency to form o/a emulsions, resulting in large amounts of liquefied ammonia and relatively small amounts of raw It is particularly effective in emulsification of mixed fuels containing hydrocarbons for commercial use.
In addition, one to three of the methyl groups [—CH ₃ ] of the trimethylammonium group are substituted with an alkanol group [C _m H _2m OH] (m is 2 or 3) to have a quaternary ammonium group as a polar site. long-chain alkylmethylalkanolammonium [C _k H _2k+1 N ⁺ (CH ₃ ) _p (C _m H _2m OH) _qX ⁻ ] (k is an integer of 7 to 18, m is 2 or 3, p and q are p+q = 3 or a positive integer, X is one of Cl, Br and I), the ionic surfactant (B) is a liquid phase mainly composed of liquefied ammonia or liquefied ammonia, and When an emulsion is formed with a liquid phase mainly composed of hydrogen or raw material hydrocarbons, it exhibits film formation and ionization effects at the interface similar to those having the trimethylammonium group. In addition, these ionic surfactants (B) having a quaternary methylalkanolammonium group are particularly useful during the formation of an emulsion containing a raw material alcohol in addition to liquefied ammonia and a liquid state raw material hydrocarbon. can be effective.

Furthermore, as the polar site of the ionic surfactant (B), those having a carboxyl group [-C (= O) OH] also between the raw material hydrocarbon or the liquid phase mainly composed of the raw material hydrocarbon It can be used satisfactorily when forming an emulsion. For example, an ionic surfactant (B) of a long-chain alkylcarboxylic acid [rheometric formula: C _k H _2k+1 C(=O)OH] (k is an integer of 7 to 18) having a carboxyl group as a polar moiety, While participating in the film formation at the interface by the nonionic surfactant (A), the coexisting ammonia (and the long-chain alkyl (or long-chain Chain alkenyl) amine) is ionized by giving H ⁺ [ionization formula: -C (=O) OH + NH ₃ (or C _k H _{2k + 1} NH ₂ etc.) = - C (= O) O ^- + NH ₄ ⁺ (or C _k H _2k+1 NH ₃ ⁺ etc.)], resulting in electrostatic repulsion between the micelles and preventing contact and fusion of the micelles. In addition, the ionic surfactant (B) having such a long-chain alkyl or alkenyl group and a carboxyl group can form both the a/o emulsion and o/a emulsion, but the former is particularly preferred. It tends to form easily, and is therefore particularly effective when emulsifying a mixed fuel containing a large amount of feedstock hydrocarbon and a relatively small amount of liquefied ammonia.
Furthermore, long-chain dialkyl (or long-chain dialkenyl) amines having two long-chain alkyl or alkenyl groups and a secondary amino group [>NH] [ratio: (C _k H _2k+1 ) ₂ NH ₂ , or (C _l H _2l-1 ) ₂ NH ₂ ] (k and l are integers of 7 to 18) (A), or two long-chain alkyl or alkenyl groups and a dimethylamino group [>N ⁺ ( CH ₃ ) ₂ ·X ⁻ ], quaternary long-chain dialkyl or dialkenyldimethylammonium [ratio: (C _k H _2k+1 ) ₂ N ⁺ (CH ₃ ) _r (C _n H _2n OH) _s ·X′ ⁻ , or (C _l H _2l−1 ) ₂ N ⁺ (CH ₃ ) _r (C _n H _2n OH) _s ·X′ ⁻ ] (n is 2 or 3, r and s are 0 or a positive integer, X' is any of Cl, Br and I) (B) each have a single long-chain alkyl or alkenyl group and a primary amino group (—NH ₂ ) as described above; For (A) a simple long-chain alkyl (or long-chain alkenyl) amine, or (B) a quaternary long-chain alkyltrimethylammonium having a single long-chain alkyl or alkenyl group and a trimethylammonium group When added in small amounts, o/a emulsions tend to form more readily.

The mixing ratio of the nonionic surfactant (A) and the ionic surfactant (B) in the above mixed surfactant ((A) + (B)) is approximately 0.7 in terms of molar ratio. :0.3 to 0.9:0.1 is preferred, and in particular, about 0.80:0.20 provides the best emulsion formation (Examples 3 and 11 described later) and Reference Examples 1 and 2).
Further, in the above, the carbon numbers k, l, t and u of the long-chain alkyl or alkenyl groups of the nonionic surfactant (A) and the ionic surfactant (B) are determined according to the preparation and storage of the ammonia mixed fuel. It is appropriately selected depending on the temperature to be applied. Generally, the higher the temperature, the more suitable the carbon number is. For example, if the preparation and mixing temperature is in the vicinity of the liquefaction temperature (-33°C) of ammonia under atmospheric pressure (for example, about several tens of degrees below zero), solidification and precipitation of the surfactant at low temperatures can be suppressed. Therefore, it is suitable that k, l, t and u are about 7 to 8. In the vicinity of room temperature (25° C.), for example, in the case of about 0 to 50° C., the number of carbon atoms is suitable to be about 10 to 14 in order to achieve both stability of arrangement and fluidity at the separated liquid phase interface. often. At higher temperatures, generally higher carbon numbers are suitable. Therefore, each surfactant has a suitable temperature range to exhibit its function. On the other hand, the temperature at which the ammonia mixed fuel is prepared and stored is often selected according to the type of combustion improver. For example, when the combustion improver is liquefied petroleum gas and its component hydrocarbon species, it is preferable that the saturated vapor pressure is as low as possible from the viewpoint of the pressure resistance of the mixing vessel and ease of operation. The temperature for preparation and mixing is from the vicinity of the liquefying temperature of ammonia under atmospheric pressure to the vicinity of normal temperature (25°C), that is, about -several 10°C to 50°C. In addition, when the combustion improver is naphtha, gasoline, kerosene, light oil, or their component hydrocarbon species, the temperature for preparation and mixing is normal temperature (25 ° C.) from the viewpoint of viscosity and stirring and mixing properties. , for example, a temperature range of about 0 to 50° C. or higher is often selected. In addition, when using a mixed surfactant having a plurality of chain lengths (carbon numbers) in which the chain lengths (carbon numbers k, l, t and u) are distributed in a certain range, a more stable emulsion can be formed. There is also For example, the number of carbon atoms in long-chain alkyl groups derived from inexpensive coconut oil has a specific distribution (k, t ≈ 8 to 18: in general, k, t = 12 accounts for about 60%, which is the largest ), mixed surfactants having these may tend to form stable emulsions.
Therefore, a surfactant having a long-chain alkyl group or alkenyl group suitable for the temperature range corresponding to the liquid phase composition to be emulsified is selected as described above, and by maintaining that temperature range, ammonia mixed fuel At least a part of the liquid phase portion of the ammonia-mixed fuel, or even the whole, is in an emulsion state of the ammonia and the combustion improver, so that good combustion can be achieved.

In addition, the nonionic and ionic surfactants having each of the above molecular structures are effective against polar ammonia molecules (and against raw material alcohol molecules with 3 or less carbon atoms that can be additionally added). .

Furthermore, the nonionic and ionic surfactants used in the above ammonia mixed fuel do not have a molecular structure portion that has a durability problem against the alkalinity exhibited by ammonia, and are chemically stable. . On the other hand, for example, it is preferable that an ester group (-C(=O)-O-), a urethane group (-O-C(=O)-NH-), etc., which are likely to deteriorate under alkaline conditions, be included in the molecular structure. do not have. In particular, in the case where the combustor that burns the ammonia mixed fuel is a reciprocating engine or the like that has a movable part that requires slidability, the slidability may be deteriorated when the mixed fuel is burned. It is preferred to avoid surfactants that produce ash by-products. For example, as the ionic surfactant, it is possible to use a surfactant having a polar part such as a sulfonate (polar part is -SO ₃ ^- ·Na ⁺ etc.). Since ash containing sodium sulfate and the like that is produced later is produced as a by-product that is disadvantageous in sliding, it is not preferable as a surfactant used in the ammonia mixed fuel of the present invention.
In Examples 3 to 12 described later, when n-butane, which is one component of liquefied petroleum gas, is used as a combustion improver, and a predetermined amount of various mixed surfactants are added and mixed, an emulsion (in this case, o /a emulsion) is formed to eliminate the upper and lower two-phase separation state, and the lower limit temperature at which the upper and lower two phases are uniformly solubilized and the saturated vapor pressure at that time are listed (the standard for comparison is Example 2 in which no surfactant is added) ). From these examples, it can be seen that emulsification by adding a mixed surfactant can reduce the temperature required for solubilization, thereby suppressing an increase in the saturated vapor pressure of the ammonia-mixed fuel. For this reason, emulsification by adding these mixed system surfactants increases the solubility of the combustion improver n-butane in ammonia at a predetermined temperature, and also increases the required pressure resistance of the storage container during storage. can be reduced.

(Ammonia mixed fuel manufacturing device and manufacturing method)
FIG. 2 is a diagram showing an example of the configuration of an ammonia-mixed fuel manufacturing apparatus according to one embodiment.
The production apparatus 10 shown in FIG. 2 is an apparatus for producing an ammonia mixed fuel when the combustion improver is liquefied petroleum gas and component hydrocarbon species of the liquefied petroleum gas. Liquefied petroleum gas and hydrocarbon species contained as its constituent components have a higher calorific value during combustion than conventional liquid fossil fuels such as gasoline, kerosene, light oil, and heavy oil. It is preferable in terms of less CO ₂ generation. In addition, liquefied petroleum gas and its component hydrocarbon species have a saturated vapor pressure close to that of ammonia in a liquid state at the same temperature, and are easier to ignite because they have a lower ignition temperature than ammonia, and are more easily ignited than ammonia. It has a high burning velocity (about 5 to 6 times that of ammonia in terms of laminar burning velocity) and is easy to burn. For this reason, liquefied petroleum gas and the hydrocarbon species contained as its components are preferred as combustion improvers for ammonia. An ammonia-mixed fuel containing such a combustion improver can be produced by the production apparatus 10 shown in FIG.
The manufacturing apparatus 10 includes an ammonia storage closed container 12, a combustion improver storage closed container 14, a mixing closed container 16, an ammonia introduction line 18, a combustion improver introduction line 20, a gas phase discharge line 21, a liquid phase discharge line 22, and agitation. A thermometer 24 , a thermometer 33 and a pressure gauge 31 are mainly provided. In addition to this, the manufacturing apparatus 10 shown in FIG. , 20c, 28c and a controller 32. FIG. The regulating

valves

18c, 20c, 28c are inlet valves for introducing the raw materials into the closed vessel 16 for mixing. Furthermore, the closed mixing container 16 has a temperature adjusting jacket 17 for adjusting the temperature inside the closed mixing container 16, a temperature adjusting medium inlet nozzle 17a at its lower part, and a temperature adjusting medium outlet nozzle at its upper part. 17b is provided.

The ammonia storage closed container 12 is a cylinder or tank for storing ammonia in a liquid state (liquefied ammonia).
The combustion improver storage sealed container 14 is a cylinder or tank that stores a liquid state combustion improver that assists the combustion of ammonia. The combustion improver here is, as described above, at least one of (a) liquefied petroleum gas and (b) raw material hydrocarbon which is at least one hydrocarbon species contained as a component in liquefied petroleum gas. is one.

A stirrer 24 is provided in the closed container 16 for mixing. The closed container 16 for mixing obtains a dissolved solution state or an emulsified mixture by stirring and mixing liquid state ammonia and a combustion improver with a stirrer 24, and a mixture obtained by stirring and mixing with a stirrer. is configured to maintain a vapor-liquid equilibrium state. Specifically, the closed mixing container 16 has a pressure-resistant structure and airtightness so that the inside of the closed mixing container 16 can maintain the saturated vapor pressure of ammonia, the combustion improver, and their mixture.

The ammonia introduction line 18 is provided with a flow meter 18a and control

valves

18b and 18c configured to introduce a predetermined amount of ammonia into the closed container 12 for storing ammonia and the closed container 16 for mixing as an ammonia fixed quantity introduction mechanism. The control device 32 receives the measurement results of the ammonia flow rate by the flow meter 18a, generates control signals for controlling the opening degrees of the regulating

valves

18b and 18c, and sends the generated control signals to the regulating

valves

18b and 18c. In the case of constant introduction, when the control device 32 determines that the time integral value of the flow rate of ammonia from the start of introduction of ammonia reaches the set amount to be introduced into the mixing closed container 16, the control device The control signal generated by 32 causes the regulating

valves

18b, 18c to be fully closed, stopping the introduction.
The flow meter 18a may be, for example, a flow meter that determines the flow rate from the floating height of a float that rises due to the upward flow of fluid in the ammonia introduction line 18, a critical nozzle type or thermal flow sensor type mass flow meter, or a mass flow meter. A controller, an ultrasonic flow meter, a Coriolis flow meter, or the like is used. At this time, the introduction amount of ammonia can be obtained by time integration of the flow rate measurement value from the start to the end of introduction of ammonia.
In addition, instead of the flow meter 18a in FIG. It is also possible to control the amount of ammonia introduced from the weighed value of the vessel. However, this control method cannot be applied to continuous production of an ammonia-mixed fuel having a constant composition by continuously introducing raw material ammonia and a combustion improver, as shown in FIG. 5, which will be described later. In that case, the ammonia quantitative introduction mechanism is composed of the weighing device and the

control valves

18b and 18c. Upon quantitative introduction, the control device 32 receives the result of weighing by the scaler, generates control signals for controlling the opening degrees of the regulating

valves

18b and 18c, and sends the generated control signals to the regulating

valves

18b and 18c. At the time of quantitative introduction, the weighing result of the amount of introduced ammonia (the value obtained by subtracting the mass of the closed mixing vessel 16 before starting the introduction of ammonia) reached the set amount to be introduced into the closed mixing vessel 16. When the control device 32 determines that, the

control valves

18b and 18c are fully closed by the control signal generated by the control device 32, and the introduction is stopped.

The combustion improver introduction line 20 connects the combustion improver storage closed container 14 and the mixing closed container 16 . In the combustion improver introduction line 20, a flow meter 20a and control

valves

20b and 20c configured to introduce a predetermined amount of the combustion improver from the combustion improver storage closed container 14 to the mixing closed container 16 are provided. is provided as The flowmeter 20a has the same mechanism as the liquefied ammonia flowmeter 18a. The control device 32 receives the measurement results from the flow meter 20a, generates control signals for controlling the opening degrees of the regulating

valves

20b and 20c, and sends the generated control signals to the regulating

valves

20b and 20c. In the case of constant introduction, when the control device 32 determines that the time integral value of the flow rate of the combustion improver from the start of the introduction of the combustion improver reaches the set amount to be introduced into the closed mixing container 16, A control signal generated by the control device 32 fully closes the regulating

valves

20b and 20c to stop the introduction.
Also, in the same manner as when introducing the liquefied ammonia, the amount of the combustion improver to be introduced is grasped from the weighed value obtained by the weighing device (not shown) that weighs the weight of the mixing sealed container 16 instead of the flowmeter 20a. can also be controlled. However, this control method cannot be applied to continuous production of an ammonia-mixed fuel having a constant composition by continuously introducing raw material ammonia and a combustion improver, as shown in FIG. 5, which will be described later. In that case, the combustion improver fixed quantity introduction mechanism is composed of the weighing device and the

control valves

20b and 20c. When introducing a fixed quantity, the control device 32 receives the result of weighing the combustion improver by the scaler, generates a control signal for controlling the opening degree of the regulating

valves

20b, 20c, and transmits the generated control signal to the regulating

valves

20b, 20c. send to At the time of constant introduction, the weighing result of the amount of the combustion improver introduced (the value obtained by subtracting the mass of the closed mixing container 16 before the start of the introduction of the combustion improver) becomes the set amount to be introduced into the closed mixing container 16. When the control device 32 determines that it has reached, the

control valves

20b and 20c are fully closed by a control signal generated by the control device 32, and the introduction is stopped.
The saturated vapor pressure of ammonia in a liquid state and the saturated vapor pressure of the liquefied petroleum gas or the combustion improver, which is a component hydrocarbon of the liquefied petroleum gas, are both considerably higher than the atmospheric pressure at around normal temperature (25° C.). Therefore, if the internal pressure of the closed container 16 for mixing is approximately atmospheric pressure and is sufficiently lower than the saturated vapor pressure of these, as shown in FIG. Even if a pump is not provided, each of the closed ammonia storage container 12 and the closed combustion improver storage container 14 can be introduced into the closed mixing container 16 by discharging the liquid phase due to the saturated vapor pressure inside the closed container 14 .

Nitrogen gas introduction mechanism 30 exists in each introduction line and mixing closed container 16 as necessary from the viewpoint of explosion protection at the time of starting up the manufacturing apparatus 10 and after the completion of manufacturing the ammonia mixed fuel. It is provided to replace the gas to be used with nitrogen gas. The nitrogen gas introduction mechanism 30 is provided with a nitrogen gas introduction valve 30 a for introducing a predetermined amount of nitrogen gas into the ammonia introduction line 18 and the combustion improver introduction line 20 . The degree of opening of the nitrogen gas introduction valve 30a is controlled by control signals generated by the controller 32 based on control signals for controlling the degrees of opening of the

adjustment valves

18b, 18c, 20b, and 20c.
The introduction of the liquefied ammonia and the liquefied petroleum gas or the combustion improver, which is a component hydrocarbon species of the liquefied petroleum gas, into the closed mixing container 16 described above is preferably carried out by the following procedure. When these liquefied gases, ammonia and the combustion improver, are introduced into the closed container for mixing (12, 14), they are discharged by their respective saturated vapor pressures into the closed container for mixing (16). can be introduced. At that time, in order to complete the introduction of both, during these introductions, the internal pressure of the ammonia storage closed container 12 (the saturated vapor pressure of ammonia) and the internal pressure of the combustion improver storage closed container 14 (the saturated high pressure of the combustion improver ), the saturated vapor pressure of both mixtures in the closed mixing vessel 16 must always be lower than in the case of For this reason, before a series of introduction steps, the temperature of the liquid phase of the mixture in the closed mixing container 16 is adjusted to a sufficiently low saturated vapor pressure (for example, about 0.05 to 0.05) by temperature control described later. .1 MPa or less) (in many cases, it is substantially cooled to a lower temperature than the external environment).
After that, the gas phase discharge valve 21a is opened (becomes open to the atmosphere), and the nitrogen gas introduction mechanism 30 allows a predetermined amount of nitrogen gas to pass through each introduction line into the mixing sealed container 16, and from an explosion-proof viewpoint, If necessary, the air in each introduction line and the closed container 16 for mixing is once replaced with nitrogen gas. Next, predetermined amounts of the liquefied ammonia, the combustion improver, and the surfactant are sequentially introduced into the closed mixing container 16 through the respective introduction lines by the quantitative introduction mechanism described above. In order to avoid a situation in which the internal pressure of the closed container 16 for mixing rises during the introduction of these, the liquefied ammonia, the combustion improver, etc. cannot be introduced any more. It is preferable that the components having the lowest saturated vapor pressure at the temperature during stirring and mixing in the closed container 16 for mixing are introduced in order. Among raw materials of liquefied ammonia as liquefied gas, liquefied petroleum gas as combustion improver, and its constituent hydrocarbon species, those having the lowest saturated vapor pressure at the set temperature are introduced into closed mixing vessel 16 in that order. Here, for example, between ammonia and propane, which is one component of liquefied petroleum gas, it should be noted that the saturated vapor pressure of propane is higher than that of ammonia at temperatures below about 15°C, and the reverse occurs at temperatures above that. , the order of introduction needs to be chosen. At that time, first, the nitrogen gas filling the closed container 16 for mixing is sufficiently eliminated by the vaporized gas of the liquefied gas component having the lowest saturated vapor pressure, which is introduced first among the raw materials of the liquefied gas. , is preferably replaced. After this gas replacement, the gas phase discharge valve 21a is closed, and the

adjustment valves

18b, 18c or the

adjustment valves

20b, 20c are opened. is started, and after the introduction of the predetermined amount is completed, the regulating

valves

18b, 18c or the regulating

valves

20b, 20c are closed. When the second and subsequent liquefied gas raw materials are introduced, the gas replacement described above is not performed, and a predetermined amount of the remaining liquefied gas raw materials are similarly introduced in descending order of saturated vapor pressure.

According to the above configuration and procedure, even if the ammonia introduction line 18 and the combustion improver introduction line 20 are not provided with liquid feed pumps, the liquefied ammonia and the liquefied petroleum gas or liquefied gas in the respective

closed storage containers

12 and 14 By discharging the combustion improver, which is a component hydrocarbon species of petroleum gas, at saturated vapor pressure, ammonia and the combustion improver can be introduced into the closed mixing vessel 16 whose internal pressure is suppressed to a lower level. However, the saturated vapor pressure of the mixture of ammonia and the combustion improver (in many cases, the saturated vapor pressure of the mixture is equal to the saturated vapor pressure of the ammonia and the combustion improver) in the closed mixing vessel 16 into which the ammonia and the combustion improver have already been introduced. In some cases, it is advantageous to be able to pressurize and introduce the raw material ammonia and the above-mentioned combustion improver against the saturated vapor pressure (higher than the saturated vapor pressure when it is alone). In particular, as will be described later, when ammonia and the above-mentioned combustion improver are continuously introduced into the closed container for mixing 16 in an additional fixed quantity to continuously produce an ammonia-mixed fuel, the ammonia introduction line 18 and/or the aid Each of the fuel introduction lines 20 needs to be provided with a liquid feed pump. In that case, the liquid feed pump has a head sufficiently higher than the saturated vapor pressure of the mixture of ammonia and the combustion improver in the mixing sealed container 16, and a sufficient pump that matches the production rate and discharge rate of the ammonia mixed fuel. In addition to high-head centrifugal pumps, positive displacement types such as gear types, screw types, plunger types, and uniaxial eccentric screw types are suitable. To be elected. In addition, when such a high-lift liquid-sending pump is provided in the ammonia introduction line 18 and the combustion improver introduction line 20, the ammonia and the combustion improver can be fed into the mixing sealed container 16 without relying on the order of introduction described above. It is also possible to forcibly introduce
When liquid-sending pumps are provided in the ammonia introduction line and/or the combustion improver introduction line, the respective liquid-sending pumps are also driven or stopped in conjunction with the regulating

valves

18b, 18c and/or the regulating

valves

20b, 20c. At this time, if the liquid-sending pump is a non-displacement-type centrifugal pump or the like, the liquid-sending amount is controlled by adjusting the opening degree of each of the adjustment valves. On the other hand, when using the above-mentioned vane type, gear type, screw type, plunger type, uniaxial eccentric screw type, etc. volume type liquid transfer pump, the opening degree of each of the above adjustment valves is almost fully opened during liquid transfer, By controlling the number of revolutions of the motor of the liquid transfer pump itself, the liquid is controlled to have a predetermined discharge amount. After the series of introductions described above is completed, the regulating

valves

18b, 18c, 20b, and 20c are all closed and the closed mixing container 16 is sealed, the liquid phase temperature of the mixture in the closed mixing container 16 is , by a temperature control mechanism described later, the predetermined temperature at the time of introduction for lowering the saturated vapor pressure is switched to a preferable temperature range in the production of the ammonia mixed fuel described later, and the temperature range is changed during the subsequent production of the ammonia mixed fuel. It is preferred that the temperature is maintained. The series of controls described above is performed based on the control signal generated by the control device 32 .

The liquid phase discharge line 22 is usually provided at the bottom, preferably the bottom, of the closed mixing vessel 16, and substantially the entire amount of the mixture obtained by stirring and mixing with the stirrer 24 is discharged from the closed mixing vessel 16 as ammonia mixed fuel. configured for ejection.
However, when the combustion improver is liquefied petroleum gas, naphtha, gasoline, kerosene, light oil, or component hydrocarbon species thereof, the liquid phase of the mixture with ammonia in the closed mixing container 16 is separated into upper and lower layers. situations may arise. At this time, the liquid phase portion of the lower layer separated by the difference in specific gravity is discharged from the liquid phase discharge line 22 provided at the bottom of the closed container 16 for mixing, as shown in FIG.
On the other hand, as a modification of the manufacturing apparatus 10 of FIG. ₂ , as shown in FIG. By extending upward from the bottom of the container, the liquid phase portion of the upper layer can also be discharged separately. That is, the liquid phase discharge line of the manufacturing apparatus ₁₀ includes both forms of 22 in FIG. ₂ and 222 in _FIG . Also included are those that have both. These liquid

phase discharge lines

22, 22 ₁ , 22 ₂ are provided with regulating

valves

22a, 22a ₁ , 22a ₂ , and control signals from the control device 32 control the opening of the regulating

valves

22a, 22a ₁ , 22a ₂ . controlled. 3(a) and 3(b) show only the parts related to the above configuration in the manufacturing apparatus 10, and the other parts are omitted.

As the stirrer 24 provided in the closed container 16 for mixing, a general single stirrer blade type is sufficient for simple mixing without adding a surfactant, and when the liquid state ammonia and the combustion improver are mutually soluble. be. However, when a surfactant is added to form an emulsion, the above single stirring impeller type may be applied, but a single or multiple planetary (planetary rotation) stirring impeller with a higher dispersion effect A method of forcibly pressurizing and circulating the liquid mixture to be stirred in a narrow space, etc., can be used more effectively. If a stirrer of a type with a high stirring effect is used, the emulsion state is easily formed, but the internal pressure may rise due to the heat generated due to the viscous friction of the liquid mixture to be stirred. This inconvenience can be resolved by adjusting the temperature inside the closed container 16 for mixing by means of a series of temperature control mechanisms in the embodiment described later.

In the manufacturing apparatus 10 of one embodiment, a temperature control mechanism configured to control the temperature of the mixture of ammonia and the combustion improver in the closed mixing container 16 to a predetermined temperature is provided. This temperature control mechanism can realize the following three functions.
As a first function of the temperature control mechanism, ammonia in a liquid state, liquefied petroleum gas, and a combustion improver that is a component hydrocarbon species thereof are introduced into the closed mixing container 16 and stirred and mixed by the stirrer 24. In this case, the internal pressure of the closed container 16 for mixing (if the nitrogen in the gas phase is sufficiently replaced in advance by the vaporized gas component of the raw material ammonia or the combustion improver, the internal pressure becomes equal to the saturated vapor pressure of the mixture) ) is within a temperature range that does not exceed the set pressure resistance of the closed vessel 16 for mixing. That is, the liquid phase temperature of the mixture is controlled so that the saturated vapor pressure of the mixture in the closed mixing container 16 does not exceed the set pressure resistance of the closed mixing container 16 . As a result, the saturated vapor pressure of the mixture at the highest possible mixing temperature can be set to the design pressure resistance of the closed mixing container 16 (generally, a pressure value with a safety margin added is adopted). Since there is no need to unnecessarily increase the pressure resistance of the closed mixing container 16, the closed mixing container 16 and the manufacturing apparatus 10 can be reduced in weight and cost. In addition, once the liquid phase composition of the mixture in the closed container 16 for mixing is determined, there is a uniform relationship between the saturated vapor pressure and the temperature of the mixture based on vapor-liquid equilibrium (saturated vapor pressure and The relationship with temperature is generally represented with high accuracy by an approximation formula such as Antoine's formula, for example). In addition to the liquefied petroleum gas or its component hydrocarbons, naphtha, gasoline, kerosene, light oil, and their component hydrocarbons, as well as raw material alcohol, are used as combustion improvers for the above pressure resistance design. Furthermore, it can be applied to a case where a plurality of these are used in combination as a combustion improver, and the closed container 16 for mixing and the manufacturing apparatus 10 can be similarly lightened and reduced in cost.
In addition to the stirrer 24, the temperature control mechanism includes a thermometer 33, a pressure gauge 31, a temperature control jacket 17, a heating and cooling mechanism for the temperature control medium m, and a circulation pump for the temperature control medium m. Includes constant temperature bath. The constant temperature bath is installed outside the manufacturing apparatus 10 and is not shown in FIG. As the temperature control medium m, an inert liquid that does not easily solidify or volatilize in the control temperature range, such as water, ethylene glycol, diethylene glycol, etc., is selected. In FIG. 2, the temperature control jacket 17 is a heat exchanger that covers the outer periphery of the mixing container 16, and a liquid temperature control medium m adjusted to a predetermined temperature flows through the jacket 17 and mixes. By heating or cooling the outer circumference of the closed vessel 16 for mixing, the temperature of the mixture of ammonia and the combustion improver inside the closed vessel 16 for mixing is adjusted to the target temperature by heat exchange. The temperature control medium m is adjusted to a predetermined temperature in the constant temperature bath, and flows through a pipe (not shown) into the temperature control medium inlet nozzle 17a provided at the bottom of the jacket 17, After the heat exchange is performed, it is discharged from the temperature control medium outlet nozzle 17b provided on the upper part of the jacket 17 and returned to the constant temperature bath via a pipe (not shown). When adjusting the temperature of the mixture inside the closed mixing vessel 16, the stirrer 24 is first driven with a predetermined output based on a control signal for the stirrer 24 generated by the control device 32, and the inside of the closed mixing vessel 16 is is stirred. At the same time, the temperature control of the constant temperature bath is actuated based on the control signal generated by the control device 32, and the temperature control medium m whose temperature has been adjusted in the constant temperature bath flows into the jacket 17 and is circulated in the constant temperature bath. . During the temperature adjustment of the mixture, the stirring and circulation of the temperature adjustment medium m are continued, and the liquid phase temperature near the gas-liquid interface in the closed mixing container 16 is measured by the thermometer 33 and the temperature adjustment jacket 17. The internal gas phase pressure is measured by the pressure gauge 31 over time, and the control device 32 receives the measurement results by the thermometer 33 and the pressure gauge 31 over time.

As a second function of the temperature control mechanism, when the ammonia and the combustion improver are introduced into the closed mixing container 16, the mixture in the closed mixing container 16 is The gas phase internal pressure and liquid phase temperature are controlled as follows. For example, in the process of introducing a series of liquefied gas raw materials into the closed mixing vessel 16, as described above, the gas phase internal pressure (saturated vapor pressure) of the mixture of liquefied gas raw materials already introduced into the closed mixing vessel 16 is always lower than the lowest saturated vapor pressure in the closed storage vessel for each of the raw material liquefied ammonia, liquefied petroleum gas and its component hydrocarbon species to be introduced from now on. and the liquidus temperature is adjusted below the required temperature. In addition, in the step of producing the ammonia mixed fuel by stirring and mixing after the introduction of the raw materials into the closed mixing vessel 16 is completed, the liquid phase of the mixture of raw materials in the closed mixing vessel 16 is in the preferred temperature range described later. is preferably held at . In these temperature adjustments, the difference between the control target value of the gas phase internal pressure in the closed mixing container 16 and the actual internal pressure measurement value by the pressure gauge 31, or the control target temperature value of the mixture and the thermometer 33 The temperature flowing into the temperature control jacket 17 is such that the difference from the actual temperature value is within a predetermined allowable range (for example, within ±0.01 MPa for the former and within ±1° C. for the latter). The temperature of the regulating medium m is regulated by controlling the power output for heating/cooling of the thermostat based on the control signal generated by the controller 32 .
In order to increase the response speed and accuracy of the temperature control mechanism, the temperature of the temperature control medium m in the constant temperature bath must The relationship is recognized in advance by the control device 32, and the control signal generated by the control device 32 based on those relationships uses PID control or the like for the temperature of the temperature adjustment medium m in the thermostatic bath to control the above Preferably, the power output for heating and cooling the thermostat is controlled. In the process of these controls, there is a possibility that the gas phase internal pressure of the closed mixing vessel 16 measured by the pressure gauge 31 may reach the design pressure resistance of the closed mixing vessel 16 due to some unforeseen circumstances. If the control device 32 determines that the is stopped (of which the latter is effective when the temperature of the temperature control medium m is higher than the temperature of the surrounding environment), a further increase in the internal pressure is avoided.
In the above, on the premise of ensuring safety such as explosion protection, instead of adjusting the temperature in the closed mixing container 16 by heat exchange with the temperature adjusting medium m in the temperature adjusting jacket 17, for example, a Peltier element Alternatively, a combination of a Peltier element and an electric heater or the like may be provided around the outer periphery of the closed mixing container 16 (not shown in FIG. 2) to control the temperature. In this case, the temperature control in the closed mixing vessel 16 is based on the control signal generated by the control device 32 that receives the internal temperature value measured by the thermometer 33, and the heating or cooling output by the Peltier element or the like is controlled. It is done by being controlled.

As the third function of the temperature control mechanism, in the manufacturing apparatus 10 of another preferred embodiment, when the ammonia and the combustion improver are introduced into the mixing sealed container 16 and then stirred and mixed by the stirrer 24 , the entire liquid phase portion of the mixture of ammonia and the combustion improver in the closed mixing vessel 16 maintaining the gas-liquid equilibrium state is such that the ammonia and the combustion improver dissolve in each other according to the liquid phase composition of the mixture. The temperature of the mixture is adjusted by the above-described temperature control mechanism so that the mixture is in a temperature range such that it is in a solution state or an emulsion state of ammonia and the combustion improver. As a result, the mixture as a whole becomes an ammonia mixed fuel in which the combustion improver is stably and uniformly dispersed. Subsequent uniform and rapid combustion is possible. The stabilization and homogenization of the ammonia-mixed fuel by the solutionization of the entire liquid phase portion or the emulsification by the temperature control described above can be achieved by using the above-mentioned liquefied petroleum gas and its component hydrocarbon species as combustion improvers, as described later. Naphtha, gasoline, kerosene, light oil, and their component hydrocarbon species, when using raw material alcohol, furthermore, when using a combination of these as a combustion improver, can also be applied, and the combustibility can be improved.
In the above, the "temperature range in which the ammonia and the combustion improver are in a solution state or an emulsion state of the ammonia and the combustion improver" includes the type of the combustion improver and the liquid phase composition of the mixture. An appropriate temperature range is selected accordingly, and the temperature control mechanism adjusts the temperature within that range. In the case where the combustion improver is liquefied petroleum gas or its constituent hydrocarbon species, FIG. The above temperature range will be described below.

For example, as described above, the ammonia mixed fuel in the closed mixing container 16 has two liquid phases in a relatively low temperature range below the critical solution temperature (about 33 ° C. in the case of an ammonia-propane mixed system). It becomes a vapor-liquid equilibrium system with a composition range that separates into As described above, each of the phase-separated two phases is in a single “solution state in which ammonia and a combustion improver are dissolved in each other”, and if at least one of the two phases can be taken out, The result is an ammonia mixed fuel with a stably and uniformly dispersed combustion improver. Since both of these two phases can be taken out to the outside by the configuration described later, if the temperature range corresponds to the liquid phase composition in which such a two-phase separation state is obtained, it is the above-mentioned "a solution in which ammonia and a combustion improver are mutually dissolved. state, or a temperature range in which an emulsion state of ammonia and a combustion improver is achieved.
Also, as described above, in a mixture of ammonia and liquefied petroleum gas or its component hydrocarbon species, there exists a temperature above which the entire liquid phase becomes a single-phase solution. For example, as shown in FIG. 1(a) above, in the ammonia-propane mixed system, both compositions at points A and B (ammonia concentration x _A =16.2% by mass and x _B =86.5% by mass %), the entire solution is uniform when both are held at 20° C. or higher. The temperature range is such that it becomes a dissolved solution state or an emulsion state of ammonia and the combustion improver. Furthermore, in the temperature range above the above-mentioned critical solution temperature (about 33 ° C. in the case of the ammonia-propane mixed system), the composition region in which phase separation occurs disappears, and the mixture becomes a uniform solution at any liquid phase composition. It can be taken outside. Therefore, regardless of the composition, the temperature range above the critical solution temperature is "a temperature range in which the ammonia and the combustion improver are in a solution state or an emulsion state of the ammonia and the combustion improver". .
Furthermore, for example, in the composition at point C (ammonia concentration x _C =77% by mass) in the ammonia-propane mixed system shown in FIG. When a system surfactant (same as that used in Example 3) is added and mixed with stirring to maintain the temperature at about 17° C. or higher, the phase separation part is emulsified and disappears, and the whole is in a uniform state. can be When no surfactant is added, the solution is homogenized at 23°C. The specifications and operation method of the manufacturing apparatus 10 when using a surfactant will be described later. Therefore, in the composition at point C (ammonia concentration of 77% by mass) in the figure, when a predetermined amount (about 1% by mass) of the above predetermined amount of suitable mixed surfactant is added, the is the above-mentioned "temperature range in which the ammonia and the combustion improver are in a solution state or an emulsion state of the ammonia and the combustion improver". At this time, as the mixed surfactant, it is preferable to select one that exhibits the best performance in this temperature range. In other words, if such a surfactant is selected, the above temperature range also matches the temperature range in which the emulsifying performance of the surfactant can be sufficiently brought out.
As described above, the uniform ammonia mixed fuel produced in "a temperature range in which the ammonia and the combustion improver are in a solution state or an emulsion state of the ammonia and the combustion improver" according to the composition, If it is taken out in that state and subjected to combustion, it exhibits high combustibility.

Next, in the closed container 16 for mixing in FIG. Concerning the situation of compositional fluctuation due to the liquidus temperature of the ammonia mixed fuel of petroleum gas component hydrocarbon species), the case of the vapor-liquid equilibrium of the ammonia-propane system at 20 ° C. in the above-mentioned Fig. 1 (a) is taken as an example. , will be described below. The mixture with ammonia similarly forms an azeotropic system of liquid-phase two-phase separation. Even when using other component hydrocarbon species of liquefied petroleum gas as a combustion improver, there are differences in the temperature range, pressure range, and composition range. However, the situation is qualitatively the same.

(i) In the case of a liquid phase composition in which the liquid phase is a single phase In the gas-liquid-liquid equilibrium diagram at 20 ° C. in FIG. A region between points P and A where propane is the main component, where the concentration is 0% by mass to x _A , and between points B and Q where ammonia is the main component, where the concentration of liquid phase ammonia is x _B ~ 100% by mass. By introducing liquefied ammonia and liquefied propane into the closed mixing container 16 at the charging composition ratio corresponding to each, and stirring and mixing, the liquid phase composition of the above two regions is obtained. A phase ammonia blend fuel is prepared. This can be discharged from the liquid phase discharge line 22 by discharge based on the saturated vapor pressure in the closed vessel 16 for mixing.
However, it should be noted that the composition of the above single-phase ammonia mixed fuel changes as follows as the emission progresses. In the following, for the sake of simplification, it is assumed that the liquid phase is sufficiently stirred and mixed even during discharge, the composition and temperature of the entire liquid phase are always uniform, and the liquid phase temperature does not change. In practice, the endothermic heat associated with evaporation, which will be described later, causes the liquid phase temperature to drop somewhat as the liquid phase is expelled, but this is compensated for by the temperature regulation mechanism described above.

For example, when discharging an ammonia mixed fuel mainly composed of propane such that the liquid phase ammonia concentration at the start of discharge is x _A of the saturated concentration, which corresponds to point A in FIG. As the gas-liquid interface decreases as it progresses, the volume of the gas phase portion increases, and the pressure in the closed container 16 for mixing is reduced. In response to this change, the mixture of ammonia and propane evaporates (boiling) from the liquid phase to the gas phase in the volume of the gas phase in the closed mixing container 16, thereby dynamically maintaining the gas-liquid equilibrium. be. Since the composition of the evaporative gas in equilibrium with the liquid phase composition x _A at the start of discharge is the azeotropic composition y _O with a higher ammonia concentration than x _A , relatively more ammonia evaporates from the liquid phase. The ammonia concentration of the phase drops somewhat from _xA . As the discharge of the ammonia mixed fuel further progresses, the state of the liquid phase in the closed mixing container 16 changes from point A (ammonia concentration x _A ) in FIG. (ammonia concentration 0% by mass), the state of the gas changes so as to move along the liquidus line AP and evaporates to the gas phase side along with that is the point O (ammonia concentration y ₀ ) to point P of pure propane, moving along the vapor line OP. In this process, the internal pressure in the closed mixing vessel 16 decreases from the azeotropic vapor pressure at point O to the saturated vapor pressure of pure propane at point P as the liquid phase is discharged.
When discharging an ammonia-mixed fuel having a liquid-phase ammonia concentration between 0% by mass and x _A , the above operation is performed from a midpoint on each of the liquidus line AP and the gaseous line OP. is equivalent to starting
On the other hand, when discharging an ammonia mixed fuel containing mainly ammonia such that the liquid phase propane concentration at the start of discharge is 1-x _B of the saturated concentration, which corresponds to point B in FIG. 1(a), Shows the following state changes: That is, as the discharge of the ammonia-mixed fuel progresses, the state of the liquid phase in the mixing closed container 16 (that is, the ammonia-mixed fuel discharged from the liquid-phase discharge line 22) changes from that shown in FIG. From point B (ammonia concentration x _B ) to point Q of pure ammonia (ammonia concentration of 100% by mass), the gas evaporates to the gas phase side. The state changes from point O (ammonia concentration y _O ) in FIG. The inner pressure decreases from the azeotropic vapor pressure at the O point to the saturated vapor pressure of pure ammonia at the Q point as the liquid phase is discharged.
When discharging an ammonia-mixed fuel having a liquid-phase ammonia concentration of between x _B and 100% by mass, the above-mentioned behavior can be determined from points in the middle of each of the above-described liquidus line BQ and gaseous line OQ. is equal to the beginning of
Therefore, in the compositional region where the liquid phase becomes a single-phase solution, it is necessary to allow the above compositional change accompanying the progress of discharge of the ammonia-mixed fuel. However, in the above, if the agitation of the liquid phase is stopped during the discharge and the mass transfer of each component in the liquid phase and at the gas-liquid interface is suppressed, the vicinity of the liquid phase discharge line 22 in the closed mixing container 16 that is discharged can reduce the liquid phase composition change of Furthermore, when the opening degree of the liquid phase discharge valve 22a is widened to speed up the discharge speed of the ammonia-mixed fuel, a larger portion of the ammonia-mixed fuel in the mixing sealed container 16 is discharged while suppressing the composition change. can be made If the change in composition during discharge could cause some trouble when used as fuel, the liquid phase discharge valve 22a is closed at that point to terminate the discharge.

(ii) In the case of a liquid phase composition in which the liquid phase separates into two phases In the gas-liquid-liquid equilibrium diagram at 20 ° C. in FIG. _A ∼ x is the region between points A and _B of B, and the liquid phase composition (ammonia concentration x _C ) at point C (average state of the entire two liquid phases) at an arbitrary position in this region is the starting composition ratio corresponding to , liquefied ammonia and liquefied propane are introduced into the closed mixing container 16 and stirred and mixed to form a propane-based liquid phase having an ammonia concentration of the saturated concentration x _A and a propane concentration of 1-x the saturated concentration. _B (at this time, the ammonia concentration is x _B ), and a two-phase separated state is formed with a liquid phase mainly composed of ammonia. At this time, since the specific gravity of liquefied propane is smaller than that of liquefied ammonia, the propane _- based phase with ammonia concentration xA is the upper layer, and the ammonia _- based phase with ammonia concentration xB is the lower layer. In general, the other constituent hydrocarbon species of the liquefied petroleum gas and the liquefied petroleum gas mixtures thereof also all have lower specific gravities than the liquefied ammonia, so that the phase dominated by these will always be in the upper layer. At this time, as long as the two-phase separation state continues, the lower layer, which is mainly composed of ammonia having a certain ammonia concentration x _B , is used as the ammonia mixed fuel, and is discharged based on the saturated vapor pressure in the closed mixing vessel 16 to the liquid phase. It can be discharged from the discharge line 22 .
In the above, in order to discharge as much of the ammonia-based lower layer as possible, which has a constant ammonia concentration xB, the position of the above point _C (the average state of the entire two liquid phases) must be aligned with the line segment AB It is preferable that the liquefied ammonia and the liquefied propane are introduced into the closed mixing vessel 16 at a charge composition ratio such that the position is closer to the point B from the vicinity of the center of . This is because when point C is close to point A, the absolute amount of the lower layer of ammonia concentration x _B that can be discharged decreases due to the principle of leverage described above, and when the discharge of the lower layer ends, the upper layer of ammonia concentration x _A can be discharged. If point C is too close to point B, evaporation during liquid phase discharge explained in (i) above (when point C is close to point B, propane is relatively The upper layer quickly disappears due to the change (increase) in the average concentration of the liquid phase accompanying the above (i), and the ammonia concentration increases from x _B is.

As described above, in the closed mixing container 16 of FIG. is slightly higher than the bottom of the upper layer at the start of discharge (22 ₂ in FIG. 3A), leaving the lower layer with ammonia concentration x _B described above, propane with ammonia concentration x _A It is also possible to discharge only the upper layer of the main body as an ammonia mixed fuel. In this case, in order to discharge the upper layer as much as possible, the position of the above point C (average state of the entire two liquid phases) is the position of the point A from near the center of the line segment AB. Preferably, liquefied ammonia and liquefied propane are introduced into the closed mixing vessel 16 in proportion.
Furthermore, as described above, the discharge ports in the closed mixing container 16 are the liquid phase discharge line 22 at the bottom of the closed mixing container 16 as shown in FIG. If the position of the outlet is a little higher than the bottom of the upper layer at the start of discharge, and the liquid _phase discharge line 221 is combined (Fig. 3(b)), the lower layer of ammonia concentration x _B and the upper layer of the ammonia concentration x _A can be simultaneously discharged as an ammonia mixed fuel. In this case, liquefied ammonia and liquefied propane are introduced into the closed mixing vessel 16 at a charge composition ratio such that the position of point C (the average state of the entire two liquid phases) is near the center of line segment AB. preferably.
However, in the above, as the discharge of the upper layer with the ammonia concentration _xA and/or the lower layer with the ammonia concentration xB progresses, the gas _- liquid interface and/or the interface between the upper layer and the lower layer descends, eventually , liquid-

phase discharge lines

22, 22 ₁ , 22 ₂ in the upper and/or lower layers in the closed container 16 for mixing, the height positions of the respective in-vessel discharge ports are lowered gas-liquid interfaces and/or the upper and lower layers and the discharge of the upper and/or lower layers can no longer be continued. Therefore, if it is desired to avoid mixing of a different phase (non-target liquid phase layer or gas phase) in the discharge, the liquid

phase discharge valves

22a, 22a ₁ , 22a ₂ are closed by then.

In the above, when liquefied ammonia and liquefied propane are introduced into the closed mixing vessel 16 at a charging composition ratio corresponding to the liquid phase composition (ammonia concentration x _C ) in the two-phase separation region, the ammonia concentration x in the upper layer _A (x _A corresponds to the saturated concentration of ammonia in the upper layer) and the ammonia concentration x _B (1−x _B corresponds to the saturated concentration of propane in the lower layer) in the lower layer are the temperature control mechanism By keeping the temperature of the liquid phase in the closed container for mixing 16 at a predetermined temperature while stirring and mixing, the following control can be achieved.
For example, the ammonia concentrations x _A ' and x _B ' at both ends of the two-phase separation region at 0° C. shown in FIG. 5% by mass. At 20° C., the liquid phase composition range of the two-phase separation region is narrower than at 0° C., with x _A being about 16.2 mass % and x _B being about 86.5 mass %. As described above, the liquidus temperature in the closed container 16 for mixing is maintained at 0° C. to 20° C. by the temperature control mechanism, so that the upper layer and/or having the above compositions (x _A , x _B ) Or the lower layer can be drained. As the holding temperature of the liquid phase during stirring and mixing is further lowered below 0° C., x _A and x _B approach 0 wt % and 100 wt %, respectively. In addition, when the liquidus temperature is further increased beyond 20°C, the two-phase separation region gradually shrinks and x _A and x _B approach each other, reaching the critical solution temperature (about 33°C) and reaching the two-phase separation region. vanishes, and x _A and x _B become equal to the ammonia concentration x _O (=y _O ≈32% by mass) at the azeotropic point O at the critical solution temperature.
Therefore, in the ammonia-propane mixed system, liquefied ammonia and liquefied propane are introduced into the closed mixing vessel 16 at a charge composition ratio corresponding to an arbitrary liquid phase composition (ammonia concentration x _C ) in the two-phase separation region, By maintaining the liquidus temperature in the closed mixing container 16 at a predetermined constant value from a low temperature of less than 0° C. to the critical solution temperature (about 33° C.), the ammonia concentrations in the upper and lower layers are respectively reduced to 0. A predetermined value x _A within the range from the vicinity of mass% to the ammonia concentration x _O (= y _O ) at the azeotropic point O at the critical solution temperature (about 33 ° C.), and the critical solution temperature (about 33 ° C. ) can be controlled to a predetermined value x _B within a range from the ammonia concentration x _O (=y _O ) at the azeotropic point O to the vicinity of 100% by mass. This allows the upper layer and/or the lower layer having these compositions to be discharged as a single-phase solution ammonia mixed fuel from the liquid phase discharge lines _22-1 and/or _22-2 , respectively.
In addition, as a special situation, the raw material ammonia and propane are introduced at a composition ratio equal to the above azeotropic composition x _O (= y _O ≈ 32% by mass) at the critical azeotropic temperature (about 33 ° C.), and a closed mixing When each introduced into the container 16 and stirred and mixed, and the liquid phase temperature is maintained at the critical azeotropic temperature (about 33 ° C.) or higher by the temperature control mechanism, the liquid phase of the mixture in the closed container 16 for mixing becomes a single-phase solution with the above azeotropic composition. Since the composition of the vapor when evaporating from the liquid phase is always the same azeotropic composition as the liquid phase, the liquid phase composition is maintained at the azeotropic composition regardless of the progress of evaporation accompanying the discharge of the liquid phase. Meanwhile, the entire amount of the liquid phase in the mixing sealed container 16 can be discharged from the liquid phase discharge line 22 (22 ₁ ) as a single-phase solution ammonia-mixed fuel.
According to the production apparatus 10 of the present embodiment, not only the ammonia-propane system described above, but also other liquefied petroleum gases in which a mixture with ammonia similarly exhibits an azeotropic gas-liquid equilibrium of liquid phase two-phase separation When using a component hydrocarbon species or a mixture of liquefied petroleum gas as a combustion improver, there are differences in the temperature range, pressure range, and composition range in which the two phases are separated, but by using the same apparatus and method, As in the case of the ammonia-propane system described above, it is possible to discharge the liquid phase of the mixture in the closed mixing container 16 as an ammonia mixed fuel while controlling the discharge composition.
However, as described above, as the ammonia mixed fuel is discharged, the gas-liquid interface of the mixture in the mixing sealed container 16 and the interface between the upper and lower layers at the time of liquid phase separation descend, and the liquid

phase discharge line

22, 22 ₁ , 22 ₂ reaching the outlet position in the closed container for mixing, the heterophase can be mixed in the ammonia mixed fuel, and the evaporation of the mixture progresses, thereby the composition of the discharged ammonia mixed fuel Note that can vary.

In the manufacturing apparatus 10 of one embodiment, in addition to the above-described configurations shown in FIGS. 2 and 3 (a) and (b), as shown in FIG. A nitrogen gas introduction line 30b is provided so that the nitrogen gas can be introduced into the gas phase portion in the closed mixing vessel 16 at a discharge pressure equal to or higher than the vapor pressure. In FIG. 4 as well, when the components have the same configurations and actions as those of the components shown in FIG. As a result, it is possible to quickly discharge the ammonia mixed fuel while suppressing the change in the liquid phase composition due to the progress of evaporation of the mixture in the mixing sealed container 16 accompanying the discharge of the ammonia mixed fuel as described above. Become. This embodiment can be applied to both the case where the liquid phase of the mixture in the closed container 16 for mixing becomes a single phase and the case of two-phase separation (separation into upper and lower layers). FIG. 4 shows the former form.
The nitrogen gas introduction line 30b is led from a storage container such as a general pressurized nitrogen gas cylinder filled with an internal pressure of about 14.7 MPa. Alternatively, if the pressure is the same, it may be branched from the piping of the nitrogen gas introduction mechanism 30 as shown in FIG. The nitrogen gas introduction line 30b is provided with a nitrogen gas pressure reducing valve 30c, a nitrogen gas pressure gauge 30d, and a nitrogen gas regulating valve 30e between its upstream side and the closed container 16 for mixing. The nitrogen gas introduced through the nitrogen gas introduction line 30b is controlled by the pressure reducing valve 30c so that the indicated value of the nitrogen gas pressure gauge 30d is equal to or higher than the saturated vapor pressure of the mixture in the closed mixing container 16 (for example, the saturated vapor pressure +0 The pressure is reduced to about 0.05 to 0.1 Mpa). When the liquid phase of the mixture is discharged from the closed container 16 for mixing, the nitrogen gas control valve 30e is opened in conjunction with the opening of the liquid

phase discharge valves

22a, 22a ₁ and 22a ₂ to The mixture is discharged from the liquid phase discharge line as an ammonia-mixed fuel in a form forced out by the introduced nitrogen gas. These valve operations are controlled by controller 32 .
When the ammonia mixed fuel is discharged by introducing the nitrogen gas, the introduced nitrogen diffuses and dilutes the evaporative gas from the mixture in the container in the gas phase part in the closed mixing container 16, thereby Strictly speaking, the composition of the liquid phase may change because the gas-liquid equilibrium is shifted at the gas-liquid interface, and the vaporization of the gas from the liquid phase continues even during the discharge of the liquid phase. However, substantially the composition change of the liquid phase is reduced. In particular, when the concentration of ammonia in the mixture is relatively low and the concentration of the combustion improver (liquefied petroleum gas or its component hydrocarbon species) is high, the specific gravity of the evaporative gas in these mixtures is greater than that of nitrogen gas, Since it is easier to stay in the vicinity of the gas-liquid interface below the gas phase portion, the deviation of the gas-liquid equilibrium is suppressed, and the change in the composition of the ammonia mixed fuel described above is suppressed. In addition, as the container shape of the closed container 16 for mixing is longer in the vertical direction and the introduction flow rate of nitrogen gas is higher, the discharge of the internal fluid approaches the so-called “plug flow”, and the above-mentioned nitrogen gas and evaporative gas convection and diffusive dilution are less likely to occur, thus suppressing the aforementioned composition change.

In addition to the above-described configuration shown in FIG. so that ammonia and the combustion improver can be continuously introduced into the closed mixing vessel 16 via the introduction lines 18 and 20 against the saturated vapor pressure of the mixture in the closed mixing vessel 16. A metered introduction mechanism is configured. An example of this embodiment is shown in FIG. In FIG. 5 as well, when the components have the same configurations and actions as those of the components shown in FIG.
With these configurations, the height position of the gas-liquid interface of the mixture in the closed container 16 for mixing, and the height position of the interface between the upper and lower layers when the liquid phase of the mixture separates into two phases are maintained constant, and , the liquid phase whose composition is kept constant can be continuously discharged as an ammonia-mixed fuel. This embodiment can also be applied to either the case where the liquid phase of the mixture in the closed container 16 for mixing becomes a single phase or the case of two-phase separation (separation into upper and lower layers). FIG. 5 shows the form of discharging both the phase-separated upper and lower two layers of the latter.
In this embodiment, in addition to the constituent devices shown in FIG. Liquid feed pumps 18d and 20d are provided in the ammonia introduction line 18 and the combustion improver introduction line 20, respectively, so that the raw material liquefied ammonia and the combustion improver can be introduced. As these liquid-sending pumps, the high-lift pumps described above are selected. In addition,

discharge flowmeters

22b, 22b ₁ and 22b ₂ for measuring the flow rate of the liquid phase portion discharged as the ammonia-mixed fuel from the mixing sealed container 16 through the liquid

phase discharge lines

22, 22 ₁ and 22 ₂ , and , and composition evaluation means 22c, 22c ₁ , 22c ₂ for evaluating the composition (ammonia concentration, etc.) of the liquid phase portion are provided in the liquid

phase discharge lines

22, 22 ₁ , 22 ₂ . These may be on either upstream or downstream side of the liquid

phase discharge valves

22a, 22a ₁ , 22a ₂ .
When the ammonia mixed fuel is discharged, the liquid _phase discharge valves 22a, 22a ₁ and 22a ₂ _are opened and the liquid phase discharge is started. and the liquid phase composition as measured by the composition evaluating means _{22c, 22c 1 , 22c 2} _, _measured by the liquid _phase The flow rates of ammonia and combustion improver in the exhaust liquid phase through

exhaust lines

22, 22 ₁ , 22 ₂ are calculated respectively. Further, the calculated discharge flow rate of ammonia and the combustion improver is equal to the introduction flow rate of the raw material liquefied ammonia and the combustion improver introduced into the closed mixing vessel 16, which are measured by the

flowmeters

18a and 20a. In addition, the control signal transmitted by the control device 32 controls the outputs of the liquid feed pumps 18d and 20d and/or the opening degrees of the regulating

valves

18c and 20c. During this process, the mixing stirring and temperature control of the liquid phase of the mixture in the closed mixing container 16 are continued. According to these controls, the height position of the gas-liquid interface and the interface between the upper and lower layers of the mixture in the closed container 16 for mixing is kept constant, and the composition of the gas-liquid phase and the saturated vapor pressure are also kept constant. Therefore, even if the discharge of the liquid phase progresses, the original gas-liquid equilibrium state is maintained as it is, and evaporation to the gas phase does not occur, so the liquid phase composition is also kept constant. Therefore, the ammonia mixed fuel can be produced with a constant composition and discharged continuously.

In the continuous production of the ammonia-mixed fuel with a constant composition by the continuous addition of the raw material, the composition evaluation means 22c, 22c ₁ , 22c ₂ are capable of rapid in-line measurement and evaluation in the liquid phase discharge line. For example, based on a predetermined calibration method (calibration curve), N-H stretching vibration (in the case of ammonia quantification) and C-H stretching vibration (quantification of hydrocarbons) by a Fourier transform infrared spectrophotometer In the case of ), the evaluation of the absorption intensity in the infrared absorption band of each component, the refractive index of the discharged liquid phase measured by a refractometer, and the sound velocity measurement by ultrasonic irradiation using an ultrasonic concentration meter. Ammonia or combustion improver concentration evaluation means based on, but not limited to, these. The data measured by the composition evaluation means is either converted into the concentration of ammonia or a combustion improver by a calibration method incorporated in the composition evaluation means itself, or is transmitted to the control device 32 as it is, and the latter controls the control. After being converted into the concentration of ammonia or combustion improver in the device 32, by multiplying the flow rate values of the liquid

phase discharge lines

22, 22 ₁ and 22 ₂ transmitted from the

discharge flowmeters

22b, 22b ₁ and 22b ₂ , The respective discharge flow rates of ammonia and combustion improver are calculated. If the relationship between the initial amounts of liquefied ammonia and the combustion improver introduced into the closed mixing container 16 before discharging the liquid phase and the liquid phase composition is known, the initial amounts of each introduced , the composition evaluation means 22c, 22c ₁ and 22c ₂ can be omitted.

The manufacturing apparatus 10 of one embodiment includes a surfactant storage container 26 for storing a surfactant, a An activator introduction line 28 and a liquid feed pump 28d are provided. A surfactant introduction line 28 connects the surfactant storage container 26 and the closed mixing container 16 . Since the surfactant introduction line 28 has a low saturated vapor pressure, it is not voluntarily introduced into the closed mixing container 16. Therefore, the liquid feed pump 28d is used to transfer the surfactant from the storage container 26 to the closed mixing container 16. supplied to The surfactant introduction line 28 is provided with a flow meter 28a and regulating

valves

28b and 28c configured to introduce a predetermined amount of surfactant into the mixing sealed container 16 as a quantitative introduction mechanism for the surfactant. . The control device 32 receives the measurement results from the flow meter 28a, generates control signals for controlling the opening degrees of the regulating

valves

28b and 28c, and sends the generated control signals to the regulating

valves

28b and 28c. However, as will be described later, when the state of the surfactant is a viscous slurry or mud, the flowmeter 28a and the

control valves

28b and 28c are adapted to specifications that are less likely to clog. There is a need. Furthermore, as will be described later, it is necessary to use a liquid feed pump 28d suitable for transferring viscous slurry or muddy surfactant, and quantitative control by opening and closing the

adjustment valves

28b and 28c is difficult. In such a case, the discharge amount of the liquid transfer pump 28d itself is controlled by a control signal generated by the control device 32, so that a fixed amount of liquid is supplied. In other words, the liquid feed pump 28d is also included in the quantitative introduction mechanism for the surfactant. In addition, the nitrogen gas introduction mechanism 30 is present in the surfactant introduction line 28 as necessary from the viewpoint of explosion protection, such as when the production apparatus 10 is started up and after the production of the ammonia mixed fuel is completed. Replace gas. For this purpose, a nitrogen gas introduction valve 30a for introducing a predetermined amount of nitrogen gas into the surfactant introduction line 28 is provided. The control device 32 controls the degree of opening of the nitrogen gas introduction valve 30a.
Therefore, in the closed container 16 for mixing, the surfactant is agitated and mixed together with the liquid ammonia and the combustion improver by the agitator 24 so that the mixture containing the surfactant is discharged from the liquid phase discharge line 22. Configured. Thus, by using a surfactant, it is possible to easily produce an ammonia-mixed fuel in which polar ammonia and a non-polar combustion improver are in an emulsion state.

When the combustion improver is the above-mentioned liquefied petroleum gas or its component hydrocarbon species, at least part of it is compatible with ammonia in the liquid phase in the gas-liquid equilibrium state at around normal temperature (25 ° C.), but the compatible The part that phase separates without the phase separation can also be emulsified by adding a surfactant.
As the surfactant used for emulsifying the ammonia mixed fuel, as described above, at least 1 a species of nonionic surfactant (A) and at least one ionic surfactant (B) that is highly capable of ionizing at the interface and causing electrostatic repulsion between the micelles to prevent contact and fusion. It is preferably a mixed surfactant containing and. As these nonionic surfactant (A) and ionic surfactant (B), those having the above-described molecular structures can be preferably used. When using these mixed surfactants, they are preferably thoroughly mixed and dispersed before being stored in a surfactant storage container.
The surfactants described above are generally in a liquid or solid state near room temperature (25° C.). Ionic surfactants and nonionic surfactants having a long-chain alkyl group with a large number of carbon atoms (long chain length) often become solid near room temperature (25° C.). After mixing the above nonionic surfactant (A) and ionic surfactant (B), it becomes a liquid state or a stable slurry state in which the solid content is difficult to settle, and sufficient fluidity is obtained at the time of introduction. When using a mixed surfactant having It can be introduced into container 16 . On the other hand, when the above mixed surfactant is in a state of lacking fluidity such as solid or nearly so, and it is difficult to introduce it as it is, liquefied ammonia, liquefied petroleum gas, and its components, which are raw materials of mixed fuel By adding a small amount of any of the hydrocarbon species to the surfactant in advance and mixing and dispersing it, a fluid state (e.g., slurry or mud) that can be introduced by the above-described surfactant introduction system is formed. is preferred. When introducing the surfactant into the mixing sealed container 16, if the mixed surfactant is a viscous liquid or slurry or muddy, the liquid feed pump 28d can also quantitatively discharge such an object. and a type capable of feeding liquid is adopted.
The surfactant itself has a low saturated vapor pressure, which is almost zero, at room temperature (25° C.) and atmospheric pressure. When the surfactant itself, which is in a liquid state or a stable slurry state in which the solid content does not easily settle, is introduced into the closed mixing container 16 by feeding the surfactant as it is, the above-mentioned ammonia or the like is used when introducing the surfactant. It is necessary to avoid a situation in which the internal pressure of the closed mixing container 16 rises due to the previous introduction of the liquefied gas, and the surfactant cannot be introduced any more. For this reason, the surfactant is preferably introduced into the closed mixing vessel 16 before the liquefied gas ammonia, liquefied petroleum gas, and the combustion improver, which is a component hydrocarbon species thereof. At this time, the surfactant is controlled by the control signal generated by the control device 32 based on the time integral value of the flow rate measured by the flow meter 28a, opening and closing the

adjustment valves

28b and 28c, and the liquid feed pump 28d. Dosage is introduced by driving and stopping. On the other hand, as described above, when the surfactant is in a solid or near solid state and is slurried or sludged by the addition of liquefied ammonia, liquefied petroleum gas, or any of its component hydrocarbon species, When introduced into the closed container for mixing 16, they should be introduced quantitatively in conjunction with the introduction of any of the same raw material liquefied ammonia, raw liquefied petroleum gas, and component hydrocarbon species thereof. is preferred.

2 and 3 ( The production apparatus 10 shown in a), (b), FIG. 4, and FIG. 5 can be suitably used according to conditions such as composition and mixing temperature. For example, in the above-mentioned ammonia-propane mixture, due to the effect of emulsification by adding and mixing a surfactant, the composition range and temperature range separating into upper and lower layers change compared to when no surfactant is added. do. However, even when emulsified with the addition of a surfactant, there is a composition range and a temperature range that separates the upper and lower layers, and the formation of a single layer due to a temperature rise itself does not allow the surfactant to be used. It is essentially the same as when it is not added.
Therefore, for example, by using the manufacturing apparatus 10 having the configuration shown in FIG. If the composition and temperature conditions are to It can be discharged as mixed fuel. Further, for example, the manufacturing apparatus ₁₀ having the configuration shown in _FIG . The upper and/or lower layers of the liquid phase separated into upper and lower layers can be discharged as an emulsified ammonia-mixed fuel. Further, by using the manufacturing apparatus 10 of FIG. 4 having the nitrogen gas introduction line 30b, it is possible to quickly discharge the mixed fuel as an emulsified ammonia mixed fuel while suppressing the change in composition accompanying the progress of the liquid phase discharge.

Furthermore, according to the configuration shown in FIG. 5, in which the raw material ammonia, the combustion improver, and the surfactant are continuously introduced into the closed mixing vessel 16 at an introduction flow rate equal to the discharge flow rate, the liquid phase separated into upper and lower two layers An emulsified ammonia mixed fuel can be continuously produced and discharged from the upper layer and/or the lower layer while suppressing a composition change accompanying the progress of liquid phase discharge. Here, in the manufacturing apparatus 10 of FIG. 5, the quantitative introduction mechanism for ammonia and the combustion improver (

liquid feed pumps

18d, 20d,

discharge flowmeters

22a, 22a ₁ , 22a ₂ , Mechanism including liquid phase composition evaluation means 22b, 22b ₁ , 22b ₂ , and control device 32) In addition, it was configured to introduce the surfactant into the closed mixing container 16 at an introduction flow rate equal to the discharge flow rate. , a surfactant metering introduction mechanism (including a liquid feed pump 28d). Here, the liquid feed pump 28d needs to be introduced against the saturated vapor pressure of the mixture in the closed container 16 for mixing, so the same is required for the above-mentioned liquefied ammonia and the booster for the combustion improver. A pump of the same type as the liquid transfer pump is selected.
In this embodiment, the controller 32 determines the concentration of the surfactant in the ammonia-mixed fuel from the respective amounts of the ammonia, the combustion improver, and the surfactant previously introduced as raw materials into the closed mixing vessel 16. Calculate Further, the control device 32 receives the measured values of the discharge flow rate of the ammonia mixed fuel measured by the

discharge flow meters

22a, 22a ₁ and 22a ₂ from the time when the discharge of the ammonia mixed fuel is started. to determine the discharge flow rate of the surfactant discharged through the liquid

phase discharge lines

22, 22 ₁ , 22 ₂ . The control device 32 controls the output of the liquid feed pump 28d and the adjustment valve 28b so as to continuously and quantitatively introduce the surfactant from the surfactant storage container 26 into the mixing sealed container 16 at a flow rate equal to this discharge flow rate. , and a control signal for adjusting the opening of 28c.

2, 4, and 5 are partially changed as described later, the components contained in the liquefied petroleum gas as (a) and the liquefied petroleum gas as (b) described above can be obtained as components. (a) at least one of naphtha, gasoline, kerosene, and gas oil, and (b) naphtha, gasoline, kerosene, and gas oil. Ammonia blended fuels can also be produced using at least one of the component hydrocarbon species of. In this case, the combustion improver storage sealed container 14 is a container for storing at least one of naphtha, gasoline, kerosene, light oil, or at least one hydrocarbon species contained as a component thereof. These raw hydrocarbons, which are liquid near normal temperature (25 ° C.) and atmospheric pressure, have a lower ignition temperature than ammonia and are easily ignited. about 5 to 7 times) and is easily combustible. Therefore, naphtha, gasoline, kerosene, and light oil, and the hydrocarbon species contained as their components, can also be used as combustion improvers for ammonia.
In the case of using naphtha, gasoline, kerosene, and light oil, which are liquid near normal temperature (25° C.) and near atmospheric pressure, and combustion improvers that are component hydrocarbon species thereof, the combustion improver in the combustion improver storage sealed container 14 Since the saturated vapor pressure of is almost zero near normal temperature (25° C.), the liquid phase is not expelled by the saturated vapor pressure and does not spontaneously flow into the closed container 16 for mixing. The combustion improver introduction line 20 must be further provided with a liquid feed pump 20d for supplying the combustion improver from the combustion improver storage closed container 14 to the mixing closed container 16. As shown in FIG. At this time, the combustion improver fixed quantity introduction mechanism also includes the liquid feed pump 20d described above, and its drive and output are controlled by the control signal generated by the controller 32 . When these liquid-sending pumps are provided, these liquid-sending pumps are interlocked with the degree of opening or opening/closing of the

control valves

20b and 20c in response to a control signal generated by the control device 32 when supplying a constant amount of the combustion improver. , is output controlled or driven or deactivated.
When introducing naphtha, gasoline, kerosene, light oil, a combustion improver in the case of these component hydrocarbon species, and a surfactant described later into the closed mixing container 16 by liquid feeding using the liquid feeding pump 20d Therefore, it is necessary to avoid a situation in which the internal pressure of the closed mixing container 16 rises due to the prior introduction of ammonia, which is a liquefied gas, so that these gases cannot be introduced any more. For this reason, naphtha, gasoline, kerosene, light oil, and their component hydrocarbon species, combustion improvers, and surfactants, are preferably added prior to ammonia, especially when high-lift liquid feed pumps are not used. , is introduced into the closed container 16 for mixing. During its introduction, in most cases no particular temperature control is required. However, when ammonia is subsequently introduced, as described above, the saturated vapor pressure of the mixture in the closed mixing container 16 must always be lower than the internal pressure of the closed ammonia storage container 12 (saturated vapor pressure of ammonia). Therefore, the temperature of the liquid phase of the mixture in the closed mixing container 16 must be maintained at a predetermined temperature at which the saturated vapor pressure is sufficiently low. Also, as described above, when the surfactant is in a solid or near solid state, it can be slurried or muddled by the addition of liquefied ammonia, naphtha, gasoline, kerosene, light oil, and any of these component hydrocarbon species. It is preferable to introduce into the closed mixing vessel 16 in a liquefied state. , and any of its constituent hydrocarbon species.

When the combustion improver is naphtha, gasoline, kerosene, diesel, or at least one of their component hydrocarbon species, surfactant When no additive is added, in the equilibrium state, both a phase separated into two layers, a phase mainly composed of polar liquefied ammonia and a phase mainly composed of the combustion improver, and a case that the whole solution becomes uniform occur. obtain. In doing so, as in the case of liquefied petroleum gas and its constituent hydrocarbon species, the elevated temperature causes a change from a two-phase separation state to a homogeneous solution state. In addition, the aforementioned critical solution temperature also exists, above which any composition becomes completely miscible. However, when the combustion improver is naphtha, gasoline, kerosene, diesel, and their component hydrocarbon species, the blended fuel with liquefied ammonia generally does not exhibit azeotropic behavior, and its saturated vapor pressure is equal to that of pure is approximately equal to or lower than the saturated vapor pressure of ammonia. In the case of two layers, naphtha, gasoline, kerosene, light oil, and their component hydrocarbon species have a higher specific gravity than liquefied ammonia, so liquefied petroleum gas and its component hydrocarbon species Conversely, in a closed container, the phase mainly composed of these combustion improvers becomes the lower layer of the phase mainly composed of liquefied ammonia.

Even when the combustion improver is naphtha, gasoline, kerosene, diesel oil, and their component hydrocarbon species, the combustion improver and/or ammonia are dissolved in the other liquid phase beyond the solubility determined by the vapor-liquid equilibrium described above. If desired, emulsification by addition of a suitable surfactant is required. In particular, when the combustion improver is kerosene, light oil, and their component hydrocarbons, in a low temperature range from about normal temperature (25 ° C.) to about 50 ° C. where the vapor pressure can be kept low, the combustion improver and / or Since the solubility of ammonia remains at a low concentration of about 5% by mass or less, addition of a surfactant is important. At that time, the solubility of the liquefied ammonia and the combustion improver that can be mixed and dispersed is substantially controlled by the performance of the surfactant and its addition amount. For this reason, it is preferred that a sufficient amount of a suitable surfactant is added so that the entire mixture forms a uniformly emulsified layer. When the amount of the surfactant added is small, it is preferable that the transiently emulsified portion is rapidly burned and used up before it separates into upper and lower layers. Alternatively, after being stored for a certain period of time in a closed container for storage, which will be described later, it may be subjected to combustion after returning to a well-dispersed emulsion state by re-stirring and mixing. When naphtha, gasoline, or their component hydrocarbon species (particularly aromatic hydrocarbon species), which have relatively high compatibility with ammonia even without the addition of a surfactant, are used as a combustion improver, the addition of a surfactant is required. It may not be necessary. In this case, the surfactant introduction system (surfactant storage container 26, surfactant introduction line 28, flow meter 28a,

control valves

28b, 28c, and liquid feed pump 28d) can be omitted.
When the combustion improver is naphtha, gasoline, kerosene, light oil, or component hydrocarbon species thereof, the upper layer portion of the two-phase separated liquid phase shown in FIGS. 3(a) and 3(b) and FIG. Using the liquid phase discharge line 22 ₂ and the equipment attached thereto (liquid phase discharge valve 22a ₂ , discharge flow meter 22b ₂ , and composition evaluation means 22c ₂ ), the upper layer and / or lower layer of the two-phase separation liquid phase can be discharged as an ammonia mixed fuel.

In order to produce a homogeneous and stable ammonia mixed fuel in which the combustion improver contains naphtha, gasoline, kerosene, diesel, or at least one of these component hydrocarbon species, the above-described combustion improver is basically Mixed system surfactants with molecular structures common to those of liquefied petroleum gas and its component hydrocarbon species can be successfully used. However, as noted above, the chain length of the long chain alkyl or alkenyl groups in the surfactant is often preferred to be longer than in liquefied petroleum gas and its component hydrocarbon species. When a sufficient amount of such a suitable mixing system surfactant is added and mixed with stirring, the phase separated part (ammonia or combustion improver) is dispersed in the other phase by emulsification, and the entire mixed fuel is homogenized. can be At that time, as in the case where the combustion improver is liquefied petroleum gas and its component hydrocarbon species, as described above, it is preferable to maintain the temperature within a range in which the emulsification performance of the surfactant is sufficiently exhibited. . If the ammonia-mixed fuel produced as described above is taken out and burned in that state, it exhibits high combustibility.
Incidentally, even when the combustion improver is naphtha, gasoline, kerosene, light oil, or its constituent hydrocarbon species, when using the production apparatus of FIG. Upon exiting 22, compositional changes in the exiting liquid phase proceed in the same manner as if the combustion improver were liquefied petroleum gas or its constituent hydrocarbon species. That is, as the liquid phase is discharged, the gas-liquid interface of the mixture in the closed mixing container 16 descends, causing evaporation (boiling) of the mixture from the liquid phase to the gas phase. At that time, regardless of the liquid phase composition, the ammonia concentration in the evaporative gas becomes higher than the ammonia concentration in the liquid phase, so the ammonia concentration in the liquid phase decreases as the liquid phase discharge progresses. is.
On the other hand, if the manufacturing apparatus 10 of FIG. 4 (equipment equipped with a fuel improver liquid feeding pump 20d not shown) is used, it is possible to mix and By pressurizing nitrogen into the gas phase in the closed vessel 16 for gas, it is possible to rapidly discharge the mixed fuel as an ammonia mixed fuel while suppressing the composition change in the discharged liquid phase. ₅ (the liquid phase discharge line 222 and the equipment attached thereto are often omitted), the ammonia, the combustion improver, and the surfactant in the discharged liquid phase can be By continuously metering in the raw material liquefied ammonia, the combustion improver, and the surfactant at a flow rate equal to the respective discharge flow rates (the pumps for these liquids are selected to have a high head as described above). ), it can be continuously discharged as an ammonia-mixed fuel without causing the above compositional change in the discharged liquid phase.
As described above, even when the combustion improver is naphtha, gasoline, kerosene, light oil, or any of these component hydrocarbon species, the fuel improver liquid feed pump 20d (not shown) is used as shown in FIG. 2 and FIG. provided) and the production apparatus 10 shown in FIG. At that time, in addition to the quantitative introduction of liquefied ammonia, the combustion improver and the surfactant, and the temperature adjustment during stirring and mixing, a series of controls including the above-mentioned are performed as described above. It is performed based on the control signal of the control device 32 basically in the same manner as in the case of any of the species.

FIG. 6 is a diagram showing an example of a configuration of a manufacturing apparatus 10 according to another embodiment, which is different from the configuration of the manufacturing apparatus 10 shown in FIG. The example shown in FIG. 6 shows the configuration of the apparatus in the case of using the raw material alcohol (c) having 3 or less carbon atoms in the molecule, such as methanol, as the combustion improver. The raw material alcohol has a lower ignition temperature than ammonia, so it is easily ignited, and has a higher burning rate than ammonia (about 6 to 7 times that of ammonia in terms of laminar combustion rate), so it burns easily. In addition, compared to liquid fossil fuels such as heavy oil, light oil, kerosene, gasoline, etc., which have been widely used, less CO ₂ is generated per calorific value during combustion. Therefore, raw material alcohol is preferable as a combustion improver for ammonia. In addition, since the raw material alcohol is polar and forms a hydrogen bond between molecules with ammonia, the liquid phase portion of the mixed fuel with ammonia in a gas-liquid equilibrium state is It becomes a compatible solution state. In that case, the mixed fuel does not exhibit azeotropic behavior and its saturated vapor pressure is lower than that of pure ammonia at the same temperature. For this reason, a surfactant is not necessary in many cases, and in the manufacturing apparatus 10, a surfactant introduction system (surfactant storage container 26, surfactant introduction line 28, flow meter 28a,

adjustment valves

28b, 28c, and the liquid feed pump 28d) can be omitted. Moreover, if the external environment temperature is normal temperature (25° C.) or its vicinity, for example, about 0° C. to 40° C., in many cases, there is no particular need to adjust the temperature during stirring and mixing. Therefore, when the combustion improver is raw material alcohol, the configuration of the manufacturing apparatus 10 can be simplified. 6 have the same configuration and action as those of the components shown in FIG. 2, the same reference numerals are given and the description thereof is omitted.
Raw material alcohol is stored in the combustion improver storage sealed container 14 shown in FIG. The raw material alcohol has a low saturated vapor pressure, and is not discharged under the saturated vapor pressure in the combustion improver storage closed container 14, and is not spontaneously introduced into the mixing closed container 16. Therefore, the liquid feed pump 20d is provided. there is The raw material alcohol is supplied from the combustion improver storage sealed container 14 to the mixing closed container 16 by the liquid feed pump 20d. Further, when introducing the raw material alcohol, which is liquid near normal temperature (25° C.) and near atmospheric pressure, it is not necessary to particularly adjust the temperature. Especially when the lift is not high, the gas phase internal pressure in the closed mixing container 16 is always lower than the saturated vapor pressure in the closed container for storage of the raw material liquefied ammonia to be introduced from now on. The temperature within 16 must be maintained.

Even when the combustion improver is raw material alcohol, when the manufacturing apparatus of FIG. Or, as with its constituent hydrocarbon species, compositional changes in the draining liquid phase proceed. That is, as the liquid phase is discharged, the gas-liquid interface of the mixture in the closed mixing container 16 descends, causing evaporation (boiling) of the mixture from the liquid phase to the gas phase. At that time, regardless of the liquid phase composition, the ammonia concentration in the evaporative gas becomes higher than the ammonia concentration in the liquid phase, so the ammonia concentration in the liquid phase decreases as the liquid phase discharge progresses. is.
On the other hand, if the manufacturing apparatus 10 of FIG. 4 (equipped with a fuel improver liquid feed pump 20d not shown) is used, the mixture for mixing can be used in the same manner as in the case where the fuel improver is liquefied petroleum gas or its component hydrocarbon species, as described above. By pressurizing the introduction of nitrogen into the gas phase in the closed container 16, it is possible to rapidly discharge the mixture as an ammonia-mixed fuel while suppressing the composition change in the discharged liquid phase. 5 (the liquid _- phase discharge line 222 and the equipment attached thereto are omitted), the discharge flow rate of ammonia and the combustion improver in the discharged liquid phase is equal to that of each, By continuously and quantitatively introducing the raw material liquefied ammonia and the combustion improver (the above-described high pump is selected as the pump for supplying these liquids), the composition change in the discharged liquid phase is caused. can be discharged continuously as an ammonia-mixed fuel.
As described above, even when the combustion improver is raw material alcohol, FIG. 2 or FIG. ( _The liquid phase discharge line 222 and the equipment attached thereto, and the system for introducing the surfactant are omitted.) By using the manufacturing apparatus 10, the ammonia mixed fuel can be manufactured with each effect. At that time, in addition to the constant introduction of liquefied ammonia and the combustion improver, temperature control during stirring and mixing, a series of controls including those described above are carried out, as described above, where the combustion improver is either liquefied petroleum gas or its component hydrocarbon species. is performed based on the control signal of the control device 32, basically in the same manner as in the case of .

The combustion improver in the ammonia mixed fuel of one embodiment may be any one of the above (a) to (c), but may be a combination of a plurality of the above (a) to (c). good. For example, at least one of the liquefied petroleum gas as the above (a) and the hydrocarbon species that is a component of the liquefied petroleum gas as the above (b), and the raw material alcohol of (c) are used in combination as a combustion improver. can also FIG. 7 is a diagram showing an example of the configuration of the production apparatus of this another embodiment, and the example shown in FIG. are both used as a combustion improver. 7 have the same configuration and action as those of the components shown in FIG. 2, the same reference numerals are given and the description thereof is omitted.
The manufacturing apparatus 10 includes combustion improver storage sealed

containers

14 ₁ and 14 ₂ . _The combustion improver storage closed container 14-1 stores the liquefied petroleum gas or the component hydrocarbon species of the liquefied petroleum gas, and the combustion improver storage closed container _14-2 stores raw material alcohol. Combustion improver introduction lines ₂₀ ₁ and ₂₀ ₂ extending from the combustion improver storage closed containers 14 ₁ and ₁₄ ₂ to the mixing closed container 16 are provided. , 20a ₂ and regulating

valves

20b ₁ , 20c ₁ , 20b ₂ , 20c ₂ are provided. The control device 32 receives measurement results from the

flowmeters

20a ₁ and 20a ₂ , generates control signals for controlling the opening degrees of the

adjustment valves

20b ₁ , 20c ₁ , 20b ₂ and 20c ₂ , and adjusts the generated control signals. It is sent to

valves

20b ₁ , 20c ₁ , 20b ₂ and 20c ₂ . Nitrogen gas introduction mechanism 30 exists in each introduction line and mixing closed container 16 as necessary from the viewpoint of explosion protection at the time of starting up the manufacturing apparatus 10 and after the completion of manufacturing the ammonia mixed fuel. A nitrogen gas introduction valve 30a is provided for introducing a predetermined amount of nitrogen gas into the combustion improver introduction lines _20.sub.1 and _20.sub.2 . The opening degree of the nitrogen gas introduction valve 30a is controlled by the controller 32. As shown in FIG.

Note that the saturated vapor pressure of raw material alcohol is low, and is close to zero at room temperature (25° C.). Therefore, the combustion improver is not discharged at the saturated vapor pressure in the closed combustion _improver storage container 142 and is not voluntarily introduced into the mixed combustion _improver closed container 16. _A liquid feed pump _20d2 is provided for supplying from the container 142 to the closed container 16 for mixing. When introducing the raw material alcohol, which is liquid near normal temperature (25°C) and atmospheric pressure, there is no particular need to adjust the temperature, but the subsequent introduction of liquefied ammonia, liquefied petroleum gas, and their component hydrocarbon species. In this case, if a high-head liquid-sending pump is not particularly used for these, the internal pressure of the gas phase in the closed vessel 16 for mixing is set to The temperature in the mixing enclosure 16 should be kept always below the lowest saturated vapor pressure in the storage enclosure. In many cases, this results in substantial cooling to a lower temperature than the external environment. Ammonia, liquefied petroleum gas, component hydrocarbon species of the liquefied petroleum gas, and raw material alcohol are quantitatively introduced into the closed container for mixing 16, and the temperature adjustment at the time of quantitative introduction is based on the control signal generated by the controller 32. , is performed by the aforementioned metering introduction mechanism and temperature control mechanism.
Further, as another embodiment using a plurality of combinations of the above (a) to (c) as a combustion improver, the configuration shown in FIG. In place of the component hydrocarbon species, at least one of naphtha, gasoline, kerosene and light oil as (a), and any of these component hydrocarbon species as (b), together with the raw material alcohol, as a combustion improver. It can also be used to produce an ammonia mixed fuel. In this case, for example, naphtha, gasoline, kerosene, light oil, and component hydrocarbon species thereof are stored in the combustion improver storage closed container _14-1 and introduced into the mixing closed container ₁₆ through the combustion improver introduction line 20-1. . The saturated vapor pressure of naphtha, gasoline, kerosene, light oil, and their component hydrocarbon species is low, and is almost zero at around room temperature (25° C.) like the raw material alcohol. , the combustion improver introduction line 20-1 is also provided with a liquid feed pump 20d _-1 _. When introducing naphtha, gasoline, kerosene, light oil, component hydrocarbon species thereof, and raw material alcohol, which are liquids near normal temperature (25° C.) and atmospheric pressure, there is no particular need to perform temperature control. When the liquefied ammonia is introduced into the closed container for mixing, the gas phase internal pressure in the closed container for mixing 16 is always lower than the saturated vapor pressure in the closed container for storage of the raw material liquefied ammonia. The temperature within 16 must be maintained. Also in this case, the quantitative introduction and temperature adjustment are performed based on the control signal of the controller 32 .

The above-mentioned non-polar liquefied petroleum gas, naphtha, gasoline, kerosene, light oil, and their component hydrocarbon species (hereinafter collectively referred to as "raw hydrocarbons") that are almost incompatible with liquefied ammonia. , liquefied ammonia, and raw material alcohol are used in combination as a combustion improver, the effect of the raw material alcohol, which has an affinity for both the polar liquefied ammonia and the non-polar raw material hydrocarbon, causes surface activity. Even without the addition of the agent, the compatible portion is greatly increased. However, depending on the mixing ratio, a surfactant may be required for homogenization by emulsification. For example, when the raw material alcohol is methanol, the amount of methanol added is about 10% by mass or less of the total, and the amount of liquefied ammonia is about 10 to 70% by mass (the rest is the raw material hydrocarbon). In some cases, the raw material hydrocarbon is not completely dissolved, and a phase consisting mainly of it is separated in the liquid phase. A surfactant is required to emulsify and uniformly disperse the phase-separated portion.
As the surfactant at this time, the above-described mixed surfactant can be suitably used. When the mixed surfactant is added and stirred and mixed, the ammonia-mixed fuel is at least partially in an emulsion state. Further, depending on the composition of the mixture of ammonia and combustion improver, it is possible to make the whole into an emulsion state by adding a sufficient amount of surfactant and stirring and mixing. At that time, heating generally improves the solubility and dispersibility of the raw material hydrocarbons. Based on the control signal of the control device 32, it is preferable to agitate while being controlled by the temperature control mechanism described above. Furthermore, as the mixed surfactant, it is preferable to select one having an alkyl group or alkenyl group with a chain length suitable for sufficiently exhibiting emulsifying power (emulsification ability) in the temperature range. . In addition, when the above mixed surfactant becomes a solid or a state close to it and is difficult to introduce as it is, any of the raw materials of the ammonia mixed fuel, liquefied ammonia, raw hydrocarbon, or raw alcohol, is used. It is preferable to add a small amount in advance to the surfactant, mix and disperse the surfactant to obtain a state (for example, slurry or mud) that can be introduced by the surfactant introduction system. On the other hand, when the total amount of liquefied ammonia and raw material alcohol is sufficiently large and the amount ratio of the non-polar raw material hydrocarbon is small, a substantially uniformly dissolved solution state can be obtained without adding a surfactant. In some cases. In such a case, the surfactant introduction system (surfactant storage container 26, surfactant introduction line 28, and liquid feed pump 28d) can be omitted from the manufacturing apparatus 10. FIG.

Further, as still another embodiment in which a plurality of combinations of the above (a) to (c) are used as a combustion improver, at least one of liquefied petroleum gas and component hydrocarbon species of liquefied petroleum gas, and naphtha , gasoline, kerosene, light oil, and at least one of these component hydrocarbon species can be used together as a combustion improver to produce an ammonia mixed fuel by a production apparatus similar to that of FIG.
In this case, in FIG. 7, the liquefied petroleum gas and its component hydrocarbon species, which do not require a liquid feed pump when introduced into the mixing closed vessel ₁₆ , are stored in the combustion improver storage closed vessel 141, and the liquid feed pump is used. (20d ₂ in FIG. 5), naphtha, gasoline, kerosene, light oil, and their constituent hydrocarbon species are stored in a combustion improver storage closed container 14 ₂ and mixed through

introduction lines

20 ₁ and 20 ₂ . Each is introduced into the sealed container 16 .
Among these combustion improvers, ie, liquefied petroleum gas, naphtha, gasoline, kerosene, light oil, and component hydrocarbon species thereof, component hydrocarbon species of liquefied petroleum gas are In the liquid phase, it is partially compatible with liquefied ammonia, but is almost incompatible with component hydrocarbon species of naphtha, gasoline, kerosene, and light oil that are liquid near normal temperature (25°C) and atmospheric pressure. Therefore, in order to produce an ammonia-mixed fuel that is uniformly and stably dispersed, emulsification by addition of a surfactant is required.
As the surfactant at this time, the above-described mixed surfactant can be suitably used. When the mixed surfactant is added and mixed and dispersed, the ammonia mixed fuel becomes at least partially in an emulsion state. Also, depending on the composition of the mixture of ammonia and combustion improver, it is possible to make the whole mixture into an emulsion state by adding a sufficient amount of surfactant. At that time, since the solubility of the raw material hydrocarbon is generally improved by heating, if necessary, the control device 32 is operated so that the temperature of the mixture in the closed mixing container 16 is equal to or higher than a predetermined temperature suitable for mixing and dispersing. It is preferable to stir while being controlled by the temperature control mechanism described above based on the control signal. Furthermore, as the mixed surfactant, it is preferable to select one having an alkyl group or alkenyl group with a chain length suitable for sufficiently exhibiting emulsifying power in the temperature range. In addition, if the above mixed surfactant is in a solid state or in a state close to it and is difficult to introduce as it is, a small amount of liquefied ammonia or a raw material hydrocarbon, which is the raw material of the ammonia mixed fuel, is added to the surfactant in advance. Then, by mixing and dispersing, it is preferable to make a state (for example, slurry or mud) that can be introduced by a surfactant introduction system.

As described above, when the ammonia mixed fuel is produced in each case where the combustion improver is a combination of a plurality of the above (a) to (c), each raw material component is placed in the closed container 16 for mixing. When introducing is based on the discharge due to the saturated vapor pressure in the closed container for storing the raw materials, or when the liquid transfer pump is not particularly high-lifted, a guideline for the preferred order of introduction to the closed container for mixing 16 is summarized. Then, it is advantageous to introduce all of the introduction targets into the closed mixing vessel, including the ammonia and the combustion improver, in order from the introduction target with the lower saturated vapor pressure at the temperature in the closed mixing vessel. Specifically, it is as follows. That is, first, raw material alcohol, naphtha, gasoline, kerosene, light oil and component hydrocarbon species thereof, which are liquids having a low saturated vapor pressure at around room temperature (25 ° C.), and surfactants are heated at room temperature (25 ° C.). Ammonia, liquefied petroleum gas, and their component hydrocarbon species, which have high saturated vapor pressures in the vicinity, are introduced into the closed mixing container 16 using a liquid feed pump prior to them. Before and after the introduction of these predetermined amounts, the regulating

valves

20b ₂ , 20c ₂ , 28b, and 28c are opened and closed, and during the introduction, each introduction amount is controlled to be the predetermined amount. Next, after the inside of the closed container 16 for mixing is sufficiently cooled by the temperature control mechanism, among liquefied gases such as liquefied ammonia, liquefied petroleum gas and their component hydrocarbon species, the saturated vapor pressure at the set temperature is low. It is introduced into the closed container for mixing 16 in order from the first by discharging due to its own saturated vapor pressure. At this time, the gas phase in the closed container 16 for mixing is preliminarily replaced with the vaporized gas of the liquefied gas having the lowest saturated vapor pressure, which is introduced first. Before and after the introduction of these predetermined amounts, the regulating

valves

18b, 18c, 20b ₁ and 20c ₁ are opened and closed, and during the introduction, each introduction amount is controlled to be the predetermined amount. In addition, when the surfactant is in a solid state or in a state close to it, which is difficult to introduce by itself, liquefied ammonia, liquefied petroleum gas, naphtha, gasoline, kerosene, light oil, and component hydrocarbon species thereof may be used. is preferably introduced into the closed mixing vessel 16 in a slurried or sludged state by the addition of either of , liquefied petroleum gas, naphtha, gasoline, kerosene, light oil, and any of these component hydrocarbon species. After the quantitative introduction of each raw material is completed and all the adjustment valves are closed, the temperature of the liquid phase inside the closed container for mixing 16 is controlled by the temperature control mechanism so that it is kept within a preferable temperature range. , is agitated by an agitator 24 to produce an ammonia mixed fuel.
In any of the above cases where the combustion improver is a combination of a plurality of the above (a) to (c), the quantitative introduction mechanism and the temperature control mechanism are configured in the same manner as described in the explanation of FIG. , based on the control signal of the control device 32, metered introduction and temperature adjustment are performed. After that, the temperature is controlled based on the control signal generated by the control device 32 so that the temperature is maintained in an appropriate temperature range according to the liquid phase composition of the mixture. An ammonia-mixed fuel in which the combustion improver is stably and uniformly dispersed can be produced.

In addition, as described above, when the combustion improver is a combination of a plurality of the above (a) to (c), when manufacturing the ammonia mixed fuel in each case, the manufacturing apparatus of FIG. 7 is used. , when the liquid phase portion of the emulsified mixture is discharged from the liquid phase discharge line 22, the above-described change in the composition of the discharged liquid phase progresses. That is, as the liquid phase is discharged, the gas-liquid interface of the mixture in the closed mixing container 16 descends, causing evaporation (boiling) of the mixture from the liquid phase to the gas phase. At that time, the composition of the evaporative gas is complicated because various combustion improvers coexist (the main components of the evaporative gas are ammonia, liquefied petroleum gas or its component hydrocarbon species, and / or a mixture of alcohol for raw materials. gas), and the composition of the evaporative gas differs from that of the liquid phase, as in the case of using various combustion improvers described above. changes.
On the other hand, if a manufacturing apparatus in which the nitrogen gas introduction line 30b of the manufacturing apparatus 10 of FIG. 4 is provided in accordance with the configuration of the manufacturing apparatus 10 of FIG. By pressurized introduction, it is possible to rapidly discharge as an ammonia-mixed fuel while suppressing the composition change in the discharged liquid phase. Further, if a manufacturing apparatus in which the continuous quantitative introduction mechanism of the raw material of the manufacturing apparatus 10 of FIG. 5 is provided in accordance with the configuration of the manufacturing apparatus 10 of FIG. By continuously and quantitatively introducing raw material liquefied ammonia, various combustion improvers, and surfactants at a flow rate equal to the discharge flow rate of each of the surfactants is selected), it can be continuously discharged as an ammonia mixed fuel without causing the above compositional change in the discharged liquid phase.
As described above, even in the production of the ammonia-mixed fuel in each case where the combustion improver is a plurality of combinations of the above (a) to (c), the production apparatus 10 of FIG. By adding the functions of the manufacturing apparatus 10 of FIGS. 4 and 5 to the manufacturing apparatus 10, the ammonia mixed fuel can be manufactured with the respective effects. At that time, a series of controls including those described above are performed based on the control signal of the control device 32, in addition to the quantitative introduction of the liquefied ammonia, the combustion improver and the surfactant, the temperature control during stirring and mixing.

In the above, the ammonia introduction line 18, the liquid phase discharge line 22, and the closed container 16 for mixing of the manufacturing apparatus 10 are configured, and the parts that are in contact with the fluid containing ammonia (pipes, containers, regulating valves, stirrers, coolers, etc. Equipment, fixed quantity introduction mechanism) are made of materials that are durable against ammonia. For example, copper and copper-containing alloys such as cupronickel and brass, aluminum and aluminum-containing alloys such as duralumin, and zinc and zinc-containing alloys such as tin are not preferable in terms of corrosion resistance to ammonia. Also, iron or steel, especially if it has a high carbon content, is prone to stress corrosion cracking. Therefore, it is necessary to select a material that has a low carbon content and is confirmed to be durable against ammonia. Materials that can be used include, for example, iron or steel materials that are recognized to be durable against ammonia, as well as austenitic stainless steel (however, stainless steel with a relatively high nickel content is susceptible to stress corrosion cracking due to ammonia). and caution is required), ceramics such as glass and quartz, and plastics and rubbers such as polyethylene, polypropylene, polytetrafluoroethylene, chloroprene rubber, and perfluoroelastomer. These materials are excellent in corrosion resistance at about 60° C. or less and can be suitably used. When mixing and stirring in the closed mixing vessel 16, if liquid ammonia (liquefied ammonia) or liquefied raw material hydrocarbons are used, cavitation may easily occur. It is preferable to use a material that is resistant to erosion caused by cavitation.

According to the manufacturing apparatus 10 of one embodiment, the mixing sealed container 16 includes a mixed state evaluation device configured to evaluate the mixed state of the mixture (in FIG. 2, as an example thereof, a sight glass 29 described later is provided. (not shown otherwise) is preferably provided. In this case, it is preferable that the controller 32 adjusts the strength of stirring and mixing by the stirrer 24 and the stirring and mixing time according to the evaluation result of the mixing state evaluation device. In this case, the controller 32 is an agitation regulator that regulates the agitation mixing intensity and the agitation mixing time.
As a mixed state evaluation device, for example, a pressure-resistant sight glass 29 (viewing window) provided at least in the upper and lower layers so that it is possible to observe whether the internal mixture is separated into two phases or whether it is in an emulsion state, Alternatively, a device having a fiber scope and a monitor that displays the state of the liquid through the pressure-resistant sight glass or the fiber scope may be used. As the mixing state evaluation device, a measuring instrument for evaluating differences in physical properties such as turbidity, dielectric constant, and refractive index between at least the upper and lower layers of the liquid inside the closed container 16 for mixing can also be used. Furthermore, in addition to the above device configuration, the mixed state evaluation device may also include a microscope capable of observing the micro-dispersed state of the mixture, and an automatic recognition evaluation device based on artificial intelligence (AI) technology. However, if the gas-liquid equilibrium data is known and a raw material system with a compatible composition and temperature condition is used, for example, ammonia and a raw material alcohol having 3 or less carbon atoms are mixed without adding a raw material hydrocarbon. If it is known in advance that the materials will be compatible or emulsified almost uniformly, for example, the mixed state evaluation device may not be necessary.

Further, when introducing the liquefied ammonia into the closed mixing container 16, as shown in FIG. A temperature control device 18 e configured to regulate is preferably provided in the ammonia introduction line 18 .
Further, when introducing the liquefied petroleum gas and the combustion improver, which is _a component hydrocarbon species thereof, into the closed mixing container ₁₆ through the combustion improver introduction line 20-1, as shown in FIG. Preferably, the combustion improver introduction line _20-1 is provided with _a temperature control device 20e1 configured to adjust the temperature of the combustion improver passing through to the same temperature as the internal temperature of the closed mixing vessel 16. These temperature control devices are constituted by, for example, heat exchangers or Peltier elements. When these liquefied gas raw materials are introduced, the internal pressure of the closed container 16 for mixing is controlled by the above-described temperature control mechanism to increase the internal pressure of the closed containers ₁₂ and 141 for storage of liquefied ammonia and liquefied petroleum gas or their component hydrocarbon species. is temperature regulated to be below the saturated vapor pressure of the atmosphere, and in many cases this will result in cooling to a temperature substantially lower than the external environment. Therefore, the temperature regulation of the respective introduction line by the above-mentioned temperature regulation devices also often results in cooling to a temperature lower than that of the external environment.
As a result, when these liquefied gas raw materials are introduced into the closed mixing vessel 16, the internal temperature does not rise, so unnecessary vaporization of the mixture occurs in the closed mixing vessel 16. It is possible to suppress increasing the saturated vapor pressure.
In addition, when these are introduced, if the liquid feed pump is not provided, the temperature of the external environment is too low, and the saturated vapor inside the ammonia storage closed container ₁₂ and/or the combustion improver storage closed container 14-1 Heating devices 13 and/or 15 are provided in said ammonia storage enclosure 12 and/or combustion improver storage enclosure 14 in the event that the pressure is insufficient for each introduction into the mixing enclosure 16. By providing and appropriately heating, the saturated vapor pressure of each can be increased. As the

heating devices

13 and 15, for example, an electric heater, a constant temperature bath containing a heating medium whose temperature is appropriately controlled, or the like is used.
_The temperature control mechanism provided in the closed container for mixing 16, the temperature control devices 18e and _20e1 provided in the introduction lines 18 and 201, and the temperature control devices provided in the closed container for storage 12 and 141, _respectively . Heating by the

heating devices

13 and 15 is controlled by a control device 32 based on the results of

thermometers

33, 18f and _20f1 provided in the closed mixing container 16 and

introduction lines

18 and 201, _respectively .

FIG. 8 is a block diagram of an example of essential parts of the manufacturing apparatus 10 of one embodiment. As shown in FIG. 8, the manufacturing apparatus 10 includes an ammonia-mixed fuel storage closed container 50 configured to store the ammonia-mixed fuel in a vapor-liquid equilibrium state. The closed container for storage 50 is provided with an inlet 52 into which the ammonia mixed fuel is injected, and a lower portion, preferably a bottom surface, of the closed container for storage 50 configured to discharge the ammonia mixed fuel in a liquid state to the outside. and an outlet 54 . The injection port 52 is provided with a connection mechanism 56 configured to inject the ammonia-mixed fuel from the liquid phase discharge line 22 into the storage closed container 50 while maintaining airtightness and internal pressure. As an airtight structure, the injection port 52 is provided with a sealing mechanism (not shown) such as a gasket or an O-ring. Since the inner wall of the storage closed container 50 contacts ammonia similarly to the mixing closed container 16, the storage closed container 50 and the connecting mechanism 56 are made of a material having corrosion resistance to ammonia.
An ammonia-mixed fuel supply line 60 for discharging the ammonia-mixed fuel in a liquefied state to the outside is connected to the discharge port 54 . The ammonia-mixed fuel supply line 60 is provided with a discharge valve 58 that controls the supply amount of the ammonia-mixed fuel by the control device 32 .

When introducing and filling the ammonia-mixed fuel from the mixing closed container 16 into the storage closed container 50, prior to that, in order to avoid mixing of air etc. that existed in the storage closed container 50, storage is performed. It is necessary that residual air and the like in the closed container 50 for the gas-phase is exhausted in advance by evacuation through the gas-phase exhaust line 59, or replaced with volatilized vapor of the ammonia-mixed fuel. In the former case, a vacuum pump (not shown) is connected to the ammonia mixed fuel supply line 60, the liquid phase discharge valve 22a is kept closed, the discharge valve 58 is opened, and the internal pressure of the storage closed container 50 is reduced by the vacuum pump to approximately After being evacuated to about 0.01 MPa or less, the discharge valve 58 is closed. After that, the liquid-phase discharge valve 22a is opened, and the ammonia-mixed fuel is filled in the preservation sealed container 50. As shown in FIG. In the latter case, in addition to the configuration shown in FIG. 9, the gas in the gas phase portion in the closed storage container 50 is added to the upper portion, preferably the uppermost surface, of the closed storage container 50 as shown in FIG. 10 described later. It is preferable to provide a vapor phase discharge line 59 (the vapor phase discharge line 59 is provided with a vapor phase discharge valve 59a) for discharging to the top. At this time, after opening the vapor phase discharge valve 59a while keeping the liquid phase discharge valve 22a closed, the liquid phase discharge valve 22a is slightly opened to introduce a small amount of ammonia mixed fuel into the preservation closed container 50, and the volatilized vapor. After purging residual air and the like in the storage closed container 50 by closing the gas phase discharge valve 59a, the storage closed container 50 is replaced with gas. After that, the liquid-phase discharge valve 22a is opened, and the ammonia-mixed fuel is filled in the preservation sealed container 50. As shown in FIG.
When filling the above ammonia mixed fuel, a temperature control device (not shown), which will be described later, is provided to increase the filling amount in the storage sealed container 50 (to reduce the volume of the gas phase portion after filling ), it is preferable that the inside of the sealed storage container 50 can be sufficiently cooled so that the saturated vapor pressure inside is about 0.05 to 0.1 MPa or less. As a result, the storage closed container 50 can be efficiently filled with the ammonia mixed fuel through the liquid phase discharge line 22 by the discharge based on the saturated vapor pressure of the ammonia mixed fuel in the closed mixing container 16 .

As shown in FIG. 8, the closed storage container 50 of the manufacturing apparatus 10 of one embodiment is preferably provided with a stirrer 63 configured to stir and mix the ammonia-mixed fuel.

The storage sealed container 50 of the manufacturing apparatus 10 of one embodiment is provided with a temperature control device (not shown) configured to appropriately adjust the temperature of the ammonia-mixed fuel inside the storage sealed container 50. Examples of the temperature control device include a heat exchanger for controlling the temperature of the closed mixing container 16 by flowing a temperature control medium, or a Peltier element. The temperature control by the temperature control device is controlled by a control signal generated by the control device 32 based on the temperature measurement value of the thermometer 61 that measures the liquid phase temperature inside the storage sealed container 50 .
This temperature control device has the following three functions in the same manner as the temperature control mechanism in the above-described closed container 16 for mixing. The first is cooling control of the internal temperature so that the internal pressure of the preservation sealed container 50 is within a temperature range that does not exceed the set pressure resistance. During this temperature control, the control device 32 generates Based on the control signal, the storage sealed container 50 is rapidly cooled by the temperature control device.
The second is the cooling control for reducing the internal pressure of the preservation sealed container 50 so that the ammonia-mixed fuel can be efficiently and smoothly charged as described above.
The third is that the entire liquid phase portion of the mixture of ammonia and the combustion improver in the storage closed container 50 maintaining the gas-liquid equilibrium state is mixed with the ammonia and the combustion improver depending on the liquid phase composition of the mixture. are dissolved in each other, or the temperature of the mixture is controlled so as to be in a temperature range in which the ammonia and the combustion improver are in an emulsion state. For this purpose, the storage closed container 50 is equipped with the temperature control device and the stirrer 63, and when the ammonia-mixed fuel in the storage closed container 50 is stirred and mixed by the stirrer 63, The entire liquid phase portion of the ammonia mixed fuel is in a temperature range in which the ammonia and the combustion improver are in a solution state or an emulsion state of the ammonia and the combustion improver depending on the liquid phase composition of the ammonia mixed fuel. As such, the temperature control device is preferably configured to control the temperature of said ammonia blended fuel. Here, the "temperature range in which the ammonia and the combustion improver are in a solution state in which the ammonia and the combustion improver are dissolved with each other, or the temperature range in which the ammonia and the combustion improver are in an emulsion state" is the temperature range in which the ammonia mixed fuel of each mixed raw material system is compatible with each other. Alternatively, a temperature range suitable for homogenization by emulsification is selected. This temperature control is also performed by the temperature control device based on the control signal generated by the control device 32 according to the temperature measured by the thermometer 61 .
When the ammonia-mixed fuel is discharged from the mixing closed container 16 and filled into the storage closed container 50, the entire charged ammonia-mixed fuel is uniform and uniform regardless of the type of combustion improver contained. It is in a solution state or a uniform emulsion state (not divided into upper and lower layers). By maintaining the temperature inside the storage sealed container 50 equal to the liquid phase temperature in the mixing closed container 16, the above uniform and uniform solution state or uniform emulsion state can be maintained. can. In addition, even if the above stirring and mixing and temperature control are stopped for a certain period after the ammonia mixed fuel is filled in the storage closed container 50, the same amount as during stirring and mixing and filling is performed before the ammonia mixed fuel is burned. If the temperature is adjusted again, a uniform and homogeneous solution state or a uniform emulsion state can be restored.

Also when the ammonia mixed fuel is discharged from the closed storage container 50, the composition of the mixed fuel changes as described in the case of discharging from the closed mixing container. In addition to the configuration of the storage closed container 50 shown in FIG. A nitrogen gas injection line 64 having the same configuration as the nitrogen gas introduction line 30b shown in FIG. and a gas phase discharge line 59 for discharging (the gas phase discharge line 59 is provided with a gas phase discharge valve 59a).
With the above configuration, it is possible to quickly discharge the ammonia mixed fuel while suppressing the change in the liquid phase composition due to the progress of evaporation of the mixture in the storage closed container 50 accompanying the discharge of the ammonia mixed fuel. can.
The nitrogen gas injection line 64 is led from a storage container (not shown) such as a general pressurized nitrogen gas cylinder filled to an internal pressure of about 10-15 MPa. The nitrogen gas injection line 64 is provided with a pressure reducing valve 64a, a pressure gauge 64b, and a regulating valve 64c between its upstream side and the closed container 16 for mixing. The nitrogen gas introduced through the nitrogen gas injection line 64 is controlled by the pressure reducing valve 64a so that the indicated value of the pressure gauge 64b is equal to or higher than the saturated vapor pressure of the mixture in the sealed storage container 50 (the indicated value of the pressure gauge 62). The pressure is reduced to (for example, the saturated vapor pressure plus about 0.05 to 0.1 MPa). When the liquid phase of the mixture is discharged from the closed storage container 50, the control valve 64c is opened in conjunction with the opening of the discharge valve 58, and the nitrogen gas injected from the gas phase side forces the liquid phase out. The ammonia-mixed fuel is discharged to the ammonia-mixed fuel supply line 60. The series of operations of these valves are controlled by control signals transmitted by the controller 32 . As described above, when the ammonia-mixed fuel is discharged from the storage closed container 50, the storage closed container 50 Nitrogen gas is pressurized and injected into the gas phase portion of the inside, thereby substantially reducing the change in composition and expediting the discharge. When the ammonia-mixed fuel is injected again into the storage sealed container 50 from the mixed closed container 16 through the liquid phase discharge line 22, the gas phase discharge valve 59a is opened in advance, and the liquid phase discharge valve 22a is slightly closed. After opening to introduce a small amount of ammonia-mixed fuel into the storage closed container 50 and purging the gas (air, nitrogen, etc.) in the storage closed container 50 with the volatilized vapor, the gas phase discharge valve 59a is closed. , the inside of the sealed storage container 50 is replaced with gas.

In the production apparatus 10 of another embodiment, the discharge port 54 is provided on the bottom surface of the storage closed container 50, and the discharge port 54 is provided with a discharge volume flow rate of the ammonia mixed fuel discharged in the liquid phase from the discharge port 54. , a volumetric flow meter 65 configured to continuously measure is provided. Furthermore, when the ammonia mixed fuel is injected into the storage sealed container 50 through the injection port 52, the ammonia mixed fuel is injected until reaching a predetermined full filling amount or a predetermined amount less than the full filling amount, In addition, when the ammonia mixed fuel is discharged from the storage closed container 50 through the discharge port 54, while maintaining the airtightness and internal pressure of the storage closed container 50, the discharge volume flow rate measured by the volume flow meter 65 is increased. A filling and discharging control mechanism configured to continuously decrease the internal volume of the closed storage container 50 at a volume change rate substantially equal to .
The reason why the composition change occurs when the ammonia mixed fuel is discharged is that, as described above regarding the similar situation in the closed container 16 for mixing, the volume of the liquid phase discharged accompanying the discharge of the ammonia mixed fuel is stored. As the volume of the gas phase portion in the storage closed container 50 increases and the internal pressure decreases, the ammonia mixed fuel evaporates (boiling) from the liquid phase to the gas phase in the storage closed container 50. This is because the vapor composition of is different from the liquid phase composition. Therefore, if the volume and internal pressure of the gas phase portion are maintained such that the gas-liquid equilibrium state in the storage closed container 50 is maintained even during the discharge of the liquid phase, the evaporation does not occur and the discharged ammonia mixture does not occur. The composition of the fuel is also kept constant. Therefore, as described above, when the ammonia-mixed fuel is discharged from the storage sealed container 50, while maintaining the airtightness and internal pressure of the storage sealed container 50, the discharge volume flow rate measured by the volume flow meter 65 If the injection/discharge control mechanism is provided so as to continuously decrease the internal volume of the closed storage container 50 at the same volume change rate, the ammonia-mixed fuel can be discharged while maintaining the discharge composition constant.

FIG. 10 shows a manufacturing apparatus 10 of one embodiment provided with an example of the injection/ejection control mechanism that falls within the scope of the above embodiments. The sealed container for storage 50 has an upright outer cylindrical shape, and seals the body (for example, cylindrical) having a constant internal cross-sectional area orthogonal to the axial direction of the outer cylinder, and the lower end opening of the body. a bottom plate provided with an inlet 52 and a discharge port 54; a reciprocating drive 68 configured to move.
Here, the injection/discharge control mechanism is configured to perform the following controls. That is, when the ammonia-mixed fuel is injected into the storage sealed container 50 through the injection port 52, the reciprocating drive device 68 moves the lower surface of the piston 67 in the cylinder 66 to the full-filled position (hereinafter referred to as H position), or after being pushed up to a predetermined position below the full-filling position, it stops. At this time, it is preferable that the closed mixing container 16 and the cylinder 66 are arranged relative to each other so that the H position is about the height of the gas-liquid interface of the ammonia-mixed fuel in the closed mixing container 16 . In this state, the ammonia mixed fuel is stored in cylinder 66 .
After filling the ammonia mixed fuel, when the ammonia mixed fuel is discharged from the storage closed container 50 through the discharge port 54, the amount of ammonia mixed fuel in the storage closed container 50 measured by the pressure gauge 62 A linear velocity approximately equal to the value calculated by dividing the discharge volumetric flow rate measured by the volumetric flowmeter 65 by the internal cross-sectional area of the body of the cylinder 66 while resisting the saturated vapor pressure (equal to the internal pressure). After the piston 67 is continuously pushed down by the reciprocating drive device 68, the lower surface of the piston 67 stops at the discharge end position (hereinafter referred to as the L position) near the bottom plate of the cylinder 66. As shown in FIG. At the time of this discharge, since the product of the internal cross-sectional area and the linear velocity becomes substantially equal to the discharge volume flow rate, the internal volume of the storage sealed container 50 is continuously changed at a volume change rate substantially equal to the discharge volume flow rate. As a result, the ammonia mixed fuel can be discharged while suppressing the composition change.

In the embodiment of FIG. 10, the body and the bottom plate of the sealed storage container 50 are the cylinder 66, and the upper surface is the piston 67 that reciprocates. It is preferable that there are no obstacles that impede the back-and-forth movement. For this reason, as shown in FIG. 11, the conduit (sheath, etc.) of the thermometer 61 and the conduit of the pressure gauge 62 are arranged so that the tip of each conduit faces the inner surface of the lowermost part of the cylinder 66 or the inner surface of the bottom surface. installed so as to be the same. At this time, the inner wall of the surrounding cylinder 66 is countersunk so that the temperature measuring portion at the tip of the conduit (such as a sheath) of the thermometer 61 is in contact with the liquid. The manometer 62 conduit is preferably extended so that the side of the manometer is above the gas-liquid interface of the ammonia-blended fuel to eliminate the effects of liquid column pressure if greater accuracy is required. In addition, when the stirrer 63 is installed, the bottom plate is provided with a counterbore facing downward so that the operating part such as the stirring blade is positioned below the bottom surface of the cylinder 66, and is installed in it, or It is preferable to provide a circulation pipe (not shown) for extracting the ammonia-mixed fuel from the inside of the cylinder 66 to the outside and return it to the inside again, and to dispose the operating part of the stirrer 63 in the pipe. Furthermore, the inlet 52 and the outlet 54 are also preferably provided on the bottom surface of the cylinder 66 so as not to be blocked by the reciprocating movement of the piston 67 .
In the example of FIG. 10, the piston 67 is moved up and down (reciprocated) by a reciprocating drive device 68 including a motor 68a with variable output and rotational speed and a crank mechanism 68b. In the reciprocating drive device 68 of this example, the rotation of the motor 68a is decelerated by the reduction gear and then transmitted to the crank mechanism 68b. The reciprocating drive device 68 is appropriately adjusted according to the pressure (measured value of the pressure gauge 62), the required variable range of the elevation (reciprocation) speed of the piston 67 accompanying injection and discharge, and the required accuracy of the elevation (reciprocation) stop position. Designed.
The piston 67 can move up and down (reciprocate) by half-turning the crank of the crank mechanism 68b in the forward and reverse directions within the range from its upward position to its downward position. At this time, the H and L positions of the piston 67 are set at the top dead center or slightly below the top dead center and at the bottom dead center or slightly above the bottom dead center, respectively. The H position and L position are calibrated and recognized by a position sensor that detects the position of the crank of the piston 67 or the crank mechanism 68b, or an angle sensor that detects the rotation angle of the motor 68a (not shown). reaches the H position or L position, the power supply to the motor 68a is cut off, and preferably the motor 68a is forcibly stopped by a brake mechanism (not shown).
At the start of the injection of the ammonia-mixed fuel, the piston 67 is at point L, and after the liquid phase discharge valve 22a is opened, the piston 67 moves to point H at a linear velocity that keeps the measured value of the pressure gauge 62 substantially constant. Alternatively, it rises to a predetermined position below the H point, and after the ammonia mixed fuel is injected and filled into the cylinder 66, the liquid phase discharge valve 22a is closed and the ammonia mixed fuel is stored in that state. After that, when the discharge valve 58 is opened and the ammonia mixed fuel is discharged, the descending speed of the piston 67 near the center between the H point and the L point is obtained from the discharge flow rate value measured by the volumetric flow meter 65. The motor 68a is driven at a rotational speed substantially equal to the linear velocity applied, and is stopped when the piston 67 reaches the L position. The above series of operations are controlled by control signals from the control device 32 .
In the present embodiment, the reciprocating drive device 68 is not necessarily limited to the crank mechanism 68b described above, and may be a reciprocating drive mechanism such as a rack and pinion mechanism, a ball screw mechanism, or a feed screw mechanism. A device can also be employed.

In the manufacturing apparatus 10 provided with the storage closed container 50 of another embodiment, when the ammonia mixed fuel is injected into the storage closed container 50 through the injection port 52, a predetermined full filling Ammonia mixed fuel is injected until it reaches the amount or a predetermined amount equal to or less than the full filling amount, and after the ammonia mixed fuel is injected into the storage closed container 50, the ammonia is discharged from the storage closed container 50 through the outlet 54. When the mixed fuel is discharged, it is stored at a pressure higher than the saturated vapor pressure of the ammonia mixed fuel at the temperature of the ammonia mixed fuel in the closed storage container 50 while maintaining the airtightness of the closed storage container 50. It has an injection/discharge control mechanism configured to push out the ammonia-mixed fuel from the sealed container 50 .
According to the above configuration, the ammonia-mixed fuel in the closed storage container 50 is compressed at a pressure exceeding its saturated vapor pressure in the process of discharging, so that the gas phase disappears and the whole becomes liquid. It is discharged from the discharge port 54 . Therefore, since evaporation (boiling) does not occur in the process of discharging, the gas can be discharged at a high pressure equal to or higher than the saturated vapor pressure without causing the aforementioned change in the composition of the discharged gas.

FIG. 11 shows a manufacturing apparatus 10 of one embodiment provided with an example of the injection/ejection control mechanism that falls within the scope of the above embodiments. Since the embodiment of FIG. 11 has substantially the same configuration as the previous embodiment shown in FIG. 10 are assigned to the corresponding constituent members, and the description common to the manufacturing apparatus 10 of FIG. 10 will be omitted below.
In the manufacturing apparatus 10 of FIG. 11, when the ammonia mixed fuel is injected and filled, the injection and filling are performed by the same operation as in the case of the manufacturing apparatus 10 of FIG. 10, and the ammonia mixed fuel is stored in that state. be. When discharging, when the motor 68a gradually lowers the piston 67, the initial value (=saturated vapor pressure) of the pressure gauge 62 before the start of lowering is maintained for a while, and then the gas phase in the cylinder 66 disappears. At this point, the internal pressure begins to rise. While further lowering the piston 67, when the measured value of the pressure gauge 62 reaches a predetermined pressure value that does not exceed the pressure resistance of the storage sealed container 50, the discharge valve 58 is opened to a predetermined opening, and ammonia is mixed. Fuel is discharged. If the opening of the discharge valve 58 and the descending speed of the piston 67 are adjusted so that the measured value of the pressure gauge 62 maintains the predetermined pressure during discharge, the ammonia-mixed fuel supply line 60 is discharged through the discharge port 54 . It is possible to change the discharge flow rate of the ammonia mixed fuel (measured by the volume flow meter 65) led to. The series of operations described above is controlled by a control signal from the control device 32 .

In this embodiment, since the constituent members such as the storage sealed container 50 (the cylinder 66 and the piston 67) and the pressure gauge 62 may be subjected to sudden pressure fluctuations before and after the gas phase disappears, the pressure resistance that can withstand it is required. and structure.
In addition to the configuration of the storage sealed container 50 of the present embodiment, the configuration of the mixing closed container 16 having the continuous quantitative introduction mechanism of the raw materials described in the embodiment of FIG. 5 can be provided. In that case, the H point and L point are adjusted to be the top dead center and the bottom dead center of the piston 67, respectively, and are interlocked with the continuous lifting (reciprocation) of the piston 67 by the crank mechanism 68b that rotates at a constant speed. Then, it is preferable that the discharge valve 58 and the liquid phase discharge valve 22a are configured to be opened and closed at appropriate degrees of opening. As a result, while the ammonia-mixed fuel is continuously produced by the closed container 16 for mixing in FIG. At this time, the preservation sealed container 50 of the present embodiment becomes functionally equivalent to a so-called plunger pump.
In addition, in the case where the raw material continuous quantitative introduction mechanism shown in FIG. , a rack and pinion mechanism, a ball screw mechanism, or a reciprocating drive device such as a feed screw mechanism may be employed.
Further, in the present embodiment described above, since the gas phase portion disappears in the cylinder 66 during the discharge process, the cylinder 66 is not only configured to stand upright as shown in FIG. Even with such a configuration, it is possible to achieve most of the functions described above.

Furthermore, as shown in FIG. 12, in the storage sealed container 50 of the manufacturing apparatus 10 of one embodiment, the mixed state of the ammonia mixed fuel is evaluated in the same manner as the mixed state evaluation device described in the mixing sealed container 16. It is preferable that a mixed state evaluation device 69 configured as above is provided. FIG. 12 is a block diagram of an example of essential parts of the manufacturing apparatus 10 of one embodiment. Based on the evaluation result of the mixed state obtained by the mixed state evaluation device 69, the control device 32 generates a control signal for adjusting the stirring mixing strength and the stirring mixing time by the stirrer 63, and based on this, the stirrer 63 provides agitation. In particular, the ammonia-mixed fuel obtained by emulsifying liquid ammonia and raw material hydrocarbons may re-separate over time during storage in the closed storage container 50 . In this case, by re-stirring the ammonia mixed fuel with the stirrer 63, the ammonia mixed fuel can be put into an emulsion state again before being supplied to the combustor or the like.

The connection mechanism 56 (see FIGS. 8 to 11) of the manufacturing apparatus 10 of one embodiment is configured to be detachable from each other with respect to the connection between the introduction line for introducing the ammonia-mixed fuel into the storage sealed container 50 and the injection port 52. , storage enclosure 50 is a container that can be mounted on a vehicle (not shown) in any one of land, water, and air space. For example, in the case of the form shown in FIG. It may extend from another temporary storage container (not shown) in which the manufactured ammonia mixed fuel is temporarily stored. The construction of this temporary storage container is basically similar to any of the constructions of the storage enclosures previously described. Transportation equipment includes, for example, vehicles (small/large vehicles, motorbikes, etc.) including tank trucks capable of transporting ammonia and ammonia-mixed fuel, railway vehicles, etc. in land areas, and liquefied ammonia transportation vehicles in water areas. Commercial ships including ships, passenger ships, warships, ships in general such as various work ships, submarines, etc. In the airspace, helicopters, aircraft, airships, drones, etc. are included. Storage enclosure 50 has a size and structure that allows it to be moved or transported. According to the above configuration, the storage closed container 50 filled with the ammonia mixed fuel is separated by the detachable connection mechanism 56 and mounted on the transportation equipment, or the storage closed container 50 is mounted. After being installed in the transportation equipment in advance and filled with the ammonia mixed fuel, the ammonia mixed fuel produced by the manufacturing apparatus 10 is separated by the detachable connection mechanism 56, so that the ammonia mixed fuel can be efficiently delivered to the transportation equipment. Can be well loaded and transported.

(Ammonia mixed fuel supply device)
FIGS. 13A and 13B are block diagrams illustrating an example of the configuration of an ammonia-mixed fuel supply device 70 according to one embodiment.
A supply device 70 shown in FIG. 13A (a range surrounded by a dashed line) includes at least the ammonia-mixed fuel manufacturing device 10 and the ammonia-mixed fuel supply line 60 described above. In FIG. 13(a), only the closed container for mixing 16 and the closed container for storage 50 are shown for simplification. The ammonia-mixed fuel supply line 60 supplies the ammonia-mixed fuel discharged from the outlet 54 of the closed storage container 50 to the combustor 100 configured to burn the ammonia-mixed fuel. The ammonia mixed fuel stored in the storage closed container 50 is produced in the mixing closed container 16 and then transferred to the storage closed container 50 through the liquid phase discharge line 22 .
The supply device 70 shown in FIG. 13( b ) (area surrounded by broken lines) also includes at least the above-described ammonia-mixed fuel production device 10 and the ammonia-mixed fuel supply line 60 . The form shown in FIG. 13(b) is a form in which the manufacturing apparatus 10 is provided with the mixing closed container 16, but is not provided with the storage closed container 50. FIG. A part of the ammonia mixed fuel supply line 60 becomes the liquid phase discharge line 22 of the closed container 16 for mixing. That is, the ammonia-mixed fuel discharged from the closed mixing container 16 passes through the ammonia-mixed fuel supply line 60 to the combustor 100 configured to burn the ammonia-mixed fuel without passing through the storage closed container 50. supplied.

13(a) and 13(b), an ammonia-mixed fuel supplier 80 is provided on the ammonia-mixed fuel supply line 60. In FIG. The ammonia-mixed fuel supply device 80 is configured to supply the ammonia-mixed fuel to the combustor 100 at a predetermined flow rate and a predetermined discharge pressure. The ammonia-mixed fuel supply device 80 is, for example, a pressurizer or a liquid-sending pump (for example, the above-mentioned figure) that pressurizes the ammonia-mixed fuel to the pressure required by the combustor 100 and supplies it by controlling the flow rate, if necessary. 11 ), and an injector for discharging the ammonia mixed fuel into the combustor 100 . These are not shown.
The combustor 100 is, for example, a direct-injection combustor that supplies liquid-state ammonia-mixed fuel directly to the combustion chamber. A predetermined amount of air, oxygen-enriched air, oxygen gas, or the like required for combustion is separately introduced into the combustor through a separate introduction line (not shown). After being vaporized in the combustor 100, the ammonia-mixed fuel comes into contact with and diffusely mixes with the air, oxygen-enriched air, oxygen gas, or the like, and is combusted. Also, the combustor may be a combustor in which a pre-vaporizer (not shown) pre-vaporizes a liquid state ammonia mixed fuel and supplies the gas. In this case, air, oxygen-enriched air, or oxygen may be premixed in a predetermined ratio with the vaporized ammonia mixed fuel. When the ammonia-mixed fuel supplier 80 supplies gas by vaporizing the ammonia-mixed fuel, the ammonia-mixed fuel supplier 80 may include the pre-vaporizer. In the above combustor, if necessary, a spark plug for igniting the vaporized gas of the ammonia mixed fuel, or heating the vaporized gas of the ammonia mixed fuel to the ignition temperature or higher so that the combustion proceeds smoothly. Auxiliary equipment such as an auxiliary burner is provided as appropriate. These are not shown.
The supply device 70 configured as described above can supply the ammonia-mixed fuel to the combustor 100 at a predetermined discharge pressure.

The ammonia-mixed fuel supply line 60, the combustor 100, the combustion gas discharge line (not shown) that discharges the exhaust gas from the combustor 100 to the outside air, and their surrounding constituent materials are restricted to materials having corrosion resistance to ammonia. In addition, a portion that is in contact with a gas containing vaporized ammonia gas and is heated to about 400° C. or more by combustion heat or the like, for example, around an ammonia mixed fuel injector that discharges the ammonia mixed fuel into the combustor 100, the combustor 100 High-temperature gas-contacting parts in contact with the internal combustion gas and high-temperature parts in the combustion gas line preferably have resistance to high-temperature corrosion due to nitriding embrittlement based on nitrogen in ammonia, although this depends on the concentration of ammonia. . In particular, chromium steel alloys such as iron, steel, cast iron, and stainless steel may lack corrosion resistance at locations of 400° C. or higher that are in contact with high-concentration ammonia gas. Therefore, for these parts, it is necessary to use metals such as pure nickel with high corrosion resistance, Inconel (trademark), Hastelloy (trademark), Nimonic (trademark), etc. that contain a high nickel content. may become

FIG. 14 is a block diagram showing an example of the configuration of the feeding device 70 of one embodiment.
In the ammonia-mixed fuel supply line 60 of the supply device 70 (the area surrounded by the dashed line) shown in FIG. be provided. The supply device 70 includes an ammonia mixed fuel recirculation line 112 . Ammonia-mixed fuel recirculation line 112 stores the part of the ammonia-mixed fuel flowing through ammonia-mixed fuel supply line 60 from branch 110 that is branched without being supplied to combustor 100 in closed container 16 for mixing or in closed container for storage. It is configured to flow back into vessel 50 . As shown in FIG. 14 , in a branching section 110 configured by a branch valve (not shown), one portion of the ammonia-mixed fuel is supplied from the ammonia-mixed fuel supplier 80 at a predetermined flow rate and a predetermined discharge pressure required by the combustor 100 . In order to flow back into the closed mixing container 16 or the closed container 50 for storage, the branched ammonia mixed fuel is subjected to the same pressure conditions as the ammonia mixed fuel in the closed mixing container 16 or the closed container 50 for storage. A pressure adjustment mechanism (not shown) is preferably provided in the ammonia-mixed fuel recirculation line 112 to adjust so that As this pressure adjusting mechanism, for example, a circulation pump or the like that can adjust the discharge pressure to be equal to the pressure in the mixing closed container 16 or the storage closed container 50 can be used. During the above branching and recirculation, the control device 32 calculates the required amount of ammonia-mixed fuel to be burned in the combustor 100 according to the required output of combustion in the combustor 100, and calculates this required amount , the surplus amount of the ammonia mixed fuel supplied from the feeder 80 is branched at the branching part 110, and passed through the ammonia mixed fuel recirculation line 112 to the closed container 16 for mixing or the closed container 50 for storage. A control signal is sent to the branch valve of the branch section 110 and the pressure adjustment mechanism provided in the ammonia-mixed fuel recirculation line 112 so that the ammonia mixed fuel recirculation line 112 is recirculated. Based on these control signals, the opening degree of the branch valve of the branch section 110 and the pressure adjustment mechanism are controlled. Further, for stable operation of the above control, the ammonia-mixed fuel recirculation line 112 may be provided with a flow control valve (not shown), and the opening of this flow control valve is similarly controlled by the control signal of the controller 32. is controlled appropriately.
According to the supply device 70 configured as described above, a required amount of ammonia-mixed fuel can be continuously supplied to the combustor 100 at a stable predetermined discharge pressure.

(Combustion device for ammonia mixed fuel)
FIG. 15 is a block diagram illustrating an example of the configuration of an ammonia mixed fuel combustion apparatus 120 according to one embodiment.
In this embodiment, the combustion device 120 produces thermal energy by burning the produced ammonia mixed fuel, or converts the thermal energy produced by combustion into mechanical energy or other energy such as electrical energy. It is a device that converts and discharges combustion gases into the atmosphere, and the respective energy obtained can be utilized for various uses described below.
The combustion device 120 includes an ammonia mixed fuel supply device 70 (see FIG. 9), a combustor 100 and a combustion gas discharge line 130 .
Combustor 100 is configured to burn the ammonia blended fuel described above.
The supply device 70 is configured to supply the ammonia blended fuel to the combustor 100 as described above.
Combustion gas discharge line 130 is configured to discharge combustion gas resulting from combustion of the ammonia mixed fuel in combustor 100 to the atmosphere.

Additionally, the combustion device 120 of one embodiment optionally includes a selective catalytic reactor 128 . As shown in FIG. 15, when the combustion device 120 includes a selective catalytic reactor 128, the selective catalytic reactor 128 is accompanied by nitrogen oxides, an ammonia concentration meter 122, a feed rate calculator 124, and a metering device. A supply device 126 is provided.

In this combustion device 120, as shown in FIG. 15, a selective catalytic reactor 128 is preferably provided on the combustion gas discharge side of the combustor 100, that is, on the combustion gas discharge line . The selective catalytic reactor 128 removes nitrogen oxides (including air pollutants such as nitrogen monoxide and nitrogen dioxide) in the combustion gas discharged from the combustor 100. Hereinafter, these may be collectively referred to as NOx. ) by catalytic reduction. That is, the selective catalytic reactor 128 is a by-product when the ammonia mixed fuel is burned in the combustor 100, is contained in the combustion gas, and is discharged from the combustion chamber of the combustor 100 to the combustion gas discharge line. Nitrogen oxides NOx passing through 130 are reductively decomposed.

Ammonia is known and widely used as a NOx reducing agent that selectively reductively decomposes NOx with high efficiency in the presence of an appropriate catalyst. In the selective catalytic reactor 128, as the NOx reducing agent, the ammonia remaining in the combustion gas without being completely burned in the combustor 100 and discharged, or additionally supplied separately from the ammonia storage closed container 12 described above. It is possible to use either the ammonia that is supplied as a fuel or the ammonia-mixed fuel that is separately supplied from the storage closed container 50 described above.
FIG. 15 shows the above-described ammonia remaining in the combustion gas without being completely burned in the combustor 100 and discharged, the ammonia separately supplied from the above-described ammonia storage closed container 12, and the above-described storage closed container. 50 shows an embodiment in which either one of the ammonia mixed fuel separately supplied from 50 is used together as a reducing agent. In this, a selective catalytic reaction supply line 132 configured to join a predetermined amount of either one of liquid state ammonia and ammonia mixed fuel to the combustion gas discharge line 130 is provided. is preferred. That is, the selective catalytic reaction supply line 132 is led from either the closed ammonia storage container 12 for storing ammonia in a liquid state or the closed storage container 50 for storing the ammonia mixed fuel.

In the embodiment of FIG. 15, in addition to the residual ammonia in the combustion gas discharged from the combustor 100, either the liquid state ammonia or the ammonia in the ammonia mixed fuel is added to the selective catalytic reactor 128. NOx coexisting in the combustion gas can be reliably reduced and decomposed. At the confluence portion 130a of the combustion gas and one of the ammonia, the exhaust heat of the combustion gas vaporizes the ammonia, which is supplied to the selective catalytic reactor 128, and is reduced in the selective catalytic decomposition of NOx. act as an agent. The coexisting feedstock hydrocarbons or feedstock alcohols also act as reducing agents in the selective catalytic reactor 128, particularly when the ammonia mixed fuel is supplied for catalytic reduction. Therefore, the synergistic effect of the reducing power of ammonia and the raw material hydrocarbon or raw material alcohol makes it possible to decompose nitrogen oxides NOx more efficiently.
Also, the catalyst in the selective catalytic reactor 128 is preferably kept at a predetermined temperature so that the selective catalytic reduction described above proceeds efficiently. To this end, the selective catalytic reactor 128 is provided or selected at a location within the flue gas discharge line 130 such that the temperature of the flue gas passing through the flue gas discharge line 130 generally corresponds to the predetermined temperature. Preferably, the temperature within the selective catalytic reactor 128 is adjusted accordingly by providing a temperature controller (not shown) that regulates the temperature of the catalyst within the selective catalytic reactor 128 . For example, when liquid ammonia in the ammonia storage closed container 12 is used as the reducing agent, a honeycomb body made of a mixed oxide of vanadium, tungsten (or molybdenum), and titanium is preferably used as the catalyst. The temperature of the catalyst used and suitable for selective catalytic reduction at that time is about 300 to 470°C. As the temperature controller for maintaining the catalyst temperature within such a temperature range, for example, an electric heater is used.

Combustion device 120 is configured to combine a predetermined amount of either one of liquid state ammonia and ammonia mixed fuel into combustion gas discharge line 130 for use as a reducing agent for nitrogen oxides NOx in selective catalytic reactor 128. , as shown in FIG. 15, it is preferable to include a nitrogen oxide/ammonia concentration measuring device 122, a supply amount calculating device 124, and a fixed quantity supplying device 126. FIG.
The nitrogen oxide/ammonia concentration measuring instrument 122 is provided in the combustion gas discharge line 130 on the combustion chamber side of the combustor 100 with respect to the junction 130a of the selective catalytic reaction supply line 132 and the combustion gas discharge line 130. , the concentration of nitrogen oxides and the concentration of ammonia on the side of the combustion chamber with respect to the confluence portion 130a. A known measuring instrument can be used as the nitrogen oxide and ammonia concentration measuring instrument 122 .

The supply amount calculation device 124 calculates the amount of ammonia or ammonia mixed fuel to be supplied through the selective catalytic reaction supply line 132 based on the measurement result measured by the nitrogen oxide/ammonia concentration measuring device 122. configured as The supply amount calculation device 124 has, for example, a reference table that predetermines the relationship between the concentration to be measured and the amount of ammonia or ammonia mixed fuel, and from the measurement results measured by the nitrogen oxide and ammonia concentration measuring device 122, By referring to the lookup table, the amount of ammonia or ammonia mixed fuel to be supplied through the selective catalytic reaction supply line 132 is calculated.
The constant supply device 126 is provided in the selective catalytic reaction supply line 132 and is configured to control the supply amount of ammonia or ammonia-mixed fuel based on the amount calculated by the supply amount calculation device 124 . The amount of ammonia or ammonia-mixed fuel supplied is controlled by the degree of opening of a regulating valve (not shown) provided in the selective catalytic reaction supply line 132, or a liquid-sending mechanism such as a liquid-sending pump provided in the quantitative supply device 126. (not shown) by adjusting the liquid delivery output. As a result, even if the concentration of nitrogen oxides or ammonia in the combustion gas fluctuates, the amount of the reducing agent can be appropriately adjusted according to this fluctuation.
NOx in the combustion gas can be reliably removed by catalytic reduction with ammonia supply as described above. However, if further confirmation of the concentration of NOx and residual ammonia still remaining in the combustion gases discharged from the selective catalytic reactor 128 and released to the atmosphere is required, the concentrations shown in FIG. In addition to the configuration, another set of nitrogen oxide/ammonia concentration measuring instruments ( not shown) is preferably attached.

The combustor 100 is, for example, an internal combustion engine such as a gas turbine, a jet engine, a reciprocating engine, or a rotary engine configured to extract mechanical power using thermal energy of combustion gas generated by combustion of ammonia mixed fuel. There may be. In addition, the combustion device 120 is a steam turbine (including a boiler), a Stirling engine, etc., configured to extract mechanical power by utilizing the thermal energy of the combustion gas generated by combustion of the ammonia mixed fuel. An external combustion engine may be provided. In this case, there are cases where the external combustion engine and the combustor 100 are close to each other and can be regarded as substantially the same, and other cases where they are separated from each other. In the case of a separate body, a combustion gas transfer line, not shown, is provided connecting between the combustor 100 and the external combustion engine. A combustion gas discharge line 130 for combustion gas used in the external combustion engine and discharged into the atmosphere is provided after the external combustion engine.
Furthermore, the combustor 100 may include a heating processing device (not shown) configured to perform heating processing using thermal energy of combustion gas generated by combustion of the ammonia-mixed fuel. Heat processing tools use the thermal energy of combustion gas to calcine, roast, melt, cut, weld, weld, cast, anneal, bend iron, heat reduce, and incinerate materials such as metals, ceramics, and resins. It is an instrument. In this case, as in the case of an external combustion engine, there are cases in which the heating and processing instrument and the combustor 100 are close to each other and can be regarded as substantially the same, and in other cases they are separated from each other. In the case of a separate unit, a combustion gas transfer line, not shown, is provided connecting between the combustor 100 and the hot processing tool. A combustion gas discharge line for the combustion gas used in the heating and processing equipment and discharged into the atmosphere is provided at the rear stage of the heating and processing equipment.

(Application of other ammonia mixed fuels)
Combustion of ammonia mixed fuels can be used for propulsion engines of power generation equipment and transportation equipment.
A power generation facility is, for example, a power generation facility that generates power in any one of land, water, and air space. In this case, at least one of the above-described internal combustion engine and the above-described external combustion engine is installed in the power generation facility as the combustor 100 for the ammonia mixed fuel. The generator of the power generation facility is configured to generate power using the mechanical power extracted using the thermal energy of the combustion gas of the ammonia mixed fuel, and the power output end of the power generation facility is generated by the generator. configured to output electrical power. In this case, the power plant comprises a control mechanism configured to control the amount of power at the power output.

A vehicle is a device configured to move or transport goods in any one of land, water, and air, the propulsion mechanism of which is configured to produce thrust to move the vehicle. It is a power engine. In this case, at least one of an ammonia-mixed fuel combustion device with an internal combustion engine and an ammonia-mixed fuel combustion device with an external combustion engine is mounted as a propulsion engine on the transportation equipment. Further, the vehicle is configured to utilize mechanical power extracted by at least one of the internal combustion engine and the external combustion engine from the thermal energy of the combustion gas of the ammonia mixed fuel as at least part of the thrust of the vehicle. Equipped with a power conversion transmission mechanism.
As transportation equipment, for example, in land areas, vehicles including tank trucks (small and large automobiles, motorbikes, etc.) that can transport ammonia and ammonia mixed fuel, railway vehicles, etc. In water areas, liquefied ammonia transportation Commercial ships including ships, passenger ships, warships, ships in general such as various work ships, submarines, etc., and in airspace, helicopters, aircraft, airships, drones, etc. In this case, the power conversion transmission mechanism is a series of well-known mechanisms that appropriately change the direction, torque, or speed of power used for propulsion drive and transmit it to the final drive unit. Including cranks, various gears, chains, belts, transmissions, drive shafts, drive wheels, propellers or screws, etc. In addition to the above-described internal combustion engine and external combustion engine, there are other power sources that can supply power. In addition to the mechanism, it includes a synchronizing mechanism of both powers and a resultant force mechanism such as a coaxial drive.

In addition, transportation equipment may be equipped with the power generation equipment described above. In this case, the transportation equipment uses the thermal energy of the combustion gas of the ammonia-mixed fuel to generate electric power output from the power generation facility for at least one of the following: propulsion of the transportation equipment, operation control of the transportation equipment, and maintenance and management of the transportation equipment. Preferably, there is at least one of an electric propulsion mechanism and a power supply mechanism configured to use at least a portion of the power requirements of the first. In this case, the transport equipment may include at least one of an ammonia-mixed fuel combustion device with an internal combustion engine and an ammonia-mixed fuel combustion device with an external combustion engine. In this case, the mechanical power extracted by at least one of the internal combustion engine and the external combustion engine from the energy of the combustion gas of the ammonia-mixed fuel is converted into at least a part of the power for propulsion of the transportation equipment and used. equipped with a power conversion transmission mechanism.

By efficiently burning ammonia using the ammonia mixed fuel in this way, it can be suitably used for internal combustion engines, external combustion engines, heat processing equipment, and power generation equipment that can comply with GHG emission regulations.

As described above, the ammonia mixed fuel, the ammonia mixed fuel production apparatus, the ammonia mixed fuel production method, the ammonia mixed fuel supply apparatus, the ammonia mixed fuel combustion apparatus, the power generation equipment using the ammonia mixed fuel, and the ammonia mixture of the present invention Although the transportation equipment using fuel has been described in detail, the present invention is not limited to the above embodiments and the following examples, and various improvements and modifications may be made without departing from the gist of the present invention. Of course.

(Example 1)
Using the ammonia mixed fuel manufacturing apparatus shown in FIG. 2, liquefied ammonia [NH ₃ ] and liquefied propane [C ₃ H ₈ ] are placed in this order in a closed vessel for mixing (contents about 2 L) whose temperature is adjusted to about 5 ° C. ) at a charged mass ratio of about 75:25 (total mass of about 490 g) (prior to these introductions, the inside of the closed mixing vessel 16 was first filled with nitrogen gas, then with volatilized vapor of liquefied ammonia, gas is replaced sequentially). After the introduction of the liquefied ammonia and liquefied propane was completed, all the valves were closed, and while the liquid phase temperature was adjusted to about 20°C, stirring and mixing was performed using a single impeller stirrer. , and separated into two phases, a lower layer mainly composed of ammonia, and stabilized. At this time, the volume ratio between the upper layer and the lower layer was approximately 15:85 (total volume approximately 810 cm ³ ), and the internal pressure (saturated vapor pressure) was approximately 1.6 MPa. At this time, while maintaining airtightness, capillaries were inserted into the upper and lower layers using the gas phase discharge line 21 (not shown), and samples of about 0.5 cm ³ each were collected from the upper and lower layers. , the ammonia concentrations of the upper and lower layers were measured by gas chromatography and found to be about 16 mass % and about 87 mass %, respectively (liquid phase average ammonia concentration of the entire upper and lower layers was about 77 mass %).
After that, when the liquidus temperature is raised while stirring is continued, the interface between the two liquid phases of the upper layer and the lower layer rises, the upper layer disappears at about 23 ° C., and an ammonia mixed fuel in which the whole is uniformly dissolved is obtained. rice field. At this time, the internal pressure (saturated vapor pressure) of the closed vessel for mixing was about 1.7 MPa. When the liquidus temperature was increased further, the liquid phase remained homogeneous, but when the liquidus temperature was subsequently lowered below about 23°C, it separated into two phases again. Further, even after the liquid phase temperature was kept at about 23° C. for about one day, the liquid phase was not separated and the internal pressure was kept at about 1.7 MPa.

(Example 2)
Using the same mixed fuel production apparatus as in Example 1, liquefied ammonia and liquefied n-butane [n-C ₄ H ₁₀ ] were mixed in a sealed vessel for mixing, the temperature of which was adjusted to about 5°C, starting with liquefied n-butane. (Internal capacity: about 2 L). Prior to the introduction of these components, the inside of the closed container 16 for mixing was first replaced with nitrogen gas and then with volatilized vapor of liquefied n-butane. After the introduction of the liquefied ammonia and the liquefied n-butane was completed, all the valves were closed, and while the liquid phase temperature was adjusted to about 20°C, stirring and mixing were performed using a single stirring blade stirrer. It separated into two phases, a butane-based upper layer and an ammonia-based lower layer, and stabilized. At this time, the volume ratio between the upper layer and the lower layer was approximately 7:93 (total volume approximately 940 cm ³ ), and the internal pressure (saturated vapor pressure) was approximately 1.0 MPa.
After that, when the liquidus temperature is raised while stirring is continued, the interface between the two liquid phases of the upper layer and the lower layer rises, the upper layer disappears at about 32 ° C., and an ammonia mixed fuel in which the whole is uniformly dissolved is obtained. rice field. At this time, the internal pressure (saturated vapor pressure) of the closed container for mixing was about 1.4 MPa. When the liquidus temperature was increased further, the liquid phase remained homogeneous, but when the liquidus temperature was subsequently lowered below about 32°C, it separated into two phases again. Further, even after the liquid phase temperature was kept at about 32° C. for about 10 hours, the liquid phase was not separated and the internal pressure was kept at about 1.4 MPa.

(Example 3)
Using the same ammonia mixed fuel production apparatus as in Example 1, first, as a mixed surfactant, having one long-chain alkyl group derived from coconut oil and a primary amino group [-NH ₂ ] in the molecule. A nonionic primary amine long-chain alkylamine [rheometric formula: C _k H _2k+1 NH ₂ , k ≈ 8 to 18], one long-chain alkyl chain with 12 carbon atoms in the molecule, and chloride and an ionic quaternary ammonium chloride [rheometric formula: C ₁₂ H ₂₅ N ⁺ (CH ₃ ) ₃ · Cl ^- ] having a quaternary trimethylammonium group and a mixed system at a molar ratio of about 80:20 A surfactant was introduced into the closed container for mixing so that the concentration in the ammonia mixed fuel to be produced was 1 mass % (introduction amount: 5.76 g). After that, in exactly the same manner as in Example 2, liquefied n-butane and liquefied ammonia were added to the inside of a closed container for mixing (contents: about 2 L) temperature-controlled at about 5° C., and charged mass ratio: about 85:15. (total mass about 570 g). Preliminary gas replacement was also performed in the same manner as in Example 2.
After the introduction was completed, the mixture was stirred and mixed for about 30 minutes with a single-type impeller agitator while adjusting the liquid phase temperature to about 20°C. However, the volume of the n-butane-based upper layer was smaller than in Example 2, and the entire liquid phase was slightly turbid and emulsified.
After that, when the liquidus temperature was increased while stirring was continued, the upper layer disappeared at about 26°C, which was about 6°C lower than in Example 2, and an ammonia-mixed fuel that was uniformly emulsified as a whole was obtained. At this time, the internal pressure (saturated vapor pressure) of the closed container for mixing was approximately 1.1 MPa, which was approximately 0.3 MPa lower than in Example 2. When the liquidus temperature was increased further, the liquid phase remained a homogeneous emulsion, but when the liquidus temperature was subsequently lowered below about 26°C, it separated into two phases again.
Even after the emulsified ammonia-mixed fuel was kept at about 26° C. for about 10 hours, the liquid phase was not separated and the internal pressure was kept at about 1.1 MPa.

(Reference example 1)
In Example 3 above, the compounding ratios of the nonionic long-chain alkylamine and the ionic quaternary ammonium chloride were 0:100 (that is, ionic alone), 20:80, 50:50, 65: 35, 90:10, and 100:0 (that is, nonionic alone), respectively, and introduced so that the concentration in the ammonia mixed fuel to be produced was 1% by mass, except that the introduced amount 5.76 g), and in each case where stirring and mixing were performed under the same conditions as in Example 3, the temperature at which the whole was homogenized was investigated in the same manner as in Example 3. Then, when the compounding ratio is 0:100, 20:80, 50:50, 65:35, and 100:0, the homogenized temperature is the same as in Example 2 in which no surfactant is added. The temperature was about 32° C., and almost no emulsification effect was observed by addition of the surfactant. However, when the compounding ratio is 0:100, 20:80, 50:50, and 65:35, the interface between the upper and lower layers becomes a curved surface that is significantly curved downward, and the nonionic alkylamine at the interface A significant change in the interfacial tension between the upper and lower layers was observed upon presence. In addition, when the compounding ratio was 90:10, the homogenization temperature was about 30°C, which was slightly higher than about 26°C when the compounding ratio was 80:20 in Example 3, and emulsification was observed. However, it was judged that the emulsion-forming ability was lowered.

(Example 4)
A mixed surfactant having the same components and the same blending ratio as those used in Example 3 was introduced into a closed container for mixing so that the concentration in the ammonia mixed fuel to be produced was 5% by mass (introduction amount 30 g), and stirring and mixing were performed at about 20° C. under the same conditions as in Example 3, except that the stirring and mixing time was extended to about 2 hours.
After that, when the liquidus temperature was raised while stirring was continued, the upper layer disappeared at about 21°C, which was about 11°C lower than that in Example 2, and an ammonia-mixed fuel in which the whole was uniformly emulsified was obtained. . At this time, the internal pressure (saturated vapor pressure) of the closed container for mixing was about 1.0 MPa, which was about 0.4 MPa lower than in Example 2.
Even after the emulsified ammonia-mixed fuel was kept at about 21° C. for about 10 hours, the liquid phase was not separated and the internal pressure was kept at about 1.0 MPa.

(Example 5)
A nonionic long-chain alkylamine having a single long-chain alkyl group having 8 carbon atoms and a primary amino group [—NH ₂ ] in the molecule, which has an alkyl chain length different from that of Example 3 [rhythmic formula: C ₈ H ₁₇ NH ₂ ], and an ionic quaternary ammonium chloride [ratio: C ₁₂ H ₂₅ N ⁺ (CH ₃ ) ₃ ·Cl ⁻ ], common to Example 3, and in a molar ratio of about 80:20 was introduced so that the concentration in the ammonia mixed fuel to be produced was 1% by mass (introduction amount: 5.76 g). Stirring and mixing was performed at about 20° C. under the same conditions.
After that, when the liquidus temperature was raised while stirring was continued, the upper layer disappeared at about 27°C, which was about 5°C lower than in Example 2, and an ammonia-mixed fuel in which the whole was uniformly emulsified was obtained. . At this time, the internal pressure (saturated vapor pressure) of the closed container for mixing was about 1.1 MPa, which was about 0.3 MPa lower than in Example 2.
Even after the emulsified ammonia-mixed fuel was kept at about 27° C. for about 10 hours, the liquid phase was not separated and the internal pressure was kept at about 1.1 MPa.

(Example 6)
In common with Example 3, a long-chain alkylamine that is a nonionic primary amine having 8 to 18 carbon atoms [property formula: C _k H _2k+1 NH ₂ , k≈8 to 18], and a carbon An ionic quaternary ammonium bromide having one long-chain alkyl group of number 12 and a quaternary trimethylammonium bromide group [property formula: C ₁₂ H ₂₅ N ⁺ (CH ₃ ) ₃ ·Br ⁻ ] and a mixed surfactant containing at a molar ratio of about 80:20 was introduced so that the concentration in the ammonia mixed fuel to be produced was 1% by mass (introduction amount: 5.76 g). Stirring and mixing were carried out at about 20° C. under the same conditions as above.
After that, when the liquidus temperature was raised while stirring was continued, the upper layer disappeared at about 30°C, which was about 2°C lower than that in Example 2, and an ammonia-mixed fuel in which the whole was uniformly emulsified was obtained. . At this time, the internal pressure (saturated vapor pressure) of the closed container for mixing was approximately 1.2 MPa, which was approximately 0.2 MPa lower than that in Example 2.
Even after the emulsified ammonia-mixed fuel was kept at about 30° C. for about 10 hours, the liquid phase was not separated and the internal pressure was kept at about 1.2 MPa.

(Example 7)
A nonionic long-chain compound having one long-chain alkyl group with 8 to 18 carbon atoms derived from coconut oil and a tertiary diethanolamide group [-C(=O)N(C ₂ H ₄ OH) ₂ ] in the molecule. A chain alkyldiethanolamide [proper formula: C _k H _2k+1 C(=O)N(C ₂ H ₄ OH) ₂ ] (where k is an integer from 8 to 18) and the ionic 4 A mixed surfactant containing ammonium chloride (rheological formula: C ₁₂ H ₂₅ N ⁺ (CH ₃ ) ₃ · Cl ^- ) at a molar ratio of about 80:20 in the ammonia mixed fuel to be produced Stirring and mixing was performed at about 20° C. under the same conditions as in Example 3, except that the concentration was 1% by mass (introduction amount: 5.76 g).
After that, when the liquidus temperature was raised while stirring was continued, the upper layer disappeared at about 30°C, which was about 2°C lower than that in Example 2, and an ammonia-mixed fuel in which the whole was uniformly emulsified was obtained. . At this time, the internal pressure (saturated vapor pressure) of the closed vessel for mixing was about 1.3 MPa, which was lower than that of Example 2 by about 0.1 MPa.
Even after the emulsified ammonia-mixed fuel was kept at about 30° C. for about 10 hours, the liquid phase was not separated and the internal pressure was kept at about 1.3 MPa.

(Example 8)
A nonionic polyoxyethylene alkyl ether having one long-chain alkyl group having 13 carbon atoms and a polyoxyethylene group [--O(C ₂ H ₄ O) ₅ -H] in the molecule [rheological formula: C ₁₃ H ₂₇ O(C ₂ H ₄ O) ₅ —H] and an ionic quaternary ammonium chloride (ratio: C ₁₂ H ₂₅ N ⁺ (CH ₃ ) _3.Cl ^- ) in a molar ratio of about 80:20 was introduced so that the concentration in the ammonia mixed fuel to be produced was 1% by mass (introduction amount: 5.76 g). Stir mixing was carried out at about 20° C. under the same conditions as in Example 3.
After that, when the liquidus temperature was raised while stirring was continued, the upper layer disappeared at about 29°C, which was about 3°C lower than that in Example 2, and an ammonia-mixed fuel in which the whole was uniformly emulsified was obtained. . At this time, the internal pressure (saturated vapor pressure) of the closed container for mixing was approximately 1.2 MPa, which was approximately 0.2 MPa lower than that in Example 2.
Even after the emulsified ammonia mixed fuel was kept at about 29° C. for about 10 hours, the liquid phase was not separated and the internal pressure was kept at about 1.2 MPa.

(Example 9)
In the molecule, one long-chain alkyl group having 8 to 18 carbon atoms derived from coconut oil and a tertiary polyoxyethyleneamino group [-N((C ₂ H ₄ O) _d -H) ((C ₂ H ₄ O) _e −H)] (d and e are positive integers such that d+e=5), and a nonionic long-chain tertiary amine [property formula: C _s H _2s+1 N ⁺ ((C ₂ H ₄ O) _d —H)((C ₂ H ₄ O) _e —H)] (s is an integer of 8 to 18, and d and e are positive integers such that d+e=5) and the ionic and a quaternary ammonium chloride (rheological formula: C ₁₂ H ₂₅ N ⁺ (CH ₃ ) ₃ · Cl ⁻ ) at a molar ratio of about 80:20, the ammonia mixed fuel to be produced. Stirring and mixing were carried out at about 20° C. under the same conditions as in Example 3, except that the content was 1% by mass (introduction amount: 5.76 g).
After that, when the liquidus temperature was raised while stirring was continued, the upper layer disappeared at about 29°C, which was about 3°C lower than that in Example 2, and an ammonia-mixed fuel in which the whole was uniformly emulsified was obtained. . At this time, the internal pressure (saturated vapor pressure) of the closed container for mixing was approximately 1.2 MPa, which was approximately 0.2 MPa lower than that in Example 2.
Even after the emulsified ammonia mixed fuel was kept at about 29° C. for about 10 hours, the liquid phase was not separated and the internal pressure was kept at about 1.2 MPa.

(Example 10)
A nonionic long-chain primary amine having 8 carbon atoms (rheological formula: C ₈ H ₁₇ NH ₂ ) and a long-chain alkyl having 10 to 18 carbon atoms derived from coconut oil in the molecule, common to Example 5 An ionic long-chain carboxylic acid having one group and a carboxyl group [-C(=O)OH] [rheometric formula: C _k H _2k+1 C(=O)OH, k is an integer of 10 to 18] and a mixed surfactant containing at a molar ratio of about 80:20 was introduced so that the concentration in the ammonia mixed fuel to be produced was 1% by mass (introduction amount: 5.76 g). Stirring and mixing were carried out at about 20° C. under the same conditions as above.
After that, when the liquidus temperature was raised while stirring was continued, the upper layer disappeared at about 29°C, which was about 3°C lower than that in Example 2, and an ammonia-mixed fuel in which the whole was uniformly emulsified was obtained. . At this time, the internal pressure (saturated vapor pressure) of the closed container for mixing was approximately 1.2 MPa, which was approximately 0.2 MPa lower than that in Example 2.
Even after the emulsified ammonia mixed fuel was kept at about 29° C. for about 10 hours, the liquid phase was not separated and the internal pressure was kept at about 1.2 MPa.

(Example 11)
A nonionic long-chain tertiary amine having a tertiary polyoxyethylene amino group in common with Example 9 [ratio: C _s H _2s+1 N ⁺ ((C ₂ H ₄ O) _d -H) (( C ₂ H ₄ O) _e —H)] (d and e are positive integers such that d + e = 5), and an ionic long-chain carboxylic acid having 10 to 18 carbon atoms, common to Example 10 [ formula: C _k H _2k+1 C(=O)OH, k≈10 to 18] in a molar ratio of about 80:20, the concentration in the ammonia mixed fuel to be produced is 1% by mass. Stirring and mixing was carried out at about 20° C. under the same conditions as in Example 3 except that the amount of the solution introduced was 5.76 g.
After that, when the liquidus temperature was raised while stirring was continued, the upper layer disappeared at about 28°C, which was about 4°C lower than that in Example 2, and an ammonia-mixed fuel in which the whole was uniformly emulsified was obtained. . At this time, the internal pressure (saturated vapor pressure) of the closed container for mixing was approximately 1.2 MPa, which was approximately 0.2 MPa lower than that in Example 2.
Even after the emulsified ammonia-mixed fuel was kept at about 27° C. for about 10 hours, the liquid phase was not separated and the internal pressure was kept at about 1.2 MPa.

(Reference example 2)
In Example 11 above, the compounding ratio of the nonionic long-chain tertiary amine having a tertiary bis(polyethoxy)amino group and the ionic long-chain carboxylic acid was 0:100 (that is, ionic only), and 20 : 80, and stirring and mixing was performed under the same conditions except that each was introduced so that the concentration in the ammonia mixed fuel to be produced was 1% by mass (introduction amount: 5.76 g). In each case, the temperature at which the whole was homogenized was investigated in the same manner as in Example 3. Then, in both cases of blending ratios of 0:100 and 20:80, the homogenization temperature was about 32 to 33° C., which was the same as or slightly higher than in Example 2 in which no surfactant was added. Almost no effect of emulsification by addition of active agent was observed.

(Example 12)
A mixed surfactant having the same components and the same blending ratio as those used in Example 11 was introduced into the closed container for mixing so that the concentration in the ammonia mixed fuel to be produced was 5% by mass (introduction amount 30 g), and stirring and mixing were performed at about 20° C. under the same conditions as in Example 3, except that the stirring and mixing time was extended to about 2 hours.
After that, when the liquidus temperature was raised while stirring was continued, the upper layer disappeared at about 23°C, which was about 9°C lower than that in Example 2, and an ammonia-mixed fuel in which the whole was uniformly emulsified was obtained. . At this time, the internal pressure (saturated vapor pressure) of the closed container for mixing was about 1.1 MPa, which was about 0.3 MPa lower than in Example 2.
Even after the emulsified ammonia-mixed fuel was kept at about 23° C. for about 10 hours, the liquid phase was not separated and the internal pressure was kept at about 1.1 MPa.

(Example 13)
Using the ammonia mixed fuel production apparatus shown in FIG. 2, liquefied ammonia and methanol (CH ₃ OH) are first added to the inside of a closed container for mixing (inner capacity of about 2 L) whose temperature is adjusted to about 15 ° C. , was introduced at a feed mass ratio of about 70:30 (total mass of about 660 g). Prior to the introduction of these components, the inside of the closed container 16 for mixing was first replaced with nitrogen gas and then with volatilized vapor of liquefied ammonia. After these introductions were completed, all the valves were closed, and the mixture was stirred and mixed with a single impeller agitator while adjusting the liquid phase temperature to about 19°C. Soon after, the liquid phase became a homogeneous solution. At this time, the internal pressure (saturated vapor pressure) was approximately 0.7 MPa, which is approximately 0.1 MPa lower than the approximately 0.8 MPa saturated vapor pressure of pure ammonia at the same temperature.
After that, even if the liquid phase temperature was raised to about 40° C. while stirring was continued, the liquid phase remained in a homogeneous solution state. In addition, even after the liquid phase temperature was maintained at about 19° C. for about one day, the liquid phase was maintained in a compatible state and the internal pressure was maintained at about 0.7 MPa.
In addition, in Example 13 above, the same conditions were used except that the charging mass ratio of liquefied ammonia and methanol was changed to about 50:50 (total mass: about 710 g) and about 30:70 (total mass: about 710 g). In the same manner as in Example 13, the mixed state was examined when stirring and mixing were performed. As a result, the liquid phase becomes a uniform solution in both cases where the starting composition ratio is about 50:50 and about 30:70, and the internal pressure (saturated vapor pressure) at the liquid phase temperature of about 19° C. is about 0.0. 5 MPa, and about 0.3 MPa. In addition, in the case of any of these feed composition ratios, even after holding for about one day while maintaining the liquid phase temperature at about 19 ° C., the liquid phase is maintained as dissolved, and the internal pressure is also about 0.5 MPa, respectively. and kept at about 0.3 MPa.

(Example 14)
^Using the ammonia mixed fuel manufacturing apparatus shown in FIG. First, it was introduced into a closed container for mixing (contents about 2 L) whose temperature was adjusted to about 15 ° C. with a charging mass ratio of liquefied ammonia: regular gasoline = about 40: 60 (total mass about 670 g). . Prior to the introduction of these components, the inside of the closed container 16 for mixing was first replaced with nitrogen gas and then with volatilized vapor of liquefied ammonia. After these introductions were completed, all the valves were closed, and the liquid phase was stirred and mixed with a single stirring impeller agitator while adjusting the liquid phase temperature to about 46° C. Soon, the liquid phase became a homogeneous solution. At this time, the internal pressure (saturated vapor pressure) was approximately 1.7 to 1.8 MPa, which is approximately equal to the saturated vapor pressure of pure ammonia at the same temperature.
After that, even if the liquid phase temperature was further increased while stirring was continued, the liquid phase remained in a homogeneous solution state. On the other hand, when the liquid phase temperature is lowered to about 44 ° C. while stirring is continued, a different phase begins to be released and floats in the solution, and at about 43 ° C., a new liquid phase phase-separated above the solution layer. (liquefied ammonia) appeared clearly (the internal pressure at this time was about 1.5 MPa). In addition, even after holding for about one day while maintaining the liquid phase temperature at about 46° C., the liquid phase was maintained in a compatible state and the internal pressure was maintained at about 1.7 to 1.8 MPa.

10 manufacturing apparatus 12 ammonia storage closed container 14, 14 ₁ , 14 ₂ combustion improver storage closed container 16 mixing closed container 17 temperature control jacket 17a temperature control medium inlet nozzle 17b temperature control medium outlet nozzle 18 ammonia introduction line 18a, 20a, 20a ₁ , 20a ₂ , 28a Flow meters 18b, 20b, 28b, 18c, 19c, 20b ₁ , 20c ₁ , 20b ₂ , 20c ₂ , 20c, 22a, 28c, 58 Regulating valves 18d, 20d ₁ Cooling device 19d, 20d, 20d ₂ , 28d liquid feed pumps 20, 20 ₁ , 20 ₂ combustion improver introduction line 21 gas phase discharge line 21a gas phase discharge valves 22, 22 ₁ , 22 ₂ liquid phase discharge lines 22a, 22a ₁ , 22a ₂ liquid phases Discharge valves 22b, 22b ₁ , 22b ₂ Discharge flowmeters 22c, 22c ₁ , 22c ₂ Composition evaluation means 24, 63 Stirrer 26 Surfactant storage container 28 Surfactant introduction line 30 Nitrogen gas introduction mechanism 30a Nitrogen gas introduction valve 30b Nitrogen gas introduction line 30c Nitrogen gas pressure gauge 30d Nitrogen gas pressure reducing valve 30e Nitrogen gas regulating valve 31 Pressure gauge 32 Control device 33 Thermometer 50 Sealed storage container 52 Inlet 54 Outlet 56 Connection mechanism 58 Outlet valve 59 Vapor phase outline 59a Gas phase discharge valve 60 Ammonia mixed fuel supply line 61 Thermometer 62 Pressure gauge 63 Stirrer 64 Nitrogen gas injection line 64a Pressure reducing valve 64b Pressure gauge 64c Regulating valve 65 Volume flow meter 66 Cylinder 67 Piston 68 Reciprocating drive device 68a Motor 68b Crank Mechanism 69 Mixed state evaluation device 70 Supply device 80 Supply device 100 Combustor 110 Branching part 112 Ammonia mixed fuel recirculation line 120 Combustion device 122 Nitrogen oxide/ammonia concentration measuring device 124 Supply amount calculation device 126 Constant supply device 128 Selective catalytic reaction vessel 130 combustion gas discharge line

Claims

An ammonia mixed fuel,
Ammonia in a liquefied state;
and a combustion improver that assists combustion of the ammonia,
The combustion improver is
(a) liquefied petroleum gas, naphtha, gasoline, kerosene, and diesel;
(b) a feedstock hydrocarbon which is at least one hydrocarbon species contained as a component in any one of the liquefied petroleum gas, the naphtha, the gasoline, the kerosene, and the light oil; and (c) carbon a raw material alcohol that is an alcohol of number 3 or less;
is at least one of
The ammonia mixed fuel is in a gas-liquid equilibrium state, and at least a part of the liquid phase portion of the ammonia mixed fuel is in a solution state in which the ammonia and the combustion improver are mutually dissolved, or the ammonia and the combustion improver are dissolved. An ammonia mixed fuel characterized by being in an emulsion state with
The ammonia mixed fuel is a liquid in which the entire liquid phase portion of the ammonia mixed fuel is in a solution state in which the ammonia and the combustion improver are mutually dissolved, or in an emulsion state of the ammonia and the combustion improver. The ammonia mixed fuel according to claim 1, which maintains a predetermined temperature according to phase composition.
The ammonia mixed fuel according to claim 1 or 2, wherein the ammonia mixed fuel is isolated and stored in a closed environment in which gas-liquid equilibrium is maintained.
The ammonia mixed fuel contains at least one of the liquefied petroleum gas, the raw material hydrocarbon, and the raw material alcohol as the combustion improver,
The raw material hydrocarbon is at least one hydrocarbon species contained as a component in the liquefied petroleum gas,
The ammonia mixed fuel according to any one of claims 1 to 3, wherein the raw material alcohol is methanol.
The ammonia mixed fuel according to any one of claims 1 to 4, wherein the ammonia mixed fuel further contains 0.1 to 10% by mass of a surfactant.
The ammonia mixed fuel according to claim 5, wherein the surfactant includes at least one nonionic surfactant and at least one ionic surfactant.
The surfactant is
(A) In the molecular structure, a primary or secondary amino group [—NH 2 or >NH], a polyoxyalkyleneamino group [>N(C a H 2a O) c —H, or —N ((C b H 2b O) d —H)((C b H 2b O) e —H)] (a and b are 2 or 3, c is an integer of 1 to 8, and d and e are 0 such that d+e=1 to 8 or positive integer), amide group [-C(=O)NH 2 ], polyoxyalkyleneamide group [-C(=O)N((C f H 2f O) g -H) ((C f H 2f O) h —H)] (f is 2 or 3, g and h are 0 or positive integers such that g+h=1 to 8), and a polyoxyalkylene group [—O(C i H 2i O ) j —H] (i is 2 or 3 and j is an integer of 1 to 8), at least one group as a nonionic polar moiety,
and any of an alkyl group [C k H 2k+1 -] (k is an integer of 7 to 18) and an alkenyl group [C l H 2l-1 -] (l is an integer of 7 to 18) at least one nonionic surfactant having at least one group as a nonpolar site,
(B) In the molecular structure, a quaternary methylammonium group, a quaternary methylalkanolammonium group, or a quaternary alkanolammonium group [—N + (CH 3 ) p (C m H 2m OH) qX − , or >N + (CH 3 ) r (C n H 2n OH) s ·X′ − ] (m and n are 2 or 3, p and q are 0 or positive integers satisfying p+q=3, r and s are r+s=2 0 or a positive integer, X and X′ are Cl, Br and I), and a carboxyl group [—C(=O)OH], any of the ionic polar having at least one group as a moiety,
and at least an alkyl group [C t H 2t+1 -] (t is an integer of 7 to 18) and an alkenyl group [C u H 2u-1 -] (u is an integer of 7 to 18) 7. The ammonia mixed fuel of claim 6, comprising at least one ionic surfactant having at least one non-polar site on one side.
A manufacturing device for manufacturing an ammonia mixed fuel,
an ammonia storage closed container for storing ammonia in a liquefied state;
(a) liquefied petroleum gas, naphtha, gasoline, kerosene, and light oil; and (c) a raw material alcohol, which is an alcohol having 3 or less carbon atoms. A closed container for storing a combustion improver,
The ammonia and the combustion improver are stirred and mixed with a stirrer to obtain a dissolved solution state or an emulsified mixture, and the mixture obtained by stirring and mixing with the stirrer maintains a vapor-liquid equilibrium state. a mixing enclosure configured to allow
an ammonia introduction line provided with an ammonia fixed quantity introduction mechanism configured to connect the ammonia storage closed container and the mixing closed container and introduce a predetermined amount of the ammonia into the mixing closed container;
Combustion improver metered introduction configured to connect the combustion improver storage closed container and the mixing closed container, and to introduce a predetermined amount of the combustion improver from the combustion improver storage closed container into the mixing closed container. A combustion improver introduction line provided with a mechanism;
and at least one liquid phase discharge line configured to discharge the mixture obtained by stirring and mixing the agitator in the closed mixing vessel as an ammonia mixed fuel from the closed mixing vessel. Ammonia mixed fuel manufacturing equipment.
When the ammonia and the combustion improver are introduced into the closed mixing vessel and stirred and mixed by the stirrer, the saturated vapor pressure of the mixture in the closed mixing vessel increases to the closed mixing vessel. 9. The apparatus for producing an ammonia mixed fuel according to claim 8, further comprising a temperature control mechanism configured to control the temperature of said mixture so that the temperature does not exceed a set pressure resistance.
When the ammonia and the combustion improver are introduced into the closed mixing vessel and stirred and mixed by the stirrer, the mixture maintains a gas-liquid equilibrium state in the closed mixing vessel, and the mixture is in a solution state in which the ammonia and the combustion improver are mutually dissolved, or in an emulsion state of the ammonia and the combustion improver, depending on the liquid phase composition of the mixture. 10. The apparatus for producing an ammonia mixed fuel according to claim 9, wherein the temperature control mechanism is configured to control the temperature of the mixture.
The ammonia mixed fuel contains at least one of the liquefied petroleum gas, the raw material hydrocarbon, and the raw material alcohol as the combustion improver,
The raw material hydrocarbon is at least one hydrocarbon species contained as a component in the liquefied petroleum gas,
The raw material alcohol is methanol,
The ammonia mixture according to any one of claims 8 to 10, wherein the combustion improver storage sealed container stores at least one of the liquefied petroleum gas, the raw material hydrocarbon, and the raw material alcohol. Fuel manufacturing equipment.
When discharging the ammonia-mixed fuel from the liquid-phase discharge line, nitrogen gas is supplied to the gas phase portion in the closed mixing vessel at a discharge pressure equal to or higher than the saturated vapor pressure of the mixture in the closed mixing vessel. The apparatus for producing an ammonia-mixed fuel according to any one of claims 8 to 11, further comprising a nitrogen gas introduction line configured to allow introduction of nitrogen gas and connected to the closed container for mixing.
the liquid phase discharge line comprises a discharge flow meter configured to continuously measure the discharge flow rate of the ammonia-blended fuel discharged through the liquid phase discharge line;
A flow rate equal to the discharge flow rate of the ammonia discharged through the liquid phase discharge line, which is calculated from the discharge flow rate of the ammonia mixed fuel measured by the discharge flow meter and the liquid phase composition of the ammonia mixed fuel. so that the ammonia can be continuously quantitatively introduced from the ammonia storage closed container into the mixing closed container, and in parallel, the discharge flow rate of the ammonia mixed fuel, the liquid phase composition of the ammonia mixed fuel, The combustion improver can be continuously and quantitatively introduced into the mixing closed container from the combustion improver storage closed container at a flow rate equal to the discharge flow rate of the combustion improver discharged through the liquid phase discharge line, which is calculated from 12. The apparatus for producing an ammonia-mixed fuel according to claim 8, wherein said quantitative introduction mechanism for ammonia and said quantitative introduction mechanism for combustion improver are respectively configured as follows.
Furthermore, a surfactant storage container for storing the surfactant,
A surface active agent provided with a quantitative surfactant introduction mechanism configured to connect the surfactant storage container and the closed mixing container and introduce a predetermined amount of the surfactant into the closed mixing container. and an agent introduction line,
The surfactant is stirred and mixed together with the ammonia and the combustion improver by the stirrer in the closed mixing container, and the liquid phase discharge line discharges the mixture containing the surfactant. 13. The apparatus for producing an ammonia mixed fuel according to any one of 8 to 12.
The ammonia quantitative introduction mechanism and the combustion improver quantitative introduction mechanism are the ammonia quantitative introduction mechanism and the combustion improver quantitative introduction mechanism according to claim 13,
further comprising the exhaust flow meter of claim 13;
The surfactant quantitative introduction mechanism is the surfactant in the ammonia mixed fuel calculated from the respective amounts of the ammonia, the combustion improver, and the surfactant previously introduced into the mixing closed container. at a flow rate equal to the discharge flow rate of the surfactant discharged through the liquid phase discharge line, determined by multiplying the concentration of the agent by the discharge flow rate of the ammonia blend fuel measured by the discharge flow meter; 15. The apparatus for producing an ammonia-mixed fuel according to claim 14, wherein said surfactant is continuously introduced from said surfactant storage container into said closed container for mixing.
The apparatus for producing ammonia mixed fuel according to claim 14 or 15, wherein the surfactant includes at least one nonionic surfactant and at least one ionic surfactant.
The surfactant is
(A) In the molecular structure, a primary or secondary amino group [—NH 2 or >NH], a polyoxyalkyleneamino group [>N(C a H 2a O) c —H, or —N ((C b H 2b O) d —H)((C b H 2b O) e —H)] (a and b are 2 or 3, c is an integer of 1 to 8, and d and e are 0 such that d+e=1 to 8 or positive integer), amide group [-C(=O)NH 2 ], polyoxyalkyleneamide group [-C(=O)N((C f H 2f O) g -H) ((C f H 2f O) h —H)] (f is 2 or 3, g and h are 0 or positive integers such that g+h=1 to 8), and a polyoxyalkylene group [—O(C i H 2i O ) j —H] (i is 2 or 3 and j is an integer of 1 to 8), at least one group as a nonionic polar moiety,
and any of an alkyl group [C k H 2k+1 -] (k is an integer of 7 to 18) and an alkenyl group [C l H 2l-1 -] (l is an integer of 7 to 18) at least one nonionic surfactant having at least one group as a nonpolar site,
(B) In the molecular structure, a quaternary methylammonium group, a quaternary methylalkanolammonium group, or a quaternary alkanolammonium group [—N + (CH 3 ) p (C m H 2m OH) qX − , or >N + (CH 3 ) r (C n H 2n OH) s ·X′ − ] (m and n are 2 or 3, p and q are 0 or positive integers satisfying p+q=3, r and s are r+s=2 0 or a positive integer, X and X′ are Cl, Br and I), and a carboxyl group [—C(=O)OH], any of the ionic polar having at least one group as a moiety,
and at least an alkyl group [C t H 2t+1 -] (t is an integer of 7 to 18) and an alkenyl group [C u H 2u-1 -] (u is an integer of 7 to 18) 17. The apparatus for producing an ammonia mixed fuel according to claim 16, comprising at least one ionic surfactant having at least one non-polar site on one side.
The combustion improver is at least one of (a) and (b) above,
When the ammonia and the combustion improver are stirred and mixed in the closed container for mixing, the liquid phase portion of the mixture separates into upper and lower two layers, and the liquid phase portion separated into the upper and lower two layers The quantitative introduction mechanism for ammonia and the auxiliary for introducing the ammonia and the combustion improver into the closed container for mixing at a predetermined amount ratio so that the whole of each layer is in a solution state or an emulsion state. The fuel quantitative introduction mechanism is configured, and the temperature control mechanism is configured so that the stirring and mixing is performed while maintaining a predetermined liquidus temperature,
By discharging the liquid phase portion of at least one of the upper and lower two layers from the closed container for mixing through one or two of the liquid phase discharge lines, the ammonia and the combustion improver are one or more 10. The apparatus for producing an ammonia mixed fuel according to claim 8 or 9, which produces one or two ammonia mixed fuels in solution state or emulsion state with two predetermined composition ratios.
The mixing sealed container is provided with a mixing state evaluation device configured to evaluate the mixing state of the mixture,
Ammonia mixed fuel according to any one of claims 8 to 18, comprising a stirring adjustment device that adjusts the stirring mixing strength and stirring mixing time by the stirrer according to the evaluation result of the mixed state evaluation device. manufacturing equipment.
When the ammonia and the combustion improver are introduced into the closed container for mixing, the temperature of the ammonia passing through the ammonia introduction line and the temperature of the combustion improver passing through the combustion improver introduction line are A temperature control device configured to adjust the temperature of the ammonia and the temperature of the combustion improver so as to be equal to the temperature of the mixture inside the closed container is provided in each of the ammonia introduction line and the combustion improver introduction line. An ammonia mixed fuel production apparatus according to any one of claims 8 to 19, provided.
a heating device for heating the ammonia in the ammonia storage closed container and/or the combustion enhancer in the combustion enhancer storage closed container when the ammonia and the combustion enhancer are introduced into the mixing closed container; The apparatus for producing an ammonia mixed fuel according to any one of claims 8 to 20, which is provided in the ammonia storage closed container and/or the combustion improver storage closed container.
further comprising an ammonia mixed fuel storage closed container configured to store the ammonia mixed fuel in a gas-liquid equilibrium state;
The storage closed container includes an inlet into which the ammonia mixed fuel is injected, and an outlet provided at the bottom of the storage closed container configured to discharge the ammonia mixed fuel to the outside. ,
Any of claims 8 to 21, wherein the injection port is provided with a connection mechanism configured to inject the ammonia-mixed fuel from the liquid phase discharge line into the storage closed container while maintaining airtightness and internal pressure. 2. The apparatus for producing an ammonia mixed fuel according to claim 1.
The ammonia mixed fuel manufacturing apparatus according to claim 22, wherein the storage closed container is provided with a stirrer configured to stir and mix the ammonia mixed fuel.
The storage sealed container is provided with a mixing state evaluation device configured to evaluate the mixing state of the ammonia mixed fuel,
A stirring adjustment device that adjusts the strength of stirring and mixing by the stirrer provided in the storage closed container and the stirring and mixing time based on the evaluation result of the mixed state obtained by the mixed state evaluation device. Item 24. An ammonia-mixed fuel manufacturing apparatus according to Item 23.
The storage closed container adjusts the temperature of the ammonia-mixed fuel inside the storage closed container so that the internal pressure of the storage closed container does not exceed the set pressure resistance of the storage closed container. 25. Apparatus for producing ammonia blended fuel according to claim 23 or 24, wherein a temperature control device configured to regulate is provided.
When the ammonia mixed fuel in the storage closed container is stirred and mixed by the stirrer, the entire liquid phase portion of the ammonia mixed fuel is mixed with the ammonia according to the liquid phase composition of the ammonia mixed fuel. The temperature control device is configured to adjust the temperature of the ammonia mixed fuel so that it is in a temperature range in which the combustion improver and the combustion improver are in a solution state or an emulsion state of the ammonia and the combustion improver. The apparatus for producing an ammonia mixed fuel according to any one of claims 23 to 25, wherein
When the ammonia mixed fuel is discharged from the discharge port, nitrogen gas is introduced into the gas phase portion in the storage closed container at a discharge pressure equal to or higher than the saturated vapor pressure of the ammonia mixed fuel in the storage closed container. The ammonia-mixed fuel manufacturing apparatus according to any one of claims 22 to 26, further comprising a nitrogen gas introduction line connected to the storage closed container.
The storage closed container has the discharge port on the bottom surface of the storage closed container,
The outlet is provided with a volumetric flow meter configured to continuously measure the volumetric flow rate of the ammonia mixed fuel discharged from the outlet in a liquid phase,
When the ammonia-mixed fuel is injected into the storage closed container through the injection port, the ammonia-mixed fuel is injected until a predetermined amount equal to or less than the full filling amount of the storage closed container is reached. After the ammonia-mixed fuel is injected into the storage closed container, when the ammonia-mixed fuel is discharged from the storage closed container through the discharge port, the storage closed container is airtight and an injection/discharge control mechanism configured to continuously decrease the internal volume of the storage closed container at a rate of volume change substantially equal to the discharge volumetric flow rate measured by the volumetric flowmeter while maintaining the internal pressure; The apparatus for producing an ammonia mixed fuel according to any one of claims 22 to 26, further comprising:
The closed container for storage is
A body having an upright outer cylindrical shape and having a constant internal cross-sectional area orthogonal to the axial direction of the outer cylindrical shape, and the inlet and the outlet for sealing the lower end opening of the body are provided. a cylinder having a bottom plate;
a piston capable of reciprocating vertically in the cylinder while maintaining airtightness;
a reciprocating drive device configured to reciprocate the piston in the vertical direction;
The injection and discharge control mechanism is
When the ammonia-mixed fuel is injected into the closed storage container through the injection port, the piston is moved in the cylinder by the reciprocating drive to a predetermined full-filled position or at the full-filled state. Stop after being pushed up to a predetermined position below the position,
Furthermore, after filling the ammonia mixed fuel, when the ammonia mixed fuel is discharged from the storage closed container through the discharge port, the saturated vapor pressure of the ammonia mixed fuel in the storage closed container While resisting, the piston moves at a linear velocity approximately equal to the value calculated by dividing the exhaust volumetric flow rate measured by the volumetric flowmeter by the internal cross-sectional area of the barrel of the cylinder. 29. The apparatus for producing ammonia mixed fuel according to claim 28, configured to stop near the bottom plate after being continuously pushed down by a reciprocating drive.
When the ammonia-mixed fuel is injected into the storage closed container through the injection port, the ammonia-mixed fuel is injected until a predetermined amount equal to or less than the full filling amount of the storage closed container is reached. configured to
After the ammonia mixed fuel is injected into the storage closed container, when the ammonia mixed fuel is discharged from the storage closed container through the discharge port, the storage closed container is kept airtight. while the ammonia mixed fuel is extruded from the storage closed container at a pressure higher than the saturated vapor pressure of the ammonia mixed fuel at the temperature of the ammonia mixed fuel in the storage closed container. The apparatus for producing ammonia mixed fuel according to any one of claims 22 to 26, further comprising an emission control mechanism.
The closed container for storage is
A body having an outer cylindrical shape and having a constant internal cross-sectional area orthogonal to the axial direction of the outer cylindrical shape, and the inlet and the outlet for sealing an opening at one end of the body are provided. a cylinder having a bottom plate;
a piston capable of reciprocating in the cylinder in the axial direction while maintaining airtightness;
a reciprocating drive device configured to reciprocate the piston in the axial direction;
The injection and discharge control mechanism is
When the ammonia-mixed fuel is injected into the closed storage container through the injection port, the piston is moved in the cylinder by the reciprocating drive to a predetermined full-filled position or at the full-filled state. configured to stop after being pushed up to a predetermined position below the position;
After the ammonia mixed fuel is filled, when the ammonia mixed fuel is discharged from the storage closed container through the discharge port, the storage closed container is kept airtight. 29. The piston of claim 28 configured to stop near the bottom plate after being continuously depressed by the reciprocating drive at a pressure above the saturated vapor pressure of the ammonia-blended fuel within. Ammonia mixed fuel manufacturing equipment.
The connection mechanism is configured to be detachable from each other with respect to the connection between the introduction line for introducing the ammonia-mixed fuel into the storage sealed container and the injection port,
32. The apparatus for producing an ammonia-mixed fuel according to any one of claims 22 to 31, wherein said closed container for storage is mounted on a transportation device in any one of land area, water area, and air area.
The ammonia mixed fuel manufacturing apparatus according to any one of claims 8 to 32,
an ammonia mixed fuel supply line for supplying the ammonia mixed fuel discharged from the liquid phase discharge line to a combustor configured to burn the ammonia mixed fuel. Fuel supply device.
The ammonia mixed fuel manufacturing apparatus according to any one of claims 21 to 32,
an ammonia mixed fuel supply line for supplying the ammonia mixed fuel discharged from the discharge port of the storage sealed container to a combustor configured to burn the ammonia mixed fuel. Ammonia mixed fuel supply device.
35. The ammonia mixed fuel supply line is provided with an ammonia mixed fuel supply machine configured to supply the ammonia mixed fuel to the combustor at a predetermined flow rate and a predetermined discharge pressure. 2. The ammonia mixed fuel supply device according to 1.
The ammonia-mixed fuel supply line is provided with a branch part that branches the ammonia-mixed fuel at a predetermined amount ratio on the way to the combustor,
A portion of the ammonia-mixed fuel flowing through the ammonia-mixed fuel supply line that is branched without being supplied to the combustor is recirculated into the mixing closed container or the storage closed container. An ammonia-mixed fuel supply device according to any one of claims 33 to 35, comprising an ammonia-mixed fuel recirculation line.
a combustor configured to burn the ammonia mixed fuel according to any one of claims 1 to 7;
The ammonia mixed fuel supply device according to any one of claims 33 to 36,
and a combustion gas discharge line configured to discharge combustion gas generated by combustion of the ammonia mixed fuel in the combustor into the atmosphere.
In the combustion gas discharge line, by-produced when the ammonia mixed fuel is burned in the combustor, contained in the combustion gas, discharged from the combustion chamber of the combustor and passed through the combustion gas discharge line 38. Apparatus for combustion of ammonia mixed fuel according to claim 37, further comprising a selective catalytic reactor configured to decompose nitrogen oxides by catalytic reduction with said ammonia or said ammonia mixed fuel vapor gas. .
A predetermined amount of either one of the ammonia and the ammonia mixed fuel is removed from either one of the closed ammonia storage container that stores the ammonia and the closed storage container that stores the ammonia mixed fuel. 39. A selective catalytic reaction feed line configured to join the combustion gas at a junction provided in the combustion gas discharge line between the combustion chamber and the selective catalytic reactor according to claim 38. Combustion device for ammonia mixed fuel according to 1.
provided in the combustion gas discharge line on the combustion chamber side with respect to the junction of the selective catalytic reaction supply line and the combustion gas discharge line, and on the combustion chamber side with respect to the junction; a nitrogen oxide concentration measuring instrument and an ammonia concentration measuring instrument configured to respectively measure the concentration of nitrogen oxides and the concentration of ammonia;
Based on the concentration results measured by the nitrogen oxide concentration measuring instrument and the ammonia concentration measuring instrument, the amount of the ammonia or the ammonia mixed fuel to be supplied through the selective catalytic reaction supply line is determined. a supply amount calculation device configured to calculate
Provided in the selective catalytic reaction supply line, the supply amount of the ammonia or the ammonia mixed fuel supplied through the selective catalytic reaction supply line is calculated based on the calculation result of the amount by the supply amount calculation device. 40. Apparatus for combustion of ammonia mixed fuel according to claim 39, comprising a dosing device configured to control.
41. The combustor according to any one of claims 37 to 40, wherein said combustor is used as an internal combustion engine configured to extract mechanical power using the energy of said combustion gas produced by combustion of said ammonia mixed fuel. Ammonia mixed fuel combustion equipment.
an external combustion engine configured to extract mechanical power using the energy of the combustion gas generated by combustion of the ammonia-mixed fuel;
and a combustion gas transfer line configured to transfer said combustion gases from said combustor to said external combustion engine.
A heating processing tool configured to perform heating processing using the energy of the combustion gas generated by burning the ammonia mixed fuel;
and a combustion gas transfer line configured to transfer the combustion gas from the combustor to the heat processing tool.
In any one of land area, water area, and air area, a power generation facility that generates electricity,
At least one of the ammonia mixed fuel combustion apparatus comprising the internal combustion engine according to claim 41 and the ammonia mixed fuel combustion apparatus comprising the external combustion engine according to claim 42 is provided. ,
a generator configured to generate power using mechanical power extracted from energy of the combustion gas of the ammonia mixed fuel by the at least one of the internal combustion engine and the external combustion engine;
a power output end configured to output power generated by the generator;
and a control mechanism configured to control the amount of power at the power output.
Vehicles configured to move or transport goods in any one of land, water, and air,
At least one of the ammonia mixed fuel combustion apparatus provided with the internal combustion engine according to claim 41 and the ammonia mixed fuel combustion apparatus provided with the external combustion engine according to claim 42 is installed. ,
The mechanical power extracted from the energy of the combustion gas of the ammonia-mixed fuel by the at least one of the internal combustion engine and the external combustion engine is used as at least part of power for propulsion of the transportation equipment. A transportation device characterized by comprising a power conversion transmission mechanism configured as described above.
Vehicles configured to move or transport goods in any one of land, water, and air,
The power generation equipment according to claim 44 is mounted,
An electric propulsion mechanism configured to use the energy of the combustion gas of the ammonia mixed fuel to use the power output from the power generation facility for at least part of the power required to propel the transportation equipment,
an operation control mechanism configured to use the electric power for at least part of required electric power in operation control of the transportation equipment; and
a maintenance feed mechanism configured to use the electric power for at least part of power required for maintenance of the transportation equipment.
Further, the mechanical power extracted from the energy of the combustion gas of the ammonia mixed fuel by at least one of the internal combustion engine and the external combustion engine provided in the power generation facility is used as power for propulsion of the transportation equipment. 47. A vehicle according to claim 46, further comprising a power conversion transmission mechanism configured to convert and use at least a portion of a.
A method for producing an ammonia mixed fuel,
(1) ammonia in a liquefied state;
(a) liquefied petroleum gas, naphtha, gasoline, kerosene, and diesel oil;
(b) a feedstock hydrocarbon which is at least one hydrocarbon species contained as a component in any one of the liquefied petroleum gas, the naphtha, the gasoline, the kerosene, and the light oil; and
(c) a raw material alcohol that is an alcohol having 3 or less carbon atoms;
A combustion improver that assists combustion of the ammonia, which is at least one of
(2) The ammonia and the combustion improver are stirred and mixed in the closed vessel for mixing while maintaining a gas-liquid equilibrium state with the liquid phase portion remaining, whereby the liquid phase of the ammonia and the combustion improver is preparing a mixture in which at least part of the portion is in a solution state in which the ammonia and the combustion improver are mutually dissolved or in an emulsion state of the ammonia and the combustion improver;
(3) A method for producing an ammonia mixed fuel, characterized in that the mixture is discharged from the closed container for mixing as an ammonia mixed fuel.
When the ammonia and the combustion improver are introduced into the closed mixing vessel and stirred and mixed, the saturated vapor pressure of the ammonia and the combustion improver in the closed mixing vessel increases to that of the closed mixing vessel. 49. The method for producing an ammonia mixed fuel according to claim 48, wherein the temperature of said mixture of said ammonia and said combustion improver is adjusted so as not to exceed a set pressure resistance.
When making the mixture,
introducing the ammonia in the liquid state and the combustion improver in the liquid state at a predetermined amount ratio into the closed container for mixing;
While stirring and mixing the ammonia and the combustion improver in the closed container for mixing,
A temperature at which the entire liquid phase portion of the mixture becomes a solution state in which the ammonia and the combustion improver are mutually dissolved, or an emulsion state of the ammonia and the combustion improver, according to the predetermined amount ratio. 50. A method for producing an ammonia blended fuel according to claim 48 or 49, comprising adjusting the temperature of said mixture to be within a range.
The ammonia mixed fuel contains at least one of the liquefied petroleum gas, the raw material hydrocarbon, and the raw material alcohol as the combustion improver,
The raw material hydrocarbon is at least one hydrocarbon species contained as a component in the liquefied petroleum gas,
The method for producing an ammonia mixed fuel according to any one of claims 48 to 50, wherein the raw material alcohol is methanol.
48. When discharging the mixture from the closed mixing container, nitrogen gas is injected into the closed mixing container at a discharge pressure equal to or higher than the saturated vapor pressure of the mixture in the closed mixing container. 51. A method for producing an ammonia mixed fuel according to any one of items 1 to 51.
When the mixture is discharged from the closed mixing vessel, the ammonia is continuously added to the closed mixing vessel at a flow rate equal to the discharge flow rate of the ammonia contained in the mixture discharged from the closed mixing vessel. Stirring and mixing is continued while replenishing the container, and in parallel, the combustion improver is continuously mixed at a flow rate equal to the discharge flow rate of the combustion improver contained in the mixture discharged from the closed mixing container. 52. Any one of claims 48 to 51, wherein the ammonia-mixed fuel in which the mixture composition of the ammonia and the combustion improver is maintained constant is continuously produced by continuing stirring and mixing while replenishing the mixture in the sealed container. 3. A method for producing the ammonia mixed fuel according to claim 1.
When preparing the mixture, a surfactant is introduced into the closed container for mixing and stirred and mixed together with the ammonia and the combustion improver to contain the surfactant as one component of the mixture. , the method for producing an ammonia mixed fuel according to any one of claims 48 to 52, wherein the mixture in the emulsion state is produced.
55. The method according to claim 54, wherein when the mixture is produced, the surfactant is introduced into the closed container for mixing so that the concentration of the surfactant in the mixture is 0.1 to 10% by mass. method for producing an ammonia blended fuel.
When continuously producing the ammonia-mixed fuel in which the mixture composition of the ammonia and the combustion improver is maintained constant by the method according to claim 53, when discharging the mixture from the closed mixing vessel Furthermore, while continuously replenishing the surfactant into the closed mixing container at a flow rate equal to the discharge flow rate of the surfactant contained in the mixture discharged from the closed mixing container 56. The method for producing an ammonia mixed fuel according to claim 54 or 55, wherein the ammonia mixed fuel in which the concentration of the surfactant is maintained constant is continuously produced by continuing stirring and mixing.
The method for producing an ammonia mixed fuel according to any one of claims 54 to 56, wherein the surfactant comprises at least one nonionic surfactant and at least one ionic surfactant. .
The surfactant is
(A) In the molecular structure, a primary or secondary amino group [—NH 2 or >NH], a polyoxyalkyleneamino group [>N(C a H 2a O) c —H, or —N ((C b H 2b O) d —H)((C b H 2b O) e —H)] (a and b are 2 or 3, c is an integer of 1 to 8, and d and e are 0 such that d+e=1 to 8 or positive integer), amide group [-C(=O)NH 2 ], polyoxyalkyleneamide group [-C(=O)N((C f H 2f O) g -H) ((C f H 2f O) h —H)] (f is 2 or 3, g and h are 0 or positive integers such that g+h=1 to 8), and a polyoxyalkylene group [—O(C i H 2i O ) j —H] (i is 2 or 3 and j is an integer of 1 to 8), at least one group as a nonionic polar moiety,
and any of an alkyl group [C k H 2k+1 -] (k is an integer of 7 to 18) and an alkenyl group [C l H 2l-1 -] (l is an integer of 7 to 18) at least one nonionic surfactant having at least one group as a nonpolar site,
(B) In the molecular structure, a quaternary methylammonium group, a quaternary methylalkanolammonium group, or a quaternary alkanolammonium group [—N + (CH 3 ) p (C m H 2m OH) qX − , or >N + (CH 3 ) r (C n H 2n OH) s ·X′ − ] (m and n are 2 or 3, p and q are 0 or positive integers satisfying p+q=3, r and s are r+s=2 0 or a positive integer, X and X′ are Cl, Br and I), and a carboxyl group [—C(=O)OH], any of the ionic polar having at least one group as a moiety,
and at least an alkyl group [C t H 2t+1 -] (t is an integer of 7 to 18) and an alkenyl group [C u H 2u-1 -] (u is an integer of 7 to 18) and at least one of said ionic surfactants having at least one non-polar site on one side.
When introducing all the objects to be introduced into the closed mixing vessel, including the ammonia and the combustion improver, into the closed mixing vessel, all the introduced objects to be introduced into the closed mixing vessel The method for producing an ammonia-mixed fuel according to any one of claims 48 to 58, wherein the objects to be introduced are introduced into the closed mixing container in order from the one having the lowest saturated vapor pressure at the internal temperature.
When the ammonia and the combustion improver are stirred and mixed in the closed container for mixing, the above introducing ammonia and the combustion improver into the closed mixing vessel, and stirring and mixing in the closed mixing vessel maintained at a predetermined liquidus temperature;
An ammonia-mixed fuel is produced in which the ammonia and the combustion improver are in a solution state or an emulsion state at a composition ratio within a predetermined range by discharging the liquid phase portion from the mixing closed container. 60. A method for producing an ammonia mixed fuel according to any one of 48 to 59.
The combustion improver is at least one of (a) and (b) above,
When the ammonia and the combustion improver are stirred and mixed in the closed container for mixing, the liquid phase portion of the mixture separates into upper and lower two layers, and the liquid phase portion separated into the upper and lower two layers The ammonia and the combustion improver are introduced into the closed container for mixing at a predetermined amount ratio so that each of them is entirely in a solution state or an emulsion state, and the mixture is maintained at a predetermined liquidus temperature. and performing the stirring and mixing in a closed container for
By discharging the liquid phase portion of at least one of the upper and lower two layers from the closed container for mixing, the ammonia and the combustion improver are in a solution state or an emulsion state at a predetermined composition ratio of one or two. 49. The method for producing an ammonia fuel blend according to claim 48, wherein the one or two ammonia fuel blends are produced such that