WO2022230988A1 - Combustible mélangé à de l'ammoniac, dispositif de production d'un combustible mélangé à de l'ammoniac, procédé de production d'un combustible mélangé à de l'ammoniac, dispositif d'alimentation d'un combustible mélangé à de l'ammoniac, dispositif de combustion d'un combustible mélangé à de l'ammoniac, équipement de production d'énergie utilisant un combustible mélangé à de l'ammoniac, et dispositif de transport utilisant un combustible mélangé à de l'ammoniac - Google Patents

Combustible mélangé à de l'ammoniac, dispositif de production d'un combustible mélangé à de l'ammoniac, procédé de production d'un combustible mélangé à de l'ammoniac, dispositif d'alimentation d'un combustible mélangé à de l'ammoniac, dispositif de combustion d'un combustible mélangé à de l'ammoniac, équipement de production d'énergie utilisant un combustible mélangé à de l'ammoniac, et dispositif de transport utilisant un combustible mélangé à de l'ammoniac Download PDF

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WO2022230988A1
WO2022230988A1 PCT/JP2022/019333 JP2022019333W WO2022230988A1 WO 2022230988 A1 WO2022230988 A1 WO 2022230988A1 JP 2022019333 W JP2022019333 W JP 2022019333W WO 2022230988 A1 WO2022230988 A1 WO 2022230988A1
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ammonia
mixed fuel
combustion
mixing
closed container
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PCT/JP2022/019333
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English (en)
Japanese (ja)
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直樹 八田
大樹 谷本
聡一郎 櫻井
哲郎 村山
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株式会社三井Ｅ＆Ｓマシナリー
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Priority to KR1020237036849A priority Critical patent/KR20230159607A/ko
Publication of WO2022230988A1 publication Critical patent/WO2022230988A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/04—Methanol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C9/00—Aliphatic saturated hydrocarbons
    • C07C9/02—Aliphatic saturated hydrocarbons with one to four carbon atoms
    • C07C9/08—Propane
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C9/00—Aliphatic saturated hydrocarbons
    • C07C9/02—Aliphatic saturated hydrocarbons with one to four carbon atoms
    • C07C9/10—Aliphatic saturated hydrocarbons with one to four carbon atoms with four carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/12—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L8/00—Fuels not provided for in other groups of this subclass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/30—Use of alternative fuels, e.g. biofuels

Definitions

  • 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
  • GHG emissions 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.
  • conventional fossil fuels e.g., gasoline, kerosene, light oil, heavy oil, coal, etc
  • Non-Patent Document 1 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a method for producing an ammonia mixed fuel, and a supply apparatus for an ammonia mixed fuel 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 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.
  • 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.
  • the supply device may include a plurality of combustors.
  • 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,
  • 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.
  • propulsion of the transportation equipment 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.
  • 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.
  • 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
  • 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
  • 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 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.
  • a combustion improver 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.
  • component hydrocarbon hydrocarbon
  • liquefied petroleum gas 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.
  • 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.
  • 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.
  • 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.
  • 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
  • n-butane approximately 365°C
  • a component of liquefied petroleum gas cyclohexane (approximately 245°C)
  • n-Hexane approximately 220°C
  • toluene approximately 480°C
  • n-decane approximately 210°C
  • a component of kerosene n-hexadecane (approximately 200°C)
  • component of light oil Both have low ignition points, compensating for
  • 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).
  • 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.
  • 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.
  • these raw material alcohols 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.
  • it can be in an emulsion state of ammonia and a combustion improver.
  • 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
  • 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.
  • 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)
  • ammonia is dissolved under gas-liquid equilibrium conditions in a closed space be able to.
  • 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. .
  • 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).
  • 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.
  • the combustibility of the mixed fuel as a whole is more uniformly improved.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • a combustion improver for example, ammonia when the content is about 80% by mass or more and 99% by mass or less.
  • 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.
  • 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.
  • 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.
  • the added amount of either liquefied ammonia or the combustion improver is the upper limit amount that can be solubilized or emulsified.
  • the combustion improver kerosene, light oil, and their component hydrocarbon species
  • the combustion improver 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.
  • the other phase of the separated liquid phase is mainly composed of the combustion improver, its combustibility is high.
  • 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).
  • the mass ratio of each is appropriately determined according to the application and purpose of the 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.
  • the overall combustibility of the ammonia-mixed fuel can be improved more uniformly.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 .
  • 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.
  • raw materials such as metabolites of plants and microorganisms that perform photosynthesis.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Emulsification by mixing is generally required.
  • Non-Patent Documents 4 and 5 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.
  • 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.
  • propane and n-butane which are the main components of liquefied petroleum gas
  • FIGS. 1(a) and 1(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
  • 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).
  • 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.
  • the solid line in the figure indicates the relationship (liquidus line) between the liquid phase composition (x) and the saturated vapor pressure (p).
  • the lower dashed line is the relationship between the gas phase composition (y) and the saturated vapor pressure (p) in equilibrium with the liquid phase (gas phase 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.
  • 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.
  • 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 liquid phase mainly composed of propane contains ammonia through the trajectory of PA in FIG. ) can be thermodynamically stably dissolved without phase separation.
  • 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.
  • 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.
  • 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.
  • VLLE vapor-liquid-liquid equilibrium
  • 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.
  • FIG. 2 shows the liquid-liquid equilibrium (VLLE) relationship.
  • VLLE liquid-liquid equilibrium
  • 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.
  • 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
  • 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.
  • liquid phase composition ammonia concentration x C
  • ammonia concentration x 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.
  • the critical solution temperature about 33 ° C.
  • the temperature of the mixed fuel is maintained above the above-mentioned temperature according to the liquid phase composition of the mixed fuel.
  • 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)).
  • the effect of the combustion improver can be maximized and the mixed fuel can be burned extremely uniformly.
  • the vapor-liquid equilibrium and the saturated vapor pressure in vapor-liquid equilibrium are respectively Generally higher than the saturated vapor pressure alone.
  • 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.
  • 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.
  • 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.
  • 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
  • a surfactant at least in the temperature range of about 0 to 40 ° C.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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),
  • a/o ammonia in oil
  • a/o ammonia in oil
  • 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),
  • o/a (oil in ammonia) emulsion 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.
  • 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)
  • 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.
  • the ammonia mixed fuel Normally, about 0.1 to 10% by mass is added to the ammonia mixed fuel.
  • 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.
  • 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.
  • a surfactant that facilitates the formation of an a/o emulsion is selected or formulated.
  • surfactants that are more likely to form o/a emulsions are selected or formulated.
  • 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.
  • 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.
  • 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?
  • H + and anionic/cationic species, etc. are transferred and received between ionic and nonionic surfactant molecules and between these surfactant molecules and ammonia molecules.
  • ionic and nonionic are distinguished by the presence or absence of ionization including such a series of processes.
  • 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.
  • 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
  • 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.
  • 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).
  • 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.
  • 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.
  • (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
  • ( B) is an ionic surfactant as a secondary component which constitutes a particularly preferred surfactant.
  • 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.
  • the ionic surfactant (B) is mainly ionized in the membrane and contributes to electrostatic repulsion between the micelles.
  • 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”).
  • 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.
  • 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.
  • 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.
  • long-chain alkyl (and long-chain alkenyl) polyoxyalkyleneamines long-chain alkyl (and long-chain alkenyl) polyoxyalkyleneamides having a polyoxyalkylene group (polyether) partial structure
  • 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.
  • 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
  • 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.
  • nonionic surfactants 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • room temperature 25° 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.
  • each surfactant has a suitable temperature range to exhibit its function.
  • the temperature at which the ammonia mixed fuel is prepared and stored is often selected according to the type of combustion improver.
  • the combustion improver is liquefied petroleum gas and its component hydrocarbon species
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • surfactants that produce ash by-products.
  • a surfactant having a polar part such as a sulfonate (polar part is -SO 3 - ⁇ Na + etc.).
  • a surfactant used in the ammonia mixed fuel of the present invention 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.
  • n-butane which is one component of liquefied petroleum gas
  • a predetermined amount of various mixed surfactants are added and mixed
  • an emulsion in this case, o /a emulsion
  • 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) ).
  • 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.
  • 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.
  • 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.
  • the manufacturing apparatus 10 shown in FIG. , 20c, 28c and a controller 32 the manufacturing apparatus 10 shown in FIG. , 20c, 28c and a controller 32.
  • the regulating valves 18c, 20c, 28c are inlet valves for introducing the raw materials into the closed vessel 16 for mixing.
  • 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.
  • 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.
  • 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.
  • 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.
  • the flow meter 18a in FIG. It is also possible to control the amount of ammonia introduced from the weighed value of the vessel.
  • 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.
  • the ammonia quantitative introduction mechanism is composed of the weighing device and the control valves 18b and 18c.
  • the control device 32 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.
  • 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.
  • 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 .
  • 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.
  • 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.
  • 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.
  • the combustion improver fixed quantity introduction mechanism is composed of the weighing device and the control valves 20b and 20c.
  • 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.
  • 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.
  • 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.).
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the combustion improver which is a component hydrocarbon species of petroleum gas
  • 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.
  • Each of the fuel introduction lines 20 needs to be provided with a liquid feed pump.
  • 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.
  • positive displacement types such as gear types, screw types, plunger types, and uniaxial eccentric screw types are suitable. To be elected.
  • liquid-sending pump 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • stirrer 24 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.
  • 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.
  • 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.
  • 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.
  • 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 .
  • 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).
  • the closed mixing container 16 and the manufacturing apparatus 10 can be reduced in weight and cost.
  • 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).
  • Antoine's formula an approximation formula
  • 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.
  • the constant temperature bath is installed outside the manufacturing apparatus 10 and is not shown in FIG.
  • 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.
  • an inert liquid that does not easily solidify or volatilize in the control temperature range such as water, ethylene glycol, diethylene glycol, etc.
  • 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.
  • a liquid temperature control medium m adjusted to a predetermined temperature flows through the jacket 17 and mixes.
  • 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).
  • the stirrer 24 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.
  • 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.
  • 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 .
  • 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 .
  • 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
  • the power output for heating and cooling the thermostat is controlled.
  • 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.
  • 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.
  • a Peltier element 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the combustion improver is liquefied petroleum gas or its constituent hydrocarbon species, FIG. The above temperature range will be described below.
  • 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.
  • 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.
  • a temperature above which the entire liquid phase becomes a single-phase solution for example, as shown in FIG.
  • 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".
  • 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 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”.
  • the above temperature range also matches the temperature range in which the emulsifying performance of the surfactant can be sufficiently brought out.
  • 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.
  • the composition of the above single-phase ammonia mixed fuel changes as follows as the emission progresses.
  • 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.
  • 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.
  • 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 .
  • 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.
  • 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.
  • the above operation is performed from a midpoint on each of the liquidus line AP and the gaseous line OP. is equivalent to starting
  • 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.
  • 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.
  • the ammonia concentration is x B
  • a two-phase separated state is formed with a liquid phase mainly composed of ammonia.
  • 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
  • the ammonia - based phase with ammonia concentration xB is the lower layer.
  • 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.
  • 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 .
  • the position of the above point C (the average state of the entire two liquid phases) must be aligned with the line segment AB
  • 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.
  • 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.
  • liquefied ammonia and liquefied propane are introduced into the closed mixing vessel 16 in proportion.
  • 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.
  • 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.
  • 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
  • the ammonia concentrations x A ' and x B ' at both ends of the two-phase separation region at 0° 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 %.
  • 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.
  • x A and x B approach 0 wt % and 100 wt %, respectively.
  • 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,
  • ammonia concentration x C an arbitrary liquid phase composition
  • 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.
  • 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.
  • 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
  • a component hydrocarbon species or a mixture of liquefied petroleum gas as a combustion improver
  • 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.
  • 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.
  • 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.
  • FIG. 4 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • FIG. 5 shows the form of discharging both the phase-separated upper and lower two layers of the latter.
  • 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.
  • the high-lift pumps described above are selected.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the flowmeter 28a and the control valves 28b and 28c are adapted to specifications that are less likely to clog. There is a need.
  • 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.
  • the liquid feed pump 28d is also included in the quantitative introduction mechanism for the surfactant.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.)
  • the part that phase separates without the phase separation can also be emulsified by adding a surfactant.
  • a 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.
  • nonionic surfactant (A) and ionic surfactant (B) those having the above-described molecular structures can be preferably used.
  • 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.).
  • the above mixed surfactant 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
  • a fluid state e.g., slurry or mud
  • 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.
  • 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.
  • 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.
  • 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.
  • the surfactant when 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.
  • 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.
  • conditions such as composition and mixing temperature.
  • the composition range and temperature range separating into upper and lower layers change compared to when no surfactant is added. do.
  • 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.
  • 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)
  • a surfactant metering introduction mechanism (including a liquid feed pump 28d).
  • 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.
  • 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.
  • the components contained in the liquefied petroleum gas as (a) and the liquefied petroleum gas as (b) described above can be obtained as components.
  • Ammonia blended fuels can also be produced using at least one of the component hydrocarbon species of.
  • 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.
  • 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.
  • 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 .
  • 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.
  • 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.
  • 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.
  • the elevated temperature causes a change from a two-phase separation state to a homogeneous solution state.
  • the aforementioned critical solution temperature also exists, above which any composition becomes completely miscible.
  • 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.
  • 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
  • the phase mainly composed of these combustion improvers becomes the lower layer of the phase mainly composed of liquefied ammonia.
  • 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.
  • emulsification by addition of a suitable surfactant is required.
  • 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.
  • 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.
  • 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.
  • liquid phase discharge line 22 2 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.
  • 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.
  • 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.
  • phase separated part (ammonia or combustion improver) is dispersed in the other phase by emulsification, and the entire mixed fuel is homogenized.
  • 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.
  • 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.
  • the manufacturing apparatus 10 of FIG. 4 equipment equipped with a fuel improver liquid feeding pump 20d not shown
  • the manufacturing apparatus 10 of FIG. 4 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.
  • 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.
  • the fuel improver liquid feed pump 20d (not shown) is used as shown in FIG.
  • 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.
  • raw material alcohol is preferable as a combustion improver for ammonia.
  • 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.
  • 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.
  • 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.
  • 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.
  • the fuel improver is liquefied petroleum gas or its component hydrocarbon species, as described above.
  • the discharge flow rate of ammonia and the combustion improver in the discharged liquid phase is equal to that of each,
  • the composition change in the discharged liquid phase is caused. can be discharged continuously as an ammonia-mixed fuel.
  • 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.)
  • the manufacturing apparatus 10 the ammonia mixed fuel can be manufactured with each effect.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 .
  • raw hydrocarbons 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.
  • a surfactant may be required for homogenization by emulsification.
  • 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).
  • 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.
  • the above-described mixed surfactant can be suitably used.
  • the ammonia-mixed fuel is at least partially in an emulsion state.
  • 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.
  • 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. .
  • 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.
  • a state for example, slurry or mud
  • the surfactant introduction system surfactant storage container 26, surfactant introduction line 28, and liquid feed pump 28d
  • 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.
  • 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.
  • 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 .
  • 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.
  • the above-described mixed surfactant can be suitably used.
  • the ammonia mixed fuel becomes at least partially in an emulsion state.
  • 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.
  • 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.
  • 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.
  • each raw material component is placed in the closed container 16 for mixing.
  • 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.
  • 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.
  • 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.
  • 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.
  • liquefied gases such as liquefied ammonia, liquefied petroleum gas and their component hydrocarbon species
  • liquefied ammonia liquefied petroleum gas, naphtha, gasoline, kerosene, light oil, and component hydrocarbon species thereof may be used.
  • 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.
  • the manufacturing apparatus of FIG. 7 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the continuous quantitative introduction mechanism of the raw material of the manufacturing apparatus 10 of FIG. 5 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.
  • the production apparatus 10 of FIG. By adding the functions of the manufacturing apparatus 10 of FIGS.
  • the ammonia mixed fuel can be manufactured with the respective effects.
  • 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.
  • 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.
  • materials that are durable against ammonia.
  • 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.
  • iron or steel, especially if it has a high carbon content, is prone to stress corrosion cracking.
  • 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.
  • 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.
  • 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.
  • the controller 32 is an agitation regulator that regulates the agitation mixing intensity and the agitation mixing time.
  • 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
  • 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.
  • 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.
  • 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.
  • AI artificial intelligence
  • 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.
  • a temperature control device 18 e configured to regulate is preferably provided in the ammonia introduction line 18 .
  • 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.
  • 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.
  • the internal temperature does not rise, so unnecessary vaporization of the mixture occurs in the closed mixing vessel 16.
  • the saturated vapor pressure of each can be increased.
  • 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.
  • 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.
  • 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.
  • 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 .
  • 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.
  • 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.
  • 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.
  • 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.
  • the storage closed container 50 is replaced with gas.
  • 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.
  • 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.
  • 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 .
  • 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.
  • a 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.
  • 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.
  • 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.
  • the temperature control device is preferably configured to control the temperature of said ammonia blended fuel.
  • 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.
  • 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 .
  • 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).
  • a solution state or a uniform emulsion state (not divided into upper and lower layers).
  • the composition of the mixed fuel changes as described in the case of discharging from the closed mixing container.
  • 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).
  • 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).
  • the control valve 64c 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 .
  • 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.
  • the gas phase discharge valve 59a 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.
  • 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.
  • 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.
  • 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.
  • the injection/discharge control mechanism is configured to perform the following controls.
  • 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.
  • H position the full-filled position
  • 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 .
  • 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).
  • 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.
  • the ammonia mixed fuel can be discharged while suppressing the composition change.
  • 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.
  • 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.
  • 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 .
  • 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.
  • 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.
  • 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).
  • 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.
  • the liquid phase discharge valve 22a is closed and the ammonia mixed fuel is stored in that state.
  • 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 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.
  • the ammonia mixed fuel 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.
  • the mixed fuel 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.
  • 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.
  • 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.
  • 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 .
  • 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.
  • 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.
  • 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.
  • the discharge valve 58 and the liquid phase discharge valve 22a are configured to be opened and closed at appropriate degrees of opening.
  • the preservation sealed container 50 of the present embodiment becomes functionally equivalent to a so-called plunger pump.
  • a rack and pinion mechanism, a ball screw mechanism, or a reciprocating drive device such as a feed screw mechanism may be employed.
  • 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.
  • 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.
  • 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 .
  • the ammonia mixed fuel 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.
  • 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.
  • vehicle not shown
  • 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.
  • 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.
  • 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.
  • 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 ) 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.
  • 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.
  • an ammonia-mixed fuel supplier 80 is provided on the ammonia-mixed fuel supply line 60.
  • 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.
  • 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.
  • 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.
  • a pre-vaporizer (not shown) pre-vaporizes a liquid state ammonia mixed fuel and supplies the gas.
  • air, oxygen-enriched air, or oxygen may be premixed in a predetermined ratio with the vaporized ammonia mixed fuel.
  • the ammonia-mixed fuel supplier 80 may include the pre-vaporizer.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 .
  • 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
  • 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.
  • 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.
  • 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.
  • FIG. 15 is a block diagram illustrating an example of the configuration of an ammonia mixed fuel combustion apparatus 120 according to one 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.
  • the combustion device 120 of one embodiment optionally 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.
  • 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.
  • nitrogen oxides including air pollutants such as nitrogen monoxide and nitrogen dioxide
  • these may be collectively referred to as NOx.
  • 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.
  • the selective catalytic reactor 1208 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 .
  • a temperature controller (not shown) that regulates the temperature of the catalyst within the selective catalytic reactor 128 .
  • 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.
  • an electric heater is used as the temperature controller for maintaining the catalyst temperature within such a temperature range.
  • 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.
  • a nitrogen oxide/ammonia concentration measuring device 122 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a combustion gas transfer line 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.
  • 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.
  • 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.
  • a power generation facility is, for example, a power generation facility that generates power in any one of land, water, and air space.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the mechanism includes a synchronizing mechanism of both powers and a resultant force mechanism such as a coaxial drive.
  • transportation equipment may be equipped with the power generation equipment described above.
  • 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.
  • propulsion 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.
  • 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.
  • 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.
  • ammonia mixed fuel 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.
  • 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).
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • Example 3 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.
  • 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.
  • 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.
  • 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. .
  • 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.
  • 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).
  • 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.
  • 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
  • Example 3 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.
  • saturated vapor pressure saturated vapor pressure
  • Example 11 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.
  • 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. .
  • 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.
  • CH 3 OH methanol
  • the liquid phase became a homogeneous solution.
  • the internal pressure saturated vapor pressure
  • the liquid phase temperature was raised to about 40° C. while stirring was continued, the liquid phase remained in a homogeneous solution state.
  • 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.
  • Example 13 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).
  • the mixed state was examined when stirring and mixing were performed.
  • 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.
  • the internal pressure saturated vapor pressure
  • the liquid phase temperature was 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).
  • the liquid phase was maintained in a compatible state and the internal pressure was maintained at about 1.7 to 1.8 MPa.

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Abstract

L'invention concerne un combustible mélangé à de l'ammoniac qui contient : de l'ammoniac liquide ; et un agent améliorant la combustion liquide qui améliore la combustion de l'ammoniac. L'agent améliorant la combustion est au moins un élément parmi (a) du naphta, de l'essence, du kérosène et de l'huile diesel, (b) un hydrocarbure de matériau qui est au moins une espèce d'hydrocarbure contenue en tant que composant dans au moins l'un du gaz de pétrole liquéfié, du naphta, de l'essence, du kérosène et de l'huile diesel, et (c) un alcool d'un matériau qui est un alcool ayant trois atomes de carbone ou moins. Le combustible mélangé à de l'ammoniac est dans un état d'équilibre vapeur-liquide, et au moins une partie de la partie de phase liquide du combustible mélangé à de l'ammoniac est dans un état de solution dans lequel l'ammoniac et l'agent améliorant la combustion sont mutuellement dissous, ou dans un état d'émulsion de l'ammoniac et de l'agent améliorant la combustion.
PCT/JP2022/019333 2021-04-30 2022-04-28 Combustible mélangé à de l'ammoniac, dispositif de production d'un combustible mélangé à de l'ammoniac, procédé de production d'un combustible mélangé à de l'ammoniac, dispositif d'alimentation d'un combustible mélangé à de l'ammoniac, dispositif de combustion d'un combustible mélangé à de l'ammoniac, équipement de production d'énergie utilisant un combustible mélangé à de l'ammoniac, et dispositif de transport utilisant un combustible mélangé à de l'ammoniac WO2022230988A1 (fr)

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CN116223556A (zh) * 2023-02-16 2023-06-06 北京中科富海低温科技有限公司 一种二元气液相平衡测试系统及方法
CN116223556B (zh) * 2023-02-16 2023-07-28 北京中科富海低温科技有限公司 一种二元气液相平衡测试系统及方法
CN117111567A (zh) * 2023-10-19 2023-11-24 广州恒广复合材料有限公司 一种洗护组合物中季铵盐生产工艺控制方法及装置
CN117111567B (zh) * 2023-10-19 2023-12-29 广州恒广复合材料有限公司 一种洗护组合物中季铵盐生产工艺控制方法及装置
CN117907079A (zh) * 2024-03-19 2024-04-19 中海石油气电集团有限责任公司 低温液氨中应力腐蚀裂纹扩展速率实验装置及测量方法

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