JPS6232186A - Preparatin of combustible gas in variable composition and equipment therefor - Google Patents

Abstract

PURPOSE:To perform mass production of combustible gas of a desired composition continuously on a commercial basis from one type of raw material, by mixing carbon particles into gaseous or liquid hydrocarbon fuel for partial combustion. CONSTITUTION:A gaseous or liquid hydrocarbon fuel is burned in a carbon particle generator 1 under short supply of air to produce carbon particles (soot). The sooty carbon particles taken out of the generator 1 together with exhaust gas are separated from the exhaust gas in a carbon particle collector 2. A predetermined amount of stored carbon particles are fed continuously into a gas producing oven 5 through a feeder 3. In the gas producing oven 5, raw material fuel such as propane gas is burned partially under short supply of air and is converted into a low-calorie gas with a predetermined calorific value. The low-calorie gas as it is fed, as trial gas,etc., into a low-calorie gas turbine, burner, etc. under development for use as fuel.

Description

Detailed Description of the Invention ■1 Purpose of the Invention (Field of Industrial Application) The present invention is directed to a water gas or synthesis gas, which is mainly composed of carbon monoxide (Co> and hydrogen (H2)). The present invention relates to a method and apparatus for producing a flammable gas.More specifically, the present invention relates to a method and apparatus for producing a flammable gas (including water gas and synthetic gas in this specification) from a gaseous or liquid raw material hydrocarbon by partial combustion. The present invention relates to a metamorphic treatment method and apparatus that allows the composition to be varied during production.

(Prior Art) In recent years, the development of coal conversion and utilization technology, that is, the development of coal gasification or liquefaction technology, has been proposed as a national project and is being promoted in various countries. As part of this development, the gas produced by coal gasification (hereinafter referred to as coal gasified gas or produced gas), especially 2000 kcal/N
There is a need for parallel development of low-calorie gas turbines, burners, etc. that use low-calorie gas of less than m3 as fuel.

When developing this type of low-calorie gas turbines and burners, it is necessary to use simulated gas to evaluate the performance, efficiency, stability, etc. of the combustor, as coal casing technology is currently in the open stage. A large amount is required on a large scale. Furthermore, if the composition of the raw coal is heterogeneous or of different types, the calorific value and composition of the generated gas will vary, so it is necessary to prepare a wide variety of simulated gases to match this. Therefore, the present inventors used the conventional partial combustion method (Chemistry Encyclopedia 7) to continuously produce synthesis raw material gases such as ammonia and methanol from hydrocarbon raw materials.
Page 918: Published by Kyoritsu Shuppan Co., Ltd. on October 15, 1981) to continuously produce flammable gas with a predetermined calorific value on an industrial scale in large quantities at low cost using hydrocarbon fuel itself as a raw material. I thought about it.

In this partial combustion method, a part of the raw material hydrocarbon is combusted with oxygen or air, and the residual hydrocarbon is transformed using the generated heat to continuously produce synthesis raw material gas. This is a suitable manufacturing method for obtaining.

(Problems to be Solved by the Invention) However, in this conventional partial combustion method, once the raw material fuel and the air shortage are determined, the calorific value and composition of the resulting combustible gas are uniquely determined. be. Therefore, when producing simulated gas using the partial combustion method,
Even if the desired calorific value is obtained, the composition may be completely different from that of the generated gas that is planned to be used.

As a simulated fuel gas, it is most important that the calorific value is as specified, but its composition cannot be completely ignored, especially since the presence of hydrogen greatly affects the performance of the combustor. , unless it is made to approximate the actual gas, its significance as a simulated gas will diminish. Of course, it is also possible to slightly change the composition of the simulated gas by changing the raw material fuel, but in this case, the composition cannot be changed freely and cannot be said to be sufficient for practical use.

According to the gas conversion treatment using the conventional partial combustion method,
Not only in the production of the above-mentioned simulated gas, but also in the production of other combustible gases, there is the inconvenience that the composition etc. cannot be changed to the optimum one depending on the application.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a shift conversion treatment method and apparatus that can continuously produce a large amount of combustible gas of any composition from the same raw material on an industrial scale. More specifically, it is an object of the present invention to provide a method and apparatus for converting combustible gas and fuel gas, in which the calorific value and composition can be freely changed.

Il. Structure of the Invention (Means for Solving Problems) In order to achieve the above object, the combustible gas conversion treatment method of the present invention includes adding a predetermined amount of carbon particles to a gaseous or liquid hydrocarbon fuel. Part of the heat required for metamorphosis of the remaining hydrocarbons and carbon monoxide (q, component composition is variable) are mixed and partially combusted.

Further, the combustible gas conversion processing apparatus of the present invention includes a carbon particle generator that generates carbon particles, a carbon particle collector that collects carbon particles from the exhaust gas of the carbon particle generator,
It consists of a supply means for quantitatively and continuously supplying a predetermined amount of carbon particles to a gas conversion furnace, and a gas conversion furnace that mixes the carbon particles supplied from the supply means into a hydrocarbon fuel and partially burns the mixture. Carbon particles generated by incomplete combustion or thermal decomposition of system fuel are collected and continuously supplied quantitatively in a predetermined amount to the gas conversion furnace in the same high temperature state, where they are mixed with hydrocarbon fuel and partially combusted. That's what I do.

(Example) First, a specific example of an apparatus for implementing the present invention will be described in detail based on the drawings.

FIG. 1 shows a block diagram of an example of an apparatus for implementing the present invention. In the figure, 1 is a carbon particle generator, 2 is a carbon particle collector, 3 is a supply means, 4 is a combustor, and 5 is a gas conversion furnace.

Here, the carbon particle generator @1 is for generating carbon in a fixed form through incomplete combustion or thermal decomposition, and in this embodiment, hydrocarbon gas or liquid fuel is supplied with air or an oxidizing agent. A so-called gas or oil furnace type furnace is used, in which soot-like carbon particles with a diameter of 10 to 20 μm or less are deposited in the vapor phase by combustion in a lack of air. . As this carbon particle generator 1, the above-mentioned furnace type carbon particle generator is used because it is preferable because it continuously generates carbon in a state where it is easy to burn, that is, in a small and soft state. It is also possible to employ carbon particle generators of types such as a lamp method, a thermal method, and an acetylene black method.

The carbon particle collection device 2 collects only carbon particles from the carbon particle generator 1 described above, and has any known structure or structure.
The present invention can be carried out using any type of dust collector; for example, it is preferable to use a cyclone type dust collector, an electrostatic dust collector, or a combination of these with a back filter. Of course, it is also possible to implement other collection means, such as one having a structure that simply collides exhaust gas with a wall surface to separate solid and gas, and collects only soot-like carbon. The pack filter mentioned above is usually made of glass fiber filter cloth.

The supply means 3 is for continuously supplying a predetermined amount of carbon particles collected by the carbon particle collection device 2 to the gas conversion furnace 5, and is a known supply means capable of controlling the supply amount. Any of these can be implemented, and for example, a metering slurry pump or a flow rate regulating valve incorporated into an air transport pipe or the like can also be implemented.

The waste conversion furnace 5 partially burns hydrocarbon-based gas or liquid fuel in the absence of air while supplying air or an oxidizing agent, thereby converting the raw material gas into a gas having a predetermined calorie and composition. . A carbon particle collection device 2 is connected to the combustor 4 of this gas conversion furnace 5, and is provided so that a controlled amount of soot-like carbon particles can be introduced into the flame. still,
The gas conversion furnace 5 is provided so that steam or water can be injected, and it is also possible to use these to rapidly cool the generated gas or perform a partial conversion action.

The method for converting combustible gas according to the present invention will be described in detail below using the converting apparatus configured as described above.

First, the carbon particle generator 1 burns a gas or liquid hydrocarbon fuel in an air-deficient state to generate carbon particles, that is, soot. This soot is preferably of the vapor phase type obtained by burning a gaseous fuel such as propane gas or a liquid fuel such as light oil or kerosene in an air-deficient state. Vapor-phase precipitation type soot has a small diameter of about 0.02 to 0.05 μm and is porous with a porosity of approximately 98% or more, and has a specific surface area of BET ([3runaver-Emmet
110-175 TIl/by the T-celler method
It has a much larger specific surface area than coke and is in a state where it is easily combustible. Of course, it is also possible to use soot in the form of residual carbon. The above-mentioned soot-like carbon particles taken out of the carbon particle generator 1 together with the exhaust gas are separated from the exhaust gas in the carbon particle collector 2 and then stored once, and a predetermined amount is quantitatively supplied via the supply means 3. The gas is continuously supplied to the gas conversion furnace 5.

In the gas conversion furnace 5, a raw material fuel such as propane gas is partially combusted in an air-deficient state and converted into a low-calorie gas having a predetermined calorific value. Then, this low-calorie gas is supplied as a simulated gas or the like to a low-calorie gas turbine, burner, etc. currently under development, and used as fuel. Normally, in gas conversion by partial combustion, when the raw material fuel and the air shortage are determined, the calorific value and composition are determined at the same time. For example, if propane gas is used as raw material fuel,
The combustion reaction of propane reaches the chemical equilibrium of 79.1 C3H8+λ・5・02+5・π koN2−+a−CO1b−CO2C−H2+d−H2079,1+5・汀,gN2 (1). In addition, in this formula, λ represents the air ratio.

For this reason, the calorific value and composition of the combustible scum produced by metamorphosing propane gas are not shown in FIG. 2 and are shown as solid lines. Therefore, when the calorific value is specified and the air ratio is determined, the composition of the generated combustible gas (particularly t[2, CO) is uniquely determined. For example, if propane gas costs 1 trillion, the calorific value is 1000kcal/Nm3 (D and 8kl, 1f
1219vo1%, C017VO1%, 1200kca
l/Nm 3 Notoki kl, H223V01%, CO1
When it is 9.5vo1% and 1400kcal/Nm3, H228VO1% and Co22vo1%.

However, when the above-mentioned carbon particles are charged into the gas conversion furnace 5 for a prescribed amount and burned, the combustion reaction of propane gas is as follows: C3Ha+χ・C+λ(5+χ)・0279.1 +5π]N2−+ a′ −CO+b′ −
CO279,1 +C'・H2+d'・H20+5・Old N2...(
2) chemical equilibrium is reached. In addition, in this formula, χ is the molar ratio of carbon particles to propane.

The above reaction is maintained by mixing propane and air preheated to a relatively high temperature and feeding the mixture to burner 4 for combustion. The temperature of the combustion zone is usually over 1000°C,
Preferably controlled at around 1200'C, e.g. 1500'C for the combustion embodiment shown in FIGS.
It is being held in

Further, carbon particles are supplied into the flame or mixed in fuel gas in advance.

By changing the amount of carbon particles added, the calorific value and composition can be varied, and arbitrary values can be obtained. In other words, as shown by the dashed line in Fig. 2, by varying the amount of carbon particles χ introduced, when only propane is combusted, the curve becomes gentler than when χ = 0>, and the composition can be changed. By the combustion of carbon particles,
Part of the heat required for thermal decomposition and gas conversion of residual hydrocarbons and carbon monoxide can be obtained directly in addition to gas conversion of hydrocarbon fuel. Furthermore, even if carbon dioxide is produced through the combustion of carbon, it transforms into gaseous carbon monoxide at high temperatures. For example, taking as an example a material with a heat generation of m 1000 kcal/Nm 3 , the composition can be arbitrarily changed as shown in the following table.

Amount of carbon particles added to the surface (CfjR vs. TruH2 (Vo1%) i Co(V
o1%) amount molar ratio) χ 5 10.5 24 'to 7.5 27 *However, the calorific value of the generated gas must be 1000 kCal/Nm3.

FIG. 3 shows this state in relation to the air ratio.

As is clear from the figure, even when the same raw material fuel is partially combusted under a constant air ratio, the heat generation can be freely changed by changing the amount of carbon particles added to the H2 and Co/+12 ratios. ! I can understand what I'm getting. Moreover, this compositional variability can be made even wider by changing the combustion of the raw materials.

Incidentally, carbon particles are generally difficult to burn when used alone, but the ones supplied from the carbon particle generator 1 are soot-like with a small diameter, porous (high porosity), relatively large specific surface area, and high temperature. (approximately around 1000°C), gas conversion furnace 5
It burns easily when thrown into a flame.

In addition, this gas transformation can be controlled by injecting water or steam into the transformation furnace 5, or by further transforming some of the carbon monoxide in the gas into hydrogen and carbon dioxide, or by contacting red-hot carbon particles with steam. can be controlled by generating a water gas reaction.

In this way, according to the method for converting combustible scum of the present invention, by appropriately selecting the raw material fuel and controlling the amount of carbon particles added, the relationship between the calorific value and the composition can be subtly changed to produce an arbitrary calorific value and composition. It is possible to produce gases of different compositions, especially low-calorie gases. For example, this low-calorie gas is suitable for use as a simulated gas for combustion equipment and the like developed as part of petroleum conversion utilization technology. Further, this gas conversion method is suitable not only for producing a simulated gas but also for producing raw material waste or fuel gas by converting the gas into a gas having an optimal composition depending on the application. For example, it is possible to suppress hydrogen from the fuel gas, which has a large effect on the performance of the combustor, and increase only the required amount of carbon monoxide.

III. Effects of the Invention As is clear from the above explanation, the combustible gas conversion treatment method of the present invention mixes carbon particles into gaseous or liquid hydrocarbon fuel and partially burns it, so that the amount of input carbon particles is reduced. Combustion can replenish some of the heat required to transform residual hydrocarbons and directly increase the amount of oxidized carbon, changing the composition of the transformed gas. In other words, in the conventional partial combustion method, it is possible to freely change both the amount of heat generated and the composition, which are uniformly fixed once the raw material fuel and air shortage are determined. (It is also possible to freely change the composition in the case of q.

Furthermore, the combustible scum metamorphosis treatment device of the present invention includes a carbon particle generator that generates carbon particles, a carbon particle collection device that collects carbon particles from the exhaust gas of the carbon particle generator,
Consisting of a supply means that quantitatively and continuously supplies a predetermined amount of captured carbon particles to a gas conversion furnace, and a gas conversion furnace that mixes the carbon particles supplied from the supply means into a hydrocarbon fuel and partially combusts the mixture, Carbon particles generated by incomplete combustion or thermal decomposition of hydrocarbon fuels are collected and continuously supplied quantitatively to the gas conversion furnace in a high-temperature state. Carbon particles that are difficult to burn alone are collected at high temperatures. Big, small and soft (
Since it is made into a combustible state (porous, low density) and can be mixed with hydrocarbon fuel for partial combustion, there is no risk of non-flammability of the mixed carbon particles, and continuous partial combustion with the raw material fuel is possible. , a combustible gas of a desired composition can be continuously produced as easily and inexpensively as necessary on an industrial scale.

[Brief explanation of the drawing]

Fig. 1 is a block diagram showing the principle of an example of an apparatus for implementing the present invention, and Fig. 2 is a graph showing the relationship between the calorific value and the composition of the flammable gas obtained by the method of the present invention when propane gas is used as the raw material. , FIG. 3 is a graph showing the relationship between the air ratio and calorific value of the combustible gas obtained by the method of the present invention when propane gas is used as the raw material. DESCRIPTION OF SYMBOLS 1... Carbon particle generator, 2... Carbon particle collector, 3... Supply means, 4... Combustor, 5... Gas conversion furnace.

Claims (6)

[Claims] (1) A method for converting combustible gas, which comprises mixing carbon particles into a gaseous or liquid hydrocarbon fuel and partially combusting the mixture. (2) The method for converting flammable gas according to claim 1, wherein the carbon particles are charged at a high temperature. (3) The combustible gas metamorphosis treatment method according to claim 1 or 2, wherein the carbon particles are of a vapor phase precipitation type. (4) Metamorphosis of flammable gas according to any one of claims 1 to 3, wherein the carbon particles are oil having a relatively large specific area or carbon black produced by a gas furnace method. Processing method. (5) The carbon particles are collected from carbon particles generated by incomplete combustion or thermal decomposition of carbon-hydrogen fuel, and are continuously supplied quantitatively in a predetermined amount to the gas conversion furnace in a high-temperature state. 2. The method for converting combustible gas according to claim 1, wherein the combustible gas is mixed into system fuel and partially combusted. (6) A carbon particle generator that generates carbon particles, a carbon particle collector that collects carbon particles from the exhaust gas of this carbon particle generator, and a quantitative continuous supply of a predetermined amount of carbon particles to a gas conversion furnace. A combustible gas shift processing apparatus comprising a supply means and a gas shift furnace that mixes carbon particles supplied from the supply means into a carbon-hydrogen fuel and partially combusts the mixture.