JPS60166388A - Production of synthetic gas from slurry of solid carbon fuel - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

TECHNICAL FIELD OF THE INVENTION This invention relates to the gasification of solid carbon fuel slurries containing ash. In particular, for example, a slurry of a solid carbon fuel containing ash, such as a slurry of coal dispersed in a liquid medium (i.e., water, liquid hydrocarbon fuel, coal, or mixtures thereof), may be partially treated in a non-catalytic manner. Relating to the catalytic gasification of carbon and carbon particulates present in the unchanged portion of an ash-containing solid carbon fuel contained in a raw effluent syngas stream from the free-stream gas generation of an oxidizing refractory lining. [Prior Art] As the supply of oil dwindles, coal, the most abundant fossil fuel in the United States, will play an increasingly important role in meeting the nation's energy needs. One ton of coal contains the same energy as 3-4 barrels of crude oil. Therefore, in the future it will be necessary to increase the fractionation of liquid and gaseous fuels from coal.

The gas produced by the present invention can be used as a gaseous fuel or as a raw material for catalytic synthesis of liquid fuels, with or without further processing and purification.

Synthesis gas, fuel gas, and reducing gas are produced from coal using conventional gasification methods. For example, U.S. Patent No. 3.54
No. 4.291 and No. 4.289.502, the former relates to a method for partial oxidation of a slurry of coal and the latter to an apparatus for producing clean and cooled synthesis gas by partial oxidation of solid carbon fuel. No catalyst or solid carbon fuel is used in the methods described in US Pat. Nos. 3,998,123 and 4,060,397. U.S. Pat. No. 4,094,650 relates to a method for producing CHa-containing gases in a fluidized bed of catalysts consisting of carbon-alkali metal reaction products. The catalytic material is transferred to an uncooled reaction vessel where it is maintained in a fluidized bed by flowing upwardly a mixture of steam and a portion of recycled product gas. Normal residence times in the generator range from about 1-5 seconds.

If the residence time is short, a small amount of solid fuel particles may pass through the reaction zone of the gas generator unreacted. If the residence time is short like this, the liquid carrier cover that prevents the rotation of each solid fuel particle cannot be evaporated, and the gas can come into contact with and react with the carbon in the solid fuel particles. I can't do it either. When this occurs, the combustion efficiency of the production process is reduced and the cost of cleaning the raw syngas to remove unaltered particles of solid fuel is increased. This problem is solved by the present method of converting almost all of the carbon in the ash-containing solid carbon fuel into carbon oxide.

[Summary of the invention]

The process of the present invention is a continuous process for producing a stream of nitrogen, synthesis gas, fuel gas, or reducing gas for the noncatalytic partial oxidation of a solid carbon fuel slurry containing ash with a free oxygen-containing gas. The liquid carrier for carrying the solid fuel slurry is selected from the class consisting of water, liquid hydrocarbon fuels, and mixtures thereof. The effluent gas stream is first converted into a slurry of ash-containing solid carbon fuel in a free-flow non-catalytic refractory lined gas generator from approximately 2350'F to 2900°F. (about 1287°C to 1593°C), about 10 to 20
Produced by partial oxidation at pressures in the range of 0 atmospheres. If the liquid carrier is a liquid hydrocarbon sinter, a temperature control agent such as H20 may be used.

The partial oxidation gas generator is operated to convert about 75 to 95 weight percent of the carbon in the fuel supply to the reaction zone into oxidized carbon. The hot effluent gas stream leaving the gas generator is H20,N
2. H2S, CO8, CH4, NHa, A, HCl
, HCN, and H2, CO, and CO2. Additionally carried in the hot effluent gas stream leaving the reaction zone are residual unreacted portions of the ash-containing solid carbon fuel, carbon particulates or soot, and non-combustible inorganic ash and solid carbon. There is molten slag from the reaction part of the fuel.

The hot effluent gas stream leaving the reaction zone of the gas generator passes through the unobstructed vertical center passage of the free-stream radiant cooler, with or without removing some of the particulate slag it contains. The catalyst is passed through and in contact therewith, supplying heat to evaporate the solution of the catalyst consisting of the alkali metal or alkaline earth metal compound or both and water. The yield of at least one of the alkali metal/alkaline earth metal components is in the range of about 5-50% by weight (based on carbon involved). The molar ratio of H20/C in the reaction stream is approximately 0.7-25
．． 0. or greater; e.g., about 1.0-20.0
; for example, about 1.5-6.0. A tubular wall, consisting of a plurality of pipes or coils through which cooling water passes, lines the inner wall of the radiant cooler and serves to reduce the temperature of the hot effluent gas stream therethrough. The hot exit gas flow ranges from about 2300 below to 2800? (from about 1260℃ to 1
600℃] in a radiant cooler, approximately 135℃
0'F to 1600? (approximately 732°C to 871°C), for example at a temperature of 1500″F (815°C).

As the catalytically reacted effluent gas stream passes through the unobstructed center passage of the radiant cooler, the carbon particles present in the remaining unreacted portion of the ash-containing solid carbon fuel are removed.
reacting at least a portion (i.e., about 50-100% by weight), preferably all, with H20 in the effluent gas stream;
At the same time, the ash and slag carried in the effluent gas stream are fluxed with at least an alkali metal or alkaline earth metal compound in a radiant cooler.
flux), so that the liquid slag droplets transform into solid particles at low temperatures. This facilitates the removal of slag from the effluent gas. Advantageously, a portion of the heat of the hot effluent gas stream can be recovered by indirect heat exchange with chilled water flowing within the tubular walls of the radiant cooling zone. A by-product stream is thereby formed.

〔Example〕

The present invention provides a synthesis gas stream, a fuel gas stream, or a slurry of ash-containing solid carbon fuel in a liquid carrier.
A continuous method of producing a reducing gas stream. The product gas is used by conventional methods, with or without further processing and purification, depending on the composition of the ash-containing solid carbon fuel feedstock.

In this production method, a hot effluent gas is produced by partially oxidizing a slurry of ash-containing solid carbon fuel in a liquid carrier with a free oxygen-containing gas in the presence of a temperature regulating agent.

A substitute partial oxidation synthesis gas generator is disclosed in U.S. Patent No. 2.8.
No. 18.326. A burner is mounted along the central vertical axis at the top of the gas generator to introduce the feed stream. A suitable ring burner is shown in US Pat. No. 2,928,460.

The gas generator is a vertical cylindrical steel pressure vessel lined with refractory material.

The term ash-containing solid carbon fuel includes, for example, coal such as anthracite, bituminous coal, sub-bituminous coal, coke from coal, brown coal, residue of coal liquefaction, oil shale, tar sand, petroleum coke. , asphalt, pitch, carbon particulates (soot), concentrated sewage sludge, and
These mixtures are ground to a particle size that passes through the SDS 1.40 mm No. 14. The solid carbon fuel slurry that is pumped has a solids content in the range of about 25-70% by weight, such as 45-68% by weight, depending on the characteristics of the fuel and slurrying medium. The slurrying medium can be water, liquid hydrocarbon, or both.

The term liquid hydrocarbon as used here includes, for example:
Liquefied petroleum gas, petroleum distillates and petroleum residues, gasoline,
From naphtha, kerosene, crude asphalt, gas oil, residual oil, tar sand and silica oil, oils obtained from coal, aromatic hydrocarbons (e.g. benzene, toluene, xylene fractions), coal tar, fluidized catalytic cranking operations. circulating gas oil, furfural extract of coke gas oil, and mixtures thereof. Also included in the definition of liquid hydrocarbons are chemical processes involving oxygenated hydrocarbons, including carbohydrates, cellulosic substances, aldehydes, organic acids, alcohols, ketones, oxygenated fuel oils, and oxygenated hydrocarbon organics. and mixtures thereof.

The use of a temperature control material to control the temperature of the reaction zone of the scum generator is typically determined by the carbon to hydrogen ratio of the feedstock and the oxygen content of the oxidant stream. Suitable temperature regulating materials include steam, water, C
O2-enriched gas, liquid CO2, recycled synthesis gas, a portion of the cooled clean waste gas from the gas turbine used downstream of this production process mixed with or without air, substantially By-product oxide nitrogen, obtained from air separation units used to produce pure oxygen in
and mixtures of the above-mentioned temperature regulating materials.

Water is used in a feed slurry of water and solid hydrocarbon fuel,
Serves as a carrier and temperature regulator. However, steam is used in slurries of liquid and solid hydrocarbon fuels to provide a temperature regulating agent.

Generally, temperature regulating materials are used with liquid hydrocarbon fuels and also with pure oxygen.

The temperature regulating material may be introduced into the gas generator in admixture with either or both the solid fuel feed and the free oxygen-containing gas. Alternatively, the temperature regulating material may be introduced into the reaction zone of the gas generator by a separate conduit of the fuel burner.

HgO is introduced into the gas generator, either as a temperature regulating agent or as a slurrying medium, or
When introduced as both, the weight ratio of water to solid carbon in the solid hydrocarbon fuel, or in the liquid hydrocarbon fuel if present, is approximately 0.3-2.
0, preferably in the range of about 0.5-1.0.

The term free oxygen-containing gas used here refers to air,
Oxygen-enriched air, the latter being defined as oxygen with more than 21 moles of oxygen, substantially pure oxygen, i.e., 95%
It contains more than 100% of oxygen (the remainder consists of N2 and rare gas). Free oxygen-containing gases range from about room temperature to 120
0? (approximately) 648°C). The atomic ratio of free oxygen in the oxidant to carbon in the raw material (0/C, atom/atom) is preferably about 0.7.
to 1.5, for example about 0.80 to 1.2.

In the feed stream to the gas generator, the relative proportions of solid hydrocarbon fuel, liquid hydrocarbon, if present, water or other temperature regulating agent, and oxygen in the fuel feed to the partially oxidized gas generator A significant portion of the carbon, e.g. 75-95 wt., such as 80-90 wt.
It is converted into carbon oxide such as CO2, and the temperature of the autogeneous reaction zone is about 23,507 to 2,900? It is carefully controlled to maintain a temperature in the range of approximately 1287°C to 1593°C. Advantageously, for solid hydrocarbon slurry feeds containing ash,
The ash in the solid hydrocarbon fuel forms a molten slag at such reaction temperatures. The molten slag and fly ash (f, 1y-ash) easily separate from the hot effluent gas. Additionally, the hot effluent gas leaves the reaction zone at a temperature and pressure suitable for the next step in the production process. The pressure in the reaction zone ranges from about 10-200 atmospheres.

The reaction zone time of the partial oxidation gas generator is in the range of about 0.5-10 seconds, such as typically about 1.0-5 seconds.

The effluent gas stream leaving the partial oxidation gas generator depends on the feed rate and composition, but has the following molar compositions: 8.0-60.0 for O N2 and 8.0-70.0 for CO.
゜COt is 1.0 50.0, H*O is 2.0-5
0.0°CHa is 0.0 2.0, H2S is 0.0
-2.0, CO5 is 0.0-1.0, N2 is o
, o-go, o, and AIl'i0.0-2.0° Also present in the effluent gas stream are trace amounts (ppm) of the following gaseous impurities: HCN 0-100 (e.g. about 2-2
0): HCt is 〇-about 20.000 (e.g. about 200-
2.000); Machining N Hs is 〇-about 10.000
(e.g. about Zoo-1000) ppm.

The effluent gas stream carries approximately 0.5 to 20% by weight (
1 to 4% by weight) of carbon particulates (based on the carbon in the feed to the gas generator) and the remainder of the ash-containing solid hydrocarbon fuel feed that has not been chemically altered.

The molten slag obtained by melting the ash of coal is also
carried by the gas stream leaving the generator.

Approximately 23,507 to 2,900"F (approximately 1,287 to 1
The effluent gas R leaving the reaction zone of the partial oxidation gas generator at a temperature in the range of 593° C.) passes through a radiant cooler where it dissolves one or both of the alkali metals and alkaline earth metal compounds in the water. contact with a spray of catalyst solution consisting of:

Radiant coolers, as shown in U.S. Pat. No. 3,551,347 and U.S. Pat. No. 4,309,196,
Preferably, it is connected directly to the outlet of the reaction zone of the gas generator. This connection method is described in German Patent No. 2,
No. 650,512. The effluent gas stream from the gas generator passes either downwardly or upwardly through a radiant cooler.

reaction? ! A portion of the combustion residue carried in the exit gas stream may be removed before entering the radiant cooler. This can occur, for example, in a cyclone or in an impact
ent) by gravity and/or gas-solid separation means such as separators, without substantially lowering the temperature of the effluent gas stream. A separation chamber (with refractory lining) between the first slag and/or the second varnish slag and the residue is connected to the outlet of the reaction zone of the gas generator in order to separate by gravity a portion of the transported material. This method is described and illustrated in U.S. Pat. No. 4,251,228.

Any suitable radiant cooler, such as those previously described, may be used in the method of the present invention. A radiant cooler, consisting primarily of a cylindrical vertically elongated pressure vessel. The steel walls of the container are provided inside with a tube wall extending the entire length of the container. Cooling water, or a coolant such as water and steam, flows through each tube in the tube wall. In this way, the outer shell of the radiant cooler is protected from the hot gas stream flowing freely through the unobstructed longitudinal central passage of the vessel, which is surrounded by the walls of the tube. The tube wall consists of a plurality of vertical tubes or coils arranged in concentric adjacent rows spaced from the central longitudinal axis of the container.

In one embodiment, a plurality of thin-walled vertical tubes with or without side cooling fins line the inside wall of the radiant cooler. Adjacent rows of tubes are vertically welded to form an annular gas tight tube ak. The lower and upper ends of each of the tubes are connected to the ladder to the lower and upper rings, respectively.

If the coolant in the tube walls is water or a mixture of water and steam, the maximum temperature reached by the pressure shell of the cooler will be the same as the temperature of the steam saturated in the radiant cooler. Boiler feed water is introduced into the bottom header and enters the upper header through a number of separate upright pipes. The steam and water mixture is removed in the upper header and introduced into an external cylindrical steam vessel where separation takes place. Saturated steam removed from the steam vessel is used elsewhere in the system to provide heat and power. Optionally, at least a portion of this saturated steam is superheated. The hot water separated in the steam vessel is returned to the bottom hengoo of the radiant cooler. Optionally,
A plurality of nozzles may be secured to the outside of the tube wall for cleaning and maintenance purposes. This directs the flow of water, steam or air against the walls of the tube. Therefore, the walls of the pipes are flushed with water and the alkali metals and/or alkaline earth metal compounds deposited there are removed by the flushing water and collected for reuse in the lower part of the tank. Ru.

The hot effluent gas stream enters a vertical radiant cooler piece,
Flows freely through an unobstructed central passage.

The temperature of the hot exit gas stream decreases steadily as it passes through the radiant cooler. Due to radiation and reflux, a portion of the sensible heat of the hot exit gas stream is absorbed in indirect heat exchange by the cooling water and steam flowing inside the tube wall. The temperature of the gas stream is primarily regulated in this way.

The aqueous solution of catalyst is sprayed into the effluent gas stream in the radiant cooler through a spray nozzle or atomizer. The hot effluent gas stream and the aqueous catalyst solution are brought into intimate contact and mixed within the radiant cooler using any suitable number or combination of spray nozzles, atomizers, or other suitable mixing methods. For example, if at least one spray nozzle is installed below the inlet force in the radiant cooler, the incoming hot effluent gas stream is immediately contacted with a spray of an aqueous solution of catalyst. If necessary, use a sprayer to atomize the catalyst solution.
The nozzle is also mounted vertically along the central passage or central longitudinal axis of the radiant cooler.

A preferred aqueous solution of the catalyst is a solution containing at least one water-soluble alkali metal salt, hydroxide, or alkali metal compound in an amount from about 10% by weight to saturation. I got something.

Alternatively, the aqueous solution of catalyst may contain at least one water-soluble alkaline earth metal salt or hydroxide in an amount from about 10% by weight to saturation.

Furthermore, the aqueous solution of catalyst comprises a mixture of at least one water-soluble alkali metal salt or hydroxide and at least one alkaline earth metal salt or hydroxide in an amount from about io weight percent to saturation. May contain.

Alkali metal components selected from Group IA of the periodic table of elements, such as cesium, potassium, sodium, and
Lithium etc. are effective in this order. For example, Kx
Potassium and natrilam compounds such as CO3 and Na2COs or mixtures thereof have a cost point of
It looks very effective.

6 alkaline earth metal components from Group IIA of the Periodic Table of Elements,
For example, barium, strontium, calcium, magnesium, etc. are generally effective in this order. CaC
O5 is cost effective.

Water-soluble Group IA and/or Group IA compounds suitable for practicing the invention include carbonates, monobicarbonates;

Hydroxides, silicates, sulfates, sulfites, aluminates, borates. hydrates of these compounds, and
Suitable waste materials rich in these compounds can also be used. Alkali metal and/or alkaline earth metal halides are less preferred and are generally used in equipment 2 for the next step.
For example, it should not be used to avoid halide corrosion of stainless steel and other ferrous alloys in quenching and refining systems.

After the aqueous solvent has evaporated, an aqueous solution of the alkali metal and/or alkaline earth metal compound at a temperature in the range of 1 to 200° C. (approximately 93° C.) is mixed with the alkali metal and/or alkaline earth metal compound. Of this, the yield of particulate carbon and components closely associated with the carbon in the unchanged solid fuel contained in the effluent gas passing through the radiant cooler is about 5-50%, such as 10-20% by weight. % by weight (basic weight of carbon included).
) and concentration into a radiant cooler. Further, the molar ratio of H20/C in the hot gas stream immediately after contact with the aqueous catalyst solution of the radiant cooler ranges from about 0.7 to 25.0 or more, such as from about 1.0 to 20; Approximately 1.
It is in the range of 5η1 to 6.0.

The residence time of the hot gas stream passing through the radiant cooler ranges from about 5 seconds to 50 seconds, such as about 15 seconds to 40 seconds.

In a preferred embodiment, the gas stream is at approximately the same temperature as it exits the reaction zone of the partial oxidation gas generator, i.e., from about 2350"F to below 2900"F (from about 1287C to 15
It enters the radiant cooler in the range of 93°C), but in the conduit it is usually slightly lower, resulting in a temperature drop of about 50°C to 100°C (about 10°C to 37°C). A partially chilled gas stream is defined as having a temperature of about 13°C, e.g. below 1500°C (815°C).
It exits the opposite end of the radiant cooler after it has finally cooled to a temperature in the range of 50 below - 1600'F' (approximately 732°C - 871°C).

The pressure of the gas stream in the radiant cooler is almost the same as the gas generator pressure, and in the conduit the pressure is usually slightly reduced to about 1-
A drop of 2 atmospheres is given. At such temperature and pressure, ↑
Furthermore, to produce hydrogen monoxide and carbon monoxide, a catalytic reaction of carbon and steam is preferred over a catalytic methane production reaction. At least a portion (i.e., 50-100% by weight, preferably all) of the carbon in the unchanged remainder of the ash-containing solid carbon fuel and carbon particulates included;
Reacts with HzO in the effluent gas stream and further produces CO”Ht’C
generate. In this process, the content of H2+Cox in the gas stream increases in amount, for example in the range of about 5-40 moles, such as about 10-20 moles.

Cox and u, CO+COz are shown.

In a second embodiment of the process of the invention, only a portion of the available carbon contained in the effluent gas stream is first transformed by a catalytic steam-carbon reaction, and then the remainder of the unmodified carbon is converted into A catalytic methanogenic reaction lowers the temperature and causes a chemical change to increase the methane concentration in the gas stream to a range of about 3 to 5 moles.

The catalytic steam-carbon reaction takes place at a relatively high temperature in the front of the radiant cooler and in the conditions described above in the preferred embodiment. The catalytic methane production reaction then occurs at the end of the radiant cooler from about 1300 below to about 900 below (from about 704°C to 482°C).
Occurs at relatively low temperatures in the range (°C). Such low temperatures are preferred for methane production.

Thus, in this second embodiment, the effluent gas flow from the reaction zone of the partial oxidation gas generator ranges from approximately 2300°F to 280°F.
It enters the radiant cooler at a temperature ranging from about 1260°C to 1537°C below 0°C. Different reactions occur one after the other in two successive steps (or zones) of the radiant cooler. However, both sections of the gas cooler require catalyst addition and Hz O/C
The molar ratios are as described above for the preferred embodiment'f? :,
It is almost the same as the case. In the first step, at a given flow rate, the temperature of the gas stream passing through the first section of the radiant cooler is reduced primarily by indirect heat exchange with the cooling water in the tube walls or with water and steam. adjusted. Additionally, approximately 50-75% by weight of the carbon particulates contained and the unchanged portion of the ash-containing solid carbon fuel reacts with H2O in the effluent gas stream to generate additional H2 and COx.
By the time f is produced, the temperature of the gas stream has steadily increased from about 13007 to 1350'F (about 704 to 732°C) at the same time.
) has fallen to a temperature within the range. At this point, a second step begins, in which a melting medium solution consisting of an alkali metal and/or alkaline earth metal compound in water is optionally introduced into the radiant cooler in the manner previously described. , contacted with the effluent gas stream at a low temperature as described above.H2O.

Co, Co2. The H2 and the remainder of the unchanged carbon particulates contained in the catalyzed effluent gas stream and the carbon in the ash-containing solid carbon fuel react together in a second step to form further CHI. This methanogenic reaction is
While the catalytic gas flow passes through the second section of the radiant cooler, its temperature decreases by approximately 900°C, mainly due to indirect heat exchange with the cooling water in the tube wall or with water and steam. From 1000? (approximately 482℃-537℃
) until it reaches a range of .

Advantageously, useful thermal energy is extracted from the p1 exothermic catalytic methanogenic reaction by indirect heat exchange between the gas stream flowing down the central passage of the radiant cooler and the cooling water flowing within the tube walls. It will be collected. In this way a by-product vapor stream is formed.

At least a portion of the molten slag contained in the hot gas stream in the radiant cooler is fluxed with an alkali metal and/or alkaline earth metal compound. This produces a material with greater fluidity and lower melting point. To cool the molten fluxed slag to a lower solidification temperature, the residence time of the catalyst gas stream in the radiant cooler can be extended to increase the amount of converted carbon.

Preferably, the temperature of the gas stream exiting the radiant cooler is below the melting point of the fluxed slag. As a result, the flux-treated slag becomes granular and drips by gravity into the water bath at the bottom of the slag chamber. A suitable device for this purpose is U.S. Pat.
251.228 is shown in FIG. 1 of the drawings.

The relatively clean, partially cooled gas stream is passed through a downstream device such as a conventional convection gas cooler 1 and an expansion turbine for producing mechanical energy or electrical energy or both. It exits the downstream leak of the radiant cooler at a temperature below the maximum safe operating temperature of the lower device used to recover energy from the hot gas stream.

For example, the gas flow is about 150? to 600”F (approximately 65℃)
-315°C] downstream convection gas cooler;
Or exit other energy utilization equipment ffi. This gas stream is then optionally subjected to steps consisting of gas scrubbing, water gas conversion or methane production reactions, and purification, depending on its intended use, such as synthesis gas, reducing gas, fuel gas, etc.

For example, the partially cooled gas stream discharged from a radiant cooler is
It passes through a convection cooler and is cooled to a temperature in the range of about 1507 to 6007 (about 65°C to 315°C) in indirect heat exchange with boiler feed water (BFW). This converts boiler feed water into by-product steam. A portion of this steam is recycled to the gas generator for use as a temperature regulator. The rest is drained. Partial cooling gas R from the radiant cooler may pass through an expansion turbine. The gas stream exiting the convection gas cooler, the gas stream discharged from the expansion turbine, is scrubbed to the extent that it contains almost no particulates remaining. For example, carbon atoms in a gas stream,
Slag and catalyst are all removed by washing the gas stream with water in a washer. Almost all remaining water-soluble catalyst dissolves into the wash water stream.

Furthermore, the remaining water-insoluble particulates (washed out from said gas stream 7j) are almost entirely removed by said wash water stream n.
included in. Clean gas is separated from the wash water stream in a conventional separation vessel. Optionally, a portion of the catalyst is recovered from the wash water by conventional methods, mixed with make-up catalyst solution and recycled to the radiant cooler.

A further advantage of the method of the invention is that while the gas stream is passing through the radiant cooler, HCN, HC
All of the unwanted free gas impurities selected from the group consisting of L, CO8, and mixtures thereof are removed by the catalytic reaction process. Thus, hydrolysis of hydrogen cyanide in the presence of a catalyst produces ammonia and water-soluble alkali metal and/or alkaline earth metal formates. Additionally, partial hydrolysis of carbonyl sulfide in the presence of the catalyst produces carbon dioxide and hydrogen sulfide. Also, free hydrogen chloride in the gas stream is neutralized by reacting with a portion of the base catalyst to form water-soluble salts. These salts are simply removed from the gas stream along with the remaining particulates and catalyst by scrubbing the gas stream with water in the downstream gas scrubber of the system in the manner previously described.

The invention provides that the catalyst solution is introduced directly into the radiant cooler and not elsewhere, for example mixed with the feed introduced into the partial oxidation gas generator. The advantages of the method include:

(1) The sensible heat of the effluent gas stream from the partial oxidation gas generator is efficiently utilized at high temperatures to provide the energy necessary to initiate and carry out the exothermic steam-carbon reaction.

(2) Residence time in the partial oxidation gas generator is reduced.

As a result, gas generators are quick and inexpensive.

(3) The refractory lining of the gas generator is not eroded by contact with alkali metals or alkaline earth metal compounds.

(4) Low-grade solid fuels can be used as feed to partially oxidized gas generators without the expense of high quality.

(5) The catalyst solution is thoroughly mixed with the materials contained in the hot gas stream of the radiant cooler. When the liquid solvent evaporates, the nascent, clean catalyst is released at an elevated temperature and becomes intimately mixed with and in contact with the carbon particulates, the carbon in the solid carbon fuel, and the molten slag. At the same time, supplementary HiO is introduced. The conversion rate of the steam-carbon reaction is thereby increased.

(6) Facilitates separation of molten slag carried in the effluent gas stream passing through the radiant cooler. A portion of the catalyst reacts with the condensed material in the molten slag, producing, for example, insoluble potassium aluminosilicate. This lowers the melting point of the slag and increases its fluidity. The molten slag more easily settles into a pool of water at the bottom of the slag chamber.

(7) There are almost 11 carbons that have not changed. For this reason, gas cleaning rice is considerably reduced. The preferred steam-carbon reaction produces 2 moles of synthesis gas for each mole of carbon, whereas partial oxidation of carbon produces 1 mole of synthesis gas. This increases the amount of product gas obtained from a given amount of solid carbon fuel.

(8) The alkali metal and/or alkaline earth metal compounds deposited on the tube wall of the radiant cooler serve to clean the tube when the outer surface of the tube is flushed with water.

(9) The gas stream passing through the radiant cooler is simultaneously purified. Free and unwanted gaseous impurities in the group consisting of HCN, HO2, CO8, and mixtures thereof are removed.

(10) The amount of oxygen consumed by the gas generator is reduced.

The result is considerable economic savings.

The present invention has been variously explained above, and the summary of the explanation is as follows.

1, (1) from about 1287°C to 159°C in the presence of a temperature regulator in the reaction zone of a free-flow refractory lining of a gas generator.
At autogeneous temperatures in the range of 4°C (approximately 2350°C to below 2900°C) and pressures in the range from approximately 100 to 200 atm, approximately 7% of the solid carbon fuel slurry containing an ash content is
5-95% by weight of carbon is reacted with free oxygen-containing gases by non-catalytic partial oxidation to produce Hz, Co, Co2, HzO, N2. HtS.

CO8, CH4, NHs, A, , HCl,
producing a hot gas stream containing at least one substance selected from the group consisting of: ) passing the hot gas stream through a gas cooling zone; in the cooling zone contacting the hot gas stream with an aqueous solution of a catalyst consisting of a water-soluble alkali metal compound and/or alkaline earth metal compound and water; The alkali metal and/or alkaline earth metal components of the compound are listed in the Periodic Table of Elements IA
and/or nA group metals; Next, the catalyst solution is sufficiently mixed with the accompanying substance to completely evaporate water (+ii) The catalyst HxO is heated in the gas cooling zone.
at least a portion of the carbon and carbon particulates in the entrained unchanged ash-containing solid carbon fuel remainder entrained in the gas stream in the presence of a temperature of about 1260 °C;
Entry temperatures range from -1538°C (approximately 2300-2800"F) to approximately 732°C-872°C (approximately 1350"F).
1600? ) by indirect heat exchange with a refrigerant to a discharge temperature in the range of (N) ash-containing solid carbon; A continuous process for producing synthesis gas, fuel gas, or reducing gas from a slurry of fuel.

2, (+) from about 1287°C to 159°C in the presence of a temperature regulator in the reaction zone of the free-flow refractory lining of the gas generator.
About 75-95% by weight carbon in a slurry of solid carbon fuel containing ash at autogenius temperatures in the range of 4°C (about 235,077) = 2900'F and pressures in the range of about lθ atm to 200 atm. is reacted with free oxygen-containing gas by non-catalytic partial oxidation to obtain Hz, Co, C
O2f: Contains HzO, N2, Hz S.

CO8, CH4, NHs + A, HCl, HC
a hot gas stream containing at least one substance selected from the group consisting of (11) Passing the hot gas stream through a two-zone gas cooling zone; in the first zone of the cooling zone, the hot gas stream is passed through a water-soluble alkali metal compound and/or contact with an aqueous solution of a catalyst consisting of an earth metal compound and water, wherein the alkali metal and/or alkaline earth metal component of the compound is selected from the metals of Group IA and/or Group HA of the Periodic Table of the Elements; ; Next, the catalyst solution is sufficiently mixed with the accompanying substance to evaporate water; (i
ii) said catalyst H in a first section of said gas cooling zone;
20, the carbon in the ash-containing solid carbon fuel remaining unchanged t)-O reacts with a portion of the carbon particulates entrained in the gas stream; at the same time passing through the first section of the gas cooling zone. The temperature of the gas stream to be approximately 1260℃-1538℃ (approximately 230℃
Entry temperature ranging from 0″F-2800′F) to 704°C
p by indirect heat exchange with a coolant to a temperature in the range of -733°C (approx. 1300-1350?); in this case the Hx+Cox content of the gas stream increases; (IV) From (1) of the gas flow into the second gas cooling zone.
H20,CO, with or without further contact with the aqueous solution of the catalyst.

COz+H! + and reacting the remainder of the carbon in the ash-containing solid carbon fuel with the unchanged particulate carbon entrained in the catalyzed gas stream; at the same time the temperature of the gas stream passing through the second section of the gas cooling zone; about 704℃-73
3℃ (about 1300?-13507) 17) 11111
from the ambient temperature to approximately 482°C-538°C (approximately 900'F-1
000T) by indirect heat exchange with a refrigerant to a discharge temperature in the range of 000 T); Fuel slurry power
continuous process for producing synthesis gas, fuel gas, or reducing gas from

3. The aqueous solution of the catalyst is carbonate bicarbonate, hydroxide 7
Silicates, sulfates, sulfites, borates.

and from about 10% by weight to saturation of a water-soluble alkali metal and/or alkaline earth metal compound selected from the group of compounds consisting of mixtures thereof, wherein said alkali metal component is K, Na.

selected from the group consisting of Li, and mixtures thereof, and/or the alkaline earth metal component is selected from the group consisting of Ba, Ca,
, MP, and mixtures thereof.

4. Item 1 or 2, characterized in that the aqueous solution of the catalyst comprises water and a salt or hydroxide of one metal selected from the group of metals consisting of Na, Ca, and mixtures thereof. The method described in section.

5. Immediately after contacting the aqueous solution of catalyst in the gas cooling zone, the molar ratio H20/C of the hot gas stream is in the range of about 0.7 v-25.0 or more. , or the method described in paragraph 2.

6. At least a portion of the material entrained in the hot gas stream leaving the gas generator at (+) is absorbed by gravity and/or gas before introducing the hot gas stream into the gas cooling zone at (11). - The method according to item 1 or 2, characterized in that the solid is removed by a solid separation method.

7. The gas cooling zone consists of a radiant cooler with an unobstructed central passage through which the hot gas stream passes, and a tube wall around which cooling water passes to completely cool the passing hot gas stream. 1 or 2, wherein the contacting in (11) is carried out by spraying an aqueous solution of the catalyst onto a hot gas stream passing through the central passage of the radiant cooler. Method.

8. Fluxing at least a portion of the molten slag in the gas stream passing through the gas cooling zone with a portion of the alkali metal compound and/or alkaline earth metal compound to further increase the fluidity and lower the melting point. 3. A method according to claim 1 or claim 2, characterized in that a material is produced, the material is cooled below its melting point to form particles, and the particles are separated from the waste stream by gravity.

9. reacting a portion of a water-soluble catalyst consisting of an alkali metal compound and/or an alkaline earth metal compound with substantially all of the free HCl in the hot gas stream passing through the gas cooling zone to form a water-soluble fund; The partially cooled gas stream leaving the cooling zone is passed through a convection gas cooler for indirect heat exchange with cooling water or through an expansion turbine: a gas washing zone then washes the gas stream with water to produce clean gas. The wash water that is washed out of the gas stream and contains almost all the water-soluble salts and residual water-soluble catalyst dissolved in it, as well as almost all the residual water-insoluble particulate matter. and substantially all of the CO8 in the hot gas stream passing through the gas cooling zone in the presence of said catalytic compound.
and HxO'jr, and the partially cooled gas stream leaving the cooling zone is passed through a convection gas cooler for indirect heat exchange with cooling water, or passed through an expansion turbine, and then passed through a gas washing zone where the gas stream is is washed with water, and a clean gas stream and a wash water containing substantially all the residual water-soluble catalyst washed out from said gas stream are dissolved and also contains substantially all the residual water-insoluble particulate matter. 2. The method according to claim 1 or 2, comprising the step of generating a divided flow.

10 Almost all free HCN in the hot gas stream passing through the I420 and gas cooling zone in the presence of the catalyst compound
are reacted together to form ammonia and alkali metal and/or
or producing a water-soluble formate of an alkaline earth metal, passing the partially cooled gas stream leaving the cooling zone through a convection gas cooler for indirect heat exchange with cooling water, or through an expansion diturbine; The gas stream is then washed with water in a gas scrubbing zone to ensure that almost all of the water-soluble formate and residual water-soluble catalyst dissolved and almost all of the residual water-insoluble particulates washed out of the clean gas stream and the gas stream. 3. A method according to claim 1 or 2, characterized in that it comprises the step of generating a separate stream of wash water containing the substance.

Patent applicant: Texaco Development φ Corporation Agent: Masaki Yamakawa (and 2 others)

Claims (1)

[Scope of Claims] (1) In the reaction zone of a free-flow refractory lining of a gas generator, from about 1287°C to 1594°C in the presence of a temperature regulating material.
at autogenia temperatures ranging from approximately 23,507 to 2,900 °C and pressures ranging from approximately 10 atm to 200 atm.
Approximately 75-95 in slurry of solid carbon fuel containing ash
by weight of carbon is reacted with free oxygen-containing gases by non-catalytic partial oxidation to form H2, Co, CO2, H2O
, Nz, H2S. Contains at least one substance selected from the group consisting of CoS, CH4, NH3, HClXHCN, and contains accompanying substances consisting of carbon fine particles, unchanged ash-containing solid carbon fuel residue, and molten slag. producing a hot gas stream; (11) passing the hot gas stream through a gas cooling zone where the hot gas stream is treated with a water-soluble alkali metal compound and/or an alkaline earth metal compound and water; wherein the alkali metal and/or alkaline earth metal component of said compound is selected from metals of Group IA and/or Group IIA of the Periodic Table of the Elements;
thoroughly mixing the catalyst solution with the entrained substance to evaporate water; (iii) cooling the catalyst H20 in the gas cooling zone;
reacting at least a portion of the carbon and carbon particulates in the entrained unchanged ash-containing solid carbon fuel residue in the gas stream; at the same time, the temperature of the gas stream is increased to about 1260° C.
Entry temperatures range from -1538°C (approximately 2300 to -2800 below) to approximately 732°C - 872°C (approximately 1350 below -1
600@P) by indirect heat exchange with a refrigerant;
Slurry of ash-containing solid carbon fuel comprising the step of discharging a partially cooled gas stream enriched with z+COx
continuous process for producing synthesis gas, fuel gas, or reducing gas from (i) from about 1287°C to 1594°C in the reaction zone of the free-flow refractory lining of the gas generator in the presence of a temperature regulating material;
At pressures ranging from about 10 atm to 200 atm, at autogenius temperatures ranging from about 23,507 to below 2900,
Approximately 75-95 in slurry of solid carbon fuel containing ash
wt% of carbon is reacted with free oxygen-containing gases in a non-catalytic partial oxidation to produce N2, CO, C (including H,
zO, N2, N2S. Contains at least one substance selected from the group consisting of CO3, CH4, NHs, A, HCt, and HCN, and contains accompanying substances consisting of carbon fine particles, the remainder of unchanged ash-containing solid carbon fuel, and molten slag. (11) pass the hot gas stream through a two-zone gas cooling zone; in the first zone of the cooling zone, the hot gas stream is contact with an aqueous solution of a catalyst consisting of a compound and/or an alkaline earth metal compound and water, wherein the alkali metal and/or alkaline earth metal component of the compound is a group IA compound of the periodic table of the elements; The catalyst solution is then thoroughly mixed with the entrained material and the water is evaporated; (
110 the catalyst Hz in the first section of the gas cooling zone
in the presence of O to react the carbon in the remainder of the unchanged ash-containing solid carbon fuel with a portion of the carbon particulates entrained in the gas stream; at the same time the gas stream passes through a first section of the gas cooling zone. The temperature of about 1260℃-1538℃ (about 2300?-2
Entry temperatures ranging from 800'F to 704°C - 733°C
by indirect heat exchange with a coolant to a temperature in the range of (approximately 1300'F-1350?); in this case the N2+COX content of the gas stream increases: into a second section of the gas cooling zone, with or without further contact with the aqueous solution of catalyst, N20, CO. reacting CO2, N2, and the remainder of the carbon in the ash-containing solid carbon fuel with the unchanged particulate carbon entrained in the catalyzed gas stream; the gas simultaneously passing through a second section of the gas cooling zone; The temperature of the flow is about 704℃-733℃
(about 1300?-13507) to about 48
reduced by indirect heat exchange with a coolant to a discharge temperature in the range of 2° C.-538° C. (approximately 900° C.-1000° F.); (■) the increased amount of CH4 from the second section of the gas cooling zone; A continuous method for producing synthesis gas, fuel gas, or reducing gas from a slurry of ash-containing solid carbon fuel comprising the step of discharging a cooling gas stream.