US2713590A

US2713590A - Heat treatment of solid carboncontaining materials

Info

Publication number: US2713590A
Application number: US57088A
Authority: US
Inventors: George H Palmer; Alexander Cruzan
Original assignee: MW Kellogg Co
Current assignee: MW Kellogg Co
Priority date: 1948-10-28
Filing date: 1948-10-28
Publication date: 1955-07-19
Anticipated expiration: 1972-07-19

Description

July 19, 1955 G. H. PALMER ETAL 2,713,590

CONTAINING MATERIALS HEAT TREATMENT OF' SOLID CARBON- Filed OGC. 28, 1948 4 Sheets-Sheet l July 19, 1955 G. H. PALMER ET AL 2,713,590

HEAT TREATMENT 0F SOLID CARBON- CONTAINING MATERIALS Filed Oct. 28, 1948 4 Sheets-Sheet 2 FIG.2

JNVEN'J'ORS EE0/TG5 H PALMER B) ,URL/ZA /v ALEX/1 NUE/T .ATTENEY July 19, 1955 G. H. PALMER ETAL l2,713,590

CONTAINING MATERIALS HEAT TREATMENT 0F SOLID CARBON- Filed Oct. 28, 1948 4 Sheets-Sheet 5 El EMM@ July 19, 1955 G. H. PALMER ET-AL 2,713,590

HEAT TREATMENT OF SOLID CARBON-CONTAINING MATERIALS Filed Oct. 28, 1948 4 Sheets-Sheet 4 N m 2 G N q) I E N l/)J 03 uw: Q fa i lq Lo N 3 CD m L Q0 N Q Se N LL Y 5% 5% N N N N N INVENTORE EEO/:'51: PALMER Bgm/ZA N ALEX/1 /vz/EF? .A TTDEZVE'Y 'the production of which Unit . States Patent Patented July 19, 195.3

HEAT TREATMENT F SOLID CARBN- CNTAINNG MATERIALS George H. Palmer, Fatevi/ood, N. 5., and Cruzan Alexu ander, Jackson Heights, N. Y., assignors to The M. W. Kellogg Company, Jersey City, N. I., a corporation of Delaware Application ctoher 28, 1948, Serial No. 57,088 16 Claims. (Cl. Z50-449.6)

It has been known that coal may be treated with `oxygen and steam in a reaction zone at relatively high temperatures to convert the coal to hydrogen and carbon monoxide, which products are useful for various purposes such as fuel or as a feed gas for the synthesis of organic compounds. In general, the coal or coke is contacted with steam in a reaction Zone at a temperature above about l000 F. The operating conditions employed are such that a substantial proportion of the steam reacts with coal to produce hydrogen and carbon monoxide, products is favored by high temperature.

It has been proposed to maintain the required temperature for the gasification of the coal by simultaneously introducing oxygen with the steam into the gasification zone. The temperature of reaction recommended was not always that best suited for the production of the maximum amount of carbon monoxide. For example, relatively low temperatures were proposed as being practical because of the economic advantage gained in the saving of oxygen and in order to obtain a fuel gas having methane which increased the heating value of the resulting gas. Working at these lower temperatures would inevitably result in the production of some carbon dioxide at the expense of carbon monoxide. The production of carbon dioxide is favored at lower temperatures by both the steam-coal reaction and the oxygen-coal reaction. Carbon dioxide thus produced would constitute product gas, It is much which may for reasons costly operation. to be desired, therefore, to provide a process operate at the relatively or minimizes the amount of carbon dioxide producedl companied by the minimum amount of carbon dioxide formation.

A further used in a suspended condition.

Another object of this invention is to provide a method for removal and separation of ash and like undesirable material from a process for the gasification of carboncontaining solid materials.

Au object of this invention is to provide a gasification process in which volatile components of the solid carboncontaining materials may be recovered.

A further object is to provide a gasification process which is substantially proposed processes.

Various other objects and advantages of the present invention will become apparent to those skilled in the art from the accompanying description and disclosure.

According to the improved process of this invention, carbon-containing solid material and any accompanying separate reaction zone, carbon-containing solid material, any accompanying carbon dioxide and oxygen are reacted under optimum exothermic conditions such that is maintained at the desired level by liberation of the sensible heat of the coal circulated.

C sensible heat of the coal circulated thereto. Conveniently, unconvcrted coal or coke from the endothermic rcaction zone is returned to the exothermic reaction zone for further conversion thereof; fresh coal being added to the process at the desired point in the system, either intermittently or continuously.

The preferred method of operation is by the use of the so-called fluidized technique in which the coal is in a finely-divided form and present in the reaction zone in a conventional uidized pseudo-liquid condition. Gaseous reactants and products are passed upwardly through a mass of finely-divided coal at a suiiicient velocity to maintain the coal in such a lluidized condition whereby the finely-divided particles of coal circulate throughout a dense phase in the lower portion of the reaction zone. The use of the uidized technique also has the advantage of substantially uniform temperature conditions within the iluidized mass because of the high heat transfer rate between the gas and solid particles. Fluidized coal or coke is circulated between the reaction zones by means of conventional methods, such as by the use of aerated standpipes of sufficient length to overcome pressure drops or by the use of solids pumps, such as a Fuller-Kinyon pump.

In this type of operation the coal is used in a finelydivided form, preferably a major proportion of the coal has a particle size less than about 250 microns. The finely-divided condition of the coal may be obtained 'oy crushing and grinding large pieces of coal in suitable equipment, such as a ball mill, or by explosion pulverization.

It is believed that the present invention may be best described by reference to the accompanying drawings which show the inventive features of the present invention as applied, for example, to the synthesis of organic compounds and to the production of a fuel of high heating value.

Figure 1 of the drawings is a diagrammatic illustration in elevation of an arrangement of apparatus for thc synthesis of organic compounds embodying the present invention in which the coal in the gasification step is maintained in a fluidized pseudo-liquid dense phase condition in both the exothermic and endothermic reaction zones.

Figure 2 of the drawings is a modification of the operating technique shown in Figure 1 and illustrates an arrangement of apparatus for the operation of the invention in which the coal is carried in the gaseous reactants in a relatively less dense condition than the conventional dense phase of Figure l.

Figure 3 of the drawings is a diagrammatic illustration in elevation of an arrangement of apparatus for the production of a fuel gas of high heating value cmbodying teachings of the present invention in which finely-divided coal in the gasification step is maintained in a pseudo-liquid dense phase condition.

Figures 4 and 5 illustrate modifications of the present invention for the introduction of fresh coal into the system and the removal of ash from the system.

Referring with particularity to Figure l of the drawings, an oxygen-containing gas, such as substantially pure oxygen or enriched air, is passed by means of conduit 4 through a conventional heat exchanger 2S to conduit 6. Coal or coke is introduced into conduit 6 and mixed with the oxygen-containing gas, and the resulting mixture is passed to partial combustion chamber 7, which comprises a conventional cylindrical chamber having a refractory lining. Oxygen is passed upward through a mass of finely-divided coal or coke in chamber 7 at a velocity sufficient to maintain the finely-divided solids in a fluidized pseudo-liquid condition characterized by an interface S between a lower dense phase and an upper relatively dilute phase. Sufficient oxygen is utilized in proportion to the mass of coal or coke that a uniform temperature between about 1800 and about 2000 F.

is maintained in chamber 7' at approximately atmospheric pressure. A suitable oxidation temperature in chamber 7 is about 1900 F. Under the conditions utilized in chamber 7 coal is converted to a major proportion of carbon monoxide and a minor proportion of carbon dioxide. However, under the temperature conditions employed in chamber 7 a minimum amount of carbon dioxide is produced, in some instances less than about one per cent of the product gases. An eiiluent gas containing carbon monoxide and some entrained ash and unburncd coal or coke is passed to a solids separator ll which may comprise a conventional cyclone separator. lf desired, a cyclone separator or ceramic filters may be positioned within chamber '7 to at least partially remove e entrained coal and ash. Since the ash is a relatively lighter material than the coal, the solids Withdrawn from reactor 7 through conduit 9 contain a higher proportion of ash than present in the dense phase. Hence, permitting solids to pass overhead from reactor 7 and separating them from the eflluent in separator 1i is a convenient and effective manner of preventing the build-up of ash in the system. Solids thus separated are withdrawn from separator 11 through conduit 26.

Finely-divided coal and/ or coke at a relatively high temperature is withdrawn from the dense phase of chamber through a conduit or standpipe 13 and introduced into a gas stream consisting essentially of steam passing through conduit 16. An aerating or stripping gas, such as steam, carbon dioxide, or recycle gas from the synthesis step to be discussed further hereinafter, may be introduced into conduit or standpipe 13 for aerating and/ or stripping the solid particles therein. Steam is introduced into the system through conduit 16 and may be by-passed through conduit 17 to heat exchanger 28 for supcrheating. The resulting mixture of steam and solids withdrawn from chamber 7 are passed through conduit 16 to a gasification chamber i8, which comprises a conventional cylindrical reaction chamber similar to that of chamber '7. Alternatively or additionally to coal introduced into the system through conduit 6, fresh coal may be introduced into conduit 16 by means of conduit 24. This may be a particularly desirable location for introducing coal, since the coal is contacted at this point at a temperature somewhat lower than that existing in chamber 7. Volatile components are distilled from the coal at a temperature at which the tendency for their decomposition is minimized. The relatively low temperature at this point also reduces the tendency of the fresh coal to fuse and the finely-divided particles to agglomerato or stick together.

The finely-divided coal in chamber 18 is maintained in a luidized condition characterized by an interface 19 between a lower' dense phase and an upper dilute phase similar to that described with respect to chamber 7. For the production of a gas of optimum composition with respect to hydrogen and carbon monoxide by the steamcoal reaction, the temperature of chamber 18 is maintained between about 1500 and about l700 F. at atmospheric pressure by regulating the temperature and quantity of the solids circulated from chamber '7 to chamber 1S. Under the optimum conditions maintained in chamber' 18 steam is reacted with the coal or col'e to produce hydrogen and carbon monoxide with a minimum formation of carbon dioxide, methane and water vapor, usually less than 5 per cent, in the product. An efuent comprising hydrogen and carbon monoxide and entrained coal or coke and ash is removed from chamber i8 through conduit 2i. and is passed to separator il as previously discussed. Ash and coal are separated from the effluent and removed from separator ii. through conduit 26. As in the case of chamber 7, cyclone separator or ceramic filters may be positioned within chamber 18, in addition to or substitution for, the case may warrant, separator 1l for removing at least a portion of the entrained solids from the cfiluent. Unconverted coal gage may be employed without departing from the scope of this invention. Pressures below about 150 pounds per square inch gage are preferred, however. At elevated pressures somewhat higher temperatures are necessary for the respective reaction zones in order to prevent the increased production of undesirable by-products. In general, partial combustion chamber 7 is operated at a temperature corresponding to a temperature between 1800 and about 2000" F. for atmospheric pressure operations, and gasification chamber 13 is operated at a temperature corresponding to about 1300 to about 1700 F. for atmospheric pressure operations. Excess coal is employed in the system to supply suiiicient heat carrier material for transferring a portion of the exothermic heat of reaction from chamber 7 to chamber 18.

A gaseous efiiuent comprising hydrogen and carbon monoxide in a ratio of about 0.5:1 to about 2:1 at a temperature usually above about 1500 F. when producing a synthesis feed gas is removed from solids separator heat exchanger 28 the synthesis feed gas passes of finely-divided catalyst such of the Periodic Table, for example reduced iron or cobalt, under suitable operating 1 conditions for the conversion of hydrogen and carbon monoxide to normally liquid organic compounds comprising hydrocarbons and oxygenated organic compounds. When using reduced iron as the catalyst a temperature between about 550 employed, and preferably a pressure corresponding subthan, the pressure em- Higher pressures, up to as high as 700 pounds per square inch gage, may be employed. When pressures are employed in synthesis reactor 31 which are above the pressure employed in the gas-making step, a suitable compressor must be used. The mass of finely-divided catalyst in reactor 31 is maintained in a fluidized condition characterized by an interface 32 between a lower dense phase and an upper relatively dilute phase. Catalyst is withdrawn from the dense phase of reactor 31 through conduit or standpipe 34 and passed through a conventional catalyst cooler 36 and reintroduced into conduit 29. The temperature of synthesis reactor 31 may be controlled within relatively narrow limits by removal of exothermic heat of reaction by means of catalyst cooler 36. Catalyst may be withreactor 31 by means not shown.

Synthesis reactor 31 may be cooled also by indirect cooling means positioned within the dense phase, if desired. A suitable vaporizing or cooling liquid may also be introduced directly into the dense phase for cooling purposes. A cyclone separator or iilters may be posiand about 750 F. is f tioned within or externally of reactor 31 to remove e11- trained catalyst from the reaction eiiluent.

A reaction effluent comprising hydrogen, carbon dioxide, methane an accumulators or fractional distillation Columns with suitable auxiliary equipment for the separation and recovery of the products of the process.

hydrocarbons and oil-soluble oxygenated'chemicals, are removed from recovery unit 38 through conduit 41. Uncondensed vapors, such as hydrogen, carbon dioxide and methane, are removed from recovery unit 38 through conduit 42 and may be passed directly to conduit 17 for introduction into gasification chamber 18. ferrcd to introduce methane into 1?, so that it can be reformed with steam therein to produce hydrogen and carbon monoxide.

All or a portion of the jected to conditions of temperature and pressure to the carbon dioxide. Gases substantially free from carbon dioxide and containing methane are removed from abmay be'passed, if desired, through conduit 47 to conduit 42 for circulation to gasification chamber 1S.

or carbon dioxide rich gases are preferably passed to combustion chamber 7 in which optimum conditions exist for the conversion of carbon dioxide to carbon monoxide.

is returned from absorption unit 44 through conduit 47 to conduit 42.

In order to prevent the build-up of nitrogen in the system, particularly when enriched air is used as the oxygen-containing gas, a portion of the vapors in conduit 42 or conduit 47 are vented to the atmosphere. Air itself may be used as the oxygen-containing gas in line 4 without departing from the scope of this invention, and under such circumstances a large proportion of the vapors in conduit 42 is vented to the atmosphere.

In the operation of Figure l described above the sole source of heat is the partial combustion of coal in chamber 7. However, external heating means may be provided in addition to the partial combustion of coal for producing heat. Such external means may comprise preheating furnaces for the steam and/or oxygen-containing gas. A catalytic material or heat-carrying material, such as an ore, may be used in combination with the coal in chambers 7 and 18 without departing from the scope of this invention. For example, an iron ore containing magnetite may be admixed with the coal introduced into conduit 6 or introduced tirough conduit 2d. The magnetite promotes the production ol hydrogen and carbon monoxide and also serves as a heat-carrying material for the lioW of heat from partial combustion chamber 7 to gasification chamber X8.

Various methods may be utilized to obtain the iinelydivided condition of the coal for use in a iluioized process described with respect to Figure l. rl'he coal may be crushed lirst in a jaw Crusher and then ball-milled to the desired size. Alternatively, the coul may be introduced into a stream ol steam which is injected into the system by reducing the pressure at least 50 to lo() pounds, thereby pulverizing the coal by explosion pulverizatiou (expansion of the steam in the pores of the coal).

Figure 2 ol the drawings is a moditication of the invention in which gasilication chamber l ot .Figure l is operated with a suliliciently high linear gas velocity therein that the net movement of the coal is in the direction of liow of the gas stream passing therethrough. as a result of the gas velocity. The description ot Figure 2 will be brief, since the operating conditions may be substantially thc same as those described with respect to Figure l, and it should be understood that the product gas obtained the-refr ni may be utilized for the synthesis of organic compounds in the manner described with respect to Figure l. Steam passes through conduit 6l and heat exchanger 82 to gasilication chamber 62, which comprises an elongated conduit generally of relatively small diameter as compared to the chamber lll of Figure l. The steam in conduit el picks up hot coal or colte from conduit 76 and the resulting mixture is converted to hydrogen and carbon monoxide in chamber 62. Additionally', steam may be introduced longitudinally at spaced intervals along chamber 62 through

conduits

66, 67, and 63, as shown, to aid in maintaining the desired concentration of steam at any particular point in chamber 62. The velocity of the gases in chamber 62 is preferably above 5 feet per second, usually between 8 and about 40 feet per second, depending on such factors as particle size and density, reaction conditions, etc., such that the iinely-divided coal or colle moves in the direction of the Flowing gases and may at very high velocities travel at substantially the same rate as the gases. The concentration of the coal in the gases is much less than the concentration of coal in a conventional pscudoliquid dense phase, which is usually 20 pounds per cubic foot of gas or greater, and for this reason stiel-:ing and agglomeration of the coal or coke is minimized. The concentration of finely-divided solids is generally in the range oi about l to about l() pounds per cubic toot of gas. Unconverted coal or coke, ash, hydrogen, carton monoxide, and steam are Withdrawn from gasification chamber 62 through conduit 63 and are passed at the above relatively high velocity to separator 64. Separator' 64 may con'ipr a conventional settling zone, a cyclone separator, or the like, for separation of unconverted coal or eolie and ash from the gasification effluent. Since the gasification effluent in conduit (3 is at a relatively low temperature because or endothermic reaction in chamber 62, it may bc desirable to introduce fresh coal into the process into conduit 63 through conduit 69. ln this manner the fresh coal contacts the gases of the process at the minimum temperature whereby the valuable vaporizable products of the process are distilled Without substantial cracking thereof. Moreover, since the stream of gases in conduit 6E is at a relatively high velocity and the solids are Well dispersed therein, the tendency for thc fresh coal to agglomerate and stick is minimized. lt is therefore a particular feature of this invention to introduce fresh coal into the high velocity eiliuent stream from chamber 62 and maintain the coal therein long enough to substantially completely distill vaporizable components from the fresh coal. Thus, the

ti length of conduit 63 may be adapted to achieve sufficient holding time for distillation of the fresh coal.

Separated coal is passed from separator 64 into partial combustion chamber 72 by gravity. Oxygen is introduced into partial combustion chamber 72 at a plurality of points spaced longitudinally along chamber 72, such as by means of conduits 73 and 74, in order to minimize hot spots or local overheating. In partial combustion chamber 72 coal or coke is converted to carbon monoxide and carbon dioxide accompanied by liberation of heat. Coal and/or coke is withdrawn from gasification chamber 72 at a relatively high temperature by means of standpipe 76. The quantity of oxygen and the shape of chamber 72 is suoli that a suiiiciently high upward gas velocity is maintained therein to maintain the iinelydivided coal or coke in a iiuidized pseudo-liquid condition similar to that described With respect to combustion chamber 7 of Figure l. The velocity may be sufficiently low that little, if any, circulation of the solids in the dense phase is obtained. In this modilication the solids liow substantially countercurrently to upflowing gases. A portion of the finely-divided coal and/or coke is withdrawn from chamber 72 through conduit 78 to prevent the build-up of ash in the system. Ash may be sep arated from unconverted coal or coke withdrawn through conduit 73 and the separated unconverted material returned to the process, if desired.

ln order to produce a maximum amount of hydrogen and methane from the coal, fresh coal is preferably introduced directly into separator through conduit '77. ln this manner the fresh coal is contacted with the hot gases from partial combustion chamber 72, which gases are at a relatively high temperature favorable to the conversion of the volatile components of the coal to hydrogen and methane.

An acrating or stripping gas may be introduced into standpipe 76 through conduit 83. Such aerating or stripping gas. may comprise recycle gases, carbon dioxide, or oxygen. il/hen s 'A ping is eilectcd in conduit 76 to remove occluued cf on monoxide, a relatively larger proportion of gas is introduced into conduit 33 than when mere aerating is effected in conduit 76 to assure free low ol solids therethrough.

A gaseous eliiuent comprising hydrogen, carbon monoxide, carbon dioxide, l unconverted steam is removed from separator 64.l through conduit 8l and is passed through heat exchanger 82. The effluent gases in conduit Sl may be passed to a synthesis reactor, as described in Figure l, or may be usal as a, fuel gas. When the coal contains valuable volatilizable components and is introduced into the system through conduit 69 the eti'luent gases in conduit 8l are jassed to a cooling system for condensation and recovery ol water and valuable organic components of the coal, such as tars, naphthalcne, anthraccne, bcnzol, toluol. phenol, crcsol, Xylol, and normally gaseous nd liquid hydrocarbons, as well as some nitrogen and sulfur compounds.

Figure 3 of 'the drawings, illustrating another embodiment of the present invention, diagrammatically shows in elevation an arrangement ol apparatus for the production of a fuel gas of high heating value in accordance with the teachings of this invention. A gaseous stream comprising oxygen or a mixture of oxygen and other gases, such as carbon dioxide, is passed through conduit 91 to a partial combustion chamber 92. Recycle coal is introduced into the "as stream in conduit 91 by means of conduit or standpip W2 and is carried to chamber 92. As explained in the discussion of chamber' 7 of Figure l, gasification chamber 62 is operated at optimum exothcrmic conditions for the conversion of coal or coke to carbon monoxide accompanied by the liberation of heat. The preferred temperature range for gasification chamber 92 is between about 1800 and about 2000 F. The gas is passed upward through chamber 92 at a velocity sulcient to suspend the coal in a so-called pseudo-liquid dense phase in which the fine solid particles circulate throughout the dense phase. A gaseous effluent comprising carbon monoxide and containing ash and in some cases entrained coal or coke is passed through conduit 93 and a conventional heat exchanger or cooler 94 and thence to a solids separator 96. The gaseous effluent from chamber 92 is cooled by heat exchanger 9d. Solids separator 96 may comprise any conventional type of separating means for separating solids from gases, such as an enlarged settling zone or a cyclone separator.

Cyclone separators or filters may be'positioned Within chamber 92 to at least remove a portion of the entrained solids carried with the gaseous effluent. the use of cyclone separators within chamber 92, additional means, such as separator 96, 1s usuallyv employed to remove additional entrained solids, particularly ash.

Coal and/or coke at a relatively high temperature is removed from combustion chamber 92 by means of standpipe 97 and passed to conduit 98. Water is introduced into conduit 98 and passes through a heater or heat formation of carbon dioxide. tage of the present process, therefore, that the oxidation reaction and the steam-coal reaction can be carriedout in separate reaction zones. Thus, the additional carbon dioxide which would be formed bythe oxygen-coal reacmonoxide together with small proportions of carbon dioxide.

A gaseous effluent comprising hydrogen, carbon monoxide, carbon dioxide, methane, and entrained ash and in some instances coal or coke is removed from chamber 101 through conduit 103 and may be passed directly separation of the solids from the effluent.

In the preferred modification of Figure 3, fresh coal is introduced directly into chamber 101 by means of contain also volatile components of the coal and is passed through conduit 104 to a separator 106 which comprises a cooler and an accumulator for condensing liquid products from the effluent. These valuable liquid products, which in most instances are the volatile compassed from separator 106 through conduit 108 to a conventional carbon dioxide absorber 109.

In carbon dioxide absorber 109, the gaseous stream Substantially all of the carbon dioxide is removed from the eiuent in absorber 109. A gas consisting essentially of hydrogen, carbon monoxide and methane is removed from absorber 109 and passed through conduit 111 to separator 96 to be combined with the effluent from cham ber 92. A high heating value gas comprising hydrogen,

product of the process.

In most instances the removal of carbon dioxide from duit 118. Desorbed carbon dioxide is removed from desorption zone 114 through conduit 116 and may be chamber 92. The carbon dioxide thus produced in gasiflcation chamber 101 is converted to carbon monoxide in 101 to at least partially remove entrained coal or coke and ash from the reaction effluent.

Ash and coal separated from the effluents by separator 96 are removed therefrom through conduit 119 for disposal or recirculation to either or both

chambers

92 and 101.

Fresh coal is introduced into the process from hopper 127 through either conduit 128 or conduit 129. Coal recover the maximum amount of Volatile components without the decomposition thereof. Unconverted coal and/or coke is removed from gasification chamber 101 through a standpipe 102 for circulation to combustion chamber 92, as previously discussed.

Upon continuous introduction of coal into the process pletely burn the coal. Oxygen, together with an inert gas if desired, is passed through eiongated flows 1n the direction of flow of the gas stream, it is oxygen, carbon dioxide and carbon monoxide at a relatively high temperature are removed from separator 124 and passed through conduit 126 and heat exchanger 99 to combustion chamber 92. The effluent from reactor 123 may supply the necessary oxygen and heat for the conversion of coal in chamber 92 to carbon monoxide. The carbon dioxide formed in reactor 123 is converted to carbon monoxide by contact with coal in chamber 92, thus making substantially complete utilization of the coal and of the oxygen of the system.

Reactor E23 may be positioned vertically, horizontally, or angularly without departing from the scope of this invention. It is preferred, however, to position elongated chamber 123 vertically using an upward gas velocity therein above about 5 feet per second to move the coal and ash in the direction of the gaseous stream.

The effluent from chamber 10i, such as that in

conduit

103 or 104, may be heat exchanged with the water in conduit 9S to utilize the heat content of. that stream. Various other process streams may be heat exchanged without departing from the scope of this invention. Chamber 107i may also be operated similar to chamber 62 of Figure 2 in which the solids move in the direction of flow of the gases. In such instance, separators, etc., must be provided for removing entrained solids as described in Figure 2.

An important feature of the present invention is the introduction of fresh solid carbon-containing materia into the system at any point at which conditions are best suited for the particular solid and the desired results to be obtained. rvIhe point of introduction of the solids, such as fresh coal, into the system `vill depend upon various factors such as the type of coal, i. e., the ash content and fusion temperature thereof, Whether it is desirable to recover the volatile components of the coal without substantial cracking and the particular temperature prevailing at the point of introduction of the coal. En Figure l, fresh coal is introduced into the inlet line 6 to partial combustion chamber 7 and/or inlet line 16 of gasification chamber 1S. ln Figure 2, fresh coal is introduced into the high velocity outlet gas stream of gasification chamber 62 and/or into the gaseous eliiuent from partial combustion chamber 72. ln Figure fresh coal is introduced directly into partial combustion chamber 92 and/ or gasification chamber 1M. Several other modifications for introducing the coal may be practicel. For example, Figure 4 of the drawings diagiarninatically illustrates a modification of the gasi'iication chamber, such as chamber l of Figure l, or chamber' 1&1; of Figure 3. According to the modification of Figure 4, numeral 131 indicates a cylindrical gas"ication chamber containing a lower pseudo-liquid dense phase 432 of finely-divided solids separated from an upper pseudo-liquid dense phase 133 of fresh coal by means of a perforated plate or screen 134. Steam is introduced into the lower portion of gasification chamber 131 through conduit 136 and coal and/or coke in dense phase i332 is reacted with steam to produce hydrogen and carbon monoxide. Entrained coal and reaction products comprising hydrogen and carbon monoxide pass upwardly through gasification chamber 131 through perforated plate 134 into the pseudo-liquid dense phase of fresh coal 133. Fresh coal is introduced into upper dense phase 133 by means of conduit 137 in the top of chamber 131. The gaseous effluent passing through dense phase 133 is at the minimum temperature for the process and at this temperature the volatile components of the coal are distilled from the coal. A gaseous eiiiuent passes from dense phase 1.33 and is removed from gasification chamber 3l. through outlet conduit 133. This gaseous effluent may be treated in substantially the same manner as described with respect to Figure 3 in order to separate and recover valuable volatile components of the coal. Coal or coke may be removed from upper dense phase i3?, and introduced into lower dense phase L32 of gasification chamber 131 by means of standpipe l39 positioned within chamber 131. Alternatively or additionally, coal or coke may be withdrawn directly from the dense phase l33 of chamber it by means of outlet conduit M1 and passed to any portion of the system desired, such as directly to a partial combustion chamber (not shown) for the conversion of the coal to carbon monoxide, or to dense phase T132. Also, coal may be removed from the lower dense phase E32 of chamber 131 through a standpipe and may be passed or recycled to a partial combustion chamber (not shown), or treated to remove ash ihere rom as described with respect to Figure 3. When coal is passed directly from dense phase 133 to dense se i3?. substantially all of the coal is removed through duit 2 for recycling to a partial combustion cham- Up .r and lower portions of chamber 131 including the respective dense phases of

solids

132 and 133,

constructed as separate Zones suitably connected departing from the scope of this invention. A aerating or stripping gas may be introduced conduits E39, 141 and M2. Jure 5 represents another modification of the present invention which is particularly useful for the recovery o? volatile components of the coal with minimum contamination with the gaseous components hydrogen, carbon monoxide and carbon dioxide. In this modification the size of equipment for recovering the volatile components of the coal is minimized. According to the niodificzun shown in Figure 5, numeral 152 indicates a reaction chamber, either a gasification chamber or a partial combustion chamber' as previously described. Reactants are introduced into chamber l5?. through inlet conduit ll. A reaction effluent containing cntrained coal or colte is removed from reaction chamber 152 through conduit 5.53 and is passed to a conventional solids separator 54. Hot coal or coke is separated from tno reaction effluent in separator 154 and is passed through standpipe or conduit l5? to a volatilization chamber l5?. Vflic reaction effluent is removed from separator 154 through conduit 156.

in volatiization chamber 15% hot solids from chamber are admixed with fresh coal introduced therein through conduit itil. ln this manner the fresh coal is heated to a suhiciently high temperature to distill the volatile components therefrom. An elluent comprising the volatile components of the coal and substantially free from hydrogen, carbon monoxide and carbon dioxide is removed from chamber l through outlet conduit 159. Yfhis effluent may be passed to conventional separation and recovery equipment (not shown) for the recover of the volatile components of the fresh coal. A portion of the effluent in conduit 159 is recycled through conduit tot in order to aid in maintaining the coal in chamber l5@ in an aerated or fluidized condition therein. Fresh coal may conveniently be introduced into conduit 161 by means of conduit 162 and thereby injected into chamber 153. The passage of a gas upwardly through chamber 353 intimately mixes the fresh coal with the hot solids from chamber i221, thus maintaining substantial uniform temperature conditions. Coal and/or coke may be intermittently or continuously removed from chamber 158 through conduit 163 and passed to either a gasification chamber or a partial combustion chamber (not shown), as desired. lf the coal or colte removed from chamber SS through conduit 163 is at a higher temperature than the temperature of the gasification chamber, it is preferred to introduce the hot coal into the gasification charnber. However', if the coal or coke removed from chamber 158 is at a lower temperature than the temperature of the gasification chamber of the system, it is best to pass the coal to the partial combustion chamber so that it may be heated prior to circulation to the gasification chamber.

Coal may be passed directly from chamber lSZ, such as from a dense phase of rinely-divided coal thereinto material withdrawn from the reaction Zones when coal is the feed material.

Various pumps, coolers, separators and auxiliary equipment have been eliminated from the drawings as a matter of convenience and clarity and their use and location will become apparent to those skilled in the art. Various alterations and modifications of the present invention will become apparent to those skilled in the art without departing from the scope of this invention.

Having described our invention, we claim:

l. A process for producing a gaseous mixture of hydrogen and carbon monoxide which comprises passing steam and iinely-divided carbon-containing material through a rst reaction zone at a velocity eiective to move said finely-divided carbon-containing material as a fluidized mass through said rst reaction zone in the direction of flow of the gases therethrough, mainand about l700 F. such that hydrogen and carbon monoxide are produced as the principal products of the reaction between steam and carbon, withdrawing an efHuent from said rst reaction zone comprising hydrogen, carbon monoxide, entrained ash and unconverted carbon-containing material and passing same at a relatively high velocity of at least feet per second to a solids separator in which solids are separated from the euent, fresh carbon-containing material zone, passing pure oxygen upward through said second reaction zone at a velocity such that nely-divided solids are maintained in a pseudo-liquid fluidized condition therein, maintaining said second reaction zone under exothermic conditions of reaction at a temperature between about 1800 and about 2000 F. such that a product gas containing a major amount of carbon monoxide and a minor amount of less than about 1% carbon dioxide is produced, the reaction conditions in said second reaction zone have an over-all exothermic eect such that moving a suicient quantity of finely-divided solids from said second reaction zone substantially at the temperature of said second reaction zone and passing same to said rst reaction zone to maintain the temperature therein in the above range.

2. A process for producing a gaseous mixture of hydrogen and carbon monoxide which comprises passing steam and finely-divided carbon-containing material through a rst reaction zone at a velocity effective to move said finely-divided carbon-containing material as a uidized mass through said first reaction zone in the direction `of ilow of the gases therethrough, maintaining in said first reaction zone endothermic conditions of reaction and a temperature between about 1300 and about l700 F. such that hydrogen and carbon monoxide monoxide which comprises passing steam and finely-divided carbon-containing material through a first reaction zone at a velocity effective to move said finely-divided carbon-containing material as a iiuidized mass through said rst reaction zone in the direction of ow changing the aforesaid oxygen and steam bined eluents prior to charging the same to the reaction 15 zones in the aforesaid manner, and removing a sufficient quantity of finely-divided solids from said second reaction zone substantially at the temperature of said second reaction zone and passing same to said first reaction zone to maintain the temperature therein in the above range.

4. A process for producing a gaseous mixture cornprising hydrogen and carbon monoxide which comprises supplying pure oxygen for passage upwardly through a mass of finely divided carbon containing solid material in a first reaction Zone at a velocity effective to suspend said solids in a iiuidized condition, reacting a portion of the carbon containing solids with oxygen containing gas in the first reaction zone at a temperature of about 1800 to about 2000* F. thus producing a product gas containing a major amount of carbon monoxide and a minor amount of less than about 1% carbon dioxide, the reaction conditions in said first reaction Zone have an overall exothermic effect such that no external source of heat is necessary to maintain the aforesaid temperature therein, passing steam upwardly through a mass of finely divided carbon containing solid material in a second reaction zone at a velocity effective to suspend said solids in a iiuidized condition, reacting the solids and steam in the second reaction zone at a temperature of about 1300 to about 1700 F. thus producing carbon monoxide and hydrogen as the principal products of the reaction, withdrawing a portion of carbon containing solids from the first reaction zone and passing same to the second reaction zone wherein the reaction conditions produce endothermie heat effects in a quantity sufficient to maintain the aforesaid temperature therein, separately removing efliuents from said first and second reaction zones as the product of the process containing entrained finely divided ash and unconverted carbon containing material, passing said separate effluents to a common solids separating Zone wherein the effluents are combined and the ash and carbon material are removed from the emuents, and heat exchanging the aforesaid oxygen stream and steam with the combined effluents prior to charging the same to the reaction zones in the aforesaid manner.

5. A process for producing a gaseous mixture comprising hydrogen and carbon monoxide which comprises supplying pure oxygen for upward flow through a mass of finely divided carbon containing solid material in a first reaction zone at a velocity effective to suspend the solids in a uidized condition, reacting a portion of the carbon containing solids with oxygen in the first reaction zone at a temperature of about 180()o to about 2000" F. thus producing a product gas containing substantially all carbon monoxide and less than about 1% carbon dioxide, the reaction conditions in said first reaction zone have an overall exothermie effect such that no external source of heat is required to maintain the aforesaid temperature therein, passing steam upwardly through a mass of finely divided carbon containing solid material in a second reaction zone at a velocity effective to suspend said solids in a fiuidized condition, reacting the solids and steam in the second reaction zone at a temperature of about l500 to about i700 F. thus producing principally carbon monoxide and hydrogen and less than about 5% of carbon dioxide, methane and water in the reaction product effluent, withdrawing a portion of carbon containing solids from the first reaction zone and passing same to the second reaction zone wherein the reaction conditions produce endothermic heat effects in a. quantity sufficient to maintain the aforesaid temperature therein, separately removing efliuents from said first and second reaction zones as the product of the process containing entrained finely divided ash and unconverted carbon containing material, passing said separate efliuents to a common solids separating zone wherein the eflluents are combined and the ash and carbon material are removed from the effluents, and heat exchanging the aforesaid oxygen stream and steam with the combined CTI effluents prior to charging same to the reaction zones in the aforesaid manner.

6. A process for producing a gaseous mixture cornprising hydrogen and carbon monoxide which comprises supplying pure oxygen for passage upwardly through a mass of finely divided carbon containing solid material in a rst reaction Zone at a velocity effective to suspend the solids in a fiuidized condition, reacting a portion of the carbon containing solids with the oxygen in the first reaction zone at a temperature of about 1800 to about 2000" F. thus producing a product gas containing a major amount of carbon monoxide and a minor amount of less than about 1% carbon dioxide, the reaction conditions in said reaction Zone have an overall exothermic effect such that no external source of heat is necessary to maintain the aforesaid temperature therein, passing steam upwardly through a mass of finely divided carbon containsolid material in a second reaction zone at a velocity effective to suspend said solids in a fiuidized condition, reacting the solids and steam in the second reaction zone at a temperature of about 1300" to about 1700 F. thus producing a major amount of carbon monoxide and hydrogen and a minor amount of carbon dioxide, withdrawing a portion of carbon containing solids from the first reaction zone and passing same to the second reaction zone wherein the reaction conditions produce endothermic heat effects in a quantity sufficient to maintain the temperature therein, passing the effluent comprising carbon monoxide, carbon dioxide and hydrogen from the second reaction Zone to a carbon dioxide absorber in which the carbon dioxide is removed therefrom, recycling the carbon dioxide thus removed to the first reaction Zone for conversion to carbon monoxide, combining the effluent from the second reaction Zone substantially free of carbon dioxide and the effluent comprising carbon monoxide from the first reaction Zone as the product of the process and heat exchanging the aforesaid oxygen stream and steam with the combined effluents prior to charging the same to the reaction Zones in the aforesaid manner.

7. A process for producing a gas of relatively high heat value comprising hydrogen, carbon monoxide and methane from coal which comprises supplying pure oxygen for passage upwardly through a mass of finely divided carbon-containing material in a first reaction Zone at a velocity effective to suspend said coal in a uidized condition, reacting a portion of the carbon with the oxygen in the first reaction zone at a temperature of about l800 to about 2000" F. thus producing a product gas containing a major amount of carbon monoxide and a minor amount of less than about 1% carbon dioxide, the reaction conditions in said first reaction zone have an overall exothermic effect such that no external source of heat is necessary to maintain the aforesaid temperature therein, passing steam upwardly through a mass of finely divided carbon containing material in a second reaction Zone at a velocity effective to suspend said carbon-containing material in a fiuidized condition, reacting the carbon and steam in the second reaction zone at a temperature of about 1300 to about l500 F. thus producing hydrogen, carbon monoxide, methane and carbon dioxide as the principal products of the reaction, withdrawing a portion of finely divided solids from the first reaction zone and passing same to the second reaction zone wherein reaction conditions produce endothermic heat effects in a quantity sufficient to maintain the aforesaid temperature therein, introducing fresh coal into a second reaction zone whereby the volatile components of said coal are distilled, removing an effluent comprising hydrogen, carbon monoxide, methane, carbon dioxide and volatile components of the coal from the second reaction zone, condensing the normally liquid volatile components of the coal from the effluent from the second reaction zone, passing the remainder of the effluent from the second reaction zone substantially free of normally liquid volatile components to a carbon dioxide absorber wherein carbon dioxide is same to the reaction zones in the aforesaid manner.

8. A process for producing a gas of relatively high heating value comprising hydrogen, carbon monoxide and methane from coal which comprises supplying pure oxygen for passage upwardly through a vmass of iinely divided carbon-containing material in a first reaction zone at a velocity effective to suspend the carbon-containing materal in a iluidized condition, reacting a portion of carbon with the oxygen in the first reaction zone at a temperature of about 1800 to about 2000 F. thus producinga product gas containing a major amount of carbon monoxide and a minor amount of less than about 1% carbon dioxide, the reaction conditions in said first reaction zone have an overall exothermic effect so that no external source of heat is necessary to maintain the aforesaid temperature therein, passing steam upwardly through a mass of finely divided carbon-containing reaction zone at a velocity effective to suspend the carboncontaining material in a fluidized condition, reacting the carbon and steam in the second reaction Zone at a temperature of about 1300 to about l500 F. thus producing hydrogen, carbon monoxide, methane and carbon dioxide as the principal products of the reaction, withdrawing a portion of nely divided solids from the rst reaction zone and passing same to the second reaction zone wherein the reaction conditions produce endothermic heat effects in a quantity suiiicient to maintain the aforesaid temperature therein, removing an eliiuent comprising hydrogen, cardioxide from the reaction zone to a carbon dioxide absorber wherein the carbon dioxide is separated from the elluent and recovered, passing the recovered carbon dioxide to the irst reaction zone wherein it is converted to carbon monoxide, and combining the eiliuent comprising hydrogen, methane and carbon monoxide from the second reaction zone substantially free of carbon dioxide with the effluent comprising carbon monoxide from the rst reaction zone as the product of the process and heat exchanging the aforesaid oxygen and steam with the combined efliuents prior to charging the same to the reaction zones in the aforesaid manner.

9. A process for the gasification of coal and the recovery of volatile components therefrom which comprises supplying pure oxygen for passage upwardly through a mass of iinely divided carbon containing solid material in a iirst reaction zone at a velocity effective to suspend the solids therein, reacting a portion of the carbon with the oxygen in the iirst reaction zone at a temperature of about l800 to about 2000 F. suitable for the production of a product gas containing a major amount of carbon action zone have an overall exothermic effect such that no external heat is necessary to maintain the required temperature therein, simultaneously passing steam upwardly through a mass of finely divided carbon containing solid material in a second reaction zone at a velocity effective to suspend the solids therein, reacting steam with part of the carbon material in the second reaction lzone at a temperature of about 1300 to about 1700 F. suitable for producing principally carbon monoxide and hydrogen, passing the eiuent from the second reaction zone upwardly through a mass of iinely divided coal in a ldistillation zone at a velocity eifective to suspend the coal in a iluidized condition, circulating finely divided solids bedistilled, passing finely divided carbon containing material to about 1700 F. oxide and hydroxen as reaction, the reaction conditions in the second reaction tion zone to maintain the solids therein in an aerated iinely divided carbon-containing masame to the reaction zones in the aforesaid manner.

11. A process for producing normally liquid organic compounds from coal which supplying pure oxygen for zone at a temperature of about l800 to about 2000 F. thus producing a product gas containing a major amount of carbon monoxide and a minor amount of less than about 1% carbon dioxide, the reaction conditions in the first reaction zone have an overall exothermic effect such that no external source of heat is necessary to maintain the aforesaid temperature therein, passing steam upwardly through a mass of finely divided carbon-containing material in a second reaction zone at a velocity effective to suspend the finely divided material in a fluidized condition, reacting the steam and carbon in the second reaction zone at a temperature of about 1500 to about 1700 F. thus producing hydrogen and carbon monoxide as the principal products of the reaction, circulating finely divided solid material between said reaction zones to maintain the temperatures therein within the aforesaid ranges, separately removing effluents from said first and second reaction zones containing entrained finely divided ash and unconverted carbon containing material, passing said separate effluents to a common solids separator in which the effluents are combined and ash and carbon containing materials are removed from the eflluents, heat exchanging the aforesaid oxygen and steam with the combined effluents prior to charging the same to the reaction zones in the aforesaid manner, passing said combined effluents after heat exchange with said oxygen and steam to a synthesis reaction zone in which hydrogen and carbon monoxide are converted to normally liquid organic compounds, removing an effluent comprising normally liquid organic compounds, methane and carbon dioxide from said synthesis reaction zone, separating normally liquid organic compounds from the eflluent of said synthesis reaction zone as the product of the process, separating the carbon dioxide from the normally gaseous components of said eluent from said synthesis reaction Zone, passing the carbon dioxide thus separated to the said first reaction zone, and passing normally gaseous components of said effluent from said synthesis reaction zone substantially free from carbon dioxide to said second reaction Zone.

l2. A process for producing normally liquid organic compounds from carbon containing solid materials which comprises supplying pure oxygen for passage through a mass of finely divided carbon containing solid material in a first reaction zone at a velocity effective to suspend the solid material therein, reacting part of the carbon with oxygen in the first reaction zone at a temperature of about 1800 to about 2000 F. thus producing a product gas containing a major amount of carbon monoxide and a minor amount of less than about 1% carbon dioxide, passing steam through a mass of finely divided carbon containing solid material in a second reaction zone at a velocity effective to suspend the carbon material therein, reacting carbon with steam in the second reaction zone at a temperature of about 1500 to about 1700 F. thus producing hydrogen and carbon monoxide as the principal products of the reaction, withdrawing a portion of the finely divided solids from the first reaction zone and passing same to the second reaction zone wherein the reaction conditions produce endothermic heat effects in a quantity sufficient to maintain the desired temperature therein, separately removing effluents from said first and said second reaction zones and combining same, heat exchanging the aforesaid oxygen and steam with the combined effluents prior to passing the same to the reaction zones in the aforesaid manner, passing said combined effluents to a synthesis reaction zone in which hydrogen and carbon monoxide are converted to normally liquid organic compounds, removing an effluent comprising normally liquid organic compounds, methane and carbon dioxide from the effluent of said synthesis reaction zone as a product of the process, separating 'the carbon dioxide from the normally gaseous components of said effluent from said synthesis reaction zone, and passing the carbon dioxide thus separated to said first reaction Zone.

13. A process for producing normally liquid organic compounds from carbon containing solid material which comprises supplying pure oxygen for passage through carbon containing solid material in a first reaction zone, reacting part of the carbon with the oxygen in the first reaction zone at an elevated temperature about 1800 to 2000 F. suitable for producing a product gas containing a major amount of carbon monoxide and a minor amount r. l.. I si prising carbon of less than about 1% carbon dioxide, the reaction conditions in the first reaction Zone are such that an overall exothermic heat effect is produced, passing steam through a mass of carbon containing solid material in a second reaction zone under conditions including a temperature of about 1300" to 1700 F. suitable for producing hydrogen and carbon monoxide as the principal products of the reaction, the reaction conditions in the second reaction zone are such that an overall endothermic heat effect is produced, transferring the exothermic heat produced in the first zone to the second reaction zone by passing finely divided carbon-containing material from the former zone to the latter Zone in order to maintain the desired temperature therein, separately removing eflluents from said first and said second reaction zones and combining same, heat exchanging the oxygen and steam with the combined effluents prior to passing the same to the reaction Zones in the aforesaid manner, passing said combined eflluents to a synthesis reaction Zone in which hydrogen and carbon monoxide are converted to normally liquid organic compounds, removing an effluent comprising normally liquid organic compounds, methane and carbon dioxide from said synthesis reaction Zone, separating normally liquid organic compounds from the effluent of said synthesis reaction zone as a product of the process, and passing normally gaseous components of said effluent containing carbon dioxide from said synthesis reaction Zone to said first reaction zone.

14. A process for producing a gaseous mixture comprising carbon monoxide and hydrogen which comprises supplying pure oxygen for passage upwardly through a mass of ash-producing finely divided carbon containing solid material in a first reaction zone at a velocity effective to suspend the solids in a fluidized condition, reacting a portion of carbon containing solids with oxygen in the first reaction Zone at a temperatui'e of about 1800 to about 2000 F. thus producing a product gas containing a major amount of carbon monoxide and a minor amount of less than about 1% carbon dioxide, the reaction conditions in said first reaction zone have an overall exothermic effect such that no external source of heat is necessary to maintain the aforesaid temperature therein, passing steam upwardly through a mass of ash-producing finely divided carbon containing solid material in a second reaction zone at a velocity effective to suspend the solids in a fluidized condition, reacting the steam and part of the solid material in the second reaction zone at a temperature of about 1300 to about 1700 F. thus producing principally carbon monoxide and hydrogen, withdrawing a portion of solid material from the first reaction zone and passing same to the second reaction zone wherein the reaction conditions produce endothermic effects in a quantity sufficient to maintain the desired temperature in the second reaction zone, withdrawing a portion of finely divided solid material including carbon from the second reaction zone and passing same to a third reaction zone wherein the carbon is reacted with oxygen coritaining gas and completely converted to an effluent commonoxide, carbon dioxide, unreacted oxygen and finely divided ash, the quantity of solid material withdrawn from the second reaction zone and passed to the third reaction zone is suflicient to prevent substantially ash build-up in the system, separating the ash from the eflluent of the third reaction zone and discharging the same from the system, recycling the effluent containing carbon dioxide and substantially free of ash to the first reaction Zone, separately removing effluents from the first and second zones and combining same as the prod-- uct of the process and heat exchanging the aforesaid oxygen and steam with the combined effluents prior to charging the same to the reaction zones in the aforesaid manner.

15. The process of claim 4 wherein fresh coal is charged to the first reaction zone.

2,713,590 21 22 16. The process of claim 4 wherein fresh coal is 2,472,219 Lyons June 7, 1949 charged to the second reaction zone. 2,482,187 Johnson Sept. 20, 1949 2,499,372 DOuville Mar. 7, 1950 References Cited in the file 0f this patent 2,521,195 Wheeler, Jr. Sept. 5, 1950 5 2,560,403 Arveson July 10, 1951 UNITED STATES PATENTS 2,579,398 Roetheli Dec. 18, 1951 1,992,909 DaVS Feb. 26, 1935 2,588,076 Gohr Mar. 4, 1952 2,176,441 Ulrich et al. Oct. 17, 1939 2,436,938 scharmann et a1. Mar. 2, 1948 FOREIGN PATENTS 2,445,327 Keith July 20, 1948 10 582,055 Great Britain Nov. 4, 1946 2,460,508 Johnsofr- Feb. 1, 1949 586,391 Great Britain Mar. 18, 1947

Claims

11. A PROCESS FOR PRODUCING NORMALLY LIQUID ORGANIC COMPOUNDS FROM COAL WHICH COMPRISES SUPPLYING PURE OXYGEN FOR PASSAGE UPWARDLY THROUGH A MASS OF FINELY DIVIDED CARBON-CONTAINING MATERIAL AT A VELOCITY EFFECTIVE TO SUSPEND THE SAME IN A FLUIDIZED CONDITION, REACTING PART OF THE CARBON WITH THE OXYGEN IN THE FIRST REACTION ZONE AT A TEMPERATURE OF ABOUT 1800* TO ABOUT 2000* F. THUS PRODUCING A PRODUCT GAS CONTAINING A MAJOR AMOUNT OF CARBON MONOXIDE AND MINOR AMOUNT O LESS THAN ABOUT 1% CARBON DIOXIDE, THE REACTION CONDITIONS IN THE FIRST REACTION ZONE HAVE AN OVERALL EXOTHERMIC EFFECT SUCH THAT NO EXTERNAL SOURCE OF HEAT IS NECESSARY TO MAINTAIN THE AFORESAID TEMPERATURE THEREIN, PASSING STEAM UPWARDLY THROUGH A MASS OF FINELY DIVIDED CARBON-CONTAINING MATERIAL IN A SECOND REACTION ZONE AT A VELOCITY EFFECTIVE TO SUSPEND THE FINELY DIVIDED MATERIAL IN A FLUIDIZED CONDITION, REACTING THE STEAM AND CARBON IN THE SECOND REACTION ZONE AT A TEMPERATURE OF ABOUT 1500* TO ABOUT 1700* F. THUS PRODUCING HYDROGEN AND CARBON MONOXIDE AS THE PRINCIPAL PRODUCTS OF THE REACTION, CIRCULATING FINELY DIVIDED SOLID MATERIAL BETWEEN SAID REACTION ZONES TO MAINTAIN THE TEMPERATURES THEREIN WITHIN THE AFORESAID RANGES, SEPARATELY REMOVING EFFLUENTS FROM SAID FIRST AND SECOND REACTION ZONES CONTAINING ENTRAINED FINELY DIVIDED ASH AND UNCOVERTED CARBON CONTAINING MATERIAL, PASSING SAID SEPARATE EFFLUENTS TO A COMMON SOLIDS SEPARATOR IN WHICH THE EFFLUENTS ARE COMBINED AND ASH AND CARBON CONTAINING MATERIALS ARE REMOVED FROM THE EFFLUENTS, HEAT EXCHANGING THE AFORESAID OXYGEN AND STEAM WITH THE COMBINED EFFLUENTS PRIOR TO CHARGING THE SAME TO THE REACTION ZONES IN THE AFORESAID MANNER, PASSING SAID COMBINED EFFLUENTS AFTER HEAT EXCHANGE WITH SAID OXYGEN AND STEAM TO A SYNTHESIS REACTION ZONE IN WHICH HYDROGEN AND CARBON MONOXIDE ARE CONVERTED TO NORMALLY LIQUID ORGANIC COMPOUNDS, REMOVING AN EFFLUENT COMPRISING NORMALLY LIQUID ORGANIC COMPOUNDS, METHANE AND CARBON DIOXIDE FROM SAID SYNTHESIS REACTION ZONE, SEPARATING NORMALLY LIQUID ORGANIC COMPOUNDS FROM THE EFFLUENT OF SAID SYNTHESIS REACTION ZONE AS THE PRODUCT OF THE PROCESS, SEPARATING THE CARBON DIOXIDE FROM THE NORMALLY GASEOUS COMPONENTS OF SAID EFFLUENT FROM SAID SYNTHESIS REACTION ZONE, PASSING THE CARBON DIOXIDE THUS SEPARATED TO THE SAID FIRST REACTION ZONE, AND PASSING NORMALLY GASEOUS COMPONENTS OF SAID EFFLUENT FROM SAID SYNTHESIS REACTION ZONE SUBSTANTIALLY FREE FROM CARBON DIOXIDE TO SAID SECOND REACTION ZONE.