GB2058829A - Gasification of carbon- containing materials - Google Patents

Abstract

Carbon-containing materials are gasified to produce synthesis gas, carbon monoxide or a mixture of hydrogen and carbon monoxide, in a three zone unified system (oxidizer, reducer and gasifier) using a solid oxidant (e.g. a metal oxide) as the oxygen and heat source for the gasification with carbon monoxide or steam and carbon monoxide. Synthesis gas contacts the metal oxide prior to the gasification to release the oxygen and convert the synthesis gas to carbon dioxide or steam and carbon dioxide as the gasification medium. <IMAGE>

Description

SPECIFICATION Gasification of carbon-containing materials BACKGROUND OF THE INVENTION This invention relates to the gasification of carbon-containing materials. In one aspect of this invention relates to the treatment of carbon-containing materials, such as coal, coke and hydrocarbons to produce oxides of carbon therefrom. In still another aspect this invention relates to a process for the production of high purity synthesis gas, carbon monoxide or a mixture of hydrogen and carbon monoxide, from carbon-containing materials.

Coal and coke may be treated with oxygen and/or steam at relatively high temperatures to convert the coal or coke to hydrogen and carbon monoxide, which products are useful for various purposes including the synthesis of organic compounds therefrom. When steam is used alone to gasify coal or coke it is necessary to supply heat from an external source. The heat released by gasifying coal with relatively pure oxygen tends to be excessive. As the result, steam and oxygen are normaliy used together in such proportions that the net reaction heat is sufficient to maintain the desired temperatures for the gasification of the coal or coke.In using the combination of steam and oxygen in the above manner the oxygen may be used in a substantially pure form and by such method the process is continuous, thermally efficient, and produces a gas comprising hydrogen and carbon monoxide.

The use of oxygen is an economic burden and increases process complexity. If the oxygen is to be supplied to the process as air rather than as purified oxygen, the economic advantage obtained by using air is obviated by the fact that product gas contains large amounts of diluent nitrogen. It is desirable, therefore, to provide a process which eliminates purification of the oxygen but produces a gas substantially free from nitrogen.

U.S. Patent No. 2,602,809 discloses the gasification of solid carbon-containing materials using metal oxides, such as Fe304 or Fe203, which serve as the principal source of oxygen for the reaction.

The process disclosed employs a counter-current flow of coal and metal oxide in a fluidized state in a reactor for effecting reduction of the metal oxide to release oxygen and effecting oxidation of the coal with the released oxygen to form carbon oxides. The reduced metal oxide is reoxidized for reuse with air whereby it is heated by the heat from the exothermic air oxidation reaction. If a synthesis gas product is desired, a portion of the reduced metal is reoxidized with steam at an elevated temperature to produce hydrogen. This hydrogen is then mixed with the carbon monoxide obtained from the coal gasification to produce the synthesis gas.

SUMMARY This invention provides a unified process for producing high purity synthesis gas from carboncontaining materials. In this process a metal-oxygen containing material is used as the transfer agent of oxygen and heat for oxidatively gasifying carbon-containing material. The metal-oxygen containing material can be characterized as a heat and oxygen carrier and is herein referred to generally as an oxidant. In a major part of this invention steam, carbon dioxide, synthesis gas or mixtures thereof is employed to fluidize and transport the oxidant through an upflow, cocurrent system. Synthesis gas is first oxidized and heated by the oxidant to form carbon dioxide or water and carbon dioxide in an oxidant reducing zone prior to contact of the oxidant and gases with the carbon-containing material in a gasifying zone.The carbon-containing materials are oxidized to predominantly carbon monoxide or carbon monoxide and hydrogen in a manner such that the nitrogen contained in the air does not contaminate the product synthesis gas. The gasification of the carbon-containing materials is accomplished by the alternate oxidation and reduction of a fluidized oxidant. After the gasification, the reduced oxidant which may be in the form of the elemental metal or lower oxidized state is reoxidized in an oxidizing zone and the cycle repeated. As used herein, reduced oxidant refers to either elemental metal or a lower oxidation state resulting from the reduction of the oxidant.

Typical objects of this invention are (1) to provide a process for gasifying carbon-containing materials, (2) to provide a process for converting carbon-containing materials to carbon oxides, (3) to provide a process for the production of a synthesis gas and (4) to provide an improved process for the gasification of carbon-containing materials wherein heated oxidant is at least partially reduced by synthesis gas with the formation of carbon dioxide or steam and carbon dioxide prior to contact with the carbon-containing material and gasification thereof.

Various other objects, aspects and advantages of this invention will become apparent to those skilled in the art from the accompanying description, drawings and appended claims.

According to this invention, a three zone system is employed wherein an oxidant such as iron chromite ore, at an elevated temperature, is fluidized and at least partially reduced by synthesis gas in a reducing zone, with the formation of carbon dioxide or steam and carbon dioxide. The partially-reduced oxidant and associated gases move under fluidized conditions to a gasifying zone where contact with carbon-containing material is made under conditions whereby the carbon-containing material is oxidized to carbon oxides, mainly to carbon monoxide. The gaseous effluent from the gasifying zone is removed for purification and the reduced oxidant is transferred to an oxidizing zone where it is contacted with air under conditions to reoxidize and heat the oxidant.A portion of the heat liberated by the air oxidation is stored as sensible heat in the oxidant which provides heat for the reducing and gasifying zones. The heated oxidation is returned to the reducing zone.

In the preferred method of operation of the various zones, particulate oxidant is maintained fluidized and continuously circulated through the reaction system. Throughout the gasifying zone linear gas velocities are maintained such that the solid materials are entrained in the gases. Gas velocities above about ten (10) feet (3.05 meters) per second are employed for such operation. Actual gas velocities employed will be dependent upon the size, shape and densities of the solid materials employed. In this type of operation, means will be provided internally or externally of the gasifying zone for separating solid materials entrained in the gaseous effluent.

The oxidant usable in the present invention will generally be a particulate material of a size capable of fluidization comprising a metal oxide which is reducible and reoxidizable under the conditions of operation of the system. Various metal oxides and metal oxide-containing materials may be used as the oxidant for providing oxygen to the reducing and gasifying zones. Suitable oxidant materials contain oxides of iron, cobalt, nickel, molybdenum, manganese, barium, vanadium, chromium, copper, cerium, uranium and mixtures thereof. Natural occurring ores, such as iron chromite ore, containing iron oxide may be used as an oxidant.

The temperature employed in the reduction and gasification can vary over a wide range.

Preferably, such reaction will be conducted from 8000 C. to 12000 C. Pressure on the system can also vary. The system can for example be operated under pressures from 5 psig to 2000 psig (34.5 to 13,789 kPa).

As previously indicated, the process of this invention utilizes an upflow fluidized system with the oxidant and carbon-containing material flowing cocurrent. The fluidization and transportation of the materials are obtained by introducing a carrier gas into the system. The carrier gas can be inert to the various reactions, but preferably is steam, carbon dioxide, synthesised gas or mixtures thereof which enters into the reaction and thus eliminates excess gas handling. The carrier gas is introduced at such rates to fluidize and transport the materials and to maintain turbulent flow of the materials in the system. Introduction of the gases at velocities of 10 to 30 ft/sec. (3.05 to 9.14 meters/sec.) will generally be sufficient. However, this variable is dictated by the size, shape and density of the materials moving through the system.

This invention will be more specifically described with reference to the Drawings, of which the single Figure is a diagrammatic illustration of the apparatus in the system described with regard to gasifying coal using a mixture of hydrogen and carbon monoxide synthesis gas.

According to the Figure, fresh oxidant, as needed, from supply 1 is introduced through conduit 2 tc oxidizing zone 3. Air is compressed in compressor 4 and introduced through conduit 5 into the bottom of oxidizer zone 3. Oxidizing zone 3 is maintained under conditions whereby the oxidant is oxidized by oxygen from the air through an exothermic reaction. The exothermic reaction heats the oxidant. The oxidant is transported from the oxidizing zone 3 through conduit 6 into the lower portion of reducing zone 7. Synthesis gas is introduced through conduit 8 into the bottom of reducing zone 7 at such a rated to fluidize and move the oxidant upwardly through the reducing zone 7 into gasifying zone 9. In reducing zone 7 contact of the synthesis gas with the heated oxidant causes reduction of the oxidant and formation of water and carbon dioxide from the synthesis gas.Coal from supply 10 is introduced through conduit 11 to dryer-pulverizer 12 where it is ground to a particle size in the range of 40 to 200 microns and dried to less than 2 percent moisture by contact with the effluent from oxidizing zone 3 introduced through conduit 1 3. Gases from dryer-pulverizer 12 are removed through conduit 14. The dried/pulverized coal is fed through conduit 1 5 into feeder 1 6. Coal is metered from feeder 1 6 through conduit 1 7 and conduit 1 8 into gasifying zone 9. Additional synthesis gas and steam are introduced through conduits 31 and 32 to move the coal into gasifying zone 9.In gasifying zone 9, the coal is oxidized to predominately carbon monoxide and hydrogen through contact and turbulent mixing with the upflowing mixture of heated oxidant and gases from reducing zone 7. The reaction gases and oxidant are separated. Such separation can be accomplished by a cyclone separator positioned in the upper portion of gasifying zone 9. Reduced oxidant is removed from the upper portion of gasifying zone 9 through conduit 1 9 and introduced into reducing zone 3 for reoxidation and reheating. Gaseous effluent is removed from gasifying zone 9 through conduit 20 and introduced to cyclone 21.

Alternatively, the reaction gases and oxidant can be removed together from gasifying zone 9 through conduit 20 and separated in a first cyclone, not shown. In this case, conduit 1 9 would connect with the first cyclone and reducing zone 3 to convey the oxidant and the gaseous effluent would be fed to cyclone 21. In cyclone 21 entrained solids such as ash and fines are separated and removed through conduit 22 for disposal. The gaseous effluent is then fed through conduit 23 into sulfur removal zone 24. Desulfurized gaseous effluent is fed through conduit 25 into gas compressor 26. The desulfurized effluent is fed through conduit 27 to an acid gas removal zone 28 where carbon dioxide is removed through conduit 29 and substantially pure synthesis gas is removed through conduit 30. A portion of the gaseous effluent from sulfur removal zone 24 is fed through conduits 31 and 8 to the reducing zone 7 and through conduits 31 and 18 to transport coal to the gasifying zone 9. As shown in the drawing, heat exchange of the various gas streams may take place. Also, not shown, the solid oxidant and coal may be stripped with a gas such as carbon dioxide between the various zones to remove gases such as nitrogen.

When steam, carbon dioxide or mixtures thereof is to be used, it can be introduced through conduit 32 into conduit 1 8 in place of or in addition with synthesis gas from conduit 31. If steam, carbon dioxide or mixtures thereof is to be used as the sole gas for fluidizing and reducing the oxidant, it will be introduced to reducing zone 7 through conduit 8 in place of synthesis gas from conduit 31.

Various steps and auxiliary operations, such as the dryer-pulverizer 12, feeder 16, compressors 4 and 26, cyclone 21, sulfur removal 24 and acid gas removal 28 are well known standard operations and need not be further described here.

The particle size of the carbon-containing material, if a solid, and oxidant employed in the process of this invention may vary over a wide range. However, the solids will generally be employed in a particle size ranging from 40 to 200 microns.

Any carbon-containing material may be gasified in accordance with this invention. It is particularly useful for gasifying solid carbon-containing materials such as coal, including a broad range of coal from lignites to anthracites, chars, peat, coke, coke breeze, wood chips, kelp and the like. Also, liquid and gaseous hydrocarbons, for example, crude oils whole or fractions such as asphalts and vacuum residuals, shale oil, refined oils such as fuel, cycle, Bunker C and tars, chemical plant streams such as aromatic oils and heavy tars, and tars from the tar sands can be employed as the carbon-containing material as feed for this invention.

EXAMPLES The practice of this invention will now be more fully illustrated in the following Examples.

In the following Examples, the reactor employed for carrying out the particular coal gasification runs comprises a 24-inch (61 cm.) long stainless steel schedule 40 pipe with a 2.05-inch (5.2 cm.) inside diameter main section fitted at the bottom with a 40 degree included angle conical section and at the top with an expanded section with a 2.5-inch (6.4 cm.) inside diameter and 9-1/2 (24.1 cm.) inches long, including conical joining section, capped with a flange. Fluidizing gas is introduced through the bottom of the conical section of the reactor and coal is introduced at a mid-way point of the conical section. Gasifying agents are introduced through a sparger extending from the top of the reactor downward through the fluidized bed and into the conical section. Product gases are removed through the top of the reactor for analysis.The reactor is enclosed in an insulated electric resistance heater.

EXAMPLE 1 This Example illustrates the gasification of various coals using steam as the gasifying agent and iron chromite ore from the Transvaal mines of South Africa as the oxidant.

In each run, the reactor contains 1 200 grams (75 to 350 microns) of oxidant fluidized with nitrogen. The oxidant is maintained at a temperature of 1 0500 C. and a pressure of 5.0 psig (34.5 kPa).

Coal entrained in 3.0 L/min of nitrogen is fed to the reactor along with approximately 3.6 gm/min of water as steam as the gasifying agent. Each run is continued for about 30 minutes with reaction gases periodically sampled and analyzed. The gas velocity at the coal entry is approximately 0.7 ft/sec (0.2 meters/sec) and at the reaction gas outlet is approximately 1.2 ft/sec (0.36 meters/sec). The results for each particular coal tested are given in the following Table 1 where Production is the cubic feet ofgas produced per pound of coal converted, Selectivity is the mole percent of the carbon converted to CO and Productivity is the pounds of carbon converted per hour per cubic foot of oxidant bed.

TABLE 1 COAL FEED RATE RUN COAL (gm/min) A Wyoming Sub-bituminous 3.4 B Texas Lignite 3.9 C Illinois #6 Bituminous 3.7 D Indiana Bituminous 3.4 TABLE 1 (cont.) PRODUCTION PRODUCTIVITY TIME ft /Ib H2/CO SELECTIVITY Ib/hr/ft3 RUN (min) (m3/kg) MOLE RATIO MOLE % (kg/hr./m3) A 4 28.3 (1.77) 0.4 64.8 13.1(209.6) 6 39.3 (2.45) 1.1 73.1 13.7 (2192) 8 52.9 (3.30) 2.0 71.9 12.8 (204.8) 10 44.9(2.8) 1.4 77.7 13.0 (208.0) 15 48.6 (3.03) 1.5 81.9 12.4 (198.4) 20 51.0 (3.18) 1.5 86.0 11.8(188.8) 25 48.9 (3.05) 1.5 82.6 12.6 (201.6) 30 49.4 (3.08) 1.6 81.1 12.5 (200.0) B 4 26.9 (1.68) 0.8 63.8 14.5 (232.0) 6 34.9 (2.18) 1.2 80.0 13.3 (212.8) 8 35.7 (2.23) 1.2 81.1 14.5 (232.0) 10 35.9 (2.24) 1.2 82.5 14.6 (233.6) 15 36.8 (2.30) 1.3 83.8 14.4 (230.4) 20 37.1 (2.32) 1.3 83.8 14.1(225.6) 25 37.0(2.31) 1.3 83.8 14.1(225.6) 30 37.2 (2.32) 1.3 84.4 14.0 (224.0) C 4 21.4(1.34) 0.6 16.8 9.6 (153.6) 6 30.8(1.92) 1.0 61.3 10.0 (160.0) 8 39.5 (2.46) 1.5 71.6 9.8 (156.8) 10 44.3 (2.76) 1.6 75.0 9.4 (150.4) 15 46.5(2.90) 1.6 76.9 9.1 (145.6) 20 43.9 (2.74) 1.6 78.5 10.2(163.2) 25 43.4 (2.71) 1.6 79.2 10.5 (168.0) 30 43.8 (2.73) 1.6 81.3 10.0(160.0) D 8 1.8 75.5 9.9(153.4) 10 - 1.8 76.4 9.9 (158.4) 15 - 1.9 76.7 10.3(164.8) 20 1.8 79.0 10.6(169.6) 25 1.8 79.5 11.0(176.0) 30 1.8 78.5 11.0(176.0) EXAMPLE 2 This Example illustrates the gasification of coal in the presence of an inert heat carrier and thus the improvement of using an oxidant when the results of this Example are compared with those of Run A of Example 1.

Example 1, Run A is followed except the reactor contains 1,000 grams of alpha alumina oxide instead of an oxidant. The Wyoming sub-bituminous coal at 3.5 gm/min and 3.7 gm/min of water as steam are fed.

PRODUCTION PRODUCTIVITY TIME ft3/Ib HJCO SELECTIVITY Ib/hr/ft3 (min) (m3/kg) MOLE RATIO MOLE % (kg/hr./m3) 4 37.9 (2.36) 1.6 71.9 10.2 (163.2) 6 47.8 (2.98) 1.6 73.5 11.8 (188.8) 8 48.5(3.03) 1.6 73.7 12.1(193.6) 10 47.2 (2.95) 1.6 73.5 11.9(190.4) 15 46.4(2.90) 1.6 74.0 12.1(193.6) 20 45.9 (2.86') 1.6 75.2 11.7 (187.2) 25 45.5 (2.84) 1.6 74.3 11.6(185.6) 30 45.4(2.83) 1.6 75.4 11.5 (184.0) EXAMPLE 3 This Example illustrates the gasification of coal using steam and CO2 as the gasifying agent as opposed to steam alone as shown in Example 1.

Example 1 Runs A and B are followed except that, as gasifying agent, 1.8 gm/min of water as steam and 2.24 L/min of CO2 are fed.

PRODUCTION PRODUCTIVITY TIME ft3lb H/CO SELECTIVITY Ib/hr/ft3 RUN (min) (m3/kg) MOLE RATIO MOLE % (kg/hr/m3) A 4 42.4 (2.65) 0.4 74.6 14.3 (228.8) 6 45.3 (2.83) 0.5 80.2 13.8 (220.8) 8 46.6 (2.91) 0.6 82.2 13.2 (211.2) 10 48.4 (3.02) 0.6 83.0 13.4 (214.4) 15 46.5 (2.90) 0.6 82.5 13.7 (219.2) 20 47.8 (z98) 0.2 82.5 14.3 (288.8) 25 47.3 (2.95) 0.1 82.6 14.1 (225.6) 30 47.0(2.93) 0.1 83.8 14.1 (225.6) B 4 0.5 83.1 14.5 (232.0) 6 0.5 83.4 14.5 (232.0) 8 0.5 83.0 14.3 (228.8) 10 - 0.5 85.4 14.7 (235.2) 15 - 0.5 85.2 15.0 (240.0) 20 0.1 84.6 15.1(241.6) 25 0.1 84.6 15.2 (243.2) 30 0.1 84.9 15.2 (243.2) EXAMPLE 4 This Example illustrates the gasification of coal with repeated reoxidations of iron chromite ore as the oxidant.

The reactor is charged with 1200 grams of oxidant and heated to 105000. 3.6 gm/min of Wyoming sub-bituminous coal entrained in 3.0 L/min of nitrogen together with 3.5 gm/min steam are fed to the reactor for 20 minutes during which time the reaction gases are sampled and analyzed. The reactor is purged with steam and nitrogen. Air is fed to the reactor for 30 minutes to reoxidize the oxidant. Coal, nitrogen and steam in the same quantities are again fed to the reactor for 30 minutes with the reaction gases sampled and analyzed. Again, the reactor was purged with steam and nitrogen and air fed for 30 minutes to again reoxidize the oxidant Again, coal, nitrogen and steam in the same quantities are fed to the reactor with the reaction gases sampled and analyzed. The results are shown in the following Table 4.

PRODUCTION PRODUCTIVITY TIME ft3/Ib HzCO SELECTIVITY Ib/hr/ft3 RUN (min) (m3/kg) MOLE RATIO MOLE % (kg/hr/m3) 1 18 14.3 (0.89) 1.7 78.6 14.3 (228.8) 20 13.2 (0.82) 1.8 79.0 13.2 (211.2) 2 20 15.8 (0.99) 1.4 79.9 15.8 (252.8) 30 15.7 (0.98) 1.4 83.1 15.7 (251.2) 3 20 11.8(0.74) 1.5 86.0 11.8 (188.8) 30 12.5 (0.78) 1.6 81.1 12.5 (200.0) EXAMPLE 5 This Example illustrates the reduction of oxidant with a gaseous fluid in the absence of coal.

The reactor is filled with 11 60 grams of iron chromite ore and maintained at 10500 C. and 5 psig.

A mixture of 3.65 L/min of H2 and 3.50 L/min of CO is fed to the reactor. Product gases and oxidant are sampled and analyzed at 1 minute intervals. The results are as follows: PRODUCT GAS, MOLE % TIME OXIDANT OXIDATION (min) CO2 CO H2 H20* O/FE 0 - - - - 1.50 1 48.7 4.0 0.3 47.1 1.42 2 45.8 4.3 1.1 48.9 1.34 3 41.1 8.1 2.3 48.6 1.27 4 26.4 22.5 9.4 41.8 1.22 5 14.6 33.6 25.4 26.5 1.19 6 12.4 35.3 30.6 21.7 1.16 7 11.5 37.9 33.4 17.2 1.14 8 6.7 40.9 38.7 13.7 1.12 9 4.7 45.1 42.0 8.4 1.11 * as steam EXAMPLE 6 This Example illustrates the reoxidation of the reduced oxidant obtained in Example 5.

Air fed at 7.2 Limin to the reactor containing the 1160 grams of reduced iron chromite ore maintained at 1050"0 and at 5 psig (34.5 kPa). Reactor gases and oxidant are periodically sampled and analyzed. The results are as follows: AIR, MOLE % TIME OXIDANT OXIDATION (min) - 2 N2 O/Fe 0 1.20 1 1.4 98.6 1.22 5 1.5 98.5 1.34 7 6.5 93.5 1.39 9 12.4 87.6 1.41 11 16.1 83.9 1.43 19 18.4 81.6 1.46 21 18.8 81.2 1.46 EXAMPLE 7 This Example illustrates the gasification of coal using steam, CO2 and steam and CO2, as gasifying agents.

Example 1 Run A is followed except that, as the gasifying agent, in Run A 1.8 gm/min of water as steam and 2.24 L/min cf CO2 is fed, in Run B 3.6 gm/min of water as steam is fed and in Run C 4.48 L/min CO2 is fed. The results of analyses of product gas periodic samples are as follows: PRODUCTION PRODUCTIVITY TIME ft3lb H2/CO SELECTIVITY Ib/hr/ft3 RUN (min) (m3/kg) MOLE RATIO MOLE % (kg/hr/m3) B 5 46.3 (2.89) 1.4 79.9 12.3 (196.8) 10 46.6(2.91) 1.4 81.0 12.0(192.0) 15 46.9(2.93) 1.4 83.1 12.4(198.4) A 5 58.4 (3.02) 0.6 83.0 13.4 (214.4) 10 46.5 (2.90) 0.6 82.5 13.7 (219.2) C 5 47.8 (2.98) 0.2 82.5 14.3 (228.8) 10 47.3 (2.95) 0.1 82.6 14.1(225.6) EXAMPLE 8 This Example illustrates the advantages of this invention in pre-reduction of the oxidant in gasification product distribution.

Example 1, Run A is repeated in a 30-minute run with periodic analysis of the reaction gas composition and oxidant oxidation. The results are as follows: TIME OXIDANT OXIDATION CO2 CH4 CO H2 (min) O/Fe MOLE % 0 1.5 2 1.3 79.2 1.8 14.2 4.8 4 1.2 28.9 2.4 49.5 20.1 6 1.1 13.1 1.7 40.2 45.2 8 1.1 10.1 1.5 29.4 59.0 10 1.0 9.3 1.5 37.4 51.8 20 0.9 5.8 1.8 36.4 56.0 30 0.8 6.3 2.0 35.5 56.2 EXAMPLE 9 This Example with reference to the drawing illustrates the continuous gasification of coal according to this invention. Iron chromite ore is circulated at the rate of 1 90 gm/min through the oxidizing zone 3, conduit 6, reducing zone 7, gasifying zone 9 and conduit 19.The ore-containing FeO entering oxidizing zone 3 through conduit 19 is contacted with air fed to the bottom of the oxidizing zone 3 at the rate of 11.2 L/min and 8.9 L/min of nitrogen is withdrawn from the top of oxidizing zone 3 through conduit 13. The exothermic oxidation taking place in oxidizer 3 provides 65.8 kcal/mole of FeO oxidized and heats the ore to 1 500C. and oxidizes the FeO to Fe203. The ore-containing Fe203 is removed from oxidizer 3 through conduit 6 and introduced into reducing zone 7. Synthesis gas composed of equal volumes of H2 and CO is fed through conduit 8 into reducing zone 7 at the rate of 4.48 L/min. The Fe203 is reduced by the synthesis gas producing steam and CO2. The reduction is endothermic and requires 4.6 kcal/mole of Fe203 reduced whereby the temperature in reducing zone 7 is 1 1250C. The reduced ore and gases flow into gasifying zone 9 to which 3.4 gm/min of finely divided coal is introduced through conduit 1 8. The gasification of the coal with the ore and steam and CO2 is endothermic and requires 36.2 kcal/mole whereby the temperature in gasifying zone 9 is 1 0250C. The reduced ore-containing FeO is withdrawn from gasifying zone 9 and introduced through conduit 1 9 again into oxidizing zone 3. The gasifying zone 9 effluent is removed through conduit 20 at the rate of 10.311min and contains 10 mole percent CO2, 1 mole percent CH4, 54 mole percent CO and 35 mole percent H2.As used in this Example and invention, FeO means a mixture of iron oxides having an average oxygen to iron ratio about 1.0 to 1.2 and FeO203 means a mixture of iron oxides having an average oxygen to iron ratio of 1.4 to 1.6.

EXAMPLE 10 This Example illustrates the continuous gasification of No. 6 Fuel Oil according to this invention.

Example 9 is repeated using 2.8 gm/min No. 6 Fuel Oil as the feed in place of the 3.4 gm/min coal.

Iron chromite ore is circulated at the rate of 200 gm/min instead of 1 90 gm/min and the gasification reaction requires 48 kcal/mole instead of 36.2 kcal/mole. The effluent from the gasifying zone 9 is removed at the rate of 12.1 L/min instead of 10.3 L/min and contains 1 3 mole percent CO2, 1 mole percent CH4, 42 mole percent CO and 44 mole percent H2.

In Example 11, the reactor employed for carrying out the particular gasification runs comprises a 19-3/4-inch (48.3 cm) long stainless steel schedule 40 pipe with a 1.61-inch (4.1 cm) inside diameter main section fitted at the bottom with a conical section of Type 310 stainless steel 1-1/4(3.2cm) inch long and tapering to 1/4 inch (0.63 cm) diameter capped at the top with a flange. Fluidizing gas and carbon-containing material is introduced through the bottom of the conical section of the reactor.

Product gases are removed through the top of the reactor for analysis. The reactor is enclosed in an insulated electric resistance heater.

EXAMPLE 11 This Example illustrates the gasification of various carbon-containing materials using carbon monoxide as the gasifying agent and iron chromite ore from the Transvaal mines of South Africa as the oxidant.

In each run, the reactor contains 580 grams (75 to 350 microns) of oxidant fluidized with nitrogen. The oxidant is maintained at a temperature of 10500 C. The carbon-containing material is fed to the reactor along with approximately 1.5 L/min of carbon dioxide as the gasifying agent. Each run is continued for about 1 5 minutes with reaction gases periodically sampled and analyzed. The gas velocity in the reactor is approximately 0.3 ft/sec and the gas/solid contact time is approximately 1.9 sec. The results for each particular material tested are given in the following Table 2 where Production is the cubic feet of gas produced per pound of material converted.

TABLE 2 FEED RATE RUN CARBON MATERIAL (gm/min) A Kentucky Coal Char 1.06 (75.8 wt.% carbon - 1.2 wt.% Hydrogen) B U.S. Steel Clean Coke 1.005 (83.5 wt.% carbon - 1.4 wt.% Hydrogen) TABLE 2 (cont.) PRODUCTION TIME ft3/lb PRODUCT MOLE % CARBON CONVERSION RUN (min) (mp7kg) CO CO2 MOLE % A 1 - 0.46 99.54 29.8 3 9.6 (.60) 6.88 93.12 55.8 5 9.7 (.61) 6.56 93.44 52.2 7 8.8 (.55) 10.11 89.31 44.7 9 9.3 (.58) 32.99 67.01 41.0 11 9.3 (.58) 42.99 50.71 37.3 13 10.4 (.65) 51.58 47.75 41.0 B 1 - 0.55 99.45 15.8 3 8.8 (.55) 3.41 96.59 25.0 5 9.5 (.59) 4.64 95.36 46.5 7 9.2 (.57) 5.83 93::78 50.1 9 7.6 (.47) 33.85 66.15 55.0 11 7.9 (.49) 45.22 54.78 50.0 13 11.5(.72) 51.44 48.27 39.3 15 10.3 (.64) 57.50 42.50 35.8 After removal of CO2, the product gases in Run A contained 93% CO and 7% H2 and in Run B 95% CO and 5% H2.

EXAMPLE 12 This Example with reference to the drawing illustrates the continuous gasification of coal char according to this invention. Iron chromite ore is circulated at the rate of 1 90 gm/min through the oxidizing zone 3, conduit 6, reducing zone 7, gasifying zone 9 and conduit 19. The ore-containing FeO entering oxidizing zone 3 through conduit 19 is contacted with air fed to the bottom of the oxidizing zone 3 at the rate of 11.2 L/min and 8.9 L/min of nitrogen is withdrawn from the top of oxidizing zone 3 through conduit 13. The exothermic oxidation taking place in oxidizer 3 provides 65.8 kcal/mole of FeO oxidized and heats the ore to 1 1 50"0. and oxidizes the FeO to Fe203. The ore-containing Fe203 is removed from oxidizer 3 through conduit 6 and introduced into reducing zone 7.Carbon monoxide is fed through conduit 8 into reducing zone 7 at the rate of 4.48 L/min. The Fe203 is reduced by the carbon monoxide producting CO2. The reduction is approximately thermoneutral whereby the temperature in reducing zone 7 is 11 350C. The reduced ore and gases flow into gasifying zone 9 to which 2.94 gm/min of finely divided Illinois &num;6 coal char is introduced through conduit 18. The gasification of the coal char with the ore and CO2 is endothermic and requires 40.0 kcal/mole whereby the temperature in gasifying zone 9 is 1 0250C. The reduced ore-containing FeO is withdrawn from gasifying zone 9 and introduced through conduit 19 again into oxidizing zone 3. The gasifying zone 9 effluent is removed through conduit 20 at the rate of 9 Vmin and contains 15 mole percent CO2, 84.8 mole percent CO and 0.2 mole percent H2. As used in this Example and invention, FeO means a mixture of iron oxides having an average oxygen to iron ratio of 1.0 to 1.2 and Fe203 means a mixture of iron oxides having an average oxygen to iron ratio of 1.4 to 1.6.

Stainless Steels referred to herein Stainless steels Schedule 40 and Type 310 are alloys having the following compositions by weight: Schedule 40 Type 310 Carbon 0.5% Carbon 0.5% Manganese 1.5% Manganese 1.5% Silicon 1.25% Silicon 0.5% Chromium 19% Chromium 25% Nickel 35% Nickel 20% Iron -- Balance to 100% Iron - Balance to 100%

Claims (13)

1. A continuous process for the gasification of carbon-containing materials in a fluidization system comprising a reduction zone and a gasification zone characterized by: (a) introducing particulate solid oxidant at an elevated temperature into said reduction zone, (b) introducing carrier gas substantially devoid of free oxygen into said reduction zone at such a rate to fluidize said oxidant and cause it to move upwardly through said system, (c) maintaining said reduction zone under conditions such that said oxidant is reduced and said carrier gas is oxidized to carbon dioxide or a mixture of gaseous water and carbon dioxide, (d) introducing carbon-containing material into said gasification zone whereby said carbon containing material is entrained in and mixed with said upward moving oxidant and carbon dioxide or mixture of gaseous water and carbon dioxide, (e) maintaining said gasification zone under conditions such that said carbon-containing material and carbon dioxide or mixture of steam and carbon dioxide are endothermically reacted to carbon monoxide or a mixture of carbon monoxide and hydrogen, and (f) withdrawing a gaseous effluent comprising carbon monoxide or carbon monoxide and hydrogen from said gasification zone.

2. A process of Claim 1, in which in step (c) said carrier gas is oxidized to carbon dioxide, in step (d) said carbon-containing material is entrained in and mixed with said upward moving oxidant and gaseous CO2, in step (e) said carbon-containing material and carbon dioxide are endothermically reacted to carbon monoxide, and in step (f) a gaseous effluent comprising carbon monoxide is withdrawn from said gasification zone.

3. A process of Claim 1, in which in step (c) said carrier gas is oxidized to gaseous water and carbon dioxide, in step (d) said carbonaceous material is injected into and mixed with said upward moving oxidant, gaseous H20 and CO2, in step (e) said carbon-containing material, steam and carbon dioxide are endothermically reacted to a mixture of carbon monoxide and hydrogen, and in step (f) a gaseous effluent comprising carbon monoxide and hydrogen is withdrawn from said gasification zone.

4. The process of Claim 1 characterized in that said carbon-containing material is selected from coal char, coal, coke, peat or oil.

5. A process of any of Claims 1 to 4, in which said oxidant is a natural or synthetic metal-oxidecontaining material.

6. A process of Claim 5, in which said material is iron chromite ore.

7. A process of Claim 6, in which said material contains iron oxide, copper oxide, cobalt oxide, cerium oxide or manganese oxide.

8. A process of any of the preceding claims, in which the temperatures maintained in said reduction and gasification zones are from 8000 C. to 12000 C.

9. A process of Claim 1, in which said carrier gas is carbon monoxide.

10. A process of any of the preceding claims, in which the superficial gas velocity in the reduction and gasification zones is above 3 meters per second.

11. A continuous process for the gasification of low-hydrogen-containing carbon-containing materials in a fluidization system comprising a reduction zone and a gasification zone and an associated oxidation zone characterized by: (a) introducing particulate solid oxidant at an elevated temperature into said reduction zone, (b) introducing carrier gas substantially devoid of free oxygen into said reduction zone at such a rate to fluidize said oxidant and cause it to move upwardly through said system, (c) maintaining said reduction zone under conditions such that said oxidant is reduced and said carrier gas is oxidized to gaseous carbon dioxide, (d) introducing carbon-containing material into said gasification zone whereby said carbon containing material is entrained in and mixed with said upward moving oxidant and CO2, (e) maintaining said gasification zone under conditions such that carbon-containing material and carbon dioxide are endothermically reacted to carbon monoxide, (f) withdrawing a gaseous effluent comprising carbon monoxide from said gasification zone, (g) withdrawing from said gasification zone and introducing into said oxidation zone said reduced oxidant, (h) introducing an oxidizing gas into said oxidation zone, (i) maintaining said oxidation zone under exothermic conditions such that said oxidant is reoxidized to a higher oxidized state and reheated to an elevated temperature sufficient to effect oxidation of said carrier gas and gasification of said carbon-containing material, and ~ (j) withdrawing from said oxidation zone and introducing into said reduction zone said reoxidized heated oxidant.

12. A continuous process for the gasification of carbon-containing materials in a fluidization system comprising a reduction zone and a gasification zone and an associated oxidation zone characterized by: (a) introducing particulate solid oxidant at an elevated temperature into said reduction zone, (b) introducing carrier gas substantially devoid of free oxygen into said reduction zone at such a rate to fluidize said oxidant and cause it to move upwardly through said system.

(c) maintaining said reduction zone under conditions such that said oxidant is reduced and said carrier gas is oxidized to gaseous water and carbon dioxide, (d) introducing carbon-containing material and steam into said gasification zone whereby said carbon-containing material is injected into and mixed with said upward moving oxidant, gaseous H20 and CO2, (e) maintaining such gasification zone under conditions such that said carbon-containing material, steam and carbon dioxide are endothermically reacted to a mixture of carbon monoxide and hydrogen, (f) withdrawing a gaseous effluent comprising carbon monoxide and hydrogen from said gasification zone, (g) withdrawing from said gasification zone and introducing into said oxidation zone said reduced oxidant, (h) introducing an oxidizing gas into said oxidation zone, (i) maintaining said oxidation zone under exothermic conditions such that said oxidant is reoxidized to an oxidized state and reheated to an elevated temperature sufficient to effect oxidation of said carrier gas and gasification of said carbon-containing material, and (j) withdrawing from said oxidation zone and introducing into said reduction zone said reoxidized heated oxidant.

13. A process according to Claim 1 substantially as described. in the Examples.