Process for production of synthesis gas

• US 4,017,271 A
• Filed: 06/19/1975
• Issued: 04/12/1977
• Est. Priority Date: 06/19/1975
• Status: Expired due to Term

• Current Assignee: Rockwell International Corporation
• Original Assignee: Rockwell International Corporation
• Inventors: Parkins, William E., Barclay, Kenneth M., Birk, James R.
• Primary Examiner(s): Lindsay, Jr., Robert L.
• Assistant Examiner(s): Yeung, George C.
• Application Number:
  US05/588,563
• Time in Patent Office: 663 Days
• Field of Search: 48/203, 48/210, 48/197 R, 260/449 M, 252/373, 423/415, 423/244, 110/1 J
• US Class Current: 48/197.00R
• CPC Class Codes: C01B 2203/0283 containing a CO-shift step, i.e. a water gas shift step
• CPC Class Codes: C01B 2203/0415 Purification by absorption in liquids
• CPC Class Codes: C01B 2203/0475 the impurity being carbon dioxide
• CPC Class Codes: C01B 2203/84 Energy production
• CPC Class Codes: C10G 19/00 Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
• CPC Class Codes: C10J 2300/093 Coal
• CPC Class Codes: C10J 2300/0943 Coke
• CPC Class Codes: C10J 2300/0946 Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
• CPC Class Codes: C10J 2300/0956 Air or oxygen enriched air
• CPC Class Codes: C10J 2300/0959 Oxygen
• CPC Class Codes: C10J 2300/0969 Carbon dioxide
• CPC Class Codes: C10J 2300/0976 as steam
• CPC Class Codes: C10J 2300/0986 Catalysts
• CPC Class Codes: C10J 2300/1662 to methane
• CPC Class Codes: C10J 2300/1671 with the production of electricity
• CPC Class Codes: C10J 2300/1815 for carbon dioxide
• CPC Class Codes: C10J 2300/1846 Partial oxidation, i.e. injection of air or oxygen only
• CPC Class Codes: C10J 3/57 Gasification using molten salts or metals C10J3/02, C10J3/46 take precedence
• CPC Class Codes: C10J 3/78 High-pressure apparatus
• CPC Class Codes: C10J 3/84 with means for removing dust or tar from the gas

Abstract

A process for the production of a synthesis gas, capable of being upgraded to a high BTU pipeline gas, by the partial oxidation and substantially complete gasification of a carbonaceous material under CO-promoting conditions wherein the carbonaceous material, oxygen, and recycled carbon dioxide from the process are introduced into a molten salt containing an alkali metal carbonate and a minor portion of an alkali metal sulfide, the system being operated at a selected temperature and pressure between 1400° and 2000° F and between 1 and 100 atmospheres. The molar ratio of carbon dioxide to oxygen employed is controlled at from about 0.6:1 to about 1.2:1 to control the CO production and also to maintain the molten salt at a desired operating temperature. Sulfur and ash introduced with the fuel are retained in the molten salt. The gaseous effluent, containing a molar ratio of carbon monoxide to carbon dioxide substantially greater than one, is reacted in a water gas shift reaction, followed by removal of the carbon dioxide present in the gaseous effluent from the shift reaction to produce the synthesis gas, capable of being reacted further under appropriate conditions to produce pipeline gas, methanol, ammonia, or gasoline. At least a portion of the removed carbon dioxide is recycled for admixture with the oxygen to form the feed gas to the molten salt containing the carbonaceous material.

Claims

1. A process for producing a synthesis gas capable of being upgraded to a pipeline gas, which process comprises:

providing a reaction zone containing a molten salt consisting essentially of a major portion of sodium carbonate and a minor portion of at least 1 wt.% of sodium sulfide, said molten salt containing carbon in an amount of about 1 to 10% by weight of the molten salt and having a total solids concentration of less than about 25 wt.%,

maintaining said molten salt at a temperature between about 1400° and

2000°

F,

introducing a sulfur-containing carbonaceous material, substanially pure oxygen, and recycled carbon dioxide from the process into said molten salt reaction zone, said substantially pure oxygen and carbon dioxide being introduced in an amount sufficient to provide about 0.6 to about 1.2 mole of carbon dioxide per mole of oxygen,

controlling the foregoing conditions without the introduction of steam to promote CO production and decompose said carbonaceous material, whereby the sulfur component of the carbonaceous material is retained in the molten salt, the reaction being carried out at a pressure between 1 and 100 atmospheres,

obtaining from said reaction zone an initial gaseous effluent containing carbon monoxide, hydrogen, hydrocarbons and carbon dioxide, and being essentially free of sulfur-containing pollutants,

subjecting said gaseous effluent to a water gas shift reaction,

recovering a resultant gaseous mixture of carbon dioxide, carbon monoxide and hydrogen from said shift reaction,

removing the carbon dioxide from said resultant gaseous mixture,

recycling a portion of said carbon dioxide for introduction thereof into said molten salt reaction zone, and

separately recovering from the carbon dioxide removal process a substantially carbon-doxide-free synthesis gas capable of being upgraded to a pipeline gas.

2. A process as defined in claim 1, wherein said ratio of carbon dioxide to oxygen is between about 0.8 and about 1.1 mole of carbon dioxide per mole of oxygen.

3. A process as defined in claim 2, wherein said molten salt contains carbon in an amount of about 3.5 to about 7.5% by weight of the melt composition.

4. A process as defined in claim 3, wherein the molar ratio of carbon monoxide to carbon dioxide in said initial gaseous effluent is at least 9:

1.

5. The process as defined in claim 2, wherein said temperature is between about 1600°

and about 1800°

F.

6. The process as defined in claim 1, wherein said carbonaceous material is selected from the group consisting of coal, coke, fuel oil, petroleum crude, petroleum residue, lignite and peat.

7. The process as defined in claim 1, wherein said carbonaceous material is coal, said process is carried out at a pressure between about 5 and about 30 atmospheres, and said initial gaseous effluent contains carbon monoxide, hydrogen and hydrocarbons as principal combustible components, together with carbon dioxide.

8. The process as defined in claim 7, wherein said molten salt is at a temperature between about 1600°

and about 2000°

F.

9. The process as defined in claim 1, wherein said water gas shift reaction is carried out so that the molar ratio of hydrogen to carbon monoxide in said gaseous mixture from said water gas shift reaction is about 3:

1, and wherein, following said removal of carbon dioxide from said gas mixture, the resultant synthesis gas has a molar ratio of hydrogen to carbon monoxide of about 3;

1 and is subjected to methanation, and wherein a pipeline gas consisting essentially of methane is recovered.

10. A process as defined in claim 1, wherein said water gas shift reaction is carried out so that the molar ratio of hydrogen to carbon monoxide in said gaseous mixture from said water gas shift reaction is about 2:

1, and wherein, following said removal of carbon dioxide from said gaseous mixture, the resultant synthesis gas has a molar ratio of hydrogen to carbon monoxide of about 2;

1 and is subjected to catalytic synthesis for production of methanol.

11. The process as defined in claim 8, wherein said molten salt contains carbon in an amount of about 3:

5 to about 7.5% by weight of the melt composition, and the molar ratio of carbon monoxide to carbon dioxide in said initial gaseous effluent is at least 9;

1.

12. A process for producing a pipeline gas which comprises providing a reaction zone containing a molten salt consisting essentially of sodium carbonate containing from about 1 to about 25 wt.% sodium sulfide, said molten salt containing carbon in an amount of about 3.5 to 7.5% by weight of the molten salt and having a total solids concentration of less than about 25 wt.%,

maintaining said molten salt at a temperature between about 1600°

and about 1800°

F,

introducing a sulfur-containing coal and a mixture of pure oxygen and recycled carbon dioxide from the process into said molten salt reaction zone, said mixture of oxygen and carbon dioxide consisting of about 0.8 to about 1 mole of carbon dioxide per mole of oxygen,

controlling the foregoing conditions without the introduction of steam to promote CO production and decompose said coal, the reaction being carried out at a pressure between 5 and 30 atmospheres whereby the sulfur component of the coal is retained in the molten salt,

obtaining from said reaction zone an initial gaseous effluent principally containing carbon monoxide, and also containing hydrogen, hydrocarbons and carbon dioxide, the molar ratio of carbon monoxide to carbon dioxide in said gaseous effluent being at least 9;

1, said gaseous effluent having a BTU content of from about 250 to 325 BTU/scf and being essentially free of sulfur-containing pollutants,

sugjecting said gaseous effluent to a water gas shift reaction carried out to provide a molar ratio of hydrogen to carbon monoxide in the resultant gaseous mixture from said water gas shift reaction of about 3;

1,

recovering said resultant gaseous mixture containing carbon dioxide, carbon monoxide and hydrogen,

removing carbon dioxide from said last-mentioned mixture,

recycling a portion of said carbon dioxide for admixture with oxygen prior to introduction thereof into said molten salt,

subjecting the remaining synthesis gas mixture of hydrogen and carbon monoxide in a molar proportion of about 3;

1 to methanation, and

recovering a pipeline gas consisting essentially of methane.