Method for converting biomass into fischer-tropsch products with carbon dioxide recycling

• US 10,214,418 B2
• Filed: 10/25/2017
• Issued: 02/26/2019
• Est. Priority Date: 09/27/2011
• Status: Active Grant

• Current Assignee: Thermochem Recovery International, Inc.
• Original Assignee: Thermochem Recovery International, Inc.
• Inventors: Chandran, Ravi, Leo, Daniel Michael, Freitas, Shawn Robert, Newport, Dave G., Whitney, Hamilton Sean Michael, Burciaga, Daniel A.
• Primary Examiner(s): Call, Douglas B
• Application Number:
  US15/793,252
• Publication Number:
  US 20180050909A1
• Time in Patent Office: 489 Days
• Field of Search: 252373
• CPC Class Codes: B01D 17/0208 by sedimentation
• CPC Class Codes: B01D 2252/102 Ammonia
• CPC Class Codes: B01D 2252/103 Water
• CPC Class Codes: B01D 2252/20436 Cyclic amines
• CPC Class Codes: B01D 2252/504 Mixtures of two or more absorbents
• CPC Class Codes: B01D 2252/602 Activators, promoting agents, catalytic agents or enzymes
• CPC Class Codes: B01D 2256/16 Hydrogen
• CPC Class Codes: B01D 2256/20 Carbon monoxide
• CPC Class Codes: B01D 2257/304 Hydrogen sulfide
• CPC Class Codes: B01D 2257/306 Organic sulfur compounds, e.g. mercaptans
• CPC Class Codes: B01D 2257/406 Ammonia
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 2257/60 Heavy metals or heavy metal compounds
• CPC Class Codes: B01D 2257/708 Volatile organic compounds V.O.C.'s
• CPC Class Codes: B01D 2259/402 using two beds
• CPC Class Codes: B01D 29/27 Filter bags
• CPC Class Codes: B01D 29/66 by flushing, e.g. counter-current air-bumps
• CPC Class Codes: B01D 46/0036 by adsorption or absorption
• CPC Class Codes: B01D 47/10 Venturi scrubbers
• CPC Class Codes: B01D 5/0027 by direct contact between vapours or gases and the cooling medium
• CPC Class Codes: B01D 5/006 : with evaporation or distillation
• CPC Class Codes: B01D 5/0072 : with filtration
• CPC Class Codes: B01D 5/0075 : with heat exchanging B01D5/0039 takes precedence
• CPC Class Codes: B01D 5/009 : Collecting, removing and/or treatment of the condensate
• CPC Class Codes: B01D 50/60 : Combinations of devices covered by groups B01D46/00 and B01D47/00
• CPC Class Codes: B01D 53/0423 : Beds in columns
• CPC Class Codes: B01D 53/0462 : Temperature swing adsorption
• CPC Class Codes: B01D 53/047 : Pressure swing adsorption
• CPC Class Codes: B01D 53/0476 : Vacuum pressure swing adsorption
• CPC Class Codes: B01D 53/12 : according to the "fluidised technique"
• CPC Class Codes: B01D 53/1406 : Multiple stage absorption
• CPC Class Codes: B01D 53/1412 : Controlling the absorption process
• CPC Class Codes: B01D 53/1431 : Pretreatment by other processes
• CPC Class Codes: B01D 53/1462 : Removing mixtures of hydrogen sulfide and carbon dioxide
• CPC Class Codes: B01D 53/1468 : Removing hydrogen sulfide
• CPC Class Codes: B01D 53/1487 : Removing organic compounds
• CPC Class Codes: B01D 53/18 : Absorbing units; Liquid distributors therefor B01D3/16, B01D3/26, B01D3/30 take precedence; packing elements B01J19/30, B01J19/32
• CPC Class Codes: B01D 53/265 : by refrigeration (condensation)
• CPC Class Codes: B01D 53/326 : in electrochemical cells
• CPC Class Codes: B01D 53/48 : Sulfur compounds
• CPC Class Codes: B01D 53/76 : Gas phase processes, e.g. by using aerosols
• CPC Class Codes: B01D 61/362 : Pervaporation
• CPC Class Codes: B01D 61/3621 : comprising multiple pervaporation steps
• CPC Class Codes: C01B 2203/0227 : containing a catalytic reforming step
• CPC Class Codes: C01B 2203/0233 : the reforming step being a steam reforming step
• CPC Class Codes: C01B 2203/025 : containing a partial oxidation step
• CPC Class Codes: C01B 2203/0261 : containing a catalytic partial oxidation step [CPO]
• CPC Class Codes: C01B 2203/04 : containing a purification step for the hydrogen or the synthesis gas
• CPC Class Codes: C01B 2203/0415 : Purification by absorption in liquids
• CPC Class Codes: C01B 2203/042 : Purification by adsorption on solids
• CPC Class Codes: C01B 2203/043 : Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
• CPC Class Codes: C01B 2203/0435 : Catalytic purification
• CPC Class Codes: C01B 2203/045 : Purification by catalytic desulfurisation
• CPC Class Codes: C01B 2203/0465 : Composition of the impurity
• CPC Class Codes: C01B 2203/0475 : the impurity being carbon dioxide
• CPC Class Codes: C01B 2203/048 : the impurity being an organic compound
• CPC Class Codes: C01B 2203/0485 : the impurity being a sulfur compound
• CPC Class Codes: C01B 2203/061 : Methanol production
• CPC Class Codes: C01B 2203/062 : Hydrocarbon production, e.g. Fischer-Tropsch process
• CPC Class Codes: C01B 2203/068 : Ammonia synthesis
• CPC Class Codes: C01B 2203/0877 : by direct injection of fluid
• CPC Class Codes: C01B 2203/1235 : Hydrocarbons
• CPC Class Codes: C01B 2203/1241 : Natural gas or methane
• CPC Class Codes: C01B 2203/142 : At least two reforming, decomposition or partial oxidation steps in series
• CPC Class Codes: C01B 2203/147 : Three or more purification steps in series
• CPC Class Codes: C01B 2203/84 : Energy production
• CPC Class Codes: C01B 3/24 : of hydrocarbons
• CPC Class Codes: C01B 3/38 : using catalysts
• CPC Class Codes: C01B 3/382 : Multi-step processes
• CPC Class Codes: C01B 3/386 : Catalytic partial combustion
• CPC Class Codes: C01B 3/52 : by contacting with liquids; Regeneration of used liquids C01B3/508 takes precedence
• CPC Class Codes: C01B 3/56 : by contacting with solids; Regeneration of used solids C01B3/508 takes precedence
• CPC Class Codes: C01B 3/58 : including a catalytic reaction
• CPC Class Codes: H05K 999/99 : dummy group
• CPC Class Codes: Y02C 20/40 : of CO2
• CPC Class Codes: Y02P 20/129 : Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
• CPC Class Codes: Y02P 30/00 : Technologies relating to oil refining and petrochemical industry

Abstract

A system and method for processing unconditioned syngas first removes solids and semi-volatile organic compounds (SVOC), then removes volatile organic compounds (VOC), and then removes at least one sulfur containing compound from the syngas. Additional processing may be performed depending on such factors as the source of syngas being processed, the products, byproducts and intermediate products desired to be formed, captured or recycled and environmental considerations.

Claims

1. A method to convert biomass into Fischer Tropsch products, comprising:

(a) steam reforming biomass in the presence of carbon dioxide to generate unconditioned syngas comprising at least hydrogen, carbon monoxide and ammonia;

(b) hydrocarbon reforming the unconditioned syngas with an oxidant source to generate additional hydrogen and carbon monoxide and produce a syngas of improved quality, wherein the oxidant source includes one or more from the group consisting of carbon dioxide, steam, air, and oxygen;

(c) after step (b), cooling the syngas of improved quality;

(d) after step (c), removing at least a portion of the steam from the syngas of improved quality;

(e) after step (d), compressing the syngas of improved quality;

(f) after step (e), removing from the syngas of improved quality, one or more volatile organic compounds from the group consisting of benzene, toluene, phenol, styrene, xylene, and cresol;

(g) after step (f), removing ammonia from the syngas of improved quality, thereby producing an ammonia-depleted syngas of improved quality;

(h) after step (g), removing carbon dioxide from the ammonia-depleted syngas of improved quality, thereby forming an ammonia-and-carbon-dioxide-depleted syngas of improved quality;

(i) recycling a first portion of the removed carbon dioxide for use in step (a);

(j) after step (i), introducing the ammonia-and-carbon-dioxide-depleted syngas of improved quality to a Fischer-Tropsch (FT) catalytic synthesis process and generating Fischer-Tropsch products including at least a Medium Fraction Fischer-Tropsch Liquid (MFFTL) and wax.

2. The method according to claim 1, comprising:

in step (b), reacting the unconditioned syngas with a hydrocarbon source to generate said additional hydrogen and carbon monoxide, the hydrocarbon source being one or more from the group consisting of natural gas, syngas, refinery offgases, methanol, ethanol, petroleum, methane, ethane, propane, butane, hexane, benzene, toluene, xylene, paraffin wax, and naphthalene.

3. The method according to claim 1, wherein:

after step (c) and prior to step (d), the syngas of improved quality has a metal concentration between 0 and 30 parts per million;

the method further comprising;

after step (f), removing at least one metal with a sorbent such that the metal concentration is below 10 parts per billion.

4. The method according to claim 1, wherein:

after step (c) and prior to step (d), the syngas of improved quality has a carbonyl sulfide concentration of 0 to 15 parts per million, the method further comprising;

after step (f), hydrolyzing carbonyl sulfide into hydrogen sulfide and carbon dioxide such that the carbonyl sulfide concentration is below 30 parts per billion.

5. The method according to claim 1, comprising:

in step (d), scrubbing the syngas of improved quality with a Fischer-Tropsch liquid previously created by step (j).

6. The method according to claim 5, comprising:

in step (d), scrubbing the syngas of improved quality with a medium fraction Fischer-Tropsch Liquid (MFFTL).

7. The method according to claim 1, comprising:

in step (d), scrubbing the syngas of improved quality with a solvent.

8. The method according to claim 7, wherein the solvent is biodegradable.

9. The method according to claim 1, comprising:

recycling a second portion of the removed carbon dioxide for use as an oxidant in step (b).

10. The method according to claim 9, comprising:

recycling a third portion of the removed carbon dioxide for use as a purge.

11. The method according to claim 1, comprising:

after step (g), removing sulfur from the ammonia-depleted syngas of improved quality.

12. The method according to claim 11, comprising:

removing the sulfur before step (h).

13. The method according to claim 12, comprising:

removing the sulfur using an amine.

14. The method according to claim 1, comprising:

after step (d) and before step (e), filtering the syngas of improved quality.

15. The method according to claim 1, comprising:

in step (e), compressing the syngas of improved quality from a first pressure ranging from 15 PSIG to 50 PSIG to a second higher pressure ranging from 100 PSIG to 2,000 PSIG.

16. A method to convert biomass into Fischer Tropsch products, comprising:

(a) steam reforming biomass to generate unconditioned syngas comprising at least hydrogen, carbon monoxide, ammonia and sulfur;

(b) hydrocarbon reforming the unconditioned syngas with an oxidant source to generate additional hydrogen and carbon monoxide and produce a syngas of improved quality, wherein the oxidant source includes one or more from the group consisting of carbon dioxide, steam, air, and oxygen;

(c) after step (b), cooling the syngas of improved quality;

(d) after step (c), removing at least a portion of the steam from the syngas of improved quality;

(e) after step (d), compressing the syngas of improved quality;

(f) after step (e), removing from the syngas of improved quality, one or more volatile organic compounds from the group consisting of benzene, toluene, phenol, styrene, xylene, and cresol;

(g) after step (f), removing ammonia from the syngas of improved quality, thereby producing an ammonia-depleted syngas of improved quality;

(h) after step (g), removing sulfur from the ammonia-depleted syngas of improved quality, thereby producing an ammonia-and-sulfur-depleted syngas of improved quality;

(i) after step (h), introducing an ammonia-and-sulfur-depleted syngas of improved quality to a Fischer-Tropsch (FT) catalytic synthesis process and generating Fischer-Tropsch products including at least a Medium Fraction Fischer-Tropsch Liquid (MFFTL) and wax.

17. The method according to claim 16, comprising:

in step (b), reacting the unconditioned syngas with a hydrocarbon source to generate said additional hydrogen and carbon monoxide, the hydrocarbon source being one or more from the group consisting of natural gas, syngas, refinery offgases, methanol, ethanol, petroleum, methane, ethane, propane, butane, hexane, benzene, toluene, xylene, paraffin wax, and naphthalene.

18. The method according to claim 16, wherein:

after step (c) and prior to step (d), the syngas of improved quality has a metal concentration between 0 and 30 parts per million;

the method further comprising;

after step (f), removing at least one metal with a sorbent such that the metal concentration is below 10 parts per billion.

19. The method according to claim 16, wherein:

after step (c) and prior to step (d), the syngas of improved quality has a carbonyl sulfide concentration of 0 to 15 parts per million, the method further comprising;

after step (f), hydrolyzing carbonyl sulfide into hydrogen sulfide and carbon dioxide such that the carbonyl sulfide concentration is below 30 parts per billion.

20. The method according to claim 16, comprising:

in step (d), scrubbing the syngas of improved quality with a Fischer-Tropsch liquid previously created by step (j).

21. The method according to claim 16, comprising:

in step (d), scrubbing the syngas of improved quality with a medium fraction Fischer-Tropsch Liquid (MFFTL).

22. The method according to claim 16, comprising:

in step (d), scrubbing the syngas of improved quality with a solvent.

23. The method according to claim 22, wherein the solvent is biodegradable.

24. The method according to claim 16, comprising:

after step (h), removing carbon dioxide from the ammonia-and-sulfur depleted syngas of improved quality, and

recycling a first portion of the removed carbon dioxide for use in step (a) to generate unconditioned syngas.

25. The method according to claim 24, further comprising:

recycling a second portion of the removed carbon dioxide for use as an oxidant in step (b).

26. The method according to claim 25, comprising:

recycling a third portion of the removed carbon dioxide for use as a purge.

27. The method according to claim 16, comprising:

after step (g), removing carbon dioxide from the ammonia-depleted syngas of improved quality; and

recycling a first portion of the removed carbon dioxide for use in step (a) to generate unconditioned syngas.

28. The method according to claim 16, comprising:

in step (h), removing sulfur using an amine.

29. The method according to claim 16, comprising:

after step (d) and before step (e), filtering the syngas of improved quality.

30. The method according to claim 16, comprising:

in step (e), compressing the syngas of improved quality from a first pressure ranging from 15 PSIG to 50 PSIG to a second higher pressure ranging from 100 PSIG to 2,000 PSIG.