Bio-oil production with optimal byproduct processing

• US 8,772,556 B2
• Filed: 09/22/2010
• Issued: 07/08/2014
• Est. Priority Date: 09/22/2010
• Status: Expired due to Fees

• Current Assignee: MARD Incorporated
• Original Assignee: Kior Inc.
• Inventors: Ditsch, Andre
• Primary Examiner(s): BHAT, NINA NMN
• Application Number:
  US12/888,193
• Publication Number:
  US 20120067773A1
• Time in Patent Office: 1,385 Days
• Field of Search: 585/240, 585/242, 481/277, 481/97.R, 201/21, 422/145, 202/121, 202/99, 202/120, 208/126, 208/127
• US Class Current: 585/240
• CPC Class Codes: C01B 2203/0233 the reforming step being a steam reforming step
• CPC Class Codes: C01B 2203/0283 containing a CO-shift step, i.e. a water gas shift step
• 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 2203/1241 Natural gas or methane
• CPC Class Codes: C01B 3/16 using catalysts
• CPC Class Codes: C01B 3/38 using catalysts
• CPC Class Codes: C10B 49/22 according to the "fluidised bed" technique
• CPC Class Codes: C10B 53/02 of cellulose-containing material production of pyroligneous acid C10C5/00
• CPC Class Codes: C10G 2/30 from carbon monoxide with hydrogen
• CPC Class Codes: C10G 2300/1011 Biomass
• CPC Class Codes: C10G 2300/42 Hydrogen of special source or of special composition
• CPC Class Codes: C10G 2400/20 C2-C4 olefins
• CPC Class Codes: C10G 3/52 Hydrogen in a special composition or from a special source
• CPC Class Codes: C10K 1/005 Carbon dioxide
• CPC Class Codes: Y02E 50/10 Biofuels, e.g. bio-diesel
• CPC Class Codes: Y02E 50/30 Fuel from waste, e.g. synthetic alcohol or diesel
• CPC Class Codes: Y02P 20/145 the feedstock being materials of biological origin
• CPC Class Codes: Y02P 30/40 Ethylene production

Abstract

A process and system for the conversion of biomass under high severity in the presence of a catalyst to produce a bio-oil, olefins, methane, and carbon monoxide (CO). The methane and/or CO can be used to generate hydrogen and the generated hydrogen can be used for hydrotreating the bio-oil. Additionally, or alternatively, a syngas stream, a carbon dioxide-rich stream, and/or a methane-rich stream can be recovered for use in the bio-oil production process and/or for use in a conventional petroleum refinery and/or petrochemical plant.

Claims

1. A process for producing bio-oil and processing byproducts of bio-oil production, said process comprising:

(a) pyrolyzing biomass in a conversion reactor in the presence of a catalyst to thereby produce a reactor effluent comprising bio-oil, carbon monoxide (CO), and methane, wherein the weight ratio of said CO to said bio-oil in said reactor effluent is at least 0.5;

1, wherein the weight ratio of said methane to said bio-oil in said reactor effluent is at least 0.05;

1;

(b) condensing and separating a substantial portion of said bio-oil from said reactor effluent, thereby leaving an uncondensed stream comprising at least a portion of said methane and at least a portion of said CO; and

(c) generating hydrogen by reacting water with at least a portion of said CO and/or at least a portion of said methane, thereby producing a hydrogen-enriched stream comprising generated hydrogen, wherein said process produces said generated hydrogen at a rate that is at least 0.5 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis.

2. The process of claim 1 wherein said generating of step (c) comprises methane reforming.

3. The process of claim 1 wherein said generating of step (c) comprises a water gas shift reaction.

4. The process of claim 1 wherein said generating of step (c) comprises methane reforming followed by a water gas shift reaction.

5. The process of claim 1 further comprising hydrodreating at least a portion of said condensed and separated bio-oil using at least a portion of said generated hydrogen.

6. The process of claim 5 wherein at least 75 weight percent of the hydrogen used in said hydrotreating is said generated hydrogen.

7. The process of claim 1 wherein said pyrolyzing is carried out at a temperature of at least 300°

C. and not more than 1,000°

C., wherein said pyrolyzing includes catalytic cracking, wherein the oxygen content of said condensed and separated bio-oil is less than 25 weight percent.

8. The process of claim 1 wherein the weight ratio of said CO to said bio-oil in said reactor effluent is at least 1:

1 and not more than 10;

1, wherein the weight ratio of said methane to said bio-oil in said reactor effluent is at least 0.1;

1 and not more than 1;

1.

9. The process of claim 1 wherein said generating of step (c) produces said generated hydrogen at a rate that is at least 1 percent and not more than 20 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis.

10. The process of claim 1 wherein said reactor effluent further comprises olefins, wherein the weight ratio of said olefins to said bio-oil in said reactor effluent is at least 0.1:

1.

11. The process of claim 10 further comprising, prior to said generating of step (c), removing at least 50 weight percent of said olefins originally present in said reactor effluent.

12. The process of claim 10 wherein ethylene and propylene in combination make up at least 50 weight percent of said olefins present in said reactor effluent.

13. The process of claim 1 wherein said conversion reactor produces said bio-oil at a rate that is at least 4 percent and not more than 50 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis, wherein said conversion reactor produces said CO at a rate that is at least 10 percent and not more than 80 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis, wherein said conversion reactor produces said methane at a rate that is at least 0.5 percent and not more than 30 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis, wherein said conversion reactor produces olefins at a rate that is at least 2 percent and not more than 40 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis, wherein said conversion reactor produces water at a rate that is at least 4 percent and not more than 50 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis.

14. The process of claim 1 further comprising recovering from said hydrogen-enriched stream at least one of the following recovered streams:

(i) a syngas stream comprising at least a portion of said generated hydrogen and at least a portion of said CO, wherein said generated hydrogen and said CO make up at least 75 weight percent of said syngas stream,

(ii) a hydrogen-rich stream, wherein said generated hydrogen makes up at least 75 weight percent of said hydrogen-rich stream,

(iii) a carbon dioxide-rich stream comprising at least 75 weight percent carbon dioxide (CO₂), and/or

(iv) a methane-rich stream, wherein said methane makes up at least 75 weight percent of said methane-rich stream.

15. The process of claim 14 wherein said generated hydrogen and said CO make up at least 95 weight percent of said syngas stream, wherein said generated hydrogen makes up at least 95 weight percent of said hydrogen-rich stream, wherein said CO₂ comprises at least 95 weight percent of said CO₂-rich stream, wherein said methane makes up at least 95 weight percent of said methane-rich stream.

16. The process of claim 14 wherein said recovering comprises pressure swing adsorption.

17. The process of claim 14 wherein said recovered streams include said syngas stream.

18. The process of claim 17 wherein said process produces said syngas stream at a rate that is at least 5 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis.

19. The process of claim 17 further comprising converting at least a portion of said syngas stream to ethanol and/or Fischer-Tropsch liquids.

20. The process of claim 14 wherein said recovered streams include said hydrogen-rich stream and said CO₂-rich stream.

21. The process of claim 20 wherein said process produces said hydrogen-rich stream at a rate that is at least 0.5 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis, wherein said process produces said CO₂-rich stream at a rate that is at least 5 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis.

22. The process of claim 20 further comprising using at least a portion of said hydrogen-rich stream to hydrotreat at least a portion of said condensed and separated bio-oil and sequestering at least a portion of said CO₂-rich stream.

23. The process of claim 14 wherein said recovered streams include said hydrogen-rich stream, said CO₂-rich stream, and said methane-rich stream.

24. The process of claim 23 wherein said process produces said hydrogen-rich stream at a rate that is at least 0.5 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis, wherein said process produces said CO₂-rich stream at a rate that is at least 5 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis, wherein said process produces said methane-rich stream at a rate that is at least 0.5 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis.

25. The process of claim 23 further comprising using at least a portion of said hydrogen-rich stream to hydrotreat at least a portion of said condensed and separated bio-oil, sequestering at least a portion of said CO₂-rich stream, and using at least a portion of said methane-rich stream in a cogeneration process.

26. A process for producing bio-oil and processing byproducts of bio-oil production, said process comprising:

(a) pyrolyzing biomass in a riser reactor in the presence of a catalyst to thereby produce a reactor effluent comprising bio-oil, carbon monoxide (CO), olefins, and methane, wherein the weight ratio of said CO to said bio-oil in said reactor effluent is at least 0.5;

1, wherein the weight ratio of said olefins to said bio-oil in said reactor effluent is at least 0.1;

1, wherein the weight ratio of said methane to said bio-oil in said reactor effluent is at least 0.05;

1;

(b) condensing and separating a substantial portion of said bio-oil from said reactor effluent, thereby leaving an uncondensed stream comprising at least a portion of said methane and at least a portion of said CO; and

(c) generating hydrogen from at least a portion of said uncondensed stream to thereby produce a hydrogen-enriched stream comprising generated hydrogen;

(d) recovering from at least a portion of said hydrogen-enriched stream at least one of the following recovered streams;

(i) a syngas stream comprising hydrogen and at least a portion of said CO, wherein said hydrogen and said CO make up at least 75 weight percent of said syngas stream,

(ii) a hydrogen-rich stream, wherein hydrogen makes up at least 75 weight percent of said hydrogen-rich stream,

(iii) a carbon dioxide-rich stream comprising at least 75 weight percent carbon dioxide (CO₂), or

(iv) a methane-rich stream, wherein said methane makes up at least 75 weight percent of said methane-rich stream,

wherein when said syngas stream is recovered in step (d) said process produces said syngas stream at a rate that is at least 5 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis, wherein when said hydrogen-rich stream is recovered in step (d) said process produces said hydrogen-rich stream at a rate that is at least 0.5 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis, wherein when said CO₂-rich stream is recovered in step (d) said process produces said CO₂-rich stream at a rate that is at least 5 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis, wherein when said methane-rich stream is recovered in step (d) said process produces said methane-rich stream at a rate that is at least 0.5 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis.

27. The process of claim 26 wherein said recovered streams include said syngas stream and not said hydrogen-rich stream and not said methane-rich stream and not said CO₂-rich stream.

28. The process of claim of claim 27 further comprising converting at least a portion of said syngas stream to ethanol and/or Fischer-Tropsch liquids.

29. The process of claim 26 wherein said recovered streams include said hydrogen-rich stream and said CO₂-rich stream and not said syngas stream and not said methane-rich stream.

30. The process of claim 29 wherein said process produces said hydrogen-rich stream at a rate that is at least 1 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis, wherein said process produces said CO₂-rich stream at a rate that is at least 10 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis.

31. The process of claim 26 wherein said recovered streams include said hydrogen-rich stream, said CO₂-rich stream, and said methane-rich stream and not said syngas stream.

32. The process of claim 31 wherein said process produces said hydrogen-rich stream at a rate that is at least 1 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis, wherein said process produces said CO₂-rich stream at a rate that is at least 10 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis, wherein said process produces said methane-rich stream at a rate that is at least 1 percent of the rate of introduction of said biomass into said conversion reactor on a weight basis.

33. The process of claim 26 wherein said generating of step (c) comprises reacting water with at least a portion of said CO and/or at least a portion of said methane to generate said hydrogen-enriched stream.

34. The process of claim 33 further comprising hydrotreating at least a portion of said condensed and separated bio-oil using at least a portion of said generated hydrogen.

35. The process of claim 26 wherein the weight ratio of said CO to said bio-oil in said reactor effluent is at least 1:

1, wherein the weight ratio of said olefins to said bio-oil in said reactor effluent is at least 0.4;

1, wherein the weight ratio of said methane to said bio-oil in said reactor effluent is at least 0.2;

1, wherein said condensed and separated bio-oil has an oxygen content of less than 25 weight percent.

36. A system for producing bio-oil, said system comprising:

a biomass feedstock source for providing solid particulate biomass;

a conversion reactor for thermally converting at least a portion of said solid particulate biomass feedstock into a reactor effluent comprising bio-oil, carbon monoxide (CO), olefins, and methane;

a partial condenser for partially condensing at least a portion of said reactor effluent into a bio-oil stream and an uncondensed stream;

an olefin removal unit for removing olefins from said uncondensed stream thereby providing an olefin-depleted stream;

a hydrogen generation unit having a water inlet, wherein said hydrogen generation unit is operable to generate hydrogen by reacting water with CO and/or methane from said olefin-depleted stream; and

a hydrotreater for reacting at least a portion of said bio-oil stream with at least a portion of the generated hydrogen from said hydrogen generation unit.

37. The system of claim 36 further comprising a pressure swing adsorption unit for recovering at least a portion of the generated hydrogen from said hydrogen generation unit.

38. The system of claim 36 wherein said hydrogen generation unit comprises a methane reformer and/or a water gas shift reactor.

39. The system of claim 36 wherein said conversion reactor is a riser reactor.