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Title:
CONVERSION OF PYROLYSIS GAS WITH A BIOREACTOR
Document Type and Number:
WIPO Patent Application WO/2014/165457
Kind Code:
A1
Abstract:
Systems, methods, and apparatuses are provided for converting a pyrolysis gas with a bioreactor.

Inventors:
ABDULLAH ZIA (US)
SMITH STEPHANIE A (US)
Application Number:
PCT/US2014/032425
Publication Date:
October 09, 2014
Filing Date:
March 31, 2014
Export Citation:
Click for automatic bibliography generation   Help
Assignee:
ABDULLAH ZIA (US)
SMITH STEPHANIE A (US)
International Classes:
C07C29/151; C12M1/00; C07C31/12; C10B53/02; C10J3/72; C10K3/04; C10L1/02
Foreign References:
US20100298450A12010-11-25
US20100317077A12010-12-16
US20070275447A12007-11-29
Other References:
PETER DRRE: "Fermentative production of butanolthe academic perspective", CURRENT OPINION IN BIOTECHNOLOGY, vol. 22, no. 3, 31 December 2011 (2011-12-31), pages 331 - 336, XP028278574, ISSN: 0958-1669, [retrieved on 20110421], DOI: 10.1016/J.COPBIO.2011.04.010
Attorney, Agent or Firm:
GEGENHEIMER, C., Michael et al. (505 King AvenueColumbus, OH, US)
Download PDF:
Claims:
CLAIMS

1. A biomass conversion system 1000, the biomass conversion system may include:

a catalytic pyrolysis subsystem 118(5;

a butanol reactor sy stem 1200;

a microorganism growth system 1388 may include a microorganism growth apparatus 1302; and

a butanol separation sy stem 1400;

wherein:

the catalytic pyrolysis subsystem 1100 is operatively connected to the butanol reactor system 1288,

the butanol reactor system 1200 is operatively connected to the microorganism growth system 1300, and

the butanol reactor system 1200 is operatively connected to the butanol separation system 1400.

2. The biomass conversion system 1880 of claim 1 :

the catalytic pyrolysis subsystem 1180 may include a pyrolysis reactor 1182 operatively connected to a gas cyclone 1104, a quench tower 1106, a high temperature shift apparatus 1108, and a low temperature shift apparatus 1110;

the butanol reactor system 1208 may include a butanol reactor 1282 operatively connected to a gas compressor 1208 and a medium reservoir 1210;

the microorganism growth system 1380 may include a microorganism growth apparatus 1302; and

the butanol separation system 1400 may include a solids filtration apparatus 1482 operatively connected to a gas stripping apparatus 1404, a condensation apparatus 1406, and a decanting apparatus 1408;

wherein:

the catalytic pyrolysis subsystem 1100 is operatively connected to the butanol reactor system 1280,

the butanol reactor system 1208 is operatively connected to the microorganism growth system 1300, and the butanol reactor system 1200 is operatively connected to the butanol separation system 1488.

3. The biomass conversion system 1800 of claim 1 , the catalytic pyrolysis 540 subsystem 1100 may include a pyrolysis reactor 11 2.

4. The biomass conversion system 1000 of claim 1 , the catalytic pyrolysis subsystem 1180 may include a pyrolysis reactor 1182 operatively connected to one or more of: a gas cyclone 1104, a quench tower 1106, a high temperature shift apparatus 188, and a low temperature shift apparatus 1110.

545 5. The biomass conversion system 1880 of claim 4, further may include a char gasifier/reformer 1111 , the gas cyclone 1104 being operatively connected to direct char to the char gasifier/reformer 1111, the char gasifier/reformer 1 11 being configured to accept char output from gas cyclone 1104 and to produce hydrogen from the char output, and the char gasifier/reformer 11 1 being operatively coupled to direct the hydrogen to the high

550 temperature shift apparatus 1188.

6. The biomass conversion system 1000 of claim 1 , the butanol reactor system 1200 may include a butanol reactor 1282.

7. The biomass conversion system 1800 of claim i , the butanol reactor system 1208 may include a butanol reactor 1202 operatively connected to one or more of a gas

555 compressor 1208 and a medium reservoir 1210.

8. The biomass conversion system 1000 of claim 1 , the microorganism growth system 1300 may include a microorganism growth apparatus 1382.

9. The biomass conversion system 1880 of claim 1 , the butanol separation system 1408 may include a solids filtration apparatus 1482.

560 10. The biomass conversion system 1000 of claim 1 , the butanol separation

system 1400 may include a solids filtration apparatus 1402 operatively connected to one or more of a gas stripping apparatus 1404, a condensation apparatus 1406, and a decanting apparatus 1408.

1 1 . The biomass conversion system 1800 of claim 1 , the butanol reactor 1202 being operaiiveiy connected to one or more of a first mixing apparatus 1204, a second mixing apparatus 1206, a gas compressor 1208, a medium reservoir 1210, and a third mixing apparatus 1212,

12. The biomass conversion system 18(5(1 of claim 1, configured for large -scale production of a biofuef product. 13. The biomass conversion system 1000 of claim 1, configured for batch production of a biofuel product.

14. The biomass conversion system 1800 of claim 1 , configured for substantially continuous production of a biofuel product.

15. A catalytic pyrolysis system 2000, the catalytic pyrolysis system may include: a catalytic pyrolysis reactor 28(54 configured to pyrolyze a biomass 2802 to produce at least one of: a syn gas, a bio oil 2006, a char 2008, a hvdrocarbonaceous substance (Crrj 2014, C02 2816, and CO 2018; and

one of: a water-gas shift reactor 2822 configured to intake the CO 2018 and produce C02 2026 and ¾ 2038; and a char gasifier/re former 2111 configured to intake the char 2008 and gasify the char 21)88 to produce H2 2031.

16. The cataly tic pyro lysis system 2800 of claim 15, may include:

the catalytic pyrolysis reactor 2804 configured to pyrolyze the biomass 2002 to produce at least the bio oil 2(506 and the CO 2018;

the water-gas shift reactor 2822 configured to intake the CO 2018 and produce the C02 2026 and the H2 2830; and

a size -based separation device configured to separate the C02 2826 and the H2 2030.

17. The catalytic pyrolysis system 2800 of claim 15, the catalytic pyrolysis reactor 2804 being configured to pyrolyze the biomass 2802 to produce the bio oil 2086 with a low oxygen content. 18. The catalytic pyrolysis system 2800 of claim 15, further may include an upgrader 201(5 operativeiy coupled to the catalytic pyrolysis reactor 2804, the upgrader 2818 being configured to upgrade the bio oil 2006 to yield an infrastracture-compatible hydrocarbon fuel 2812.

19. The catalytic pyrolvsis system 2800 of claim 15, the catalytic pyro lysis reactor

595 2804 being configured to pyrolyze the biomass 2802 to produce at least at least one of the hydrocarbonaceous substance (CnHm) 2814, the C02 2816, and ihe CO 2018.

2.0. The catalytic pyrolvsis system 2800 of claim 19, the catalytic pyro lysis reactor 2804 being configured to direct the CnHm 2014 to a container or stream.

21. The catalytic pyro lysis system 2800 of claim 19, the catalytic pyro lysis reactor 600 2804 being operativelv coupled to a butanol bioreactor system, the catalytic pyrolysis reactor

2804 being configured to direct the CO? 2016 into a CO? stream 2020 to the butanol bioreactor system.

22. The catalytic pyroly sis system 2800 of claim 15, may include the water-gas shift reactor 2022 operatively coupled to the catalytic pyrolysis reactor 2084, the catalytic

605 pyrolysis reactor 2084 being configured to direct the CO 201 to the water-gas shift reactor 2822, the water-gas shift reactor 2022 being configured to accept the CO and water 2024 to produce H? and CO?.

23. The catalytic pyroly sis system 2800 of claim 15, may include the char gasiiier/reiormer 2111 operativelv coupled to the catalytic pyrolysis reactor 2004, the

610 catalytic pyrolysis reactor 2004 being configured to direct char 2088 to the char

gasifier/reformer 2111 , the char gasifier/reformer 2111 being configured to accept the char 2808 to produce H?.

24. The catalytic pyroly sis system 2800 of claim 23, the char gasifier/reformer 2111 being configured to direct the H? to a butanol bioreactor.

615 25. The catalytic pyrolysis system 2800 of claim 15, further may include a size- based separation device configured to separate the CO? 2026 and the H? 2830.

26. The cataly tic pyrolysis system 2800 of claim 25, the size-based separation device being operativel coupled to direct at least one of the CO? 2826 and the H? 2030 to a butanol bioreactor.

620 27. The catalytic pyrolysis system 2800 of claim 15, the catalytic pyrolysis reactor

2804 being configured to operate as a biomass gasifier configured to pyrolyze the biomass 2802 to produce the syngas and substantially none of the bio oil 2006,

28. The catalytic pyroly sis system 2800 of claim 27, the catalytic pyrolysis reactor 2804 being configured to direct the syngas to the water-gas shift reactor 2022 to produce H2

625 and C02.

29. The catalytic pyrolysis system 2800 of claim 15, the catalytic pyrolysis reactor 2804 being configured to operate as a biomass gasifier configured to conduct a water-gas shift reaction.

30. The catalytic pyrolysis system 2880 of claim 15, configured for large-scale 630 production of a biofuei product.

31. The biomass conversion system 1880 of claim 15, configured for batch production of a biofuei product.

32. The catalytic pyrolysis system 2880 of claim 15, configured for substantially continuous production of a biofuei product.

635 33. A hollow fiber membrane bioreactor 3880, the hollow fiber membrane

bioreactor may include:

a cartridge 3802 may include a CO? hollow fiber 3084, a H2 hollow fiber 3806, and a biofilm 3888;

a H? gas inlet 3018;

640 a C02 gas inlet 3012;

an air-sparged media inlet 3014;

a port 3015:

a media outlet 381 ;

a H2 gas outlet 3018; and

645 a CO? gas outlet 3820.

34. The hollow fiber membrane bioreactor 3008 of claim 33, the ( '() ·■ gas inlet 3812 being configured to accept C02 from a CO? outlet of a size based separation device.

35. The hollow fiber membrane bioreactor 3000 of claim 33, the H2 gas inlet 3810 being configured to accept H2 from a H2 outlet of a size based separation device.

650 36. The hollow fiber membrane bioreactor 3000 of claim 33, the H2 gas inlet 3010 being configured to accept ¾ from a char gasifier/reformer 2111.

37. The hollow fiber membrane bioreactor 3000 of claim 33, the air-sparged media inlet 3014 being configured to direct gro wth media may include oxygen into the hollow fiber membrane bioreactor 3000.

655 38. The hollow fiber membrane bioreactor 3008 of claim 33, the H2 gas inlet

3010; the CO? gas inlet 3012; and the air-sparged media inlet 3014 being configured together for direct mixing of the (¾, the H?, and the CO?,.

39. The hollow fiber membrane bioreactor 3000 of claim 33, the H2 gas inlet 3810; the CO? gas inlet 3012; and the air-sparged media inlet 3014 being configured together

660 for indirect mixing of the 02, the ¾, and the C02.

40. The hollow fiber membrane bioreactor 3000 of claim 33, the biofilm 3088 may include hydrogen bacteria.

41. The hollow fiber membrane bioreactor 3008 of claim 33, configured such that metabolic activity of bacteria comprised by the biofilm 3008 drive the diffusion of the gases

665 out of C02 hollow fiber 3084 and H2 hollow fiber 3006.

42. 'The hollow fiber membrane bioreactor 3008 of claim 33, configured such that metabolic activity of bacteria comprised by the biofilm 3008 consume dissolved oxygen from the biofilm 3008 as the oxygen enters hollow fiber membrane bioreactor 3080 via the air- sparged media inlet 3014.

670 43. The hollow fiber membrane bioreactor 3000 of claim 33, further may include one or more probes embedded in the biofilm 3008, the one or more probes configured to sense one or more of the 02, the H2 and the C02.

44. The hollow fiber membrane bioreactor 3000 of claim 33, further may include one or more probes at the media outlet 3816, the one or more probes configured to sense one

675 or more of the O?, the H2 and the CO2.

45. The hollow fiber membrane bioreactor 3088 of claim 33, configured for large- scale production of a biofuel product,

46. The hollow fiber membrane bioreactor 3000 of claim 33, configured for batch production of a biofuel product.

680 47. The hollow fiber membrane bioreactor 3008 of claim 33, configured for

substantially continuous production of a biofuel product.

48. The hollow fiber membrane bioreactor 3000 of claim 33, configured for operation using a selected microorganism.

49. The hollow fiber membrane bioreactor 3008 of claim 33, configured for 685 operation using a genetically modified hydrogen bacteria for the production of biofuel.

50. The hollow fiber membrane bioreactor 3088 of claim 33, configured for operation using a genetically modified hydrogen bacteria for the production of biofuel.

51 . A method for converting a hiomass, may include:

pyrolyzing a btomass 2882 to produce at least one of: a syn gas, a bio oil 2006, 690 a char 2008, a hydrocarbonaceous substance (CnHm) 2014, CO? 2016, and CO 2018;

and

producing one of: CO2 2026 and ¾ 2030 from the CO 2018 in a water-gas shift reaction: or ¾ 2031 from the char 2008 in a char gasifying/reforming reaction.

52. The method 4000 of claim 51, may include:

695 pyrolyzing the biomass 2002 in a catalytic pyrolysis reactor 2004 to produce at least the bio oil 2006 and the CO 2018 (4002);

directing the CO 2018 to a water-gas shift reactor 2822 to produce at least ¾ and C02 (4804);

using a size-based separation device to separate the H2 and the C02 into an H2 700 gas stream 2038 and a C02 gas stream 2028 (4006); directing the ¾ gas stream 2030 to a H2 gas inlet 3010 of a bioreactor 3800 (4008); and

directing ihe C02 gas stream 2028 to a CO? gas inlet 3012 of the bioreactor 3000 (4010).

705 53. The method of claim 51, further may include separating the ¾ and the CO2 into an H2 gas stream 2030 and a C02 gas stream 2028 based on size.

54. The method of claim 53, further may include directing the H2 gas stream 2030 to a H2 gas inlet 3010 of a bioreactor 3000 (4008).

55. The method of claim 53, further may include directing the C02 gas stream 710 2028 to a C02 gas inlet 3012 of a bioreactor 3000 (4010).

56. The method of claim 51 , pyrolyzing the biomass 2002 may include producing the bio oil 2006 with a low oxygen content.

57. The method of claim 51 , further may include upgrading the bio oil 2006 to yield an infrastructure-compatible hydrocarbon fuel 2012.

715 58. The method of claim 51 , pyrolyzing the biomass 2002 producing at least at least one of the hvdrocarbonaceous subsianee (Cr,Hm) 2014, the C02 2016, and the CO 2018.

59. The method of claim 58, further may include directing the CrjHm 2014 to a container or stream.

60. The method of claim 58, further may include directing the CO? 2816 to a 720 butanol bioreactor process.

61. The method of claim 51 , further may include directing the CO 2018 to a water-gas shift, reaction to produce !¾ and C02.

62. The method of claim 51, further may include directing the char 2808 to the char gasifying/reforming process to produce S¾.

725 63. The method of claim 62, further may include directing the H2 to a butanol bioreactor process.

64. The method of claim 51, further may include separating the C02 2026 and the H? 2830 based on size.

65. The method of claim 64, further may include directing at least one of the C02 730 2826 and the H2 2(538 to a butanol bioreaetor process.

66. The method of ciaim 51, pyrolyzing the biomass 2082 may include producing the syngas and substantially none of the bio oil 2Θ86.

67. The method of claim 66, further may include directing the syngas to a water- gas shift reaction to produce H2 and CO2.

735 68. The method of ciaim 51 , configured for large-scale production of a bioiuel product.

69. The meihod of ciaim 51, configured for batch production of a bioiuel product.

70. The method of ciaim 51, configured for substantially eoniinuous production of a bioiuel product.

740

Description:
CONVERSION OF PYROLYSIS GAS WITH A BIO EACTQR

CROSS-REFERENCE TO RELATED APPLICATIONS

[9001] This application claims priority from U.S. Provisional Patent Application No. 61/806,922, filed on March 31, 2013, which is incorporated by reference herein in its entirety.

BACKGROUND

[8002] The extraction of bio oil from biomass for use as a biofuel is an area of interest in the search for reliable alternative energy sources. Biomass may be subjected to pyrolysis to create a hot pyrolysis vapor. Bio oil may be extracted from the hot pyrolysis vapor. Additionally, biomass may be subjected to gasification to create a syn gas. Finally, biomass may be used in conjunction with a bioreactor containing microorganisms to produce alkanols, such as butanol,

[001)3] Systems, methods, and apparatuses are needed for processing biomass to produce pyrolysis vapor, syn gas, and alkanols,

SUMMARY

[0(504] In one embodiment, a biomass conversion system is provided. The biomass conversion system may include a catalytic pyrolysis subsystem. The biomass conversion system may include a butanol reactor system. The biomass conversion system may include a microorganism growth system may include a microorganism growth apparatus. The biomass conversion system may include a butanol separation system. The catalytic pyrolysis subsystem may be operatively connected to the butanol reactor system. The butanol reactor system may be operatively connected to the microorganism growth system. The butanol reactor system may be operatively connected to the butanol separation system. [8005] In one embodiment, a biomass conversion system is provided, the biomass conversion system may include: a catalytic pyrolysis subsystem may include a pyrolysis reactor operatively connected to a gas cyclone, a quench tower, a high temperature shift apparatus, and a low temperature shift apparatus; a butanol reactor system may include a butanol reactor operatively connected to a gas compressor and a medium reservoir; a microorganism growth system may include a microorganism growth apparatus; and a butanol separation system may include a solids filtration apparatus operatively connected to a gas stripping apparatus, a condensation apparatus, and a decanting apparatus; wherein the catalytic pyrolysis subsystem is operatively connected to the butanol reactor system, wherein the butanol reactor system is operatively connected to the microorganism growth system, and wherein the butanol reactor system is operatively connected to the butanol separation system. 0006] in one embodiment, a catalytic pyrolysis system is provided. The catalytic pyrolysis system may include a catalytic pyrolysis reactor. The catalytic pyrolysis reactor may be configured to pyroiyze a biomass to produce at least one of: a syn gas, a bio oil, a char, a hydrocarbonaceous substance (C„H m ), C0 2 , and CO. The catalytic pyrolysis system may include one of: a water-gas shift reactor configured to intake the CO and produce C0 2 and H?; and a char gasifier/reformer configured to intake the char and gasify the char to produce ¾.

[001)7] in one embodiment, a catalytic pyrolysis system is provided, the catalytic pyrolysis system may include: a catalytic pyrolysis reactor configured to pyroiyze a biomass to produce at least a bio oil and CO; a water-gas shift reactor configm'ed to intake the CO and produce CO ? , and ¾; and a size-based separation device configured to separate the CO ? , and the H 2 .

[0008J In one embodiment, a hollow fiber membrane bioreactor is provided, the hollow fiber membrane bioreactor may include: a cartridge may include a CO? hollow fiber, a H ? hollow fiber, and a biofiim; a H ? gas inlet; a CO ? gas inlet; an air-sparged media inlet; a port; a media outlet; a H 2 gas outlet; and a C0 2 gas outlet. [0009] In one embodiment, a method for converting a biomass is provided, the method may include: pyrolyzing a biomass in a catalytic pyrolysis reactor to produce at least a bio oil and a CO; directing the CO to a water-gas shift reactor to produce at least H? and a CO?,; using a size-based separation device to separate the ¾ and the CO? into a H 2 gas stream and a C0 2 gas stream; directing the H 2 gas stream to a H 2 gas inlet of a bioreactor; and directing the C0 2 gas stream to a C0 2 gas inlet of the bioreac tor.

[0010] in one embodiment, a method for converting a biomass is provided. The method may include pyrolyzing a biomass to produce at least one of: a syn gas, a bio oil, a char, a hydrocarbonaceous substance (C n H m ), C0 2 , and CO. The method may include producing one of: C0 2 and H 2 from the CO in a water-gas shift reaction; or H 2 from the char in a char gasifying/reforming reaction.

[8011] In another embodiment, a method for converting a biomass is provided, the method may include: pyrolyzing a biomass in a catalytic pyrolysis reactor to produce at least a bio oil and a char stream; directing the char stream to a gasifier/reformer to produce at least 11?; directing the H? as a gas stream to a H 2 gas inlet of a bioreactor.

BRIEF DESCRIPTION OF THE DRAWINGS

[0012] The accompanying figures, which are incorporated in and constitute a part of the specification, illustrate example systems, methods, and apparatuses, and are used merely to illustrate example embodiments.

[8013 FIG. 1A illustrates an example arrangement of a biomass conversion system.

[0 14; FIG, IB illustrates an example arrangement of a biomass conversion system. [8015] FIG. 2 illustrates an example arrangement of a catalytic pyrolysis system.

[8016] FIG, 3 illustrates an example arrangement of a hollow fiber membrane bioreactor.

[8017] FIG. 4 illustrates an example method for converting biomass.

DETAILED DESCRIPTION

[8018] The processing of biomass to extract bio oil therefrom may involve the pyrolysis 95 of biomass to create a hot pyrolysis vapor. Pyrolysis processes may include fast pyrolysis of biomass material at temperatures of about 500 °C. When biomass undergoes pyrolysis, three groups of components may be created, including: non-condensable gases, vapor that may be quenched into bio oil, and solids known as char and coke,

100 [8019] A biomass conversion system may be used to process biomass. The system may ¬ be used to convert biomass into at least two products, including, for example, a bio oil and an alkanol, e.g., butanol. The system may convert biomass into the at feast two products by using a catalytic pyrolysis system and a butanol bioreactor. The biomass conversion system may be configured to produce bi.omass-deri.ved fuels and blended fuels that may be

105 distributed through existing infrastructure used for petroleum-derived fuels.

[8028] In one embodiment, the biomass conversion system comprises a butanol bioreactor and recovery system paired to a catalytic pyrolysis system. The biomass conversion system may be fully integrated to convert waste biomass into multiple energy 110 products, including bio oil and butanol.

[8021] In one embodiment, the butanol bioreactor may comprise microorganisms, such as chemoautographs or "hydrogen bacteria." In one embodiment, the microorganisms use C0 2 and 1 1 · for the production of organic molecules under aerobic, dark conditions. In one embodiment, the microorganisms are genetically modified to produce butanol

115 [8022] The catalytic pyrolysis subsystem of the biomass conversion system may comprise at least one catalyst. In one embodiment, the catalytic pyrolysis subsystem uses ihermai decomposition of biomass, which is influenced by at leasi one catalyst to yield desirable products, such as bio oil with low oxygen content (e.g., about 20%-30% oxygen 120 content) as compared to bio oil yielded in conventional fast pyrolysis (e.g., about 40%-50% oxygen content).

[8(523] In one embodiment, the biomass conversion system produces butanol in conjunction with bio oil. The butanol may be infrastructure-compatible, and may be blended 125 with other fuels.

[8824] In one embodiment, CO is produced in the catalytic pyrolysis subsystem. In one embodiment, the CO is converted into C0 2 and ¾, e.g., via a water-gas shift reaction. In one embodiment, the C0 2 and H 2 can be directed to the input streams of the butanol bioreactor.

130

[8825] In one embodiment, the biomass conversion system is configured for communication with an oil distribution system for direct processing of waste biomass into an infrast c ure-compatible biofuel.

135 [8826] FIG. 1A illustrates an example arrangement of a biomass conversion system

1000. System 1000 may comprise a catalytic pyrolysis subsystem 1100 may include a pyrolysis reactor 1102 operativeiy connected to a gas cyclone 1184, a quench tower 1106, a high temperature shift apparatus 1188, and a low temperature shift apparatus 1110.

140 [8827] In one embodiment, catalytic pyrolysis subsystem 1108 is operativeiy connected to a butanol reactor system 1288 may include a butanol reactor 1202 operativeiy connected to a first mixing apparatus 1204, a second mixing apparatus 1286, a gas compressor 1208, a medium reservoir 1210, and a third mixing apparatus 1212. 145 [8028] FIG. IB illustrates an alternate example arrangement of biomass conversion system 1000. System 1008 may comprise catalytic pyrolysis subsystem 1188 may include pyrolysis reactor 1182 operatively connected to gas cyclone 1104, quench tower 1106, high temperature shift apparatus 1108, and low temperature shift apparatus 1110. Gas cyclone 1104 may be operatively connected to direct char to char gasifier/reformer 1111. Char

150 gasifier/reformer 1111 may gasify char output from gas cyclone 1104 to produce hydrogen.

Char gasifier/reformer 1111 may be operatively connected to direci ihe hydrogen to high temperature shift apparatus 1188.

[0029] Caialytie pyrolysis subsystem 1100 may be operaiively connected io a butanol reactor system 1200 may include a butanol reactor 1202 operatively connected to a first 155 mixing apparatus 1204, a second mixing apparatus 1206, a gas compressor 1288, a medium reservoir 1210, and a third mixing apparatus 1212.

[0030] In one embodiment, butanol reactor system 1200 is operatively connected to a microorganism growth system 1300 may include a microorganism growth apparatus 1302.

160

[0031] In one embodiment, butanol reactor system 1200 is operatively connected to a butanol separation system 1400 may include a solids filtration apparatus 1482 operatively connected to a gas stripping apparatus 1404, a condensation apparatus 1406, and a decanting apparatus 1408.

165

[0032] FIG, 2 illustrates an example arrangement of a catalytic pyrolysis system 2000. Catalytic pyrolysis system 2000 may comprise a biomass 2002 and a catalytic pyrolysis reactor 2084. Biomass may be pyrolyzed within catalytic pyrolysis reactor 2004, producing at least one of a bio oil 2806, char 2808, hydrocarbonaceous substance (C n H m ) 2014, CO? 170 2816, and CO 2018. For example, biomass may be pyrolyzed within catalytic pyrolysis reactor 2084, producing at least one of a bio oil 2006 and a char 2008. [8033] In one embodiment, bio oil 2086 comprises a bio oil with a low oxygen content. Bio oil 2886 may be upgraded (2018) to yield an infrastructure-compatible hydrocarbon fuel 175 2812,

[8834] In one embodiment, biomass is pyrolyzed within catalytic pyrolysis reactor 2884 to produce at least one of a hydrocarbonaceous substance (C n H m ) 2814, C0 2 2816, and CO 2818. In one embodiment, C n H m 2814 is directed to a container or stream as a potential 180 product or iuel In another embodiment, C0 2 2816 is directed into a C0 2 stream 2028 to be used in a butanol bioreactor system (not shown). In another embodiment, CO 2818 is directed to a water-gas shift reactor 2822.

[8035] In one embodiment, CO 2818 is directed to water-gas shift reactor 2822 to 185 produce H 2 and C0 2 . In one embodiment, water 2824 is directed to water-gas shift reactor 2822 to react with CO 2018 to produce H 2 and CO?. C0 2 2826 generated in water-gas shift reactor 2022 may be directed to C0 2 stream 2028, In another embodiment, catalytic pyrolysis system 2800 comprises a char gasifier/reformer 2111. Char gasifier/reformer 2111 may accept char 2888 and gasify the char to provide hydrogen stream 2831, which may be 1 0 directed to a butanol bioreactor (not shown).

[8036] In one embodiment, catalytic pyrolysis system 2880 produces at least one of H 2 and CO?. In another embodiment, catalytic pyrolysis reactor 2084 produces at least one of H 2 and CO ? .. In another embodiment, water-gas shift reactor 2822 produces at least one of 1¾ 195 and CO?. Catalytic pyrolysis system 2088 may comprise a size-based separation device, such as a membrane, configured to separate H 2 and C0 2 generated by catalytic pyrolysis system 2808. In one embodiment, H 2 and CO? generated by catalytic pyrolysis system 2008 are separated by a size-based separation device as each leaves water-gas shift reactor 2822,

200 [8037] In one embodiment, the H 2 and CO ? generated by catalytic pyrolysis system 2880 is divided into separate streams. The streams may enter a bioreactor (not shown). In one embodiment, catalytic pyrolysis system 2800 comprises a CO ? gas stream 2828, which is directed to a butanol bioreactor (not shown). In another embodiment, catalytic pyroiysis system 2800 comprises a ¾ gas stream 2030, which may be directed to a butanol bioreactor 205 (not shown).

[8038] In one embodiment, catalytic pyroiysis system 2800 operates as a biomass gas fler, such that no bio oil is produced, and at least a portion of the biomass is converted to syn gas. The syn gas may be directed to water-gas shift reactor 2822 to produce H 2 and CO ? .. 210 In another embodiment the water gas shift can be conducted in the biomass gasifier, when it is operated as a reformer.

[8039] Use of H ? and C0 2 in a butanol bioreactor (not shown) may require mixing of H 2 and C0 2 with air. In one embodiment, H 2 and C0 2 are mixed with air such that 215 concentrations may be about 5% CO ? /45% H ? /50% air. In this embodiment, the final concentration of oxygen in the mixture may be about 10% (assuming 21% oxygen in air). In one embodiment, a ratio of gases of about 5% C<¾/45% l¼ 50% air supports the growth of a hydrogen bacteria, which may be used in a butanol bioreactor (not shown). In another embodiment, other ratios of gases are used to support growth of hydrogen bacteria.

220

[0040] FIG, 3 illustrates an example arrangement of a hollow fiber membrane bioreactor 3800. Bioreactor 3800 may comprise a cartridge 3002 may include a C0 2 hollow fiber 3084, a H 2 hollow fiber 3006, and a biofilm 3008. Bioreactor 3008 may comprise a H 2 gas inlet 3810, a CO2 gas inlet 3012, and an air-sparged media inlet 3014. Bioreactor 3080 may 225 comprise a port 3815, a media outlet 381 , a H 2 gas outlet 3018, and a C0 2 gas outlet 3820.

[8041] In one embodiment, the H ? and C0 2 generated by catalytic pyroiysis system 2800 in FIG. 2 are separated by a size-based separation device as each leaves water-gas shift reacior 2022. The separated streams of ¾ and CO? may be directed to ¾ gas inlet 3010 and 230 CO? gas inlet 3012, respectively. [8042] Oxygen may enter bioreactor 3088 by sparging the growth media with air, which is introduced to bioreactor 3800 via media inlet 3014. In one embodiment, direct mixing of the O?, 1¾, and C0 2 is not required. In one embodiment, biofilm 3008 contains hydrogen 235 bacteria. In one embodiment, the metabolic demands of the bacteria within biofilm 3808 drive the diffusion of the gases out of CO? hollow fiber 3804 and H 2 hollow fiber 3886. In another embodiment, the bacteria within biofilm 3888 consume dissolved oxygen from biofilm 3088 as the oxygen enters bioreactor 3080 via media inlet 3014,

240 [ΘΘ43] In one embodiment, the concentrations of the (¾, J¾ and C0 2 gases are measured via probes (not shown) embedded within biofilm 3808. In another embodiment, the concentrations of the O?, H 2 and CO? gases are measured via probes embedded within the media leaving media outlet 3016.

245 [ΘΘ44] In one embodiment, catalytic pyrolysis system 2000 and bioreactor 3080 are configured to be constructed in a manner that makes the biomass conversion system capable of large-scale production of a biofuel product In another embodiment, catalytic pyrolysis system 2008 and bioreactor 3000 are configured to be constructed in a manner that makes the biomass conversion system capable of substantially continuous operation for biofuel

250 production.

[8045] In one embodiment, bioreactor 3008 is configured for use with a specific microorganism designed for producing a specific product. In another embodiment, bioreactor 3800 is configured for use with a genetically modified hydrogen bacteria for the production 255 of biofuel.

[8046] One concern in the design and operation of the biomass conversion system is the mixing of feedstock gases, such as hydrogen and oxygen, which can form an explosive mixture. The risk of forming an explosive mixture of feedstock gases may be mitigated by at 260 least one of: (a) selecting membranes to control gas flux; (b) controlling the length scales in the system so that there are no "pockets" greater than about 1 -2 mm that would allow undesirable raixmg of hydrogen and oxygen; and (c) rastallrag exhaust features in the system and flushing the system with air to dilute any hydrogen below its lower explosive limit. In another embodiment, the system uses immobilized bacteria and no membranes, with 265 controlled length scales and flushing of the system, to mitigate hydrogen concentrations.

[8047] In one embodiment, the biomass conversion system employs artificial immobilization of the organisms in the system. The artificial immobilization may control the genetically modified organism. In one embodiment, the system uses natural biofilms. 270 Biofilms may cause immobilization, which may improve productivity of an organism. In one embodiment, the biomass conversion system has an intrinsically higher cell density than would normally be achieved for the purpose of biofuel production.

[8(548] In one embodiment, the biomass conversion system uses pyrolysis gas or syn gas 275 as sources of H 2 and C0 2 for growth of the hydrocarbon bacteria.

[8049] FIG, 4 illustrates an example method 4000 for converting biomass. Method 4000 may comprise pyrofyzing a biomass 2002 in a catalytic pyrolysis reactor 2084 to produce at least a bio oil 2806 and a CO 2818 (step 4002). CO 2018 may be directed to a water-gas shift 280 reactor 2022 to produce at least H 2 and a C0 2 (step 4004). A size-based separation device may be used to separate the H 2 and the C0 2 into a H 2 gas stream 2038 and a C0 2 gas stream 2828 (step 4006). The ¾ gas stream 2030 may be directed to a H 2 gas inlet 3810 of a bioreaetor 3008 (step 4808) while the C0 2 gas stream 2828 may be directed to a C0 2 gas inlet 3812 of the bioreaetor 3080 (step 4810).

285 [8050] In various embodiments, a biomass conversion system 1080 is provided. The biomass conversion system may include a catalytic pyrolysis subsystem 1180. The biomass conversion system may include a butanof reactor system 1208, The biomass conversion system may include a microorganism growth system 1300 may include a microorganism growth apparatus 1302. The biomass conversion system may include a butanoi separation

290 system 1408. The catalytic pyrolysis subsystem 1108 may be operatively connected to the butanoi reactor system 1200. The butanoi reactor system 1208 may be operatively connected to the microorganism growth system 1308. The butanoi reactor system 1280 may be operatively connected to the buianol separation system 1408.

295 [8851] In some embodiments, the catalytic pyroiysis subsystem 1108 may include a pyro lysis reactor 1102 operatively connected to a gas cyclone 1184, a quench tower 1106, a high temperature shift apparatus 1108, and a low temperature shift apparatus 1118. The butanoi reactor system 1280 may include a buianol reactor 1202 operatively connected to a gas compressor 1208 and a medium reservoir 1210. The microorganism growth system 1300

300 may include a microorganism growth apparatus 1302. The butanoi separation system 1400 may mclude a solids filtration apparatus 1402 operatively connected to a gas stripping apparatus 1404, a condensation apparatus 1406, and a decanting apparatus 1408.

[8052] In several embodiments, the catalytic pyroiysis subsystem 1100 may include a 305 pyroiysis reactor 1102. The pyroiysis reactor 1102 may be operatively connected to one or more of: a gas cyclone 1104, a quench tower 1186, a high temperature shift, apparatus 1188, and a low temperature shift apparatus 1110.

[8053] In various embodiments, the biomass conversion system 1000 may include a char 310 gasifier/reformer 1111. The gas cyclone 1184 may be operatively connected to direct char to the char gasifier/reformer 1111. The char gasifier/reformer 1111 may be configured to accept char output from gas cyclone 1104 and to produce hydrogen from the char output. The char gasifier/reformer 1111 may be operatively coupled to direct the hydrogen to the high temperature shift apparatus 188.

315

[8054] In some embodiments, the butanoi reactor system 1200 may include a butanoi reactor 1202. The butanoi reactor 1202 may be operatively connected to one or more of a gas compressor 1208 and a medium reservoir 1210.

320 [8055] In several embodiments, the microorganism growth system 1308 may include a microorgamsm growth apparatus 1302. The butanoi separation system 1400 may include a solids filtration apparatus 1402. The butanol separation system 1400 may include a solids filtration apparatus 1402 operatively connected to one or more of a gas stripping apparatus 1404, a condensation apparatus 1486, and a decanting apparatus 1408, The butanol reactor 325 1202 may be operatively connected to one or more of a first mixing apparatus 1284, a second mixing apparatus 1206, a gas compressor 1208, a medium reservoir 1210, and a third mixing apparatus 1212.

[8056] In various embodiments, the biomass conversion system 1088 may be configured 330 for large-scale production of a biofuel product. The biomass conversion system 1000 may be configured for batch production of a biofuel product. The biomass conversion system 1800 may be configured for substantially continuous production of a biofuel product.

[8057] In various embodiments, a catalytic pyrolysis system 2000 is provided. The 335 catalytic pyrolysis system may include a catalytic pyrolysis reactor 2004. The catalytic pyrolysis reactor 2004 may be configured to pyrolyze a biomass 2002 to produce at least one of: a syn gas, a bio oil 2006, a char 2088, a hydrocarbonaceous substance (C n H m ) 2014, CO ? . 2816, and CO 2018. The catalytic pyrolysis system 2008 may include one of: a water-gas shift reactor 2822 configured to intake the CO 2018 and produce C0 2 2026 and H 2 2030; and 340 a char gasifier/reformer 2111 configured to intake the char 2088 and gasify the char 2008 to produce ¾ 2031.

[8058] In some embodiments, the catalytic pyrolysis system 2008 may include the catalytic pyrolysis reactor 2084 configured to pyrolyze the biomass 2002 to produce at least 345 the bio oil 2006 and the CO 2818. The water-gas shift reactor 2822 may be configured to intake the CO 2018 and produce the C0 2 2026 and the H? 2030. A size-based separation device may be included, and configured to separate the C0 2 2826 and the 1¾ 2830.

[8059] In several embodiments, the catalytic pyrolysis reactor 2004 may be configured to 350 pyrolyze the biomass 2082 to produce the bio oil 2006 with a low oxygen content. An upgrader 2810 may be operatively coupled to the catalytic pyrolysis reactor 2004. The upgrader 2010 may be configured to upgrade the bio oil 208 to yield an infrastructure- compatible hydrocarbon fuel 2012.

355 [0060] In various embodiments, the catalytic pyrolysis reactor 2084 may be configured to pyrolyze the biomass 2002 to produce at least at least one of the hydrocarbonaceous substance (C n H m ) 2014, the C0 2 2816, and the CO 2018. The catalytic pyrolysis reactor 2804 may be configured to direct the C n H m 2814 to a container or stream. The catalytic pyrolysis reactor 2884 may be operatively coupled to a butanol bioreactor system. The

360 catalytic pyrolysis reactor 2084 may be configured to direct the C0 2 2016 into a C0 2 stream 2828 to the butanol bioreactor system.

[8061] In some embodiments, the catalytic pyrolysis system 2800 may include the water- gas shift reactor 2822 operatively coupled to the catalytic pyrolysis reactor 2804. The 365 catalytic pyrolysis reactor 2884 may be configured to direct the CO 2818 to the water-gas shift reactor 2022. The water-gas shift reactor 2822 may be configured to accept the CO and water 2024 to produce H? and CO?.

[8862] In several embodiments, the catalytic pyrolysis system 2008 may include the char 370 gasifier/reformer 2111 operatively coupled to the catalytic pyrolysis reactor 2004. The catalytic pyrolysis reactor 2084 may be configured to direct char 2008 to the char gasifier/reformer 2111. The char gasifier/reformer 2111 may be configured to accept the char 2808 to produce H 2 . The char gasifier/reformer 2111 may be configured to direct the H 2 to a butanol bioreactor.

375

[8063] In various embodiments, the catalytic pyrolysis system 2808 may include a size- based separation device configured to separate the CO ? . 2826 and the ¾ 2038. The size- based separation device may be operatively coupled to direct at least one of the CO? 2026 and the H 2 2038 to a butanol bioreactor. The catalytic pyrolysis reactor 2804 may be configured 380 to operate as a biomass gasifier configured to pyrolyze the biomass 2002 to produce the syngas and substantially none of the bio oil 2006. The catalytic pyrolysis reactor 2004 may be configured to direct the syngas to the water-gas shift reactor 2822 to produce H? and CO?.

[8064] In some embodiments, the catalytic pyrolysis reactor 2004 may be configured to 385 operate as a biomass gasifier configured to conduct a water-gas shift reaction. The catalytic pyrolysis system 2600 may be configured for large-scale production of a biofuel product. The biomass conversion system 1000 may be configured for batch production of a biofuel product. The catalytic pyrolysis system 2000 may be configured for substantially continuous production of a biofuel product.

390

[8065] In various embodiments, a hollow fiber membrane bioreactor 3000 is provided. The hollow fiber membrane bioreactor may include a cartridge 3002. The cartridge 3802 may include a CO? hollow fiber 3004, a 1¾ hollow fiber 3006, and a biofilm 3808. The hollow fiber membrane bioreactor may include a H? gas inlet 3010. The hollow fiber 395 membrane bioreactor may include a C0 2 gas inlet 3012. The hollow fiber membrane bioreactor may include an air-sparged media inlet 3014. The hollow fiber membrane bioreactor may include a port 3015. The hollow fiber membrane bioreactor may include a media outlet 3016. The hollow fiber membrane bioreactor may include a H? gas outlet 3018. The hollow fiber membrane bioreactor may include a CO?, gas outlet 3020.

400

[8066] In some embodiments, the CO gas inlet 3012 may be configured to accept CO ? , from a CO ? outlet of a size based separation device. The H ? gas inlet 3010 may be configured to accept H ? from a H ? outlet of a size based separation device. The H ? gas inlet 3010 may be configured to accept H ? from a char gasifie /reformer 2111. The air-sparged 405 media inlet 3014 may be configured to direct growth media may include oxygen into the hollow fiber membrane bioreactor 3800. The H? gas inlet 3010; the CO? gas inlet 3012; and the air-sparged media inlet 3014 may be configured together for direct mixing of the O?, the H ? , and the CO ? . The H ? gas inlet 3810; the CO? gas inlet 3012; and the air-sparged media iniei 3014 may be configured together for indirect mixing of the O ? , the H?, and the CO ? ,

410 [8067] In several embodiments, the hollow fiber membrane bioreactor 3000 may include hydrogen bacteria. The hollow fiber membrane bioreactor 3800 may be configured such that metabolic activity of bacteria included by the biofilm 3008 may drive the diffusion of the gases out of C0 2 hollow fiber 3804 and H 2 hollow fiber 3806. The metabolic activity of 415 bacteria included by the biofilm 3008 may consume dissolved oxygen from the biofilm 3808 as the oxygen enters hollow fiber membrane bioreactor 3080 via the air-sparged media inlet 3814.

[0068] In various embodiments, one or more probes may be embedded in the biofilm 420 3008. The one or more probes may be configured to sense one or more of the 0 2 , the S¾ and the CO ? . The one or more probes may be configured at the media outlet 3016 to sense one or more of the 0 2 , the 1¾ and the CO?.

[8069] In some embodiments, the hollow fiber membrane bioreactor 3000 may be configured for large-scale production of a biofuel product. The hollow fiber membrane

425 bioreactor 3000 may be configured for batch production of a biofuel product. The hollow fiber membrane bioreactor 3000 may be configured for substantially continuous production of a biofuel product. The hollow fiber membrane bioreacior 3008 may be configured for operation using a selected microorganism. The hollow fiber membrane bioreactor 3800 may ¬ be configured for operation using a genetically modified hydrogen bacteria for the production

430 of biofuel. The hollow fiber membrane bioreactor 3080 may be configured for operation using a genetically modified hydrogen bacteria for the production of biofuel.

[8070] In various embodiments, a method for converting a biomass is provided. The method may include pyrolyzing a biomass 2002 to produce at least one of: a syn gas, a bio oil 435 2806, a char 2008, a hydrocarbonaceous substance (C n H m ) 2014, ( ' () · 2016, and CO 2018.

The method may include producing one of: CO? 2026 and H 2 2830 from the CO 2018 in a water-gas shift reaction; or H? 2031 from the char 2008 in a char gasifying/reforming reaction. 440 [8071] In some embodiments, the method may include pyxolyzing the biomass 2882 in a catalytic pyrolysis reactor 2084 to produce at least the bio oil 2006 and the CO 2018 (4002). The method may include directing the CO 2018 to a water-gas shift reactor 2022 to produce at least H 2 and CO? (4804), The method may include using a size-based separation device to separate the ¾ and the C0 2 into an ¾ gas stream 2830 and a C0 2 gas stream 2028 (4006).

445 The method may include directing the H 2 gas stream 2038 to a H 2 gas inlet 3010 of a bioreaetor 3008 (4008). The method may include directing the CO? gas stream 2028 to a ( ' () :· gas inlet 3012 of the bioreaetor 3000 (4010).

[8072] In several embodiments, the method may include separating the H 2 and the C0 2 450 into an H 2 gas stream 2030 and a CO? gas stream 2028 based on size. The method may include directing the PI? gas stream 2830 to a 1¾ gas inlet 3010 of a bioreaetor 3000 (4088). The method may include directing the C0 2 gas stream 2828 to a C0 2 gas inlet 3012 of a bioreaetor 3800 (4018). Pyrolyzing the biomass 2002 may include producing the bio oil 2806 with a low oxygen content.

455

[8073] In various embodimenis, the method may include upgrading the bio oil 2806 to yield an infrastructure-compatible hydrocarbon fuel 2812. Pyrolyzing the biomass 2882 may include producing at least at least one of the hydrocarbonaceous substance (C n H m ) 2014, the C0 2 2016, and the CO 2018. The method may include directing the C n H m 2814 to a 460 container or stream. The method may include directing the CO? 2816 to a butanol bioreaetor process. The method may include directing the CO 2018 to a water-gas shift reaction to produce PI? and CO2. The method may include directing the char 2008 to the char gasifying/reforming process to produce 1¾. The method may include directing the H 2 to a butanol bioreaetor process.

465

[8074] In some embodiments, the method may include separating the C0 2 2826 and the H 2 2038 based on size. The method may include directing at least one of the CO ? . 2826 and the PI? 2030 to a butanol bioreaetor process. Pyrolyzing the biomass 2002 may include producing the syngas and substantially none of the bio oil 2086. The method may include 470 directing the syngas to a water-gas shift reaction to produce H 2 and C0 2 . The method may be configured for large-scale production of a biofuel product. The method may be configured for batch production of a biofuel product. The method may be configured for substantially continuous production of a biofuel product.

475 [8075] To ihe extent that ihe term "includes" or "including" is used in the specification or the claims, it is intended to be inclusive in a manner similar to the term "may include" as that term is interpreted when employed as a transitional word in a claim. Furthermore, to the extent that ihe term "or" is employed (e.g., A or B) it is intended to mean "A or B or both." When the applicants intend to indicate "only A or B but not both" then the term "only A or B

480 but not both" will be employed. Thus, use of the term "or" herein is the inclusive, and not the exclusive use. See Bryan A. Garner, A Dictionary of Modern Legal Usage 624 (2d. Ed. 1995), Also, to ihe extent ihai the terms "in" or "into" are used in the specification or the claims, it is intended to additionally mean "on" or "onto." To the extent that the term "selectively" is used in the specification or the claims, it is intended to refer to a condition of

485 a component wherein a user of the apparatus may activate or deactivate the feature or function of the component as is necessary or desired in use of the apparatus. To the extent that the term "operatively connected" is used in the specification or the claims, it is intended to mean that the identified components are connected in a way to perform a designated function. To the extent that the term "substantially" is used in the specification or the claims,

490 it is intended to mean that the identified components have the relation or qualities indicated with degree of error as would be acceptable in the subject industr ''. As used in the specification and the claims, the singular forms "a," "an," and "the" include the plural. Finally, where the term "about" is used in conjunction with a number, it is intended to include ± 10% of the number. In other words, "about 10" may mean from 9 to 1 1.

495

[8076] As stated above, while the present application has been illustrated by the description of embodiments thereof, and while the embodiments have been described in considerable detail, if is not the intention of the applicants to restrici or in any way limit the scope of the appended claims to such detail. Additional advantages and modifications will 500 readily appear to those skilled in the art, having the benefit of the present application.

Therefore, the application, in its broader aspects, is not limited to the specific details, illustrative examples shown, or any apparatus referred to. Departures may be made from such details, examples, and apparatuses without departing from the spirit or scope of the general inventive concept.