Catalytic fast pyrolysis process with impurity removal

• US 10,336,628 B2
• Filed: 06/22/2016
• Issued: 07/02/2019
• Est. Priority Date: 06/30/2015
• Status: Active Grant

• Current Assignee: Anellotech, Inc.
• Original Assignee: Anellotech, Inc.
• Inventors: Shi, Jian, Sorensen, Charles, Mazanec, Terry, Song, Ruozhi, Goud, Sandeep, Han, Scott, Cheng, Yu-Ting, Frank, Victoria L., Igoe, Jr., William F., Schneidkraut, Marc
• Primary Examiner(s): McCaig, Brian A
• Application Number:
  US15/189,835
• Publication Number:
  US 20170002270A1
• Time in Patent Office: 1,105 Days
• CPC Class Codes: C02F 1/04 by distillation or evaporation
• CPC Class Codes: C02F 1/42 by ion-exchange ion-exchange in general B01J
• CPC Class Codes: C02F 1/441 by reverse osmosis
• CPC Class Codes: C02F 11/10 by pyrolysis
• CPC Class Codes: C02F 2101/10 Inorganic compounds
• CPC Class Codes: C02F 2101/101 Sulfur compounds
• CPC Class Codes: C02F 2101/12 Halogens or halogen-containing compounds
• CPC Class Codes: C02F 2101/16 Nitrogen compounds, e.g. ammonia
• CPC Class Codes: C02F 2303/10 Energy recovery
• CPC Class Codes: C02F 2303/18 Removal of treatment agents after treatment
• CPC Class Codes: C02F 2303/26 Reducing the size of particles, liquid droplets or bubbles, e.g. by crushing, grinding, spraying, creation of microbubbles or nanobubbles
• CPC Class Codes: C02F 9/00 Multistage treatment of water, waste water or sewage
• 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: C10B 57/06 containing additives
• CPC Class Codes: C10B 57/08 Non-mechanical pretreatment of the charge C10L9/00 takes precedence, e.g. desulfurization
• CPC Class Codes: C10G 1/002 in combination with oil conversion- or refining processes
• CPC Class Codes: C10G 1/02 by distillation
• CPC Class Codes: C10G 2300/1014 of vegetal origin
• CPC Class Codes: D21C 3/22 Other features of pulping processes
• CPC Class Codes: Y02E 50/10 : Biofuels, e.g. bio-diesel
• CPC Class Codes: Y02P 20/145 : the feedstock being materials of biological origin
• CPC Class Codes: Y02P 30/20 : using bio-feedstock
• CPC Class Codes: Y02W 10/30 : Wastewater or sewage treatment systems using renewable energies

Abstract

The present invention provides an improved catalytic fast pyrolysis process for increased yield of useful and desirable products. In particular, the process comprises an improved catalytic fast pyrolysis process for producing aromatic compounds, such as, for example, benzene, toluene and xylenes, from biomass feedstock containing impurities, such as, for example alkali and alkaline earth metal, sulfur and nitrogen components.

Claims

1. An improved catalytic fast pyrolysis process comprising steps of:

a) treating biomass containing alkali and alkaline earth metal components to reduce alkali and alkaline earth metal content to result in treated biomass,

b) feeding the treated biomass of step a), catalyst composition, and transport fluid to a catalytic fast pyrolysis process fluidized bed reactor maintained at reaction conditions to manufacture a raw fluid product stream,

c) feeding the raw fluid product stream of step b) to a solids separation and stripping system to produce separated solids and a fluid product stream,

d) feeding the fluid product stream of step c) to a vapor/liquid separation system to produce a liquid phase stream comprising water and components selected from the group consisting of char, coke, ash, catalyst fines, water soluble organics and heavy organics, and combinations thereof, and a vapor phase stream comprising benzene, toluene xylenes, olefins having carbon numbers of 2 to 4, methane, carbon monoxide, and carbon dioxide, and

e) feeding the vapor phase stream of step d) to a product recovery system to recover benzene, toluene, xylenes and, optionally, olefins.

2. The process of claim 1 wherein step a) comprises steps 1) sizing the biomass to ≤

20 cm size particles, 2) washing the sized biomass of step 1) in at least one washing cycle with a washing fluid sufficiently to reduce the content of alkali and alkaline earth metals, 3) optionally rinsing the washed biomass of step 2) with rinsing fluid, 4) drying the biomass to reduce water content, and optionally 5) sizing the dried biomass to ≤

1 cm size particles.

3. The process of claim 2 wherein the washed biomass of step 2) comprises ≤

50 ppm potassium, or ≤

100 ppm calcium, or both.

4. The process of claim 2 wherein the biomass particles resulting from sizing step 1) or sizing step 5) have a size of from 0.005 to 1 cm.

5. The process of claim 2 wherein the washing fluid of step 2) is selected from the group consisting of acidified water, alkaline water, and combinations thereof.

6. The process of claim 5 wherein the washing fluid of step 2) comprises acidified water with pH greater than 2.0 but no more than 5.0.

7. The process of claim 2 wherein the washing fluid of step 2) comprises water recovered from the liquid phase stream of step d) and/or water recovered from the drying step 4).

8. The process of claim 2 wherein the washing fluid of step 2) comprises water obtained from municipal supply, river, or freshwater lake, wherein the total concentration of Ca, Mg, K, and Na of the washing fluid is ≤

181 ppm.

9. The process of claim 2 wherein the washing fluid of step 2) comprises an aqueous solution of organic acids or mineral acids selected from the group consisting of acetic acid, formic acid, nitric acid, carbonic acid, other carboxylic acids, sulfuric acid, phosphoric acid, or hydrochloric acid, ammonium salt, alkyl ammonium salt, aryl ammonium salt, ethylene glycol, glycerol, carbon dioxide, or ammonia, or combinations thereof.

10. The process of claim 2 wherein a particle size distribution of at least 50% of the sized biomass of step 1) is from 1 to 1400 microns as measured by laser diffraction.

11. The process of claim 2 wherein an average aspect ratio of the particles of the sized biomass of step 1) is from 1.1 to at least 40.

12. The process of claim 2 wherein an average aspect ratio of the particles of the sized biomass of step 1) is from 3 to 20.

13. The process of claim 2 wherein washing step 2) is ≤

120 minutes.

14. The process of claim 2 wherein washing step 2) comprises 2 or more washing cycles, each cycle for ≤

60 minutes.

15. The process of claim 14 wherein the washing fluid of each subsequent washing cycle has a pH greater than or equal to the pH of the washing fluid of the preceding washing cycle.

16. The process of claim 2 wherein a sum of all contacting times for all washing cycles is ≤

120 minutes.

17. The process of claim 2 wherein a cellulose/hemicellulose ratio in the washed biomass of step 2) is changed from a cellulose/hemicellulose ratio in the sized biomass of step 1) by no more than 10%.

18. The process of claim 2 wherein a cellulose/hemicellulose ratio in the washed biomass of step 2) changes by no more than 10% from a cellulose/hemicellulose ratio of the unwashed biomass.

19. The process of claim 2 wherein a percent of organic matter lost from the biomass of step a) is less than 5% as measured by chemical oxygen demand of the washing and rinsing fluids.

20. The process of claim 2 wherein the rinsing fluid of step 3) comprises acidic water.

21. The process of claim 2 wherein the rinsing fluid of step 3) comprises water which comprises ≤

5 ppm potassium or ≤

20 ppm calcium, or both.

22. The process of claim 2 wherein the rinsing fluid of step 3) comprises water which is produced by distillation, or by reverse osmosis, or ion exchange, or is de-ionized, or any combination thereof.

23. The process of claim 22 wherein the rinsing fluid comprises deionized water and is re-cycled to step 3).

24. The process of claim 2 wherein the washing fluid of step 2) comprises water, which after use in washing step 2) is used in a heat exchanger to heat fresh washing fluid.

25. The process of claim 2 wherein a contacting time of rinsing step 3) is ≤

30 minutes.

26. The process of claim 2 wherein a total elapsed time of washing step 2) and rinsing step 3) is ≤

10 hours.

27. The process of claim 2 wherein a mass ratio of washing fluid to biomass in step 2) is at least 3.

28. The process of claim 2 wherein the sized biomass of step 1) is fed to step 2) as a batch, semi-continuously, or continuously.

29. The process of claim 2 wherein the washing fluid is fed to step 2) as a batch, semi-continuously, or continuously.

30. The process of claim 2 wherein the washing fluid of step 2) comprises water, is recovered following step 2) and is used as irrigation water.

31. The process of claim 1 wherein the biomass to be treated in step a) is comminuted to result in particles of from 0.42 to 12.7 mm in size, or the biomass that has been treated in step a) is comminuted to result in particles of from 0.42 to 12.7 mm in size, or both the biomass to be and having been treated in step a) are comminuted to result in particles of from 0.42 to 12.7 mm in size.

32. The process of claim 1 wherein a sum of recovered benzene, toluene and xylenes of step e) are at least 10% yield based on carbon in the treated biomass fed to step b).

33. The process of claim 1 wherein the catalyst composition of step b) comprises a crystalline molecular sieve characterized by a silica/alumina mole ratio greater than 5 and a Constraint Index from 1 to 12.

34. The process of claim 1 wherein the fluidized bed reaction conditions of step b) include a temperature of from 300 to 1000°

C. and pressure from 100 to 1500 kPa.

35. The process of claim 1 wherein the catalyst composition of step b) comprises a crystalline molecular sieve having the structure of ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, zeolite beta, mordenite, ferrierite, or combinations thereof.

36. The process of claim 1 wherein the catalyst composition of step b) comprises a crystalline molecular sieve having the structure of ZSM-5.

37. The process of claim 1 wherein from about 5 to about 99% of the recovered toluene or olefins of step e) is recycled to the fluidized bed reactor of step b).

38. The process of claim 1 wherein at least 35% of the alkali and alkaline earth metals in the biomass containing alkali and alkaline earth metal components are removed in treating step a).

39. The process of claim 1 wherein at least 50% of potassium and at least 20% of calcium in the biomass containing alkali and alkaline earth metal components are removed in treating step a).

40. The process of claim 1 wherein at least 35% of chlorine, at least 5% of sulfur and at least 5% of nitrogen in the biomass containing alkali and alkaline earth metal components are removed in treating step a).

41. The process of claim 1 wherein at least a portion of the catalyst composition is removed from the reactor of step b) and regenerated in an oxidation process to produce regenerated catalyst composition, and the regenerated catalyst composition is returned to the fluidized bed reactor of step b).

42. The process of claim 41 wherein at least a portion of the catalyst composition removed from the reactor of step b) is washed with washing fluid to remove alkali and alkaline earth metals therefrom prior to being returned to the fluidized bed reactor of step b).

43. The process of claim 1 wherein at least 90% of the alkali and alkaline earth metals in the biomass containing alkali and alkaline earth metal components are removed in step a).

44. The process of claim 1 wherein at least 95% of potassium and at least 90% of calcium in the biomass containing alkali and alkaline earth metal components are removed in step a).

45. The process of claim 1 wherein at least a portion of the catalyst composition is removed from the reactor of step b) and regenerated in an oxidation process to produce regenerated catalyst composition, and the regenerated catalyst composition is returned to the fluidized bed reactor of step b) along with fresh catalyst composition, wherein an average Brø

nsted acid site density of the catalyst composition removed from the reactor is no less than 75% of a Brø

nsted acid site density of the fresh catalyst as measured by isopropyl amine adsorption.

46. The process of claim 1 wherein an average concentration of Na plus K in the catalyst composition in the reactor of step b) is less than 0.1 moles per kg of catalyst.

47. The process of claim 1 wherein an average concentration of Na plus K in the catalyst composition in the reactor of step 2) is less than 3000 ppm.

48. The process of claim 1 wherein the treated biomass of step a) comprises ≤

50 ppm potassium, or ≤

100 ppm calcium, or both.

49. An improved catalytic fast pyrolysis process comprising steps of:

a) treating biomass containing at least 500 ppm alkali and alkaline earth metal components to reduce alkali and alkaline earth metal content to result in treated biomass by a method comprising steps 1) sizing the biomass to ≤

20 cm size particles, 2) washing the sized biomass of step 1) in at least one washing cycle with a washing fluid sufficiently to reduce the content of alkali and alkaline earth metals, including a mass ratio of washing fluid to biomass of at least 5, 3) optionally rinsing the washed biomass of step 2) with rinsing fluid, 4) drying the biomass to reduce water content, and optionally 5) sizing the dried biomass particle size to ≤

1 cm,

b) feeding the treated biomass of step a), catalyst composition comprising a crystalline molecular sieve having the structure of ZSM-5, and transport fluid to a catalytic fast pyrolysis process fluidized bed reactor maintained at reaction conditions including a temperature from 300 to 1000°

C., pressure from 100 to 1500 kPa and catalyst- to- biomass mass ratio of from 0.1 and 40 to manufacture a raw fluid product stream,

c) feeding the raw fluid product stream of step b) to a solids separation and stripping system to produce separated solids and a fluid product stream,

d) feeding the fluid product stream of step c) to a vapor/liquid separation system to produce a liquid phase stream comprising water and components selected from the group consisting of char, coke, ash, catalyst fines, water soluble organics and heavy organics, and combinations thereof, and a vapor phase stream comprising benzene, toluene and xylenes, and

e) feeding the vapor phase stream of step d) to a product recovery system to recover benzene, toluene and xylenes.

50. The process of claim 49 wherein the biomass particles resulting from sizing step 1) or step 5) have a size of from 0.005 to 1.0 cm.

51. The process of claim 49 wherein the washing fluid of step 2) is selected from the group consisting of acidified water, alkaline water, and combinations thereof.

52. The process of claim 49 wherein the washing fluid of step 2) comprises water recovered from the liquid phase stream of step d) and/or water recovered from the drying step 4).

53. The process of claim 49 wherein the rinsing fluid of step 3) comprises water which is produced by distillation, or by reverse osmosis, or ion exchange, or is de-ionized, or any combination thereof.

54. The process of claim 49 wherein the washing fluid of step 2) comprises an aqueous solution of organic acids or mineral acids selected from the group consisting of acetic acid, formic acid, nitric acid, carbonic acid, other carboxylic acids, sulfuric acid, phosphoric acid, or hydrochloric acid, ammonium salt, alkyl ammonium salt, aryl ammonium salt, ethylene glycol, glycerol, carbon dioxide, or ammonia, or combinations thereof.

55. The process of claim 49 wherein the biomass treated in step a) and/or the treated biomass of step a) are comminuted to result in particles of from 0.42 to 12.7 mm in size.

56. The process of claim 49 wherein at least 35% of the alkali and alkaline earth metals in the biomass containing alkali and alkaline earth metal components are removed in treating step a).

57. The process of claim 49 wherein at least 50% of potassium and at least 20% of calcium in the biomass containing alkali and alkaline earth metal components are removed in treating step a).

58. The process of claim 49 wherein at least 35% of chlorine, at least 5% of sulfur and at least 5% of nitrogen in the biomass containing alkali and alkaline earth metal components are removed in treating step a).

59. The process of claim 49 wherein the treated biomass of step a) comprises less than 15,000 ppm alkali and alkaline earth metal components.

60. The process of claim 49 wherein the biomass containing alkali and alkaline earth metal components of step a) comprises at least 500 ppm chlorine, at least 500 ppm sulfur, at least 0.5% nitrogen, or a combination thereof, and the treated biomass of step a) comprises less than less than 500 ppm chlorine, less than 500 ppm sulfur, less than 0.5% nitrogen, or a combination thereof.

61. The process of claim 49 wherein the treated biomass of step a) comprises less than 250 ppm of chlorine, less than 200 ppm of sulfur, less than 0.2% by weight of nitrogen, or a combination thereof.