Process for producing BTX and alcohols by catalytic pyrolysis of biomass and fermentation of the gaseous pyrolysis effluent

Patent metadata

Field	Value
Publication number	US-10570337-B2
Application number	US-201716306086-A
Country	US
Kind code	B2
Filing date	May 3, 2017
Priority date	May 31, 2016
Publication date	Feb 25, 2020
Grant date	Feb 25, 2020

Abstract

A process is described for producing BTX and alcohols from biomass, by a) catalytic pyrolysis of the biomass in a fluidized-bed reactor producing a gaseous pyrolysis effluent; b) separation of said gaseous pyrolysis effluent into at least one BTX fraction and a gaseous effluent containing at least carbon monoxide and carbon dioxide, c) sending all of the gaseous effluent from separation b) into fermentation producing a liquid fermentation stream containing at least one stream containing at least one oxygenated compound chosen from alcohols, diols, acid alcohols, carboxylic acids, aldehydes, ketones and esters, d) separating the fermentation stream obtained on conclusion of c) into at least the stream containing at least one oxygenated compound, an aqueous fraction, and an unreacted gaseous effluent, e) recycling at least part of unreacted gaseous effluent into the catalytic pyrolysis a).

First claim

The invention claimed is:

1. A process for producing BTX and alcohols from biomass, comprising at least the following steps:
a) catalytic pyrolysis of said biomass in a fluidized-bed reactor producing a gaseous pyrolysis effluent,
b) separation of said gaseous pyrolysis effluent into at least one BTX fraction and a gaseous effluent comprising at least carbon monoxide and carbon dioxide,
c) sending all of the gaseous effluent comprising at least carbon monoxide and carbon dioxide derived from the separation step b) into a fermentation step producing a liquid fermentation stream comprising at least one stream comprising at least one oxygenated compound chosen from alcohols containing 2 to 6 carbon atoms, diols containing 2 to 4 carbon atoms, acid alcohols containing 2 to 4 carbon atoms, carboxylic acids containing 2 to 6 carbon atoms, aldehydes containing 2 to 12 carbon atoms, ketones containing 3 to 12 carbon atoms and esters containing 2 to 12 carbon atoms, alone or as a mixture,
d) separating said fermentation stream obtained on conclusion of step c) into at least said stream comprising at least one oxygenated compound, an aqueous fraction and an unreacted gaseous effluent,
e) recycling at least part of said unreacted gaseous effluent into the catalytic pyrolysis step a).

2. The process according to claim 1 , in which the catalytic pyrolysis step a) takes place in the presence of a zeolite catalyst comprising at least one zeolite chosen from ZSM-5, ferrierite, zeolite beta, zeolite Y, mordenite, ZSM-23, ZSM-57, EU-1 and ZSM-11, whether or not doped with a metal chosen from iron, gallium, zinc and lanthanum.

3. The process according to claim 1 , in which the catalytic pyrolysis step a) is performed at a temperature of between 400 and 1000° C., at an absolute pressure of between 0.1 and 0.5 MPa and at a WHSV of between 0.01 and 10 h −1 .

4. The process according to claim 1 , in which said fermentation step c) is performed in the presence of at least one microorganism chosen from the following microorganisms: Acetogenium kivui, Acetoanaerobium noterae, Acetobacterium woodii, Alkalibaculum bacchi CP11 (ATCC BAA-1772), Blautia producta, Butyribacterium methylotrophicum, Caldanaerobacter subterraneous, Caldanaerobacter pacificus subterraneous, hydrogenoformans Carboxydothermus, Clostridium aceticum, Clostridium acetobutylicum, Clostridium acetobutylicum P262 (DSM 19630 from DSMZ Germany), Clostridium autoethanogenum (DSM 19630 from DSMZ Germany), Clostridium autoethanogenum (DSM 10061 from DSMZ Germany), Clostridium autoethanogenum (DSM 23693 from DSMZ Germany), Clostridium autoethanogenum (DSM 24138 from DSMZ Germany), Clostridium carboxidivorans P7 (ATCC PTA-7827), Clostridium coskatii (ATCC PTA-10522), Clostridium drakei, Clostridium ljungdahlii PETC (ATCC 49587), Clostridium ERI2 ljungdahlii (ATCC 55380), Clostridium ljungdahlii C-01 (ATCC 55988), Clostridium ljungdahlii 0-52 (ATCC 55889), Clostridium magnum, Clostridium pasteurianum (DSM 525 from DSMZ Germany), Clostridium ragsdali P11 (ATCC BAA-622), Clostridium scatologenes, Clostridium thermoaceticum, Clostridium ultunense, Desulfotomaculum kuznetsovii, Eubacterium limosum, sulfurreducens Geobacter, Methanosarcina acetivorans, Methanosarcina barken, Morrella thermoacetica, Morrella thermoautotrophica, Oxobacter pfennigii, Peptostreptococcus productus, Ruminococcus productus, Thermoanaerobacter kivui , and mixtures thereof.

5. The process according to claim 4 , in which the microorganisms are chosen from Clostridium autoethanogenum, Clostridium ljungdahlii, Clostridium aceticum, Morella thermoacetica, Acetobacterium woodii and Alkalibaculum bacchi for producing ethanol and/or acetate, Clostridium autoethanogenum, Clostridium ljungdahlii and C. ragdalei for producing 2,3-butanediol and Clostridium carboxidivorans, Clostridium drakei, Clostridium scatologenes and Butyribacterium methylotrophicum for producing butyrate and butanol; and mixtures thereof.

6. The process according to claim 1 , in which said fermentation step c) is performed at a growth temperature of between 20 and 80° C., at an absolute pressure of between 0.1 and 0.4 MPa and at a pH of between 3 and 9.

7. The process according to claim 1 , in which the alcohols containing 2 to 6 carbon atoms are chosen from ethanol, n-propanol, isopropanol, butanol, isobutanol and hexanol, the diols containing 2 to 4 carbon atoms are chosen from 2,3-butylene glycol (2,3-butanediol), the acid alcohol containing 2 to 4 carbon atoms is lactic acid, the carboxylic acids containing 2 to 6 carbon atoms are chosen from acetic acid, butyric acid and hexanoic acid, the aldehydes containing 2 to 12 carbon atoms are chosen from ethanal, propanal, butanal, pentanal, 3-methylbutanal, hexanal, furfural and glyoxal, alone or as a mixture, the ketones containing 3 to 12 carbon atoms are chosen from acetone, butanone, cyclohexanone, acetophenone and acetylacetone, alone or as a mixture, and the esters containing 2 to 12 carbon atoms are chosen from methyl formate, methyl acetate, methyl propionate, methyl butanoate, methyl pentanoate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate and butyl butyrate, alone or as a mixture.

8. The process according to claim 6 , in which the stream comprising at least one oxygenated compound comprises ethanol, n-propanol, isopropanol, butanol, isobutanol, hexanol, acetic acid, butyric acid, hexanoic acid, lactic acid, acetone, butanone or 2,3-butylene glycol (2,3-butanediol), alone or as a mixture.

9. The process according to claim 1 , in which a hydrogen supplement is introduced into said fermentation step c).

10. The process according to claim 1 , in which the separation step d) is performed by steam originating from the catalytic pyrolysis step.

11. The process according to claim 1 , in which said stream of oxygenated compounds separated out on conclusion of step d) is at least partly recycled into said catalytic pyrolysis step a).

12. The process according to claim 10 , in which a supplement of oxygenated compounds chosen from alcohols containing 2 to 6 carbon atoms chosen from ethanol, n-propanol, isopropanol, butanol, isobutanol and hexanol, diols containing 2 to 4 carbon atoms chosen from 2,3-butylene glycol (2,3-butanediol), lactic acid, carboxylic acids containing 2 to 6 carbon atoms chosen from acetic acid, butyric acid and hexanoic acid, aldehydes containing 2 to 12 carbon atoms and ketones containing 3 to 6 carbon atoms chosen from acetone and butanone, alone or as a mixture, and esters containing 2 to 12 carbon atoms, are added in said catalytic pyrolysis step a).

13. The process according to claim 1 , in which said stream of oxygenated compounds separated out on conclusion of step d) is not recycled into the catalytic pyrolysis step a).

14. The process according to claim 1 , wherein in step e) all of said unreacted gaseous effluent is recycled into the catalytic pyrolysis step a).

Assignees

• Ifp Energies Now

Inventors

• Feugnet Frederic
• Lopes Ferreira Nicolas
• Kasztelan Slavik

Classifications

• B01D2257/50

  Carbon oxides · CPC title

• C12P7/065

  with microorganisms other than yeasts · CPC title

• C10G1/086

  Characterised by the catalyst used · CPC title

• C10B53/02 Primary

  of cellulose-containing material (production of pyroligneous acid C10C5/00) · CPC title

• C10G1/002

  in combination with oil conversion- or refining processes · CPC title