Combined first and second generation biofuels process

• US 8,431,755 B2
• Filed: 07/21/2010
• Issued: 04/30/2013
• Est. Priority Date: 07/21/2010
• Status: Active Grant

• Current Assignee: Air Liquide Large Industries U.S. LP (L'Air Liquide SA)
• Original Assignee: Air Liquide Large Industries U.S. LP (L'Air Liquide SA)
• Inventors: Vauk, Dennis A.
• Primary Examiner(s): BHAT, NINA NMN
• Application Number:
  US12/840,699
• Publication Number:
  US 20120022299A1
• Time in Patent Office: 1,014 Days
• Field of Search: 585/240, 585/242, 585/733, 585/800, 446/05, 481/277, 481/271
• US Class Current: 585/240
• CPC Class Codes: C01B 2203/025 containing a partial oxidation 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 2203/0445 Selective methanation
• CPC Class Codes: C01B 2203/047 the impurity being carbon monoxide
• CPC Class Codes: C01B 2203/06 Integration with other chemical processes
• CPC Class Codes: C01B 2203/0883 by indirect heat exchange
• CPC Class Codes: C01B 3/34 by reaction of hydrocarbons with gasifying agents
• CPC Class Codes: C10G 2300/1014 of vegetal origin
• CPC Class Codes: C10G 3/00 Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids production from non-melting solid oxygen-containing carbonaceous materials C10G1/00
• CPC Class Codes: C10G 3/52 Hydrogen in a special composition or from a special source
• CPC Class Codes: C12P 7/06 Ethanol, i.e. non-beverage
• CPC Class Codes: Y02E 50/10 Biofuels, e.g. bio-diesel
• CPC Class Codes: Y02P 20/129 Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
• CPC Class Codes: Y02P 20/145 the feedstock being materials of biological origin
• CPC Class Codes: Y02P 30/20 using bio-feedstock

Abstract

A process to integrate a first biofuels process and a second generation cellulosic biofuels process is provided. The pyrolysis means which produces the char stream and a bioliquid stream. The low pressure hydrotreating component, a high pressure hydrotreating component, the low pressure hydrotreating component which produces the hydrocarbon stream, the high pressure hydrotreating component which produces the steam stream and bioliquid stream. A distillation means, which produces a green gasoline stream and a green diesel stream from the bioliquid stream. The second biofuels process may be a first generation bio-ethanol process, which produces a bio-ethanol stream. The hydrogen production unit, which produces the hydrogen stream and the steam stream. The hydrogen production unit may be a steam reformer or partial oxidation unit.

Claims

1. An integrated process for producing biofuels from a biofuel feedstock, comprising a cellulosic component and a starch component, the process comprising:

introducing the cellulosic component and a hydrogen stream generated by a hydrogen production unit, into a first biofuels process,

introducing the starch component and a steam stream into a second biofuels process,

introducing a char stream generated by a pyrolysis of the first biofuels process; and

a hydrocarbon stream generated by a low pressure hydrotreating component into the hydrogen production unit.

2. The process of claim 1, wherein said steam stream is generated by a high pressure hydrotreating component of the first biofuels process and/or the hydrogen production unit.

3. The process of claim 1, wherein the first biofuels process is a second generation cellulosic biofuels process.

4. The process of claim 1, wherein the second biofuels process is a first generation bio-ethanol process.

5. The process of claim 1, wherein:

the first biofuels process is a second generation cellulosic biofuels process comprising;

the pyrolysis means, the pyrolysis means producing the char stream and a bioliquid stream,

the low pressure hydrotreating component, a high pressure hydrotreating component, the low pressure hydrotreating component producing the hydrocarbon stream, the high pressure hydrotreating component producing the steam stream, and

a distillation means, producing a green gasoline stream and a green diesel stream from the bioliquid stream,

the second biofuels process is a first generation bio-ethanol process, producing a bio-ethanol stream, and

the hydrogen production unit, produces the hydrogen stream and the steam stream.

6. The process of claim 1, where the hydrogen production unit is a steam reformer.

7. The process of claim 5 wherein the hydrogen production unit has a furnace, a process effluent stream, a flue gas stream, a feed stream and a fuel stream, wherein the feed stream is the hydrocarbon stream, the fuel stream is the char stream, and the feed is combined with the steam stream, produced from the hydrogen production unit, and fed to the furnace.

8. The process of claim 7 where the process effluent stream indirectly exchanges heat with a first feed water stream in a first waste heat boiler and the flue gas stream indirectly exchanges heat with a second feedwater stream in a second waste heat boiler to produce the steam stream.

9. The process of claim 7 further comprising:

contacting the process effluent with a catalyst in a water gas shift reactor to convert carbon monoxide to hydrogen and carbon dioxide, thereby producing a shift effluent,

indirectly exchanging heat between the shift effluent and a first feed water stream in a first waste heat boiler to produce the steam stream, thereby producing a cooled shift effluent,

feeding the cooled shift effluent into a pressure swing adsorption (PSA) unit to separate hydrogen from carbon monoxide, un-reacted hydrocarbons and carbon dioxide, thereby producing the hydrogen stream and a PSA tail gas stream,

sending the hydrogen stream to the high pressure hydrotreating component, and

sending the PSA tail gas to the furnace wherein it is used as fuel for the furnace in combination with the char stream.

10. The process of claim 9, wherein the high pressure hydrotreating component is a bioliquid hydrotreater.

11. The process of claim 9, wherein the PSA tail gas comprises carbon monoxide, un-reacted hydrocarbons and carbon dioxide and some portion of hydrogen.

12. the process of claim 9 where at least a portion of the steam stream is fed to the furnace and at least a portion of the steams stream produced is exported to the second biofuels process.

13. The process of claim 5 where the hydrogen production unit consists of a partial oxidation unit.

14. The process of claim 13 wherein the partial oxidation unit further comprises:

introducing the char stream and the hydrocarbon stream as feed,

generating an oxygen stream by air separation in a cryogenic process and introducing the oxygen stream into the partial oxidation unit,

combining the oxygen stream, the char stream, and the hydrocarbon stream in the partial oxidation unit thereby producing a syngas stream,

cooling the syngas stream in a first heat exchanger thereby creating a cooled syngas stream,

combining the cooled syngas stream with a water stream or a steam stream, thereby producing a wet syngas stream,

introducing the wet syngas stream into a water gas shift reactor wherein a water gas shift reaction is promoted by contact with a catalyst, thereby producing a shifted syngas stream,

indirectly exchanging heat between the shifted gas stream and a feed water stream in a waste heat boiler to produce a steam stream, thereby producing a cooled shifted syngas stream,

further cooling the cooled shifted syngas stream in an air cooler, thereby producing a further cooled shifted syngas stream, and

sending said further cooled shifted syngas stream to a first absorbtion unit where a hydrogen stream is separated from a first off-gas stream.

15. The process of claim 14, wherein the syngas stream comprises hydrogen, carbon monoxide and carbon dioxide.

16. The process of claim 14, wherein the catalyst promotes the conversion of carbon monoxide to hydrogen to produce a shifted syngas with at least 90% of the carbon monoxide converted to hydrogen.

17. The process of claim 14 where the first adsorption unit consists of a pressure swing adsorption (PSA) unit producing hydrogen with a purity of greater than 99.5%.

18. The process of claim 14, wherein the hydrogen stream is sent to the bioliquid hydrotreater.

19. The process of claim 14, wherein the first off-gas stream, comprising a PSA tail gas consisting of carbon monoxide, carbon dioxide, unreacted hydrocarbon, nitrogen and argon impurities of the oxygen stream, comprising:

compressing at least part of the first off-gas stream in a compressor thereby producing a compressed off-gas stream, and a remainder stream and

recycling the compressed off-gas stream to the first adsorption unit for further recovery of hydrogen or

sending the compressed off-gas stream to a second adsorption unit for further recovery of hydrogen, and thereby producing a second off-gas stream, and a second hydrogen stream,

combining the remainder stream and the second off-gas stream to form a combined off-gas stream, and

sending the combined off-gas stream to the bioliquid hydrotreater to be used as fuel in furnaces within the bioliquid hydrotreater and/or the fractionation section.

20. The process of claim 14 wherein the second adsorption unit is a PSA.

21. The process of claim 14 wherein the first adsorption unit comprises an absorber for the removal of carbon dioxide and further purification of hydrogen comprising:

removing carbon dioxide in the absorber, by contacting the cooled shifted syngas stream with an activated MDEA stream, or similar solvent stream, thereby producing a purified hydrogen stream from the overhead of the absorber and a rich solvent stream from the bottom of the absorber,

sending the rich solvent stream to a regenerator where a steam stream is used to regenerate the solvent stream thereby producing a regenerated solvent stream which is returned to the absorber,

heating the purified hydrogen stream in a heat exchanger, thereby producing a heated purified hydrogen stream, which is sent to a methanation reactor where it is contacted with a catalyst to promote the reaction of remaining carbon monoxide and carbon dioxide to produce a methane stream and a further purified hydrogen stream, wherein the further purified hydrogen stream has a purity of greater than 97%, and the further purified hydrogen stream is sent to the high pressure hydrotreating component.

22. A biofuels production process, comprising:

providing a biofuel feedstock, comprising a cellulosic component and a starch component,

separating the cellulosic component from the starch component,

introducing the cellulosic component to a pyrolysis process, thereby producing at least a char stream and a bio-oil stream,

introducing the bio-oil stream and a purge hydrogen stream into a low pressure hydrotreating process, thereby producing a first intermediate liquid stream, and a hydrocarbon stream,

introducing the first intermediate liquid stream and a hydrogen stream into a high pressure hydrotreating process, thereby producing a second intermediate liquid stream, the purge hydrogen stream, and the steam stream,

introducing the second intermediate liquid stream to a distillation column, thereby producing a product green gasoline stream and a product green diesel stream,

introducing the char stream, the hydrocarbon stream, into a hydrogen production unit, thereby producing the hydrogen stream, and a second steam stream,

combining the steam stream and the second steam stream to form combined steam stream,

introducing the starch component, and the combined steam stream into an ethanol plant, thereby producing a bio-ethanol stream.