Integrated methods of preparing renewable chemicals

• US 8,450,543 B2
• Filed: 01/07/2011
• Issued: 05/28/2013
• Est. Priority Date: 01/08/2010
• Status: Active Grant

• Current Assignee: Gevo Incorporated
• Original Assignee: Gevo Incorporated
• Inventors: Peters, Matthew W., Taylor, Joshua D., Henton, David E., Manzer, Leo E., Gruber, Patrick R., Obaidi, Yassin Al, Griffith, Josefa M.
• Primary Examiner(s): Bullock, In Suk
• Assistant Examiner(s): Pregler, Sharon
• Application Number:
  US12/986,918
• Publication Number:
  US 20110172475A1
• Time in Patent Office: 872 Days
• Field of Search: 585/14, 585/240, 585/254, 585/303, 585/310, 585/324, 585/640, 585/647, 585/241, 585/242, 585/250, 585/252, 585/257, 585/275, 585/300, 585/314, 585/330, 585/379, 585/440, 443/85, 443/98, 444/03, 444/37, 208142-145
• US Class Current: 585/240
• CPC Class Codes: C07C 1/24 by elimination of water
• CPC Class Codes: C07C 11/02 Alkenes
• CPC Class Codes: C07C 11/04 Ethylene
• CPC Class Codes: C07C 11/08 with four carbon atoms
• CPC Class Codes: C07C 11/167 1, 3-Butadiene
• CPC Class Codes: C07C 15/02 Monocyclic hydrocarbons
• CPC Class Codes: C07C 15/04 Benzene
• CPC Class Codes: C07C 15/08 Xylenes
• CPC Class Codes: C07C 37/20 using aldehydes or ketones
• CPC Class Codes: C07C 37/50 by reactions decreasing the number of carbon atoms C07C37/04, C07C37/045, C07C37/055, C07C37/08 take precedence
• CPC Class Codes: C07C 407/00 Preparation of peroxy compounds
• CPC Class Codes: C07C 45/28 of CHx-moieties
• CPC Class Codes: C07C 45/53 of hydroperoxides
• CPC Class Codes: C07C 51/16 by oxidation C07C51/145 takes precedence
• CPC Class Codes: C07C 67/00 Preparation of carboxylic acid esters
• CPC Class Codes: C07C 67/08 by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
• CPC Class Codes: C07C 9/16 Branched-chain hydrocarbons
• CPC Class Codes: C07D 301/19 with organic hydroperoxides
• CPC Class Codes: C10G 29/205 by reaction with hydrocarbons added to the hydrocarbon oil
• 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 50/00 : Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
• CPC Class Codes: C10G 69/12 : including at least one polymerisation or alkylation step
• CPC Class Codes: Y02P 20/52 : using catalysts, e.g. selective catalysts
• CPC Class Codes: Y02P 30/20 : using bio-feedstock

Abstract

Isobutene, isoprene, and butadiene are obtained from mixtures of C₄ and/or C₅ olefins by dehydrogenation. The C₄ and/or C₅ olefins can be obtained by dehydration of C₄ and C₅ alcohols, for example, renewable C₄ and C₅ alcohols prepared from biomass by thermochemical or fermentation processes. Isoprene or butadiene can be polymerized to form polymers such as polyisoprene, polybutadiene, synthetic rubbers such as butyl rubber, etc. in addition, butadiene can be converted to monomers such as methyl methacrylate, adipic acid, adiponitrile, 1,4-butadiene, etc. which can then be polymerized to form nylons, polyesters, polymethylmethacrylate etc.

Claims

1. An integrated process for preparing renewable hydrocarbons, comprising:

(a) providing renewable isobutanol and renewable ethanol;

(b) dehydrating the renewable isobutanol, thereby forming a renewable butene mixture comprising one or more renewable linear butenes and renewable isobutene;

(c) dehydrating the renewable ethanol, thereby forming renewable ethylene;

(d) reacting at least a portion of the renewable butene mixture and at least a portion of the renewable ethylene to form one or more renewable C₃-C₁₆ olefins;

(e) forming renewable hydrogen by one or more of;

(e1) isolating and dehydrogenating at least a portion of the linear butenes formed in step (b) and/or one or more renewable C₄-C₁₆ olefins formed in step (d) thereby forming one or more renewable C₄-C₁₆ dienes and renewable hydrogen;

(e2) isolating and dehydrocyclizing at least a portion of one or more renewable C₆-C₁₆ olefins formed in step (d), thereby forming one or more renewable C₆-C₁₆ aromatics and renewable hydrogen;

(e3) isolating and dehydrocyclizing at least a portion of one or more renewable C₆-C₁₆ dienes formed in step (e1) to form one or more renewable C₆-C₁₆ aromatics and renewable hydrogen; and

(f) hydrogenating at least a portion of the renewable C₃-C₁₆ olefins with the renewable hydrogen formed in step (e), thereby forming a renewable saturated hydrocarbon fuel or fuel additive, wherein the amount of said dehydrogenating and/or dehydrocyclizing in step (e), and/or the amount of hydrogenating in step (f) are controlled so that the amount of renewable hydrogen formed in step (e) is essentially completely consumed in step (f).

2. The integrated process of claim 1, wherein the one or more renewable linear butenes comprise 2-butene.

3. The integrated process of claim 1, wherein said reacting of step (d) comprises one or more reactions selected from the group consisting of disproportionation, metathesis, oligomerization, isomerization, alkylation, dehydrodimerization, dehydrocyclization, and combinations thereof.

4. The integrated process of claim 1, wherein said reacting of step (d) comprises dimerizing at least a portion of the renewable isobutene, thereby forming a renewable isobutene dimer mixture comprising at least one C₈ hydrocarbon selected from the group consisting of a 2,4,4-trimethylpentene, a 2,5-dimethylhexene, and 2,5-dimethylhexadienes, and combinations thereof.

5. The integrated process of claim 1, wherein said reacting of step (d) comprises trimerizing at least a portion of the renewable isobutene, thereby forming a renewable isobutene trimer mixture comprising 2,2,4,6,6-pentamethylheptene.

6. The integrated process of claim 1, wherein said reacting of step (d) comprises tetramerizing at least a portion of the renewable isobutene, thereby forming a renewable isobutene tetramer mixture, wherein the renewable isobutene tetramer mixture comprises 2,2,4,6,6,8,8-heptamethylnonene.

7. The integrated process of claim 1, wherein said reacting of step (d) comprises isomerizing at least a portion of the renewable isobutene of step (b) to form an isobutene isomerization mixture comprising renewable 2-butene, wherein said reacting of step (d) further comprises disproportionating at least a portion of the renewable ethylene formed in step (c) and at least a portion of the renewable 2-butene formed by isomerizing at least a portion of the renewable isobutene of step (b), thereby forming renewable propylene.

8. The integrated process of claim 2, wherein said reacting of step (d) comprises disproportionating at least a portion of the renewable ethylene formed in step (c) and at least a portion of the renewable 2-butene formed in step (b), thereby forming renewable propylene.

9. The integrated process of claim 2, wherein said reacting of step (d) comprises disproportionating at least a portion of the renewable ethylene formed in step (c), and at least a portion of the renewable 2-butene formed in step (b) and renewable 2-butene formed by isomerizing the renewable isobutene formed in step (b), thereby forming renewable propylene.

10. The integrated process of claim 1, wherein step (e) comprises step (e1).

11. The integrated process of claim 10, wherein the one or more renewable C₄-C₁₆ dienes formed in step (e1) comprise butadiene.

12. The integrated process of claim 1, wherein step (e) comprises step (e2).

13. The integrated process of claim 12, wherein the one or more renewable C₆-C₁₆ aromatics formed in step (e2) comprise renewable p-xylene.

14. The integrated process of claim 1, wherein step (e) comprises step (e1) and step (e2).

15. The integrated process of claim 1, wherein step (e) comprises step (e1) and step (e3).

16. The integrated process of claim 1, wherein step (e) comprises step (e1), step (e2), and step (e3).

17. The integrated process of claim 4, wherein at least a portion of the renewable isobutene dimer mixture is hydrogenated in step (f), whereby the renewable saturated hydrocarbon fuel or fuel additive comprises isooctane, wherein the renewable isobutene dimer mixture is hydrogenated in step (f), whereby the renewable saturated hydrocarbon fuel or fuel additive comprises isooctane.

18. The integrated process of claim 5, wherein at least a portion of the renewable isobutene trimer mixture is hydrogenated in step (f), whereby the renewable saturated hydrocarbon fuel or fuel additive comprises one or more pentamethylheptanes, wherein the renewable isobutene trimer mixture is hydrogenated in step (f), whereby the renewable saturated hydrocarbon fuel or fuel additive comprises one or more pentamethylheptanes.

19. The integrated process of claim 1, wherein said reacting of step (d) further comprises mixing said renewable butene mixture and/or said renewable ethylene with at least a portion of a non-renewable butene and/or a butene mixture and/or non-renewable renewable ethylene to form one or more C₃-C₁₆ olefins, and at least a portion of said one or more C₃-C₁₆ olefins are renewable.