Process to make olefins from isobutanol

Patent metadata

Field	Value
Publication number	US-9227885-B2
Application number	US-201514830898-A
Country	US
Kind code	B2
Filing date	Aug 20, 2015
Priority date	Aug 3, 2010
Publication date	Jan 5, 2016
Grant date	Jan 5, 2016

Abstract

A process for the conversion of an alcohol mixture may include introducing into a reactor a stream including the alcohol mixture mixed with a stream including olefins having 4 carbon atoms or more. The process may include contacting the stream with a single catalyst at a temperature above 500° C. in the reactor at conditions effective to dehydrate isobutanol, forming C 4 + olefins, and to catalytically crack the C 4 + olefins. The single catalyst may be an acid catalyst adapted to cause both the dehydration and catalytic cracking. The process may include recovering an effluent including ethylene, propylene, and water, and fractionating the effluent.

First claim

The invention claimed is:

1. A process for the conversion of an alcohols mixture comprising about 20 to 100 weight percent isobutanol to make essentially propylene, comprising:
a) introducing in a reactor a stream comprising the alcohols mixture, mixed with a stream comprising olefins having 4 carbon atoms or more (C 4 + olefins), optionally water, optionally an inert component,
b) contacting said stream with a single catalyst at a temperature above 500° C. in said reactor at conditions effective to dehydrate at least a part of the isobutanol and other alcohols, if any, forming C 4 + olefins and catalytically crack the C 4 + olefins wherein the single catalyst is an acid catalyst adapted to cause both the dehydration and the catalytic cracking,
c) recovering from said reactor an effluent comprising: ethylene, propylene, water, optionally unconverted alcohols of the alcohols mixture, various hydrocarbons, and optionally the optional inert component of step a),
d) fractionating said effluent of step c) to produce at least an ethylene stream, a propylene stream, a fraction consisting essentially of hydrocarbons having 4 carbon atoms or more, water and optionally the optional inert component of step a), optionally recycling ethylene in whole or in part at an inlet of the reactor, optionally recycling the fraction consisting essentially of hydrocarbons having 4 carbon atoms or more at the inlet of the reactor.

2. The process according to claim 1 , wherein, before recycling said hydrocarbons having 4 carbon atoms or more at the inlet of the reactor, said hydrocarbons having 4 carbon atoms or more are sent to a second fractionator to purge the heavies.

3. The process according to claim 1 , wherein the alcohol mixture is subjected to purification to reduce a content of metal ions selected from Na, Fe, K, Ca and Al in the alcohol mixture.

4. The process according to claim 1 , wherein the temperature in the reactor of step a) and b) is up to 650° C.

5. The process according to claim 1 , wherein the temperature in the reactor of step a) and b) ranges from 520° C. to 600° C.

6. The process according to claim 1 , wherein the temperature in the reactor of step a) and b) ranges from 540° C. to 590° C.

7. The process according to claim 1 , wherein the alcohol mixture comprises 40 to 100 weight percent of isobutanol.

8. The process according to claim 1 , wherein the alcohol mixture comprises 60 to 100 weight percent of isobutanol.

9. The process according to claim 1 , wherein the alcohol mixture comprises 80 to 100 weight percent of isobutanol.

10. The process according to claim 1 , wherein the alcohol mixture comprises essentially isobutanol.

11. The process according to claim 1 , further comprising fermenting carbohydrates coming from biomass, or from the syngas route or from the base-catalysed Guerbet condensation to obtain the isobutanol.

12. The process according to claim 1 , further comprising producing the isobutanol by the direct 2-keto acid pathway from carbohydrates that are isolated from biomass.

13. The process according to claim 1 , wherein ethylene is further polymerized optionally with one or more comonomers.

14. The process according to claim 1 , wherein propylene is further polymerized optionally with one or more comonomers.

15. The process according to claim 1 , wherein the stream comprising olefins having 4 carbon atoms or more (C 4 + olefins) comprises from 10 to 100 weight percent olefins.

16. The process according to claim 1 , wherein the stream comprising olefins having 4 carbon atoms or more (C 4 + olefins) comprises a hydrocarbon mixture containing normal and branched C 4 -C 10 olefins, optionally in a mixture with normal and branched paraffins, C 4 -C 10 aromatics, or combinations thereof.

17. The process according to claim 1 , wherein the mixture of the stream comprising olefins having 4 carbon atoms or more (C 4 + olefins) and the alcohol mixture contains at least 1 weight percent of the alcohol mixture at the inlet of the reactor.

18. The process according to claim 1 , wherein the single catalyst is a crystalline silicate containing at least one 10 member ring in the structure thereof.

19. The process according to claim 18 , wherein the single catalyst is selected from the group consisting of MFI, MEL, FER, MTT, MWW, TON, EUO, MFS, CON and ZSM-48.

20. The process according to claim 18 , wherein the single catalyst is selected from the group consisting of ZSM-5, silicalite-1, boralite C, TS-1, ZSM-11, silicalite-2, boralite D, TS-2, SSZ-46, ferrierite, FU-9, ZSM-35, ZSM-23, MCM-22, PSH-3, ITQ-1, MCM-49, ZSM-22, Theta-1, NU-10, ZSM-50, EU-1, ZSM-57, CIT-1 and ZSM-48.

21. The process according to claim 18 , wherein the crystalline silicate has a ratio Si/A1 of at least 100.

22. The process according to claim 21 , wherein the crystalline silicate is an MFI or MEL and is modified with at least 0.1 weight percent of a metal that is Mg, Ca, La, Ni, Ce, Zn, Co, Ag, Fe, or Cu.

23. The process according to claim 18 , wherein the crystalline silicate is a dealuminated crystalline silicate.

24. The process according to claim 18 , wherein the crystalline silicate is mixed with a binder.

25. The process according to claim 18 , wherein the binder is selected from clays, silica, metal silicate, metal borates, metal oxides, and gels including mixtures of silica and metal oxides.

Assignees

• Total Res & Technology Feluy

Inventors

• Adam Cindy
• Minoux Delphine
• Nesterenko Nikolai
• Van Donk Sander
• Dath Jean-Pierre

Classifications

• C08F210/06

  Propene · CPC title

• C07C2529/40

  of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 · CPC title

• C07C1/20 Primary

  starting from organic compounds containing only oxygen atoms as heteroatoms · CPC title

• C07C4/06

  Catalytic processes {(C07C4/025 takes precedence)} · CPC title

• C07C29/00

  Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring · CPC title