Process to make olefins from isobutanol

Patent metadata

Field	Value
Publication number	US-9522853-B2
Application number	US-201514857068-A
Country	US
Kind code	B2
Filing date	Sep 17, 2015
Priority date	Aug 3, 2010
Publication date	Dec 20, 2016
Grant date	Dec 20, 2016

Abstract

A process for the conversion of an alcohol mixture to make propylene may include introducing into a reactor a stream that includes the alcohol mixture. The alcohol mixture may include 20 to 100 weight percent isobutanol. The process may include contacting the stream with a single catalyst at a temperature above 450° C. in the reactor at conditions effective to dehydrate the 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 the catalytic cracking. The process may include recovering from the reactor an effluent that includes ethylene, propylene, water, and various hydrocarbons. The process may include fractionating the effluent to produce an ethylene stream, a propylene stream, a fraction of hydrocarbons having 4 carbon atoms or more, and water.

First claim

The invention claimed is:

1. A process comprising:
a) introducing in a reactor a stream comprising an alcohol mixture, optionally water, optionally an inert component, wherein the alcohol mixture comprises from 40 to 100 weight percent isobutanol based on a total weight of the alcohol mixture,
b) contacting said stream with a single catalyst at a temperature above 450° 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 to 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 alcohol mixture, various hydrocarbons, and 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 comprising hydrocarbons having 4 carbon atoms or more, water and 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 comprising hydrocarbons having 4 carbon atoms or more at the inlet of the reactor;
wherein the single catalyst comprises a dealuminated crystalline silicate containing at least one 10 member ring in the structure thereof.

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 comprising hydrocarbons having more than 4 carbon atoms, water and optionally oxygenates.

3. The process according to claim 1 , wherein the alcohol mixture is subjected to purification to reduce a content of metal ions in the alcohol mixture.

4. The process of claim 3 , wherein the metal ions are selected from Na, Fe, K, Ca and Al.

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

6. The process according to claim 1 , wherein the fraction comprising hydrocarbons having 4 carbon atoms or more recovered at step d) comprises 2-butene, and wherein the process further comprises reacting ethylene with the 2-butene from the fraction comprising hydrocarbons having 4 carbon atoms or more recovered at step d) to produce propylene.

7. The process according to claim 1 , further comprising recovering n-butenes from the fraction comprising hydrocarbons having 4 carbon atoms or more recovered at step d) and reacting the n-butenes in an automethathesis to produce propylene and pentenes.

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

9. 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.

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

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

12. The process according to claim 1 , wherein the crystalline silicate is an MFI, MEL, FER, MTT, MWW, TON, EUO, MFS, CON or ZSM-48.

13. The process according to claim 1 , wherein the crystalline silicate is 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-2, ITQ-1, MCM-49, ZSM-22, Theta-1, NU 10, ZSM-50, EU-1, ZSM-57, CIT-1, or ZSM-48.

14. The process according to claim 1 , wherein the crystalline silicate has a Si/Al ratio of at least 100.

15. The process of claim 14 , wherein the crystalline silicate is an MFI or MEL and is modified with a metal and comprises a metal content of at least 0.1 weight percent based on a total weight of the crystalline silicate, and wherein the metal is selected from the group consisting of Mg, Ca, La, Ni, Ce, Zn, Co, Ag, Fe and Cu.

16. The process of claim 1 , wherein the crystalline silicate is mixed with a binder.

17. The process of claim 16 , wherein the binder is selected from clays, silica, metal silicate, metal borates, metal oxides, and gels including mixtures of silica and metal oxides.

18. The process according to claim 1 , wherein the crystalline silicate is silicalite-1, boralite C, TS-1, silicalite-2, boralite D, TS-2, SSZ-46, Ferrierite, FU-9, ZSM-35, ZSM-23, MCM-22, PSH-2, ITQ-1, MCM-49, ZSM-22, Theta-1, NU 10, ZSM-50, EU-1, ZSM-57, CIT-1, or ZSM-48.

19. The process according to claim 1 , wherein the crystalline silicate is silicalite-1, boralite C, TS-1, silicalite-2, boralite D, TS-2, SSZ-46, FU-9, ZSM-35, ZSM-23, MCM-22, PSH-2, ITQ-1, MCM-49, ZSM-22, Theta-1, NU 10, ZSM-50, EU-1, ZSM-57, CIT-1, or ZSM-48.

Assignees

• Total Res & Technology Feluy

Inventors

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

Classifications

• C07C6/04

  at a carbon-to-carbon double bond · CPC title

• Y02P20/52

  using catalysts, e.g. selective catalysts · CPC title

• C10G2300/1022

  Fischer-Tropsch products · CPC title

• C10G2400/20

  C2-C4 olefins · CPC title

• C10G2300/4081

  Recycling aspects · CPC title