Preparation of olefin by alcohol dehydration, and uses thereof for making polymer, fuel or fuel additive

Patent metadata

Field	Value
Publication number	US-11834384-B2
Application number	US-201916979620-A
Country	US
Kind code	B2
Filing date	Mar 15, 2019
Priority date	Mar 16, 2018
Publication date	Dec 5, 2023
Grant date	Dec 5, 2023

Abstract

A process for the preparation of olefin by alcohol dehydration, for making polymer, fuel or fuel additive and use of olefin obtainable by said process for making polymer, fuel or fuel additive. Preferred olefin is C5 olefin obtained from dehydration of an alcohol or alcohol mixture, preferably from fusel oil.

First claim

The invention claimed is:

1. A C 5 olefin mixture containing:
(i) at least 50 wt % of an olefin mixture comprising (i-a) 2-methyl-but-2-ene, (i-b) 2-methyl-but-1-ene and (i-c) 3-methyl-but-1-ene, and
(ii) (ii-a) one C 4 olefin chosen among 1-butene, 2-butene, 2-methylpropene, and/or (ii-b) one C6 olefin chosen among 1-hexene, 2-hexene, 3-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2,3-dimethyl-2-butene, cyclohexene, 2-methyl-2-pentene, 3-methyl-2-pentene, 3,3-dimethyl-1-butene, 1-methyl-cyclopentene, 3-methyl-cyclopentene, 4-methyl-cyclopentene, methylene-cyclopentane,
the C 5 olefin mixture optionally comprising (ii-c) one C 15 hydrocarbon,
the C 5 olefin mixture being obtained by a process comprising the steps of:
a) providing an initial composition comprising at least 20 wt % of a C 5 branched alcohol based on the total weight of the initial composition, and
b1) dehydrating the initial composition and separating the obtained dehydrated composition to provide a first stream enriched in C 2 olefins, a second stream enriched in C 5 olefins, and a third stream containing heavier compounds, the C 5 olefin mixture being recovered from the second stream enriched in C 5 olefins, or
b2) separating the initial composition to provide a first stream enriched in C 2 alcohols, a second stream enriched in C 5 alcohols, and a third stream enriched in heavier compounds, and dehydrating the second stream enriched in C 5 alcohols to obtain the C 5 olefin mixture,

wherein the initial composition is obtained by fermentation of biomass feedstocks, and
wherein the initial composition comprises at least 20 wt % Cs branched alcohol, at least 1 wt % ethanol, at least 0.1 wt % n-propanol, at least 1 wt % C 4 alcohols, at most 1.5 wt % esters and at least 5 wt % water, based on the total weight of the initial composition.

2. The C 5 olefin mixture according to claim 1 , further comprising (i-d) cis-2-pentene and/or trans-2-pentene.

3. The C 5 olefin mixture according to claim 1 , wherein the branched alcohol is isoamyl alcohol.

4. The C 5 olefin mixture according to claim 1 , wherein the biomass feedstock is raw or refined fusel oil.

5. The C 5 olefin mixture according to claim 1 , wherein the dehydration step is carried out in the presence of a dehydration catalyst, containing at least one of (a) zeolites, (b) alumina, (c) silica-alumina, and (d) alumino silicate or any mixture thereof.

6. A process for the preparation of the C 5 olefin mixture according to claim 1 ,
comprising the steps of:
a) providing an initial composition comprising at least 20 wt % of a C 5 branched alcohol based on the total weight of the initial composition, and
b1) dehydrating the initial composition and separating the obtained dehydrated composition to provide a first stream enriched in C 2 olefins, a second stream enriched in C 5 olefins, and a third stream containing heavier compounds, the C 5 olefin mixture being recovered from the second stream enriched in C 5 olefins, or
b2) separating the initial composition to provide a first stream enriched in C 2 alcohols, a second stream enriched in C 5 alcohols, and a third stream enriched in heavier compounds, and dehydrating the second stream enriched in C 5 alcohols to obtain the C 5 olefin mixture,
wherein the initial composition is obtained by fermentation of biomass feedstocks.

7. The process according to claim 6 , wherein the C 5 olefin mixture further comprises (i-d) cis-2-pentene and/or trans-2-pentene.

8. The process according to claim 6 , wherein the C 5 branched alcohol is isoamyl alcohol.

9. The process according to claim 6 , wherein the initial composition comprises at least 20 wt % C 5 branched alcohol, at least 1 wt % ethanol, at least 0.1 wt % n-propanol, at least 1 wt % C 4 alcohols, at most 1.5wt % esters and at least 5 wt % water, based on the total weight of the initial composition.

10. The process according to claim 6 , wherein the biomass feedstocks are raw or refined fusel oil.

11. The process according to claim 10 , wherein the feedstocks are a C 4+ or C 4 -C 6 cut isolated from fusel oil.

12. The process according to claim 6 , wherein the dehydration step is carried out in the presence of a dehydration catalyst, containing at least one of (a) zeolites, (b) alumina, (c) silica-alumina, and (d) alumino silicate or any mixture thereof.

13. The process according to claim 12 , wherein the zeolites have the MFI, MTT, FER, MEL, TON, MWW, EUO, or MFS structure.

14. The process according to claim 12 , wherein the dehydration catalyst is chosen from gamma-alumina, H-ZSM-5, H-FER, ZSM-5 containing phosphorous or any mixture thereof.

15. The process according to claim 6 , wherein the initial composition is obtained by fermentation of feedstocks by microalgae or microorganisms.

16. A process for making an oligomer or a polymer, said process comprising:
combining, in the presence of a catalyst or an initiating system, at least (i) an optionally substituted vinyl aromatic, (ii) a C 4 -C 6 conjugated diene and/or a C 15 hydrocarbon, and (iii) the C 5 olefin mixture according to claim 1 .

17. The process according to claim 16 , for making an adhesive composition comprising a tackifying resin and an elastomer and/or a polyolefin, the tackifying resin being the oligomer or polymer.

18. The process according to claim 17 , wherein the elastomer is selected from the group consisting of styrene-isoprene block copolymers, polyacrylate resins, poly ethylene vinyl acetate (EVA) resins, poly styrene butadiene resins, random styrene butadiene (SBR) copolymers, styrene butadiene block copolymers, styrene butadiene styrene (SBS) block copolymers, styrene isoprene butadiene styrene (SIBS) copolymers, styrene ethylene propylene styrene (SEPS) copolymers, styrene ethylene butylene styrene (SEBS) block copolymers, amorphous polyolefin (APO) resins, and mixtures thereof.

19. The process according to claim 16 , wherein the optionally substituted vinyl aromatic is chosen among styrene, alpha-methyl-styrene, a vinyl toluene, a vinyl xylene, a vinyl ethyl benzene, a vinyl ethyl toluene, a vinyl ethyl xylene, a vinyl isopropyl toluene, a vinyl isopropyl xylene, and their mixtures, wherein the C 4 -C 6 conjugated diene is selected from 1,3-butadiene, isoprene, piperylene, 1-methyl-cyclopentadiene, 2-methyl-cyclopentadiene, 5-methyl-cyclopentadiene, and wherein the C 15 hydrocarbon is farnesene, and their mixtures and their cis and/or trans isomers, and wherein the oligomer or polymer is not hydrogenated, partially hydrogenated or fully hydrogenated.

20. The process according to claim 16 , wherein the polymer has a glass transition temperature Tg above 35° C., a number average molecular mass Mn from 400 to 2400 g/mol, a mass average molecular mass Mw from 900 to 4000 g/mol, a Z-average molecular mass Mz from 1500 to 6000 g/mol, a molecular weight distribution Mw/Mn from 1.50 to 1.90.

21. The process according to claim 16 , wherein the oligomer or polymer is a tackifying resin.

22. A process for making a fuel or fuel additive, said process comprising:
conducting the process of claim 6 ,
wherein the C 5 olefin mixture contains diisoamyl ether.

Assignees

• Total Marketing Services

Inventors

• Richardson Christine-Joy
• Germanaud Laurent
• KRESSMANN STéPHANE
• Henning Steven
• Nelson Keith
• Minoux Delphine

Classifications

• C07C1/24 Primary

  by elimination of water · CPC title

• C07C2/08

  Catalytic processes · CPC title

• C08F210/08

  Butenes · CPC title

• C10L1/1608

  Well defined compounds, e.g. hexane, benzene · CPC title

• C07C11/10

  with five carbon atoms · CPC title