PROCESS TO MAKE ALPHA OLEFINS FROM ETHANOL

• US 20110288256A1
• Filed: 12/10/2009
• Published: 11/24/2011
• Est. Priority Date: 12/11/2008
• Status: Active Grant

• Current Assignee: Total Research & Technology Feluy SA (Totalenergies Se)
• Original Assignee: Total Petrochemicals Research Feluy (Totalenergies Se)
• Inventors: Vermeiren, Walter
• Granted Patent: US 9,029,619 B2
• Time in Patent Office: Days
• US Class Current: 526/348.6
• 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 11/107 with six carbon atoms
• CPC Class Codes: C07C 2/06 of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: Y02P 20/52 using catalysts, e.g. selective catalysts

Abstract

The present invention relates to a process to make alpha olefins comprising:

• • dehydrating ethanol to recover an ethylene stream,
  • introducing said ethylene stream into an oligomerization zone containing an oligomerization catalyst and into contact with said oligomerization catalyst,
  • operating said oligomerization zone at conditions effective to produce an effluent consisting essentially of 1-butene, 1-hexene, optionally heavier alpha olefins and unconverted ethylene if any,
  • introducing the above effluent into a fractionation zone to recover a stream consisting essentially of 1-butene, a stream consisting essentially of 1-hexene, optionally a stream consisting essentially of heavier alpha olefins and an optional ethylene stream.

In an advantageous embodiment the 1-hexene or at least one heavier alpha olefins, if any, are isomerized to an internal olefin and subsequently transformed by metathesis with the aid of additional ethylene into different alpha-olefins with even or odd number of carbons. By way of example 1-hexene is isomerized into 2-hexene and by methathesis with ethylene converted to 1-pentene and propylene.

In another embodiment the oligomerization zone is only a dimerization zone and butene is produced. 1-butene is isomerized to 2-butene and sent to a methathesis zone in the presence of ethylene to be converted to propylene. In said embodiment the dehydration catalyst is selected in the group consisting of a crystalline silicate having a ratio Si/Al of at least about 100, a dealuminated crystalline silicate, and a phosphorus modified zeolite.

Claims

1. Process to make alpha olefins comprising:

a) providing a dehydration zone containing a dehydration catalyst,

b) introducing a feedstock comprising ethanol, water, an inert component into said dehydration zone and into contact with said dehydration catalyst,

c) operating said dehydration zone at conditions effective to dehydrate at least a portion of the ethanol to essentially ethylene,

d) recovering from step c) an effluent comprising essentially ethylene, water, unconverted ethanol if any and the inert component,

e) introducing said effluent into a fractionation zone to recover an ethylene stream,

f) introducing said ethylene stream into an oligomerization zone containing an oligomerization catalyst and into contact with said oligomerization catalyst,

g) operating said oligomerization zone at conditions effective to produce an effluent consisting essentially of 1-butene, 1-hexene, heavier alpha olefins and unconverted ethylene if any,

h) introducing the effluent from step g) into a fractionation zone to recover a stream consisting essentially of 1-butene, a stream consisting essentially of 1-hexene, a stream consisting essentially of heavier alpha olefins and an ethylene stream.

2. Process according to claim 1 wherein,

the oligomerization of step g) is operated at conditions effective to produce an effluent consisting essentially of 1-butene, 1-hexene, 1-octene, heavier alpha olefins and unconverted ethylene if any, and

in step h) are recovered a stream consisting essentially of 1-butene, a stream consisting essentially of 1-hexene, a stream consisting essentially of 1-octene, a stream consisting essentially of heavier alpha olefins and an ethylene stream.

3. Process according to claim 1 wherein the dehydration catalyst is selected from the group consisting of a crystalline silicate having a ratio Si/Al of at least about 100, a dealuminated crystalline silicate, and a phosphorus modified zeolite.

4. Process according to claim 1 wherein the ethylene stream recovered at step h) is recycled back to the oligomerization zone of step f).

5. Process according to claim 1 wherein the 1-hexene or at least one heavier alpha olefins, if any, recovered at step h) are isomerized to an internal olefin and subsequently transformed by metathesis with the aid of additional ethylene into different alpha-olefins with even or odd number of carbons.

13. Process according to claim 1 wherein the ethanol is from biological origin.

21. A monomer produced according to the process of claim 13.

23. The monomer of claim 21 wherein said monomer is ethylene.

26. A polyethylene copolymer produced from the monomer of claim 23.

27. The polyethylene copolymer of claim 26 further comprising at least one monomer from biological origin.

6. Process to make alpha olefins comprising:

a) providing a dehydration zone containing a dehydration catalyst selected in the group consisting of a crystalline silicate having a ratio Si/Al of at least about 100, a dealuminated crystalline silicate, and a phosphorus modified zeolite,

b) introducing a feedstock comprising ethanol, water, an inert component into said dehydration zone and into contact with said dehydration catalyst,

c) operating said dehydration zone at conditions effective to dehydrate at least a portion of the ethanol to essentially ethylene,

d) recovering from step c) an effluent comprising essentially ethylene, water, unconverted ethanol if any and the inert component,

e) introducing said effluent into a fractionation zone to recover an ethylene stream,

f) introducing said ethylene stream into a dimerization zone containing a dimerization catalyst and into contact with said dimerization catalyst,

g) operating said dimerization zone at conditions effective to produce an effluent consisting essentially of 1-butene, heavier alpha olefins and unconverted ethylene if any,

h) introducing the effluent from step g) into a fractionation zone to recover a stream consisting essentially of 1-butene, a stream consisting essentially of heavier olefins and an ethylene stream.

7. Process according to claim 6 wherein the ethylene stream recovered at step h) is recycled back to the dimerization zone of step f).

8. Process according to claim 6 wherein there are additional steps comprising:

i) isomerizing the stream consisting essentially of 1-butene recovered at step h) to a stream comprising an increased quantity of 2-butene,

j) introducing the effluent comprising 2-butene, recovered from the previous step, into a methathesis zone containing a methathesis catalyst and into contact simultaneously with ethylene and said methathesis catalyst, wherein, the methathesis zone is operated at conditions effective to produce propylene,

k) introducing the effluent of step j) into a fractionation zone to recover propylene, unreacted ethylene, unreacted 2-butene and heavier components,

l) optionally recycling the unreacted ethylene and unreacted 2-butene to the methathesis zone.

16. Polyethylene copolymers made from any ethylene and from alpha olefins from biological origin made according to claim 20.

17. Polyethylene according to claim 16 wherein the ethylene is from fossil origin and there are between 0.1 and 15 w % of biological origin alpha-olefins.

18. Polyethylene copolymers made from ethylene and alpha olefins wherein at least 1% of the ethylene and 1% of the alpha-olefins are from biological origin and made according to claim 20.

19. Polypropylene where the propylene is at least 1% made from biological origin according to claim 20.

20. Process according to claim 8 wherein the ethanol is from biological origin.

22. A monomer produced according to the process of claim 20.

24. The monomer of claim 22 wherein said monomer is propylene.

25. A polypropylene produced from the monomer of claim 24.

28. A polyethylene copolymer produced from any ethylene and the monomer of claim 24.

9. Process to make alpha olefins comprising:

a) providing a dehydration zone containing a dehydration catalyst selected in the group consisting of a crystalline silicate having a ratio Si/Al of at least about 100, a dealuminated crystalline silicate, and a phosphorus modified zeolite,

b) introducing a feedstock comprising ethanol, water, an inert component into said dehydration zone and into contact with said dehydration catalyst,

c) operating said dehydration zone at conditions effective to dehydrate at least a portion of the ethanol to essentially ethylene,

d) recovering from step c) an effluent comprising essentially ethylene, water, unconverted ethanol if any and the inert component,

e) introducing said effluent into a fractionation zone to recover an ethylene stream,

f) introducing said ethylene stream into a dimerization zone containing a dimerization catalyst and into contact with said dimerization catalyst,

g) operating said dimerization zone at conditions effective to produce an effluent consisting essentially of 2-butene, heavier alpha olefins and unconverted ethylene if any,

h) introducing the effluent from step g) into a fractionation zone to recover a stream consisting essentially of 2-butene, a stream consisting essentially of heavier olefins and an ethylene stream.

10. Process according to claim 9 wherein the ethylene stream recovered at step h) is recycled back to the dimerization zone of step f).

11. Process according to claim 9 wherein there are additional steps comprising:

i) introducing said 2-butene into a methathesis zone containing a methathesis catalyst and into contact simultaneously with ethylene and said methathesis catalyst, wherein, the methathesis zone is operated at conditions effective to produce propylene,

j) introducing the effluent of step i) into a fractionation zone to recover propylene, unreacted ethylene, unreacted 2-butene and heavier components,

k) optionally recycling the unreacted ethylene and unreacted 2-butene to the methathesis zone.

12. Process to make alpha olefins comprising:

a) providing a dehydration zone containing a dehydration catalyst selected in the group consisting of a crystalline silicate having a ratio Si/Al of at least about 100, a dealuminated crystalline silicate, and a phosphorus modified zeolite,

b) introducing a feedstock comprising ethanol, water, an inert component into said dehydration zone and into contact with said dehydration catalyst,

c) operating said dehydration zone at conditions effective to dehydrate at least a portion of the ethanol to essentially ethylene,

d) recovering from step c) an effluent comprising essentially ethylene, water, unconverted ethanol if any and the inert component,

e) introducing said effluent into a fractionation zone to recover an ethylene stream,

f) introducing said ethylene stream into a trimerization zone containing a trimerization catalyst and into contact with said trimerization catalyst,

g) operating said trimerization zone at conditions effective to produce an effluent consisting essentially of 1-hexene, light-ends, heavier alpha olefins and unconverted ethylene if any,

h) introducing the effluent from step g) into a fractionation zone to recover a stream consisting essentially of 1-hexene, a stream consisting essentially of heavier olefins and an ethylene stream.

14. (canceled)

15. (canceled)