Process for alkylation using ionic liquid catalysts

Patent metadata

Field	Value
Publication number	US-9914675-B2
Application number	US-201514675203-A
Country	US
Kind code	B2
Filing date	Mar 31, 2015
Priority date	Mar 31, 2015
Publication date	Mar 13, 2018
Grant date	Mar 13, 2018

Abstract

Alkylation processes are described. The processes utilize ionic liquid catalysts having a kinematic viscosity range of about 50 cSt to about 100 cSt at 25° C. Catalysts within this range produce alkylate having higher octane than catalysts outside this range, especially at higher process temperatures which are preferable from an operating cost standpoint. The alkylate can have one or more of a research octane number of at least about 93, a selectivity of C 8 of at least about 65%, and a mole ratio of trimethylpentane to dimethylhexane of greater than about 7:1.

First claim

What is claimed:

1. An alkylation process comprising:
passing an isoparaffin having from 4 to 10 carbon atoms and an olefin having from 3 to 10 carbon atoms to an alkylation reactor containing an unsupported, halometallate based ionic liquid catalyst to generate an alkylate having a research octane number of at least about 93,
wherein the ionic liquid catalyst has an initial kinematic viscosity in a range of about 50 cSt to about 100 cSt at a temperature of 25° C., and
wherein the alkylation reactor is operated at reaction conditions comprising an operating temperature greater than about 20° C., a molar ratio of isoparaffin to olefin of less than about 20:1, an overall olefin feed rate of greater than about 8 mol olefin/mol ionic liquid catalyst/hr, and a total residence time in a range of about 1 min to about 10 min.

2. The process of claim 1 wherein the ionic liquid catalyst has the initial kinematic viscosity in the range of about 60 cSt to about 90 cSt at a temperature of 25° C.

3. The process of claim 1 wherein the ionic liquid catalyst has an initial kinematic viscosity in a range of about 30 cSt to about 60 cSt at a temperature of 38° C.

4. The process of claim 1 wherein the operating temperature is in a range of about 20° C. to about 30° C.

5. The process of claim 4 wherein the isoparaffin has 4 carbon atoms and the olefin has 4 carbon atoms, wherein the reaction has a selectivity for C8 of at least about 67%, and wherein the alkylate has a mole ratio of trimethylpentane to dimethylhexane of greater than about 12.

6. The process of claim 4 wherein the alkylate has a research octane number of at least about 95.

7. The process of claim 1 wherein the operating temperature is greater than about 30° C.

8. The process of claim 7 wherein the isoparaffin has 4 carbon atoms and the olefin has 4 carbon atoms, wherein the reaction has a selectivity for C8 of at least about 65%, and wherein the alkylate has a mole ratio of trimethylpentane to dimethylhexane of greater than about 7.

9. The process of claim 1 wherein the ionic liquid catalyst comprises a phosphonium based ionic liquid, an imidazolium based ionic liquid having long side chains, a pyridinium based ionic liquid having long side chains, an ammonium based ionic liquid having long side chains, an imidazolium based ionic liquid having a brominated anion, a pyridinium based ionic liquid having a brominated anion, an ammonium based ionic liquid having a brominated anion, imidazolium, pyridinium, ammonium based ionic liquids with halometallate anions having an anion to cation ratio greater than 1.5 and less than 2, or combinations thereof.

10. The process of claim 1 wherein the ionic liquid catalyst is tributylpentylphosphonium heptachloroaluminate, tripropylhexylphosphonium heptachloroaluminate, tributylmethylphosphonium heptachloroaluminate, benzyltrimethylammonium heptachloroaluminates, tetrabutylphosphonium heptachloroaluminate, or combinations thereof.

11. The process of claim 1 wherein a conversion of the olefin is at least about 96%.

12. An alkylation process comprising:
passing an isoparaffin having 4 carbon atoms and an olefin having 4 carbon atoms to an alkylation reactor containing an unsupported, halometallate based ionic liquid catalyst to generate an alkylate,
wherein the ionic liquid catalyst has an initial kinematic viscosity in a range of about 50 cSt to about 100 cSt at a temperature of 25° C.,
wherein the alkylation reactor is operated at reaction conditions comprising an operating temperature greater than about 20° C., a molar ratio of isoparaffin to olefin of less than about 20:1, an overall olefin feed rate of greater than about 8 mol olefin/mol ionic liquid catalyst/hr, and a total residence time in a range of about 1 min to about 10 min,
wherein the reaction has a selectivity for C8 of at least about 65%, and
wherein the alkylate has a mole ratio of trimethylpentane to dimethylhexane of greater than 7:1.

13. The process of claim 12 wherein the ionic liquid catalyst has an initial kinematic viscosity in a range of about 30 cSt to about 60 cSt at a temperature of 38° C.

14. The process of claim 12 wherein the operating temperature is in a range of about 20° C. to about 30° C.

15. The process of claim 14 wherein the reaction has a selectivity for C8 of at least about 67%, wherein the alkylate has a mole ratio of trimethylpentane to dimethylhexane of greater than about 12:1, and wherein the alkylate has a research octane number of at least about 95.

16. The process of claim 12 wherein the operating temperature is greater than about 30° C.

17. The process of claim 16 wherein the reaction has a selectivity for C8 of at least about 65%, and wherein the alkylate has a research octane number of at least about 93.

18. The process of claim 12 wherein the ionic liquid catalyst comprises a phosphonium based ionic liquid, an imidazolium based ionic liquid having long side chains, a pyridinium based ionic liquid having long side chains, an ammonium based ionic liquid having long side chains, an imidazolium based ionic liquid having a brominated anion, a pyridinium based ionic liquid having a brominated anion, an ammonium based ionic liquid having a brominated anion, or combinations thereof.

19. The process of claim 12 wherein the ionic liquid catalyst comprises tributylpentylphosphonium heptachloroaluminate, tripropylhexylphosphonium heptachloroaluminate, tributylmethylphosphonium heptachloroaluminate, benzyltrimethylammonium heptachloroaluminates, tetrabutylphosphonium heptachloroaluminate, or combinations thereof.

20. The process of claim 12 wherein a conversion of the olefin is at least about 96%.

Assignees

• Uop Llc

Inventors

• Buchbinder Avram M
• Nafis Douglas A
• Bhattacharyya Alakananda
• Martins Susie C

Classifications

• C07C2527/125

  Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium · CPC title

• C07C2531/02

  containing organic compounds or metal hydrides · CPC title

• C10L1/06

  for spark ignition · CPC title

• C10G29/205

  by reaction with hydrocarbons added to the hydrocarbon oil · CPC title

• C10L1/04

  essentially based on blends of hydrocarbons · CPC title