Alkylation process with recycle of hydrogen and recovery of hydrogen chloride

• US 9,302,199 B2
• Filed: 07/31/2012
• Issued: 04/05/2016
• Est. Priority Date: 07/31/2012
• Status: Active Grant

• Current Assignee: Chevron USA Incorporated (Chevron Corp.)
• Original Assignee: Chevron USA Incorporated (Chevron Corp.)
• Inventors: Timken, Hye Kyung Cho, Chang, Bong-Kyu
• Primary Examiner(s): Bullock, In Suk
• Assistant Examiner(s): LOUIE, PHILIP Y
• Application Number:
  US13/563,355
• Publication Number:
  US 20140066678A1
• Time in Patent Office: 1,344 Days
• Field of Search: 585/709
• US Class Current: 1/1
• CPC Class Codes: B01D 3/009 in combination with chemical reactions
• CPC Class Codes: B01J 38/10 using elemental hydrogen
• CPC Class Codes: C07C 2/54 by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
• CPC Class Codes: C07C 2/58 Catalytic processes
• CPC Class Codes: C07C 2527/125 Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium
• CPC Class Codes: C07C 9/16 Branched-chain hydrocarbons
• CPC Class Codes: Y02P 20/582 Recycling of unreacted starting or intermediate materials
• CPC Class Codes: Y02P 20/584 Recycling of catalysts

Abstract

We provide processes, and process units for practicing the processes, comprising

• • a. regenerating a used catalyst comprising an ionic liquid catalyst and a chloride, from an alkylation reactor, in a hydrogenation reactor to produce a regenerated catalyst effluent;
  • b. separating at least a portion of the regenerated catalyst effluent into a gas fraction comprising a hydrogen gas and into a light hydrocarbon fraction comprising a hydrogen chloride;
  • c. recycling at least a part of the gas fraction comprising the hydrogen gas to the hydrogenation reactor; and
  • d. recovering at least an amount of the light hydrocarbon fraction comprising the hydrogen chloride and recycling the at least the amount of the light hydrocarbon fraction to the alkylation reactor. The alkylation process units comprise a hydrogenation reactor, a fractionation unit, and connections for transmitting the gas fraction to the hydrogenation reactor and for transmitting the light hydrocarbon fraction to the alkylation reactor.

Claims

1. An alkylation process, comprising:

a. alkylating a reactant in an alkylation reactor (300) in the presence of an alkylation catalyst comprising an ionic liquid catalyst;

b. regenerating a used catalyst (70) comprising the ionic liquid catalyst and a chloride, from the alkylation reactor (300), in a hydrogenation reactor (100) to produce a regenerated catalyst effluent (10);

c. separating at least a portion of the regenerated catalyst effluent (10), using a hydrocarbon extraction solvent (25) comprising;

i. an alkylate gasoline comprising branched isoparaffins,

ii. the reactant for the alkylating comprising an isomerized olefin comprising isobutylene, or

iii. mixtures thereof,

into a gas fraction comprising a hydrogen gas (20), a light hydrocarbon fraction comprising a hydrogen chloride (30), and a regenerated ionic liquid catalyst stream;

d. recycling at least a part of the gas fraction comprising the hydrogen gas (20) to the hydrogenation reactor (100); and

e. recovering at least an amount of the light hydrocarbon fraction comprising the hydrogen chloride (30) and recycling the at least an amount of the light hydrocarbon fraction to the alkylation reactor (300);

wherein the gas fraction comprising the hydrogen gas (20) has a lower level of hydrogen chloride that is from 72 to 99 wt % lower than a level of hydrogen chloride in the regenerated catalyst effluent (10).

4. The alkylation process of claim 1, claim 2, or claim 3, wherein the at least an amount of the light hydrocarbon fraction additionally comprises an isoparaffin and an olefin.

5. The alkylation process of claim 1, wherein the at least an amount of the light hydrocarbon fraction is mixed with a recycled stream comprising a mixture of a second hydrogen chloride and a propane, from the alkylation reactor (300).

6. The alkylation process of claim 1, claim 2, or claim 3, wherein the at least an amount of the light hydrocarbon fraction comprising the hydrogen chloride is not pre-treated, other than optional separating, before recycling.

7. The alkylation process of claim 1, claim 2, or claim 3, wherein the at least a part of the gas fraction comprising the hydrogen gas (2) is not dried before recycling.

8. The alkylation process of claim 1, claim 2, or claim 3, wherein at least 80 wt % of the hydrogen chloride, produced in the hydrogenation reactor (100), is recovered and recycled to the alkylation reactor (300).

9. The alkylation process of claim 1, claim 2, or claim 3, additionally comprising:

removing a recycle gas purge (15) from the at least a part of the gas fraction comprising the hydrogen gas (20) prior to its recycling.

10. The alkylation process of claim 1, additionally comprising compressing the at least a part of the gas fraction comprising the hydrogen gas (20) before recycling the at least the part of the gas fraction to the hydrogenation reactor (100).

11. The alkylation process of claim 1, wherein the separating is done in a distillation column, into which is fed the isomerized olefin and an isoparaffin to be alkylated in the alkylation reactor (300).

12. The alkylation process of claim 11, wherein the isomerized olefin comprises 2-butene and the isoparaffin comprises isobutane.

13. The alkylation process of claim 11, wherein the isomerized olefin and the isoparaffin are fed to the distillation column at one or more locations above where the at least a part of the gas fraction is fed to the distillation column.

14. The alkylation process of claim 1, or claim 3, wherein the regenerated ionic liquid catalyst is recycled to the alkylation reactor (300).

15. The alkylation process of claim 1, or claim 2, wherein the regenerated catalyst effluent (10) comprises an extracted conjunct polymer naphtha (45).

16. The alkylation process of claim 1, claim 2, or claim 3, wherein the ionic liquid catalyst is selected from the group consisting of hydrocarbyl-substituted-pyridinium chloroaluminate, hydrocarbyl-substituted-imidazolium chloroaluminate, quaternary amine chloroaluminate, trialkyl amine hydrogen chloride chloroaluminate, alkyl pyridine hydrogen chloride chloroaluminate, and mixtures thereof.

17. The alkylation process of claim 1, claim 2, or claim 3, wherein a propane product, an n-butane product, and an alkylate gasoline blending component product are separated from an effluent from the alkylation reactor (300).

18. The alkylation process of claim 1, or claim 2, wherein the gas fraction comprising the hydrogen gas (20) has the lower level of hydrogen chloride that is from 85 to 99 wt % lower than the level in the regenerated catalyst effluent (10).

20. The alkylation process of claim 1, claim 2, or claim 3, wherein the hydrocarbon extraction solvent comprises the alkylate gasoline and the alkylate gasoline comprises dimethyl and trimethyl isomers.

21. The alkylation process of claim 1, claim 2, or claim 3, wherein the hydrocarbon extraction solvent comprises the isomerized olefin and an isoparaffin that are alkylated to make an alkylate gasoline blending component.

22. The alkylation process of claim 21, wherein the isoparaffin comprises an isobutane.

2. An alkylation process, comprising:

a. alkylating a reactant in an alkylation reactor (300) in the presence of an alkylation catalyst comprising an ionic liquid catalyst;

b. regenerating a used catalyst (70) comprising the ionic liquid catalyst and a chloride, from the alkylation reactor (300), in a hydrogenation reactor (100) to produce a regenerated catalyst effluent (10);

c. mixing a hydrocarbon extraction solvent (25) comprising;

i. an alkylate gasoline comprising branched isoparaffins,

ii. the reactant for the alkylating comprising an isomerized olefin comprising isobutylene, or

iii. mixtures thereof, with the regenerated catalyst effluent (10) to make a mixture;

d. separating at least a portion of the mixture into a gas fraction comprising a hydrogen gas (20) and into a light hydrocarbon fraction comprising a hydrogen chloride (30), the hydrocarbon extraction solvent (25), and a regenerated ionic liquid catalyst;

e. recycling at least a part of the gas fraction comprising the hydrogen gas (20) to the hydrogenation reactor (100);

f. recycling the regenerated ionic liquid catalyst to the alkylation reactor (300); and

g. recovering at least an amount of the light hydrocarbon fraction comprising the hydrogen chloride (30) and recycling the at least an amount of the light hydrocarbon fraction to the alkylation reactor (300);

wherein the gas fraction comprising the hydrogen gas (20) has a lower level of hydrogen chloride that is from 72 to 99 wt % lower than a level of hydrogen chloride in the regenerated catalyst effluent (10).

3. An alkylation process, comprising:

a. alkylating a reactant in an alkylation reactor (300) in the presence of an alkylation catalyst comprising an ionic liquid catalyst;

b. regenerating a used catalyst (70) comprising the ionic liquid catalyst and a chloride, from the alkylation reactor (300), in a hydrogenation reactor (100) to produce a regenerated catalyst effluent (10);

c. separating at least a portion of the regenerated catalyst effluent (10) into an offgas (50) comprising a hydrogen gas and into a separated liquid (85);

d. mixing a hydrocarbon extraction solvent (25) comprising;

i. an alkylate gasoline comprising branched isoparaffins,

ii. the reactant for the alkylating comprising an isomerized olefin comprising isobutylene, or

iii. mixtures thereof,

with the offgas (50) to make a mixture;

e. separating the mixture into a gas fraction comprising the hydrogen gas (20) and into a light hydrocarbon fraction comprising a hydrogen chloride (30);

f. recycling at least a part of the gas fraction comprising the hydrogen gas (20) to the hydrogenation reactor (100);

g. further separating the separated liquid (85), in a presence of a conjunct polymer extraction solvent (55), into an extracted conjunct polymer naphtha (45) and a regenerated ionic liquid catalyst stream (60); and

h. recovering at least an amount of the light hydrocarbon fraction comprising the hydrogen chloride and recycling the at least an amount of the light hydrocarbon fraction to the alkylation reactor (300);

wherein the gas fraction comprising the hydrogen gas (20) has a lower level of hydrogen chloride that is from 72 to 99 wt % lower than a level of hydrogen chloride in the offgas (50).

19. The alkylation process of claim 3, wherein the gas fraction comprising the hydrogen gas (20) has the lower level of hydrogen chloride that is from 85 to 99 wt % lower than the level in the offgas (50).