# US 8,772,035 B2 · Process for controlling ionic liquid catalyst activity by titration

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- Number: US 8,772,035 B2
- Document ID: US8772035B2
- Status: Granted
- Kind: B2
- Application number: 13/008,662
- Filed: 2011-01-18
- Published: 2011-07-28
- Granted: 2014-07-08
- Earliest claimed: 2008-11-26
- Assignees: Chevron U.S.A. Inc.
- Applicants: Hye Kyung Timken; Annie T. Pathiparampil
- Inventors: Hye Kyung Timken; Annie T. Pathiparampil
- Web page: https://patentgrep.com/patent/US8772035B2

## CPC

- G01N 31/10: using catalysis
- B01J 31/0284: {of an aromatic ring, e.g. pyridinium}
- B01J 31/40: Regeneration or reactivation
- C07C 2/58: Catalytic processes
- C10G 11/02: characterised by the catalyst used
- C10G 29/06: Metal salts, or metal salts deposited on a carrier
- C10G 29/205: {by reaction with hydrocarbons added to the hydrocarbon oil}
- C10G 50/00: Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
- G01N 31/16: using titration
- B01J 27/06: Halogens; Compounds thereof
- B01J 27/125: with scandium, yttrium, aluminium, gallium, indium or thallium
- B01J 31/00: Catalysts comprising hydrides, coordination complexes or organic compounds (catalyst compositions used only in polymerisation reactions C08 {; catalytic antibodies C12N9/0002})
- Y02P 20/584: Recycling of catalysts
- Y10T 436/145555: Hetero-N
- G01N: INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES (measuring or testing apparatus or processes other than immunoassay, involving enzymes or microorganisms C12M, C12Q)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

A process for determining ionic liquid catalyst deactivation including (a) collecting at least one sample of an ionic liquid catalyst; (b) hydrolyzing the at least one sample to provide at least one hydrolyzed sample; (c) titrating the at least one hydrolyzed sample with a basic reagent to determine a volume of the basic reagent necessary to neutralize a Lewis acid species of the ionic liquid catalyst; and (d) calculating the acid content of the at least one sample from the volume of basic reagent determined in step (c) is described. Processes incorporating such a process for determining ionic liquid catalyst deactivation are also described. These processes are an alkylation process, a process for controlling ionic liquid catalyst activity in a reaction producing by-product conjunct polymers, and a continuous process for maintaining the acid content of an ionic liquid catalyst at a target acid content in a reaction producing by-product conjunct polymers.

## Claims

### Claim 1

A process for controlling ionic liquid catalyst activity in a reaction producing by-product conjunct polymers, comprising:
(a) using an ionic liquid catalyst in a reaction producing by-product conjunct polymers;
(b) collecting samples of the ionic liquid catalyst at regular intervals;
(c) hydrolyzing the samples to provide hydrolyzed samples;
(d) titrating the hydrolyzed samples with a basic reagent selected from the group consisting of potassium hydroxide, sodium hydroxide, rubidium hydroxide, cesium hydroxide, and barium hydroxide until the basic reagent neutralizes a Lewis acid species of the ionic liquid catalyst, as indicated by an inflection point in a titration curve, to determine a volume of the basic reagent necessary to neutralize the Lewis acid species of each sample;
(e) calculating an acid content of the hydrolyzed samples from the volume of basic reagent determined in step (d); and
(f) regenerating the ionic liquid catalyst when the acid content of the hydrolyzed samples reaches or falls below 80% of a fresh acid content of a fresh ionic liquid catalyst that has not been subject to deactivation, to provide a regenerated ionic liquid catalyst; and wherein the fresh acid content of the fresh ionic liquid catalyst is greater than 650 meq OH/q.

### Claim 2 (depends on 1)

The process according to claim 1, wherein the reaction is selected from the group consisting of paraffin alkylation, aromatic alkylation, polymerization, dimerization, oligomerization, acetylation, olefin metathesis, copolymerization, olefin isomerization, desulfurization, catalytic cracking, acylation, and combinations thereof.

### Claim 3 (depends on 1)

The process according to claim 1, wherein the acid content of the hydrolyzed samples is 512 meq OH/g or greater.

### Claim 4 (depends on 1)

The process according to claim 1, wherein the ionic liquid catalyst is a pyridinium-based chloroaluminate ionic liquid catalyst.

### Claim 5 (depends on 1)

The process according to claim 1, wherein the samples collected in step (b) are less than 1 gram.

### Claim 6 (depends on 1)

The process according to claim 1, wherein amounts of the hydrolyzed samples that are titrated are less than 1 gram.

### Claim 7 (depends on 1)

The process according to claim 1, wherein the titrating is done within an hour of the collecting.

### Claim 8 (depends on 1)

The process according to claim 1, additionally comprising maintaining an aluminum content in the samples of ionic liquid catalyst at greater than 9.5 wt %.

### Claim 9 (depends on 1)

The process according to claim 1, additionally comprising maintaining a density in the samples of ionic liquid catalyst at greater than 1.21 g/cc.

### Claim 10 (depends on 1)

The process according to claim 1, wherein the titration is performed with safeguards to protect the hydrolyzed samples from exposure to an atmosphere.

### Claim 11 (depends on 10)

The process according to claim 10, wherein the safeguards comprise a blanket of dry nitrogen gas.

### Claim 12 (depends on 1)

The process according to claim 1, wherein the hydrolyzing and titrating are performed in a same beaker.

### Claim 13 (depends on 1)

The process according to claim 1, wherein the ionic liquid catalyst is prepared by combining 1 molar equivalent alkyl substituted pyridinium halide or 1 molar equivalent alkyl substituted imidazolium halide with 2 molar equivalents of aluminum trichloride.

### Claim 14 (depends on 1)

The process according to claim 1, wherein the process is continuous, and additionally comprises varying one or more conditions of the reaction if the acid content of the hydrolyzed samples is above or below a target acid content.

### Claim 15 (depends on 14)

The process according to claim 14, wherein the one or more conditions comprise adding a fresh ionic liquid catalyst, changing a rate of adding the fresh ionic liquid catalyst, removing a used ionic liquid catalyst, varying a rate of removing the used ionic liquid catalyst, adding a regenerated ionic liquid catalyst, varying a rate of regenerating ionic liquid catalyst, or combinations thereof.

### Claim 16 (depends on 1)

The process of claim 1, wherein the hydrolyzed samples are in a solution with water and alcohol.

### Claim 17

A process for controlling ionic liquid catalyst activity in a reaction producing by-product conjunct polymers, comprising:
(a) using an ionic liquid catalyst in a reaction producing by-product conjunct polymers;
(b) collecting samples of the ionic liquid catalyst at regular intervals;
(c) hydrolyzing the samples using nitrogen purged, de-aerated water and an alcohol to provide hydrolyzed samples in a solution;
(d) titrating the hydrolyzed samples with a basic reagent of potassium hydroxide until the basic reagent neutralizes a Lewis acid species of the ionic liquid catalyst, as indicated by an inflection point in a titration curve, to determine a volume of the basic reagent necessary to neutralize the Lewis acid species of each sample;
(e) calculating an acid content of the hydrolyzed samples from the volume of basic reagent determined in step (d); and
(f) regenerating the ionic liquid catalyst when the acid content reaches or falls below 80% of an acid content of a fresh ionic liquid catalyst to provide a regenerated ionic liquid catalyst; and
wherein the acid content of the fresh ionic liquid catalyst is greater than 650 meq OH/g.