# US 9,752,099 B2 · Conjugated linoleic acid rich vegetable oil production using heterogeneous catalysis

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- Number: US 9,752,099 B2
- Document ID: US9752099B2
- Status: Granted
- Kind: B2
- Application number: 14/960,919
- Filed: 2015-12-07
- Published: 2016-06-09
- Granted: 2017-09-05
- Earliest claimed: 2014-12-05
- Assignees: Board of Trustees of the University of Arkansas
- Applicants: Board of Trustees of the University of Arkansas
- Inventors: Andrew Proctor; Chuan Min Ruan
- Web page: https://patentgrep.com/patent/US9752099B2

## CPC

- C11C 3/14: by isomerisation {(isomerisation induced by hydrogenation C11C3/12)}
- C11C: FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM

## Abstract

The invention is directed to CLA-rich vegetable oil production from linoleic rich oils by heterogeneous catalysis. The process produces conjugated PUFA in triglyceride form, preferably at least 20% CLA-rich, by isomerization of a non-conjugated PUFA in vegetable oils using a heterogeneous transition metal catalyst promoted by an organic acid and/or thiol-containing compound. The heterogeneous catalysis isomerization process can use steam/vacuum distillation, hydrogenation unit and/or deodorization to produce CLA-rich soy oil. After processing, any catalyst residue may be removed by filtration, beaching, deodorizing, adsorbents or centrifugation to obtain high quality, CLA-rich oils.

## Claims

### Claim 1

A process for producing conjugated linoleic acid-rich oil, said process comprising the steps of:
heterogeneously catalyzing a linoleic acid-rich oil using a catalytic amount of nickel in the presence of a promoter to produce said conjugated linoleic acid-rich oil.

### Claim 2 (depends on 1)

The process of claim 1 wherein said linoleic acid-rich oil is a triacylglyceride vegetable oil.

### Claim 3 (depends on 2)

The process of claim 2 wherein said triacylglyceride vegetable oil is selected from the group consisting of soy, sunflower, corn, cottonseed and peanut oil.

### Claim 4 (depends on 1)

The process of claim 1 wherein said nickel is metal nickel, nickel sulfide (NiS) or nickel formate Ni(COO)2.

### Claim 5 (depends on 4)

The process of claim 4 wherein said metal nickel is distributed on silica/alumina, nickel alloys with iron, aluminum, chromium and carbon loaded on silica/alumina.

### Claim 6 (depends on 1)

The process of claim 1 wherein said nickel is an organic amino or thiol compound self-assembly monolayer modified nickel catalyst.

### Claim 7 (depends on 1)

The process of claim 1 wherein said catalytic amount of said nickel comprises up to about 10% nickel.

### Claim 8 (depends on 7)

The process of claim 7 wherein said catalytic amount of said nickel comprises between about 0.025% and about 1% nickel.

### Claim 9 (depends on 1)

The process of claim 1 wherein said promoter is selected from the group consisting of organic proton donors, monosulfides, disulfides, mercaptans and mixtures thereof.

### Claim 10 (depends on 9)

The process of claim 9 wherein said promoter is selected from the group consisting of methanol, ethanol, isopropyl alcohol, formic acid, acetic acid, benzoic acid, 2-mercaptoethanol, ethanethiol, 1,2-ethanedithiol, L-cysteine, cysteamine, thiolactic acid, mercaptosuccinic acid and a mixture thereof.

### Claim 11 (depends on 10)

The process of claim 10 wherein said promoter is selected from the group consisting of acetic acid, formic acid, L-cysteine, mercaptosuccinic acid and a mixture thereof.

### Claim 12 (depends on 1)

The process of claim 1 wherein said promoter is formic acid, L-cysteine or a mixture thereof.

### Claim 13 (depends on 12)

The process of claim 12 wherein said formic acid comprises up to about 10% formic acid in said linoleic acid-rich oil and about 85% formic acid as a steam.

### Claim 14 (depends on 13)

The process of claim 13 wherein said formic acid in said linoleic acid-rich oil comprises between about 0.05% and about 2% formic acid in said linoleic acid-rich oil.

### Claim 15 (depends on 12)

The process of claim 12 wherein said cysteine comprises up to about 1% cysteine.

### Claim 16 (depends on 15)

The process of claim 15 wherein said cysteine comprises between about 0.002% and about 0.4% cysteine.

### Claim 17 (depends on 12)

The process of claim 12 wherein said mixture of formic acid and cysteine comprises a cysteine-to-nickel ratio of about 1:10.

### Claim 18 (depends on 1)

The process of claim 1 said catalysis step further comprises catalyzing said linoleic acid-rich oil using said catalytic amount of said nickel in the presence of cysteine, formic acid or a mixture thereof to produce said conjugated linoleic acid-rich oil.

### Claim 19 (depends on 18)

The process of claim 18 wherein said catalysis step further comprises catalyzing said linoleic acid-rich oil using said catalytic amount of said nickel in the presence of said cysteine, formic acid or a mixture thereof at a temperature of between about 165° C. and about 250° C. to produce said conjugated linoleic acid-rich oil.

### Claim 20 (depends on 18)

The process of claim 18 wherein said catalysis step further catalyzing said linoleic acid-rich oil using said catalytic amount of said nickel in the presence of said cysteine, forming acid or a mixture thereof under nitrogen pressure with bleeding of said nitrogen to produce said conjugated linoleic acid-rich oil.

### Claim 21 (depends on 20)

The process of claim 20 wherein said catalysis step further comprises catalyzing said linoleic acid-rich oil using said catalytic amount of said nickel in the presence of said cysteine, formic acid or a mixture thereof under nitrogen pressure of up to about 76 psi to produce said conjugated linoleic acid-rich oil.

### Claim 22 (depends on 21)

The process of claim 21 wherein said nitrogen pressure is between about 40 psi and about 50 psi.

### Claim 23 (depends on 18)

The process of claim 18 wherein said catalysis step further comprises catalyzing said linoleic acid-rich oil using said catalytic amount of said nickel in the presence of said cysteine, formic acid or a mixture thereof for between about 30 minutes and about 68 hours to produce said conjugated linoleic acid-rich oil.

### Claim 24 (depends on 23)

The process of claim 23 wherein said catalysis step further comprises catalyzing said linoleic acid-rich oil using said catalytic amount of said nickel in the presence of said cysteine, formic acid or a mixture thereof for between about 30 minutes and about 6 hours to produce said conjugated linoleic acid-rich oil.

### Claim 25 (depends on 20)

The process of claim 20 wherein said catalysis step further comprises catalyzing said linoleic acid-rich oil using said catalytic amount of said nickel in the presence of said cysteine, formic acid or a mixture thereof under nitrogen pressure between about 40 psi and about 50 psi for between about 30 minutes and about 6 hours at temperature of about 210° C. to produce said conjugated linoleic acid-rich oil.

### Claim 26 (depends on 25)

The process of claim 25 wherein said nickel comprises between about 0.04% and about 1% nickel.

### Claim 27 (depends on 26)

The process of claim 26 wherein said cysteine, formic acid or a mixture thereof comprises between about 0.004% and about 0.25% cysteine and between about 0.25% and about 1% formic acid.

### Claim 28 (depends on 26)

The process of claim 26 wherein said cysteine, formic acid or a mixture thereof comprises about 10% formic acid in said linoleic acid-rich oil and about 85% formic acid as a steam.

### Claim 29 (depends on 1)

The process of claim 1 wherein said catalysis step further comprises catalyzing said linoleic acid-rich oil using said nickel in the presence of said promoter using steam/vacuum distillation to produce said conjugated linoleic acid-rich oil.

### Claim 30 (depends on 1)

The process of claim 1 wherein said catalysis step further comprises catalyzing said linoleic acid-rich oil using said nickel in the presence of said promoter using oil deodorization to produce said conjugated linoleic acid-rich oil.

### Claim 31 (depends on 1)

The process of claim 1 wherein said catalysis step further comprises catalyzing said linoleic acid-rich oil using said nickel in the presence of said promoter using hydrogenation to produce said conjugated linoleic acid-rich oil.

### Claim 32 (depends on 1)

The process of claim 1 further comprising the step of extracting any remaining nickel residue from said conjugated linoleic acid-rich soil.

### Claim 33 (depends on 32)

The process of claim 32 wherein said extraction step further comprises extracting said transition metal residue from said conjugated linoleic acid-rich soil using filtration, bleaching, deodorization, adsorbents, centrifugation or a combination thereof.

### Claim 34 (depends on 1)

The process of claim 1 further comprising the step of recovering said promoter from a steam condensate during said catalysis step.

### Claim 35 (depends on 19)

The process of claim 19 wherein said temperature is about 210° C.