# US 9,221,869 B2 · Recovery of phytosterols from residual vegetable oil streams

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- Number: US 9,221,869 B2
- Document ID: US9221869B2
- Status: Granted
- Kind: B2
- Application number: 12/921,610
- Filed: 2009-02-10
- Published: 2011-04-07
- Granted: 2015-12-29
- Earliest claimed: 2008-03-10
- Assignees: Sunpine AB
- Applicants: Lars Stigsson; Valeri Naydenov
- Inventors: Lars Stigsson; Valeri Naydenov
- Web page: https://patentgrep.com/patent/US9221869B2

## CPC

- C07J 9/00: Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
- C11C 3/003: {by esterification of fatty acids with alcohols (C11C3/02 takes precedence)}
- C11C 3/04: by esterification of fats or fatty oils
- Y02W 30/74: Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes
- C07J: STEROIDS (seco-steroids C07C)
- 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
- Y02W: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT

## Abstract

There is disclosed a method for isolation and purification of phytosterols from tall oil pitch comprising the steps of: a) contacting the tall oil pitch with a solvent to form a tall oil solvent mixture; b) separating the tall oil pitch solvent mixture in at least two separate streams wherein one process stream is enriched in acidic pitch components and a second stream enriched in free- and bound sterols in the form of steryl esters; c) subjecting the stream enriched in free- and steryl esters to treatment with an alcohol under transesterification conditions wherein a reaction mixture is formed and sterols comprising the steryl esters are liberated as free sterols; and d) separating the free sterols from the reaction mixture of step c) by crystallization and extraction with one or more solvents. There are disclosed free fatty acids and resin acids separated from the tall oil pitch. Moreover, there is disclosed a manufacture and separation of fatty acid alkyl esters by the method.

## Claims

### Claim 1

Method for recovering phytosterols from tall oil pitch (TOP) by a sequence of reaction and separation steps, comprising the steps of:
a) contacting TOP with a solvent comprising methanol at a temperature above 25 degrees and under 100 degrees C. thereby forming a TOP solvent mixture;
b) separating the TOP solvent mixture, without saponification, into at least two separate process streams or phases wherein a first process stream or phase is enriched in acidic pitch components and a second process stream or phase is enriched in free sterols and bound sterols in the form of steryl esters;
c) subjecting the second process stream or phase enriched in free sterols and steryl esters to treatment with at least one alcohol and at least one catalyst thereby forming a reaction mixture wherein at least a portion of the steryl esters is liberated as free sterols without saponification, wherein step c) is achieved by
a transesterification promoting said steryl esters being liberated as free sterols and formation of fatty acid alkyl esters (FAAE's) corresponding to said steryl esters; and
d) separating free sterols from the reaction mixture of step c).

### Claim 2 (depends on 1)

Method in accordance with claim 1, wherein TOP is contacted with the solvent in step a) under intense mixing.

### Claim 3 (depends on 1)

Method in accordance with claim 1, wherein TOP is contacted with the solvent used in step a) using at least one continuous stirred tank reactor (CSTR).

### Claim 4 (depends on 1)

Method in accordance with claim 1, wherein a major portion of acidic pitch components comprising the TOP are separated based on their affinity towards polar solvents in step b).

### Claim 5 (depends on 1)

Method in accordance with claim 1, wherein a major portion of acidic pitch components comprising the TOP are separated in step b) by neutralization, adsorption, extraction, distillation or combinations thereof.

### Claim 6 (depends on 1)

Method in accordance with claim 1, wherein the contact of TOP with the solvent in step a) and the separation of TOP into two process streams or phases in step b) are performed in a mixer settler.

### Claim 7 (depends on 1)

Method in accordance with claim 1, wherein the acidic pitch components of the TOP are separated by at least one extraction with solvent in steps a) and b).

### Claim 8 (depends on 1)

Method in accordance with claim 1, wherein the second stream or phase obtained in step b), enriched in free- and bound sterols, has an acid value below 1 mg KOH g−1.

### Claim 9 (depends on 1)

Method in accordance with claim 1, wherein the free sterols crystallized in the second process stream or phase obtained in step c) are separated as solid crude sterol fraction.

### Claim 10 (depends on 1)

Method in accordance with claim 1, wherein the second process stream or phase obtained in step b), enriched in free- and hound sterols, is dehydrated prior transesterification in step c).

### Claim 11 (depends on 1)

Method in accordance with claim 1, wherein the second process stream or phase obtained in step b), enriched in free- and bound sterols, is contacted with an amount of anhydrous methanol or ethanol prior to performing step c).

### Claim 12 (depends on 1)

Method in accordance with claim 1, wherein the transesterification in step c) is performed in a CSTR under reflux conditions.

### Claim 13 (depends on 1)

Method in accordance with claim 1, wherein the at least one catalyst used in step c) is used to promote transesterification and is an alkali catalyst selected from the group consisting of alkali- and alkali-earth hydroxides, spinel-like oxides, alkali-forms of cation exchange resins, phase-transfer catalysts and mixtures thereof.

### Claim 14 (depends on 1)

Method in accordance with claim 1, wherein the separating of free sterols from the reaction mixture of step c) in step d) is performed by at least one of crystallization and extraction with one or more solvents.

### Claim 15 (depends on 1)

Method in accordance with claim 1, wherein fatty acid alkyl esters are separated from the reaction mixture obtained after step d).

### Claim 16 (depends on 1)

Method in accordance with claim 1, wherein free sterols that have crystallized within the second process stream or phase after step b) are separated from the second process stream or phase before step c).