WO1993019144A1 - Fatty acid esters - Google Patents
Fatty acid esters Download PDFInfo
- Publication number
- WO1993019144A1 WO1993019144A1 PCT/EP1993/000529 EP9300529W WO9319144A1 WO 1993019144 A1 WO1993019144 A1 WO 1993019144A1 EP 9300529 W EP9300529 W EP 9300529W WO 9319144 A1 WO9319144 A1 WO 9319144A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- process according
- esters
- urea
- polyunsaturated fatty
- fatty acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- 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
- C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
- C11C1/08—Refining
- C11C1/10—Refining by distillation
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- 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
- C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
- C11C1/007—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids using organic solvents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- 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
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
Definitions
- the present invention relates to polyunsaturated fatty acid esters (PUFA esters), more particularly it relates to the enrichment of particular valuable and desired PUFA esters in mixtures containing such esters in lower concentrations.
- PUFA esters polyunsaturated fatty acid esters
- GLA As is it well known, GLA, EPA and DHA are the accepted terms for
- ⁇ -linolenic acid (C18:3 (n-6)), eicosapentaenoic acid (C20:5 (n-3)), docosahexaenoic acid (C22:6 (n-3)).
- the first mentioned acid occurs in vegetable oil
- the second and the third acid occur in marine oils.
- the novel process enables to separate the esters in question primarily from saturated fatty acid esters, mono unsaturated fatty acid esters and other PUFA esters.
- the process of treating the PUFA-esters with urea is conveniently carried out at temperatures between ca. 0°C and ca. 40°C, preferably in a range of ca. 20°C to ca. 25°C.
- the polar solvent is conveniently a lower alkanol, e.g. a C2-4- alcohol, in particular a C2 or 3-alcohol, e.g. ethanol, isopropanol, or a lower alkyl ketone, e.g. acetone. To a lesser extent, also methanol is feasible.
- a lower alkanol e.g. a C2-4- alcohol, in particular a C2 or 3-alcohol, e.g. ethanol, isopropanol, or a lower alkyl ketone, e.g. acetone.
- methanol is feasible.
- the concentration of the polar solvent is conveniently ca. 8 % to ca. 15%, preferably ca. 10%, of the total fatty arid esters. But also lower concentrations, e.g. 5% are feasible.
- the hydrocarbon solvent is conveniently pentane, hexane or heptane, but also cyclohexane is feasible.
- the ratio by weight of fatty arid esters to urea is of from ca. 1:0,5 to ca. 1:4, preferably ca. 1:1,0 to ca. 1:3.
- the concentration of the polyunsaturated fatty acid esters to be enriched is ca. 18 to ca. 30 % in the starting material.
- the insoluble urea complexes formed are simply removed, e.g. by centrifugation or filtration.
- the urea used can conveniently be recycled, e.g. by treatment of the separated insoluble urea complexes with a two phase solvent system.
- the hydrocarbon solvent is evaporated from the liquid phase containing the enriched polyunsaturated fatty arid esters in a manner known per se, e.g. in vacuo and preferably using columns, preferably columns with low pressure drops, e.g. such as suitable for high vacuum destinations, e.g. Sulzer columns, or thin film evaporators, preferably working step-wise, using a two evaporator chain, including conveniently the use of a falling film evaporator.
- the product obtained is finally distilled, e.g. using short path distillation, in order to remove any high boiling products.
- the ester mixture conveniently used as starting material is obtained by cleavage of the triglycerides of marine or vegetable oil, e.g. borage oil, and trans-esterification, through alkaline catalysis, in the presence of ethanol, followed by removing the ethanol and the base in a manner known per se, e.g. by distillation and separation of the two phase system.
- the starting oil is conveniently obtained, and refined by conventional means, e.g. by removal of the free fatty acids from the triglycerides, if necessary, followed by neutralisation, bleaching, deodorisation, etc. of the triglycerides.
- the novel process can also be applied to unrefined oils.
- the concentration of the polyunsaturated fatty arid esters to be enriched is ca. 18 to ca. 30 % of the mixture.
- the concentration of the esters of vegetable origin is ca. 18-25 %
- the concentration of the esters of marine origin is ca.
- esters originate from a vegetable oil, these are concentrated to ca. 50 %, wherein the esters stemming from marine oil are concentrated to ca. 65%.
- a further aspect of the present invention allows to enrich the esters stemming from marine oil actually up to even ca. 80%.
- Step a) and b) are carried out prior to the urea treatment of the present invention. They enable to obtain ester concentrations of ca. 55 to ca. 65 %, preferably ca. 60 %.
- a thin film evaporator or a falling film equipment is conveniently used, the pressure is conveniently between ca. 1 and ca. 20 mbar, preferably ca. 10 mbar, and the temperature is conveniently between ca. 40 and ca. 120°C, preferably ca. 50°C.
- step b) a thin fil evaporater is conveniently used, the pressure at the top of the column is conveniently between ca. 0,05 and ca. 0,2 mbar, and the temperature is between ca. 170° and 240°, preferably ca. 190°C.
- the column has conveniently at least 3, preferably ca. 10 stages. • foraTT ⁇ lR 1
- 4,5 1 ethanol are added and the suspension is mixed, namely for 30 hours and under nitrogen atmosphere.
- the insoluble urea inclusion complexes are centrifiiged (25°C), and these urea products are washed with hexane.
- the hexane phases are distilled, using a 0.5 m 2 evaporator, at 65°C, and at a pressure of 300 mbar, at a feed of 20 kg/hour.
- the bottom product is distilled once more, in order to remove any remaining solvent at 65°C/25 mbar, feed: 15 kg/hour:
- the GLA content of the product is now 50% as determined gas chromatographically.
- the resulting concentrate has a PUFA-content (EPA, DPA and
- 100 g of the Sambay bottom product are mixed with 10 g ethanol and added to a suspension of 120 g urea in 600 ml hexane.
- the hexane phase is evaporated to remove the solvent from the concentrate.
- the obtained final concentrate shows 78 weight-% EPA, DPA and DHA-ethyl esters.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Microbiology (AREA)
- Fats And Perfumes (AREA)
Abstract
The present invention relates to polyunsaturated fatty acid esters (PUFA esters), more particularly it relates to the enrichment of particular valuable and desired PUFA esters in mixtures containing such esters in lower concentrations. Such enrichment is effected by a particular urea treatment of the esters involved.
Description
Fatty acid esters
The present invention relates to polyunsaturated fatty acid esters (PUFA esters), more particularly it relates to the enrichment of particular valuable and desired PUFA esters in mixtures containing such esters in lower concentrations.
In the foreground of the interest is a process for the selective enrichment with polyunsaturated fatty acid esters, of which the first double bond is in the 3 or 6 position, particularly with GLA, EPA or DHA ester, of a mixture containing polyunsaturated fatty acid esters of which the first double bond is in the 3, 6 or 9 position, characterized in that the mixture is treated with urea suspended in a nonpolar hydrocarbon solvent containing a small amount of a polar solvent, in that the insolubles formed are separated and in that the fraction enriched with Δ3 and Δ6 polyunsaturated fatty acid esters, particularly with GLA, EPA or DHA ester, is collected as the liquid phase.
As is it well known, GLA, EPA and DHA are the accepted terms for
γ-linolenic acid (C18:3 (n-6)), eicosapentaenoic acid (C20:5 (n-3)), docosahexaenoic acid (C22:6 (n-3)).
The first mentioned acid occurs in vegetable oil, the second and the third acid occur in marine oils.
The novel process enables to separate the esters in question primarily from saturated fatty acid esters, mono unsaturated fatty acid esters and other PUFA esters.
The process of treating the PUFA-esters with urea is conveniently carried out at temperatures between ca. 0°C and ca. 40°C, preferably in a range of ca. 20°C to ca. 25°C.
These temperatures allow considerable energies to be saved, this in contrast to the prior art processes operating at higher temperatures.
These higher temperatures are usually necessitated if the previous urea treatment of the PUFA-esters is carried out in solution, as this is done in the prior of processes.
The polar solvent is conveniently a lower alkanol, e.g. a C2-4- alcohol, in particular a C2 or 3-alcohol, e.g. ethanol, isopropanol, or a lower alkyl ketone, e.g. acetone. To a lesser extent, also methanol is feasible.
The concentration of the polar solvent is conveniently ca. 8 % to ca. 15%, preferably ca. 10%, of the total fatty arid esters. But also lower concentrations, e.g. 5% are feasible.
The hydrocarbon solvent is conveniently pentane, hexane or heptane, but also cyclohexane is feasible.
The ratio by weight of fatty arid esters to urea is of from ca. 1:0,5 to ca. 1:4, preferably ca. 1:1,0 to ca. 1:3.
The concentration of the polyunsaturated fatty acid esters to be enriched is ca. 18 to ca. 30 % in the starting material.
As pointed out above, the insoluble urea complexes formed are simply removed, e.g. by centrifugation or filtration.
The urea used can conveniently be recycled, e.g. by treatment of the separated insoluble urea complexes with a two phase solvent system.
The hydrocarbon solvent is evaporated from the liquid phase containing the enriched polyunsaturated fatty arid esters in a manner known per se, e.g. in vacuo and preferably using columns, preferably columns with low pressure drops, e.g. such as suitable for high vacuum destinations, e.g. Sulzer columns, or thin film evaporators, preferably working step-wise, using a two evaporator chain, including conveniently the use of a falling film evaporator.
The product obtained is finally distilled, e.g. using short path distillation, in order to remove any high boiling products.
The ester mixture conveniently used as starting material is obtained by cleavage of the triglycerides of marine or vegetable oil, e.g. borage oil, and trans-esterification, through alkaline catalysis, in the presence of ethanol, followed by removing the ethanol and the base in a manner known per se, e.g. by distillation and separation of the two phase system.
The starting oil is conveniently obtained, and refined by conventional means, e.g. by removal of the free fatty acids from the triglycerides, if necessary, followed by neutralisation, bleaching, deodorisation, etc. of the triglycerides. However, the novel process can also be applied to unrefined oils.
As a matter of fact, the concentration of the polyunsaturated fatty arid esters to be enriched is ca. 18 to ca. 30 % of the mixture.
More specifically, the concentration of the esters of vegetable origin is ca. 18-25 %, and the concentration of the esters of marine origin is ca.
20 ca. 30 %.
Wherein the esters originate from a vegetable oil, these are concentrated to ca. 50 %, wherein the esters stemming from marine oil are concentrated to ca. 65%.
A further aspect of the present invention allows to enrich the esters stemming from marine oil actually up to even ca. 80%.
It involves the steps of
a) subjecting the trans-esterified triglycerides first to a degassing step in vacuo at elevated temperatures, in order to remove any residual solvent, and
b) effecting then a concentration step in vacuo at elevated temperatures through an evaporator and a rectification column, said column preferably having several theoretical stages.
Step a) and b) are carried out prior to the urea treatment of the present invention. They enable to obtain ester concentrations of ca. 55 to ca. 65 %, preferably ca. 60 %.
For step a) a thin film evaporator or a falling film equipment is conveniently used, the pressure is conveniently between ca. 1 and ca. 20 mbar, preferably ca. 10 mbar, and the temperature is conveniently between ca. 40 and ca. 120°C, preferably ca. 50°C.
In step b) a thin fil evaporater is conveniently used, the pressure at the top of the column is conveniently between ca. 0,05 and ca. 0,2 mbar, and the temperature is between ca. 170° and 240°, preferably ca. 190°C.
The column has conveniently at least 3, preferably ca. 10 stages. •foraTTψlR 1
99 kg urea are given into a 630 1 vessel and 430 1 hexane are added. 36 kg refined and trans-esterified ethyl esters (ex borage oil), containing 20% w/w GLA are also added.
4,5 1 ethanol are added and the suspension is mixed, namely for 30 hours and under nitrogen atmosphere. The insoluble urea inclusion complexes are centrifiiged (25°C), and these urea products are washed with hexane. The hexane phases are distilled, using a 0.5 m2 evaporator, at 65°C, and at a pressure of 300 mbar, at a feed of 20 kg/hour.
The bottom product is distilled once more, in order to remove any remaining solvent at 65°C/25 mbar, feed: 15 kg/hour: The GLA content of the product is now 50% as determined gas chromatographically.
There follows a short path distillation on a Canzler column (0.3 m2) at 0.04 mbar leading to a product with a GLA concentration of 53%.
Example 2
Starting from degassed, transesterified marine oil ethyl esters (ca. 27% PUFA), these esters are rectified, the PUFA enriched bottom product of the rectification is treated with urea and the obtained concentrate is finally short path distillated. These three stages are described on a laboratory scale.
The distillation conditions for the mixture of fish oil ethyl esters are as follows:
Temperature of the thin layer evaporator (0.04 m2): 200°C
Theoretical stages of the column: 12 Vacuum applied: 0.17 mbar
Reflux ratio (reflux: distillate) 1:1
Feed 70 ml/h
Distillate 40 ml/h bottom product 30 ml h
The resulting concentrate has a PUFA-content (EPA, DPA and
DHA) of about 60%.
Urea crystallisation:
100 g of the Sambay bottom product are mixed with 10 g ethanol and added to a suspension of 120 g urea in 600 ml hexane.
After stirring for 24 h at room temperature the suspension is separated by centrifugation.
The hexane phase is evaporated to remove the solvent from the concentrate.
After the urea crystalHzation the concentration of EPA, DPA and DHA is 71.1 weight-%.
To separate unwanted high boiling compunds from this concentrate, a final purification is effected by short path distillation:
The obtained final concentrate shows 78 weight-% EPA, DPA and DHA-ethyl esters.
Claims
1. A process for the selective enrichment with polyunsaturated fatty arid esters (PUFAs), of which the first double bond is in the 3 or 6 position, particularly with GLA, EPA or DHA ester, of a mixture containing polyunsaturated fatty acid esters of which the first double bond is in the 3, 6 or 9 position, characterized in that the mixture is treated with urea suspended in a nonpolar hydrocarbon solvent containing a small amount of a polar solvent, in that the insolubles obtained are separated and in that the fraction enriched with Δ3 and Δ6 polyunsaturated fatty acid esters, particularly with GLA, EPA or DHA ester, is collected as the liquid phase.
2. A process according to claim 1, wherein the urea crystallisation is carried out at temperatures between ca. 0°C ca. 40°C, preferably in a range of ca. 20°C to ca. 25°C.
3. A process according to Claim 1 or 2, wherein the polar solvent is a lower alkanol, e.g. methanol or ethanol, isopropanol, or a lower alkyl ketone, e.g. acetone.
4. A process according to Claim 3, wherein the concentration of the polar solvent is ca. 5% to 15%, preferably ca. 8 % to ca. 15 %, preferably ca. 10%, of the total fatty arid esters.
5. A process according to any one of Claims 1 to 4, wherein the hydrocarbon solvent is pentane, hexane, cyclohexane or heptane.
6. A process according to any one of Claims 1 to 5, wherein the ratio by weight of fatty arid esters to urea is of from ca. 1:0,5 to ca. 1:4, preferably ca. 1:1,0 to ca. 1:3.
7. A process according to any one of Claims 1 to 6, wherein the concentration of the polyunsaturated fatty acid esters to be enriched is ca. 18 to ca. 30 %,
8. A process according to any one of Claims 1 to 7, wherein the insoluble urea complexes formed are removed, e.g. by centrifiigation or filtration.
9. A process according to any one of Claim 1 to 8, wherein the ester mixture used is obtained by cleavage of the triglycerides of marine or vegetable oil, e.g. borage oil, and trans-esterification, through alkaline catalysis in the presence of ethanol, followed by removing the ethanol and the base in a manner known per se, e.g. by distillation and separation of the two phases.
10. A process according to any one of Claim 1 to 9, wherein the starting oil is obtained and refined by conventional means, e.g. by removal of the free fatty acids from the triglycerides, bleaching, deodorisation, etc.
11. A process according to Claim 10, wherein the concentration of the esters of vegetable origin is ca. 18-25 %, and wherein the concentration of the esters of marine origin is ca. 20 - ca. 30 %.
12. A process according to any one of Claims 1 to 11, wherein the hydrocarbon solvent is evaporated from the liquid phase containing the enriched polyunsaturated fatty acid esters in a manner known per se, e.g. in vacuo and preferably using columns, using a two evaporater chain, including the use of a falling film evaporator.
13. A process according to Claim 12, wherein the product obtained is finally distilled, e.g. using short path distillation, in order to remove any high boiling products.
14. A process according to Claim 12 or 13, wherein the est3rs originate from a vegetable oil and are concentrated to ca. 50 %.
15. A process according to Claim 12 or 13, wherein the esters stem from marine oil and are concentrated to ca. 65 %.
16. A process according to any one Claims 1 to 15, involving the recyclisation of urea, e.g. by treatment of the insoluble urea complexes with a two phase solvent system.
17. A process according to Claim 9, wherein the trans-esterified triglycerides stem from marine oil and are subjected to a degassing in vacuo at elevated temperatures, in order to remove any residual solvent.
18. A process according to Claim 17, wherein a thin layer column is used and wherein the pressure is between ca. 1 and ca. 20 mbar, preferably ca. 10 mbar, and the temperature is between ca. 40 and ca. 120°C, preferably ca. 50° C.
19. A process according to Claim 17 or 18, wherein a concentration step is effected in vacuo at elevated temperatures through an evaporator and a rectification column, said column preferably having several theoretical stages, leading to concentrations of PUFA's ca. 55 to ca. 65 %, preferably ca. 60 %.
20. A process according to Claim 19, wherein a thin layer evaporater is used and wherein the pressure at the top of the column is conveniently between ca. 0,05 and ca. 0,2 mbar, and the temperature is between ca. 170° and 240°, preferably ca. 190°C.
21. A process according to Claim 20, wherein the column has at least 3, preferably ca. 10 stages.
22. A process according to any one of Claims 9 to 21, wherein the PUFA's are concentrated to a final concentration of ca. 80 %.
***
AMENDED CLAIMS
[received by the International Bureau on 23 August 1993 (23.08.93) ; original claims 1 and 3 amended ; other claims unchanged (1 page)]
1. A process for the selective enrichment with polyunsaturated fatty arid esters (PUFAs), of which the first double bond is in the 3 or 6 position, particularly with GLA, EPA or DHA ester, of a mixture containing polyunsaturated fatty acid esters of which the first double bond is in the 3, 6 or 9 position, characterized in that the mixture is treated with urea suspended in a nonpolar hydrocarbon solvent containing a small amount of a polar solvent in that the insolubles obtained are separated and in that the fraction enriched with Δ3 and Δ6 polyunsaturated fatty acid esters, particularly with GLA, EPA or DHA ester, is collected as the liquid phase.
2. A process according to claim 1, wherein the urea crystallisation is carried out at temperatures between ca. 0°C ca. 40°C, preferably in a range of ca. 20°C to ca. 25°C.
3. A process according to Claim 1 or 2, wherein the polar solvent is a lower alkanol, e.g. apfchtinol o^ethanol, isopropanol, or a lower alkyl ketone, e.g. acetone.
4. A process according to Claim 3, wherein the concentration of the polar solvent is ca. 5% to 15%, preferably ca. 8 % to ca. 15 %, preferably ca. 10%, of the total fatty arid esters.
5. A process according to any one of Claims 1 to 4, wherein the hydrocarbon solvent is pentane, hexane, cyclohexane or heptane.
6. A process according to any one of Claims 1 to 5, wherein the ratio by weight of fatty acid esters to urea is of from ca. 1:0,5 to ca. 1:4, preferably ca. 1:1,0 to ca. 1:3.
7. A process according to any one of Claims 1 to 6, wherein the concentration of the polyunsaturated fatty arid esters to be enriched is ca. 18 to ca. 30 %,
8. A process according to any one of Claims 1 to 7, wherein the insoluble urea complexes formed are removed, e.g. by centrifiigation or filtration.
Y"~~ M i & the. <≥.γcep"έ'G cf- meJhøHOL
STATEMENT UNDER ARTICLE 19
Concerning an amendment re Art. 19 and Rule 46:
In view of the teaching of JP, A 57 164 196 a disclaimer to methanol as the polar advent is necessary in claims 1 and 3.
This disclaimer necessitates to be mentioned also a) on page 1, line 11 of the specification; and b) on page 2; here the second paragraph should be reworded to read
"The polar solvent is conveniently a lower alkanol, namely a C2-4-alcohol, in particular a C2 or 3-alcohol, e.g. ethanol, isopropanol, or a lower alkyl ketone, e.g. acetone."
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB929205880A GB9205880D0 (en) | 1992-03-18 | 1992-03-18 | Low energy pufa enrichment |
| GB9205880.9 | 1992-03-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1993019144A1 true WO1993019144A1 (en) | 1993-09-30 |
Family
ID=10712372
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1993/000529 Ceased WO1993019144A1 (en) | 1992-03-18 | 1993-03-09 | Fatty acid esters |
Country Status (3)
| Country | Link |
|---|---|
| GB (1) | GB9205880D0 (en) |
| IS (1) | IS3986A (en) |
| WO (1) | WO1993019144A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001051598A1 (en) * | 2000-01-11 | 2001-07-19 | Monsanto Technology Llc | Process for making an enriched mixture of polyunsaturated fatty acid esters |
| WO2009006317A1 (en) * | 2007-06-29 | 2009-01-08 | Martek Biosciences Corporation | Production and purification of esters of polyunsaturated fatty acids |
| ITMI20100961A1 (en) * | 2010-05-27 | 2011-11-28 | Erredue Spa | MIXTURES RICH IN OMEGA-3 FATTY ACIDS, THEIR COMPOSITIONS AND THEIR PREPARATION PROCESS |
| EP2627423A1 (en) * | 2010-10-13 | 2013-08-21 | Cognis IP Management GmbH | Device and method for distilling temperature-sensitive substances |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2785151A (en) * | 1952-10-14 | 1957-03-12 | Manuel H Gorin | Process for treating tall-oil with urea, and particularly a new form of expanded urea |
-
1992
- 1992-03-18 GB GB929205880A patent/GB9205880D0/en active Pending
-
1993
- 1993-03-09 WO PCT/EP1993/000529 patent/WO1993019144A1/en not_active Ceased
- 1993-03-17 IS IS3986A patent/IS3986A/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2785151A (en) * | 1952-10-14 | 1957-03-12 | Manuel H Gorin | Process for treating tall-oil with urea, and particularly a new form of expanded urea |
Non-Patent Citations (5)
| Title |
|---|
| DATABASE WPI Section Ch, Week 68, Derwent Publications Ltd., London, GB; Class D, AN 66-30961F * |
| DATABASE WPIL Section Ch, Week 8246, 1982 Derwent Publications Ltd., London, GB; Class D, AN 82-98542E * |
| DATABASE WPIL Section Ch, Week 8301, 1983 Derwent Publications Ltd., London, GB; Class D, AN 83-00823K * |
| DATABASE WPIL Section Ch, Week 8914, 1989 Derwent Publications Ltd., London, GB; Class D, AN 89-102945 * |
| PATENT ABSTRACTS OF JAPAN vol. 014, no. 456 2 October 1990 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001051598A1 (en) * | 2000-01-11 | 2001-07-19 | Monsanto Technology Llc | Process for making an enriched mixture of polyunsaturated fatty acid esters |
| WO2009006317A1 (en) * | 2007-06-29 | 2009-01-08 | Martek Biosciences Corporation | Production and purification of esters of polyunsaturated fatty acids |
| CN101796014A (en) * | 2007-06-29 | 2010-08-04 | 马泰克生物科学公司 | Production and purification of esters of polyunsaturated fatty acids |
| AU2008269989B2 (en) * | 2007-06-29 | 2014-02-27 | Dsm Ip Assets B.V. | Production and purification of esters of polyunsaturated fatty acids |
| ITMI20100961A1 (en) * | 2010-05-27 | 2011-11-28 | Erredue Spa | MIXTURES RICH IN OMEGA-3 FATTY ACIDS, THEIR COMPOSITIONS AND THEIR PREPARATION PROCESS |
| EP2627423A1 (en) * | 2010-10-13 | 2013-08-21 | Cognis IP Management GmbH | Device and method for distilling temperature-sensitive substances |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9205880D0 (en) | 1992-04-29 |
| IS3986A (en) | 1993-09-19 |
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