CA2319230A1 - Improved method of extraction of tall oil soap - Google Patents
Improved method of extraction of tall oil soap Download PDFInfo
- Publication number
- CA2319230A1 CA2319230A1 CA 2319230 CA2319230A CA2319230A1 CA 2319230 A1 CA2319230 A1 CA 2319230A1 CA 2319230 CA2319230 CA 2319230 CA 2319230 A CA2319230 A CA 2319230A CA 2319230 A1 CA2319230 A1 CA 2319230A1
- Authority
- CA
- Canada
- Prior art keywords
- solvent
- process according
- soap
- sterols
- tall oil
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J9/00—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
Abstract
A method for the preparation of sterols from tall oil soap comprising the steps of drying tall oil soap and extracting said dried soap with a solvent to yield an extract which is substantially enriched in sterols.
Description
BACKGROUND OF THE INVENTION
1. Field of Invention This invention pertains to the extraction of valuable chemicals from dried tall oil soap.
1. Field of Invention This invention pertains to the extraction of valuable chemicals from dried tall oil soap.
2. Related Art Tall oil soap is a by-product of the alkaline pulping of coniferous wood. Soap consists of sodium salts of fatty acids, sodium salts of diterpenic (rosin) acids, free fatty acids, free rosin acids and unsaponifiable neutral compounds such as fatty alcohols, sterols, steryl esters and waxes. The physically-bound water content of neat soap is 30 to 35%. The pH of as-is soap is typically in the range of 12 to 13, arising from the presence of entrained black liquor. In industrial practice, soap is routinely acidulated with sulphuric acid to produce crude tall oil, an article of commerce. See for example, Drew, J. and Propst, M., eds., "Tall Oil", Pulp Chemical Association, New York, NY, 1981.
Sterols, in particular phytosterols, have been identified recently as the source material for the preparation of anti-cholesterolemic agents for humans.
During the past 50 years, numerous methods have been reported for the isolation of sterols from tall oil soap. The general method involves the extraction of neat soap with a variety of organic solvents. The presence of entrained black liquor promotes and stabilizes the unwanted water-oil emulsion, which is known to be extremely difficult to break. Consequently, the efficiency of solvent extraction of neat soap for the isolation of sterols is greatly reduced.
Holmbom et al. teach in US Patent 3,965,085 the extraction of a mixture of acetone-water soap slurry, with a water-immiscible solvent such as hexane. The aqueous phase contains mainly sodium salts of fatty and resin acids. The organic phase contains mostly unsaponifiables including sterols. In US Patent 4,044,031, Johansson et al. teach the dissolution of soap in a water-immiscible mixture comprising hexane and acetone, extraction of the water-immiscible phase with another solvent mixture comprising methanol, hexane, acetone and water, and isolation of sterols from the methanolic phase by evaporative crystallization.
In US Patent 5,770,749, Kutney et al. teach the use of a mixture of ketones, hydrocarbons and water to extract sterols form soap. The hydrocarbon extract is further processed with methanol. The complexity of recovering the multi-component spent solvent is very problematic in these cited processes.
The object of the present invention is to provide an effective means to circumvent the problem of breaking complex water-oil emulsion as manifested in the solvent extraction of neat soap, and to eliminate the usage of multi-component organic solvent for extraction with the attendant logistical problems of solvent recovery.
SUMMARY OF THE INVENTION
The present invention affords an effective means to provide a sterol-enriched extract from tall oil soap which can yield sterols upon subsequent precipitation in a water-organic solvent mixture. The preferred embodiment of the present invention as given in Figure 1 comprises the following steps a) Tall oil soap [1 ] is fed into a dryer [2] to remove water [3], b) The dried tall oil soap solids [4] are transferred to a stirred tank [5].
c) A solvent such as acetone [6] is added to the stirred tank [5], which is maintained at 40 to 50 degrees Celsius.
d) After a mixing time of about 30 minutes, the insoluble solids [7] are allowed to settle and removed for disposal back to, for example, the kraft pulp mill supplying the tall oil soap raw material. The supernatant [8] is removed for transfer to a chilling vessel [9].
e) The supernatant [8] is chilled to about +3 to +4 degrees Celsius to effect the formation of sterol crystals.
f) The slurry [10] is pumped through a filter [11 ] to recover the sterol crystals [12].
g) The filtrate [13] is recycled for use in mixture with fresh solvent [6].
The sterols in the said supernatant [8] may be recovered alternatively by direct precipitation by the addition of water to the supernatant [8]. In another variant, sterols in the said supernatant [8] may be further processed by known distillation methods to increase the concentration of sterols further prior to precipitation of sterols by known means in a mixture of water and solvent.
Sterols, in particular phytosterols, have been identified recently as the source material for the preparation of anti-cholesterolemic agents for humans.
During the past 50 years, numerous methods have been reported for the isolation of sterols from tall oil soap. The general method involves the extraction of neat soap with a variety of organic solvents. The presence of entrained black liquor promotes and stabilizes the unwanted water-oil emulsion, which is known to be extremely difficult to break. Consequently, the efficiency of solvent extraction of neat soap for the isolation of sterols is greatly reduced.
Holmbom et al. teach in US Patent 3,965,085 the extraction of a mixture of acetone-water soap slurry, with a water-immiscible solvent such as hexane. The aqueous phase contains mainly sodium salts of fatty and resin acids. The organic phase contains mostly unsaponifiables including sterols. In US Patent 4,044,031, Johansson et al. teach the dissolution of soap in a water-immiscible mixture comprising hexane and acetone, extraction of the water-immiscible phase with another solvent mixture comprising methanol, hexane, acetone and water, and isolation of sterols from the methanolic phase by evaporative crystallization.
In US Patent 5,770,749, Kutney et al. teach the use of a mixture of ketones, hydrocarbons and water to extract sterols form soap. The hydrocarbon extract is further processed with methanol. The complexity of recovering the multi-component spent solvent is very problematic in these cited processes.
The object of the present invention is to provide an effective means to circumvent the problem of breaking complex water-oil emulsion as manifested in the solvent extraction of neat soap, and to eliminate the usage of multi-component organic solvent for extraction with the attendant logistical problems of solvent recovery.
SUMMARY OF THE INVENTION
The present invention affords an effective means to provide a sterol-enriched extract from tall oil soap which can yield sterols upon subsequent precipitation in a water-organic solvent mixture. The preferred embodiment of the present invention as given in Figure 1 comprises the following steps a) Tall oil soap [1 ] is fed into a dryer [2] to remove water [3], b) The dried tall oil soap solids [4] are transferred to a stirred tank [5].
c) A solvent such as acetone [6] is added to the stirred tank [5], which is maintained at 40 to 50 degrees Celsius.
d) After a mixing time of about 30 minutes, the insoluble solids [7] are allowed to settle and removed for disposal back to, for example, the kraft pulp mill supplying the tall oil soap raw material. The supernatant [8] is removed for transfer to a chilling vessel [9].
e) The supernatant [8] is chilled to about +3 to +4 degrees Celsius to effect the formation of sterol crystals.
f) The slurry [10] is pumped through a filter [11 ] to recover the sterol crystals [12].
g) The filtrate [13] is recycled for use in mixture with fresh solvent [6].
The sterols in the said supernatant [8] may be recovered alternatively by direct precipitation by the addition of water to the supernatant [8]. In another variant, sterols in the said supernatant [8] may be further processed by known distillation methods to increase the concentration of sterols further prior to precipitation of sterols by known means in a mixture of water and solvent.
EXAMPLES
The following example illustrate the preferred embodiment of the invention, without limiting the broad scope of application:
Example 1 A sample of commercial tall oil soap was dried in an air-circulating oven at degrees Celsius for 24 hours. The resulting soap solids was analyzed by a gas chromatographic method to contain 45 mg total sterols per gram of dry soap.
Typically, the extraction of dried soap solids was conducted in a 250-ml beaker with a selected solvent at 45 degrees Celsius. The mixing time was 30 minutes.
The percent sterols recovered is calculated as the amount of sterols recovered in the dried extract from the original sterols present in the dried soap. The test results show that the extraction of dried soap with acetone provides the best combination of small volume of extract, high concentration of sterols in extract and high recovery of sterols from starting dried soap.
Solvent Soap: Dried Extract Solvent Wt % Dried Sterols, Sterols, mg/g Ratio Soap Recovered Methanol 0.499 85.0 41 77 70% ethanol 0.496 78.5 50 87 +30%
methanol Isopropanol0.500 32.1 95 68 Acetone 0.483 21.9 158 77 Methyl ethyl0.500 35.4 95 75 ketone Ethyl acetate0.468 39.1 104 90 Toluene 0.250 12.1 62 17 Hexane 0.082 73.8 38 62 Diethyl 0.060 13.6 318 96 ether Example 2 Dried soap sample used in the above example was extracted with acetone in the same fashion under different operating conditions. The test results show that the extraction can be optimized by varying the extraction time, extraction temperature, and soap:solvent ratio, in accordance with the dried soap feedstock.
The following example illustrate the preferred embodiment of the invention, without limiting the broad scope of application:
Example 1 A sample of commercial tall oil soap was dried in an air-circulating oven at degrees Celsius for 24 hours. The resulting soap solids was analyzed by a gas chromatographic method to contain 45 mg total sterols per gram of dry soap.
Typically, the extraction of dried soap solids was conducted in a 250-ml beaker with a selected solvent at 45 degrees Celsius. The mixing time was 30 minutes.
The percent sterols recovered is calculated as the amount of sterols recovered in the dried extract from the original sterols present in the dried soap. The test results show that the extraction of dried soap with acetone provides the best combination of small volume of extract, high concentration of sterols in extract and high recovery of sterols from starting dried soap.
Solvent Soap: Dried Extract Solvent Wt % Dried Sterols, Sterols, mg/g Ratio Soap Recovered Methanol 0.499 85.0 41 77 70% ethanol 0.496 78.5 50 87 +30%
methanol Isopropanol0.500 32.1 95 68 Acetone 0.483 21.9 158 77 Methyl ethyl0.500 35.4 95 75 ketone Ethyl acetate0.468 39.1 104 90 Toluene 0.250 12.1 62 17 Hexane 0.082 73.8 38 62 Diethyl 0.060 13.6 318 96 ether Example 2 Dried soap sample used in the above example was extracted with acetone in the same fashion under different operating conditions. The test results show that the extraction can be optimized by varying the extraction time, extraction temperature, and soap:solvent ratio, in accordance with the dried soap feedstock.
Acetone is the Soap: Dried Extract solvent used Acetone Wt r6 Sterols,Sterols, ~
Ratio Dried mg/g Recovered Soap 45 deg.C for 0.483 21.9 158 77 minutes 45 deg. C for 1.000 10.0 175 39 minutes 8.5 deg.C for 0.480 8.6 157 30 minutes 105 deg.C soxhlet0.462 51.7 103 100 extraction for hours What is claimed is:
1. A process for the preparation of sterols from tall oil soap comprising the steps of:
a) drying tall oil soap, b) extracting the dried tall oil soap with a solvent, and c) recovering sterols from the solvent extract.
2. A process according to claim 1 in which the drying of tall oil soap is made above the prevailing boiling point of water.
3. A process according to claim 1 in which the extraction of dried soap is made with a solvent at between 20 to 150 degrees Celsius.
4. A process according to claim 1 in which the solvent is substantially miscible with water.
Ratio Dried mg/g Recovered Soap 45 deg.C for 0.483 21.9 158 77 minutes 45 deg. C for 1.000 10.0 175 39 minutes 8.5 deg.C for 0.480 8.6 157 30 minutes 105 deg.C soxhlet0.462 51.7 103 100 extraction for hours What is claimed is:
1. A process for the preparation of sterols from tall oil soap comprising the steps of:
a) drying tall oil soap, b) extracting the dried tall oil soap with a solvent, and c) recovering sterols from the solvent extract.
2. A process according to claim 1 in which the drying of tall oil soap is made above the prevailing boiling point of water.
3. A process according to claim 1 in which the extraction of dried soap is made with a solvent at between 20 to 150 degrees Celsius.
4. A process according to claim 1 in which the solvent is substantially miscible with water.
5. A process according to claim 1 in which the solvent is substantially immiscible with water.
6. A process according to claim 1 in which the solvent is a mixture of solvents.
Claims (12)
1. A process for the preparation of sterols from tall oil soap comprising the steps of:
a) drying tall oil soap, b) extracting the dried tall oil soap with a solvent, and c) recovering sterols from the solvent extract.
a) drying tall oil soap, b) extracting the dried tall oil soap with a solvent, and c) recovering sterols from the solvent extract.
2. A process according to claim 1 in which the drying of tall oil soap is made above the prevailing boiling point of water.
3. A process according to claim 1 in which the extraction of dried soap is made with a solvent at between 20 to 150 degrees Celsius.
4. A process according to claim 1 in which the solvent is substantially miscible with water.
5. A process according to claim 1 in which the solvent is substantially immiscible with water.
6. A process according to claim 1 in which the solvent is a mixture of solvents.
7. A process according to claim 1 in which sterols are recovered as crystals by chilling the solvent to a temperature between -5 degrees Celsius and +10 degrees Celsius.
8. A process according to claims 1 and 4 in which water is added to the solvent extract to effect the precipitation of sterol crystals.
9. A process according to claim 1 in which the solvent extract is evaporated to dryness.
10.A process according to claim 9 in which the dried extract is dissolved in a solvent to effect the preferential precipitation of sterol crystals.
11.A process according to claim 1 in which the extract is distilled further under low-pressure conditions to concentrate the sterols contained herein.
12. A process according to claim 11 in which the distillate is dissolved in a solvent to effect the preferential precipitation of sterol crystals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2319230 CA2319230A1 (en) | 2000-09-13 | 2000-09-13 | Improved method of extraction of tall oil soap |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2319230 CA2319230A1 (en) | 2000-09-13 | 2000-09-13 | Improved method of extraction of tall oil soap |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2319230A1 true CA2319230A1 (en) | 2002-03-13 |
Family
ID=4167117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2319230 Abandoned CA2319230A1 (en) | 2000-09-13 | 2000-09-13 | Improved method of extraction of tall oil soap |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2319230A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9487717B2 (en) | 2011-12-08 | 2016-11-08 | Invico Tech Ab | Process for obtaining a diesel like fuel |
| WO2017130127A1 (en) | 2016-01-29 | 2017-08-03 | Stora Enso Oyj | Extraction of phytosterols from tall oil soap using a solvent selected from dibromomethane, bromoform, tetrabromomethane or a combination thereof |
| WO2017137908A1 (en) | 2016-02-12 | 2017-08-17 | Stora Enso Oyj | Distillation of neutral compounds from tall oil soap |
| WO2018065876A1 (en) * | 2016-10-04 | 2018-04-12 | Stora Enso Oyj | Process for separating unsaponifiables from tall oil soap |
-
2000
- 2000-09-13 CA CA 2319230 patent/CA2319230A1/en not_active Abandoned
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9487717B2 (en) | 2011-12-08 | 2016-11-08 | Invico Tech Ab | Process for obtaining a diesel like fuel |
| WO2017130127A1 (en) | 2016-01-29 | 2017-08-03 | Stora Enso Oyj | Extraction of phytosterols from tall oil soap using a solvent selected from dibromomethane, bromoform, tetrabromomethane or a combination thereof |
| US10597602B2 (en) | 2016-01-29 | 2020-03-24 | Stora Enso Oyj | Extraction of phytosterols from tall oil soap using a solvent selected from dibromomethane, bromoform, tetrabromomethane or a combination thereof |
| WO2017137908A1 (en) | 2016-02-12 | 2017-08-17 | Stora Enso Oyj | Distillation of neutral compounds from tall oil soap |
| WO2018065876A1 (en) * | 2016-10-04 | 2018-04-12 | Stora Enso Oyj | Process for separating unsaponifiables from tall oil soap |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2003203072B2 (en) | Distalliative process of extracting and purifying phytosterols and phytostanols from tall oil pitch | |
| AU2003203072A1 (en) | Distalliative process of extracting and purifying phytosterols and phytostanols from tall oil pitch | |
| US20100305342A1 (en) | Method for the prepparation of phytosterols from tall oil pitch | |
| JP2016222926A (en) | Recovery of phytosterols from residual vegetable oil streams | |
| EP1056767B1 (en) | Method for the preparation of phytosterols from tall oil pitch | |
| CA2319230A1 (en) | Improved method of extraction of tall oil soap | |
| WO2016088139A1 (en) | An eco-friendly process for the isolation of biopolymers from agricultural residues | |
| US10597602B2 (en) | Extraction of phytosterols from tall oil soap using a solvent selected from dibromomethane, bromoform, tetrabromomethane or a combination thereof | |
| JP3370342B2 (en) | How to get oryzanol | |
| AU2004245874A2 (en) | Method for processing vegetable raw materials | |
| CA2367729A1 (en) | Process for the purification of sterols from hydrocarbon extracts using evaporative fractionation | |
| RU2080326C1 (en) | Method of treating neutral agents | |
| US20040024175A1 (en) | Method for the preparation of phytosterols from tall oil pitch | |
| WO2017137908A1 (en) | Distillation of neutral compounds from tall oil soap | |
| LU101374B1 (en) | Production of an extract of phytosterols and stanols from tall oil pitch | |
| WO2018065876A1 (en) | Process for separating unsaponifiables from tall oil soap | |
| US5565134A (en) | Method for enriching rosin acids from a hardwood-containing sulfate soap | |
| US6770767B1 (en) | Method for the extraction and isolation of neutral substances from a soap | |
| RU2233858C1 (en) | Method for complex processing larch wood | |
| RU2128662C1 (en) | Method of producing sitosterol from tall pitch | |
| US20010047101A1 (en) | Process for obtaining oryzanol | |
| EP1190025B1 (en) | Extraction and isolation method | |
| Davis | Solvent Extraction of Unsaponifiable Matter From Crude Kraft Soap | |
| WO2000009535A1 (en) | Isolation and purification of sterols from neutrals fraction of tall oil pitch by direct crystallization, single phase | |
| JPH11158196A (en) | Extraction of tall oil alcohol component contained in tall oil skimming |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |