US3859270A - Refining of fatty acids - Google Patents
Refining of fatty acids Download PDFInfo
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- US3859270A US3859270A US22837272A US3859270A US 3859270 A US3859270 A US 3859270A US 22837272 A US22837272 A US 22837272A US 3859270 A US3859270 A US 3859270A
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- Prior art keywords
- fatty acids
- fatty
- tall oil
- glycol
- purified
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- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 69
- 239000000194 fatty acid Substances 0.000 title claims abstract description 69
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 69
- 150000004665 fatty acids Chemical class 0.000 title claims abstract description 59
- 238000007670 refining Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003784 tall oil Substances 0.000 claims description 39
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 25
- -1 fatty acid esters Chemical class 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- 150000002196 fatty nitriles Chemical class 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 7
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 6
- 230000003247 decreasing effect Effects 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 235000021588 free fatty acids Nutrition 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 5
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- 229930195725 Mannitol Natural products 0.000 claims description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000594 mannitol Substances 0.000 claims description 4
- 235000010355 mannitol Nutrition 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- 235000013772 propylene glycol Nutrition 0.000 claims description 4
- 239000000600 sorbitol Substances 0.000 claims description 4
- 235000010356 sorbitol Nutrition 0.000 claims description 4
- 229940051250 hexylene glycol Drugs 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 2
- YNCZNSWQAGQAJY-UHFFFAOYSA-N but-2-yne-1,1-diol Chemical compound CC#CC(O)O YNCZNSWQAGQAJY-UHFFFAOYSA-N 0.000 claims 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical class [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 15
- 238000009835 boiling Methods 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 10
- 239000005864 Sulphur Substances 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 6
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 6
- 150000002825 nitriles Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000009874 alkali refining Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- QVHQGRAPTXUURC-UHFFFAOYSA-N butane-1,1-diol;hexane-1,6-diol Chemical compound CCCC(O)O.OCCCCCCO QVHQGRAPTXUURC-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 150000002193 fatty amides Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940074869 marquis Drugs 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- VBUNOIXRZNJNAD-UHFFFAOYSA-N ponazuril Chemical compound CC1=CC(N2C(N(C)C(=O)NC2=O)=O)=CC=C1OC1=CC=C(S(=O)(=O)C(F)(F)F)C=C1 VBUNOIXRZNJNAD-UHFFFAOYSA-N 0.000 description 1
- 239000008149 soap solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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
- C11C1/103—Refining by distillation after or with the addition of chemicals
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B13/00—Recovery of fats, fatty oils or fatty acids from waste materials
- C11B13/005—Recovery of fats, fatty oils or fatty acids from waste materials of residues of the fabrication of wood-cellulose (in particular tall-oil)
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes
Definitions
- This invention relates to removing impurities including sulfur containing impurities from fatty acids and blends of fatty acids.
- the object of the present invention relates to removing of impurities the boiling range of which is close and- /or overlapping with the boiling point of the fatty acid to be purified or with the boiling range of the fatty acid blends from which the impurities are to be removed.
- the basic features of my invention are (l) to convert the fatty acids to their diol or polyol esters thus making them less volatile and (2) to remove the unesterified impurities by distillation under vacuum. After the impurities are removed, the esters can be converted to free fatty acids by hydrolysis or saponification. Moreover, the quality of the esters can be improved by other refining methods known to those skilled in the art; e.g. alkali refining or treatment with bleaching clays.
- the diol or polyol esters can also be converted by generally known methods to other derivatives of fatty acids; e.g. fatty alcohols, fatty amides, fatty nitriles and fatty amines.
- Fatty acids and fatty acid blends which can be refined according to this invention are natural and synthetic essentially aliphatic carboxyl acids containing from 6 to 22 carbon atoms in each molecule.
- Crude tall oil is obtained as a byproduct from manufacturing or wood pulp according to the sulfate or Kraft process. It is a dark brown viscous liquid or semisolid and generally consists of 18 carbon atom fatty acids, rosin acids, unsaponifiable materials, a smaller amount of 16 carbon atom fatty acids and still smaller amounts of other carboxylic acids. Crude tall oil contains also some unidentified sulfur compounds which are largely responsible for the unpleasant odor and limited utility of crude tall oil.
- the present invention is directed to a method for removing the sulfur containing impurities in order to produce a crude tall oi] product having a high acid number.
- Fractionated distillation under vacuum as presently practiced by a number of commercial plants is aimed at removing the unsaponifiable and other undesirable materials as tall oil heads (light ends) and bottoms (tall oil pitch) fractions and at separating of fatty acids from rosin acids.
- Fraction No. 2 is a relatively pure blend of mainly 18 carbon atom unsaturated fatty acids.
- Fraction No. 3 is a blend of fatty and rosin acids relatively free from unsaponifiable material and other impurities
- Fraction No.4 is a relatively pure blend of different rosin acids, while most of the undesirable impurities are concentrated in Fractions No. l and No. 5.
- Fraction No. 2 (tall oil heads fraction) which usually amounts to 10 15 percent by weight of the crude tall oil charged to the vacuum distillation columns.
- This tall oil heads fraction normally consists of from 50 percent of fatty acids containing 14 to 18 carbon atoms but is of very low value and utility because of the undesirable impurities especially sulfur containing compounds. For instance, it is not practical to upgrade the tall oil heads fraction by processes involving catalytic hydrogenation because the sulfur compounds tend to poison the commonly used hydrogenation catalysts.
- Example No. l An advantage of the present invention as shown in Example No. l is that low sulfur content fatty acids which are also low in unsaponifiable materials can be obtained from tall oil heads fraction by practicing the teaching of this invention. Moreover, it is also shown that the refined propylene glycol diester of tall oil heads fatty acids can be converted to a fatty acid nitrile and that this nitrile can be catalytically hydrogenated to obtain a primary fatty amine. Such a conversion is not possible of unrefined tall oil heads because of the excessive amount of sulfur present.
- Monomer Acid Another fatty acid blend which contains also branched chain acids and fatty acids having six member carbon ring structures in their molecules is so-called Monomer Acid which is obtained as a by-product from clay catalyzed polymerization of unsaturated carboxylic acids.
- This Monomer Acid is the lower boiling fraction which is removed, usually under vacuum in a thin film evaporator, from the blend of polymerized unsaturated fatty acids leaving the residue which consists of mainly dimerized fatty acids and is called Dimer Acid.
- the Monomer Acid is high in unsaponifiable material and contains some sulfur compounds and other impurities.
- the crude nitrile was distilled under vacuum (428F., 2mm Hg. absolute.) which resulted kn a distilled nitrile having an acid no. of 0.3.
- the distilled nitrile was mixed with 0.75 percent of chromium promoted Raney nickel catalyst and hydrogenated in a Parr autoclave under 40 psi ammonia and 600 psi. of hydrogen and at 175F.
- the amine number of the crude hydrogenated product was 206.
- the amine number of the same product but distilled under vacuum at 480F. and 2mm Hg. absolute was 220.
- AZ Monomer Acid This product is manufactured and marketed by AZ Products Inc. It is obtained from clay catalyzed polymerization of unsaturated 18 carbon atom fatty acid and consists of mainly monomer fatty acids. 644 grams of AZ Monomer Acid, having an acid number of 174 were esterified with 71.3 grams of glycerine at 480F. until the acid number decreased to 4.5. The impurities were removed from the above triglyceride by exposing it to vacuum distillation at 530F. and L5 mm Hg. absolute. The residual ester was saponified and the fatty acids obtained distilled at 390F. and 1.7 mm Hg. absolute. The fatty acids refined in this manner had an acid number of 201.
- a method of refining impure fatty acids containing 6 to 22 carbon atoms comprising the steps of decreasing the volatility of said fatty acids by esterifying said fatty acids with hydroxyl containing organic compounds selected from the group consisting of ethylene glycol, propylene glycol, glycerine, sorbitol, mannitol, pentaerythritol, neopentyl glycol, hexylene glycol butane diol, diethylene glycol, dipropylene glycol, ethylene oxide and propylene oxide, distilling out the unesterified compounds under vacuum and recovering purified fatty acids from the residue.
- hydroxyl containing organic compounds selected from the group consisting of ethylene glycol, propylene glycol, glycerine, sorbitol, mannitol, pentaerythritol, neopentyl glycol, hexylene glycol butane diol, diethylene glycol, dipropylene glycol, ethylene
- a method as defined in claim 2 including the additional steps of converting the purified fatty acid esters to fatty nitriles and catalytically hydrogenating the fatty nitriles to the corresponding amines.
- a method of refining tall oil heads fatty acids, containing more than ppm. sulfur comprising the steps of decreasing the volatility of said tall oil heads fatty acids by esterifying said tall heads fatty acids with hydroxyl containing organic compounds selected from the group consisting of ethylene glycol, propylene glycol, glycerine, sorbitol, mannitol, pentaerythritol, neopentyl glycol, hexylene glycol, butane diol, diethylene glycol, dipropylene glycol, ethylene oxide and propylene oxide, distilling out the unesterified compounds under vacuum and recovering purified tall oil heads fatty acids containing less than 50 ppm. sulfur from the residue.
- hydroxyl containing organic compounds selected from the group consisting of ethylene glycol, propylene glycol, glycerine, sorbitol, mannitol, pentaerythritol, neopentyl glycol, hexylene glycol
- recovery step includes recovering free fatty acids of said purified tall oil heads fatty acids.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method of refining impure fatty acids and fatty acid blends by removing impurities including sulphur containing impurities, boiling range of which is close and/or overlapping with the boiling range of the fatty acids and fatty acid blends.
Description
United States Patent 1 Zvejnieks 1451 Jan. 7, 1975 1 1 REFINING OF FATTY ACIDS [75] Inventor: Andrejs Zvejnieks, Lakeland, Fla.
[73] Assignee: AZS Corporation, Atlanta, Ga.
[22] Filed: Feb. 22, 1972 [21] Appl. No.: 228,372
[52] US. Cl. 260/97.7, 260/104 [51] Int. Cl C09f [58] Field of Search 260/104, 97.7
[56] References Cited UNITED STATES PATENTS 1,820,265 8/1931 Bent 260/104 1,840,395 1/1932 Johnson 260/104 2,610,966 9/1952 Esposito 260/97.7 2,659,718 11/1953 Eckhardt l. 260/97.7
12/1968 Wheelus ..26()/97.7 4/1972 Sanderson ..260/97.7
OTHER PUBLICATIONS Encyclopedia of Chemical Technology, 1953, page 800, relied upon.
Primary Examiner-Melvyn l. Marquis Assistant ExaminerWilliam E. Parker Attorney, Agent, or Firm.lerry Lee Dier [57] ABSTRACT 10 Claims, No Drawings 1 REFINING OF FATTY ACIDS This invention relates to removing impurities including sulfur containing impurities from fatty acids and blends of fatty acids.
The object of the present invention relates to removing of impurities the boiling range of which is close and- /or overlapping with the boiling point of the fatty acid to be purified or with the boiling range of the fatty acid blends from which the impurities are to be removed.
The basic features of my invention are (l) to convert the fatty acids to their diol or polyol esters thus making them less volatile and (2) to remove the unesterified impurities by distillation under vacuum. After the impurities are removed, the esters can be converted to free fatty acids by hydrolysis or saponification. Moreover, the quality of the esters can be improved by other refining methods known to those skilled in the art; e.g. alkali refining or treatment with bleaching clays. The diol or polyol esters can also be converted by generally known methods to other derivatives of fatty acids; e.g. fatty alcohols, fatty amides, fatty nitriles and fatty amines.
Fatty acids and fatty acid blends which can be refined according to this invention are natural and synthetic essentially aliphatic carboxyl acids containing from 6 to 22 carbon atoms in each molecule.
An important source of commercial fatty and rosin acids is a material known as tall oil. Crude tall oil is obtained as a byproduct from manufacturing or wood pulp according to the sulfate or Kraft process. It is a dark brown viscous liquid or semisolid and generally consists of 18 carbon atom fatty acids, rosin acids, unsaponifiable materials, a smaller amount of 16 carbon atom fatty acids and still smaller amounts of other carboxylic acids. Crude tall oil contains also some unidentified sulfur compounds which are largely responsible for the unpleasant odor and limited utility of crude tall oil. The present invention is directed to a method for removing the sulfur containing impurities in order to produce a crude tall oi] product having a high acid number.
The most practiced process for refining of crude tall oil is fractionated distillation under vacuum. By this process it is customary to obtain the following fractions which are listed in the order of increasing ranges of boiling temperatures.
1. Light ends or tall oil heads.
2. Tall oil fatty acids.
3. Distilled tall oil.
4. Tall oil rosin 5. Tall oil pitch.
Fractionated distillation under vacuum as presently practiced by a number of commercial plants is aimed at removing the unsaponifiable and other undesirable materials as tall oil heads (light ends) and bottoms (tall oil pitch) fractions and at separating of fatty acids from rosin acids. Thus, Fraction No. 2 is a relatively pure blend of mainly 18 carbon atom unsaturated fatty acids. Fraction No. 3 is a blend of fatty and rosin acids relatively free from unsaponifiable material and other impurities, and Fraction No.4 is a relatively pure blend of different rosin acids, while most of the undesirable impurities are concentrated in Fractions No. l and No. 5. A problem with Fraction No. l is associated with the fact that the boiling range of a substantial amount of the lower boiling impurities and 16 carbon atom fatty acids overlap and is also close to the boiling range of 18 carbon atom fatty acids. Consequently, to obtain a good quality fatty acid fraction (Fraction No. 2), all 16 carbon atom fatty acids and a sizable amount of l8 carbon atom fatty acids have to be removed with Fraction No. 1 (tall oil heads fraction) which usually amounts to 10 15 percent by weight of the crude tall oil charged to the vacuum distillation columns. This tall oil heads fraction normally consists of from 50 percent of fatty acids containing 14 to 18 carbon atoms but is of very low value and utility because of the undesirable impurities especially sulfur containing compounds. For instance, it is not practical to upgrade the tall oil heads fraction by processes involving catalytic hydrogenation because the sulfur compounds tend to poison the commonly used hydrogenation catalysts.
An advantage of the present invention as shown in Example No. l is that low sulfur content fatty acids which are also low in unsaponifiable materials can be obtained from tall oil heads fraction by practicing the teaching of this invention. Moreover, it is also shown that the refined propylene glycol diester of tall oil heads fatty acids can be converted to a fatty acid nitrile and that this nitrile can be catalytically hydrogenated to obtain a primary fatty amine. Such a conversion is not possible of unrefined tall oil heads because of the excessive amount of sulfur present.
Another fatty acid blend which contains also branched chain acids and fatty acids having six member carbon ring structures in their molecules is so-called Monomer Acid which is obtained as a by-product from clay catalyzed polymerization of unsaturated carboxylic acids. This Monomer Acid is the lower boiling fraction which is removed, usually under vacuum in a thin film evaporator, from the blend of polymerized unsaturated fatty acids leaving the residue which consists of mainly dimerized fatty acids and is called Dimer Acid. The Monomer Acid is high in unsaponifiable material and contains some sulfur compounds and other impurities.
It is shown in Example No. 2 that the teachings of my invention can be used to refine this Monomer Acid.
The examples are presented to illustrate the invention and to teach its practice to those skilled in the art but are not intended to limit the scope of the invention.
EXAMPLE NO. l
Commercial tall oil heads having an acid number of 153 were esterified with an equivalent amount plus 10 percentexcess of propylene glycol by distilling out the water of reaction at 480F. to make propylene glycol diester. The unsaponifiable material was stripped from the crude propylene glycol diester by subjecting l 1 17.3
grams of it to vacuum distillation at 480F. and 1.2 mm Hg. absolute. 356 grams of distillate and 742 grams of residue were obtained in this manner.
A part of the residue was saponified by boiling with a NaOH solution in water. After saponification, the soap solution was acidified with diluted sulfuric acid, the oily fatty acid layer separated, washed with water, dried and distilled under vacuum at 480F. and 1 mm Hg. absolute. The analyses of the fractions were asfollows:
Sulfur Content Material Acid No. ppm
Starting tall oil heads l53 788 Distillate-Unsaponifiable material stripped from propylene glycol diester 29 1783 Residue-Tall oil heads fatty acids after removal of unsaponifiables, saponification and distillation 205 37 Another part of the residue (tall oil heads/propylene glycol diester) was converted to a nitrile by adding 0.5 percent of zinc oxide and sparging it with anhydrous ammonia at 560F. until the acid number of the material decreased to 3.4.
The crude nitrile was distilled under vacuum (428F., 2mm Hg. absolute.) which resulted kn a distilled nitrile having an acid no. of 0.3.
The distilled nitrile was mixed with 0.75 percent of chromium promoted Raney nickel catalyst and hydrogenated in a Parr autoclave under 40 psi ammonia and 600 psi. of hydrogen and at 175F. The amine number of the crude hydrogenated product was 206. The amine number of the same product but distilled under vacuum at 480F. and 2mm Hg. absolute was 220.
EXAMPLE NO. 2
This example was carried out with a commercial product called AZ Monomer Acid. This product is manufactured and marketed by AZ Products Inc. It is obtained from clay catalyzed polymerization of unsaturated 18 carbon atom fatty acid and consists of mainly monomer fatty acids. 644 grams of AZ Monomer Acid, having an acid number of 174 were esterified with 71.3 grams of glycerine at 480F. until the acid number decreased to 4.5. The impurities were removed from the above triglyceride by exposing it to vacuum distillation at 530F. and L5 mm Hg. absolute. The residual ester was saponified and the fatty acids obtained distilled at 390F. and 1.7 mm Hg. absolute. The fatty acids refined in this manner had an acid number of 201.
I claim:
l. A method of refining impure fatty acids containing 6 to 22 carbon atoms comprising the steps of decreasing the volatility of said fatty acids by esterifying said fatty acids with hydroxyl containing organic compounds selected from the group consisting of ethylene glycol, propylene glycol, glycerine, sorbitol, mannitol, pentaerythritol, neopentyl glycol, hexylene glycol butane diol, diethylene glycol, dipropylene glycol, ethylene oxide and propylene oxide, distilling out the unesterified compounds under vacuum and recovering purified fatty acids from the residue.
2. A method as defined in claim 1, wherein said recovery step includes recovering esters of said purified fatty acids from the residue.
3. A method as defined in claim 1, wherein said recovery step includes recovering the free fatty acids of said purified fatty acids from the residue.
4. A method as defined in claim 1, including the additional step of converting the purified fatty acids to fatty nitriles.
5. A method as defined in claim 2, includingthe additional steps of converting the purified fatty acid esters to fatty nitriles and catalytically hydrogenating the fatty nitriles to the corresponding amines.
6. A method of refining tall oil heads fatty acids, containing more than ppm. sulfur comprising the steps of decreasing the volatility of said tall oil heads fatty acids by esterifying said tall heads fatty acids with hydroxyl containing organic compounds selected from the group consisting of ethylene glycol, propylene glycol, glycerine, sorbitol, mannitol, pentaerythritol, neopentyl glycol, hexylene glycol, butane diol, diethylene glycol, dipropylene glycol, ethylene oxide and propylene oxide, distilling out the unesterified compounds under vacuum and recovering purified tall oil heads fatty acids containing less than 50 ppm. sulfur from the residue.
7. A method as defined in claim 6, wherein said recovery step includes recovering esters of said purified tall oil heads fatty acids from the residue.
8. A method as defined in claim 6, wherein said recovery step includes recovering free fatty acids of said purified tall oil heads fatty acids.
9. A method as defined in claim 6, including the additional step of converting the purified tall oil heads fatty acids to tall oil heads fatty nitriles.
10. A method as defined in claim 7, including the additional steps of converting the purified tall oil heads fatty acids este'rs to fatty nitriles and catalytically hydrogenating the fatty nitriles to their corresponding amines.
Claims (10)
1. A METHOD OF REFINING IMPURE FATTY ACIDS CONTAINING 6 TO 22 CARBON ATOMS COMPRISING THE STEPS OF DECREASING THE VOLATILITY OF SAID FATTY ACIDS BY ESTERFYING SAID FATTY ACIDS WITH HYDROXYL CONTAINING ORGANIC COMPOUNDS SELECTED FROM THE GROUP CONSISTING OF ETHYLELNE GLYCOL, PROPYLENE GLYCOL, GLYCERINE, SORBITOL, MANNITOL, PENTAERYTHRITOL, NEOPENTYL GLYCOL, HEXYLENE GLYCOL BUTINE DIOL, DEITHYLENE GLYCOL, DIPROPYLENE GLYCOL, ETHYLENE OXIDE AND PROPYLENE OXIDE, DISTILLING OUT THE UNESTERIFIED COMPOUNDS UNDER VACUUM AND RECOVERING PURF IFIIED FATTY ACIDS FROM THE RESIDUE.
2. A method as defined in claim 1, wherein said recovery step includes recovering esters of said purified fatty acids from the residue.
3. A method as defined in claim 1, wherein said recovery step includes recovering the free fatty acids of said purified fatty acids from the residue.
4. A method as defined in claim 1, including the additional step of converting the purified fatty acids to fatty nitriles.
5. A method as defined in claim 2, including the additional steps of converting the purified fatty acid esters to fatty nitriles and catalytically hydrogenating the fatty nitriles to the corresponding amines.
6. A method of refining tall oil heads fatty acids, containing more than 100 p.p.m. sulfur comprising the steps of decreasing the volatility of said tall oil heads fatty acids by esterifying said tall heads fatty acids with hydroxyl containing organic compounds selected from the group consisting of ethylene glycol, propylene glycol, glycerine, sorbitol, mannitol, pentaerythritol, neopentyl glycol, hexylene glycol, butane diol, diethylene glycol, dipropylene glycol, ethylene oxide and propylene oxide, distilling out the unesterified compounds under vacuum and recovering purified tall oil heads fatty acids containing less than 50 p.p.m. sulfur from the residue.
7. A method as defined in claim 6, wherein said recovery step includes recovering esters of said purified tall oil heads fatty acids from the residue.
8. A method as defined in claim 6, whErein said recovery step includes recovering free fatty acids of said purified tall oil heads fatty acids.
9. A method as defined in claim 6, including the additional step of converting the purified tall oil heads fatty acids to tall oil heads fatty nitriles.
10. A method as defined in claim 7, including the additional steps of converting the purified tall oil heads fatty acids esters to fatty nitriles and catalytically hydrogenating the fatty nitriles to their corresponding amines.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US22837272 US3859270A (en) | 1972-02-22 | 1972-02-22 | Refining of fatty acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US22837272 US3859270A (en) | 1972-02-22 | 1972-02-22 | Refining of fatty acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3859270A true US3859270A (en) | 1975-01-07 |
Family
ID=22856915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US22837272 Expired - Lifetime US3859270A (en) | 1972-02-22 | 1972-02-22 | Refining of fatty acids |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3859270A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991014748A1 (en) * | 1990-03-21 | 1991-10-03 | Bergvik Kemi Ab | Purification process |
| US6623604B1 (en) * | 2000-06-05 | 2003-09-23 | Cognis Corporation | Method of recovering free fatty acids having low ester content and high acid value |
| WO2007050030A1 (en) | 2005-10-26 | 2007-05-03 | Kiram Ab | Automotive fuels and fine chemicals from crude tall oil |
| WO2012112574A1 (en) * | 2011-02-14 | 2012-08-23 | Arizona Chemical Company, Llc | Fuel additives, fuels, methods of making and using same |
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| US1820265A (en) * | 1928-11-24 | 1931-08-25 | Hercules Powder Co Ltd | Ester gum and method of producing |
| US1840395A (en) * | 1930-01-24 | 1932-01-12 | Hercules Powder Co Ltd | Method for producing resin acid esters |
| US2610966A (en) * | 1949-10-17 | 1952-09-16 | Hollingshead Corp | Process for treating tall oil with alkylene oxides |
| US2659718A (en) * | 1951-08-22 | 1953-11-17 | Leach Brothers Inc | Treatment of resin acid-fatty acid mixtures |
| US3417071A (en) * | 1966-12-30 | 1968-12-17 | Arizona Chem | Bleaching and stabilizing rosin compounds with 1,3,4-thiadiazole polysulfides |
| US3655635A (en) * | 1969-01-28 | 1972-04-11 | Hercules Inc | Tall oil rosin of low sulfur content |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1820265A (en) * | 1928-11-24 | 1931-08-25 | Hercules Powder Co Ltd | Ester gum and method of producing |
| US1840395A (en) * | 1930-01-24 | 1932-01-12 | Hercules Powder Co Ltd | Method for producing resin acid esters |
| US2610966A (en) * | 1949-10-17 | 1952-09-16 | Hollingshead Corp | Process for treating tall oil with alkylene oxides |
| US2659718A (en) * | 1951-08-22 | 1953-11-17 | Leach Brothers Inc | Treatment of resin acid-fatty acid mixtures |
| US3417071A (en) * | 1966-12-30 | 1968-12-17 | Arizona Chem | Bleaching and stabilizing rosin compounds with 1,3,4-thiadiazole polysulfides |
| US3655635A (en) * | 1969-01-28 | 1972-04-11 | Hercules Inc | Tall oil rosin of low sulfur content |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991014748A1 (en) * | 1990-03-21 | 1991-10-03 | Bergvik Kemi Ab | Purification process |
| US6623604B1 (en) * | 2000-06-05 | 2003-09-23 | Cognis Corporation | Method of recovering free fatty acids having low ester content and high acid value |
| WO2007050030A1 (en) | 2005-10-26 | 2007-05-03 | Kiram Ab | Automotive fuels and fine chemicals from crude tall oil |
| US20090217573A1 (en) * | 2005-10-26 | 2009-09-03 | Kiram Ab | Automotive fuels and fine chemicals from crude tall oil |
| EP1951852A4 (en) * | 2005-10-26 | 2012-09-12 | Sunpine Ab | MOTOR FUELS AND FINE CHEMICALS FROM TALLOL |
| WO2012112574A1 (en) * | 2011-02-14 | 2012-08-23 | Arizona Chemical Company, Llc | Fuel additives, fuels, methods of making and using same |
| CN103459574A (en) * | 2011-02-14 | 2013-12-18 | 阿利桑那化学公司 | Fuel additives, fuels, methods of making and using same |
| CN103459574B (en) * | 2011-02-14 | 2015-12-23 | 阿利桑那化学公司 | Fuel dope, fuel and production and preparation method thereof |
| US9828559B2 (en) | 2011-02-14 | 2017-11-28 | Kraton Chemical, Llc | Fuel additives, fuels, methods of making and using same |
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Legal Events
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Owner name: SHEREX CHEMICAL COMPANY, INC., OHIO Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:SHEREX POLYMERS, INC. A CORP. OF DE;REEL/FRAME:005122/0786 Effective date: 19890630 |
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| AS | Assignment |
Owner name: SCHERING BERLIN POLYMERS INC., A CORP. OF DE. Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:SHEREX CHEMICAL COMPANY, INC., A CORP. OF OH.;REEL/FRAME:005430/0729 Effective date: 19900630 |