CN111440665A - Method for weak-base esterification of fatty acid and one-step ester exchange of high-acid-value oil - Google Patents
Method for weak-base esterification of fatty acid and one-step ester exchange of high-acid-value oil Download PDFInfo
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- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 54
- 239000000194 fatty acid Substances 0.000 title claims abstract description 54
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 54
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 46
- 239000002253 acid Substances 0.000 title claims abstract description 43
- 230000032050 esterification Effects 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 39
- 150000004665 fatty acids Chemical class 0.000 title claims abstract description 36
- 125000004185 ester group Chemical group 0.000 title abstract 5
- 150000002148 esters Chemical class 0.000 claims abstract description 44
- 239000004519 grease Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 18
- -1 fatty acid ester Chemical class 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000003921 oil Substances 0.000 claims description 23
- 235000019198 oils Nutrition 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 125000005456 glyceride group Chemical group 0.000 claims description 9
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 8
- 239000005642 Oleic acid Substances 0.000 claims description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 8
- 150000003384 small molecules Chemical group 0.000 claims description 7
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 6
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 6
- 229960004488 linolenic acid Drugs 0.000 claims description 6
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 6
- 235000021313 oleic acid Nutrition 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 6
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 claims description 4
- UXXXZMDJQLPQPH-UHFFFAOYSA-N bis(2-methylpropyl) carbonate Chemical compound CC(C)COC(=O)OCC(C)C UXXXZMDJQLPQPH-UHFFFAOYSA-N 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- JMPVESVJOFYWTB-UHFFFAOYSA-N dipropan-2-yl carbonate Chemical compound CC(C)OC(=O)OC(C)C JMPVESVJOFYWTB-UHFFFAOYSA-N 0.000 claims description 4
- ODCCJTMPMUFERV-UHFFFAOYSA-N ditert-butyl carbonate Chemical compound CC(C)(C)OC(=O)OC(C)(C)C ODCCJTMPMUFERV-UHFFFAOYSA-N 0.000 claims description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 235000020778 linoleic acid Nutrition 0.000 claims description 4
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- 229920000263 Rubber seed oil Polymers 0.000 claims description 3
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 claims description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims description 2
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 claims description 2
- 241001477876 Cornus wilsoniana Species 0.000 claims description 2
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 241001048891 Jatropha curcas Species 0.000 claims description 2
- 235000019482 Palm oil Nutrition 0.000 claims description 2
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- 240000000432 Pistacia chinensis Species 0.000 claims description 2
- 235000014123 Pistacia chinensis Nutrition 0.000 claims description 2
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 2
- 244000057114 Sapium sebiferum Species 0.000 claims description 2
- 235000005128 Sapium sebiferum Nutrition 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 244000248162 Xanthoceras sorbifolium Species 0.000 claims description 2
- 235000009240 Xanthoceras sorbifolium Nutrition 0.000 claims description 2
- CUXYLFPMQMFGPL-SUTYWZMXSA-N all-trans-octadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-SUTYWZMXSA-N 0.000 claims description 2
- 229940114079 arachidonic acid Drugs 0.000 claims description 2
- 235000021342 arachidonic acid Nutrition 0.000 claims description 2
- 239000008162 cooking oil Substances 0.000 claims description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002540 palm oil Substances 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 239000002383 tung oil Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 5
- 150000007524 organic acids Chemical class 0.000 abstract description 2
- 239000011973 solid acid Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000007039 two-step reaction Methods 0.000 abstract 1
- 239000002585 base Substances 0.000 description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007171 acid catalysis Methods 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000005815 base catalysis Methods 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 241000221089 Jatropha Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229940049918 linoleate Drugs 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-M linolenate Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC([O-])=O DTOSIQBPPRVQHS-PDBXOOCHSA-M 0.000 description 1
- 229940040452 linolenate Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 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
- 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
- C11C3/10—Ester interchange
Abstract
The invention discloses a method for one-step ester exchange of fatty acid weak base esterification and high acid value grease, which comprises the following steps: taking small molecular ester as an esterification medium, carrying out esterification or one-step ester exchange reaction at a lower temperature under the action of weak base, and filtering and purifying to obtain a small molecular fatty acid ester product, wherein the specific reaction formula is as follows:
Description
Technical Field
The invention belongs to the field of esterification reaction, and particularly relates to a method for one-step ester exchange of fatty acid weak base esterification and high acid value grease.
Background
The fatty acid ester synthesized by taking the grease and the derivatives thereof as raw materials is taken as a novel renewable resource and widely applied to the fields of medicines, cosmetics, high polymer materials, energy sources and the like, and the research and development of the preparation technology have important academic value and far-reaching social benefits.
In the prior art, two methods, namely esterification and ester exchange, are mainly adopted for synthesizing fatty acid ester, wherein the esterification method is characterized in that fatty acid obtained by hydrolyzing oil is reacted with methanol under the catalysis of strong acid, the ester exchange method directly takes the oil as a raw material to be reacted with the methanol under the catalysis of strong acid or strong base, the two-step method of acid catalysis esterification and ester exchange is usually adopted for the oil with high acid value, the pre-esterification is carried out by taking strong acid as a catalyst to reduce the acid value, and then the ester exchange reaction is carried out under the catalysis of strong acid or strong base. The acid catalysis process requires corrosion resistance to equipment, the alkali catalysis process is easy to saponify, and the problems of long reaction time, complex treatment after reaction, difficult removal of catalyst, easy generation of a large amount of wastewater and the like exist.
Meanwhile, in the prior art, a large amount of glycerol byproducts are generated in the alkali-catalyzed esterification reaction process taking oil as a raw material, and although pure glycerol is widely applied, crude glycerol obtained in the esterification reaction process is high in refining cost and is not economical.
When the fatty acid is used for esterification to produce the biodiesel, sulfuric acid, organic acid or solid acid is usually used as a catalyst, so that the catalyst is corrosive, has high requirements on equipment, is sensitive and volatile, is complicated to treat after reaction, is easy to generate a large amount of waste water, causes environmental pollution, and inevitably increases the production cost of the biodiesel.
Disclosure of Invention
Aiming at the defects of the prior art, the method for esterifying the fatty acid and high-acid-value oil mixture under the mild condition has the advantages of low raw material cost, mild condition, simple operation and good yield.
In order to achieve the above purpose, the invention provides the following technical scheme: a method for weak-base esterification of fatty acid and one-step ester exchange of high-acid-value grease comprises the following steps: taking small molecular ester as an esterification medium, carrying out esterification or ester exchange reaction at a lower temperature under the action of weak base, and filtering and purifying to obtain a small molecular fatty acid ester product, wherein the specific reaction formula is as follows:
wherein the long-chain aliphatic group is selected from an alkyl chain of C1-C25, and comprises an aliphatic alkyl chain containing double bonds: long chain structure of oleic acid, linoleic acid and linolenic acid.
R1Is H, a glyceride group;
R2is a small molecule group, comprising: methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert-butyl.
The invention provides a method for one-step ester exchange of fatty acid weak base esterification and high acid value grease, which comprises the following steps:
(1) small molecules are addedEstersMixing with dimethyl carbonate according to the molar ratio of 1:10-30, adding weak base with the molar mass ratio of 5-20% into a reaction kettle,
(2) stirring at a rotation speed of 500-1400 rpm, rapidly heating to a constant temperature for 30 minutes, reacting for 4-12 hours,
(3) through a suction filtration and reduced pressure distillation device,
(4) thus obtaining the product of the micromolecular fatty acid ester.
Preferably, the substituent is an alkyl chain containing C1-C25, and has an unsaturated group containing a double bond.
Preferably, R1When the group is H, the molecular structure of the raw material is fatty acid.
Preferably, R1When the group is glyceride group, the molecular structure of the raw material is fatty acid glyceride of grease.
Preferably, the small molecule ester is selected from one or a mixture of any of the following: dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diisopropyl carbonate, diisobutyl carbonate and di-tert-butyl carbonate.
Preferably, the weak base is a combination of one or more of sodium bicarbonate, sodium carbonate and potassium carbonate.
Preferably, the fatty acid is one or more of palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, arachidic acid, arachidonic acid, and erucic acid.
Preferably, the natural oil is a mixture of low-acid-value oil and high-acid-value oil, and is selected from one or a mixture of any of the following: soybean oil, rapeseed oil, rubber seed oil, jatropha curcas oil, cornus wilsoniana seed oil, shinyleaf yellowhorn oil, palm oil, pistacia chinensis seed oil, Chinese tallow tree seed oil, tung oil, waste cooking oil, acidified oil and waste kitchen grease.
Preferably, the reaction temperature is one of 80 ℃, 100 ℃ or 120 ℃.
The invention has the beneficial effects that: the fatty acid and grease mixture from natural sources is used as raw materials, and the raw materials are wide.
(2) The weak base catalysis condition replaces the fatty acid strong acid catalysis esterification condition, and the one-step weak base catalysis replaces the two-step strong acid esterification-ester exchange high acid value grease ester exchange condition; meanwhile, the method is also suitable for common low-acid-value grease, and has wide applicability.
(3) Triglyceride is converted into small molecular ester by an ester exchange method, and the molecular weight of the grease is reduced; the method has mild reaction conditions, avoids the use of strong acids such as concentrated sulfuric acid and the like and strong bases such as sodium hydroxide, potassium hydroxide and the like in the traditional method, and has simple operation and good yield.
Detailed Description
Example 1
The embodiment provides a method for one-step ester exchange of fatty acid weak base esterification and high acid value grease, which comprises the following steps: taking small molecular ester as an esterification medium, carrying out esterification or ester exchange reaction at a lower temperature under the action of weak base, and filtering and purifying to obtain a small molecular ester fatty acid ester product, wherein the specific reaction formula is as follows:
wherein the long-chain aliphatic group is selected from an alkyl chain of C1-C25, and comprises an aliphatic alkyl chain containing double bonds: long chain structure of oleic acid, linoleic acid and linolenic acid.
R1Is H;
R2is a small molecule group, including methyl.
The embodiment provides a method for weak-base esterification of fatty acid and one-step ester exchange of high-acid-value grease, which comprises the following steps:
(1) mixing the micromolecule ester and the dimethyl carbonate according to the molar ratio of 1:10, adding weak base with the molar mass ratio of 5% into a reaction kettle,
(2) stirring at 500 rpm for 30 min, heating to constant temperature for 4-12 hr,
(3) through a suction filtration and reduced pressure distillation device,
(4) thus obtaining the product of the micromolecular fatty acid ester.
The substituent is an alkyl chain containing C1-C25, and has an unsaturated group containing double bonds.
R1When the group is H, the molecular structure of the raw material is fatty acid.
R1When the group is glyceride group, the molecular structure of the raw material is the fatty glyceride structure of the grease.
The small molecular ester is selected from dimethyl carbonate and diethyl carbonate.
The weak base is sodium bicarbonate.
The fatty acid is oleic acid.
The reaction temperature was 80 ℃.
Example 2
The embodiment provides a method for weak-base esterification of fatty acid and one-step ester exchange of high-acid-value grease, which comprises the following steps: taking small molecular ester as an esterification medium, carrying out esterification or ester exchange reaction at a lower temperature under the action of weak base, and filtering and purifying to obtain a small molecular fatty acid ester product, wherein the specific reaction formula is as follows:
wherein the long-chain aliphatic group is selected from an alkyl chain of C1-C25, and comprises an aliphatic alkyl chain containing double bonds: long chain structure of oleic acid, linoleic acid and linolenic acid.
R1Is H, a glyceride group;
R2is a small molecule group, comprising: methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert-butyl.
Specifically, the embodiment provides a method for weak base esterification of fatty acid and one-step ester exchange of high-acid-value grease, which specifically comprises the following steps:
(1) small molecules are addedEstersMixing with dimethyl carbonate according to the molar ratio of 1:30, adding weak base with the molar mass ratio of 20% into a reaction kettle,
(2) stirring at 1400 rpm for 30 min, heating to constant temperature for 4-12 hr,
(3) through a suction filtration and reduced pressure distillation device,
(4) thus obtaining the product of the micromolecular fatty acid ester.
The substituent is an alkyl chain containing C1-C25, and has an unsaturated group containing double bonds.
R1When the group is H, the molecular structure of the raw material is fatty acid.
R1When the group is glyceride group, the molecular structure of the raw material is fatty acid ester of grease.
The small molecular ester is selected from dibutyl carbonate, diisopropyl carbonate, diisobutyl carbonate and di-tert-butyl carbonate.
The weak base is sodium carbonate.
The natural oil is a mixture of low-acid-value oil and high-acid-value oil, and is selected from rubber seed oil.
The reaction temperature was 100 ℃.
Example 3
The embodiment provides a method for esterification of fatty acid with weak base and one-step ester exchange of high-acid-value grease, which comprises the following steps of taking small molecular ester as an esterification medium, carrying out esterification or ester exchange reaction at a lower temperature under the action of weak base, filtering and purifying to obtain a small molecular fatty acid ester product, wherein the specific reaction formula is as follows:
wherein the long-chain aliphatic group is selected from an alkyl chain of C1-C25, and comprises an aliphatic alkyl chain containing double bonds: long chain structures in oleate, linoleate and linolenate.
R2Is a small molecule group, including butyl, isopropyl, isobutyl and tert-butyl.
The embodiment provides a method for mild esterification of a mixture of high-acid-value fatty acid and grease, which comprises the following specific steps:
(1) mixing the micromolecule ester and the dimethyl carbonate according to the molar ratio of 1:20, adding weak base with the molar mass ratio of 10% into a reaction kettle,
(2) stirring at 1000 rpm for 30 min, heating to constant temperature for 4-12 hr,
(3) through a suction filtration, decompression and distillation device,
(4) thus obtaining the product of the micromolecular fatty acid ester.
The substituent is an aliphatic group of the grease containing an alkyl chain structure of C1-C25, and the aliphatic group has an unsaturated group of a double bond.
R1When the group is H, the molecular structure of the raw material is fatty acid.
R1When the group is alkyl, the molecular structure of the raw material is fatty acid alkyl ester.
The small molecular ester is selected from diisopropyl carbonate, diisobutyl carbonate and di-tert-butyl carbonate.
The weak base is sodium carbonate and potassium carbonate.
The natural oil is a mixture of oleic acid, fatty acid ester and fatty acid glyceride, and is selected from jatropha oil.
The reaction temperature was 120 ℃.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention are equivalent to or changed within the technical scope of the present invention.
Claims (10)
1. A method for esterification of fatty acid with weak base and one-step ester exchange of high-acid-value grease is characterized in that small molecular ester is used as an esterification medium, esterification or one-step ester exchange reaction is carried out at a lower temperature under the action of weak base, and a small molecular fatty acid ester product is obtained by filtering and purifying, wherein the specific reaction formula is as follows:
wherein the long-chain fatty group is selected from alkyl chains of C1-C25, and comprises a double-bond-containing fatty alkyl chain: long chain structure of oleic acid, linoleic acid and linolenic acid.
R1Is H, a glyceride group;
R2is a small molecule group, comprising: methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert-butyl.
2. The method for the one-step ester exchange of the fatty acid weak base esterification and the high acid value grease according to claim 1, which is characterized by comprising the following steps:
(1) mixing the micromolecule ester and the dimethyl carbonate according to the molar ratio of 1:10-30, adding weak base with the molar mass ratio of 5-20% into a reaction kettle,
(2) stirring at a rotation speed of 500-1400 rpm, rapidly heating to a constant temperature for 30 minutes, reacting for 4-12 hours,
(3) through a suction filtration and reduced pressure distillation device,
(4) thus obtaining the product of the micromolecular fatty acid ester.
3. The method for the one-step ester interchange of fatty acid weak base esterification and high acid value grease as claimed in claim 1, wherein the substituent is an alkyl chain containing C1-C25, and has an unsaturated group containing double bond.
4. The method for the one-step ester exchange of fatty acid weak base esterification and high acid value grease as claimed in claim 1, wherein: r1When the group is H, the molecular structure of the raw material is fatty acid.
5. The method for the one-step ester exchange of fatty acid weak base esterification and high acid value grease as claimed in claim 1, wherein: r1When the group is glyceride group, the molecular structure of the raw material is fatty glyceride structure of the grease.
6. The method for the one-step ester exchange of fatty acid weak base esterification and high acid value grease as claimed in claim 1, wherein: the small molecular ester is selected from one or a mixture of any of the following: dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diisopropyl carbonate, diisobutyl carbonate and di-tert-butyl carbonate.
7. The method for the one-step ester exchange of fatty acid weak base esterification and high acid value grease as claimed in claim 1, wherein: the weak base is one or the combination of sodium bicarbonate, sodium carbonate and potassium carbonate.
8. The method for the one-step ester exchange of fatty acid weak base esterification and high acid value grease as claimed in claim 1, wherein: the fatty acid is one or more of palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, arachidic acid, arachidonic acid, and erucic acid ester.
9. The method for the one-step ester exchange of fatty acid weak base esterification and high acid value grease as claimed in claim 1, wherein: the natural oil is a mixture of low-acid-value oil and high-acid-value oil, and is selected from one or a mixture of any of the following: soybean oil, rapeseed oil, rubber seed oil, jatropha curcas oil, cornus wilsoniana seed oil, shinyleaf yellowhorn oil, palm oil, pistacia chinensis seed oil, Chinese tallow tree seed oil, tung oil, waste cooking oil, acidified oil and waste kitchen grease.
10. The method for the one-step ester exchange of fatty acid weak base esterification and high acid value grease as claimed in claim 1, wherein: the reaction temperature is one of 80 ℃, 100 ℃ or 120 ℃.
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