CN117247325A - Fish oil bio-based esteramine product and process preparation method thereof - Google Patents
Fish oil bio-based esteramine product and process preparation method thereof Download PDFInfo
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- CN117247325A CN117247325A CN202311212873.4A CN202311212873A CN117247325A CN 117247325 A CN117247325 A CN 117247325A CN 202311212873 A CN202311212873 A CN 202311212873A CN 117247325 A CN117247325 A CN 117247325A
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- fish oil
- ethyl ester
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- 235000021323 fish oil Nutrition 0.000 title claims abstract description 228
- 238000000034 method Methods 0.000 title claims abstract description 48
- 230000008569 process Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 125000004494 ethyl ester group Chemical group 0.000 claims abstract description 123
- 239000003054 catalyst Substances 0.000 claims abstract description 100
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 44
- 239000007787 solid Substances 0.000 claims abstract description 42
- 239000003381 stabilizer Substances 0.000 claims abstract description 41
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 238000004321 preservation Methods 0.000 claims abstract description 16
- 238000000605 extraction Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 162
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 60
- 238000003756 stirring Methods 0.000 claims description 49
- 239000000047 product Substances 0.000 claims description 37
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 36
- -1 ester amine Chemical class 0.000 claims description 33
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 31
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 30
- 238000005191 phase separation Methods 0.000 claims description 24
- 239000000725 suspension Substances 0.000 claims description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 19
- 239000004480 active ingredient Substances 0.000 claims description 17
- 239000012043 crude product Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000011780 sodium chloride Substances 0.000 claims description 16
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 15
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 15
- 229930003268 Vitamin C Natural products 0.000 claims description 15
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 15
- 235000019154 vitamin C Nutrition 0.000 claims description 15
- 239000011718 vitamin C Substances 0.000 claims description 15
- 238000001704 evaporation Methods 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000011085 pressure filtration Methods 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 239000006084 composite stabilizer Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011698 potassium fluoride Substances 0.000 claims description 3
- 235000003270 potassium fluoride Nutrition 0.000 claims description 3
- 238000005292 vacuum distillation Methods 0.000 abstract description 18
- 239000002994 raw material Substances 0.000 abstract description 6
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 70
- 150000001412 amines Chemical class 0.000 description 38
- 229910052757 nitrogen Inorganic materials 0.000 description 35
- 239000012071 phase Substances 0.000 description 32
- 239000002585 base Substances 0.000 description 31
- 229960002887 deanol Drugs 0.000 description 27
- 239000000203 mixture Substances 0.000 description 19
- 238000004458 analytical method Methods 0.000 description 18
- 235000014113 dietary fatty acids Nutrition 0.000 description 16
- 239000000194 fatty acid Substances 0.000 description 16
- 229930195729 fatty acid Natural products 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 239000012972 dimethylethanolamine Substances 0.000 description 14
- 239000003921 oil Chemical class 0.000 description 13
- 235000019198 oils Nutrition 0.000 description 13
- 238000003825 pressing Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 238000004064 recycling Methods 0.000 description 9
- 241001290266 Sciaenops ocellatus Species 0.000 description 8
- 239000008346 aqueous phase Substances 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 150000004665 fatty acids Chemical class 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 8
- 210000005239 tubule Anatomy 0.000 description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 150000004702 methyl esters Chemical class 0.000 description 6
- 239000003240 coconut oil Substances 0.000 description 5
- 235000019864 coconut oil Nutrition 0.000 description 5
- 239000006071 cream Substances 0.000 description 5
- 235000015112 vegetable and seed oil Nutrition 0.000 description 5
- 239000008158 vegetable oil Substances 0.000 description 5
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 235000019482 Palm oil Nutrition 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000002385 cottonseed oil Substances 0.000 description 2
- 235000012343 cottonseed oil Nutrition 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 150000005691 triesters Chemical class 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 235000019730 animal feed additive Nutrition 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WPUJEWVVTKLMQI-UHFFFAOYSA-N benzene;ethoxyethane Chemical compound CCOCC.C1=CC=CC=C1 WPUJEWVVTKLMQI-UHFFFAOYSA-N 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- MDKXBBPLEGPIRI-UHFFFAOYSA-N ethoxyethane;methanol Chemical compound OC.CCOCC MDKXBBPLEGPIRI-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 229940033355 lauric acid Drugs 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229940105132 myristate Drugs 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N n-hexadecanoic acid Natural products CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/10—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C219/08—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to an acyclic carbon atom of an acyclic unsaturated carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a fish oil bio-based esteramine product and a process preparation method thereof. According to the preparation method, the fish oil ethyl ester from which polyunsaturated fatty acids such as DHA and EPA are separated is used as a raw material, the transesterification reaction is carried out on the fish oil ethyl ester and an alkanolamine compound under the action of a solid base catalyst and a compound stabilizer, and the biological-based esteramine product with the purity of not less than 98% and light color can be obtained through the processes of heat preservation separation, vacuum distillation, dissolution, back extraction and the like.
Description
Technical Field
The invention relates to the technical field of fish oil resource utilization.
Background
Esteramines are typically reaction products of fatty acids, fatty acid esters, oil esters, and the like with alcohol amines, and are important fine chemicals and chemical synthesis intermediates. In the prior art, the fatty acid is obtained by reacting vegetable fatty acid, vegetable oil methyl ester, vegetable oil ethyl ester and the like with alkanolamine, for example, fatty acid ester amine with relatively concentrated fatty acid carbon chain is obtained by synthesizing lauric acid, laurate, myristic acid, myristate, hexadecanoic acid ester, stearic acid ester, oleic acid ester and the like with alkanolamine; the synthesis of coconut oil, coconut oil methyl ester, coconut oil ethyl ester, palm oil methyl ester, palm oil ethyl ester, soybean oil methyl ester, soybean oil ethyl ester, cotton seed oil methyl ester, cotton seed oil ethyl ester and the like is mainly applied to the esteramine products in daily chemical fields such as washing and cosmetics and the like, and the esteramine products all adopt low-carbon vegetable oil fatty acid or fatty acid ester and the like as raw materials, so that the reaction process is complex, the reaction efficiency is low, the time consumption is long, the purity of the obtained product is low, and further refining is needed.
The method for synthesizing triethanolamine triester stearate (2012,42 (6): 424-428) is carried out by taking stearic acid and triethanolamine as raw materials, reacting at 200 deg.C for 6-10 hours under phosphorous acid catalyst, loading onto column by classical column chromatography dry method, and separating product by column chromatography with benzene-diethyl ether, diethyl ether-methanol and 95% ethanol as eluent to obtain triester, diester and monoester products respectively.
The prior art provides a synthesis process (fine chemical engineering, 2010,27 (8): 823-827/832) of an ester group Gemini quaternary ammonium salt softener, which is used for carrying out reflux azeotropic dehydration on stearic acid and dimethylaminoethanol DMEA in toluene medium under the catalysis of hypophosphorous acid to synthesize stearylamine, wherein after the synthesis process is used for carrying out esterification for 10 hours, the yield of crude esteramine reaches 97.2%, the obtained product is directly subjected to quaternization, and the obtained quaternary ammonium salt surfactant is refined by utilizing column chromatography.
The prior patent document US6093336 discloses a method for synthesizing the dimethyl amino ethanol ester of coconut oil acid by esterification reaction of coconut oil acid and dimethyl ethanolamine under the catalysis of hypophosphorous acid, wherein after the reaction is carried out for 2 hours at 130-200 ℃, the conversion rate can reach more than 98%, but the product ester amine is distilled out at 180 ℃ under high vacuum degree, and the high vacuum distillation method has high energy consumption and is easy to cause thermal decomposition of the product and color and smell.
On the other hand, as a high-carbon oil, fish oil is a very precious natural animal oil resource, and the separated polyunsaturated fatty acids DHA, EPA and the like can be used in various fields of medicines, cosmetics, health products and the like, but in the prior art, the separated residual fish oil methyl ester, fish oil ethyl ester and the like are often used as animal feed additives or fuels, so that the overall potential of the fish oil resource is not fully exerted, and the comprehensive application of high added value of the fish oil resource is realized.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for obtaining a high-yield and high-purity esteramine product by taking fish oil ethyl ester remained after polyunsaturated fatty acid extraction of fish oil as a raw material through a simple and efficient preparation process.
The technical scheme of the invention is as follows:
a process for preparing a fish oil bio-based esteramine product comprising:
(1) Uniformly mixing fish oil ethyl ester with a compound stabilizer to obtain fish oil ethyl ester containing the stabilizer, wherein the compound stabilizer comprises sodium hypophosphite and vitamin C;
(2) Heating an alkanolamine compound and a solid base catalyst to 120-200 ℃ in an air flow of inert atmosphere gas, and mixing to obtain a suspension of the alkanolamine compound and the catalyst, wherein the solid base catalyst is porous gamma-Al 2 O 3 A catalyst supporting an active ingredient, the active ingredient including a complex oxide of K and Zn;
(3) Adding the stabilizer-containing fish oil ethyl ester into the suspension of the alkanolamine and the catalyst to perform transesterification reaction to obtain a reaction system, and condensing and recovering ethanol generated in the reaction;
(4) Controlling the temperature of the reaction system to be 100-150 ℃ and recovering the solid base catalyst;
(5) Evaporating the reaction system after the recovery of the solid base catalyst under reduced pressure, wherein the vacuum degree of the reduced pressure evaporation is-0.05 to-0.08 MPa, and the evaporation temperature is 100-150 ℃ to obtain an ester amine crude product;
(6) Carrying out back extraction on the crude product of the esteramine by using a sodium chloride aqueous solution with the mass concentration of 15-20% at the temperature of 80-110 ℃, and carrying out phase separation by keeping the temperature of 90-110 ℃ and standing at the temperature;
(7) And collecting an upper organic phase obtained by phase separation, and cooling to obtain the fish oil bio-based esteramine product.
According to some preferred embodiments of the present invention, the mass ratio of sodium hypophosphite to vitamin C in the composite stabilizer is (80-90): (20-10), more preferably 85:15.
According to some preferred embodiments of the present invention, the compound stabilizer is used in an amount of 2 to 1.0%, more preferably 8% by weight of the ethyl ester of fish oil.
According to some preferred embodiments of the invention, the molar ratio of K to Zn in the solid base catalyst is 1:0.2.
According to some preferred embodiments of the present invention, in the solid base catalyst, the active ingredient is supported by a mass of the porous γ -Al 2 O 3 10% of the mass of the (c).
According to some preferred embodiments of the invention, the solid base catalyst is used in an amount of 10% of the mass of the fish oil ethyl ester.
According to some preferred embodiments of the invention, the alkanolamine compound is selected from N, N-dimethylethanolamine and/or triethanolamine.
According to some preferred embodiments of the present invention, the alkanolamine compound is selected from the group consisting of N, N-dimethylethanolamine, the molar ratio of the fish oil ethyl ester to the N, N-dimethylethanolamine is 1 (2.5-5.0), the temperature of the transesterification reaction is 120-200 ℃, and the time of the transesterification reaction is 4-10 hours; more preferably, the mol ratio of the fish oil ethyl ester to the N, N-dimethylethanolamine is 1 (2.5-3.5), the temperature of the transesterification reaction is 130-180 ℃, and the time of the transesterification reaction is 6-8 h.
According to some preferred embodiments of the present invention, the alkanolamine compound is selected from triethanolamine, the molar ratio of the fish oil ethyl ester to the triethanolamine is 1 (0.5-1.5), the temperature of the transesterification reaction is 160-200 ℃, and the time of the transesterification reaction is 4-10 hours; more preferably, the mol ratio of the fish oil ethyl ester to the triethanolamine is 1 (1.05-1.1), the temperature of the transesterification reaction is 160-180 ℃, and the time of the transesterification reaction is 6-8 h.
According to some preferred embodiments of the present invention, the transesterification is performed by stirring and heating the suspension of the alkanolamine and the catalyst to 120-200 ℃ before adding the stabilizer-containing fish oil ethyl ester, and then slowly adding the stabilizer-containing fish oil ethyl ester.
According to some preferred embodiments of the invention, the recovery of the solid base catalyst is achieved by pressure filtration under an inert atmosphere, wherein the reaction system is kept at 100-150 ℃ during pressure filtration.
According to some preferred embodiments of the invention, the vacuum degree of the reduced pressure evaporation is-0.06 to-0.07 MPa.
According to some preferred embodiments of the invention, the reduced pressure evaporation has an evaporation temperature of 130-145 ℃.
According to some preferred embodiments of the invention, the reduced pressure evaporation time is 30 to 120min.
According to some preferred embodiments of the invention, the obtaining of the solid base catalyst comprises:
(1) Obtaining a mixed aqueous solution of potassium fluoride and zinc acetate, and adding porous gamma-Al 2 O 3 Soaking for 5-7 h at room temperature, and then slowly heating to evaporate water to obtain the alumina catalyst loaded with active ingredients;
(2) And (3) drying the alumina catalyst loaded with the active ingredients, sequentially heating to 250-350 ℃, 400-450 ℃, 450-550 ℃ in air, respectively treating for 2 hours, heating to 500-650 ℃ and calcining for 2.5-3.5 hours, and cooling to room temperature in air to obtain the solid base catalyst.
The invention further provides a fish oil bio-based esteramine product prepared by the preparation method.
The invention has the following beneficial effects:
(1) Compared with the prior esteramine synthesized by taking low-carbon vegetable oil fatty acid or fatty acid ester as a raw material, the preparation method provided by the invention has the advantages of simple reaction process, higher reaction efficiency, shorter time consumption and higher purity of the obtained product.
(2) The invention adopts gamma-Al in the preparation 2 O 3 Compared with alkali metal hydroxide catalysts and alkali metal alkoxide catalysts adopted in the prior art when vegetable oil fatty acid and the like are adopted to prepare ester amine, the solid base catalyst loaded with the K and Zn composite oxide can not be dissolved in a reaction system, can be directly filtered without acid neutralization after the reaction is finished, can effectively shorten the reaction time, reduce the reaction temperature and improve the reaction selectivity, and reduce side reactions, and is not easy to be influenced and deactivated by impurities such as water, acid and the like, and a product obtained by the reaction is not easy to generate thermal decomposition chains, and has light color (the color is less than 100).
(3) The compound stabilizer used in the preparation method can effectively improve the chemical stability of the raw material of the fish oil ethyl ester and the product of the esteramine, prevent chain scission from occurring under the conditions of high temperature, alkalinity and the like, generate side reaction products and the like, and further obtain the product with high purity and light color.
(4) The invention adopts hot brine back extraction technology in the preparation, the treatment method is simple, the quality of the obtained product is better, the purity is higher, and chromatography or recrystallization is not needed.
(5) Compared with the existing method, the preparation method provided by the invention has the advantages of simple reaction process, higher reaction efficiency, shorter time consumption, higher purity of the obtained product and the like.
(6) The invention can utilize renewable and nontoxic fish oil ethyl ester resources after polyunsaturated fatty acids such as DHA, EPA and the like are separated to carry out transesterification reaction with alkanolamine to synthesize a fish oil bio-based esteramine product with high added value, and the product can be used as an intermediate and can be further widely applied to the production of various products such as surfactants, bactericides, antistatic agents, fiber softeners, brightening agents, cosmetics, printing ink/paint, lubricating grease and the like.
Detailed Description
The present invention will be described in detail with reference to the following examples, but it should be understood that the examples are only illustrative of the present invention and are not intended to limit the scope of the present invention in any way. All reasonable variations and combinations that are included within the scope of the inventive concept fall within the scope of the present invention.
According to the technical scheme of the invention, in some specific embodiments, the process preparation method of the fish oil bio-based esteramine product comprises the following steps:
(1) Uniformly mixing fish oil ethyl ester with a compound stabilizer to obtain fish oil ethyl ester containing the stabilizer, wherein the compound stabilizer comprises sodium hypophosphite and vitamin C;
(2) Adding an alkanolamine compound and a solid base catalyst into a reaction kettle, stirring and heating to 120-200 ℃ in an inert atmosphere such as nitrogen flow, and treating for 15-20 min to obtain a suspension of the alkanolamine compound and the catalyst, wherein the solid base catalyst is porous gamma-Al 2 O 3 A catalyst supporting an active ingredient, the active ingredient including a composite oxide containing K and Zn;
(3) Adding the stabilizer-containing fish oil ethyl ester into a reaction kettle for finishing the step (2), and carrying out transesterification reaction with an alkanolamine compound in the reaction kettle to obtain a reaction system, wherein ethanol generated in the reaction is carried out by inert atmosphere air flow and is condensed and recovered;
(4) Controlling the temperature of the obtained reaction system to be 100-150 ℃, recovering the solid base catalyst, and pressing other substances of the reaction system into a decompression evaporator;
(5) Controlling the vacuum degree of the decompression evaporator to be-0.05 to-0.08 MPa, and steaming out low volatile matters under the conditions of stirring and 100-150 ℃ to obtain crude ester amine;
(6) Controlling the temperature of the crude esteramine product to be 100-120 ℃, adding sodium chloride aqueous solution with the mass concentration of 15-20% and preheated to 80-110 ℃ in advance into a back extraction kettle, pressing the obtained crude esteramine product into the back extraction kettle, fully stirring and mixing for 20-30 min, and then preserving heat and standing for 3-4 hours at 90-110 ℃ to carry out phase separation;
(7) And collecting an upper organic phase obtained by phase separation, and cooling to obtain the fish oil bio-based esteramine product.
The organic phase collected by the method is a fish oil fatty acid ester amine product containing different carbon chain compositions, namely a fish oil bio-based ester amine product, and the purity of the product is more than or equal to 98 percent.
In some preferred embodiments, the mass ratio of sodium hypophosphite to vitamin C in the composite stabilizer is (80-90): (20-10), more preferably 85:15.
In some preferred embodiments, the compound stabilizer is used in an amount of 2 to 1.0%, more preferably 8% by weight of the ethyl ester of fish oil.
In some preferred embodiments, the solid base catalyst has a molar ratio of K to Zn of 1:0.2.
In some preferred embodiments, the solid base catalyst has a loading mass of the active ingredient of the porous gamma-Al 2 O 3 10% of the mass of the (c).
In some preferred embodiments, the solid base catalyst is used in an amount of 10% of the mass of the fish oil ethyl ester.
In some preferred embodiments, the alkanolamine compound is selected from N, N-Dimethylethanolamine (DMEA) and/or Triethanolamine (TEA).
In some preferred embodiments, the alkanolamine compound is selected from the group consisting of N, N-Dimethylethanolamine (DMEA) and the molar ratio of fish oil ethyl ester to DMEA is 1 (2.5 to 5.0), more preferably 1:
(2.5-3.5), the temperature of the transesterification reaction is 120-200 ℃, more preferably 130-180 ℃, and the time of the transesterification reaction is 4-10 hours, more preferably 6-8 hours.
In some preferred embodiments, the alkanolamine compound is selected from Triethanolamine (TEA) and the molar ratio of fish oil ethyl ester to TEA is 1 (0.5 to 1.5), more preferably 1: (1.05-1.10), the temperature of the transesterification reaction is 160-200 ℃, more preferably 160-180 ℃, and the time of the transesterification reaction is 4-10 hours, more preferably 6-8 hours.
In some preferred embodiments, in step (3), before adding the stabilizer-containing fish oil ethyl ester, the suspension of the alkanolamine and the catalyst is stirred and heated to 120-200 ℃, more preferably to 125-130 ℃, and then the stabilizer-containing fish oil ethyl ester is slowly added to carry out transesterification.
More preferably, the addition time of the fish oil ethyl ester containing the stabilizing agent is 1 to 3 hours, and more preferably 2.0 to 2.5 hours.
In some preferred embodiments, in the step (4), the recovery of the solid base catalyst is realized by pressure filtration under inert atmosphere, the reaction system is subjected to heat preservation at 100-150 ℃ during pressure filtration, the solid base catalyst is left in the reaction kettle for recycling after pressure filtration, and the filtrate containing the crude esteramine enters a decompression evaporator, wherein the temperature of heat preservation is more preferably 120-130 ℃.
In some preferred embodiments, the vacuum in step (5) is controlled to be-0.06 to-0.07 MPa.
In some preferred embodiments, the temperature in step (5) is controlled to be 130-145 ℃.
In some preferred embodiments, the time to evaporate the low volatiles in step (5) is from 15 to 20 minutes.
In some preferred embodiments, the stripping operation must be carried out at a temperature of 90-110 ℃, especially 100-105 ℃, and the stripping operation is maintained at a temperature of 3-4 hours of stationary phase separation to ensure complete phase separation.
In some preferred embodiments, the obtaining of the solid base catalyst comprises:
(1) Obtaining a mixed aqueous solution of potassium fluoride (KF) and zinc acetate, and adding porous gamma-Al thereto 2 O 3 Soaking for 5-7 h at room temperature, and then slowly heating to evaporate water to obtain the alumina catalyst loaded with active ingredients;
(2) And (3) drying the alumina catalyst loaded with the active ingredients, sequentially heating to 250-350 ℃, 400-450 ℃, 450-550 ℃ in air, respectively treating for 2 hours, heating to 500-650 ℃ and calcining for 2.5-3.5 hours, and cooling to room temperature in air to obtain the solid base catalyst.
More preferably, the molar ratio of potassium fluoride (KF) to zinc acetate is 5:1.
The fish oil ethyl ester used in the examples below was obtained by extracting unsaturated fatty acids EPA and DHA, and was a bright yellow oil in appearance, an average molecular weight of 302.56, an average unsaturated bond content of 1.12 mol per mol, a density of 0.86 to 0.87, and an iodine value of 93.94gI 2 100 g, wherein the C16 and C18 fatty acids account for about 68 percent to 70 percent, the C20 fatty acids account for about 17 percent to 19 percent, the C22 and C23 fatty acids account for about 8.5 percent to 9.0 percent, and the fatty acids have an average carbon chain carbon number of 17.83.
In the following examples, the conversion of the fish oil ethyl ester was calculated using the amount of ethanol produced, i.e., 1mol of fish oil ethyl ester was reacted completely per 1mol of ethanol collected, and the purity of the fish oil ethyl ester was calculated as the ratio of the actual amine value to the theoretical amine value, and the yield of the fish oil ethyl ester was calculated as follows:
Yield = quality of product obtained x product purity/theoretical product quality.
Example 1
The solid base catalyst was prepared by the following procedure:
58.1 g (1.0 mol) of anhydrous potassium fluoride, 36.7 g (0.2 mol) of zinc acetate and 800 ml of deionized water are added into a beaker, the mixture is fully dissolved to form a uniform solution, 630 g of gamma-aluminum oxide porous carrier with the specific surface area of 180 square meters per gram and the average pore volume of 0.45ml per gram is added into the solution, stirring and soaking are carried out for 6 hours at room temperature, and then, the mixture is slowly heated and water is evaporated to obtain an alumina catalyst loaded with active ingredients;
drying the alumina catalyst loaded with the active ingredients at 120-130 ℃ for 3 hours, then loading the dried alumina catalyst into an atmosphere tube furnace, heating to 300 ℃, 450 ℃ and 500 ℃ in the air atmosphere, respectively carrying out residence treatment for 2 hours, heating to 550 ℃ and calcining for 3 hours, cooling to room temperature in the air atmosphere, pouring out, sieving to obtain the solid base catalyst with uniform granularity, and preserving in a vacuum drying oven for standby.
Example 2
Fish oil esteramine was prepared by the following procedure:
in a 1500ml reaction flask equipped with a stirrer, a thermometer, a top condenser and an equilibrium feeder, 267 g (3.0 mol) of dimethylaminoethanol, i.e. dimethylethanolamine, and 30 g (10% by weight of ethyl fish oil) of the solid base catalyst prepared in example 1 were added, and the mixture was stirred, dispersed and heated under nitrogen atmosphere, and heated to 125℃for 20 minutes to obtain a suspension of dimethylaminoethanol and the catalyst;
302.56 g of fish oil ethyl ester (1.0 mol), 1.9 g of sodium hypophosphite and 0.5 g of vitamin C are added into a 500ml beaker, and the mixture is fully stirred and dissolved uniformly to obtain fish oil ethyl ester containing a stabilizer;
when the temperature of the suspension of the dimethylaminoethanol and the catalyst in the reaction bottle reaches 125 ℃, slowly dripping the fish oil ethyl ester containing the stabilizer into the reaction bottle through an equilibrium feeder to carry out transesterification, taking out the generated ethanol by nitrogen at any time, condensing and recycling through a condenser, controlling the dripping process to be completed within 2.5 hours, wherein the temperature of materials in the reaction bottle in the dripping process is not lower than 130 ℃, and the gas phase temperature entering the condenser is not higher than 90 ℃;
when the dropping of the fish oil ethyl ester is completed in the embodiment, the reaction bottle condenser collects about 45 milliliters (about 0.8 mole) of ethanol, and the conversion rate of the fish oil ethyl ester is more than 80 percent; then the reactor is continuously stirred and heated to 170-175 ℃ for reaction, the amine value change of the analysis system is sampled every 30 minutes, the reaction is kept for 5 hours, the conversion rate of the fish oil ethyl ester reaches 98.5%, and the transesterification reaction is finished;
then stopping stirring to allow the materials in the reactor to stand for 30 minutes, and completely depositing the catalyst at the bottom of the reaction bottle; connecting the reaction bottle and the vacuum distillation bottle through a stainless steel tubule, completely pressing supernatant in the reaction bottle into the distillation bottle by utilizing nitrogen, and circularly feeding and using a catalyst at the bottom of the reaction bottle;
Starting a stirrer and a vacuum pump of a vacuum distillation flask, controlling the temperature to 140 ℃ and the vacuum degree to-0.065 MPa, firstly distilling residual ethanol and unreacted dimethylethanolamine, vacuum distilling for 30 minutes, and then breaking vacuum by using nitrogen, and recovering the system to normal pressure to obtain a crude product of fish oil ester amine;
transferring the crude product of the fish oil esteramine into a stirring extraction bottle, maintaining the temperature of the fish oil esteramine at 100-110 ℃, adding 200 ml of 100 ℃ saline with the mass concentration of 20% under stirring, fully stirring and extracting, stopping stirring, standing at 100-110 ℃ for 2 hours, carrying out heat preservation and phase separation, wherein the lower layer is a pale yellow saline phase after phase separation, and the upper layer is a red fish oil esteramine phase;
after separating the lower aqueous phase, the upper oil phase was added to the flask and allowed to cool slowly to room temperature under nitrogen to give the fish oil esteramine as a yellow-white cream.
The conversion of the ethyl ester of the fish oil in this example was 98%, 340.36g of a fish oil esteramine which was a fish oil aminoethanol esteramine containing a small amount of unreacted ethyl ester of the fish oil was obtained after the completion of the reaction, the amine value was 159.55mgKOH/g, and the purity of the obtained fish oil esteramine was 98.3% and the yield was 96.8% by analysis with the amine value.
Example 3
Fish oil esteramine was prepared by the following procedure:
into a 1500ml reaction flask equipped with a stirrer, a thermometer, a top condenser and an equilibrium feeder, 534 g (6.0 mol) of dimethylaminoethanol, i.e. dimethylethanolamine, and 60 g (10% by weight of ethyl fish oil) of the solid base catalyst prepared in example 1 were added, and the mixture was stirred, dispersed and heated under nitrogen atmosphere, and heated to 125℃for 20 minutes to obtain a suspension of dimethylaminoethanol and catalyst;
605.12 g of fish oil ethyl ester (2.0 mol), 3.8 g of sodium hypophosphite and 1.0 g of vitamin C are added into a 500ml beaker, and the mixture is fully stirred and dissolved uniformly to obtain fish oil ethyl ester containing a stabilizer;
when the temperature of the suspension of the dimethylaminoethanol and the catalyst in the reaction bottle reaches 125 ℃, slowly dripping the fish oil ethyl ester containing the stabilizer into the reaction bottle through an equilibrium feeder to carry out transesterification, taking out the generated ethanol by nitrogen at any time, condensing and recycling through a condenser, controlling the dripping process to be completed within 2.5 hours, wherein the temperature of materials in the reaction bottle in the dripping process is not lower than 130 ℃, and the gas phase temperature entering the condenser is not higher than 90 ℃;
when the ethyl fish oil is added dropwise in this example, the reaction flask condenser collects about 90 ml (about 1.6 mol) of ethanol, and the conversion rate of the ethyl fish oil is more than 80%; then the reactor is continuously stirred and heated to 170-175 ℃ for reaction, the amine value change of the analysis system is sampled every 30 minutes, the reaction is kept for 5 hours, the conversion rate of the fish oil ethyl ester reaches 97.8%, and the transesterification reaction is finished;
Then stopping stirring to allow the materials in the reactor to stand for 30 minutes, and completely depositing the catalyst at the bottom of the reaction bottle; connecting the reaction bottle and the vacuum distillation bottle through a stainless steel tubule, completely pressing supernatant in the reaction bottle into the distillation bottle by utilizing nitrogen, and circularly feeding and using a catalyst at the bottom of the reaction bottle;
starting a stirrer and a vacuum pump of a vacuum distillation flask, controlling the temperature to 140 ℃ and the vacuum degree to-0.065 MPa, firstly distilling residual ethanol and unreacted dimethylethanolamine, vacuum distilling for 30 minutes, and then breaking vacuum by using nitrogen, and recovering the system to normal pressure to obtain a crude product of fish oil ester amine;
transferring the crude product of the fish oil esteramine into a stirring extraction bottle, maintaining the temperature of the fish oil esteramine at 100-110 ℃, adding 400 ml of 100 ℃ saline with the mass concentration of 20% under stirring, fully stirring and extracting, stopping stirring, standing at 100-110 ℃ for 2 hours, carrying out heat preservation and phase separation, wherein the lower layer is a pale yellow saline phase after phase separation, and the upper layer is a red fish oil esteramine phase;
after separating the lower aqueous phase, the upper oil phase was added to the flask and allowed to cool slowly to room temperature under nitrogen to give the fish oil esteramine as a yellow-white cream.
The conversion of the ethyl ester of the fish oil of this example was 97.8%, 682.81g of a fish oil esteramine which was a fish oil aminoethanol esteramine containing a small amount of unreacted ethyl ester of the fish oil was obtained after the completion of the reaction, the amine value was 159.39mgKOH/g, and the purity of the obtained fish oil esteramine was 98.2% and the yield was 97% by analysis with the amine value.
Example 4
Fish oil esteramine was prepared by the following procedure:
in a 1500ml reaction flask with stirrer, thermometer, top condenser and balance feeder, 267 g (3.0 mol) of dimethylaminoethanol, 30 g (10% of the weight of the ethyl ester of fish oil) of solid base catalyst obtained by separation in example 2 was added, and the mixture was stirred and dispersed and heated sufficiently in a nitrogen atmosphere, and the temperature was raised to 125 ℃ for 20min to obtain a suspension of dimethylaminoethanol and catalyst;
302.56 g of fish oil ethyl ester (1.0 mol), 1.9 g of sodium hypophosphite and 0.5 g of vitamin C are added into a 500ml beaker, and the mixture is fully stirred and dissolved uniformly to obtain fish oil ethyl ester containing a stabilizer;
when the temperature of the suspension of the dimethylaminoethanol and the catalyst in the reaction bottle reaches 125 ℃, slowly dripping the fish oil ethyl ester containing the stabilizer into the reaction bottle through an equilibrium feeder to carry out transesterification, taking out the generated ethanol by nitrogen at any time, condensing and recycling through a condenser, controlling the dripping process to be completed within 2.5 hours, wherein the temperature of materials in the reaction bottle in the dripping process is not lower than 130 ℃, and the gas phase temperature entering the condenser is not higher than 90 ℃;
when the ethyl fish oil was added dropwise in this example, the reaction flask condenser collected about 43 ml (about 0.76 mol) of ethanol, and the conversion rate of ethyl fish oil was more than 76%; then the reactor is continuously stirred and heated to 170-175 ℃ for reaction, the amine value change of the analysis system is sampled every 30 minutes, the reaction is kept for 5 hours, the conversion rate of the fish oil ethyl ester reaches 97.5%, and the transesterification reaction is finished;
Then stopping stirring to allow the materials in the reactor to stand for 30 minutes, and completely depositing the catalyst at the bottom of the reaction bottle; connecting the reaction bottle and the vacuum distillation bottle through a stainless steel tubule, completely pressing supernatant in the reaction bottle into the distillation bottle by utilizing nitrogen, and circularly feeding and using a catalyst at the bottom of the reaction bottle;
starting a stirrer and a vacuum pump of a vacuum distillation flask, controlling the temperature to 140 ℃ and the vacuum degree to-0.065 MPa, firstly distilling residual ethanol and unreacted dimethylethanolamine, vacuum distilling for 30 minutes, and then breaking vacuum by using nitrogen, and recovering the system to normal pressure to obtain a crude product of fish oil ester amine;
transferring the crude product of the fish oil esteramine into a stirring extraction bottle, maintaining the temperature of the fish oil esteramine at 100-110 ℃, adding 200 ml of 100 ℃ saline with the mass concentration of 20% under stirring, fully stirring and extracting, stopping stirring, standing at 100-110 ℃ for 2 hours, carrying out heat preservation and phase separation, wherein the lower layer is a pale yellow saline phase after phase separation, and the upper layer is a red fish oil esteramine phase;
after separating the lower aqueous phase, the upper oil phase was added to the flask and allowed to cool slowly to room temperature under nitrogen to give the fish oil esteramine as a yellow-white cream.
The conversion of the ethyl ester of the fish oil of this example was 97.5%, 340.34g of a fish oil esteramine (fish oil aminoethanol estertertiary amine containing a small amount of unreacted ethyl ester of fish oil) was obtained after the reaction, the amine value was 158.9mgKOH/g, and analysis of the amine value gave a fish oil esteramine having a purity of 97.9% and a yield of 96.4%.
Example 5
Fish oil esteramine was prepared by the following procedure:
to a 1500ml reaction flask equipped with a stirrer, a thermometer, a top condenser and an equilibrium feeder, 445 g (5.0 mol) of dimethylaminoethanol, i.e., dimethylethanolamine, and 30 g (10% by weight of ethyl fish oil) of the solid base catalyst obtained in example 1 were added, and the mixture was stirred and dispersed in a nitrogen atmosphere, heated to 125℃and dispersed for 20 minutes to obtain a suspension of dimethylaminoethanol and the catalyst;
302.56 g of fish oil ethyl ester (1.0 mol), 1.9 g of sodium hypophosphite and 0.5 g of vitamin C are added into a 500ml beaker, and the mixture is fully stirred and dissolved uniformly to obtain fish oil ethyl ester containing a stabilizer;
when the temperature of a suspension of dimethylaminoethanol and a catalyst in a reaction bottle reaches 125 ℃, slowly dripping fish oil ethyl ester containing a stabilizer into the reaction bottle through an equilibrium feeder to carry out transesterification, taking out the generated ethanol by nitrogen at any time, condensing and recycling through a condenser, controlling the dripping process to be completed within 1 hour, wherein the temperature of materials in the reaction bottle in the dripping process is not lower than 130 ℃, and the temperature of gas phase entering the condenser is not higher than 90 ℃;
when the dropping of the fish oil ethyl ester is completed in the embodiment, the reaction bottle condenser collects about 23 milliliters (about 0.4 mole) of ethanol, and the conversion rate of the fish oil ethyl ester is more than 40 percent; then the reactor is continuously stirred and heated to 170-175 ℃ for reaction, the amine value change of the analysis system is sampled every 30 minutes, the reaction is kept for 5 hours, the conversion rate of the fish oil ethyl ester reaches 98.1%, and the transesterification reaction is finished;
Then stopping stirring to allow the materials in the reactor to stand for 30 minutes, and completely depositing the catalyst at the bottom of the reaction bottle; connecting the reaction bottle and the vacuum distillation bottle through a stainless steel tubule, completely pressing supernatant in the reaction bottle into the distillation bottle by utilizing nitrogen, and circularly feeding and using a catalyst at the bottom of the reaction bottle;
starting a stirrer and a vacuum pump of a vacuum distillation flask, controlling the temperature to be 130 ℃, and the vacuum degree to be-0.07 MPa, firstly distilling residual ethanol and unreacted dimethylethanolamine, vacuum distilling for 120 minutes, and then breaking vacuum by using nitrogen, and recovering the system to normal pressure to obtain a crude product of fish oil ester amine;
transferring the crude product of the fish oil esteramine into a stirring extraction bottle, maintaining the temperature of the fish oil esteramine at 100-110 ℃, adding 200 ml of 100 ℃ saline with the mass concentration of 20% under stirring, fully stirring and extracting, stopping stirring, standing at 100-110 ℃ for 2 hours, carrying out heat preservation and phase separation, wherein the lower layer is a pale yellow saline phase after phase separation, and the upper layer is a red fish oil esteramine phase;
after separating the lower aqueous phase, the upper oil phase was added to the flask and allowed to cool slowly to room temperature under nitrogen atmosphere to give the fish oil esteramine as an orange-red cream product.
The conversion of the ethyl ester of the fish oil of this example was 98.1%, 340g of fish oil esteramine (fish oil aminoethanol estertertiary amine containing a small amount of unreacted ethyl ester of fish oil) was obtained after the reaction was completed, the amine value was 159.55mgKOH/g, and the analysis was conducted on the amine value to obtain the fish oil esteramine having a purity of 98.3% and a yield of 96.7%.
Example 6
Fish oil esteramine was prepared by the following procedure:
in a 1500ml reaction flask equipped with a stirrer, a thermometer, a top condenser and an equilibrium feeder, 267 g (3.0 mol) of dimethylaminoethanol, i.e. dimethylethanolamine, and 30 g (10% by weight of ethyl fish oil) of the solid base catalyst prepared in example 1 were added, and the mixture was stirred, dispersed and heated under nitrogen atmosphere, and heated to 125℃for 20 minutes to obtain a suspension of dimethylaminoethanol and the catalyst;
302.56 g of fish oil ethyl ester (1.0 mol), 0.48 g of sodium hypophosphite and 0.12 g of vitamin C are added into a 500ml beaker, and the mixture is fully stirred and dissolved uniformly to obtain fish oil ethyl ester containing a stabilizer;
when the temperature of the suspension of the dimethylaminoethanol and the catalyst in the reaction bottle reaches 125 ℃, slowly dripping the fish oil ethyl ester containing the stabilizer into the reaction bottle through an equilibrium feeder to carry out transesterification, taking out the generated ethanol by nitrogen at any time, condensing and recycling through a condenser, controlling the dripping process to be completed within 2.5 hours, wherein the temperature of materials in the reaction bottle in the dripping process is not lower than 130 ℃, and the gas phase temperature entering the condenser is not higher than 90 ℃;
when the dropping of the fish oil ethyl ester is completed in the embodiment, the reaction bottle condenser collects about 45 milliliters (about 0.8 mole) of ethanol, and the conversion rate of the fish oil ethyl ester is more than 80 percent; then the reactor is continuously stirred and heated to 170-175 ℃ for reaction, the amine value change of the analysis system is sampled every 30 minutes, the reaction is kept for 5 hours, the conversion rate of the fish oil ethyl ester reaches 98%, and the transesterification reaction is finished;
Then stopping stirring to allow the materials in the reactor to stand for 30 minutes, and completely depositing the catalyst at the bottom of the reaction bottle; connecting the reaction bottle and the vacuum distillation bottle through a stainless steel tubule, completely pressing supernatant in the reaction bottle into the distillation bottle by utilizing nitrogen, and circularly feeding and using a catalyst at the bottom of the reaction bottle;
starting a stirrer and a vacuum pump of a vacuum distillation flask, controlling the temperature to 140 ℃ and the vacuum degree to-0.065 MPa, firstly distilling residual ethanol and unreacted dimethylethanolamine, vacuum distilling for 30 minutes, and then breaking vacuum by using nitrogen, and recovering the system to normal pressure to obtain a crude product of fish oil ester amine;
transferring the crude product of the fish oil esteramine into a stirring extraction bottle, maintaining the temperature of the fish oil esteramine at 100-110 ℃, adding 200 ml of 100 ℃ saline with the mass concentration of 20% under stirring, fully stirring and extracting, stopping stirring, standing at 100-110 ℃ for 2 hours, carrying out heat preservation and phase separation, wherein the lower layer is a pale yellow saline phase after phase separation, and the upper layer is a red fish oil esteramine phase;
after separating the lower aqueous phase, the upper oil phase was added to the flask and allowed to cool slowly to room temperature under nitrogen to give the fish oil esteramine as a reddish brown cream.
The conversion of the ethyl ester of the fish oil of this example was 98%, 342.1g of a fish oil esteramine (a fish oil aminoethanol estertertiary amine containing a small amount of unreacted ethyl ester of the fish oil) was obtained after the reaction, the amine value was 159.06mgKOH/g, and the purity of the obtained fish oil esteramine was 98% by analysis of the amine value, and the yield was 97%.
Example 7
Fish oil esteramine was prepared by the following procedure:
to a 1500ml reaction flask equipped with a stirrer, a thermometer, a top condenser and an equilibrium feeder were added 152 g (1.02 mol) of triethanolamine TEA and 30 g (10% by weight of ethyl ester of fish oil) of the solid base catalyst prepared in example 1, and the mixture was thoroughly stirred, dispersed and heated in a nitrogen atmosphere to raise the temperature to 165℃to obtain a triethanolamine and catalyst suspension;
302.56 g of fish oil ethyl ester (1.0 mol), 1.9 g of sodium hypophosphite and 0.5 g of vitamin C are added into a 500ml beaker, and the mixture is fully stirred and dissolved uniformly to obtain fish oil ethyl ester containing a stabilizer;
when the temperature of the triethanolamine and the catalyst suspension in the reaction bottle reaches 165 ℃, slowly dripping the fish oil ethyl ester containing the stabilizer into the reaction bottle through an equilibrium feeder to carry out transesterification, taking out the generated ethanol by nitrogen at any time, condensing and recycling through a condenser, controlling the dripping process to be completed within 2.5 hours, controlling the temperature of materials in dripping to be not lower than 165 ℃, and controlling the temperature of gas phase entering the condenser to be not higher than 90 ℃;
when the dripping of the fish oil ethyl ester is completed in the embodiment, the ethanol collected by the condenser of the reaction bottle is about 53 milliliters (about 0.9 mole), and the conversion rate of the fish oil ethyl ester is more than 88 percent; then the reactor is continuously stirred and heated to 175-180 ℃ for reaction, the amine value change of the analysis system is sampled every 30 minutes, the reaction is kept for 3 hours, the conversion rate of the fish oil ethyl ester reaches 99.1%, and the transesterification reaction is finished;
Then stopping stirring to allow the materials in the reactor to stand for 30 minutes, and completely depositing the catalyst at the bottom of the reaction bottle; connecting the reaction bottle and the vacuum distillation bottle through a stainless steel tubule, completely pressing supernatant in the reaction bottle into the distillation bottle by utilizing nitrogen, and circularly feeding and using a catalyst at the bottom of the reaction bottle;
starting a vacuum distillation flask for stirring and a vacuum pump, controlling the temperature to 140 ℃ and the vacuum degree to-0.085 MPa, and firstly distilling residual ethanol; vacuum distilling for 30 minutes, and recovering nitrogen to normal pressure and nitrogen flow to obtain crude fish oil ester amine;
transferring the crude product of the fish oil esteramine into a stirring extraction bottle, maintaining the temperature of the fish oil esteramine at 110-120 ℃, adding 200 ml of 100 ℃ salt water with the mass concentration of 15% under stirring, fully stirring and extracting, stopping stirring, standing at 90-100 ℃ for 4 hours, carrying out heat preservation and phase separation, wherein the lower layer is a pale yellow saline phase after phase separation, and the upper layer is a red fish oil esteramine phase;
after separating the lower aqueous phase, the upper oil phase was added to the flask and allowed to cool slowly to room temperature under nitrogen to give a yellow-red homogeneous oil of fish oil esteramine.
The conversion of the ethyl ester of the fish oil of this example was 99.1%, 453.26g of a fish oil esteramine (a fish oil triethanolamine estertertiary amine containing a small amount of unreacted ethyl ester of the fish oil) was obtained after the reaction, the amine value was 136.63mgKOH/g, and the analysis was conducted on the amine value to obtain a fish oil esteramine having a purity of 98.8% and a yield of 98%.
Example 8
Fish oil esteramine was prepared by the following procedure:
to a 1500ml reaction flask equipped with a stirrer, a thermometer, a top condenser and an equilibrium feeder were added 224 g (1.5 mol) of triethanolamine TEA and 30 g (10% by weight of ethyl ester of fish oil) of the solid base catalyst prepared in example 1, and the mixture was thoroughly stirred, dispersed and heated in a nitrogen atmosphere to raise the temperature to 165℃to obtain a triethanolamine and catalyst suspension;
302.56 g of fish oil ethyl ester (1.0 mol), 1.9 g of sodium hypophosphite and 0.5 g of vitamin C are added into a 500ml beaker, and the mixture is fully stirred and dissolved uniformly to obtain fish oil ethyl ester containing a stabilizer;
when the temperature of the triethanolamine and the catalyst suspension in the reaction bottle reaches 165 ℃, slowly dripping the fish oil ethyl ester containing the stabilizer into the reaction bottle through an equilibrium feeder to carry out transesterification, taking out the generated ethanol by nitrogen at any time, condensing and recycling through a condenser, controlling the dripping process to be completed within 2.5 hours, controlling the temperature of materials in dripping to be not lower than 165 ℃, and controlling the temperature of gas phase entering the condenser to be not higher than 90 ℃;
when the dripping of the fish oil ethyl ester is completed in the embodiment, the ethanol collected by the condenser of the reaction bottle is about 52 milliliters (about 0.88 mol), and the conversion rate of the fish oil ethyl ester is more than 90 percent; then the reactor is continuously stirred and heated to 175-180 ℃ for reaction, the amine value change of the analysis system is sampled every 30 minutes, the reaction is kept for 3 hours, the conversion rate of the fish oil ethyl ester reaches 99%, and the transesterification reaction is finished;
Then stopping stirring to allow the materials in the reactor to stand for 30 minutes, and completely depositing the catalyst at the bottom of the reaction bottle; connecting the reaction bottle and the vacuum distillation bottle through a stainless steel tubule, completely pressing supernatant in the reaction bottle into the distillation bottle by utilizing nitrogen, and circularly feeding and using a catalyst at the bottom of the reaction bottle;
starting a vacuum distillation flask for stirring and a vacuum pump, controlling the temperature to 140 ℃ and the vacuum degree to-0.085 MPa, and firstly distilling residual ethanol; vacuum distilling for 30 minutes, and recovering nitrogen to normal pressure and nitrogen flow to obtain crude fish oil ester amine;
transferring the crude product of the fish oil esteramine into a stirring extraction bottle, maintaining the temperature of the fish oil esteramine at 110-120 ℃, adding 200 ml of 100 ℃ salt water with the mass concentration of 15% under stirring, fully stirring and extracting, stopping stirring, standing at 90-100 ℃ for 4 hours, carrying out heat preservation and phase separation, wherein the lower layer is a pale yellow saline phase after phase separation, and the upper layer is a red fish oil esteramine phase;
after separating the lower aqueous phase, the upper oil phase was added to the flask and allowed to cool slowly to room temperature under nitrogen to give a yellow-red homogeneous oil of fish oil esteramine.
The conversion of the ethyl ester of the fish oil of this example was 99%, 454.18g of a fish oil esteramine (a fish oil triethanolamine estertertiary amine containing a small amount of unreacted ethyl ester of the fish oil) was obtained after the reaction, the amine value was 136.35mgKOH/g, and the purity of the obtained fish oil esteramine was 98.6% by analysis of the amine value, and the yield was 98%.
Example 9
Fish oil esteramine was prepared by the following procedure:
to a 1500ml reaction flask equipped with a stirrer, a thermometer, a top condenser and an equilibrium feeder were added 152 g (1.02 mol) of triethanolamine TEA and 30 g (10% by weight of ethyl ester of fish oil) of the solid base catalyst recovered in example 7, and the mixture was thoroughly stirred, dispersed and heated in a nitrogen atmosphere to raise the temperature to 165℃to obtain a triethanolamine and catalyst suspension;
302.56 g of fish oil ethyl ester (1.0 mol), 1.9 g of sodium hypophosphite and 0.5 g of vitamin C are added into a 500ml beaker, and the mixture is fully stirred and dissolved uniformly to obtain fish oil ethyl ester containing a stabilizer;
when the temperature of the triethanolamine and the catalyst suspension in the reaction bottle reaches 165 ℃, slowly dripping the fish oil ethyl ester containing the stabilizer into the reaction bottle through an equilibrium feeder to carry out transesterification, taking out the generated ethanol by nitrogen at any time, condensing and recycling through a condenser, controlling the dripping process to be completed within 2.5 hours, controlling the temperature of materials in dripping to be not lower than 165 ℃, and controlling the temperature of gas phase entering the condenser to be not higher than 90 ℃;
when the dripping of the fish oil ethyl ester is completed in the embodiment, about 50 milliliters (about 0.85 mol) of ethanol is collected by a reaction bottle condenser, and the conversion rate of the fish oil ethyl ester is more than 85 percent; then the reactor is continuously stirred and heated to 175-180 ℃ for reaction, the amine value change of the analysis system is sampled every 30 minutes, the reaction is kept for 3 hours, the conversion rate of the fish oil ethyl ester reaches 98.7%, and the transesterification reaction is finished;
Then stopping stirring to allow the materials in the reactor to stand for 30 minutes, and completely depositing the catalyst at the bottom of the reaction bottle; connecting the reaction bottle and the vacuum distillation bottle through a stainless steel tubule, completely pressing supernatant in the reaction bottle into the distillation bottle by utilizing nitrogen, and circularly feeding and using a catalyst at the bottom of the reaction bottle;
starting a vacuum distillation flask for stirring and a vacuum pump, controlling the temperature to 140 ℃ and the vacuum degree to-0.085 MPa, and firstly distilling residual ethanol; vacuum distilling for 30 minutes, and recovering nitrogen to normal pressure and nitrogen flow to obtain crude fish oil ester amine;
transferring the crude product of the fish oil esteramine into a stirring extraction bottle, maintaining the temperature of the fish oil esteramine at 110-120 ℃, adding 200 ml of 100 ℃ salt water with the mass concentration of 15% under stirring, fully stirring and extracting, stopping stirring, standing at 90-100 ℃ for 4 hours, carrying out heat preservation and phase separation, wherein the lower layer is a pale yellow saline phase after phase separation, and the upper layer is a red fish oil esteramine phase;
after separating the lower aqueous phase, the upper oil phase was added to the flask and allowed to cool slowly to room temperature under nitrogen to give a yellow-red homogeneous oil of fish oil esteramine.
The conversion of the ethyl ester of the fish oil of this example was 98.7%, and after the reaction was completed, a fish oil esteramine of 455.56 (a fish oil triethanolamine estertertiary amine containing a small amount of unreacted ethyl ester of fish oil) was obtained, the amine value was 135.52mgKOH/g, and the analysis was conducted on the amine value, and the purity of the obtained fish oil esteramine was 98%, and the yield was 97.7%.
Comparative example 1
The same procedure as in example 2 was used to prepare fish oil esteramine, except that the catalyst used in this comparative example was potassium hydroxide in an amount of 0.8% of the ethyl ester of fish oil.
In the comparative example, when the dripping of the fish oil ethyl ester is finished, the conversion rate is 72.4%, after the heat preservation reaction is carried out for 12 hours at 175-180 ℃, the conversion rate of the fish oil ethyl ester reaches 90.2%, and the heat preservation reaction is carried out for 18 hours, the conversion rate of the fish oil ethyl ester reaches 98%; after the completion of the reaction, 323.42g of yellow fish oil esteramine (containing a small amount of unreacted fish oil ethyl ester and a by-product of fish oil aminoethanol estertertiary amine) was obtained, the amine value was 156.63mgKOH/g, and the analysis was conducted on the amine value, whereby the purity of the obtained yellow fish oil esteramine was 96.5%, and the yield was 90.3%.
Comparative example 2
The same procedure as in example 2 was used to prepare fish oil esteramine, except that the catalyst used in this comparative example was potassium methoxide KOCH 3 The dosage of the fish oil is 1 percent of that of the fish oil ethyl ester.
In the comparative example, when the dripping of the fish oil ethyl ester is finished, the conversion rate is 75.6%, after the heat preservation reaction is carried out for 12 hours at 175-180 ℃, the conversion rate of the fish oil ethyl ester reaches 92.2%, the heat preservation reaction is carried out for 16 hours, and the conversion rate of the fish oil ethyl ester reaches 98%; after the completion of the reaction, 327.20g of yellow fish oil esteramine (fish oil aminoethanol estertertiary amine containing a small amount of unreacted fish oil ethyl ester and by-products) was obtained, the amine value was 156.63mgKOH/g, and the analysis was carried out on the amine value, so that the purity of the obtained yellow fish oil esteramine was 97.5%, and the yield was 92.3%.
It can be seen that the selectivity of the catalysts used in comparative examples 1 and 2 is significantly lower than that of the catalyst used in example 2, and the purity and yield of the obtained fish oil esteramine are significantly lower.
The above examples are only preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the concept of the invention belong to the protection scope of the invention. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be within the scope of the present invention.
Claims (10)
1. The technological preparation method of the fish oil bio-based esteramine product is characterized by comprising the following steps of:
(1) Uniformly mixing fish oil ethyl ester with a compound stabilizer to obtain fish oil ethyl ester containing the stabilizer, wherein the compound stabilizer comprises sodium hypophosphite and vitamin C;
(2) Heating an alkanolamine compound and a solid base catalyst to 120-200 ℃ in an air flow of inert atmosphere gas, and mixing to obtain a suspension of the alkanolamine compound and the catalyst, wherein the solid base catalyst is porous gamma-Al 2 O 3 A catalyst supporting an active ingredient, the active ingredient including a complex oxide of K and Zn;
(3) Adding the stabilizer-containing fish oil ethyl ester into the suspension of the alkanolamine and the catalyst to perform transesterification reaction to obtain a reaction system, and condensing and recovering ethanol generated in the reaction;
(4) Controlling the temperature of the reaction system to be 100-150 ℃ and recovering the solid base catalyst;
(5) Evaporating the reaction system after the recovery of the solid base catalyst under reduced pressure, wherein the vacuum degree of the reduced pressure evaporation is-0.05 to-0.08 MPa, and the evaporation temperature is 100-150 ℃ to obtain an ester amine crude product;
(6) Carrying out back extraction on the crude product of the esteramine by using a sodium chloride aqueous solution with the mass concentration of 15-20% at the temperature of 80-110 ℃, and carrying out phase separation by keeping the temperature of 90-110 ℃ and standing at the temperature;
(7) And collecting an upper organic phase obtained by phase separation, and cooling to obtain the fish oil bio-based esteramine product.
2. The process preparation method according to claim 1, wherein the mass ratio of sodium hypophosphite to vitamin C in the composite stabilizer is (80-90): 20-10; and/or the use mass of the compound stabilizer is 2 per mill to 1.0 percent of the mass of the fish oil ethyl ester; and/or, in the solid base catalyst, the molar ratio of K to Zn is 1:0.2; and/or, in the solid base catalyst, the loading mass of the active ingredient is the porous gamma-Al 2 O 3 10% of the mass of (a); and/or the use mass of the solid base catalyst is 10% of the mass of the fish oil ethyl ester.
3. The process preparation method according to claim 1, wherein the mass ratio of sodium hypophosphite to vitamin C in the composite stabilizer is 85:15; and/or the use mass of the compound stabilizer is 8 per mill of the mass of the fish oil ethyl ester.
4. The process according to claim 1, wherein the alkanolamine compound is selected from N, N-dimethylethanolamine and/or triethanolamine.
5. The process preparation method according to claim 4, wherein the alkanolamine compound is selected from N, N-dimethylethanolamine, the molar ratio of the fish oil ethyl ester to the N, N-dimethylethanolamine is 1 (2.5-5.0), the temperature of the transesterification reaction is 120-200 ℃, and the time of the transesterification reaction is 4-10 hours; or the alkyl alcohol amine compound is selected from triethanolamine, the mol ratio of the fish oil ethyl ester to the triethanolamine is 1 (0.5-1.5), the temperature of the transesterification reaction is 160-200 ℃, and the time of the transesterification reaction is 4-10 h.
6. The process preparation method according to claim 5, wherein the molar ratio of the fish oil ethyl ester to the N, N-dimethylethanolamine is 1 (2.5-3.5), the temperature of the transesterification reaction is 130-180 ℃, and the time of the transesterification reaction is 6-8 hours; or the alkyl alcohol amine compound is selected from triethanolamine, the mol ratio of the fish oil ethyl ester to the triethanolamine is 1 (1.05-1.1), the temperature of the transesterification reaction is 160-180 ℃, and the time of the transesterification reaction is 6-8 h.
7. The process preparation method according to claim 1, wherein the transesterification is carried out by stirring and heating the suspension of the alkanolamine and the catalyst to 120-200 ℃ before adding the stabilizer-containing fish oil ethyl ester, and then slowly adding the stabilizer-containing fish oil ethyl ester; and/or the recovery of the solid base catalyst is realized by pressure filtration under inert atmosphere, and the reaction system is subjected to heat preservation at 100-150 ℃ during the pressure filtration.
8. The process according to claim 1, wherein the vacuum degree of the reduced pressure evaporation is-0.06 to-0.07 MPa; and/or the evaporation temperature is 130-145 ℃; and/or evaporating for 30-120 min.
9. The process according to claim 1, wherein the obtaining of the solid base catalyst comprises:
(1) Obtaining a mixed aqueous solution of potassium fluoride and zinc acetate, and adding porous gamma-Al 2 O 3 Soaking at room temperature for 5-7 hr, and slowly heating to evaporate water to obtain the final productTo an alumina catalyst loaded with an active ingredient;
(2) And (3) drying the alumina catalyst loaded with the active ingredients, sequentially heating to 250-350 ℃, 400-450 ℃, 450-550 ℃ in air, respectively treating for 2 hours, heating to 500-650 ℃ and calcining for 2.5-3.5 hours, and cooling to room temperature in air to obtain the solid base catalyst.
10. A fish oil biobased esteramine product prepared by the process of any of claims 1-9.
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