CN107955054A - A kind of method that film simultaneous reaction and separation prepares phytosterin ester - Google Patents
A kind of method that film simultaneous reaction and separation prepares phytosterin ester Download PDFInfo
- Publication number
- CN107955054A CN107955054A CN201711243478.7A CN201711243478A CN107955054A CN 107955054 A CN107955054 A CN 107955054A CN 201711243478 A CN201711243478 A CN 201711243478A CN 107955054 A CN107955054 A CN 107955054A
- Authority
- CN
- China
- Prior art keywords
- acid
- film
- evaporator
- phytosterin ester
- phytosterol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000002148 esters Chemical class 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 30
- 238000000926 separation method Methods 0.000 title claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 239000002253 acid Substances 0.000 claims abstract description 39
- 230000032050 esterification Effects 0.000 claims abstract description 31
- 238000005886 esterification reaction Methods 0.000 claims abstract description 31
- 239000000194 fatty acid Substances 0.000 claims abstract description 30
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 22
- 229930182558 Sterol Natural products 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 235000003702 sterols Nutrition 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 150000003432 sterols Chemical class 0.000 claims abstract description 11
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 10
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005642 Oleic acid Substances 0.000 claims abstract description 10
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 28
- 229930195729 fatty acid Natural products 0.000 claims description 28
- 150000004665 fatty acids Chemical class 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 241000196324 Embryophyta Species 0.000 claims description 16
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 10
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 claims description 9
- OILXMJHPFNGGTO-UHFFFAOYSA-N (22E)-(24xi)-24-methylcholesta-5,22-dien-3beta-ol Natural products C1C=C2CC(O)CCC2(C)C2C1C1CCC(C(C)C=CC(C)C(C)C)C1(C)CC2 OILXMJHPFNGGTO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 235000021314 Palmitic acid Nutrition 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 7
- LGJMUZUPVCAVPU-UHFFFAOYSA-N beta-Sitostanol Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(C)CCC(CC)C(C)C)C1(C)CC2 LGJMUZUPVCAVPU-UHFFFAOYSA-N 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 7
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 6
- 238000007127 saponification reaction Methods 0.000 claims description 6
- OQMZNAMGEHIHNN-UHFFFAOYSA-N 7-Dehydrostigmasterol Natural products C1C(O)CCC2(C)C(CCC3(C(C(C)C=CC(CC)C(C)C)CCC33)C)C3=CC=C21 OQMZNAMGEHIHNN-UHFFFAOYSA-N 0.000 claims description 5
- HZYXFRGVBOPPNZ-UHFFFAOYSA-N UNPD88870 Natural products C1C=C2CC(O)CCC2(C)C2C1C1CCC(C(C)=CCC(CC)C(C)C)C1(C)CC2 HZYXFRGVBOPPNZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 235000002378 plant sterols Nutrition 0.000 claims description 5
- 230000000630 rising effect Effects 0.000 claims description 5
- NLQLSVXGSXCXFE-UHFFFAOYSA-N sitosterol Natural products CC=C(/CCC(C)C1CC2C3=CCC4C(C)C(O)CCC4(C)C3CCC2(C)C1)C(C)C NLQLSVXGSXCXFE-UHFFFAOYSA-N 0.000 claims description 5
- HCXVJBMSMIARIN-PHZDYDNGSA-N stigmasterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)/C=C/[C@@H](CC)C(C)C)[C@@]1(C)CC2 HCXVJBMSMIARIN-PHZDYDNGSA-N 0.000 claims description 5
- 235000016831 stigmasterol Nutrition 0.000 claims description 5
- 229940032091 stigmasterol Drugs 0.000 claims description 5
- BFDNMXAIBMJLBB-UHFFFAOYSA-N stigmasterol Natural products CCC(C=CC(C)C1CCCC2C3CC=C4CC(O)CCC4(C)C3CCC12C)C(C)C BFDNMXAIBMJLBB-UHFFFAOYSA-N 0.000 claims description 5
- JBYXPOFIGCOSSB-GOJKSUSPSA-N 9-cis,11-trans-octadecadienoic acid Chemical compound CCCCCC\C=C\C=C/CCCCCCCC(O)=O JBYXPOFIGCOSSB-GOJKSUSPSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- MBMBGCFOFBJSGT-KUBAVDMBSA-N all-cis-docosa-4,7,10,13,16,19-hexaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCC(O)=O MBMBGCFOFBJSGT-KUBAVDMBSA-N 0.000 claims description 4
- 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 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229940108924 conjugated linoleic acid Drugs 0.000 claims description 4
- 235000005687 corn oil Nutrition 0.000 claims description 4
- 239000002285 corn oil Substances 0.000 claims description 4
- 150000002617 leukotrienes Chemical class 0.000 claims description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000010773 plant oil Substances 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 4
- KZJWDPNRJALLNS-VJSFXXLFSA-N sitosterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CC[C@@H](CC)C(C)C)[C@@]1(C)CC2 KZJWDPNRJALLNS-VJSFXXLFSA-N 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- OILXMJHPFNGGTO-NRHJOKMGSA-N Brassicasterol Natural products O[C@@H]1CC=2[C@@](C)([C@@H]3[C@H]([C@H]4[C@](C)([C@H]([C@@H](/C=C/[C@H](C(C)C)C)C)CC4)CC3)CC=2)CC1 OILXMJHPFNGGTO-NRHJOKMGSA-N 0.000 claims description 3
- SGNBVLSWZMBQTH-FGAXOLDCSA-N Campesterol Natural products O[C@@H]1CC=2[C@@](C)([C@@H]3[C@H]([C@H]4[C@@](C)([C@H]([C@H](CC[C@H](C(C)C)C)C)CC4)CC3)CC=2)CC1 SGNBVLSWZMBQTH-FGAXOLDCSA-N 0.000 claims description 3
- BTEISVKTSQLKST-UHFFFAOYSA-N Haliclonasterol Natural products CC(C=CC(C)C(C)(C)C)C1CCC2C3=CC=C4CC(O)CCC4(C)C3CCC12C BTEISVKTSQLKST-UHFFFAOYSA-N 0.000 claims description 3
- OILXMJHPFNGGTO-ZRUUVFCLSA-N UNPD197407 Natural products C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)C=C[C@H](C)C(C)C)[C@@]1(C)CC2 OILXMJHPFNGGTO-ZRUUVFCLSA-N 0.000 claims description 3
- 235000004420 brassicasterol Nutrition 0.000 claims description 3
- OILXMJHPFNGGTO-ZAUYPBDWSA-N brassicasterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)/C=C/[C@H](C)C(C)C)[C@@]1(C)CC2 OILXMJHPFNGGTO-ZAUYPBDWSA-N 0.000 claims description 3
- 235000000431 campesterol Nutrition 0.000 claims description 3
- SGNBVLSWZMBQTH-PODYLUTMSA-N campesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CC[C@@H](C)C(C)C)[C@@]1(C)CC2 SGNBVLSWZMBQTH-PODYLUTMSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000003784 tall oil Substances 0.000 claims description 3
- 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
- ARYTXMNEANMLMU-UHFFFAOYSA-N 24alpha-methylcholestanol Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(C)CCC(C)C(C)C)C1(C)CC2 ARYTXMNEANMLMU-UHFFFAOYSA-N 0.000 claims description 2
- 235000010469 Glycine max Nutrition 0.000 claims description 2
- 244000068988 Glycine max Species 0.000 claims description 2
- 235000019482 Palm oil Nutrition 0.000 claims description 2
- 235000019486 Sunflower oil Nutrition 0.000 claims description 2
- JAZBEHYOTPTENJ-JLNKQSITSA-N all-cis-5,8,11,14,17-icosapentaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O JAZBEHYOTPTENJ-JLNKQSITSA-N 0.000 claims description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 2
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 2
- ARYTXMNEANMLMU-ATEDBJNTSA-N campestanol Chemical compound C([C@@H]1CC2)[C@@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@H](C)CC[C@@H](C)C(C)C)[C@@]2(C)CC1 ARYTXMNEANMLMU-ATEDBJNTSA-N 0.000 claims description 2
- 235000012343 cottonseed oil Nutrition 0.000 claims description 2
- 239000002385 cottonseed oil Substances 0.000 claims description 2
- 235000020669 docosahexaenoic acid Nutrition 0.000 claims description 2
- 229940090949 docosahexaenoic acid Drugs 0.000 claims description 2
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 claims description 2
- 235000020673 eicosapentaenoic acid Nutrition 0.000 claims description 2
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- JAZBEHYOTPTENJ-UHFFFAOYSA-N eicosapentaenoic acid Natural products CCC=CCC=CCC=CCC=CCC=CCCCC(O)=O JAZBEHYOTPTENJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019197 fats Nutrition 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
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- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims description 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000002600 sunflower oil Substances 0.000 claims description 2
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
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- 238000004519 manufacturing process Methods 0.000 abstract description 10
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- 239000000047 product Substances 0.000 description 24
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 20
- -1 sterol ester Chemical class 0.000 description 18
- 238000012360 testing method Methods 0.000 description 17
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
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- 150000002978 peroxides Chemical class 0.000 description 6
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- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MJVXAPPOFPTTCA-UHFFFAOYSA-N beta-Sistosterol Natural products CCC(CCC(C)C1CCC2C3CC=C4C(C)C(O)CCC4(C)C3CCC12C)C(C)C MJVXAPPOFPTTCA-UHFFFAOYSA-N 0.000 description 2
- NJKOMDUNNDKEAI-UHFFFAOYSA-N beta-sitosterol Natural products CCC(CCC(C)C1CCC2(C)C3CC=C4CC(O)CCC4C3CCC12C)C(C)C NJKOMDUNNDKEAI-UHFFFAOYSA-N 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229940074393 chlorogenic acid Drugs 0.000 description 2
- 235000001368 chlorogenic acid Nutrition 0.000 description 2
- CWVRJTMFETXNAD-JUHZACGLSA-N chlorogenic acid Chemical compound O[C@@H]1[C@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-JUHZACGLSA-N 0.000 description 2
- FFQSDFBBSXGVKF-KHSQJDLVSA-N chlorogenic acid Natural products O[C@@H]1C[C@](O)(C[C@@H](CC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O FFQSDFBBSXGVKF-KHSQJDLVSA-N 0.000 description 2
- 235000013985 cinnamic acid Nutrition 0.000 description 2
- 229930016911 cinnamic acid Natural products 0.000 description 2
- BMRSEYFENKXDIS-KLZCAUPSSA-N cis-3-O-p-coumaroylquinic acid Natural products O[C@H]1C[C@@](O)(C[C@@H](OC(=O)C=Cc2ccc(O)cc2)[C@@H]1O)C(=O)O BMRSEYFENKXDIS-KLZCAUPSSA-N 0.000 description 2
- 235000005911 diet Nutrition 0.000 description 2
- 230000000378 dietary effect Effects 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229940074391 gallic acid Drugs 0.000 description 2
- 235000004515 gallic acid Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 235000019421 lipase Nutrition 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 235000012054 meals Nutrition 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000003716 rejuvenation Effects 0.000 description 2
- 235000015500 sitosterol Nutrition 0.000 description 2
- 229950005143 sitosterol Drugs 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- 206010003211 Arteriosclerosis coronary artery Diseases 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 208000031226 Hyperlipidaemia Diseases 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 206010068052 Mosaicism Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003130 cardiopathic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 210000001268 chyle Anatomy 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 208000029078 coronary artery disease Diseases 0.000 description 1
- 208000026758 coronary atherosclerosis Diseases 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 206010013663 drug dependence Diseases 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 235000013376 functional food Nutrition 0.000 description 1
- VZCCETWTMQHEPK-UHFFFAOYSA-N gamma-Linolensaeure Natural products CCCCCC=CCC=CCC=CCCCCC(O)=O VZCCETWTMQHEPK-UHFFFAOYSA-N 0.000 description 1
- VZCCETWTMQHEPK-QNEBEIHSSA-N gamma-linolenic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/CCCCC(O)=O VZCCETWTMQHEPK-QNEBEIHSSA-N 0.000 description 1
- 235000020664 gamma-linolenic acid Nutrition 0.000 description 1
- 229960002733 gamolenic acid Drugs 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 210000002751 lymph Anatomy 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 210000003765 sex chromosome Anatomy 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 208000011117 substance-related disease Diseases 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000032895 transmembrane transport Effects 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Steroid Compounds (AREA)
Abstract
The invention discloses a kind of method that film simultaneous reaction and separation prepares phytosterin ester, the mixture of phytosterol and aliphatic acid (can add catalyst) is pumped into luwa evaporator, is uniformly applied on the cylinder inboard wall using heat-conducting oil heating by the built-in scraper plate of evaporator and carries out esterification；The moisture of the timely elimination reaction generation of high vacuum is taken in reaction while progress, so that esterification carries out completely；Feed liquid after being esterified distills (add catalyst first passes through filter filtering) through secondary molecules, obtains the phytosterin ester of purity more than 97%.Production process of the present invention is simple, product yield is high, the industrialization continuous production of esterification and purifying can be achieved, whole production process is solvent-free, is discharged in addition to finished product without poisonous and harmful waste material, and reaction process carries out under vacuum conditions, oleic acid and sterol oxidation are avoided, and reaction mass is short into film-form, heated time, reduce the formation of trans-fatty acid, product colour and quality are ensured.
Description
Technical field
The invention belongs to the preparing technical field of phytosterin ester, and in particular to prepared by a kind of film simultaneous reaction and separation
The method of phytosterin ester.
Background technology
Phytosterol (sterol) is also known as sterol, and one kind of steroids, is distributed widely in living nature.Because its in structure with
Cholesterol is similar, its norcholesterol effect mainly enters chyle by the transmembrane transport body and suppression cholesterol that compete cholesterol
Further secretion is to lymph for particulate, so as to reduce absorption of the human body to cholesterol.
Since nineteen fifty-three reports that phytosterol has effects that to reduce body's cholesterol first, courage has dropped on phytosterol
The research of sterol effect is increasingly subject to the attention of people.Moreau etc. summarizes the correlative study of phytosterol, it was demonstrated that plant steroid
The reduction degree of alcohol, stanols, sterol ester to the LDL of normal population, hyperlipidemia adult patients or children is up to 10%~14%
As many as, and HDL concentration and the concentration of triglycerides are barely affected.Phytosterol (ester) is because its unique physiological activity is by section
Scholars are described as " key of life ".
Recently as the improvement of people's living standards and the change of dietary structure, the incidence of cardiovascular and cerebrovascular disease is more next
It is higher, and have rejuvenation trend.Application of the phytosterol in food, health products and cosmetics is more and more.Because of plant steroid
Alcohol can not synthesize in vivo, can only be absorbed from meals or medicine, and phytosterol exist in crystalline form and its in water and
Low-solubility in grease, further limit the practical ranges and application effect of phytosterol.
With the improvement of people ' s living standards with the change of dietary structure, the incidence of cardiovascular and cerebrovascular disease is higher and higher,
And there is rejuvenation trend.The experimental results show that cholesterol concentration is excessive in blood, especially low-density lipoprotein courage
Sterol excessive concentration, is the principal element for triggering a variety of cardiovascular and cerebrovascular diseases.Therefore, reducing Blood Cholesterol concentration can be bright
The aobvious incidence for reducing cardiovascular and cerebrovascular disease.Since the treatment of direct drug injection thing may produce, certain drug dependence etc. is secondary to be made
With people are increasingly wished by reducing the cholesterol amount absorbed from ordinary meal, to reduce the cholesterol level in serum.
Result of study shows that phytosterin fatty acid ester has the more preferable fat-soluble and more efficient norcholesterol of specific ionization phytosterol
Effect, which is a kind of preferably reduction cholesterol, prevents and treats the cardiopathic functional food of coronary atherosclerosis class matches somebody with somebody
Material.The food of in September, 2000, U.S.'s food and Drug Administration (FDA) approval addition phytosterol and phytosterin ester can be with
Use the label of " good for health ".Phytosterin ester was also included in wherein by China in 2010 in No. 3 new resource food bulletin.
Phytosterin ester is mainly obtained by natural phytosterin by modification, and researcher has done a large amount of trials.Example
Such as, CN 101235067B disclose the method by aliphatic acid and phytosterol direct esterification synthesizing phytosterol ester, wherein described
Catalyst for calcium oxide, magnesia, lanthana etc., easily with aliphatic acid saponification occurs for the wherein aobvious alkalescence such as calcium oxide, magnesia
React and form soap, influence reaction and carry out and isolate and purify.CN 101985460B disclose direct with phytosterol by aliphatic acid
The method of lactate synthesis phytosterin ester, but this method does not disclose feasible isolation and purification method.CN 102190700A
Disclose the method by aliphatic acid and phytosterol direct esterification synthesizing phytosterol ester, wherein described catalyst molecule sieve and
Silica gel is suitable for laboratory experiment, and there are many limitations when industrial scale produces；Secondly, the molecule that isolates and purifies steams
Recycling free fatty is evaporated, the heavy phase of collection is product, cannot remove number molecular weight in this way and be more than phytosterol
The oil-soluble impurities of ester, can influence the color and luster and purity of product.CN 103467556B are disclosed in solvent-free system with ion
The method of liquid and trifluoromethanesulfonic acid Asia cerium composite catalyst catalysis cinnamic acid and phytosterol synthesizing cinnamic acid phytosterin ester,
Contain ionic liquid in catalyst described in it, which does not refer to the specific minimizing technology of ionic liquid, and ion
If liquid removes the separating effect that not exclusively, may influence column chromatography；Secondly, it is isolated and purified using silicagel column column chromatography
Method, belongs to laboratory method, and it is complicated that column etc. is filled between every batch of, it is impossible to realizes the requirement of industrial continuous production.
CN 102603846A and CN 103467556B are with ionic liquid-catalyzed synthetic fatty acid phytosterin ester, and with silica gel column layer
Analysis method isolates and purifies, but this method low separation efficiency, disposal ability are limited.CN 103509076A are disclosed with silica
For the method for catalyst synthetic fatty acid phytosterin ester, this method is to vacuumize bar in high temperature in closed container in purifying
Low-boiling point material is removed under part, under these conditions because disengagement area is small, and heating time is grown, in fact it could happen that uneven heating
The problems such as even, partial carbonization；In addition, this method additionally uses molecular distillation purification process, the heavy phase finally obtained is sterol ester
Product, the phytosterin ester that this method obtains can not remove oil-soluble impurities of the number molecular weight more than phytosterin ester and add
The a small amount of carbonization material produced in thermal process, therefore the color and luster of product and purity are poor.CN 106632568A disclose it is a kind of with
Phytosterol and aliphatic acid are raw material, are dissolved in any one in methylene chloride, petroleum ether, hexane, pentane, are being catalyzed
Esterification generation phytosterin ester is carried out under agent toluenesulfonic acid or sulphuric acid catalysis in 30~65 DEG C, then with calcium oxide or carbon
In sour calcium and strong acid catalyst, filtering, precipitation, obtain phytosterin ester product.Solvent is used in this method esterification process, and it is molten
Agent low boiling point is volatile, inflammable and explosive, and security risk is bigger in actual production, high to facility requirements such as workshop ventilations；And
The separation purifying technique used is filtering, vacuum desolvation, and the fat-soluble dark accessory substance of generation is brought and reacted to its raw material, equipment into
It can not effectively remove, influence finished product color.CN106117297A discloses a kind of using phytosterol and fatty acid methyl ester as original
Material, under catalyst sodium methoxide effect, reaction generation phytosterin ester, is then washed to neutrality, most afterwards through three-level molecular distillation
Obtain phytosterin ester.Washed after the completion of this method esterification, water-washing process easily emulsifies, and is not readily separated, and should not be seen in reaction kettle
Delamination is examined, maloperation easily occurs.CN 105524968A disclose a kind of lipase-catalyzed synthesis chlorogenic acid phytosterin ester
Method, this method rate of charge is sterol：Chlorogenic acid：Solvent=1:2~6:20~25, reaction efficiency is low, and separation uses column
Chromatography scheme, it is complicated, isolate and purify of high cost, be not suitable for industrialized production.CN 104402958B disclose it is a kind of with
Phytosterol and aliphatic acid are raw material, and isothermal reaction, separation product mixture are carried out in the presence of heat-resistant polymer catalytic membrane
With catalytic membrane, product mixtures are washed with alcohol, lower floor's oil reservoir is rotated after centrifugation, obtains phytosterin ester.This method
Repeatedly washed using alcohol in purge process, process losses are big, and the low polar impurity of oil-soluble can not remove, and influence product quality.
It is raw material that CN 104672291B, which disclose a kind of triacetyl gallic acid and phytosterol, using dimethylformamide as solvent, with
Solid super-strong acid SO4 2-/TiO2, the immobilized phosphorus heteropoly tungstic acid of tin oxide or concentrated sulfuric acid modified alta-mud be catalyst, in 25kHz frequencies
Reacted at room temperature in the bath type supersonic generator of rate, through the isolated triacetyl acetyl gallic acid of silicagel column after reaction completion
Phytosterin ester, then plus 65 DEG C of reflux of natrium carbonicum calcinatum are deacetylated, then precipitation is rotated after chloroform extraction, do not eaten
Sub- acid phytosterin ester.This method is through three-step reaction, and a step column chromatography, step extraction, process is complicated, is related to multi-solvents, nothing
Method industrialized production.CN 107227333A disclose one kind using phytosterol, vegetable oil residue as raw material, using methanol as solvent,
Under lipase-catalyzed, when 80~120 DEG C of reactions 5~12 are small, it are then centrifuged for fractionation of fatty enzyme and obtain phytosterin ester.This method
Middle catalyst selection lipase, lipase easy in inactivation under unfavorable pH and temperature conditionss, and without reference to plant in this method
The purge process of thing sterol ester.
Technological deficiency existing for above-mentioned existing phytosterin ester synthetic method mainly has：(1) majority is laboratory level, nothing
Method realizes industrialization continuous production；(2) chemical solvent is used in building-up process, there is certain edible safety sex chromosome mosaicism；(3) react
Time is grown, and purge process is complicated, and yield is low.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of using film simultaneous reaction and separation preparation plant steroid
The method of alcohol ester, to overcome, reaction efficiency existing in the prior art is low, edible safety is poor, can not consecutive production and industrialization
The problem of production cost is high.
In order to overcome problem existing in the prior art, the technical solution adopted in the present invention is：Under nitrogen protection, will plant
Thing sterol is dissolved by heating in aliphatic acid, then by gained mixture with 30~60kg/m2The flow velocity of h is pumped into temperature from feed inlet
Spend in the luwa evaporator for being 15~30Pa for 90~120 DEG C, absolute pressure, mixture is distributed to evaporator inner wall through distributing device
On, and film is spread on evaporator inner wall with the rotating speed of 20~35Hz by rotating scraped film device, control mixture is in evaporator
Film forming thickness on inner wall is 1~2cm, and the mixture of film forming absorbs heat and carries out esterification；The light phase of esterification generation is steamed
Hair forms steam stream rising, enters the external condenser that is connected directly with evaporator through gas-liquid separator, and heavy phase is from evaporator
Bottom is discharged, and sequentially enters first order molecular distiller and secondary molecules distiller is purified, obtain phytosterin ester.
In the above method, preferably by gained mixture with 40~45kg/m2The flow velocity of h is pumped into temperature from feed inlet
100~110 DEG C, absolute pressure be 20~25Pa luwa evaporators in, mixture is distributed on evaporator inner wall through distributing device, and
Film is spread on evaporator inner wall with the rotating speed of 25~30Hz by rotating scraped film device.
In the above method, the solution temperature that heating plant sterols are dissolved in aliphatic acid is 95~110 DEG C, wherein phytosterol
Mass ratio with aliphatic acid is 1: 0.75~1.1.
Above-mentioned phytosterol be using soybean oil, corn oil, rapeseed oil, sunflower oil, any one in cottonseed oil or
Two or more plant oil distillates or Tall oil are raw material, the mixed phytosterin obtained by saponification, extraction, crystallization；Or
Phytosterol described in person is in brassicasterol, campesterol, stigmasterol, cupreol, campestanol or sitostamol
Any one is two or more.
Above-mentioned aliphatic acid is saturated fatty acid or unrighted acid, saturated fatty acid be selected from stearic acid, octanoic acid, oneself
Any one in acid, laurate, palmitic acid is two or more；Unrighted acid be selected from oleic acid, linoleic acid, conjugated linoleic acid,
Any one in alpha-linolenic acid, gamma-Linolenic acid, eicosapentaenoic acid, docosahexaenoic acid is two or more；It is or described
Aliphatic acid is selected from sunflower seed oil fatty acids, rapeseed oil fatty acid, soya fatty acid, corn oil fatty acid, linseed oil fat
Any one in acid, palm oil fatty acid is two or more.
In the above method, preferably the vapo(u)rizing temperature of first order molecular distiller is 160~190 DEG C, 5~10Pa of absolute pressure；
It is preferred that the vapo(u)rizing temperature of secondary molecules distiller is 195~220 DEG C, 1~3Pa of absolute pressure.
In the above method, catalysis is added further preferably in the mixture after heating plant sterols are dissolved in aliphatic acid
Agent, the catalyst are any one in niter cake, sodium sulphate, potassium acid sulfate, disodium-hydrogen, potassium phosphate,monobasic,
The mass ratio of the phytosterol and catalyst is 1: 0.003~0.03.
In the above method, when adding catalyst, heavy phase is entering first order molecular distiller and the progress of secondary molecules distiller
Before purification, filter Filtration of catalyst is first passed through.
The present invention uses luwa evaporator, and the mixture of phytosterol and aliphatic acid (can also add catalyst) is passed through steaming
The built-in scraper plate of hair device is uniformly applied on the cylinder inboard wall of heating, is heated using conduction oil, to meet esterification need
The activation energy wanted；High vacuum, the moisture of timely elimination reaction generation so that esterification carries out are taken while reacting and carrying out
Completely.Feed liquid after being esterified is distilled (add catalyst first passes through filter filtering) through secondary molecules, you can obtains purity
More than 97% phytosterin ester.Compared with prior art, the present invention has the advantages that：
1st, the present invention is reacted with being separated, it can be achieved that being esterified continuous with purifying, realization industry using thin film evaporator
Change continuous production.
2nd, the whole production process of the present invention is solvent-free, and reaction process carries out under vacuum conditions, so it also avoid
Oleic acid and sterol oxidation, and reaction mass, into film-form, heated time is short, reduces the formation of trans-fatty acid, product face
Color and quality are ensured.
3rd, present invention esterification uses single step reaction, and purifying is distilled using secondary molecules, and production process is simple, phytosterin ester
High income, in production process in addition to finished product, no poisonous and harmful waste material discharge is free from environmental pollution.
Embodiment
With reference to embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited only to these realities
Apply example.
Embodiment 1
500kg phytosterols (are raw material using the plant oil distillate of soybean oil, are obtained by saponification, extraction, crystallization
Phytosterol, content of phytosterol 95.56%) and 450kg sunflower seed oil fatty acids (palmitic acid 7%, stearic acid 3%, oleic acid
28%, linoleic acid 60%, leukotrienes 0.1%) add in mixing kettle, 105 DEG C are heated under nitrogen protection, stirring condition, is made
Phytosterol all dissolves.By dissolved mixture with 40kg/m2The flow velocity of h is pumped into luwa evaporator from feed inlet,
The temperature of luwa evaporator is 100 DEG C, absolute pressure 20Pa.Mixture is distributed on evaporator inner wall through distributing device, and is passed through
Rotating scraped film device spreads to film with the rotating speed of 30Hz on evaporator inner wall, control mixture on evaporator inner wall into thickness
Spend and absorb heat for 2cm, the mixture of film forming and carry out esterification；The moisture of esterification generation is formed by evaporation to steam stream rising,
Entering the external condenser being connected directly with evaporator through gas-liquid separator, heavy phase is discharged from the bottom of evaporator, after testing, ester
Rate is 95.62%.
From the bottom of evaporator, discharge heavy phase enters first order molecular distiller, temperature be 175 DEG C, absolute pressure 5Pa
Lower progress first order molecular distillation, obtains the unreacted sunflower seed oil fatty acids of 126.2kg and phytosterin fatty acid ester crude product.Plant
Thing sterol aliphatic ester crude product enters first order molecular distiller, and two fractions are carried out in the case where temperature is 210 DEG C, absolute pressure is 3Pa
Son distillation, obtains 769.6kg phytosterin esters product and 17.1kg plant asphalts.
Test to obtained phytosterin ester product, the content of phytosterol that dissociates is 0.23%, and total phytosterol contains
59.59% (w/w), phytosterol ester content 97.34% are measured, phytosterin ester and phytosterol add up to 97.57%, acid number
0.51mgKOH/g, peroxide value 0meq/kg, molten condition clear, color and luster (lovibond test groove, 133.4mm)：It is yellow：
10, it is red：1.0.
Embodiment 2
500kg phytosterols (are raw material using the plant oil distillate of soybean oil, are obtained by saponification, extraction, crystallization
Phytosterol, content of phytosterol 95.56%) and 450kg sunflower seed oil fatty acids (palmitic acid 7%, stearic acid 3%, oleic acid
28%, linoleic acid 60%, leukotrienes 0.1%) add in mixing kettle, 105 DEG C are heated under nitrogen protection, stirring condition, is treated
Phytosterol adds food-grade niter cake 2.8kg after all dissolving, and stirs evenly.By gained mixture with 50kg/m2H's
Flow velocity is pumped into luwa evaporator from feed inlet, and the temperature of luwa evaporator is 100 DEG C, absolute pressure 20Pa.Mixture is through cloth
Glassware is distributed on evaporator inner wall, and film is spread on evaporator inner wall with the rotating speed of 30Hz by rotating scraped film device, control
Film forming thickness of the mixture processed on evaporator inner wall is 2cm, and the mixture of film forming absorbs heat and carries out esterification；Esterification life
Into moisture be formed by evaporation to steam stream and rise, enter the external condenser that is connected directly with evaporator, weight through gas-liquid separator
Mutually discharged from the bottom of evaporator, after testing, esterification yield 96.70%.
From the bottom of evaporator, discharge heavy phase enters first order molecular distiller, temperature be 175 DEG C, absolute pressure 5Pa
Lower progress first order molecular distillation, obtains the unreacted sunflower seed oil fatty acids of 124.3kg and phytosterin fatty acid ester crude product.Plant
Thing sterol aliphatic ester crude product enters first order molecular distiller, and two fractions are carried out in the case where temperature is 210 DEG C, absolute pressure is 3Pa
Son distillation, obtains 770.6kg phytosterin esters product and 16.4kg plant asphalts.
Test to obtained phytosterin ester product, the content of phytosterol that dissociates is 0.30%, and total phytosterol contains
59.54% (w/w), phytosterol ester content 97.22% are measured, phytosterin ester and phytosterol add up to 97.52%, acid number
0.45mgKOH/g, peroxide value 0meq/kg, molten condition clear, color and luster (lovibond test groove, 133.4mm)：It is yellow：
10, it is red：0.9.
Embodiment 3
(it is raw material using Tall oil, the phytosterol obtained by saponification, extraction, crystallization, plants by 500kg phytosterols
98.65%) and 450kg rapeseed oil fatty acids (stearic acid 2.37%, oleic acid 32.73%, linoleic acid thing sterol content is
25.27%, leukotrienes 15.82%) add in mixing kettle, 105 DEG C are heated under nitrogen protection, stirring condition, makes plant steroid
Alcohol all dissolves.By dissolved mixture with 50kg/m2The flow velocity of h is pumped into luwa evaporator from feed inlet, and knifing steams
The temperature for sending out device is 105 DEG C, absolute pressure 25Pa.Mixture is distributed on evaporator inner wall through distributing device, and is scraped by rotation
Diaphragm spreads to film with the rotating speed of 30Hz on evaporator inner wall, controls film forming thickness of the mixture on evaporator inner wall to be
1cm, the mixture of film forming absorb heat and carry out esterification；The moisture of esterification generation is formed by evaporation to steam stream rising, through gas
Liquid/gas separator enters the external condenser being connected directly with evaporator, and heavy phase is discharged from the bottom of evaporator, after testing, esterification yield
For 96.01%.
From the bottom of evaporator, discharge heavy phase enters first order molecular distiller, temperature be 185 DEG C, absolute pressure 5Pa
Lower progress first order molecular distillation, obtains the unreacted rapeseed oil fatty acids of 119.2kg and phytosterin fatty acid ester crude product.Plant
Sterol aliphatic ester crude product enters first order molecular distiller, and secondary molecules are carried out in the case where temperature is 215 DEG C, absolute pressure is 3Pa
Distillation, obtains 768.6kg phytosterin esters product and 23.1kg plant asphalts.
Test to obtained phytosterin ester product, the content of phytosterol that dissociates is 0.29%, and total phytosterol contains
60.52% (w/w), phytosterol ester content 98.19% are measured, phytosterin ester and phytosterol add up to 98.48%, acid number
0.50mgKOH/g, peroxide value 0meq/kg, molten condition clear, color and luster (lovibond test groove, 133.4mm)：It is yellow：9,
It is red：1.0.
Embodiment 4
By 500kg phytosterols (brassicasterol 0.83%, campesterol 24.80%, stigmasterol 26.23%, sitosterol
43.51%) and 450kg fatty acid mixeds (oleic acid 75.60%, linoleic acid 13.50%) add mixing kettle in, nitrogen protect,
110 DEG C are heated under stirring condition, phytosterol is all dissolved.By dissolved mixture with 45kg/m2The flow velocity of h from
Feed inlet is pumped into luwa evaporator, and the temperature of luwa evaporator is 100 DEG C, absolute pressure 25Pa.Mixture is through distributing device point
Cloth spreads to film, control mixing on evaporator inner wall with the rotating speed of 25Hz by rotating scraped film device on evaporator inner wall
It is 2cm to expect the film forming thickness on evaporator inner wall, and the mixture of film forming absorbs heat and carries out esterification；It is esterified the water of generation
Steam stream rising point is formed by evaporation to, enters the external condenser being connected directly with evaporator through gas-liquid separator, heavy phase is from steaming
Send out the bottom discharge of device, after testing, esterification yield 96.89%.
From the bottom of evaporator, discharge heavy phase enters first order molecular distiller, temperature be 180 DEG C, absolute pressure 7Pa
Lower progress first order molecular distillation, obtains the unreacted sunflower seed oil fatty acids of 120.7kg and phytosterin fatty acid ester crude product.Plant
Thing sterol aliphatic ester crude product enters first order molecular distiller, and two fractions are carried out in the case where temperature is 205 DEG C, absolute pressure is 2Pa
Son distillation, obtains 761.4kg phytosterin esters product and 29.4kg plant asphalts.
Test to obtained phytosterin ester product, the content of phytosterol that dissociates is 0.69%, and total phytosterol contains
59.47% (w/w), phytosterol ester content 96.37% are measured, phytosterin ester and phytosterol add up to 97.06%, acid number
0.60mgKOH/g, peroxide value 0meq/kg, molten condition clear, color and luster (lovibond test groove, 133.4mm)：It is yellow：9,
It is red：0.8.
Embodiment 5
By 500kg stigmasterol (stigmasterol 95.61%) and 450kg fatty acid mixeds (palmitic acid 3.06%, stearic acid
2.89%, oleic acid 84.95%, linoleic acid 7.12%, palmitic acid 3.06%) add in mixing kettle, in nitrogen protection, stirring condition
Under be heated to 100 DEG C, make phytosterol all dissolve.By dissolved mixture with 60kg/m2The flow velocity of h is pumped from feed inlet
Enter in luwa evaporator, the temperature of luwa evaporator is 120 DEG C, absolute pressure 25Pa.Mixture is distributed to evaporation through distributing device
On device inner wall, and film is spread on evaporator inner wall with the rotating speed of 20Hz by rotating scraped film device, control mixture is evaporating
Film forming thickness on device inner wall is 2cm, and the mixture of film forming absorbs heat and carries out esterification；The moisture of esterification generation is evaporated
Form steam stream to rise, enter the external condenser that is connected directly with evaporator through gas-liquid separator, heavy phase is from the bottom of evaporator
Portion discharges, after testing, esterification yield 96.71%.
From the bottom of evaporator, discharge heavy phase enters first order molecular distiller, temperature be 190 DEG C, absolute pressure 10Pa
Lower progress first order molecular distillation, obtains the unreacted sunflower seed oil fatty acids of 118.5kg and phytosterin fatty acid ester crude product.Plant
Thing sterol aliphatic ester crude product enters first order molecular distiller, and two fractions are carried out in the case where temperature is 220 DEG C, absolute pressure is 3Pa
Son distillation, obtains 753.8kg phytosterin esters product and 39.2kg plant asphalts.
Test to obtained phytosterin ester product, the content of phytosterol that dissociates is 0.49%, and total phytosterol contains
59.73% (w/w), phytosterol ester content 96.91% are measured, phytosterin ester and phytosterol add up to 97.40%, acid number
0.44mgKOH/g, peroxide value 0meq/kg, molten condition clear, color and luster (lovibond test groove, 133.4mm)：It is yellow：
10, it is red：0.8.
Embodiment 6
By 500kg phytosterols (sitosterol 95.01%) and 450kg conjugated linoleic acid (conjugated linoleic acid 79.50%, palm fibre
Palmitic acid acid 7.37%, stearic acid 1.15%, oleic acid 10.31%) add in mixing kettle, it is heated under nitrogen protection, stirring condition
95 DEG C, phytosterol is set all to dissolve.By dissolved mixture with 55kg/m2The flow velocity of h is pumped into knifing from feed inlet and steams
Send out in device, the temperature of luwa evaporator is 110 DEG C, absolute pressure 30Pa.Mixture is distributed on evaporator inner wall through distributing device,
And film is spread on evaporator inner wall with the rotating speed of 25Hz by rotating scraped film device, control mixture is on evaporator inner wall
Film forming thickness is 1cm, and the mixture of film forming absorbs heat and carries out esterification；The moisture of esterification generation is formed by evaporation to steam stream
Rise, enter the external condenser being connected directly with evaporator through gas-liquid separator, heavy phase is discharged from the bottom of evaporator, through inspection
Survey, esterification yield 97.11%.
From the bottom of evaporator, discharge heavy phase enters first order molecular distiller, temperature be 170 DEG C, absolute pressure 6Pa
Lower progress first order molecular distillation, obtains the unreacted sunflower seed oil fatty acids of 115.9kg and phytosterin fatty acid ester crude product.Plant
Thing sterol aliphatic ester crude product enters first order molecular distiller, and two fractions are carried out in the case where temperature is 195 DEG C, absolute pressure is 2Pa
Son distillation, obtains 755.1kg phytosterin esters product and 41.5kg plant asphalts.
Test to obtained phytosterin ester product, the content of phytosterol that dissociates is 0.34%, and total phytosterol contains
59.81% (w/w), phytosterol ester content 97.11% are measured, phytosterin ester and phytosterol add up to 97.44%, acid number
0.59mgKOH/g, peroxide value 0meq/kg, molten condition clear, color and luster (lovibond test groove, 133.4mm)：It is yellow：8,
It is red：1.0.
Claims (10)
1. a kind of method that film simultaneous reaction and separation prepares phytosterin ester, it is characterised in that：Under nitrogen protection, will plant
Thing sterol is dissolved by heating in aliphatic acid, then by gained mixture with 30~60kg/m2The flow velocity of h is pumped into temperature from feed inlet
Spend in the luwa evaporator for being 15~30Pa for 90~120 DEG C, absolute pressure, mixture is distributed to evaporator inner wall through distributing device
On, and film is spread on evaporator inner wall with the rotating speed of 20~35Hz by rotating scraped film device, control mixture is in evaporator
Film forming thickness on inner wall is 1~2cm, and the mixture of film forming absorbs heat and carries out esterification；The light phase of esterification generation is steamed
Hair forms steam stream rising, enters the external condenser that is connected directly with evaporator through gas-liquid separator, and heavy phase is from evaporator
Bottom is discharged, and sequentially enters first order molecular distiller and secondary molecules distiller is purified, obtain phytosterin ester.
2. the method that film simultaneous reaction and separation according to claim 1 prepares phytosterin ester, it is characterised in that：Will
Gained mixture is with 40~45kg/m2The flow velocity of h from feed inlet be pumped into temperature be 100~110 DEG C, absolute pressure be 20~
In 25Pa luwa evaporators, mixture is distributed on evaporator inner wall through distributing device, and by rotating scraped film device with 25~30Hz
Rotating speed film is spread on evaporator inner wall.
3. the method that film simultaneous reaction and separation according to claim 1 prepares phytosterin ester, it is characterised in that：Institute
The solution temperature that the heating plant sterols stated are dissolved in aliphatic acid is 95~110 DEG C, the wherein quality of phytosterol and aliphatic acid
Than for 1: 0.75~1.1.
4. the method that film simultaneous reaction and separation according to claim 1 prepares phytosterin ester, it is characterised in that：Institute
The phytosterol stated utilizes any one in soybean oil, corn oil, rapeseed oil, sunflower oil, cottonseed oil or two or more
Plant oil distillate or Tall oil are raw material, the mixed phytosterin obtained by saponification, extraction, crystallization；Or the plant
Thing sterol in brassicasterol, campesterol, stigmasterol, cupreol, campestanol or sitostamol any one or
It is two or more.
5. the method that film simultaneous reaction and separation according to claim 1 prepares phytosterin ester, it is characterised in that：Institute
The aliphatic acid stated is saturated fatty acid or unrighted acid, and saturated fatty acid is selected from stearic acid, octanoic acid, caproic acid, laurate, palm fibre
Any one in palmitic acid acid is two or more；Unrighted acid be selected from oleic acid, linoleic acid, conjugated linoleic acid, alpha-linolenic acid, γ-
Any one in leukotrienes, eicosapentaenoic acid, docosahexaenoic acid is two or more；Or the aliphatic acid is selected from certain herbaceous plants with big flowers
Flower seed oil aliphatic acid, rapeseed oil fatty acid, soya fatty acid, corn oil fatty acid, linseed oil aliphatic acid, palm oil fat
Any one in acid is two or more.
6. the method that film simultaneous reaction and separation according to claim 1 prepares phytosterin ester, it is characterised in that：Institute
The vapo(u)rizing temperature for the first order molecular distiller stated is 160~190 DEG C, 5~10Pa of absolute pressure.
7. the method that film simultaneous reaction and separation according to claim 1 prepares phytosterin ester, it is characterised in that：Institute
The vapo(u)rizing temperature for the secondary molecules distiller stated is 195~220 DEG C, 1~3Pa of absolute pressure.
8. the method that the film simultaneous reaction and separation according to claim 1~7 any one prepares phytosterin ester, its
It is characterized in that：Heating plant sterols are dissolved in the mixture after aliphatic acid also added with catalyst, the catalyst is sulphur
Any one in sour hydrogen sodium, sodium sulphate, potassium acid sulfate, disodium-hydrogen, potassium phosphate,monobasic.
9. the method that film simultaneous reaction and separation according to claim 8 prepares phytosterin ester, it is characterised in that：Institute
The phytosterol and the mass ratio of catalyst stated are 1: 0.003~0.03.
10. the method that film simultaneous reaction and separation according to claim 8 prepares phytosterin ester, it is characterised in that：
The heavy phase before purification, first pass through filter and be filtered to remove and urge entering first order molecular distiller and secondary molecules distiller
Agent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112125986A (en) * | 2020-09-21 | 2020-12-25 | 山东京博中聚新材料有限公司 | Styrene-butadiene latex demonomerization and concentration device and process |
| CN115894246A (en) * | 2021-08-20 | 2023-04-04 | 南京理工大学 | A method for continuously, safely and efficiently synthesizing 1,3,5-triethoxy-2,4,6-trinitrobenzene |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5646311A (en) * | 1993-08-06 | 1997-07-08 | Henkel Corporation | Recovery of tocopherols |
| EP1067135A2 (en) * | 1999-05-24 | 2001-01-10 | McNEIL-PPC, INC. | Preparation of sterol and stanol-esters |
| WO2009010641A2 (en) * | 2007-07-18 | 2009-01-22 | Raisio Nutrition Ltd | Transesterification process |
| CN102603845A (en) * | 2012-01-21 | 2012-07-25 | 西安海斯夫生物科技有限公司 | Method for synthesizing and separating phytosterol saturated fatty acid esters and phytosterol unsaturated fatty acid esters |
| CN104262444A (en) * | 2014-09-03 | 2015-01-07 | 陕西海斯夫生物工程有限公司 | Phytosterol aliphatic ester and catalytic synthesis method thereof |
-
2017
- 2017-11-30 CN CN201711243478.7A patent/CN107955054A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5646311A (en) * | 1993-08-06 | 1997-07-08 | Henkel Corporation | Recovery of tocopherols |
| EP1067135A2 (en) * | 1999-05-24 | 2001-01-10 | McNEIL-PPC, INC. | Preparation of sterol and stanol-esters |
| WO2009010641A2 (en) * | 2007-07-18 | 2009-01-22 | Raisio Nutrition Ltd | Transesterification process |
| CN102603845A (en) * | 2012-01-21 | 2012-07-25 | 西安海斯夫生物科技有限公司 | Method for synthesizing and separating phytosterol saturated fatty acid esters and phytosterol unsaturated fatty acid esters |
| CN104262444A (en) * | 2014-09-03 | 2015-01-07 | 陕西海斯夫生物工程有限公司 | Phytosterol aliphatic ester and catalytic synthesis method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112125986A (en) * | 2020-09-21 | 2020-12-25 | 山东京博中聚新材料有限公司 | Styrene-butadiene latex demonomerization and concentration device and process |
| CN112125986B (en) * | 2020-09-21 | 2022-12-02 | 山东京博中聚新材料有限公司 | A kind of styrene-butadiene latex stripping and concentrating device and process |
| CN115894246A (en) * | 2021-08-20 | 2023-04-04 | 南京理工大学 | A method for continuously, safely and efficiently synthesizing 1,3,5-triethoxy-2,4,6-trinitrobenzene |
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