CN116178104A - Method for improving yield of myrcene or dihydromyrcene hydration reaction and synthesized spice - Google Patents
Method for improving yield of myrcene or dihydromyrcene hydration reaction and synthesized spice Download PDFInfo
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- CN116178104A CN116178104A CN202211609707.3A CN202211609707A CN116178104A CN 116178104 A CN116178104 A CN 116178104A CN 202211609707 A CN202211609707 A CN 202211609707A CN 116178104 A CN116178104 A CN 116178104A
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- product
- dihydromyrcene
- acid
- solvent
- reaction
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- FUDNBFMOXDUIIE-UHFFFAOYSA-N 3,7-dimethylocta-1,6-diene Chemical compound C=CC(C)CCC=C(C)C FUDNBFMOXDUIIE-UHFFFAOYSA-N 0.000 title claims abstract description 118
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000006703 hydration reaction Methods 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 55
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 235000013599 spices Nutrition 0.000 title abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 93
- 239000002131 composite material Substances 0.000 claims abstract description 45
- 230000036571 hydration Effects 0.000 claims abstract description 31
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910000348 titanium sulfate Inorganic materials 0.000 claims abstract description 5
- 229940061720 alpha hydroxy acid Drugs 0.000 claims abstract description 3
- 150000001280 alpha hydroxy acids Chemical class 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 195
- 238000006243 chemical reaction Methods 0.000 claims description 152
- 239000002904 solvent Substances 0.000 claims description 107
- 238000005406 washing Methods 0.000 claims description 69
- 238000011084 recovery Methods 0.000 claims description 52
- 238000005194 fractionation Methods 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 229930008394 dihydromyrcenol Natural products 0.000 claims description 47
- XSNQECSCDATQEL-UHFFFAOYSA-N dihydromyrcenol Chemical compound C=CC(C)CCCC(C)(C)O XSNQECSCDATQEL-UHFFFAOYSA-N 0.000 claims description 46
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 claims description 44
- 239000002994 raw material Substances 0.000 claims description 40
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 37
- 239000003495 polar organic solvent Substances 0.000 claims description 36
- 238000001914 filtration Methods 0.000 claims description 35
- 239000012263 liquid product Substances 0.000 claims description 34
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 150000002148 esters Chemical class 0.000 claims description 23
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 claims description 21
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 claims description 21
- 229930007744 linalool Natural products 0.000 claims description 21
- 238000006386 neutralization reaction Methods 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 20
- 238000003786 synthesis reaction Methods 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 17
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 17
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 17
- 238000004821 distillation Methods 0.000 claims description 17
- 230000003472 neutralizing effect Effects 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 14
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004327 boric acid Substances 0.000 claims description 12
- 239000011975 tartaric acid Substances 0.000 claims description 12
- 235000002906 tartaric acid Nutrition 0.000 claims description 12
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 8
- 239000003205 fragrance Substances 0.000 claims description 8
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004310 lactic acid Substances 0.000 claims description 7
- 235000014655 lactic acid Nutrition 0.000 claims description 7
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 claims description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 5
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001630 malic acid Substances 0.000 claims description 5
- 235000011090 malic acid Nutrition 0.000 claims description 5
- 229960002510 mandelic acid Drugs 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 235000015165 citric acid Nutrition 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 229940005605 valeric acid Drugs 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 claims description 2
- 239000002304 perfume Substances 0.000 claims description 2
- 235000019439 ethyl acetate Nutrition 0.000 claims 2
- 150000001637 borneol derivatives Chemical class 0.000 claims 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims 1
- 238000007086 side reaction Methods 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 229960000583 acetic acid Drugs 0.000 description 16
- 239000002798 polar solvent Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 12
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 11
- 238000004817 gas chromatography Methods 0.000 description 10
- HEVGGTGPGPKZHF-UHFFFAOYSA-N 1-(1,2-dimethyl-3-methylidenecyclopentyl)-4-methylbenzene Chemical compound CC1C(=C)CCC1(C)C1=CC=C(C)C=C1 HEVGGTGPGPKZHF-UHFFFAOYSA-N 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 8
- XOKSLPVRUOBDEW-UHFFFAOYSA-N pinane Chemical compound CC1CCC2C(C)(C)C1C2 XOKSLPVRUOBDEW-UHFFFAOYSA-N 0.000 description 8
- UWKAYLJWKGQEPM-LBPRGKRZSA-N linalyl acetate Chemical compound CC(C)=CCC[C@](C)(C=C)OC(C)=O UWKAYLJWKGQEPM-LBPRGKRZSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 4
- 239000003729 cation exchange resin Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229930006728 pinane Natural products 0.000 description 4
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- UWKAYLJWKGQEPM-UHFFFAOYSA-N linalool acetate Natural products CC(C)=CCCC(C)(C=C)OC(C)=O UWKAYLJWKGQEPM-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000000066 reactive distillation Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- LIZVXGBYTGTTTI-UHFFFAOYSA-N 2-[(4-methylphenyl)sulfonylamino]-2-phenylacetic acid Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NC(C(O)=O)C1=CC=CC=C1 LIZVXGBYTGTTTI-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 241000779819 Syncarpia glomulifera Species 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- -1 gamma Luo Muchun Chemical compound 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001739 pinus spp. Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000003930 superacid Substances 0.000 description 2
- 229940095064 tartrate Drugs 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 229940036248 turpentine Drugs 0.000 description 2
- 229940070710 valerate Drugs 0.000 description 2
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- YYWZKGZIIKPPJZ-UHFFFAOYSA-N 4,6,6-trimethylbicyclo[3.1.1]heptan-4-ol Chemical compound C1C2C(C)(C)C1CCC2(O)C YYWZKGZIIKPPJZ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 1
- 239000005792 Geraniol Substances 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 244000178870 Lavandula angustifolia Species 0.000 description 1
- 235000010663 Lavandula angustifolia Nutrition 0.000 description 1
- GLZPCOQZEFWAFX-JXMROGBWSA-N Nerol Natural products CC(C)=CCC\C(C)=C\CO GLZPCOQZEFWAFX-JXMROGBWSA-N 0.000 description 1
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229940113087 geraniol Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000001102 lavandula vera Substances 0.000 description 1
- 235000018219 lavender Nutrition 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- IWYDHOAUDWTVEP-UHFFFAOYSA-M mandelate Chemical compound [O-]C(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-M 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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Abstract
The invention discloses a method for improving the yield of myrcene or dihydromyrcene hydration reaction and a synthesized spice, belonging to the technical field of deep processing of forest products. The invention adopts a composite catalyst composed of one or more of zirconium sulfate, titanium sulfate and alpha-hydroxy acid and cupric salt to catalyze the hydration reaction of myrcene or dihydromyrcene, thereby improving the yield of hydration products and reducing side reaction and energy consumption.
Description
Technical Field
The invention relates to the technical field of deep processing of forest products, in particular to a method for improving the yield of myrcene or dihydromyrcene hydration reaction and a synthesized spice.
Background
Linalool (Linalool) is also known as Linalool, gamma Luo Muchun, linalool, and the like. The school name is 3, 7-dimethyl-1, 6-octadien-3-ol, the molecular formula is C10H180, and the molecular weight is 154.24. The method for synthesizing linalool mainly comprises the following steps: firstly, beta-pinene is pyrolyzed into myrcene at high temperature, and then the myrcene is prepared into linalool through the steps of hydrochloride, esterification, saponification and the like. Other alcohols produced by this method include nerol, geraniol, lauryl alcohol, terpineol, and the like. The method has higher yield. And secondly, hydrogenating alpha-pinene to pinane, oxidizing the pinane to pinane hydroperoxide, reducing the pinane hydroperoxide to pinanol, and finally preparing linalool through pyrolysis. The dihydromyrcenol is prepared by chloridizing dihydromyrcenol and hydrolyzing in alkaline water. Or esterifying dihydromyrcene with acetic acid or formic acid, and saponifying and hydrolyzing under alkaline condition. Is liquid with lemon fragrance and lavender fragrance. The dihydromyrcenol has fresh flower fragrance and white lemon-like fruit fragrance, can be used as a daily chemical essence formula, is particularly suitable for being used as soap essence (the formula content can reach 20%), is a representative of 'overdose' in modern perfume essence for men, and has the yield of about 5000 t.
Chinese patent application CN200810106990.1 discloses the use of niobic acid catalyst for dihydroA method for synthesizing dihydromyrcenol by myrcene. Chinese patent application CN201010249029.5 discloses a process for continuous production of dihydromyrcenol by direct hydration of dihydromyrcenol as raw material by using cation exchange resins including Amberlyst35 cation exchange resin, NKC-9 cation exchange resin, D72 cation exchange resin, zeolite catalyst including HZSM-5, mordenite as catalyst and rectification-reaction coupling process. Chinese patent application CN200910181288.6 discloses a process for synthesizing dihydromyrcenol, which uses acid (including sulfuric acid, phosphoric acid and p-toluenesulfonic acid) as catalyst, and adopts an integrated system composed of a jet reaction device, an oil-water separation device and a rectifying device. Chinese patent application CN201110059193.4 discloses a continuous production method for hydration of fixed bed of dihydromyrcenol, the reaction materials are preheated and then continuously enter a tubular reactor, overflow after full enters an oil-water separator for separation, the lower water phase continuously circulates into a reaction system, and the oil layer enters a rectifying tower for rectification. Chinese patent application CN201210126871.9 discloses a method for continuously producing dihydromyrcenol by using a tubular reactor. Chinese patent application CN201210060876.6 discloses a method for continuously preparing dihydromyrcenol by reactive distillation, in which the reactive distillation column is filled with corrugated silk screen filler and solid acid catalyst, raw materials of dihydromyrcene and hydration solvent are respectively preheated to 80-120 deg.c, 85-95 deg.c and 70-90 deg.c, and the flow ratio is (1-3), and (1-3) is fed from upper, middle and lower portions of reactive section of reactive distillation column respectively. The temperature of the tower kettle is controlled to be 105-120 ℃ and the condensing temperature of the tower top is controlled to be 50-70 ℃. Separating oil phase and water phase from condensate, refluxing part of oil phase to tower top, and recycling water phase and other oil phase to raw material tank. Chinese patent application CN201210501734.9 discloses a method for producing dihydromyrcenol, which comprises respectively introducing dihydromyrcenol (hereinafter abbreviated as DHM) and a low-viscosity organic solvent X for hydration into a forced circulation radiation flow fixed bed reactor for cyclic reaction; the reacted liquid is separated by oil and water, and the product is rectified twice to obtain the product with the purity of 99.61 percent, the primary conversion rate is 10.6 percent and the selectivity is 98.1 percent. Chinese patent application CN201510276832.0 discloses a process for preparing dihydromyrcenol, which comprises mixing 36% acetic acid and water in a reactorMixing uniformly, and then heating to 80-120 ℃; adding a self-made niobic acid catalyst into the reaction kettle, and reacting for 1-3 hours at constant temperature; filtering the product obtained by the reaction, standing for layering, and distilling under reduced pressure to obtain the product. Chinese patent application CN201510183300.2 discloses a method for preparing dihydromyrcenol by using turpentine, wherein alpha-pinene is subjected to a specific hydrogenation mode to obtain pinane with high yield, and then the pinane is subjected to pyrolysis to obtain dihydromyrcene with high yield, so that raw turpentine is utilized to the maximum extent. Chinese patent application CN201811135211.0 discloses a method for synthesizing dihydromyrcenol by hydration method, which adopts dihydromyrcenol to prepare by direct hydration method, and adopts glacial acetic acid as solvent and SO with high specific surface area 4 2 -/La 2 O 3 -ZrO 2 The @ CNTS superacid was used as a catalyst. Chinese patent application CN201811135280.1 is a process for preparing dihydromyrcenol by direct hydration of dihydromyrcenol by using glacial acetic acid as solvent and SO with high specific surface area 4 2 -/ZrO 2 The @ CNTS superacid was used as a catalyst. Chinese patent application CN202211127038.6 discloses a method for preparing dihydromyrcenol, which adopts emulsifying agent and ultrasonic wave, and the dihydromyrcenol is hydrated with water under the catalysis of liquid acid to generate dihydromyrcenol.
The prior myrcene or dihydromyrcene hydration process has the main problems that firstly, the direct hydration reaction is accompanied with the dehydration cyclization side reaction of alcohol, so that the yield of target products is low; secondly, a reaction-rectification coupling process is required, and the energy loss is large.
Disclosure of Invention
The invention provides a method for improving the yield of myrcene or dihydromyrcene hydration reaction, which aims to solve the problems of low yield and high energy consumption of myrcene or dihydromyrcene direct hydration reaction.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
a method for improving the yield of myrcene or dihydromyrcene hydration reaction, comprising the following steps:
(1) And (3) synthesis reaction: adding laurene or dihydromyrcene, water, a polar organic solvent and a composite catalyst into a reaction kettle according to the mass ratio of 100 (15-200) (100-800) (20-150), stirring at the temperature of 50-70 ℃, and reacting for 24-48 h; the composite catalyst consists of one or more of zirconium sulfate, titanium sulfate and alpha-hydroxy acid and cupric salt;
(2) And (3) catalyst recovery: after the reaction is finished, standing, filtering an upper liquid product, transferring the filtered upper liquid product into a solvent recovery tank, adding a polar organic solvent into a reaction kettle, washing a catalyst at the bottom of the reaction kettle, filtering a washing liquid, and transferring the filtered washing liquid into the solvent recovery tank;
(3) And (3) recovering a solvent: recovering the solvent by means of reduced pressure distillation, metering the recovered solvent and adding the solvent into a reaction kettle;
(4) Product neutralization: neutralizing the product obtained in the step (3) with dilute alkali liquor, and then adding water to wash for 2-3 times;
(5) Product fractionation: transferring the product obtained in the step (4) into a fractionating tower, recovering myrcene or dihydromyrcene through reduced pressure fractionation, metering the recovered raw materials, and adding the raw materials into a reaction kettle; the hydration product obtained by separation is linalool or dihydromyrcenol.
Preferably, the cupric salt in the step (1) comprises one or more of copper sulfate, copper nitrate, copper chloride, copper formate and copper acetate.
Preferably, the α -hydroxycarboxylic acid in step (1) includes one or more of tartaric acid, citric acid, malic acid, mandelic acid, lactic acid, and glycolic acid.
Further, the composite catalyst in the step (1) further comprises boric acid.
Preferably, the composite catalyst in the step (1) is tartaric acid, boric acid and cupric salt, and the mass ratio of the composite catalyst to the cupric salt is (5-10): (0.5-2): (0.2-1).
Preferably, the polar organic solvent in the step (1) is one or more of acetic acid, propionic acid, butyric acid, valeric acid, ethyl acetate and tetrahydrofuran.
Preferably, the product fractionation in step (5) comprises the steps of:
s1, firstly discharging air of a rectifying tower to ensure that the vacuum degree in the rectifying tower is less than or equal to-0.10 MPa;
s2, conveying the product after neutralization and water washing to a rectifying tower kettle;
s3, heating to keep the temperature of the tower kettle at 110-120 ℃, keeping the temperature of the tower top at 80-90 ℃, refluxing for 1-2 h, and collecting myrcene or dihydromyrcene at a reflux ratio of 10-13:1;
s4, heating to keep the temperature of the tower kettle at 130-140 ℃, keeping the temperature of the tower top at 90-95 ℃ and the reflux ratio at 15-20:1, and collecting hydration products such as linalool or dihydromyrcenol;
s5, heating to keep the temperature of the tower kettle at 140-150 ℃, keeping the temperature of the tower top at 95-105 ℃ and the reflux ratio at 15-20:1, and collecting ester products such as linalyl or dihydromyrcenyl ester.
The invention also provides a synthetic spice which comprises laurene with GC content of (10% -30%), linalool or dihydromyrcenol (30% -60%), linalyl ester or dihydromyrcenyl ester (1% -5%).
Further, the linalyl ester or the dihydromyrcenyl ester is one or more of acetate, propionate, butyrate and valerate.
Further, the linalyl ester or dihydromyrcenyl ester is alpha-hydroxy carboxylic acid ester; the alpha-hydroxy carboxylic acid comprises one or more of tartaric acid, citric acid, malic acid, mandelic acid, lactic acid and glycolic acid.
Compared with the prior art, the invention has the advantages that:
1. the composite catalyst used in the invention has the advantages of easily available preparation raw materials, good repeatability, low corrosiveness, easy separation from products after the reaction is finished, easy industrialized popularization and application, and the like.
2. Compared with the catalysts such as sulfuric acid, the composite catalyst used in the invention has less side reaction and light color of the product.
3. Compared with the traditional reaction-rectification coupling process, the method provided by the invention has the advantages that raw materials such as dihydromyrcene, hydration solvent and the like are required to be heated to be boiled in the traditional process, so that the heat consumption is high. The reaction temperature of the method is lower than 70 ℃, which is beneficial to energy conservation.
4. Compared with the prior art, the GC content of the cyclized byproducts in the dihydromyrcene hydration product is lower than 1%, which is beneficial to improving the fragrance of the product.
5. The method can obtain the spice containing linalyl ester and dihydromyrcenol ester, and the ester product in the product can provide unique aroma.
6. After the reaction of the method is finished, the laurene or the dihydromyrcene can be separated out for reuse through the recovery of the solvent, so that the cost is greatly reduced.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
Sample analysis test method
Analytical instrument: aglient7890A gas chromatograph, agilent, inc., USA; chromatographic column: AT-35, quartz capillary column (60 m. Times.0.25 mm. Times.0.25 μm). GC analysis conditions: carrier gas, high-purity nitrogen; programming temperature: 70 ℃ (2 min), rising to 150 ℃ at 50 ℃/min, staying for 3min, rising to 230 ℃ at 30 ℃/min, staying for 40min; sample inlet temperature: the total flow is 130.5ml/min at the temperature of 250 ℃, the split ratio is 50:1, and the spacer is purged for 3ml/min; FID detection, detecting port temperature: the hydrogen flow rate is 40ml/min at 250 ℃, the air is 450ml/min, and the nitrogen is blown at 25ml/min. The sample injection amount is 0.2ul.
An area normalization method is adopted. The conversion of myrcene or dihydromyrcene is approximated by subtracting the GC content of myrcene or dihydromyrcene in the product from the GC content of myrcene or dihydromyrcene in the feed.
Myrcene or dihydromyrcene conversion = (GC content of myrcene or dihydromyrcene in raw material-GC content of myrcene or dihydromyrcene in product)/GC content of myrcene or dihydromyrcene in raw material;
selectivity of linalool or dihydromyrcenol= (linalool or dihydromyrcenol in product)/(GC content of myrcene or dihydromyrcene in raw material-GC content of myrcene or dihydromyrcene in product).
Example 1
A method for improving the hydration reaction yield of dihydromyrcene, which comprises the following steps:
(1) And (3) synthesis reaction: adding dihydromyrcene (GC content is 85%, the same applies below), water, a polar organic solvent and a composite catalyst into a reaction kettle according to the mass ratio of 100:100:550:110, stirring at the temperature of 60 ℃, and reacting for 48 hours; the composite catalyst consists of zirconium sulfate and copper sulfate according to the mass ratio of 10:1; the polar solvent is acetic acid and ethyl acetate, and the mass ratio of the polar solvent to the ethyl acetate is 25:30;
(2) And (3) catalyst recovery: after the reaction is finished, standing, filtering an upper liquid product, transferring the filtered upper liquid product into a solvent recovery tank, adding a polar organic solvent into a reaction kettle, washing a catalyst at the bottom of the reaction kettle, filtering a washing liquid, and transferring the filtered washing liquid into the solvent recovery tank;
(3) And (3) recovering a solvent: recovering the solvent by means of reduced pressure distillation, metering the recovered solvent and adding the solvent into a reaction kettle;
(4) Product neutralization: neutralizing the product obtained in the step (3) with dilute alkali solution, adding water accounting for 50% of the mass of the product, and washing for 3 times;
(5) Product fractionation: transferring the product obtained in the step (4) into a fractionating tower, recovering the dihydromyrcene through reduced pressure fractionation, metering the recovered raw materials, and adding the raw materials into a reaction kettle; the hydration product obtained by separation is dihydromyrcenol.
The product fractionation in step (5) comprises the steps of:
s1, firstly discharging air of a rectifying tower to ensure that the vacuum degree in the rectifying tower is less than or equal to-0.10 MPa;
s2, conveying the product after neutralization and water washing to a rectifying tower kettle;
s3, heating to keep the temperature of the tower kettle at 110-120 ℃, keeping the temperature of the tower top at 80-90 ℃, refluxing for 1.5h, and collecting myrcene or dihydromyrcene at a reflux ratio of 10-13:1;
s4, heating to keep the temperature of the tower kettle at 130-140 ℃, keeping the temperature of the tower top at 90-95 ℃ and the reflux ratio at 15-20:1, and collecting hydration products such as linalool or dihydromyrcenol;
s5, heating to keep the temperature of the tower kettle at 140-150 ℃, keeping the temperature of the tower top at 95-105 ℃ and the reflux ratio at 15-20:1, and collecting ester products such as linalyl or dihydromyrcenyl ester.
The ester product, such as linalyl or dihydromyrcenyl ester, is collected.
After the reaction, the product was sampled and analyzed by GC, and it was found that the conversion of dihydromyrcene was 70%, the selectivity of dihydromyrcene alcohol was 88%, and 1.7% of dihydromyrcene acetate was contained in the product.
Example 2
A method for improving the hydration reaction yield of dihydromyrcene, which comprises the following steps:
(1) And (3) synthesis reaction: adding dihydromyrcene, water, a polar organic solvent and a composite catalyst into a reaction kettle according to the mass ratio of 100:100:500:90, stirring at the temperature of 60 ℃, and reacting for 48 hours; the composite catalyst consists of titanium sulfate and copper sulfate according to the mass ratio of 8:1; the polar solvent is propionic acid and ethyl acetate, and the mass ratio is 1:1;
(2) And (3) catalyst recovery: after the reaction is finished, standing, filtering an upper liquid product, transferring the filtered upper liquid product into a solvent recovery tank, adding a polar organic solvent into a reaction kettle, washing a catalyst at the bottom of the reaction kettle, filtering a washing liquid, and transferring the filtered washing liquid into the solvent recovery tank;
(3) And (3) recovering a solvent: recovering the solvent by means of reduced pressure distillation, metering the recovered solvent and adding the solvent into a reaction kettle;
(4) Product neutralization: neutralizing the product obtained in the step (3) with dilute alkali solution, adding water accounting for 80% of the mass of the product, and washing for 3 times;
(5) Product fractionation: transferring the product obtained in the step (4) into a fractionating tower, recovering the dihydromyrcene through reduced pressure fractionation, metering the recovered raw materials, and adding the raw materials into a reaction kettle; the hydration product obtained by separation is dihydromyrcenol.
The product fractionation step described in step (5) was the same as in example 1.
After the reaction, the product was sampled and analyzed by GC, and it was found that the conversion of dihydromyrcene was 72%, the selectivity of dihydromyrcene alcohol was 90%, and 2.0% of dihydromyrcene propionate was contained in the product.
Example 3
A method for improving the hydration reaction yield of dihydromyrcene, which comprises the following steps:
(1) And (3) synthesis reaction: adding dihydromyrcene, water, a polar organic solvent and a composite catalyst into a reaction kettle according to the mass ratio of 100:100:350:110, stirring at the temperature of 60 ℃, and reacting for 48 hours; the composite catalyst consists of zirconium sulfate and copper sulfate according to the mass ratio of 8:1; the polar solvent is butyric acid;
(2) And (3) catalyst recovery: after the reaction is finished, standing, filtering an upper liquid product, transferring the filtered upper liquid product into a solvent recovery tank, adding a polar organic solvent into a reaction kettle, washing a catalyst at the bottom of the reaction kettle, filtering a washing liquid, and transferring the filtered washing liquid into the solvent recovery tank;
(3) And (3) recovering a solvent: recovering the solvent by means of reduced pressure distillation, metering the recovered solvent and adding the solvent into a reaction kettle;
(4) Product neutralization: neutralizing the product obtained in the step (3) with dilute alkali solution, adding water accounting for 50% of the mass of the product, and washing for 3 times;
(5) Product fractionation: transferring the product obtained in the step (4) into a fractionating tower, recovering myrcene or dihydromyrcene through reduced pressure fractionation, metering the recovered raw materials, and adding the raw materials into a reaction kettle; the hydration product obtained by separation is dihydromyrcenol.
The product fractionation step described in step (5) was the same as in example 1.
After the reaction, the product was sampled and analyzed by GC, and it was found that the conversion of dihydromyrcene was 75%, the selectivity of dihydromyrcene alcohol was 90.5%, and 2.5% of dihydromyrcene butyrate was contained in the product.
Example 4
A method for improving the hydration reaction yield of dihydromyrcene, which comprises the following steps:
(1) And (3) synthesis reaction: adding dihydromyrcene, water, a polar organic solvent and a composite catalyst into a reaction kettle according to the mass ratio of 100:150:450:110, stirring at the temperature of 60 ℃, and reacting for 48 hours; the composite catalyst consists of zirconium sulfate and copper sulfate according to the mass ratio of 8:1; the polar solvent is valeric acid;
(2) And (3) catalyst recovery: after the reaction is finished, standing, filtering an upper liquid product, transferring the filtered upper liquid product into a solvent recovery tank, adding a polar organic solvent into a reaction kettle, washing a catalyst at the bottom of the reaction kettle, filtering a washing liquid, and transferring the filtered washing liquid into the solvent recovery tank;
(3) And (3) recovering a solvent: recovering the solvent by means of reduced pressure distillation, metering the recovered solvent and adding the solvent into a reaction kettle;
(4) Product neutralization: neutralizing the product obtained in the step (3) with dilute alkali solution, adding water accounting for 150% of the mass of the product, and washing for 2 times;
(5) Product fractionation: transferring the product obtained in the step (4) into a fractionating tower, recovering the dihydromyrcene through reduced pressure fractionation, metering the recovered raw materials, and adding the raw materials into a reaction kettle; the hydration product obtained by separation is dihydromyrcenol.
The product fractionation step described in step (5) was the same as in example 1.
After the reaction, the product was sampled and analyzed by GC, and it was found that the conversion of dihydromyrcene was 76%, the selectivity of dihydromyrcene alcohol was 91%, and 3.1% of dihydromyrcene valerate was contained in the product.
Example 5
A method for improving the hydration reaction yield of dihydromyrcene, which comprises the following steps:
(1) And (3) synthesis reaction: adding dihydromyrcene, water, a polar organic solvent and a composite catalyst into a reaction kettle according to the mass ratio of 100:150:450:80, stirring at the temperature of 60 ℃, and reacting for 48 hours; the composite catalyst is prepared from tartaric acid, boric acid and copper sulfate according to the mass ratio of 5:2:1, the composition is as follows; the polar solvent is acetic acid and tetrahydrofuran, and the mass ratio is 2:1;
(2) And (3) catalyst recovery: after the reaction is finished, standing, filtering an upper liquid product, transferring the filtered upper liquid product into a solvent recovery tank, adding a polar organic solvent into a reaction kettle, washing a catalyst at the bottom of the reaction kettle, filtering a washing liquid, and transferring the filtered washing liquid into the solvent recovery tank;
(3) And (3) recovering a solvent: recovering the solvent by means of reduced pressure distillation, metering the recovered solvent and adding the solvent into a reaction kettle;
(4) Product neutralization: neutralizing the product obtained in the step (3) with dilute alkali solution, adding water accounting for 150% of the mass of the product, and washing for 2 times;
(5) Product fractionation: transferring the product obtained in the step (4) into a fractionating tower, recovering the dihydromyrcene through reduced pressure fractionation, metering the recovered raw materials, and adding the raw materials into a reaction kettle; the hydration product obtained by separation is dihydromyrcenol.
The product fractionation step described in step (5) was the same as in example 1.
After the reaction, the product was sampled and analyzed by GC, and it was found that the conversion of dihydromyrcene was 78%, the selectivity of dihydromyrcene alcohol was 92%, and 2.0% of dihydromyrcene acetate was contained in the product.
Example 6
A method for improving the hydration reaction yield of dihydromyrcene, which comprises the following steps:
(1) And (3) synthesis reaction: adding dihydromyrcene, water, a polar organic solvent and a composite catalyst into a reaction kettle according to the mass ratio of 100:150:450:125, stirring at the temperature of 60 ℃, and reacting for 48 hours; the composite catalyst is prepared from lactic acid, boric acid and copper sulfate according to the mass ratio of 10:1.5:1, the composition is as follows; the polar solvent is acetic acid and tetrahydrofuran, and the mass ratio is 2:1;
(2) And (3) catalyst recovery: after the reaction is finished, standing, filtering an upper liquid product, transferring the filtered upper liquid product into a solvent recovery tank, adding a polar organic solvent into a reaction kettle, washing a catalyst at the bottom of the reaction kettle, filtering a washing liquid, and transferring the filtered washing liquid into the solvent recovery tank;
(3) And (3) recovering a solvent: recovering the solvent by means of reduced pressure distillation, metering the recovered solvent and adding the solvent into a reaction kettle;
(4) Product neutralization: neutralizing the product obtained in the step (3) with dilute alkali solution, adding water accounting for 150% of the mass of the product, and washing for 2 times;
(5) Product fractionation: transferring the product obtained in the step (4) into a fractionating tower, recovering the dihydromyrcene through reduced pressure fractionation, metering the recovered raw materials, and adding the raw materials into a reaction kettle; the hydration product obtained by separation is dihydromyrcenol.
The product fractionation step described in step (5) was the same as in example 1.
After the reaction, the product was sampled and analyzed by GC, and it was found that the conversion of dihydromyrcene was 77.8%, the selectivity of dihydromyrcene alcohol was 92.3%, and 1.8% of dihydromyrcene acetate and 0.7% of dihydromyrcene lactate were contained in the product.
Example 7
A method for improving the hydration reaction yield of dihydromyrcene, which comprises the following steps:
(1) And (3) synthesis reaction: adding dihydromyrcene, water, a polar organic solvent and a composite catalyst into a reaction kettle according to the mass ratio of 100:150:450:125, stirring at the temperature of 60 ℃, and reacting for 48 hours; the composite catalyst consists of mandelic acid, boric acid and copper sulfate according to the mass ratio of 10:1.5:1; the polar solvent is acetic acid and tetrahydrofuran, and the mass ratio is 2:1;
(2) And (3) catalyst recovery: after the reaction is finished, standing, filtering an upper liquid product, transferring the filtered upper liquid product into a solvent recovery tank, adding a polar organic solvent into a reaction kettle, washing a catalyst at the bottom of the reaction kettle, filtering a washing liquid, and transferring the filtered washing liquid into the solvent recovery tank;
(3) And (3) recovering a solvent: recovering the solvent by means of reduced pressure distillation, metering the recovered solvent and adding the solvent into a reaction kettle;
(4) Product neutralization: neutralizing the product obtained in the step (3) with dilute alkali solution, adding water accounting for 50% of the mass of the product, and washing for 2 times;
(5) Product fractionation: transferring the product obtained in the step (4) into a fractionating tower, recovering the dihydromyrcene through reduced pressure fractionation, metering the recovered raw materials, and adding the raw materials into a reaction kettle; the hydration product obtained by separation is dihydromyrcenol.
The product fractionation step described in step (5) was the same as in example 1.
After the reaction is finished, the product is sampled and subjected to GC analysis, so that the conversion rate of the dihydromyrcene is 78.1%, the selectivity of the dihydromyrcene alcohol is 92.5%, and the product also contains 2.1% of dihydromyrcene acetate and 0.6% of dihydromyrcene mandelate.
Example 8
A method for improving the hydration reaction yield of dihydromyrcene, which comprises the following steps:
(1) And (3) synthesis reaction: adding dihydromyrcene, water, a polar organic solvent and a composite catalyst into a reaction kettle according to the mass ratio of 100:150:400:125, stirring at the temperature of 60 ℃, and reacting for 48 hours; the composite catalyst consists of glycolic acid, boric acid and copper sulfate according to the mass ratio of 10:1.5:1; the polar solvent is tetrahydrofuran;
(2) And (3) catalyst recovery: after the reaction is finished, standing, filtering an upper liquid product, transferring the filtered upper liquid product into a solvent recovery tank, adding a polar organic solvent into a reaction kettle, washing a catalyst at the bottom of the reaction kettle, filtering a washing liquid, and transferring the filtered washing liquid into the solvent recovery tank;
(3) And (3) recovering a solvent: recovering the solvent by means of reduced pressure distillation, metering the recovered solvent and adding the solvent into a reaction kettle;
(4) Product neutralization: neutralizing the product obtained in the step (3) with dilute alkali solution, adding water with the mass of 100% of the product, and washing for 2 times;
(5) Product fractionation: transferring the product obtained in the step (4) into a fractionating tower, recovering the dihydromyrcene through reduced pressure fractionation, metering the recovered raw materials, and adding the raw materials into a reaction kettle; the hydration product obtained by separation is dihydromyrcenol.
The product fractionation step described in step (5) was the same as in example 1.
After the reaction was completed, the product was sampled and analyzed by GC, and it was found that the conversion of dihydromyrcene was 78.5%, the selectivity of dihydromyrcene alcohol was 91.8%, and 0.9% of dihydromyrcene glycolate was contained in the product.
Example 9
A method for improving the hydration reaction yield of dihydromyrcene, which comprises the following steps:
(1) And (3) synthesis reaction: adding dihydromyrcene, water, a polar organic solvent and a composite catalyst into a reaction kettle according to the mass ratio of 100:150:400:105, stirring at the temperature of 60 ℃, and reacting for 48 hours; the composite catalyst consists of citric acid, boric acid and copper sulfate according to the mass ratio of 8:1.5:1; the polar solvent is acetic acid and tetrahydrofuran, and the mass ratio is 2:1;
(2) And (3) catalyst recovery: after the reaction is finished, standing, filtering an upper liquid product, transferring the filtered upper liquid product into a solvent recovery tank, adding a polar organic solvent into a reaction kettle, washing a catalyst at the bottom of the reaction kettle, filtering a washing liquid, and transferring the filtered washing liquid into the solvent recovery tank;
(3) And (3) recovering a solvent: recovering the solvent by means of reduced pressure distillation, metering the recovered solvent and adding the solvent into a reaction kettle;
(4) Product neutralization: neutralizing the product obtained in the step (3) with dilute alkali solution, adding water accounting for 200% of the mass of the product, and washing for 2 times;
(5) Product fractionation: transferring the product obtained in the step (4) into a fractionating tower, recovering the dihydromyrcene through reduced pressure fractionation, metering the recovered raw materials, and adding the raw materials into a reaction kettle; the hydration product obtained by separation is dihydromyrcenol.
The product fractionation step described in step (5) was the same as in example 1.
After the reaction, the product was sampled and analyzed by GC, and it was found that the conversion of dihydromyrcene was 78.8%, the selectivity for dihydromyrcene alcohol was 92.3%, and 1.8% of dihydromyrcene acetate was contained in the product.
Example 10
A method for improving the hydration reaction yield of dihydromyrcene, which comprises the following steps:
(1) And (3) synthesis reaction: adding dihydromyrcene, water, a polar organic solvent and a composite catalyst into a reaction kettle according to the mass ratio of 100:150:350:110, stirring at the temperature of 60 ℃, and reacting for 48 hours; the composite catalyst consists of zirconium sulfate, lactic acid and copper sulfate according to the mass ratio of 5:5:1; the polar solvent is acetic acid and tetrahydrofuran, and the mass ratio is 2:1;
(2) And (3) catalyst recovery: after the reaction is finished, standing, filtering an upper liquid product, transferring the filtered upper liquid product into a solvent recovery tank, adding a polar organic solvent into a reaction kettle, washing a catalyst at the bottom of the reaction kettle, filtering a washing liquid, and transferring the filtered washing liquid into the solvent recovery tank;
(3) And (3) recovering a solvent: recovering the solvent by means of reduced pressure distillation, metering the recovered solvent and adding the solvent into a reaction kettle;
(4) Product neutralization: neutralizing the product obtained in the step (3) with dilute alkali solution, adding water accounting for 200% of the mass of the product, and washing for 2 times;
(5) Product fractionation: transferring the product obtained in the step (4) into a fractionating tower, recovering the dihydromyrcene through reduced pressure fractionation, metering the recovered raw materials, and adding the raw materials into a reaction kettle; the hydration product obtained by separation is dihydromyrcenol.
The product fractionation step described in step (5) was the same as in example 1.
After the reaction, the product was sampled and analyzed by GC, and it was found that the conversion of dihydromyrcene was 78.1%, the selectivity of dihydromyrcene alcohol was 92.2%, and 2.6% of dihydromyrcene acetate and 0.5% of dihydromyrcene lactate were contained in the product.
Example 11
A method for improving the hydration reaction yield of dihydromyrcene, which comprises the following steps:
(1) And (3) synthesis reaction: adding dihydromyrcene, water, a polar organic solvent and a composite catalyst into a reaction kettle according to the mass ratio of 100:150:350:110, stirring at the temperature of 60 ℃, and reacting for 48 hours; the composite catalyst consists of zirconium sulfate, malic acid and copper sulfate according to the mass ratio of 5:5:1; the polar solvent is acetic acid and tetrahydrofuran, and the mass ratio is 2:1;
(2) And (3) catalyst recovery: after the reaction is finished, standing, filtering an upper liquid product, transferring the filtered upper liquid product into a solvent recovery tank, adding a polar organic solvent into a reaction kettle, washing a catalyst at the bottom of the reaction kettle, filtering a washing liquid, and transferring the filtered washing liquid into the solvent recovery tank;
(3) And (3) recovering a solvent: recovering the solvent by means of reduced pressure distillation, metering the recovered solvent and adding the solvent into a reaction kettle;
(4) Product neutralization: neutralizing the product obtained in the step (3) with dilute alkali solution, adding water accounting for 150% of the mass of the product, and washing for 2 times;
(5) Product fractionation: transferring the product obtained in the step (4) into a fractionating tower, recovering the dihydromyrcene through reduced pressure fractionation, metering the recovered raw materials, and adding the raw materials into a reaction kettle; the hydration product obtained by separation is dihydromyrcenol.
The product fractionation step described in step (5) was the same as in example 1.
After the reaction is finished, the product is sampled and subjected to GC analysis, so that the conversion rate of the dihydromyrcene is 78.5%, the selectivity of the dihydromyrcene alcohol is 92.4%, and the product also contains 2.3% of dihydromyrcene acetate and 0.3% of dihydromyrcene malate.
Example 12
A method for improving the hydration reaction yield of dihydromyrcene, which comprises the following steps:
(1) And (3) synthesis reaction: adding dihydromyrcene, water, a polar organic solvent and a composite catalyst into a reaction kettle according to the mass ratio of 100:150:350:110, stirring at the temperature of 60 ℃, and reacting for 48 hours; the composite catalyst consists of titanium sulfate, tartaric acid and copper sulfate according to the mass ratio of 5:5:1; the polar solvent is acetic acid and tetrahydrofuran, and the mass ratio is 2:1;
(2) And (3) catalyst recovery: after the reaction is finished, standing, filtering an upper liquid product, transferring the filtered upper liquid product into a solvent recovery tank, adding a polar organic solvent into a reaction kettle, washing a catalyst at the bottom of the reaction kettle, filtering a washing liquid, and transferring the filtered washing liquid into the solvent recovery tank;
(3) And (3) recovering a solvent: recovering the solvent by means of reduced pressure distillation, metering the recovered solvent and adding the solvent into a reaction kettle;
(4) Product neutralization: neutralizing the product obtained in the step (3) with dilute alkali solution, adding water accounting for 150% of the mass of the product, and washing for 2 times;
(5) Product fractionation: transferring the product obtained in the step (4) into a fractionating tower, recovering the dihydromyrcene through reduced pressure fractionation, metering the recovered raw materials, and adding the raw materials into a reaction kettle; the hydration product obtained by separation is dihydromyrcenol.
The product fractionation step described in step (5) was the same as in example 1.
After the reaction is finished, the product is sampled and subjected to GC analysis, so that the conversion rate of the dihydromyrcene is 78.5%, the selectivity of the dihydromyrcene alcohol is 92.4%, and the product also contains 2.3% of dihydromyrcene acetate and 0.2% of dihydromyrcene tartrate.
Example 13
A method for improving the yield of myrcene hydration reaction, which comprises the following steps:
(1) And (3) synthesis reaction: laurene (GC content is 90%, the same applies below), water, a polar organic solvent and a composite catalyst are added into a reaction kettle according to the mass ratio of 100:150:350:110, the temperature is 60 ℃, and the reaction time is 48 hours; the composite catalyst consists of zirconium sulfate, tartaric acid and copper sulfate according to the mass ratio of 5:5:1; the polar solvent is acetic acid and tetrahydrofuran, and the mass ratio is 2:1;
(2) And (3) catalyst recovery: after the reaction is finished, standing, filtering an upper liquid product, transferring the filtered upper liquid product into a solvent recovery tank, adding a polar organic solvent into a reaction kettle, washing a catalyst at the bottom of the reaction kettle, filtering a washing liquid, and transferring the filtered washing liquid into the solvent recovery tank;
(3) And (3) recovering a solvent: recovering the solvent by means of reduced pressure distillation, metering the recovered solvent and adding the solvent into a reaction kettle;
(4) Product neutralization: neutralizing the product obtained in the step (3) with dilute alkali solution, adding water accounting for 150% of the mass of the product, and washing for 2 times;
(5) Product fractionation: transferring the product obtained in the step (4) into a fractionating tower, recovering myrcene through reduced pressure fractionation, metering the recovered raw materials, and adding the raw materials into a reaction kettle; the hydration product obtained by separation is linalool.
The product fractionation step described in step (5) was the same as in example 1.
After the reaction is finished, the product is sampled and subjected to GC analysis, so that the conversion rate of myrcene is 90.2%, the selectivity of linalool is 60.7%, and the product also contains 3.8% of linalyl acetate and 0.2% of myrcene tartrate.
Example 14
A method for improving the yield of myrcene hydration reaction, which comprises the following steps:
(1) And (3) synthesis reaction: adding myrcene, water, a polar organic solvent and a composite catalyst into a reaction kettle according to the mass ratio of 100:150:350:100, stirring at the temperature of 60 ℃, and reacting for 48 hours; the composite catalyst consists of zirconium sulfate, lactic acid and copper sulfate according to the mass ratio of 6:3:1; the polar solvent is acetic acid and tetrahydrofuran, and the mass ratio is 2:1;
(2) And (3) catalyst recovery: after the reaction is finished, standing, filtering an upper liquid product, transferring the filtered upper liquid product into a solvent recovery tank, adding a polar organic solvent into a reaction kettle, washing a catalyst at the bottom of the reaction kettle, filtering a washing liquid, and transferring the filtered washing liquid into the solvent recovery tank;
(3) And (3) recovering a solvent: recovering the solvent by means of reduced pressure distillation, metering the recovered solvent and adding the solvent into a reaction kettle;
(4) Product neutralization: neutralizing the product obtained in the step (3) with dilute alkali solution, adding water accounting for 80% of the mass of the product, and washing for 3 times;
(5) Product fractionation: transferring the product obtained in the step (4) into a fractionating tower, recovering myrcene through reduced pressure fractionation, metering the recovered raw materials, and adding the raw materials into a reaction kettle; the hydration product obtained by separation is linalool.
The product fractionation step described in step (5) was the same as in example 1.
After the reaction, the product was sampled and analyzed by GC, and it was found that the conversion of myrcene was 94.2%, the selectivity of dihydromyrcene alcohol was 65.3%, and linalyl acetate and myrcene lactate were contained in an amount of 3.8% and 0.7%.
Example 15
A method for improving the yield of myrcene hydration reaction, which comprises the following steps:
(1) And (3) synthesis reaction: adding myrcene, water, a polar organic solvent and a composite catalyst into a reaction kettle according to the mass ratio of 100:150:350:75, stirring at the temperature of 60 ℃, and reacting for 48 hours; the composite catalyst consists of tartaric acid, boric acid and copper sulfate according to the mass ratio of 5:1.5:1; the polar solvent is acetic acid and tetrahydrofuran, and the mass ratio is 2:1;
(2) And (3) catalyst recovery: after the reaction is finished, standing, filtering an upper liquid product, transferring the filtered upper liquid product into a solvent recovery tank, adding a polar organic solvent into a reaction kettle, washing a catalyst at the bottom of the reaction kettle, filtering a washing liquid, and transferring the filtered washing liquid into the solvent recovery tank;
(3) And (3) recovering a solvent: recovering the solvent by means of reduced pressure distillation, metering the recovered solvent and adding the solvent into a reaction kettle;
(4) Product neutralization: neutralizing the product obtained in the step (3) with dilute alkali solution, adding water accounting for 150% of the mass of the product, and washing for 2 times;
(5) Product fractionation: transferring the product obtained in the step (4) into a fractionating tower, recovering myrcene through reduced pressure fractionation, metering the recovered raw materials, and adding the raw materials into a reaction kettle; the hydration product obtained by separation is linalool.
The product fractionation step described in step (5) was the same as in example 1.
After the reaction, the product was sampled and analyzed by GC, and it was found that the conversion of myrcene was 95.2%, the selectivity for dihydromyrcenol was 66.5%, and linalyl acetate was also contained in the product at 4.5%.
Comparative example 1
Blank experiments. And (3) synthesis reaction: adding the dihydrolauric acid and water into a reaction kettle according to the mass ratio of 1:10, starting stirring, controlling the reaction temperature to be 70 ℃ and the reaction time to be 72 hours; no catalyst. After the reaction was completed, samples were taken for GC analysis, the GC content of dihydromyrcene in the product was 85%, and dihydromyrcene alcohol was not detected. It can be seen that without the catalyst, dihydromyrcene does not react with water.
Comparative example 2
Sulfuric acid is used as a catalyst. Other conditions were the same as in example 1. The product was black in color. After the reaction, the product was sampled directly, washed to neutrality, dissolved in ethyl acetate and analyzed by GC. By GC analysis of the product, a greater number of cyclized byproducts were found with a cyclized acetate content of 10%. The selectivity of the dihydromyrcenol is 53.5 percent, which is obviously lower than the selectivity of the target product of the invention. Sulfuric acid has the disadvantages of strong corrosiveness, easy side reaction, and difficult recycling after being dissolved in the product.
Comparative example 3
Zirconium sulfate is used as a catalyst. Other conditions were the same as in example 1. The product was dark brown in color. After the reaction, the product was sampled directly, washed to neutrality, dissolved in ethyl acetate and analyzed by GC. By GC analysis of the product, a greater number of cyclized byproducts were found with a cyclized acetate content of 2%. The selectivity of the dihydromyrcenol is 68 percent and is lower than that of the target product of the invention. When zirconium sulfate is used as a catalyst, although the amount of cyclized byproducts is reduced, the product is dark in color and requires an additional decoloring step, thereby increasing the complexity of the process. The divalent copper salt is added, so that the occurrence of cyclization and chromogenic side reaction can be effectively inhibited, the complexity of the process is further reduced, and the product quality is improved.
Comparative example 4
Tartaric acid and boric acid are used as composite catalysts, and the mass ratio is 5:2. Other conditions were the same as in example 5. The product was dark brown in color. After the reaction, the product was sampled directly, washed to neutrality, dissolved in ethyl acetate and analyzed by GC. By GC analysis of the product, a greater number of cyclized byproducts were found with a cyclized acetate content of 4.5%. The selectivity of the dihydromyrcenol is 65 percent and is lower than that of the target product of the invention. When tartaric acid and boric acid are used as catalysts, the cyclisation by-products are reduced compared to sulfuric acid, but the product is dark in colour and colour, and there is still a need to add a decolorizing step and also increase the complexity of the process. In the embodiment 5, the divalent copper salt is added into the composite catalyst, so that the occurrence of cyclization and chromogenic side reaction can be effectively inhibited, the complexity of the process is reduced, and the product quality is improved.
Comparative example 5
Sulfuric acid is used as a catalyst. Other conditions were the same as in example 13. The product was black in color. After the reaction, the product was sampled directly, washed to neutrality, dissolved in ethyl acetate and analyzed by GC. Through GC analysis of the product, more cyclized byproducts such as dipentene and the like are found, and the content of the cyclized byproducts reaches 40.6 percent. The selectivity of linalool is 35% and is significantly lower than that of the target product of the invention. Sulfuric acid has the disadvantages of strong corrosiveness, easy side reaction, and difficult recycling after being dissolved in the product.
The foregoing is a further detailed description of the invention in connection with specific/preferred embodiments, and is not intended to limit the practice of the invention to such description. It will be apparent to those skilled in the art that several alternatives or modifications can be made to the described embodiments without departing from the spirit of the invention, and these alternatives or modifications should be considered to be within the scope of the invention.
Claims (10)
1. A method for improving the yield of myrcene or dihydromyrcene hydration reaction, comprising the following steps:
(1) And (3) synthesis reaction: adding myrcene or dihydromyrcene, water, a polar organic solvent and a composite catalyst into a reaction kettle according to the mass ratio of 100 (15-200): (100-800): (20-150), stirring at 50-70 ℃, and reacting for 24-48 h; the composite catalyst consists of one or more of zirconium sulfate, titanium sulfate and alpha-hydroxy acid and cupric salt;
(2) And (3) catalyst recovery: after the reaction is finished, standing, filtering an upper liquid product, transferring the filtered upper liquid product into a solvent recovery tank, adding a polar organic solvent into a reaction kettle, washing a catalyst at the bottom of the reaction kettle, filtering a washing liquid, and transferring the filtered washing liquid into the solvent recovery tank;
(3) And (3) recovering a solvent: recovering the solvent by means of reduced pressure distillation, metering the recovered solvent and adding the solvent into a reaction kettle;
(4) Product neutralization: neutralizing the product obtained in the step (3) with dilute alkali liquor, and then adding water to wash for 2-3 times;
(5) Product fractionation: transferring the product obtained in the step (4) into a fractionating tower, recovering myrcene or dihydromyrcene through reduced pressure fractionation, metering the recovered raw materials, and adding the raw materials into a reaction kettle; the hydration product obtained by separation is linalool or dihydromyrcenol.
2. The method for improving the yield of myrcene or dihydromyrcene hydration reaction according to claim 1, wherein: the cupric salt in the step (1) comprises one or more of copper sulfate, copper nitrate, copper chloride, copper formate and copper acetate.
3. The method for improving the yield of myrcene or dihydromyrcene hydration reaction according to claim 1, wherein: the alpha-hydroxycarboxylic acid in the step (1) comprises one or more of tartaric acid, citric acid, malic acid, mandelic acid, lactic acid and glycolic acid.
4. The method for improving the yield of myrcene or dihydromyrcene hydration reaction according to claim 1, wherein: the composite catalyst in the step (1) further comprises boric acid.
5. The method for increasing the yield of myrcene or dihydromyrcene hydration reaction according to claim 4, wherein: the composite catalyst is tartaric acid, boric acid and cupric salt, and the mass ratio of the composite catalyst is (5-10) (0.5-2) (0.2-1).
6. The method for improving the yield of myrcene or dihydromyrcene hydration reaction according to claim 1, wherein: the polar organic solvent in the step (1) is one or more of acetic acid, propionic acid, butyric acid, valeric acid, ethyl acetate and tetrahydrofuran.
7. The method for synthesizing chiral borneol esters according to claim 1, characterized in that: the product fractionation in step (5) comprises the steps of:
s1, firstly discharging air of a rectifying tower to ensure that the vacuum degree in the rectifying tower is less than or equal to-0.10 MPa;
s2, conveying the product after neutralization and water washing to a rectifying tower kettle;
s3, heating to keep the temperature of the tower kettle at 110-120 ℃, keeping the temperature of the tower top at 80-90 ℃, refluxing for 1-2 h, and collecting myrcene or dihydromyrcene at a reflux ratio of 10-13:1;
s4, heating to keep the temperature of the tower kettle at 130-140 ℃, keeping the temperature of the tower top at 90-95 ℃ and the reflux ratio at 15-20:1, and collecting hydration products such as linalool or dihydromyrcenol;
s5, heating to keep the temperature of the tower kettle at 140-150 ℃, keeping the temperature of the tower top at 95-105 ℃ and the reflux ratio at 15-20:1, and collecting ester products such as linalyl or dihydromyrcenyl ester.
8. A fragrance synthesized according to any one of claims 1 to 7, characterized in that: the perfume comprises myrcene (10% -30%) and linalool or dihydromyrcenol (30% -60%) and linalyl ester or dihydromyrcenyl ester (1% -5%) with GC content.
9. A synthetic fragrance according to claim 8, wherein: the linalyl ester or dihydromyrcenyl ester is one or more of acetic ester, propionic ester, butyric ester and valeric ester.
10. A synthetic fragrance according to claim 8, wherein: the linalyl ester or dihydromyrcenyl ester is alpha-hydroxy carboxylic acid ester; the alpha-hydroxy carboxylic acid comprises one or more of tartaric acid, citric acid, malic acid, mandelic acid, lactic acid and glycolic acid.
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