CN114367253B - Optical channel reactor and preparation method of high-purity all-trans vitamin A acetate and derivative crystal thereof - Google Patents
Optical channel reactor and preparation method of high-purity all-trans vitamin A acetate and derivative crystal thereof Download PDFInfo
- Publication number
- CN114367253B CN114367253B CN202210048167.XA CN202210048167A CN114367253B CN 114367253 B CN114367253 B CN 114367253B CN 202210048167 A CN202210048167 A CN 202210048167A CN 114367253 B CN114367253 B CN 114367253B
- Authority
- CN
- China
- Prior art keywords
- acetate
- light
- channel
- vitamin
- reactor
- 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.)
- Active
Links
- QGNJRVVDBSJHIZ-QHLGVNSISA-N retinyl acetate Chemical compound CC(=O)OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C QGNJRVVDBSJHIZ-QHLGVNSISA-N 0.000 title claims abstract description 151
- 239000011770 retinyl acetate Substances 0.000 title claims abstract description 145
- 235000019173 retinyl acetate Nutrition 0.000 title claims abstract description 137
- 239000013078 crystal Substances 0.000 title claims abstract description 83
- 150000004347 all-trans-retinol derivatives Chemical class 0.000 title claims abstract description 66
- 230000003287 optical effect Effects 0.000 title claims description 24
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 92
- 229960000342 retinol acetate Drugs 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000007787 solid Substances 0.000 claims abstract description 31
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 239000012295 chemical reaction liquid Substances 0.000 claims description 39
- 238000006317 isomerization reaction Methods 0.000 claims description 30
- 239000002994 raw material Substances 0.000 claims description 28
- 239000007790 solid phase Substances 0.000 claims description 27
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 24
- 239000012530 fluid Substances 0.000 claims description 23
- 239000007791 liquid phase Substances 0.000 claims description 21
- 230000001699 photocatalysis Effects 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 17
- 239000012071 phase Substances 0.000 claims description 12
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- QGNJRVVDBSJHIZ-AQDFTDIISA-N (2e,4e,6z,8e)-3,7-dimethyl-9-(2,6,6-trimethylcyclohex-1-en-1-yl)nona-2,4,6,8-tetraen-1-yl acetate Chemical compound CC(=O)OC\C=C(/C)\C=C\C=C(\C)/C=C/C1=C(C)CCCC1(C)C QGNJRVVDBSJHIZ-AQDFTDIISA-N 0.000 claims description 8
- FPIPGXGPPPQFEQ-HWCYFHEPSA-N 13-cis-retinol Chemical compound OC/C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-HWCYFHEPSA-N 0.000 claims description 8
- IINNWAYUJNWZRM-UHFFFAOYSA-L erythrosin B Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 IINNWAYUJNWZRM-UHFFFAOYSA-L 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007858 starting material Substances 0.000 claims description 8
- 239000002826 coolant Substances 0.000 claims description 7
- 238000005286 illumination Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- NALMPLUMOWIVJC-UHFFFAOYSA-N n,n,4-trimethylbenzeneamine oxide Chemical compound CC1=CC=C([N+](C)(C)[O-])C=C1 NALMPLUMOWIVJC-UHFFFAOYSA-N 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 229940032753 sodium iodate Drugs 0.000 claims description 6
- 235000015281 sodium iodate Nutrition 0.000 claims description 6
- 239000011697 sodium iodate Substances 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 5
- 229910000838 Al alloy Inorganic materials 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 4
- GUEIZVNYDFNHJU-UHFFFAOYSA-N quinizarin Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC=C2O GUEIZVNYDFNHJU-UHFFFAOYSA-N 0.000 claims description 4
- 239000002356 single layer Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 229910003460 diamond Inorganic materials 0.000 claims description 3
- 239000010432 diamond Substances 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- IICCLYANAQEHCI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodospiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 IICCLYANAQEHCI-UHFFFAOYSA-N 0.000 claims description 2
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 2
- 102100036955 Xin actin-binding repeat-containing protein 2 Human genes 0.000 claims description 2
- 108050000064 Xin actin-binding repeat-containing protein 2 Proteins 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- DBZJJPROPLPMSN-UHFFFAOYSA-N bromoeosin Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(Br)=C(O)C(Br)=C1OC1=C(Br)C(O)=C(Br)C=C21 DBZJJPROPLPMSN-UHFFFAOYSA-N 0.000 claims description 2
- 239000010962 carbon steel Substances 0.000 claims description 2
- 150000004292 cyclic ethers Chemical class 0.000 claims description 2
- 230000003247 decreasing effect Effects 0.000 claims description 2
- 229960001483 eosin Drugs 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- -1 euclidean Xin Cheng Chemical compound 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 2
- 229940081623 rose bengal Drugs 0.000 claims description 2
- 229930187593 rose bengal Natural products 0.000 claims description 2
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 235000019190 thiamine hydrochloride Nutrition 0.000 claims description 2
- 239000011747 thiamine hydrochloride Substances 0.000 claims description 2
- MYVIATVLJGTBFV-UHFFFAOYSA-M thiamine(1+) chloride Chemical compound [Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N MYVIATVLJGTBFV-UHFFFAOYSA-M 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004020 luminiscence type Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 208000012839 conversion disease Diseases 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000010924 continuous production Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 13
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 230000001276 controlling effect Effects 0.000 description 9
- 229940045997 vitamin a Drugs 0.000 description 8
- FPIPGXGPPPQFEQ-BOOMUCAASA-N Vitamin A Natural products OC/C=C(/C)\C=C\C=C(\C)/C=C/C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-BOOMUCAASA-N 0.000 description 7
- 229940011411 erythrosine Drugs 0.000 description 7
- 239000004174 erythrosine Substances 0.000 description 7
- 235000012732 erythrosine Nutrition 0.000 description 7
- 235000019155 vitamin A Nutrition 0.000 description 7
- 239000011719 vitamin A Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 230000004071 biological effect Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- ULGZDMOVFRHVEP-RWJQBGPGSA-N Erythromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=O)[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 ULGZDMOVFRHVEP-RWJQBGPGSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012527 feed solution Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 150000002266 vitamin A derivatives Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- JLQUFIHWVLZVTJ-UHFFFAOYSA-N carbosulfan Chemical compound CCCCN(CCCC)SN(C)C(=O)OC1=CC=CC2=C1OC(C)(C)C2 JLQUFIHWVLZVTJ-UHFFFAOYSA-N 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 210000000981 epithelium Anatomy 0.000 description 1
- 229960003276 erythromycin Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 230000006651 lactation Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000033458 reproduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000004492 retinoid derivatives Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/06—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms
- C07C403/12—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms by esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a light channel reactor and a preparation method of high-purity all-trans vitamin A acetate and derivative crystals thereof, wherein the reactor has a diamond-like channel structure, is suitable for a solid-liquid two-phase reaction system, can timely remove reaction generated solids from the reaction system, can realize stable continuous production, and can remarkably improve the light utilization efficiency. The light channel reactor is adopted to synthesize all-trans vitamin A acetate and derivative crystals thereof through one-step reaction, and the crystals are moved out of a reaction system in time to promote the reaction to move forward, so that the reaction conversion rate and yield are greatly improved, the generated vitamin A acetate crystals can be directly used for downstream preparation production after being dried, the synthesis process of the vitamin A acetate is greatly simplified, and the light and photosensitizer are utilized with maximum efficiency.
Description
Technical Field
The invention relates to a light channel reactor and a preparation method of high-purity all-trans vitamin A acetate and derivative crystals thereof, belonging to the technical field of vitamin A acetate and derivative production.
Background
Vitamin a, also known as retinoid, is an important drug that maintains the integrity of epithelial tissues and the permeability of cell membranes; maintaining normal vision, promoting animal growth, reproduction and lactation; enhancing resistance to disease.
The vitamin A has four conjugated double bonds on the side chain, 16 geometrical isomers theoretically exist, and only five isomers exist in nature due to steric hindrance effect, namely 9-cis, 13-cis, 11-cis, 9, 13-bi-cis vitamin A isomers and unhindered all-trans vitamin A isomers. Wherein the biological activity of all-trans vitamin A isomer is highest, and because of poor stability of vitamin A, oxidation is easy to occur when the vitamin A is exposed to air and acid, the commercial vitamin A commodity in market is usually vitamin A acetate, wherein the content of all-trans vitamin A acetate is usually higher than 93 percent of the total vitamin A isomer.
Most VA factories in the world adopt Roche (Roche) synthesis technology, the synthesized vitamin A acetate mainly comprises all-trans vitamin A acetate and isomers thereof, and because other cis-isomers have lower biological activity and are difficult to separate, the cis-isomers must be converted into all-trans vitamin A acetate so as to improve the biological activity, reduce the waste of raw materials, the melting point of all-trans vitamin A isomer is 58-60 ℃, the melting point of 9, 13-cis-isomers and impurities of the vitamin A acetate are below 15 ℃, and the separation of the all-trans vitamin A acetate mainly adopts a crystallization mode.
At present, research reports about the conversion of vitamin A cis-isomer into all-trans-isomer are presented, and the main methods are heavy metal catalysis, thermal isomerization, iodine catalysis isomerization and photocatalysis isomerization. The heavy metal catalyst can not be recovered due to the fact that expensive heavy metals are used in the heavy metal catalytic isomerization, and a certain amount of heavy metals remain in the product. Because vitamin A has poor stability, the thermal isomerization is extremely easy to cause deterioration of the vitamin A, generates impurities, causes waste of raw materials and affects the quality of products. Iodine catalytic isomerism has certain toxicity due to residual iodine in the product, and can influence the quality of the product. The photocatalytic isomerism is widely focused due to mild reaction conditions and low impurity content of the final product, and the conversion rate of various cis-isomers is high, but when the photocatalytic isomerism is applied to solid-liquid two phases, light scattering is caused, the light utilization rate is reduced, the photocatalytic process is often carried out under the temperature condition that vitamin A acetate is not easy to crystallize and separate out, the utilization rate of a photosensitizer is low, and the application of the photosensitizer is limited. In addition, even though the existing method is subjected to isomerism reaction, the purity of the vitamin A acetate still cannot meet the needs of people, the subsequent process is required to be accompanied with separation of the catalyst, the catalyst is mixed with a solvent after separation to obtain all-trans vitamin A acetate crystals meeting the purity needs through a crystallization process, the crystals are obtained through subsequent filtration/centrifugation and drying treatment, and the process is often accompanied with a complex solvent recovery flow.
Therefore, the preparation method for the all-trans-vitamin A acetate and the derivative thereof is economic, efficient and simple in process, can continuously produce the high-quality all-trans-vitamin A acetate and the derivative thereof on a large scale, and has very important significance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the optical channel reactor which has a diamond-like channel structure, is suitable for a solid-liquid two-phase reaction system, can timely remove reaction generated solids from the reaction system, can realize stable continuous production, and can remarkably improve the light utilization efficiency.
The invention also provides a preparation method of the high-purity all-trans vitamin A acetate and the derivative crystal thereof. The invention utilizes the characteristics of low requirement on photocatalysis reaction temperature and mild reaction condition, adopts the light channel reactor, can synthesize all-trans vitamin A acetate and derivative crystals thereof through one-step reaction, and promotes the reaction to move forward by timely moving the crystals out of a reaction system, thereby greatly improving the reaction conversion rate and yield, and the generated vitamin A acetate crystals can be directly used for downstream preparation production after drying treatment, thereby greatly simplifying the synthesis process of the vitamin A acetate and leading the light and photosensitizer to be utilized with maximum efficiency.
In order to achieve the above object, the present invention is realized by the following technical scheme:
the invention provides a light channel reactor, which comprises a prismatic channel with a cross section similar to a diamond, wherein the prismatic channel is formed by combining two light-emitting plates and two reflecting plates;
the two light-emitting plates form two lower surfaces of the prismatic channel, and an included angle (base angle) of fixed connection between the two light-emitting plates is 30-160 degrees, preferably 120-150 degrees, so as to form a reaction liquid flow channel;
the two reflecting plates form two upper surfaces of the prism channel, and an included angle between the two reflecting plates and the prism channel is 60-120 degrees, preferably 90 degrees;
a light source is arranged on the light-emitting plate;
the square shell is enclosed outside the diamond-like prism channel, the upper edge, the lower edge and the side edge of the diamond-like prism channel are all in sealing connection with the shell to form a plurality of channels with triangular cross sections, and the triangular channels and the diamond-like prism channels are arranged in a staggered manner;
in the diamond-like prism channel, the lower half part consisting of two light-emitting plates is a reaction liquid flow channel, a feed inlet is arranged at the front end along the flow channel direction, a solid-phase discharge port is arranged at the bottom of the rear end, and a liquid-phase discharge port is arranged at the upper part of the rear end;
The triangular channel is a cold/hot medium flow channel and is provided with an inlet and an outlet.
In the light channel reactor, preferably, a solid catcher is arranged at the solid phase discharge port of the diamond-like prism channel, and the catcher can intercept and enrich crystals or solids before the outlet for separating solid phases and liquid phases; the solid catcher is intercepted and arranged on the cross section of a reaction liquid flow channel formed by two light-emitting plates, the edges of the two sides of the solid catcher are respectively connected with the two light-emitting plates in a sealing way, and the upper edge is equal to the height of the light-emitting plates;
the solid catcher is of an inverted triangle plane structure with inclination, and the base angle of the inverted triangle plane is communicated with the solid-phase discharge port; preferably, the inclination of the inverted triangle planar structure facing the fluid is 20-70 degrees, preferably 30-60 degrees;
the upper part of the inverted triangle plane structure is provided with a filter screen, and the lower part of the inverted triangle plane structure is provided with a flat plate; when fluid flows through the solid catcher, firstly, a filter screen at the upper part intercepts solids, and is deposited at the bottom of a diamond-like prism channel under the blocking of a lower flat plate to form solid-liquid two-phase fluid enriched with solids, the solid-liquid two-phase fluid is discharged from a solid-phase discharge port along the bottom angle of an inverted triangle plane, and liquid after the solids are separated by the filter screen is discharged from a liquid-phase discharge port, so that solid-liquid separation is realized;
Preferably, the height ratio of the filter screen to the flat plate is 1:0.5 to 1.5, preferably 1:0.8-1.2;
preferably, the mesh size of the sieve is <40 mesh, preferably 20-30 mesh.
In the light channel reactor of the present invention, preferably, the rhombus-like prism channel has a ratio of width to height of a cross section of 1:0.5-1, preferably 1:0.5-0.7;
preferably, the rhomboid prism-like channel length is 3-12m, preferably 5-8m;
preferably, the plane formed by the upper edge and the lower edge of the diamond-shaped prism channel is perpendicular to the horizontal plane of the light channel reactor;
preferably, the diamond-like prismatic channels may be parallel or series, preferably parallel; may be a single layer or a multi-layer arrangement, preferably a single layer arrangement; wherein the number of the parallel connection is 1-10, preferably 1-5; the number of the series is 1 to 8, preferably 2 to 4.
In the light channel reactor, preferably, in order to facilitate the discharge of the light channel reactor, the inclined included angle between the central axis of the diamond-like prism channel and the horizontal plane of the light channel reactor is 5-15 degrees, preferably 5-10 degrees.
In the light channel reactor according to the invention, preferably the light-emitting plate roughness Ra <0.4 μm, preferably 0.2-0.4 μm, the angle between the lower edges of the two light-emitting plates is 30-160 °, preferably 120-150 °. The luminescent plates are simultaneously used as solid collectors, the two luminescent plates are mutually symmetrically and fixedly connected, and an inclined plane with a specific angle is formed between the two luminescent plates, so that on one hand, light energy required by photocatalytic reaction can be provided, scattering of internal solids to light is reduced, on the other hand, a collector structure is formed, solids are collected at the bottom of a channel through the collector, and a solid-liquid two-phase fluid flow channel is formed at the bottom of the channel.
Preferably, the light emitting plate is made of aluminum alloy, stainless steel or carbon steel, and preferably aluminum alloy.
In the light channel reactor of the present invention, preferably, the light source is one selected from incandescent lamp, energy-saving lamp, metal halogen lamp, light Emitting Diode (LED) lamp, fluorescent lamp, xenon lamp, mercury lamp, ultraviolet lamp, preferably LED lamp, mercury lamp;
preferably, the light sources are uniformly distributed on the light-emitting plate, and the number of the light sources is controlled by the power required by actual reaction.
In the optical channel reactor of the present invention, preferably, the reflecting surface of the reflecting plate needs polishing treatment, and the polishing degree Ra of the reflecting surface is less than 0.4, preferably 0.2-0.3 μm;
the included angle between the upper edges of the reflecting surfaces of the two reflecting plates is 80-120 degrees (apex angle), preferably 90 degrees, and the lower edge is connected with the upper edges (reaction liquid flow channels) of the two reflecting plates respectively, so that in the diamond-like channel formed, the top of the two light reflecting planes is close to two mutually perpendicular light reflecting planes, and the light beams irradiated to the top by the reflecting plates can return to the reaction liquid in parallel after being reflected twice by the specific structure, thereby improving the utilization efficiency of light energy and strengthening the photocatalysis reaction effect.
In the optical channel reactor, preferably, the triangular channel is provided with a plurality of pairs of inlets and outlets in a segmented manner, preferably 1-5 pairs of inlets and outlets are used for dividing the triangular channel into a plurality of stages of channels, and the inlets and the outlets can be mutually converted according to the temperature regulation and control requirement, and can be used as an inlet and an outlet. The multistage channel is used for respectively conveying coolant/heating medium fluid in sections and is used for removing heat or inputting heat to materials in the reaction flow channel, so that the temperature in the optical channel reactor can be regulated and controlled, vitamin A acetate and derivatives thereof can be separated out in a crystal form and enriched at the bottom of the reaction channel while being converted into all-trans, the forward movement of the reaction is promoted, and the scattering and absorption of light by crystal particles are prevented.
The invention also provides an application of the optical channel reactor in isomerization reaction of vitamin A acetate and derivatives thereof, which greatly simplifies the flow of producing all-trans vitamin A acetate by a witting method, and the purity of the produced vitamin A acetate crystal reaches more than 96 percent, and can be directly used for downstream preparation production after drying treatment.
The invention relates to a preparation method of high-purity all-trans vitamin A acetate and derivative crystals thereof, which adopts the optical channel reactor, and comprises the following steps:
1) Starting a light source in the reactor, respectively conveying coolant/heating medium fluid to the triangular channels in a segmented mode, and controlling the temperature in the diamond-like prism channels to be gradually decreased from the feed inlet to the solid-liquid phase discharge port;
2) Mixing vitamin A acetate and derivative isomer raw materials with a solvent and a photosensitizer, then entering a rhombus prism channel from a feed inlet, controlling the feed quantity not to exceed a reaction liquid channel formed by the light-emitting plates, and carrying out photocatalytic isomerization reaction to generate all-trans vitamin A acetate and derivatives thereof;
3) And 2) separating all-trans vitamin A acetate and derivatives thereof generated in the step 2) in a diamond-like prism channel from a feed inlet to a discharge outlet gradually in a crystal form, enriching the all-trans vitamin A acetate and derivatives thereof at the bottom of a reaction liquid channel to form a solid-liquid two-phase fluid channel, carrying out solid-liquid separation at the front end of the discharge outlet through a solid catcher, discharging a solid phase from a solid-phase discharge outlet, and discharging a liquid from a liquid-phase discharge outlet to obtain high-purity all-trans vitamin A acetate crystals and a reaction liquid after removing the crystals.
According to the method, the temperature of the feed inlet in the diamond-like prism channel in the step 1) is 15-30 ℃, preferably 1-20 ℃, and the temperature of the solid-liquid phase discharge outlet is-30-5 ℃, preferably-30-5 ℃. The invention can be realized by respectively conveying the refrigerant/heating medium fluid to the triangular channels in a segmented way and regulating and controlling the temperature of the refrigerant/heating medium fluid in real time, and has no specific requirement.
The method comprises the following steps of 2) preparing raw materials of vitamin A acetate and derivative isomers, wherein the raw materials comprise 11-cis, 9-cis, 13-cis and all-trans vitamin A acetate and derivative isomers;
preferably, the vitamin A acetate and derivative isomer raw materials comprise the following components in percentage by mass as 100 percent:
30-60%, preferably 40-60% of 11-cis-vitamin A acetate and derivatives;
1-15%, preferably 1-10% of 9-cis-vitamin A acetate and derivatives;
1-10%, preferably 1-5% of 13-cis-vitamin A acetate and derivatives;
20-65%, preferably 50-60% of all-trans vitamin A acetate and derivatives.
In addition, the vitamin A acetate and derivative isomer raw material may also contain 10-40%, preferably <30% of other components and impurities.
The vitamin A acetate and derivative isomer raw materials are derived from vitamin A acetate isomers and derivatives thereof synthesized by the witting reaction, the vitamin A acetate isomers and derivatives thereof synthesized by the witting reaction are conventional methods in the field, and a technician can select a proper existing method according to actual needs to prepare the vitamin A acetate isomers and derivatives thereof, so that the vitamin A acetate isomers and derivatives thereof are not repeated;
in the method, the solvent in the step 2) is selected from one or more of C5-C18 linear alkane, branched alkane, chlorinated alkane, C6-C12 aromatic hydrocarbon, C1-C6 ether, alcohol and nitrile; wherein, the C5-C18 linear alkane, branched alkane and chlorinated alkane are preferably one or more of n-hexane, n-heptane and petroleum ether; the aromatic hydrocarbon of C6-C9 is preferably one or more of benzene, toluene, ethylbenzene and paraxylene, more preferably benzene and/or toluene; the ethers, alcohols and nitriles of C1-C6 are preferably one or more of methanol, ethanol, propanol, isopropanol, butanol, cyclic ether, diethyl ether, acetonitrile and propionitrile, more preferably one or more of ethanol, diethyl ether, acetonitrile and propionitrile;
preferably, the solvent is used in an amount of 0.2 to 1.5 times, preferably 0.5 to 1 time, the mass of the starting material of the vitamin A acetate and its derivative isomers.
According to the method of the invention, the photosensitizer in step 2) is selected from one or more of fluorescent or semi-fluorescent substances, preferably fluorescent 2.4.6-triphenylpyran/perchlorate, perylene, quinizarine, hydroquinone, beta-Xin Kefen, sodium eosin, rose bengal, erythrosine (erythromycin), euclidean Xin Cheng, rhodamine, ethylestrol, more preferably erythrosine;
preferably, the photosensitizer is used in an amount of 50-2000ppm, preferably 200-500ppm, of vitamin A acetate and its derivative isomer raw material; the mixing form is homogeneous phase full mixing.
Preferably, the photosensitizer is added with stabilizer sodium iodate in an amount of 1-3% of the mass of the photosensitizer, more preferably 2%.
In the process of the invention, the photocatalytic isomerization reaction in the step 2) is carried out at a reaction temperature of-30 to 30 ℃, preferably-15 to 15 ℃, and the residence time of the reaction solution in the light channel reactor is 3 to 30min, preferably 5 to 15min.
In the method of the invention, the photocatalytic isomerization reaction in the step 2) has a luminous wavelength of 350-520nm, preferably 400-450nm; the illumination intensity is more than 500Lux, preferably 500-700Lux.
In the method, in the step 3), the generated all-trans vitamin A acetate and the derivative thereof are precipitated in a crystal form, and the temperature section of the precipitated crystal is-30-0 ℃, preferably-30-5 ℃ in a rhombus prism channel. After the other isomer vitamin A acetate and the derivative thereof are converted into all-trans vitamin A acetate and the derivative thereof in the reaction, the concentration of the all-trans vitamin A acetate is increased, along with the temperature reduction of the reaction liquid, the all-trans vitamin A acetate is separated out in a crystal form and is collected at the bottom of the reactor, the crystals are timely removed at a solid-phase discharge port, the right movement of reaction balance can be promoted, the scattering and absorption of the crystals to light can be prevented, and after the crystals are separated out, the concentration of the internal photosensitizer relative to the raw materials of the vitamin A acetate and the isomer of the derivative thereof is higher and higher, so that the subsequent reaction is accelerated more favorably.
In the method, in the step 3), the reaction liquid after removing the crystals can be recycled for secondary photocatalytic isomerization reaction, and particularly, part of solvent can be removed by flash evaporation and then returned to the feed inlet of the reactor.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
(1) The optical channel reactor with a specific structure can directly react from isomers containing various vitamin A acetate and derivatives to generate high-purity all-trans vitamin A acetate and derivative crystals thereof, remarkably improves the utilization efficiency of light, can stabilize continuous production, greatly simplifies the traditional production process flow, and reduces equipment investment and production cost.
(2) All-trans vitamin A acetate crystals generated by the reaction can be timely moved out of the reaction system, forward movement of the reaction process is promoted, side reactions are reduced, the reaction conversion rate and yield are greatly improved, and the light and photosensitizer are utilized most efficiently.
Drawings
FIG. 1 is a schematic cross-sectional view of a light tunnel reactor of example 1;
FIG. 2 is a schematic view of the structure of the optical channel reactor in example 1;
FIG. 3 is a schematic view of the structure of the solid trap of example 1;
in the figure: 1. the device comprises a rhombus prism-like channel, 2, a light-emitting plate, 3, a reflector, 4, a light source, 5, a feed inlet, 6, a solid-phase discharge outlet, 7, a liquid-phase discharge outlet, 8, a triangular runner, 9, an inlet, 10, an outlet, 11, a solid catcher, 12, a filter screen, 13 and a flat plate; the number of the inlets, the outlets and the number of the outlets is 10, and the number of the inlets, the number of the outlets and the number of the outlets are not shown in the figure.
Detailed Description
The following further details the technical solution of the present invention by means of examples and figures, but the present invention is not limited thereby.
The main raw material source information adopted in the embodiment of the invention is common commercial raw materials unless otherwise specified:
vitamin a acetate and derivative isomer raw materials: the vitamin A acetate isomer and the derivative thereof obtained by the witting reaction are prepared by referring to the method disclosed in the patent CN 111205209A or CN 112724059A and adjusting the reaction conditions according to actual needs;
solvent: ethanol, acetonitrile, n-hexane, tabacco, far east fine chemical limited;
photosensitizer: erythrosine, carbosulfan technologies limited.
The performance test method adopted by the embodiment of the invention comprises the following steps:
high performance liquid chromatograph: agilent LC-1200,
chromatographic conditions: the 9-cis, 11-cis, 13-cis and all-trans vitamin a acetate contents were determined by external standard method, measured according to the conditions specified in GB 14750-2010.
Isomerization conversion calculation formula: (mass of crystals-mass of starting material all-trans VA mass fraction)/(mass of starting material-mass of all-trans in starting material-mass of impurities in starting material);
Yield calculation formula: crystal mass the crystal purity/(mass of raw material-mass of impurities in raw material).
Example 1
The light channel reactor has a structure shown in figures 1 and 2, and comprises 2 prismatic channels 1 with rhombus-like cross sections connected in parallel, wherein the rhombus-like prismatic channels 1 are formed by combining two light-emitting plates 2 and two light-reflecting plates 3;
the width of the rhombus-like cross section of the rhombus-like prism channel 1 is 0.5m, and the height is 0.3m; the length of the single diamond-like prism channel 1 is 7m; the plane formed by the upper edge and the lower edge of the diamond-like prism channel 1 is perpendicular to the horizontal plane of the light channel reactor.
The optical channel reactor is arranged to be inclined, and the inclined included angle between the central axis of the diamond-like prism channel 1 and the horizontal plane where the optical channel reactor is positioned is 5 degrees.
The two light-emitting plates 2 form two lower surfaces of the prismatic channel 1, the light-emitting plates are made of aluminum alloy, the surface roughness is 0.3 mu m, and the included angle (base angle) is 120 degrees.
The two reflecting plates 3 form two upper surfaces of a prism channel, the top included angle is 90 degrees, the material is stainless steel, and the surface polishing degree Ra=0.3 mu m.
The light source 4 is arranged on the light-emitting plate, the light source 4 is an LED lamp, and LED lamp beads are uniformly distributed on the light-emitting plate.
The lower half part formed by the two luminescent plates 2 is a reaction liquid flow channel, a feed inlet 5 is arranged at the front end along the flow channel direction, a solid-phase discharge outlet 6 is arranged at the bottom of the rear end, and a liquid-phase discharge outlet 7 is arranged at the upper part of the rear end.
The square shell is sealed and connected with the edges of the diamond-like channels by the square shell outside the diamond-like prism channel 1 to form 6 channels 8 with triangular cross sections, the triangular channels 8 are staggered with the diamond-like prism channel 1, 10 inlets 9 and 10 are arranged in sections in the triangular channels 8 for controlling the temperature at two ends, and cold/heat media can be introduced in sections to control the light reaction and crystallization temperature.
A solid catcher 11 is arranged at the solid phase outlet 6 of the diamond-like prism channel 1, is intercepted and arranged on the cross section of a reaction liquid flow channel formed by two light-emitting plates 2, the edges of the two sides of the solid catcher are respectively connected with the two light-emitting plates 2 in a sealing way, and the upper edge is equal to the height of the light-emitting plates 2;
the structure of the solid catcher 11 is shown in fig. 3, and is an inverted triangle plane structure with the inclination 45 degrees facing the fluid, and the base angle of the inverted triangle plane is communicated with the solid phase discharge port 6; an inverted triangle plane structure, wherein the upper part is provided with a filter screen 12 (mesh number is 30), and the lower part is provided with a flat plate 13; the height ratio of the filter screen 12 to the flat plate 13 is 1:0.5.
Example 2 (S1)
High-purity all-trans vitamin a acetate and its derivative crystals were prepared using the optical channel reactor prepared in example 1:
the vitamin A acetate and derivative isomer raw materials comprise, by total mass, 100%, 40% of 11-cis vitamin A acetate, 10% of 9-cis vitamin A acetate, 5% of 13-cis vitamin A acetate, 20% of impurities and 25% of all-trans vitamin A acetate.
1) Starting an LED light source (light source power is 400W) in the reactor, wherein a light-emitting wave band is 400-500nm, illumination intensity is 620Lux, respectively conveying coolant/heating medium fluid to triangular channels in a segmented mode, and controlling the temperature in diamond-like prism channels to gradually decrease from 15 ℃ to-15 ℃ from a feed inlet to a solid-liquid phase discharge outlet;
2) Mixing 25kg/h of vitamin A acetate and derivative isomer raw materials with 500ppm of photosensitizer erythrosine and ethanol solvent with the same mass as the vitamin A acetate and derivative isomer raw materials at 15 ℃ and 500rpm stirring speed, then feeding the mixture into a rhombus prism channel from a feed inlet, controlling the feed amount not to exceed a reaction liquid channel formed by light-emitting plates, and carrying out photocatalytic isomerization reaction, wherein the residence time of the reaction liquid in a light channel reactor is 5min, so as to generate all-trans vitamin A acetate and derivatives thereof;
3) And 2) in the diamond-like prism channel, all-trans vitamin A acetate and derivatives thereof generated in the step 2) are gradually separated out in a crystal form from a feed inlet to a discharge outlet, are enriched at the bottom of a reaction liquid channel to form a solid-liquid two-phase fluid channel, are subjected to solid-liquid separation at the discharge outlet through a solid catcher, the solid phase is discharged from a solid-phase discharge outlet, and the liquid is discharged from a liquid-phase discharge outlet, so that high-purity all-trans vitamin A acetate crystals and reaction liquid after the crystals are removed are obtained.
The reaction liquid after the removal of the crystals can be recycled for secondary photocatalytic isomerization reaction.
And (3) subtracting the solvent from the crystals collected by the reaction, and then carrying out composition analysis on the content of vitamin A acetate isomers, and carrying out full composition analysis on the reaction solution.
The results show that: the isomerization conversion rate of the vitamin A acetate isomer to the all-trans vitamin A acetate is 95.6%, the content (purity) of the all-trans vitamin A acetate in the obtained crystal is 98wt%, 19.8kg/h of crystal can be obtained per hour, and the total yield of the all-trans vitamin A acetate is 97.6%.
Example 3 (S2)
High-purity all-trans vitamin a acetate and its derivative crystals were prepared using the optical channel reactor prepared in example 1:
The vitamin A acetate and derivative isomer raw materials comprise, by total mass, 100%, 30% of 11-cis vitamin A acetate, 15% of 9-cis vitamin A acetate, 10% of 13-cis vitamin A acetate, 10% of impurities and 65% of all-trans vitamin A acetate.
1) Starting an LED light source (the power of the light source is 400W) in the reactor, the light-emitting wave band is 400-500nm, the illumination intensity is 500Lux, the coolant/heating medium fluid is respectively transported to the triangular channels in a segmented mode, the temperature in the diamond-like prism channels is controlled to gradually decrease from 15 ℃ to-30 ℃ from the feed inlet to the solid-liquid phase discharge outlet;
2) Mixing 25kg/h of vitamin A acetate and derivative isomer raw materials with 200ppm of photosensitizer erythrosine, adding 2 wt% of stabilizer sodium iodate serving as a photosensitizer, and acetonitrile solvent which is 0.2 times of the weight of the vitamin A acetate and derivative isomer raw materials, mixing at 15 ℃ and 500rpm, entering a rhombus prism-like channel from a feed inlet, controlling the feed amount not to exceed a reaction liquid channel formed by light-emitting plates, and carrying out photocatalytic isomerization reaction, wherein the retention time of the reaction liquid in a light channel reactor is 30min, so as to generate all-trans vitamin A acetate and derivatives thereof;
3) And 2) separating all-trans vitamin A acetate and derivatives thereof generated in the step 2) in a diamond-like prism channel from a feed inlet to a discharge outlet gradually in a crystal form, enriching the all-trans vitamin A acetate and derivatives thereof at the bottom of a reaction liquid channel to form a solid-liquid two-phase fluid channel, carrying out solid-liquid separation at the discharge outlet through a solid catcher, discharging a solid phase from a solid-phase discharge outlet, and discharging a liquid from a liquid-phase discharge outlet to obtain high-purity all-trans vitamin A acetate crystals and a reaction liquid after removing the crystals.
And (3) subtracting the solvent from the crystals collected by the reaction, and then carrying out composition analysis on the content of vitamin A acetate isomers, and carrying out full composition analysis on the reaction solution.
The results show that: the isomerization conversion rate of the vitamin A acetate isomer to the all-trans vitamin A acetate is 94.6%, the content (purity) of the all-trans vitamin A acetate in the obtained crystal is 97.2wt%, 22.8kg/h of crystal can be obtained per hour, and the total yield of the all-trans vitamin A acetate is 98.5%.
Example 4 (S3)
High-purity all-trans vitamin a acetate and its derivative crystals were prepared using the optical channel reactor prepared in example 1:
the vitamin A acetate and derivative isomer raw materials comprise, by total mass, 100%, 60% of 11-cis vitamin A acetate, 1% of 9-cis vitamin A acetate, 1% of 13-cis vitamin A acetate, 20% of impurities and 20% of all-trans vitamin A acetate.
1) Starting an LED light source (the power of the light source is 400W) in the reactor, the light-emitting wave band is 400-500nm, the illumination intensity is 700Lux, the coolant/heating medium fluid is respectively transported to the triangular channels in a segmented mode, the temperature in the diamond-like prism channels is controlled to gradually decrease from 15 ℃ to-30 ℃ from the feed inlet to the solid-liquid phase discharge outlet;
2) Mixing 25kg/h of vitamin A acetate and derivative isomer raw materials with 2000ppm of photosensitizer erythrosine, adding stabilizer sodium iodate accounting for 2% of the mass of the photosensitizer, and mixing n-hexane solution accounting for 1.5 times of the mass of the vitamin A acetate and derivative isomer raw materials at 15 ℃ and 500rpm stirring speed, then entering a rhombus prism channel from a feed inlet, controlling the feed amount not to exceed a reaction liquid channel formed by light-emitting plates, and carrying out photocatalytic isomerization reaction, wherein the retention time of the reaction liquid in a light channel reactor is 20min, so as to generate all-trans vitamin A acetate and derivatives thereof;
3) And 2) separating all-trans vitamin A acetate and derivatives thereof generated in the step 2) in a diamond-like prism channel from a feed inlet to a discharge outlet gradually in a crystal form, enriching the all-trans vitamin A acetate and derivatives thereof at the bottom of a reaction liquid channel to form a solid-liquid two-phase fluid channel, carrying out solid-liquid separation at the discharge outlet through a solid catcher, discharging a solid phase from a solid-phase discharge outlet, and discharging a liquid from a liquid-phase discharge outlet to obtain high-purity all-trans vitamin A acetate crystals and a reaction liquid after removing the crystals.
And (3) subtracting the solvent from the crystals collected by the reaction, and then carrying out composition analysis on the content of vitamin A acetate isomers, and carrying out full composition analysis on the reaction solution.
The results show that: the isomerization conversion rate of the vitamin A acetate isomer to the all-trans vitamin A acetate is 98.9%, the content (purity) of the all-trans vitamin A acetate in the obtained crystal is 96.3wt%, 20.6kg/h of crystal can be obtained per hour, and the total yield of the all-trans vitamin A acetate is 99.2%.
Example 5 (S3)
High-purity all-trans vitamin a acetate and its derivative crystals were prepared using the optical channel reactor prepared in example 1:
the vitamin A acetate and derivative isomer raw materials comprise, by total mass, 100%, 45% of 11-cis vitamin A acetate, 5% of 9-cis vitamin A acetate, 3% of 13-cis vitamin A acetate, 10% of impurities and 37% of all-trans vitamin A acetate.
1) Starting an LED light source (the power of the light source is 400W) in the reactor, the light-emitting wave band is 400-500nm, the illumination intensity is 570Lux, the coolant/heating medium fluid is respectively transported to the triangular channels in a segmented mode, and the temperature in the diamond-like prism channels is controlled to gradually decrease from 30 ℃ to 0 ℃ at the solid-liquid phase discharge ports from the feed inlet;
2) Mixing 25kg/h of vitamin A acetate and derivative isomer raw materials with 500ppm of photosensitizer erythrosine, and ethanol solution with the mass 1.0 times of the vitamin A acetate and derivative isomer raw materials at 15 ℃ and 500rpm stirring speed, then feeding the mixture into a rhombus prism channel from a feed inlet, controlling the feed amount not to exceed a reaction liquid channel formed by light-emitting plates, and carrying out photocatalytic isomerization reaction, wherein the residence time of the reaction liquid in a light channel reactor is 10min, so as to generate all-trans vitamin A acetate and derivatives thereof;
3) And 2) separating all-trans vitamin A acetate and derivatives thereof generated in the step 2) in a diamond-like prism channel from a feed inlet to a discharge outlet gradually in a crystal form, enriching the all-trans vitamin A acetate and derivatives thereof at the bottom of a reaction liquid channel to form a solid-liquid two-phase fluid channel, carrying out solid-liquid separation at the discharge outlet through a solid catcher, discharging a solid phase from a solid-phase discharge outlet, and discharging a liquid from a liquid-phase discharge outlet to obtain high-purity all-trans vitamin A acetate crystals and a reaction liquid after removing the crystals.
And (3) subtracting the solvent from the crystals collected by the reaction, and then carrying out composition analysis on the content of vitamin A acetate isomers, and carrying out full composition analysis on the reaction solution.
The results show that: the isomerization conversion rate of the vitamin A acetate isomer to the all-trans vitamin A acetate is 88%, the content (purity) of the all-trans vitamin A acetate in the obtained crystal is 98.2% by weight, 21.2kg/h of crystal can be obtained per hour, and the total yield of the all-trans vitamin A acetate is 92.5%.
Example 6 (S4)
The feed composition was referred to S2 in example 3, except that the stabilizer sodium iodate was not used in the feed solution, and the reaction conditions were the same as in example 3.
The results show that: the isomerization conversion rate of the vitamin A acetate isomer to the all-trans vitamin A acetate is 92.7%, the content (purity) of the all-trans vitamin A acetate in the obtained crystal is 97.96.2%, 19.5kg/h of crystal can be obtained per hour, and the total yield of the all-trans vitamin A acetate is 94.6%.
Comparative example 1 (S1)
The vitamin A acetate isomer feed composition is S2 in reference example 2, and the difference is that the reaction adopts a common full-mixing stirring kettle, a light source is positioned on the kettle wall, the power of the light source is the same as that of a diamond channel photoreactor, and the raw materials are put into the reaction kettle for intermittent reaction under the condition of ensuring the same proportion. The reaction temperature is maintained at 15 ℃, the reaction residence time is 5min, and the reaction temperature is gradually reduced to-15 ℃ through a jacket outside the reaction kettle after the reaction is finished.
After the reaction is finished, the reaction solution is filtered, the solvent acetonitrile is adopted for washing, and the obtained crystal is weighed and the purity is measured.
The results show that: the isomerization conversion rate of the vitamin A acetate isomer to the all-trans vitamin A acetate is 15.5%, 21kg/h of crystals are obtained, and the purity of the crystalline all-trans vitamin A acetate is 82.0%. Mainly because the solid is generated in the beginning of the reaction, the solid can scatter internal light, change the photocatalysis reaction dynamics, and further the other vitamin A acetate isomers are difficult to be converted into all-trans vitamin A acetate. Resulting in precipitation of 11-cis-vitamin A acetate, affecting purity.
Comparative example 2 (S2)
The feed composition was referenced to S2 in example 2, except that the top of the reactor had no secondary light reflection planes perpendicular to each other, and a flat seal was used, and the reaction conditions were the same as S2 in example 2.
The results show that: the isomerization conversion rate of the vitamin A acetate isomer to the all-trans vitamin A acetate is 47.6%, 19.7kg/h of crystals are obtained, the purity of the crystalline all-trans vitamin A acetate is 97.6%, and the yield is 85.4%. The yield is lowered mainly because there is no secondary light reflection plane perpendicular to each other, and the optical power is lowered. Without the secondary photoreaction plane, the optical efficiency is reduced by about 25%.
Comparative example 3 (S3)
The feed composition was referenced to S2 in example 2, except that the reactor did not use a crystal trap, and the other reaction conditions and reaction conditions were the same as S2 in example 2
After the reaction is finished, the reaction solution is filtered, the solvent acetonitrile is adopted for washing, and the obtained crystal is weighed and the purity is measured.
The results show that: 18.5kg/h of crystals are obtained, the purity of the crystalline all-trans vitamin A acetate is 96.7%, and the yield is reduced to 79.5%. The results show that the lack of a crystal trap results in smaller particle crystal losses, mainly due to the difficulty in settling the small particles, which flow out with the upper liquid in the liquid outlet flow channel.
Comparative example 4 (S4)
The feed composition was referenced to S2 in example 2, except that no photosensitizer was added during the reaction, and the reaction conditions were the same as S2 in example 2.
And filtering the reaction liquid after the reaction is finished, washing the reaction liquid by adopting solvent ethanol, weighing the obtained crystal, and measuring the purity.
The results show that: 19.5kg/h of crystals were obtained, with a purity of 75%, mainly because no photosensitizer was present and the reaction did not proceed, and the crystals obtained were crystalline products of all-trans vitamin A acetate and 11-cis vitamin A acetate.
Comparative example 5 (S5)
The feed composition was referenced to S2 in example 2, except that a constant temperature of 15 ℃ was maintained during the reaction, i.e. no heating and heat removal measures were taken, and the reaction conditions were the same as S2 in example 2.
After the reaction is finished, the reaction solution is filtered, the solvent acetonitrile is adopted for washing, and the obtained crystal is weighed and the purity is measured.
The results show that: no crystals were obtained in the reaction solution, indicating that the reaction did not precipitate crystals although the conversion reaction occurred at a constant temperature of 15 ℃. Analysis of the reaction solution showed that: the isomerization conversion rate of the 9-cis-vitamin A acetate and the 11-cis-vitamin A acetate to the all-trans-vitamin A acetate is 68%, and the conversion rate is lower, mainly because the reaction is an equilibrium reaction, and the forward reaction can not be carried out after the all-trans-vitamin A acetate is increased in the reaction liquid.
Comparative example 6 (S6)
The feed composition was referred to S2 in example 2, except that no solvent was used in the feed solution, and the reaction conditions were the same as S2 in example 2.
The results show that: the obtained crystal has the purity of 65.6 percent and about 17.3kg/h, the crystal has unqualified purity, the photosensitizer cannot be well dispersed because of no solvent, the reaction liquid has deep color, and the effective penetration distance of light rays is short, so that the reaction hardly occurs.
Claims (43)
1. The light channel reactor is characterized by comprising a prismatic channel with a cross section similar to a diamond, wherein the prismatic channel is formed by combining two light emitting plates and two reflecting plates;
the two light-emitting plates form two lower surfaces of the prismatic channel, and an included angle formed by fixed connection of the two light-emitting plates is 30-160 degrees, so that a reaction liquid flow channel is formed;
the two reflecting plates form two upper surfaces of the prism channel, and an included angle between the two upper surfaces is 60-120 degrees;
a light source is arranged on the light-emitting plate;
the square shell is enclosed outside the diamond-like prism channel, the upper edge, the lower edge and the side edge of the diamond-like prism channel are all in sealing connection with the shell to form a plurality of channels with triangular cross sections, and the triangular channels and the diamond-like prism channels are arranged in a staggered manner;
in the diamond-like prism channel, the lower half part consisting of two light-emitting plates is a reaction liquid flow channel, a feed inlet is arranged at the front end along the flow channel direction, a solid-phase discharge port is arranged at the bottom of the rear end, and a liquid-phase discharge port is arranged at the upper part of the rear end;
the triangular channel is a cold/hot medium flow channel and is provided with an inlet and an outlet.
2. The light tunnel reactor of claim 1 wherein the angle of the fixed connection between the two light emitting plates is 120-150 °.
3. The light tunnel reactor of claim 1 wherein the two reflectors form two upper surfaces of the prismatic tunnel and are fixedly connected at an angle of 90 °.
4. The light channel reactor according to claim 1, wherein a solid catcher is further arranged at the solid phase outlet of the diamond-like prism channel; the solid catcher is intercepted and arranged on the cross section of a reaction liquid flow channel formed by two light-emitting plates, the edges of the two sides of the solid catcher are respectively connected with the two light-emitting plates in a sealing way, and the upper edge is equal to the height of the light-emitting plates;
the solid catcher is of an inverted triangle plane structure with inclination, and the base angle of the inverted triangle plane is communicated with the solid-phase discharge port; the inverted triangle plane structure is characterized in that the upper part is a filter screen, and the lower part is a flat plate.
5. The light tunnel reactor of claim 4 wherein the inclination of the inverted triangular planar structure to the fluid is 20-70 °.
6. The light tunnel reactor of claim 5 wherein the inclination of the inverted triangular planar structure to face the fluid is 30-60 °.
7. The light tunnel reactor of claim 4 wherein the height ratio of screen to plate is 1:0.5-1.5.
8. The light tunnel reactor of claim 7 wherein the height ratio of screen to plate is 1:0.8-1.2.
9. The light tunnel reactor of claim 4 wherein the screen has a mesh size <40 mesh.
10. The light tunnel reactor of claim 9 wherein the mesh size of the screen is 20-30 mesh.
11. The light tunnel reactor of claim 1 wherein the diamond-like prismatic tunnel has a cross-section width to height ratio of 1:0.5-1;
the length of the diamond-like prism channel is 3-12m.
12. The light tunnel reactor of claim 11 wherein the diamond-like prismatic channels have a cross-section width to height ratio of 1:0.5-0.7;
the length of the diamond-like prism channel is 5-8m.
13. The light tunnel reactor of claim 1 wherein the plane formed by the upper and lower edges of the diamond-like prism tunnel is perpendicular to the horizontal plane of the light tunnel reactor.
14. The light channel reactor of claim 1, wherein the diamond-shaped prismatic channels are connected in parallel or in series; is a single layer or a multi-layer arrangement; wherein the number of the parallel connection is 1-10, and the number of the series connection is 1-8.
15. The light tunnel reactor of claim 14 wherein the diamond-shaped prismatic channels are arranged in parallel, in a single layer.
16. The optical channel reactor according to claim 14, wherein the number of parallel connections is 1-5; the number of the series connection is 2-4.
17. The light channel reactor according to claim 1, wherein the light channel reactor is arranged to be inclined, and the inclination angle between the central axis of the diamond-like prism channel and the horizontal plane of the light channel reactor is 5-15 degrees.
18. The light tunnel reactor of claim 17 wherein the central axis of the diamond-like prism tunnel is inclined at an angle of 5-10 ° to the horizontal plane of the light tunnel reactor.
19. The light channel reactor according to claim 1, wherein the luminescent plate roughness Ra <0.4 μm.
20. The light tunnel reactor of claim 19 wherein the light emitting plate roughness Ra = 0.2-0.4 μm.
21. The light tunnel reactor of claim 1 wherein the luminescent plate is made of aluminum alloy, stainless steel, or carbon steel.
22. The light tunnel reactor of claim 1 wherein the light source is selected from one of an incandescent lamp, an energy-saving lamp, a metal halogen lamp, an LED lamp, a fluorescent lamp, a xenon lamp, a mercury lamp, and an ultraviolet lamp.
23. The light channel reactor according to claim 1, wherein the light sources are uniformly distributed on the light emitting plate, and the number of the light sources is controlled by the power required for the actual reaction.
24. The light channel reactor according to claim 1, wherein the reflecting surface of the reflecting plate is subjected to polishing treatment, and the polishing degree Ra of the reflecting surface is less than 0.4;
the lower edges of the two reflecting plates are respectively connected with the upper edges of the two luminous plates.
25. The optical channel reactor according to claim 24, wherein the reflection surface polishing Ra = 0.2-0.3 μm.
26. The optical channel reactor according to claim 1, wherein the triangular channel is provided with a plurality of opposite inlets and outlets in a segmented manner, and the triangular channel is divided into a plurality of stages of channels.
27. The light tunnel reactor of claim 26 wherein the triangular tunnel is provided with 1-5 pairs of ports in sections.
28. Use of the light channel reactor according to any one of claims 1-27 in isomerisation reactions of vitamin a acetate and derivatives thereof.
29. A method for preparing high-purity all-trans vitamin a acetate and derivative crystals thereof, which is characterized in that the method adopts the optical channel reactor as claimed in any one of claims 1 to 27, and comprises the following steps:
1) Starting a light source in the reactor, respectively conveying coolant/heating medium fluid to the triangular channels in a segmented mode, and controlling the temperature in the diamond-like prism channels to be gradually decreased from the feed inlet to the solid-liquid phase discharge port;
2) Mixing vitamin A acetate and derivative isomer raw materials with a solvent and a photosensitizer, then entering a rhombus prism channel from a feed inlet, controlling the feed quantity not to exceed a reaction liquid channel formed by the light-emitting plates, and carrying out photocatalytic isomerization reaction to generate all-trans vitamin A acetate and derivatives thereof;
3) And 2) separating all-trans vitamin A acetate and derivatives thereof generated in the step 2) in a diamond-like prism channel from a feed inlet to a discharge outlet gradually in a crystal form, enriching the all-trans vitamin A acetate and derivatives thereof at the bottom of a reaction liquid channel to form a solid-liquid two-phase fluid channel, carrying out solid-liquid separation at the front end of the discharge outlet through a solid catcher, discharging a solid phase from a solid-phase discharge outlet, and discharging a liquid from a liquid-phase discharge outlet to obtain high-purity all-trans vitamin A acetate crystals and a reaction liquid after removing the crystals.
30. The method according to claim 29, wherein the temperature of the inlet in the diamond-like prism channel in step 1) is 15-30 ℃, and the temperature of the solid and liquid phase outlet is-30-5 ℃;
the photocatalytic isomerization reaction in the step 2) is carried out at the reaction temperature of-30-30 ℃ and the residence time of the reaction solution in the optical channel reactor is 3-30 min;
the light catalytic isomerization reaction has a light emitting wavelength of 350-520nm and an illumination intensity of more than 500 Lux.
31. The method according to claim 30, wherein the temperature of the inlet in the diamond-like prism channel is 1-20 ℃ and the temperature of the outlet in the solid and liquid phases is-30-5 ℃.
32. The method according to claim 30, wherein the photocatalytic isomerization reaction is carried out at a reaction temperature of-15 to 15 ℃ and the residence time of the reaction solution in the optical channel reactor is 5 to 15 min.
33. The method of claim 30, wherein the photocatalytic isomerization reaction has a luminescence wavelength of 400-450nm; the illumination intensity is 500-700Lux.
34. The method of claim 29, wherein step 2) comprises 11-cis, 9-cis, 13-cis, and all-trans vitamin a acetate and derivative isomers;
The solvent in the step 2) is selected from one or more of C5-C18 linear alkane, branched alkane, chloralkane, C6-C12 aromatic hydrocarbon, C1-C6 ether, alcohol and nitrile; wherein, one or more of the C5-C18 straight-chain alkane, branched alkane and chlorinated alkane; one or more of the aromatic hydrocarbons of C6-C9; one or more of ethers, alcohols and nitriles of C1-C6;
the photosensitizer in step 2) is selected from fluorescent or semi-fluorescent substances.
35. The method according to claim 34, wherein the solvent in step 2) is selected from one or more of n-hexane, n-heptane, petroleum ether, benzene, toluene, ethylbenzene, p-xylene, methanol, ethanol, propanol, isopropanol, butanol, cyclic ether, diethyl ether, acetonitrile, propionitrile;
the photosensitizer in the step 2) is selected from one or more of fluorescence 2.4.6-triphenylpyran/perchlorate, perylene, quinizarine, hydroquinone, beta-Xin Kefen, sodium eosin, rose bengal, erythrosin, euclidean Xin Cheng, rhodamine, and vinylestrol.
36. The method according to claim 29, wherein the vitamin a acetate and derivative isomer starting material in step 2) comprises, based on 100% of the total mass:
30-60% of 11-cis-vitamin A acetate and derivatives;
1-15% of 9-cis-vitamin A acetate and derivatives;
1-10% of 13-cis-vitamin A acetate and derivatives;
20-70% of all-trans vitamin A acetate and derivatives.
37. The method according to claim 36, wherein the vitamin a acetate and derivative isomer starting material in step 2) comprises, based on 100% of the total mass:
40-60% of 11-cis-vitamin A acetate and derivatives;
1-10% of 9-cis-vitamin A acetate and derivatives;
1-5% of 13-cis-vitamin A acetate and derivatives;
50-60% of all-trans vitamin A acetate and derivatives.
38. The method according to claim 29, wherein the solvent is used in the amount of 0.2 to 1.5 times the mass of the starting material of the vitamin a acetate and its derivative isomers in step 2).
39. The method according to claim 38, wherein the solvent is used in an amount of 0.5 to 1 times the mass of the starting material of the vitamin a acetate and its derivative isomers.
40. The method of claim 29, wherein the photosensitizer is used in an amount of 50-2000ppm based on vitamin a acetate and its derivative isomer starting material in step 2).
41. The method of claim 40, wherein the photosensitizer is used in an amount of 200-500ppm based on vitamin A acetate and its derivative isomers in step 2).
42. The method of claim 29, wherein the sodium iodate stabilizer is added to the photosensitizer in step 2) in an amount of 1-3% of the mass of the photosensitizer.
43. The method of claim 42, wherein the photosensitizer is added with sodium iodate as a stabilizer in an amount of 2% of the mass of the photosensitizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210048167.XA CN114367253B (en) | 2022-01-17 | 2022-01-17 | Optical channel reactor and preparation method of high-purity all-trans vitamin A acetate and derivative crystal thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210048167.XA CN114367253B (en) | 2022-01-17 | 2022-01-17 | Optical channel reactor and preparation method of high-purity all-trans vitamin A acetate and derivative crystal thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114367253A CN114367253A (en) | 2022-04-19 |
| CN114367253B true CN114367253B (en) | 2024-04-09 |
Family
ID=81144777
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210048167.XA Active CN114367253B (en) | 2022-01-17 | 2022-01-17 | Optical channel reactor and preparation method of high-purity all-trans vitamin A acetate and derivative crystal thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114367253B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1653002A (en) * | 2002-05-10 | 2005-08-10 | 特洛伊人技术公司 | Double-walled chamber for ultra violet radiation treatment of liquids |
| CN103052441A (en) * | 2010-08-03 | 2013-04-17 | 国立大学法人信州大学 | Optical reactor and method for manufacturing same |
| KR20130116396A (en) * | 2012-03-07 | 2013-10-24 | 부경대학교 산학협력단 | Photoreactor with external light source |
| JP2014223598A (en) * | 2013-05-17 | 2014-12-04 | 株式会社神戸製鋼所 | Microchannel reactor |
| CN204051075U (en) * | 2014-08-06 | 2014-12-31 | 中国石油天然气股份有限公司 | Stainless steel grid packing capable of being cleaned on line for oil-water separation of produced liquid |
| CN104492358A (en) * | 2014-12-11 | 2015-04-08 | 福建师范大学 | Photocatalytic reactor |
| CN205761110U (en) * | 2016-07-19 | 2016-12-07 | 陕西理工大学 | A kind of photo catalysis reactor |
| CN107807112A (en) * | 2016-09-08 | 2018-03-16 | 中国科学院大连化学物理研究所 | A kind of light derivatization device of aflatoxin and sulfa drugs |
| JP2021028965A (en) * | 2019-08-10 | 2021-02-25 | Hoya株式会社 | Light irradiation device |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6771866B2 (en) * | 1998-09-02 | 2004-08-03 | Keiji Iimura | Photocatalyst apparatus, method of manufacture thereof and photocatalyst reactor |
| JP2004333404A (en) * | 2003-05-12 | 2004-11-25 | Hitachi Ltd | Micro-reactor, its manufacturing method and sample screening device |
-
2022
- 2022-01-17 CN CN202210048167.XA patent/CN114367253B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1653002A (en) * | 2002-05-10 | 2005-08-10 | 特洛伊人技术公司 | Double-walled chamber for ultra violet radiation treatment of liquids |
| CN103052441A (en) * | 2010-08-03 | 2013-04-17 | 国立大学法人信州大学 | Optical reactor and method for manufacturing same |
| KR20130116396A (en) * | 2012-03-07 | 2013-10-24 | 부경대학교 산학협력단 | Photoreactor with external light source |
| JP2014223598A (en) * | 2013-05-17 | 2014-12-04 | 株式会社神戸製鋼所 | Microchannel reactor |
| CN204051075U (en) * | 2014-08-06 | 2014-12-31 | 中国石油天然气股份有限公司 | Stainless steel grid packing capable of being cleaned on line for oil-water separation of produced liquid |
| CN104492358A (en) * | 2014-12-11 | 2015-04-08 | 福建师范大学 | Photocatalytic reactor |
| CN205761110U (en) * | 2016-07-19 | 2016-12-07 | 陕西理工大学 | A kind of photo catalysis reactor |
| CN107807112A (en) * | 2016-09-08 | 2018-03-16 | 中国科学院大连化学物理研究所 | A kind of light derivatization device of aflatoxin and sulfa drugs |
| JP2021028965A (en) * | 2019-08-10 | 2021-02-25 | Hoya株式会社 | Light irradiation device |
Non-Patent Citations (2)
| Title |
|---|
| 基于微流体通道的柱状预浓缩器的设计与仿真;程洁;李明;叶一霏;袁明宇;刘洋;赵阳;黄成军;;微纳电子技术(第05期) * |
| 程洁 ; 李明 ; 叶一霏 ; 袁明宇 ; 刘洋 ; 赵阳 ; 黄成军 ; .基于微流体通道的柱状预浓缩器的设计与仿真.微纳电子技术.2018,(第05期), * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114367253A (en) | 2022-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zechmeister | Cis-trans isomeric carotenoids, vitamins A and arylpolyenes | |
| CN1301985C (en) | Method for extracting Vitamin C and gulonic acid from Vitamin C mother liquor | |
| CN102850248A (en) | Technology for preparing vitamin D3 | |
| CN112221444B (en) | System and method for continuously synthesizing clethodim | |
| CN114367253B (en) | Optical channel reactor and preparation method of high-purity all-trans vitamin A acetate and derivative crystal thereof | |
| CN110878112B (en) | Gas separation flow system and method for photochemical synthesis of 9-beta, 10-alpha-dehydroprogesterone ketal | |
| CN103848880A (en) | Method for preparing 9 beta, 10-alpha-dehydroprogesterone ketal by using dual-wavelength microfluidic technology and dual-wavelength microfluidic photochemical reactor | |
| CN101538051A (en) | Method for preparing ZSM-5 zeolite catalyst | |
| CN103553993B (en) | Synthesis of resinous vitamin D by using micro-flow photoreaction technology3Method and microfluidic photochemical reactor | |
| CN114957070B (en) | Method for synthesizing apoester | |
| KR20150133833A (en) | Protein Production Method | |
| CN111205209A (en) | Device and method for preparing vitamin A acetate through multistage continuous series reaction extraction | |
| CN114031621B (en) | Improved ketorolac preparation method | |
| CN114605271A (en) | Method for synthesizing tetrabutylammonium bromide | |
| CN105439824B (en) | The synthetic method of piceatannol | |
| CN106632860A (en) | Glucosan-based cryogel microsphere separating medium and preparation method thereof | |
| CN1034197A (en) | The method for preparing dihydroxyphenyl propane | |
| Lisewski et al. | Solid state photochemistry of thymine, its N‐methylated derivatives and orotic acids in KBr matrices | |
| CN1231509C (en) | Method for producing gel-type cation exchangers | |
| CN102627520B (en) | Process for isomerization of lycopene in presence of thiourea | |
| CN1368495A (en) | Process for directly synthesizing dimethyl carbonate from CO2 and methanol | |
| CN114605332A (en) | Preparation process of metronidazole | |
| CN102153448B (en) | Method for preparing low-level alkanol aluminum by gas-solid phase reaction | |
| CN110668990A (en) | Crystallization method for preparing high-purity monodisperse I crystal form atorvastatin calcium in single kettle | |
| CN115850189A (en) | Method for continuous flow synthesis of 5-bromo-6-cyclopropylpyrimidine-4-ol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |