CN103880851B - The continuous production processes of four metal arylide porphyrins - Google Patents
The continuous production processes of four metal arylide porphyrins Download PDFInfo
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- CN103880851B CN103880851B CN201410087459.XA CN201410087459A CN103880851B CN 103880851 B CN103880851 B CN 103880851B CN 201410087459 A CN201410087459 A CN 201410087459A CN 103880851 B CN103880851 B CN 103880851B
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 30
- 239000002184 metal Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000010924 continuous production Methods 0.000 title claims abstract description 12
- 150000004032 porphyrins Chemical class 0.000 title abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 298
- 238000003756 stirring Methods 0.000 claims abstract description 125
- 239000002994 raw material Substances 0.000 claims abstract description 52
- 239000002904 solvent Substances 0.000 claims abstract description 44
- 238000010992 reflux Methods 0.000 claims abstract description 34
- 230000001360 synchronised effect Effects 0.000 claims abstract description 29
- 230000005484 gravity Effects 0.000 claims abstract description 15
- 238000011049 filling Methods 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- 239000012295 chemical reaction liquid Substances 0.000 claims description 38
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 32
- 238000000926 separation method Methods 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical class N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 claims description 23
- 150000003839 salts Chemical class 0.000 claims description 23
- -1 halide salt Chemical class 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052804 chromium Inorganic materials 0.000 claims description 16
- 239000011651 chromium Substances 0.000 claims description 16
- 229910017052 cobalt Inorganic materials 0.000 claims description 16
- 239000010941 cobalt Substances 0.000 claims description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- 229910052720 vanadium Inorganic materials 0.000 claims description 16
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052725 zinc Inorganic materials 0.000 claims description 16
- 239000011701 zinc Substances 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- 239000008096 xylene Substances 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N CHCl3 Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical group 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 abstract 6
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 239000000047 product Substances 0.000 description 67
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 238000005406 washing Methods 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 14
- 239000007787 solid Substances 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- HJTAXGKRJGUCNN-UHFFFAOYSA-N [Mg].c1cc2nc1c(-c1ccccc1)c1ccc([nH]1)c(-c1ccccc1)c1ccc(n1)c(-c1ccccc1)c1ccc([nH]1)c2-c1ccccc1 Chemical compound [Mg].c1cc2nc1c(-c1ccccc1)c1ccc([nH]1)c(-c1ccccc1)c1ccc(n1)c(-c1ccccc1)c1ccc([nH]1)c2-c1ccccc1 HJTAXGKRJGUCNN-UHFFFAOYSA-N 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 9
- JZRYQZJSTWVBBD-UHFFFAOYSA-N pentaporphyrin i Chemical compound N1C(C=C2NC(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JZRYQZJSTWVBBD-UHFFFAOYSA-N 0.000 description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 4
- 229960002089 ferrous chloride Drugs 0.000 description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 4
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 4
- 229940071125 manganese acetate Drugs 0.000 description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- YNZSKFFENDBGOV-UHFFFAOYSA-N [V].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [V].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 YNZSKFFENDBGOV-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- KIQQAJNFBLKFPO-UHFFFAOYSA-N magnesium;porphyrin-22,23-diide Chemical compound [Mg+2].[N-]1C(C=C2[N-]C(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 KIQQAJNFBLKFPO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses the continuous production processes of four metal arylide porphyrins, this technique first solvent is joined heterogeneous reaction to be separated in synchronous reaction device, described reactor comprises the stirring reaction tower with reflux, with at least two constant temperature sedimentation towers be communicated with stirring reaction tower bottom; Described stirring reaction Ta Tanei comprises gas phase zone, reaction zone; During reaction, described solvent is full of in reaction zone and constant temperature sedimentation tower, when raised temperature reaches the reflux temperature of solvent, reaction raw materials four aryl porphines and metal-salt are joined in stirring reaction tower and react or react under the condition passing into air, the four metal arylide porphyrins that reaction generates enter constant temperature sedimentation tower from the direct sedimentation in reaction zone under gravity, until when filling four metal arylide porphyrins in constant temperature sedimentation tower, described stirring reaction tower is switched to the constant temperature sedimentation tower filling solvent with another be communicated with, hocket thus, carry out continuous seepage; This technique energy high yield, low cost, continuous prodution high purity four metal arylide porphyrin.
Description
Technical Field
The invention relates to a continuous production process of tetraaryl metalloporphyrin, belonging to the field of catalyst synthesis.
Background
Metalloporphyrin is widely used as a hydrocarbon air oxidation catalyst, and can also be used as a luminescent material. In the laboratory, tetraarylporphine TRPPH (2) is commonly used as tetraarylporphine TRPPH2(1) With metal salts M in DMF2+The metallization preparation of (2):
whereas the tetraaryltrivalent metalloporphyrin TRPPMX (3) is generally prepared by reacting tetraarylporphine TRPPPH in the presence of an oxidizing agent2(1) With metal salts M in DMF2+The metallization preparation of (2):
tetraarylporphine TRPPH2The metallization process of (a) is a reversible process, and a large excess of metal salt is needed when preparing the tetraaryl metalloporphyrin TRPPM; in addition, tetraarylporphine TRPPH2And tetraarylmetalloporphyrin TRPPM, and the solubility of the product tetraarylmetalloporphyrin TRPPM was inferior to that of the reactant tetraarylporphine TRPPH2The worse. Therefore, the preparation of tetraaryl metalloporphyrins can only be carried out in dilute solutions. Despite the above measures, the synthesized tetraarylmetalloporphyrin product still contains a small amount of raw tetraarylporphin, and further chromatographic separation is required to obtain purified tetraarylmetalloporphyrin. The characteristics in the synthesis of the tetraaryl metalloporphyrin cause the difficulty of product purification in the industrial mass production of the metalloporphyrin and the treatment of a large amount of solvents, thereby increasing the production cost.
Disclosure of Invention
The invention aims to provide a process for continuously producing high-purity tetraaryl divalent metalloporphyrin by using tetraaryl porphin and metal salt as raw materials through simple process conditions at high yield and low cost.
Another objective of the present invention is to provide a process for continuously producing high purity tetraaryl trivalent metalloporphyrin from tetraaryl porphin, divalent metal salt and air by simple process conditions with high yield and low cost.
The invention provides a process for continuously producing tetraaryl metalloporphyrin by using tetraaryl porphin and metal salt as raw materials, which comprises the steps of adding a solvent into a multiphase reaction separation synchronous reactor, wherein the multiphase reaction separation synchronous reactor comprises a stirring reaction tower with a reflux device and at least two constant-temperature settling towers communicated with the bottom of the stirring reaction tower; the stirring reaction tower comprises an upper gas phase area, a middle and lower reaction area, a reflux device connecting port at the top and a raw material feeding port; a stirrer is arranged in the reaction zone of the stirring reaction tower; during reaction, filling a solvent into the reaction zone and the constant-temperature settling tower, mixing reaction raw materials of tetraaryl porphin and metal salt according to a molar ratio of 1: 1-2 when the temperature is raised to reach the reflux temperature of the solvent, adding the mixture into the stirring reaction tower in batches or continuously from a raw material inlet at the top of the stirring reaction tower for reaction, separating out tetraaryl metalloporphyrin crystals when the concentration of tetraaryl metalloporphyrin products in reaction liquid reaches the saturation solubility, directly settling from the reaction zone of the stirring reaction tower under the action of gravity and entering the constant-temperature settling tower, and extruding and rising the liquid in the constant-temperature settling tower by the settled tetraaryl metalloporphyrin to enter the stirring reaction tower; the reaction is continuously carried out until the constant temperature settling tower is filled with the tetraaryl metalloporphyrin, the stirring reaction tower is switched to be communicated with the other constant temperature settling tower filled with the solvent, and the constant temperature settling tower filled with the tetraaryl metalloporphyrin is taken down for treatment, thereby alternately carrying out the treatmentCarrying out continuous production; the solvent is benzene, toluene, xylene and CH2Cl2、CHCl3And one or more of DMF.
The scheme is suitable for the reaction without introducing air in the reaction process of raw materials.
The metal salt applicable to the scheme is one of soluble acetate or halide salt or acetylacetone salt of cobalt, zinc, copper, nickel, magnesium or vanadium.
The invention also provides a process for continuously producing the tetraaryl metalloporphyrin by taking the tetraaryl porphin, the divalent metal salt and the air as raw materials, wherein the process comprises the steps of firstly adding a solvent into a multiphase reaction separation synchronous reactor, wherein the multiphase reaction separation synchronous reactor comprises a stirring reaction tower with a reflux device and at least two constant-temperature settling towers which are communicated with the bottom of the stirring reaction tower; the stirring reaction tower comprises an upper gas phase area, a middle and lower reaction area, a reflux device connecting port at the top and a raw material feeding port; a stirrer is arranged in the reaction zone of the stirring reaction tower; during reaction, filling a solvent into the reaction zone and the constant-temperature settling tower, mixing reaction raw materials of the tetraarylporphin and the divalent metal salt according to a molar ratio of 1: 1-2 when the temperature is raised to reach the reflux temperature of the solvent, continuously or in batches adding the tetraarylporphin and the divalent metal salt from a raw material inlet at the top of the stirring reaction tower, and air is continuously introduced from the bottom of the stirring reaction tower, is dispersed by a gas distributor and then contacts with the tetraaryl porphin and the divalent metal salt in the reaction zone to react, when the reaction is carried out until the concentration of the tetraaryl metalloporphyrin product in the reaction liquid reaches the saturation solubility, the tetraaryl metalloporphyrin crystal is separated out, simultaneously directly settling from the reaction area of the stirring reaction tower under the action of gravity and entering a constant-temperature settling tower, at the moment, the reaction liquid in the constant-temperature settling tower is extruded by settled tetraaryl metalloporphyrin to rise into the stirring reaction tower; the reaction is continuously carried out until the constant temperature settling tower is filled with the tetraaryl metalloporphyrin, the stirring reaction tower is switched to be communicated with the other constant temperature settling tower filled with the solvent, and the constant temperature settling tower is filled with the solventTaking down the tetraaryl metalloporphyrin by a constant-temperature settling tower, and alternately carrying out continuous production; the solvent is benzene, toluene, xylene and CH2Cl2、CHCl3And one or more of DMF.
The scheme is suitable for the reaction needing air in the raw material reaction process.
The divalent metal salt suitable for use in the above scheme of the present invention is a divalent acetate or a divalent halide salt of iron, manganese or chromium.
The reaction raw materials are continuously or batchwise added to maintain the concentration of the tetraaryl porphin in the reaction solution at 1-5 wt%
And the excessive solvent in the stirring reaction tower is extracted from a reflux device at the top of the stirring reaction tower.
And the unreacted gas part enters a gas phase zone at the upper part of the stirring reaction tower, and is discharged and emptied through a reflux device at the top of the stirring reaction tower.
The tetraaryl porphin has a structure shown in a formula 1; the divalent metalloporphyrin has a structure of formula 2; the trivalent metalloporphyrin has a structure shown in a formula 3;
wherein,
r is hydrogen atom, alkyl, alkoxy, hydroxyl, halogen, amino or nitro;
in the divalent metal porphyrin, M is cobalt, zinc, copper, nickel, magnesium or vanadium;
in the trivalent metal porphyrin, M is iron, manganese, chromium, cobalt or vanadium.
The solubility of the tetraaryl metalloporphyrin product obtained by the reaction in the reaction liquid is less than that of the tetraaryl porphin, when the solubility of the tetraaryl metalloporphyrin in the reaction liquid reaches saturation, the reaction raw material, namely the tetraaryl porphin, is added to further move in the positive direction, a tetraaryl metalloporphyrin crystal is separated out, and the tetraaryl metalloporphyrin crystal is timely settled and separated by utilizing the property that the specific gravity of the tetraaryl metalloporphyrin is greater than that of the reaction liquid and other intermediate products, so that the reaction continuously moves in the positive direction.
The boundary between the reaction zone at the middle lower part and the gas phase zone is the height of the stirring reaction tower from the tower top to the tower wall which is more than or equal to 1/3.
And directly taking out the tetraaryl metalloporphyrin product in the constant-temperature settling tower, performing suction filtration, washing with hot water and washing with ethanol to obtain a pure tetraaryl metalloporphyrin product.
The water generated by the reaction and the solvent form an azeotrope which is extracted by refluxing through a reflux device.
The diameter-height ratio of the stirring reaction tower is 1: 20-40; preferably 1: 25-35; most preferably 1: 30.
The production process realizes continuous production by continuously and alternately switching the constant-temperature settling tower and taking down the constant-temperature settling tower filled with the tetraaryl metalloporphyrin.
The gas-liquid-solid multiphase reaction separation synchronous reactor comprises a stirring reaction tower and at least two constant temperature settling towers communicated with the bottom of the stirring reaction tower.
The stirring reaction tower comprises an upper gas phase area, a middle and lower reaction area, a top reflux device connecting port and a reaction raw material feeding port; the boundary between the reaction zone at the middle lower part and the gas phase zone is the height of the stirring reaction tower from the tower top to the tower wall which is more than or equal to 1/3.
In the stirring reaction tower, when gas needs to be introduced for reaction, a gas raw material inlet and a gas distributor can be arranged at the lower part in the stirring reaction tower.
And a connecting port at the bottom of the stirring reaction tower is connected with at least two constant temperature settling towers with the same structure and size.
And a stirrer is arranged in the reaction zone of the stirring reaction tower.
The top of the constant temperature settling tower is provided with a connecting port connected with the bottom of the stirring reaction tower; a solvent feeding port is formed in the upper part of the constant-temperature settling tower, and a product discharging port is formed in the lower part of the constant-temperature settling tower; and a bottom connecting port of the stirring reaction tower is connected with a connecting port at the top of the constant-temperature settling tower through a tee.
The top of the constant-temperature settling tower is also provided with a manhole and an observation hole.
The invention has the beneficial effects that: the invention utilizes the physicochemical characteristics of relatively low solubility of the tetraaryl metalloporphyrin and relatively high specific gravity of the intermediate product and the solvent for the first time, combines the reactor which is designed for liquid-solid or gas-liquid-solid multiphase reaction and synchronously performs reaction and separation, can react the tetraaryl porphine with metal salt or generate the tetraaryl metalloporphyrin through air oxidation, and simultaneously synchronously separates the generated tetraaryl metalloporphyrin product from an oxidation reaction system, thereby realizing the high-yield and high-selectivity continuous production of the high-purity tetraaryl metalloporphyrin and greatly reducing the production cost of the tetraaryl metalloporphyrin. The multiphase reaction separation synchronous reactor can timely separate the generated tetraaryl metalloporphyrin product, breaks through chemical equilibrium to enable the reaction to move to the positive direction, enables the reaction to be continuously carried out, on one hand, the product is precipitated at the reaction temperature, effectively avoids the phenomenon that the tetraaryl porphin raw material and the tetraaryl metalloporphyrin product are eutectoid in the cooling crystallization process in the prior art, effectively improves the product purity, and solves the defect that the product purity is reduced because a large amount of metal salt which is difficult to remove exists in the product due to the fact that the reaction molar ratio of the metal salt and the tetraaryl porphin is close to 1:1, and the problem that the balance moves to the positive direction because the concentration of the metal salt is excessive by more than 10 times in the prior art is solved, and simultaneously, the tetraaryl metalloporphyrin product is timely separated from an oxidation reaction system, and the side reactions such as high-temperature demetalization of the tetraaryl metalloporphyrin product are avoided, the yield is effectively improved; on the other hand, the production is continuously carried out, thereby effectively avoiding the use of a large amount of solvents and the recovery and treatment process of the solvents in the prior art, simplifying the process, reducing the energy consumption and greatly reducing the production cost. The reflux device provided by the invention can extract excessive solvent and water generated by reaction, can exhaust unreacted gas part when gas participates in the reaction, and simultaneously recycles the solvent carried by the air by refluxing, thereby not only ensuring the balance of a reaction system, but also continuously carrying out the reaction, reducing the energy consumption and reducing the environmental pollution. In conclusion, the process can continuously synthesize high-purity tetraaryl metalloporphyrin with high yield and low cost, the yield reaches more than 99 percent, and the purity of the tetraaryl metalloporphyrin in the product reaches more than 99 percent.
Drawings
FIG. 1 shows a liquid-solid multiphase reaction separation synchronous reactor according to the present invention;
FIG. 2 shows a gas-liquid-solid multiphase reaction separation synchronous reactor according to the present invention;
a is a top interface diagram of the constant temperature settling tower 11;
b is a top interface diagram of the stirring reaction tower 1;
c is a reflux device;
description of the figure numbers: 1 is a stirring reaction tower, 2 is a reflux device interface, 3 is a gas raw material inlet, 4 is a gas distributor, 5 is a manhole, 6 is a solvent inlet, 7 is a reaction raw material inlet, 8 is a product outlet, 9 is an observation hole, 10 is a three-way pipe, 11 is a constant temperature settling tower I, 12 is a constant temperature settling tower II, 13 is a stirrer, 14 is a heating jacket, 15 is a spherical condenser pipe, 16 is a water separator, and 17 and 18 are connectors.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the invention.
Example 1
Adopting a liquid-solid multiphase reaction separation synchronous reactor shown in figure 1, and carrying out air oxidation on tetra-p-propylphenyl porphin and cobalt acetate serving as raw materials to prepare a tetra-p-propylphenyl porphyrin cobalt product; wherein the height ratio of the stirring reaction tower diameter is 1: 20; the device is provided with a constant temperature settling tower I and a constant temperature settling tower II which are the same in size and consistent in structure; the reaction liquid outlet is arranged at the tower height position of 4/9 position at the top of the reaction tower.
Controlling a tee joint below a stirring reaction tower to communicate the stirring reaction tower with a constant-temperature settling tower I, adding toluene into a multiphase reaction separation synchronous reactor from a solvent feeding port at the top of the constant-temperature settling tower until a reaction zone of the stirring reaction tower and the constant-temperature settling tower I are filled, mixing tetra-p-propylphenyl porphin and cobalt acetate according to a molar ratio of 1:1 when the temperature is raised to reach the toluene reflux temperature, continuously adding the tetra-p-propylphenyl porphin from a raw material feeding port at the top of the stirring reaction tower, maintaining the concentration of the tetra-p-propylphenyl porphin in a reaction liquid to be 1wt% for reaction, separating out tetra-p-propylphenyl porphin cobalt crystals when the concentration of a tetra-p-propylphenyl porphin cobalt product in the reaction liquid reaches a saturation solubility, directly settling the tetra-p-propylphenyl porphin cobalt from the reaction zone of the stirring reaction tower under the action of gravity, and feeding the tetra-p-propylphenyl porphin cobalt into the constant-temperature settling tower I, wherein the reaction liquid in the constant Putting the mixture into a stirring reaction tower; continuously carrying out the reaction until the constant temperature settling tower I is filled with the tetra-p-propyl phenyl porphyrin cobalt, switching the stirring reaction tower to be communicated with a constant temperature settling tower II filled with toluene through three-way control, taking down the constant temperature settling tower I, directly taking out the tetra-p-propyl phenyl porphyrin cobalt, carrying out suction filtration, washing with hot water and washing with ethanol to obtain a pure tetra-p-propyl phenyl porphyrin cobalt product; thus, the production is performed alternately and continuously. And after the reaction is stable, sampling every 4 hours to detect the purity of the tetra-p-propylphenyl porphyrin cobalt product, detecting the amount of the tetra-p-propylphenyl porphyrin cobalt product and the components of the reaction solution, and calculating the yield and the purity of the tetra-p-propylphenyl porphyrin cobalt, wherein the results are shown in table 1.
TABLE 1 relationship between reaction time and cobalt tetra-p-propylphenylporphyrin product yield and purity
Example 2
Adopting a liquid-solid multiphase reaction separation synchronous reactor shown in figure 1, and carrying out air oxidation on tetra-p-methoxyphenyl porphin and zinc acetate serving as raw materials to prepare a tetra-p-methoxyphenyl porphyrin zinc product; wherein the height ratio of the stirring reaction tower diameter is 1: 20; the device is provided with a constant temperature settling tower I and a constant temperature settling tower II which are the same in size and consistent in structure; the reaction liquid outlet is arranged at the tower height position of 4/9 position at the top of the reaction tower.
Controlling a tee joint below a stirring reaction tower to communicate the stirring reaction tower with a constant-temperature settling tower I, adding xylene into a multiphase reaction separation synchronous reactor from a solvent feeding port at the top of the constant-temperature settling tower until a reaction zone of the stirring reaction tower and the constant-temperature settling tower I are filled, mixing tetra-p-methoxyphenyl porphine and zinc acetate according to a molar ratio of 1:1.2 when the temperature is raised to reach the reflux temperature of the xylene, continuously adding the tetra-p-methoxyphenyl porphine from a raw material feeding port at the top of the stirring reaction tower, maintaining the concentration of the tetra-p-methoxyphenyl porphine in a reaction liquid to be 1.5wt% for reaction, separating out tetra-p-methoxyphenyl porphyrin zinc crystals when the concentration of a tetra-p-methoxyphenyl porphyrin zinc product in the reaction liquid reaches a saturated solubility, and directly settling the tetra-p-methoxyphenyl porphyrin zinc from the reaction zone of the stirring reaction tower into the constant-temperature settling tower I under the action of gravity, at the moment, the reaction liquid in the constant-temperature settling tower I is extruded and ascended by settled zinc tetra-p-methoxyphenyl porphyrin to enter a stirring reaction tower; continuously carrying out the reaction until the constant temperature settling tower I is filled with the zinc tetra-p-methoxyphenyl porphyrin, switching the stirring reaction tower to be communicated with the constant temperature settling tower II filled with the dimethylbenzene through three-way control, taking down the constant temperature settling tower I, directly taking out the zinc tetra-p-methoxyphenyl porphyrin, carrying out suction filtration, washing with hot water and washing with ethanol to obtain a pure zinc tetra-p-methoxyphenyl porphyrin product; thus, the production is performed alternately and continuously. And after the reaction is stable, sampling every 4 hours to detect the purity of the zinc tetra-p-methoxyphenylporphyrin product, detecting the amount of the raw material of the tetra-p-methoxyphenylporphyrin entering the reaction system and the obtained zinc tetra-p-methoxyphenylporphyrin product and the components of the reaction solution, and calculating the yield and the purity of the zinc tetra-p-methoxyphenylporphyrin, wherein the results are shown in table 2.
TABLE 2 correlation of reaction time and zinc tetra-p-methoxyphenylporphyrin product yield and purity
Example 3
Adopting a liquid-solid multiphase reaction separation synchronous reactor shown in figure 1, and carrying out air oxidation on quadri-chlorophenylporphyrin and nickel acetylacetonate as raw materials to prepare a quadri-chlorophenylporphyrin nickel product; wherein the height ratio of the stirring reaction tower diameter is 1: 25; the device is provided with a constant temperature settling tower I and a constant temperature settling tower II which are the same in size and consistent in structure; the reaction liquid outlet is arranged at the tower height position of 2/5 position at the top of the reaction tower.
Controlling a tee joint below a stirring reaction tower to communicate the stirring reaction tower with a constant-temperature settling tower I, adding DMF (dimethyl formamide) into a multiphase reaction separation synchronous reactor from a solvent feeding port at the top of the constant-temperature settling tower until a reaction zone of the stirring reaction tower and the constant-temperature settling tower I are filled, mixing tetra-p-chlorophenylporphin and nickel acetylacetonate according to a molar ratio of 1:1.4 when the temperature is raised to reach the DMF reflux temperature, continuously adding the tetra-p-chlorophenylporphin from a raw material feeding port at the top of the stirring reaction tower, maintaining the concentration of the tetra-p-chlorophenylporphin in a reaction liquid to be 2wt% for reaction, separating out tetra-p-chlorophenylporphyrin nickel crystals when the concentration of a tetra-p-chlorophenylporphyrin nickel product in the reaction liquid reaches a saturated solubility, directly settling the tetra-p-chlorophenylporphyrin nickel from the reaction zone of the stirring reaction tower under the action of gravity, feeding the tetra-p-chlorophenylporphyrin nickel into the constant-temperature settling tower I, and extruding and raising the reaction liquid in the constant-temperature settling tower I by Performing the following steps; continuously carrying out the reaction until the constant temperature settling tower I is filled with the tetra-p-chlorophenylporphyrin nickel, switching the stirring reaction tower to be communicated with a constant temperature settling tower II filled with DMF through three-way control, taking down the constant temperature settling tower I, directly taking out the tetra-p-chlorophenylporphyrin nickel, carrying out suction filtration, washing with hot water and washing with ethanol to obtain a pure tetra-p-chlorophenylporphyrin nickel product; thus, the production is performed alternately and continuously. After the reaction is stable, the purity of the nickel tetra-p-chlorophenylporphyrin product is detected every 4 hours, the raw material of the tetra-p-chlorophenylporphyrin entering the reaction system, the amount of the obtained nickel tetra-p-chlorophenylporphyrin product and the components of the reaction solution are detected, and the yield and the purity of the nickel tetra-p-chlorophenylporphyrin are calculated, and the results are shown in Table 3.
TABLE 3 correlation between reaction time and the yield and purity of nickel tetra-p-chlorophenylporphyrin
Example 4
Adopting a liquid-solid multiphase reaction separation synchronous reactor shown in figure 1, and carrying out air oxidation on the raw materials of the tetranitrophenyl porphin and the vanadium acetylacetonate to prepare a tetranitrophenyl porphyrin vanadium product; wherein the height ratio of the stirring reaction tower diameter is 1: 35; the device is provided with a constant temperature settling tower I and a constant temperature settling tower II which are the same in size and consistent in structure; the reaction liquid outlet is arranged at the tower height position of 1/3 position at the top of the reaction tower.
Controlling a tee joint below a stirring reaction tower to communicate the stirring reaction tower with a constant-temperature settling tower I, adding dichloromethane into a multiphase reaction separation synchronous reactor from a solvent feeding port at the top of the constant-temperature settling tower until a reaction zone filled with the stirring reaction tower and the constant-temperature settling tower I are filled, mixing tetranitrophenyl porphine and vanadium acetylacetonate according to a molar ratio of 1:1.6 when the temperature is raised to reach the reflux temperature of the dichloromethane, continuously adding the tetranitrophenyl porphine from a raw material feeding port at the top of the stirring reaction tower, maintaining the concentration of the tetranitrophenyl porphine in a reaction liquid to be 2.5wt% for reaction, separating out crystals of the tetranitrophenyl vanadium porphyrin when the concentration of a tetranitrophenyl vanadium product in the reaction liquid reaches a saturated solubility, and directly settling the tetranitrophenyl vanadium porphyrin from the reaction zone of the stirring reaction tower under the action of gravity to enter the constant-temperature settling tower I, at the moment, the reaction liquid in the constant-temperature settling tower I is extruded and ascended by settled tetram-nitrophenyl porphyrin vanadium to enter a stirring reaction tower; continuously carrying out the reaction until the constant temperature settling tower I is filled with the tetranitrophenyl porphyrin vanadium, switching the stirring reaction tower to be communicated with a constant temperature settling tower II filled with dichloromethane through three-way control, taking down the constant temperature settling tower I, directly taking out the tetranitrophenyl porphyrin vanadium, carrying out suction filtration, washing with hot water, and washing with ethanol to obtain a pure tetranitrophenyl porphyrin vanadium product; thus, the production is performed alternately and continuously. And after the reaction is stable, sampling every 4 hours to detect the purity of the tetranitrophenyl porphyrin vanadium product, detecting the amount of the tetranitrophenyl porphyrin vanadium product and the components of the reaction solution, which enter the reaction system, and calculating the yield and the purity of the tetranitrophenyl porphyrin vanadium, wherein the results are shown in table 4.
TABLE 4 correlation of reaction time and yield and purity of vanadium tetranitrophenylporphyrin product
Example 5
Adopting a liquid-solid multiphase reaction separation synchronous reactor shown in figure 1, and carrying out air oxidation by using tetraphenylporphyrin and magnesium chloride as raw materials to prepare a tetraphenylporphyrin magnesium product; wherein the diameter-height ratio of the stirring reaction tower is 1: 40; the device is provided with a constant temperature settling tower I and a constant temperature settling tower II which are the same in size and consistent in structure; the reaction liquid outlet is arranged at the tower height position of 1/3 position at the top of the reaction tower.
Controlling a tee joint below the stirring reaction tower to communicate the stirring reaction tower with the constant-temperature settling tower I, adding dichloromethane into the multiphase reaction separation synchronous reactor from a solvent feeding port at the top of the constant-temperature settling tower, until the reaction area of the stirring reaction tower and the constant temperature settling tower I are filled, when the temperature is raised to reach the reflux temperature of the dichloromethane, mixing tetraphenylporphin and magnesium chloride according to a molar ratio of 1:1.8, continuously adding the mixture from a raw material inlet at the top of a stirring reaction tower, keeping the concentration of the tetraphenylporphin in a reaction solution at 3wt% for reaction, when the reaction is carried out until the concentration of the tetraphenylporphyrin magnesium product in the reaction solution reaches the saturation solubility, tetraphenylporphyrin magnesium crystals are separated out, simultaneously, tetraphenyl magnesium porphyrin directly settles from the reaction zone of the stirring reaction tower under the action of gravity and enters a constant-temperature settling tower I, at the moment, the reaction liquid in the constant-temperature settling tower I is extruded by settled tetraphenyl porphyrin magnesium to rise and enter a stirring reaction tower; continuously carrying out the reaction until the constant-temperature settling tower I is filled with tetraphenyl porphyrin magnesium, switching the stirring reaction tower to be communicated with a constant-temperature settling tower II filled with dichloromethane through tee joint control, taking down the constant-temperature settling tower I, directly taking out the tetraphenyl porphyrin magnesium, carrying out suction filtration, washing with hot water and washing with ethanol to obtain a pure tetraphenyl porphyrin magnesium product; thus, the production is performed alternately and continuously. When the reaction is stable, the purity of the tetraphenylporphyrin magnesium product is detected every 4 hours, the tetraphenylporphyrin raw material entering the reaction system and the amount of the tetraphenylporphyrin magnesium product obtained and the components of the reaction solution are detected, and the yield and purity of tetraphenylporphyrin magnesium are calculated, and the results are shown in table 5.
TABLE 5 relationship between reaction time and yield and purity of tetraphenylporphyrin magnesium product
| Reaction time (h) | Yield (%) of magnesium tetraphenylporphyrin | Tetraphenylporphyrin magnesium content (%) |
| 4 | 99.1 | 99.1 |
| 8 | 99.2 | 99.2 |
| 12 | 99.2 | 99.3 |
| 16 | 99.2 | 99.3 |
Example 6
Adopting a gas-liquid-solid multiphase reaction separation synchronous reactor shown in FIG. 2, and carrying out air oxidation on four pairs of (N, N '-dimethyl) aminophenyl porphyrin and manganese acetate serving as raw materials to prepare four pairs of (N, N' -dimethyl) aminophenyl porphyrin manganese products; wherein the height ratio of the stirring reaction tower diameter is 1: 30; the device is provided with a constant temperature settling tower I and a constant temperature settling tower II which are the same in size and consistent in structure; the reaction liquid outlet is arranged at the tower height position of 1/3 position at the top of the reaction tower.
Controlling a tee joint below a stirring reaction tower to communicate the stirring reaction tower with a constant-temperature settling tower I, adding dichloromethane into a multiphase reaction separation synchronous reactor from a solvent feeding port at the top of the constant-temperature settling tower until a reaction zone of the stirring reaction tower and the constant-temperature settling tower I are filled, mixing four pairs of (N, N ' -dimethyl) aminophenyl porphine and manganese acetate according to a molar ratio of 1:2 when the temperature is raised to reach a dichloromethane reflux temperature, continuously adding air from a raw material feeding port at the top of the stirring reaction tower, keeping the concentration of the four pairs of (N, N ' -dimethyl) aminophenyl porphine in a reaction liquid to be 3.5wt%, continuously introducing air from a gas raw material inlet at the bottom of the stirring reaction tower, dispersing the air by a gas distributor, and then contacting the four pairs of (N, N ' -dimethyl) aminophenyl porphine and manganese acetate in the reaction zone for reaction, when the reaction is carried out until the concentration of four pairs of (N, N '-dimethyl) amino phenyl porphyrin manganese products in the reaction liquid reaches the saturation solubility, four pairs of (N, N' -dimethyl) amino phenyl porphyrin manganese crystals are separated out, and simultaneously, four pairs of (N, N '-dimethyl) amino phenyl porphyrin manganese directly settle from the reaction zone of the stirring reaction tower under the action of gravity and enter the constant-temperature settling tower I, and the reaction liquid in the constant-temperature settling tower I is extruded and lifted by the four pairs of (N, N' -dimethyl) amino phenyl porphyrin manganese which settle and enters the stirring reaction tower; continuously carrying out the reaction until four pairs of (N, N ' -dimethyl) aminophenyl porphyrin manganese are filled in the constant-temperature settling tower I, switching the stirring reaction tower to be communicated with a constant-temperature settling tower II filled with dichloromethane through three-way control, taking down the constant-temperature settling tower I, directly taking out the four pairs of (N, N ' -dimethyl) aminophenyl porphyrin manganese, carrying out suction filtration, washing with hot water and washing with ethanol to obtain pure four pairs of (N, N ' -dimethyl) aminophenyl porphyrin manganese products; thus, the production is performed alternately and continuously. After the reaction is stable, the purity of four pairs of (N, N '-dimethyl) aminophenylporphyrin manganese products is detected every 4 hours, the four pairs of (N, N' -dimethyl) phenylporphyrin raw materials entering the reaction system, the amount of the obtained four pairs of (N, N '-dimethyl) aminophenylporphyrin manganese products and the components of the reaction solution are detected, and the yield and the purity of the four pairs of (N, N' -dimethyl) aminophenylporphyrin manganese are calculated, and the results are shown in Table 6.
TABLE 6 correlation between reaction time and yield and purity of manganese tetra-p- (N, N' -dimethyl) aminophenylporphyrin product
Example 7
Adopting a gas-liquid-solid multiphase reaction separation synchronous reactor shown in FIG. 2, and carrying out air oxidation on tetra-p-butylphenyl porphine and chromium acetate serving as raw materials to prepare a tetra-p-butylphenyl porphine chromium product; wherein the height ratio of the stirring reaction tower diameter is 1: 30; the device is provided with a constant temperature settling tower I and a constant temperature settling tower II which are the same in size and consistent in structure; the reaction liquid outlet is arranged at the tower height position of 1/3 position at the top of the reaction tower.
Controlling a tee joint below a stirring reaction tower to communicate the stirring reaction tower with a constant-temperature settling tower I, adding toluene into a multiphase reaction separation synchronous reactor from a solvent feeding port at the top of the constant-temperature settling tower until a reaction zone of the stirring reaction tower and the constant-temperature settling tower I are filled, mixing tetra-p-butylphenyl porphine and chromium acetate according to a molar ratio of 1:1.5 when the temperature is raised to reach a toluene reflux temperature, continuously adding the tetra-p-butylphenyl porphine and the chromium acetate from a raw material feeding port at the top of the stirring reaction tower, maintaining the concentration of the tetra-p-butylphenyl porphine in a reaction liquid to be 4wt%, continuously introducing air from a gas raw material introducing port at the bottom of the stirring reaction tower, dispersing the air by a gas distributor, contacting the tetra-p-butylphenyl porphine and the chromium acetate in the reaction zone for reaction, and separating out tetra-p-butylphenyl porphine crystals when the concentration of a tetra-p-butylphenyl porphine chromium product in the reaction liquid reaches, simultaneously, directly settling tetra-p-butyl phenyl porphyrin chromium from a reaction area of the stirring reaction tower under the action of gravity, and allowing the tetra-p-butyl phenyl porphyrin chromium to enter a constant temperature settling tower I, wherein the reaction liquid in the constant temperature settling tower I is extruded and lifted by the settled tetra-p-butyl phenyl porphyrin chromium to enter the stirring reaction tower; continuously carrying out the reaction until the constant temperature settling tower I is filled with the tetra-p-butyl phenyl porphyrin chromium, switching the stirring reaction tower to be communicated with the constant temperature settling tower II filled with toluene through three-way control, taking down the constant temperature settling tower I, directly taking out the tetra-p-butyl phenyl porphyrin chromium, carrying out suction filtration, washing with hot water and washing with ethanol to obtain a pure tetra-p-butyl phenyl porphyrin chromium product; thus, the production is performed alternately and continuously. After the reaction is stable, the purity of the chromium tetra-p-butylphenyl porphyrin product is detected every 4 hours, the raw material of tetra-p-butylphenyl porphyrin entering the reaction system, the amount of the obtained chromium tetra-p-butylphenyl porphyrin product and the components of the reaction solution are detected, and the yield and purity of the chromium tetra-p-butylphenyl porphyrin are calculated, with the results shown in table 7.
TABLE 7 correlation between reaction time and yield and purity of chromium tetra-p-butylphenyl porphyrin product
Example 8
Adopting a gas-liquid-solid multiphase reaction separation synchronous reactor shown in FIG. 2, and carrying out air oxidation on tetra-p-butylphenyl porphine and ferrous chloride serving as raw materials to prepare a tetra-p-butylphenyl porphyrin iron product; wherein the height ratio of the stirring reaction tower diameter is 1: 25; the device is provided with a constant temperature settling tower I and a constant temperature settling tower II which are the same in size and consistent in structure; the reaction liquid outlet is arranged at the tower height position of 1/3 position at the top of the reaction tower.
Controlling a tee joint below a stirring reaction tower to communicate the stirring reaction tower with a constant-temperature settling tower I, adding toluene into a multiphase reaction separation synchronous reactor from a solvent feeding port at the top of the constant-temperature settling tower until a reaction zone of the stirring reaction tower and the constant-temperature settling tower I are filled, mixing tetra-p-butylphenyl porphine and ferrous chloride according to a molar ratio of 1:1.2 when the temperature is raised to reach a toluene reflux temperature, continuously adding the tetra-p-butylphenyl porphine and the ferrous chloride from a raw material feeding port at the top of the stirring reaction tower, maintaining the concentration of the tetra-p-butylphenyl porphine in a reaction liquid to be 5wt%, continuously introducing air from a gas raw material introducing port at the bottom of the stirring reaction tower, dispersing the air by a gas distributor, contacting the tetra-p-butylphenyl porphine and the ferrous chloride in the reaction zone for reaction, and separating out tetra-p-butylphenyl porphine iron crystals when the concentration of the tetra-p-butylphenyl porphine product in the reaction liquid reaches, simultaneously, directly settling tetra-p-butyl phenyl porphyrin iron from a reaction area of the stirring reaction tower under the action of gravity, and then entering a constant temperature settling tower I, wherein the reaction liquid in the constant temperature settling tower I is extruded and lifted by the settled tetra-p-butyl phenyl porphyrin iron and then enters the stirring reaction tower; continuously carrying out the reaction until the constant temperature settling tower I is filled with the tetra-p-butyl phenyl porphyrin iron, switching the stirring reaction tower to be communicated with the constant temperature settling tower II filled with toluene through three-way control, taking down the constant temperature settling tower I, directly taking out the tetra-p-butyl phenyl porphyrin iron, carrying out suction filtration, washing with hot water and washing with ethanol to obtain a pure tetra-p-butyl phenyl porphyrin iron product; thus, the production is performed alternately and continuously. After the reaction is stable, the purity of the iron tetra-p-butylphenyl porphyrin product is detected every 4 hours, the raw material of tetra-p-butylphenyl porphyrin entering the reaction system, the amount of the obtained iron tetra-p-butylphenyl porphyrin product and the components of the reaction solution are detected, and the yield and purity of the iron tetra-p-butylphenyl porphyrin are calculated, with the results shown in table 8.
TABLE 8 correlation of reaction time and iron tetra-p-butylphenyl porphyrin product yield and purity
Claims (7)
1. The continuous production process of the tetraaryl metalloporphyrin is characterized in that a solvent is added into a multiphase reaction and separation synchronous reactor, the multiphase reaction and separation synchronous reactor comprises a stirring reaction tower with a reflux device and at least two constant temperature settling towers communicated with the bottom of the stirring reaction tower; the stirring reaction tower comprises a gas phase area at the upper part in the tower, a reaction area at the middle lower part, a reflux device connecting port at the top and a raw material feeding port; a stirrer is arranged in the reaction zone of the stirring reaction tower; during reaction, the solvent is filled in the reaction area and the constant-temperature settling tower and is heatedWhen the high temperature reaches the reflux temperature of a solvent, mixing reaction raw materials of tetraaryl porphin and metal salt according to a molar ratio of 1: 1-2, continuously or batchwise adding the mixture into a stirring reaction tower from a raw material feeding port at the top of the stirring reaction tower to react, and when the reaction is carried out until the concentration of a tetraaryl metalloporphyrin product in a reaction liquid reaches saturated solubility, separating out a tetraaryl metalloporphyrin crystal, directly settling the tetraaryl metalloporphyrin crystal from a reaction zone of the stirring reaction tower under the action of gravity, and feeding the tetraaryl metalloporphyrin crystal into a constant-temperature settling tower, wherein the liquid in the constant-temperature settling tower is extruded and lifted by the settled tetraaryl metalloporphyrin and then fed into the stirring reaction tower; continuously carrying out the reaction until the constant-temperature settling tower is filled with the tetraaryl metalloporphyrin, switching the stirring reaction tower to be communicated with the other constant-temperature settling tower filled with the solvent, taking down the constant-temperature settling tower filled with the tetraaryl metalloporphyrin for treatment, and alternately carrying out continuous production; the solvent is benzene, toluene, xylene and CH2Cl2、CHCl3And one or more of DMF;
the metal salt is one of soluble acetate or halide salt or acetylacetone salt of cobalt, zinc, copper, nickel, magnesium or vanadium;
the tetraarylporphin has a structure of formula 1:
the tetraaryl metalloporphyrin has a structure shown in a formula 2:
wherein,
r is hydrogen atom, alkyl, alkoxy, hydroxyl, halogen, amino or nitro;
m is cobalt, zinc, copper, nickel, magnesium or vanadium.
2. The process according to claim 1, wherein the reaction raw material is continuously or batchwise added to maintain the concentration of the tetraarylporphine in the reaction solution at 1-5 wt%.
3. The process of claim 1 wherein the excess solvent in the stirred tank reactor is withdrawn from a reflux unit at the top of the stirred tank reactor.
4. The continuous production process of the tetraaryl metalloporphyrin is characterized in that a solvent is added into a multiphase reaction and separation synchronous reactor, the multiphase reaction and separation synchronous reactor comprises a stirring reaction tower with a reflux device and at least two constant temperature settling towers communicated with the bottom of the stirring reaction tower; the stirring reaction tower comprises a gas phase area at the upper part in the tower, a reaction area at the middle lower part, a reflux device connecting port at the top and a raw material feeding port; a stirrer is arranged in the reaction zone of the stirring reaction tower; during reaction, filling a solvent into the reaction zone and the constant-temperature settling tower, mixing reaction raw materials of the tetraarylporphin and the divalent metal salt according to a molar ratio of 1: 1-2 when the temperature is raised to reach the reflux temperature of the solvent, continuously or in batches adding the tetraarylporphin and the divalent metal salt from a raw material inlet at the top of the stirring reaction tower, and air is continuously introduced from the bottom of the stirring reaction tower, is dispersed by a gas distributor and then contacts with the tetraaryl porphin and the divalent metal salt in the reaction zone to react, when the reaction is carried out until the concentration of the tetraaryl metalloporphyrin product in the reaction liquid reaches the saturation solubility, the tetraaryl metalloporphyrin crystal is separated out, simultaneously directly settling from the reaction area of the stirring reaction tower under the action of gravity and entering a constant-temperature settling tower, at the moment, the liquid in the constant-temperature settling tower is extruded by settled tetraaryl metalloporphyrin to rise into the stirring reaction tower; continuously carrying out the reaction until the constant-temperature settling tower is filled with the tetraaryl metalloporphyrin, switching the stirring reaction tower to be communicated with the other constant-temperature settling tower filled with the solvent, taking down the constant-temperature settling tower filled with the tetraaryl metalloporphyrin for treatment, and alternately carrying out continuous production; the solvent is benzene, toluene, xylene and CH2Cl2、CHCl3And one or more of DMF; the divalent metal salt is divalent acetate or divalent halide salt of cobalt, iron, manganese, chromium or vanadium; the tetraarylporphin has a structure of formula 1:
the tetraaryl metalloporphyrin has a structure shown in a formula 3:
wherein,
r is hydrogen atom, alkyl, alkoxy, hydroxyl, halogen, amino or nitro;
x is acetate or halogen;
m is cobalt, iron, manganese, chromium or vanadium.
5. The process according to claim 4, wherein the reaction raw material is continuously or batchwise added to maintain the concentration of the tetraarylporphine in the reaction solution at 1-5 wt%.
6. The process of claim 4, wherein the excess solvent in the stirred tank reactor is withdrawn from a reflux unit at the top of the stirred tank reactor.
7. The process of claim 4, wherein the unreacted gas portion enters the gas phase zone at the upper part of the stirred reaction column and is discharged and evacuated through a reflux device at the top of the stirred reaction column.
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