CN111893506A - Preparation method of menadione - Google Patents
Preparation method of menadione Download PDFInfo
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- CN111893506A CN111893506A CN202010755968.0A CN202010755968A CN111893506A CN 111893506 A CN111893506 A CN 111893506A CN 202010755968 A CN202010755968 A CN 202010755968A CN 111893506 A CN111893506 A CN 111893506A
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- menadione
- electrocatalyst
- preparation
- electrolyte
- solvent
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- MJVAVZPDRWSRRC-UHFFFAOYSA-N Menadione Chemical compound C1=CC=C2C(=O)C(C)=CC(=O)C2=C1 MJVAVZPDRWSRRC-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 235000012711 vitamin K3 Nutrition 0.000 title claims abstract description 65
- 239000011652 vitamin K3 Substances 0.000 title claims abstract description 65
- 229940041603 vitamin k 3 Drugs 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000003792 electrolyte Substances 0.000 claims abstract description 33
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 55
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 claims description 38
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- 239000003115 supporting electrolyte Substances 0.000 claims description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 20
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 19
- 239000012071 phase Substances 0.000 claims description 19
- 238000001953 recrystallisation Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 239000012074 organic phase Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000012043 crude product Substances 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011133 lead Substances 0.000 claims description 9
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910017971 NH4BF4 Inorganic materials 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 5
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 5
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 5
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910017673 NH4PF6 Inorganic materials 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical group [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 238000006056 electrooxidation reaction Methods 0.000 abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000012824 chemical production Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 24
- 238000005303 weighing Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 17
- 238000005868 electrolysis reaction Methods 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 15
- 239000006227 byproduct Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 10
- 238000001514 detection method Methods 0.000 description 9
- 239000008151 electrolyte solution Substances 0.000 description 9
- 238000004364 calculation method Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 238000007867 post-reaction treatment Methods 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- -1 ammonium tetrafluoroborate Chemical compound 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- QEOXDHNSZDIVRC-UHFFFAOYSA-N OB(O)F.OB(O)F.OB(O)F.OB(O)F.OB(O)F.OB(O)F.N.N.N.N.N.N.N.N.N.N.N.N Chemical compound OB(O)F.OB(O)F.OB(O)F.OB(O)F.OB(O)F.OB(O)F.N.N.N.N.N.N.N.N.N.N.N.N QEOXDHNSZDIVRC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 229910000362 cobalt(III) sulfate Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/10—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a preparation method of menadione, which comprises the steps of preparing electrolyte from 2-methylnaphthalene and an electrocatalyst, and then carrying out direct electrolytic oxidation reaction of the 2-methylnaphthalene under the condition of constant current to prepare menadione; the electrocatalyst is RClO4、RPF6Or RBF4Wherein R is Li+、Na+、K+、NH4 +One kind of (1). The electrolyte in the invention can be repeatedly used all the time, the method is simple, no oxidizing reagent is added and no three wastes are generated, and the selectivity of the product of the electrooxidation reaction reaches more than 95 percentThe method is a green synthesis technology with development prospect, and meets the requirement of environmental protection in the current chemical production process.
Description
Technical Field
The invention relates to a preparation method of menadione, in particular to a preparation method of menadione by directly electrolyzing and oxidizing 2-methylnaphthalene, belonging to the technical field of organic chemical industry.
Technical Field
Menadione is a fat-soluble vitamin medicament, is a key intermediate for synthesizing vitamin K3, is an important raw material for fine chemical engineering, and has wide application in the aspects of medicines and feed additives. The prior art for producing menadione mainly adopts a co-production process of dichromate oxidation and chrome tanning agent byproduct, the process has the defects of large amount of chromium-containing waste water, serious pollution, complex process and the like, and particularly the problem of treatment of chromium-containing waste liquid always troubles the industrial production of menadione.
The literature, "research on the process for preparing 2-methyl-1, 4-naphthoquinone by oxidizing 2-methylnaphthalene with Cr (IV)" reports that indirect electro-oxidation is used for synthesizing menadione, although hexavalent chromium can be recycled through an electrolysis mode, chromium salt is remained in menadione products, and a large amount of chromium-containing wastewater is inevitably generated in the product refining process.
In a mature organic electrochemical system, the polymerization reaction of organic matters on a polar plate can not only inactivate the polar plate, but also greatly reduce the selectivity and the product yield of a target product, and the problems always bother the enlargement of the electrosynthesis process.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for preparing menadione by direct electrooxidation, which has the advantages that the electrolyte can be recycled all the time, the method is simple, no oxidation reagent is added, no three wastes are generated, the product selectivity of the electrooxidation reaction can reach more than 95 percent by adding a specific electrocatalyst into a system, the yield reaches more than 94 percent, the problem of electrode plate inactivation caused by the polymerization reaction of organic matters on an electrode plate is solved, and the method is a green synthesis technology with development prospect.
In order to realize the aim, the invention provides a preparation method of menadione, which comprises the steps of preparing electrolyte from 2-methylnaphthalene and an electrocatalyst, and then carrying out direct electrolytic oxidation reaction on the 2-methylnaphthalene under the condition of constant current to prepare menadione;
the electrocatalyst is RClO4、RPF6Or RBF4Wherein R is Li+、Na+、K+、NH4 +One of (1);
in some examples of the invention, the electrocatalyst is LiClO4、NaClO4、NH4BF4、NaBF4、NH4PF6One or more of; the electrocatalyst is preferably LiClO4Or comprises LiClO4With NaClO4、NH4BF4、NaBF4、NH4PF6At least one of (1) and LiClO in the mixture4The content of (B) is not less than 50 wt%.
The addition of the electrocatalyst can improve the reaction selectivity and reduce the electrolysis energy consumption. With LiClO4For example, when an appropriate amount of electrocatalyst LiClO is added to the electrolysis system4On the one hand, due to LiClO4With micro-scale larger anionic groups ClO4 -The conductive capability of the electrolyte solution can be enhanced, the cell voltage can be reduced, and the energy consumption for synthesizing menadione by direct electrooxidation is greatly reduced; on the other hand, due to the existence of a proper amount of large-scale anionic groups, the further reaction of menadione is blocked by effective occupation generated by adsorption at the anode, so that the menadione product is not easy to be adsorbed by the polar plate to generate polymerization reaction, the selectivity of menadione can be improved, and the problem of deactivation of the polar plate due to the polymerization reaction of organic matters on the polar plate is avoided.
In the invention, the raw material 2-methylnaphthalene and an electrocatalyst are prepared into electrolyte, wherein the electrolyte also comprises a solvent, concentrated sulfuric acid and water. The electrolyte takes the total mass of the electrolyte as a reference and comprises the following components: 10-50 wt% of 2-methylnaphthalene, 0.1-5 wt% of an electrocatalyst, 10-60 wt% of a solvent, 10-50 wt% of concentrated sulfuric acid and the balance of water; the concentration range of the concentrated sulfuric acid can be 75-98 wt%, and the concentrated sulfuric acid with the concentration of 98 wt% is preferably adopted for preparation;
preferably, the electrolyte consists of 22-35 wt% of 2-methylnaphthalene, 1.5-3.5 wt% of an electrocatalyst, 15-45 wt% of a solvent, 12-35 wt% of concentrated sulfuric acid and the balance of water;
more preferably, the electrolyte consists of 30 wt% of 2-methylnaphthalene, 3 wt% of electrocatalyst, 20 wt% of solvent, 20 wt% of concentrated sulfuric acid and the balance of water.
In the electrolyte solution, the solvent is preferably one or more of dichloromethane, 1, 2-dichloroethane, cyclohexane, ethylcyclohexane and n-hexane, and more preferably cyclohexane and/or ethylcyclohexane.
In some examples of the present invention, the electrolyte solution is prepared by: mixing concentrated sulfuric acid and water to prepare a supporting electrolyte solution, and dissolving 2-methylnaphthalene in a solvent to prepare a raw material solution; then adding the electrocatalyst into the supporting electrolyte solution, and adding the supporting electrolyte solution into the raw material solution to prepare the electrolyte. In the electrolyte solution preparation process, the electrolyte solution and the raw material solution are prepared in no sequence, and the feeding sequence can also be changed, and in some preferred examples, the method is adopted, wherein the electrolyte solution and the raw material solution are required to be prepared respectively and then mixed, and the electrolyte solution and the raw material solution are required to be prepared respectively and then mixed.
In the invention, the direct electrolytic oxidation reaction conditions are as follows: the current density is 100 to 3000A/m2Preferably 1500 to 2500A/m2(ii) a The voltage is 5-20V; the reaction temperature is 10-80 ℃, and preferably 45-75 ℃; the reaction time is 5-20 h, preferably 8-12 h. The invention adopts the constant current condition to carry out the direct electrolytic oxidation of 2-methylnaphthalene to prepare menadione, and when the electrolysis is carried out under the constant current condition, the electrocatalyst of the invention is added, the cell voltage can be reduced, the voltage range is obviously lower than that of the conventional electrochemical method, and the electrolysis energy consumption is greatly reduced.
In some examples of the present invention, the anode plate material used in the direct electrolytic oxidation reaction is one of lead dioxide, lead, platinum and graphite, preferably platinum, and the cathode plate material is one of nickel, copper, lead and titanium, preferably lead.
In the preparation method, after the reaction is finished, the preparation method also comprises the post-treatment operation, and the steps are as follows: separating the reaction liquid into an organic phase and a water phase, washing the organic phase with water, drying and concentrating to obtain a crude product, and then recrystallizing to obtain a menadione product. The yield of the menadione product is more than or equal to 94 percent, and the purity of the menadione product is more than or equal to 98.5 percent through gas chromatography detection;
in some examples of the present invention, the organic solvent used for recrystallization is one or more of 1, 2-dichloroethane, carbon tetrachloride, n-hexane, dichloromethane, cyclohexane, ethylcyclohexane, preferably ethylcyclohexane; preferably, the mass usage amount of the recrystallization solvent is 1-1.5 times of the mass usage amount of the menadione crude product;
in some examples of the invention, the recrystallization conditions are: the recrystallization temperature is-2 to-15 ℃, and preferably-4 to-8 ℃; the recrystallization time is 10-120 min, preferably 25-50 min.
In some examples of the invention, the reaction liquid is separated into an organic phase and an aqueous phase, the separation temperature ranges from 10 ℃ to 70 ℃, and a standing liquid separation method at 20 ℃ to 35 ℃ is preferably adopted;
in some examples of the present invention, drying and concentrating to obtain crude menadione, which is a common operation in the art, preferably a method of removing the solvent by rotary evaporation of the oil phase obtained by separating the liquid to obtain crude menadione.
In the invention, in the post-treatment operation, the basic component of the separated water phase is the supporting electrolyte solution which can be recycled after being refined; in some examples of the present invention, the refining method employs a solvent extraction method, and the refined solvent is one or more of ethyl acetate, dichloromethane, 1, 2-dichloroethane, n-hexane, cyclohexane, and ethylcyclohexane, preferably dichloromethane. The method preferably comprises weighing dichloromethane 0.3 times the weight of the water phase, extracting the water phase for three times at 25 deg.C.
The technical scheme of the invention has the beneficial effects that:
the invention adopts a direct electrooxidation method to prepare menadione, and a proper amount of the electrocatalyst is added into an electrolytic system, so that the polymerization side reaction of menadione can be inhibited, the electrode inactivation is prevented, the selectivity and the conversion rate are improved, and the energy consumption can be greatly reduced.
The direct electrooxidation method of the invention is simple, the supporting electrolyte solution can be recycled, and no oxidation reagent is added and no three wastes are generated, so the method is a green synthesis technology with development prospect and very meets the requirement of environmental protection in the current chemical production process.
Detailed Description
The method provided by the present invention is described in detail below with reference to examples, and it should be noted that the scope of the present invention includes but is not limited to such examples.
Information on main raw materials of the first, examples and comparative examples:
98% sulfuric acid, Shanghai Tantake Technology, Inc.;
ethylcyclohexane, denna guangyu chemical ltd;
lithium perchlorate, alatin;
sodium perchlorate, alatin;
ammonium tetrafluoroborate, alatin;
sodium tetrafluoroborate, alatin;
ammonium hexafluoroborate, alatin;
other raw materials are all common commercial products and the reagents are all analytically pure, unless otherwise specified.
Secondly, the analysis and test method adopted in the embodiment is as follows:
an Agilent gas chromatograph: chromatography column DB-530 x 0.25; detector FID 2; the temperature of the vaporization chamber is 300 ℃, and the temperature of the detector is 300 ℃; temperature programming: at 50 ℃ for 2 min; at 100 ℃ for 1 min; 10 deg.C/min to 300 deg.C, 10 min.
Example 1
(1) Preparing electrolyte: preparing 100g of supporting electrolyte solution and LiClO by using 98 wt% concentrated sulfuric acid and deionized water according to the mass ratio of about 1:44Weighing 2.28g of the mixed solution and adding the mixed solution into a supporting electrolyte solution; dissolving 15g of raw material 2-methylnaphthalene in 35g of dichloromethane to prepare a raw material solution, adding a supporting electrolyte solution into the raw material solution to prepare an electrolyte solution, wherein the obtained electrolyte solution comprises 10 wt% of 2-methylnaphthalene and an electrocatalyst LiClO41.5 wt%, dichloromethane 23.0 wt%, concentrated sulfuric acid 13.1 wt%, and the balance deionized water;
(2) and (3) electrolytic reaction: the anode is a lead dioxide coating polar plate, the cathode is a copper polar plate, and a circuit is connected to form a closed circuit with the electrolyte systemA loop; opening the thermostatic water bath, controlling the temperature of the water bath to 35 ℃, and regulating the current by the direct current power supply to ensure that the current density is 2000A/m2The voltage is kept at 6V, and the electrolysis is started; after 8h of reaction, stopping electrolysis;
(3) and (3) post-reaction treatment: separating the reaction solution into an organic phase and a water phase at 60 ℃, washing the organic phase with water, concentrating to obtain a menadione crude product, then adopting cyclohexane with the mass of 1.5 times of that of the menadione crude product to carry out recrystallization at the temperature of-5 ℃ for 30min to obtain a pure product, wherein the weighing calculation yield is 83.0 percent, and the purity is 98.8 percent through gas chromatography detection; the selectivity of menadione is 85.0 percent, and the selectivity of menadione polymerization by-products is 10 percent (the amount of menadione polymerization by-products is calculated by the mass of electrode plate precipitates).
Refining the water phase (supporting electrolyte solution) separated in the step (3) by using cyclohexane solvent: weighing cyclohexane with the mass of 0.3 time of that of the water phase, extracting the water phase for three times at the extraction temperature of 25 ℃. Then weighing, supplementing water to ensure that the mass of the supporting electrolyte still keeps 100.75g, and recycling according to the steps. The application is carried out for 5 times, and the results are shown in the following table 1:
TABLE 1
Example 2
(1) Preparing electrolyte: preparing 100g of supporting electrolyte solution and LiClO by using 98 wt% concentrated sulfuric acid and deionized water according to the mass ratio of about 1:14Weighing 7.5g of the mixed solution and adding the mixed solution into a supporting electrolyte solution; 75g of raw material 2-methylnaphthalene is dissolved in 75g of ethylcyclohexane to prepare a raw material solution, a supporting electrolyte solution is added into the raw material solution to prepare an electrolyte, and the obtained electrolyte comprises the following components: 29.1 wt% of 2-methylnaphthalene and LiClO as an electrocatalyst42.9 wt%, 29.1 wt% of ethyl cyclohexane, 19.4 wt% of concentrated sulfuric acid and the balance of deionized water;
(2) and (3) electrolytic reaction: the anode is a platinum coating polar plate, the cathode is a lead polar plate, and the anode and the cathode are connected with a circuit to form a closed loop with an electrolyte system; opening the thermostatic water bath, controlling the temperature of the water bath to be 60 ℃, and regulating the current by the direct-current power supply to ensure that the current density is 2000A/m2The voltage is kept at 4.5V, and electrolysis is started; after reacting for 10h, stopping electrolysis;
(3) and (3) post-reaction treatment: separating the reaction liquid into an organic phase and a water phase, washing the organic phase with water, concentrating to obtain a menadione crude product, then adopting cyclohexane with the mass of 1.5 times of that of the menadione crude product to carry out recrystallization at the temperature of minus 5 ℃ for 30min to obtain a pure product, wherein the weighing calculation yield is 96.0 percent, and the gas chromatography detection purity is 99.0 percent; the selectivity of menadione is 97.0 percent, and the selectivity of menadione polymerization by-products is 2.5 percent.
Example 3
(1) Preparing electrolyte: preparing 100g of supporting electrolyte solution and LiClO by using 98 wt% concentrated sulfuric acid and deionized water according to the mass ratio of about 1:34Weighing 8.3g of the mixed solution and adding the mixed solution into a supporting electrolyte solution; 17.4g of raw material 2-methylnaphthalene is dissolved in 48.6g of ethylcyclohexane to prepare a raw material solution, a supporting electrolyte solution is added into the raw material solution to prepare an electrolyte, and the obtained electrolyte comprises the following components: 10 wt% of 2-methylnaphthalene and an electrocatalyst LiClO44.7 wt%, 27.9 wt% of ethyl cyclohexane, 11.5 wt% of concentrated sulfuric acid and the balance of deionized water;
(2) and (3) electrolytic reaction: the anode is a platinum coating polar plate, the cathode is a lead polar plate, and the anode and the cathode are connected with a circuit to form a closed loop with an electrolyte system; opening the thermostatic water bath, controlling the temperature of the water bath to be 60 ℃, and regulating the current by the direct current power supply to ensure that the current density is 1500A/m2The voltage is kept at 5.8V, and electrolysis is started; after reacting for 11h, stopping electrolysis;
(3) and (3) post-reaction treatment: separating the reaction liquid into an organic phase and a water phase, washing the organic phase with water, concentrating to obtain a menadione crude product, then adopting cyclohexane with the mass of 1.5 times of that of the menadione crude product to carry out recrystallization, wherein the recrystallization temperature is-5 ℃ and the recrystallization time is 30min to obtain a pure product, the weighing calculation yield is 83.5 percent, and the gas chromatography detection purity is 97.5 percent; the selectivity of menadione is 85.0 percent, and the selectivity of menadione polymerization by-products is 13.0 percent.
Example 4
(1) Preparing electrolyte: preparing 100g of supporting electrolyte solution and NH by using 98 wt% concentrated sulfuric acid and deionized water according to the mass ratio of about 1:44BF40.2g of the solution was weighed and added to the supporting electrolyte solution(ii) a 20g of raw material 2-methylnaphthalene is dissolved in 80g of ethylcyclohexane to prepare a raw material solution, a supporting electrolyte solution is added into the raw material solution to prepare an electrolyte, and the obtained electrolyte comprises the following components: 10 wt% of 2-methylnaphthalene and an electrocatalyst NH4BF40.1 wt%, 40 wt% of ethyl cyclohexane, 10 wt% of concentrated sulfuric acid and the balance of deionized water;
(2) and (3) electrolytic reaction: the anode is a lead dioxide coating pole plate, the cathode is a copper pole plate, and a circuit is connected to form a closed loop with an electrolyte system; opening the thermostatic water bath, controlling the temperature of the water bath to be 40 ℃, and regulating the current by the direct current power supply to ensure that the current density is 1000A/m2The voltage is kept at 6V, and the electrolysis is started; after reacting for 15h, stopping electrolysis;
(3) and (3) post-reaction treatment: separating the reaction liquid into an organic phase and a water phase, washing the organic phase with water, concentrating to obtain a menadione crude product, then adopting cyclohexane with the mass of 1.5 times of that of the menadione crude product to carry out recrystallization at the temperature of minus 5 ℃ for 30min to obtain a pure product, wherein the weighing calculation yield is 68.5%, and the gas chromatography detection purity is 97.5%; the selectivity of menadione is 71.0 percent, and the selectivity of menadione polymerization by-products is 25.0 percent.
Example 5
(1) Preparing electrolyte: preparing 100g of supporting electrolyte solution and LiClO by using 98 wt% concentrated sulfuric acid and deionized water according to the mass ratio of about 1:14Weighing 4.3g of the mixed solution and adding the mixed solution into a supporting electrolyte solution; 15g of raw material 2-methylnaphthalene is dissolved in 28g of ethylcyclohexane to prepare a raw material solution, a supporting electrolyte solution is added into the raw material solution to prepare an electrolyte, and the obtained electrolyte comprises the following components: 10.1 wt% of 2-methylnaphthalene and an electrocatalyst LiClO42.9 wt%, 19 wt% of ethyl cyclohexane, 33.9 wt% of concentrated sulfuric acid and the balance of deionized water;
(2) and (3) electrolytic reaction: the anode is a platinum coating polar plate, the cathode is a lead polar plate, and the anode and the cathode are connected with a circuit to form a closed loop with an electrolyte system; opening the thermostatic water bath, controlling the temperature of the water bath to be 55 ℃, and regulating the current by the direct current power supply to ensure that the current density is 3000A/m2The voltage is kept at 6.3V, and electrolysis is started; after reacting for 12h, stopping electrolysis;
(3) and (3) post-reaction treatment: separating the reaction liquid into an organic phase and a water phase, washing the organic phase with water, concentrating to obtain a menadione crude product, then adopting cyclohexane with the mass of 1.5 times of that of the menadione crude product to carry out recrystallization at the temperature of minus 5 ℃ for 30min to obtain a pure product, wherein the weighing calculation yield is 88.0 percent, and the gas chromatography detection purity is 98.5 percent; the selectivity of menadione is 89.0 percent, and the selectivity of menadione polymerization by-products is 10.0 percent.
Refining the water phase (supporting electrolyte solution) separated in the step (3) by using cyclohexane solvent: weighing cyclohexane with the mass of 0.3 time of that of the water phase, extracting the water phase for three times at the extraction temperature of 25 ℃. Then weighing, supplementing water to ensure that the mass of the supporting electrolyte still keeps 104.3g, and recycling according to the steps. The application is carried out for 5 times, and the results are shown in the following table 2:
TABLE 2
Examples 6 to 10
The preparation of example 5 was used, except that the electrocatalyst was replaced, and the results are shown in table 3 below:
TABLE 3
Comparative example 1
The preparation method of example 5 was employed, except that no electrocatalyst, LiClO, was added in step (1)4Obtaining a menadione pure product, wherein the weighing calculation yield is 58.5 percent, and the gas chromatography detection purity is 95.0 percent; the selectivity of menadione is 59.0 percent, and the selectivity of menadione polymerization by-products is 35.0 percent.
The separated aqueous phase (supporting electrolyte solution) was purified with the solvent cyclohexane: weighing cyclohexane with the mass of 0.3 time of that of the water phase, extracting the water phase for three times at the extraction temperature of 25 ℃. And weighing, supplementing water to ensure that the mass of the supporting electrolyte still keeps 100g, and circularly applying according to the steps. The application is carried out for 5 times, and the results are shown in the following table 4:
TABLE 4
Comparative example 2
The preparation method of example 5 was used, except that the electrocatalyst LiClO in step (1) was used4Replacing sodium sulfate to prepare a menadione pure product, weighing and calculating the yield to be 65.5 percent, and detecting the purity to be 95.5 percent by gas chromatography; the selectivity of menadione is 72.0 percent, and the selectivity of menadione polymerization by-products is 25.0 percent.
Comparative example 3
The preparation method of example 5 was used, except that the electrocatalyst LiClO in step (1) was used4Is replaced by Co2(SO4)3Obtaining a menadione pure product, wherein the weighing calculation yield is 66.7 percent, and the gas chromatography detection purity is 95.5 percent; the selectivity of menadione is 68.0 percent, and the selectivity of menadione polymerization by-products is 24.0 percent.
Comparative example 4
The preparation method of example 5 was used, except that the electrocatalyst LiClO in step (1) was used4Is replaced by CrO3Obtaining a menadione pure product, wherein the weighing calculation yield is 58.6 percent, and the gas chromatography detection purity is 94.3 percent; the selectivity of menadione is 63 percent, and the selectivity of menadione polymerization by-products is 22 percent.
Claims (10)
1. A preparation method of menadione is characterized in that the method comprises the steps of preparing electrolyte from 2-methylnaphthalene and an electrocatalyst, and then carrying out direct electrolytic oxidation reaction of the 2-methylnaphthalene under the condition of constant current to prepare menadione;
the electrocatalyst is RClO4、RPF6Or RBF4Wherein R is Li+、Na+、K+、NH4 +One kind of (1).
2. The method of claim 1, wherein the electrocatalyst is LiClO4、NaClO4、NH4BF4、NaBF4、NH4PF6One or more of; preferably LiClO4Or comprises LiClO4With NaClO4、NH4BF4、NaBF4、NH4PF6At least one of (1) and LiClO in the mixture4The content of (B) is not less than 50 wt%.
3. The preparation method according to claim 1 or 2, wherein the electrolyte comprises, based on the total mass of the electrolyte: 10-50 wt% of 2-methylnaphthalene, 0.1-5 wt% of an electrocatalyst, 10-60 wt% of a solvent, 10-50 wt% of concentrated sulfuric acid and the balance of water;
preferably, the electrolyte consists of 22-35 wt% of 2-methylnaphthalene, 1.5-3.5 wt% of an electrocatalyst, 15-45 wt% of a solvent, 12-35 wt% of concentrated sulfuric acid and the balance of water.
4. The method according to claim 3, wherein the solvent is one or more of dichloromethane, 1, 2-dichloroethane, cyclohexane, ethylcyclohexane and n-hexane, preferably cyclohexane and/or ethylcyclohexane.
5. The production method according to any one of claims 1 to 4, wherein the direct electrolytic oxidation reaction conditions are: the current density is 100 to 3000A/m2Preferably 1500 to 2500A/m2(ii) a The voltage is 5-20V; the reaction temperature is 10-80 ℃, and preferably 45-75 ℃; the reaction time is 5-20 h, preferably 8-12 h.
6. The preparation method according to any one of claims 1 to 5, characterized in that the anode plate material adopted in the direct electrolytic oxidation reaction is one of lead dioxide, lead, platinum and graphite, preferably platinum, and the cathode plate material is one of nickel, copper, lead and titanium, preferably lead.
7. The process according to any one of claims 1 to 6, wherein the reaction is terminated by a post-treatment operation comprising the steps of: separating the reaction liquid into an organic phase and a water phase, washing the organic phase with water, drying and concentrating to obtain a crude product, and then recrystallizing to obtain a menadione product.
8. The preparation method according to claim 7, characterized in that the organic solvent used for recrystallization is one or more of 1, 2-dichloroethane, carbon tetrachloride, n-hexane, dichloromethane, cyclohexane and ethylcyclohexane, preferably ethylcyclohexane; preferably, the mass usage amount of the recrystallization solvent is 1-1.5 times of the mass usage amount of the menadione crude product;
the recrystallization conditions are as follows: the recrystallization temperature is-2 to-15 ℃, and preferably-4 to-8 ℃; the recrystallization time is 10-120 min, preferably 25-50 min.
9. The preparation method according to claim 7, wherein the separated aqueous phase is a supporting electrolyte solution, and the supporting electrolyte solution is refined and recycled.
10. The preparation method according to claim 9, wherein the refining method is a solvent extraction method, and the solvent is one or more of ethyl acetate, dichloromethane, 1, 2-dichloroethane, n-hexane, cyclohexane and ethylcyclohexane, preferably dichloromethane.
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JPS57134581A (en) * | 1981-02-13 | 1982-08-19 | Shigeru Torii | Production of 1, 4-naphthoquinone derivative |
JPS60230990A (en) * | 1984-04-28 | 1985-11-16 | Agency Of Ind Science & Technol | Manufacture of 2-methyl-1,4-naphthoquinone |
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JPS57134581A (en) * | 1981-02-13 | 1982-08-19 | Shigeru Torii | Production of 1, 4-naphthoquinone derivative |
JPS60230990A (en) * | 1984-04-28 | 1985-11-16 | Agency Of Ind Science & Technol | Manufacture of 2-methyl-1,4-naphthoquinone |
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CN114032565A (en) * | 2021-11-12 | 2022-02-11 | 万华化学集团股份有限公司 | Preparation method and application of anhydrous peroxycarboxylic acid |
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