CN1085266A - Vitamin K 3Production method and electrolyzer - Google Patents
Vitamin K 3Production method and electrolyzer Download PDFInfo
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- CN1085266A CN1085266A CN92112018.4A CN92112018A CN1085266A CN 1085266 A CN1085266 A CN 1085266A CN 92112018 A CN92112018 A CN 92112018A CN 1085266 A CN1085266 A CN 1085266A
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- oxidation
- vitamin
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- waste liquid
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Abstract
The present invention is a vitamin K
3Production method and electrolyzer, it is a kind of fodder additives of a kind of hemostatic agent, its feeding industry of pharmaceutical.Beta-methylnaphthalene and oxidation liquid add catalyzer and carry out catalytic oxidation in stills for air blowing, enter medial launder through suction filter decompression, can get the Beta-methyl naphthoquinones from suction filter top, again through conventional sulfonation handle vitamin K
3Waste liquid after the oxidation is regenerated through electrolytic tank electrolysis.Characteristics are that the phase transfer catalytic oxidation method is adopted in oxidation, and oxidizing temperature is low, the reaction times is short, yield is high.The whole electrolytic regenerations of oxidation waste liquid, electrolytic speed is fast, current efficiency is higher.Vitamin K
3Cost is low, quality good.
Description
Vitamin K
3Claim 2-methyl isophthalic acid .4-naphthoquinones sodium bisulfite again, molecular formula is C
11H
8O
2NaHSO
33H
2O, a kind of hemostatic agent of genus pharmaceutical, a kind of fodder additives of its feeding industry.
Shanghai Dazhong Pharmaceutical Manufacturer is former to be the vitamin K of China's maximum
3It is oxygenant that factory, this factory adopt sodium dichromate 99 to add sulfuric acid, adds acetone extract simultaneously and generates the Beta-methyl naphthoquinones, can get vitamin K after sulfonation is handled
3, the waste liquid after the oxidation adopts neutralization, sedimentation, method for calcinating to handle, and the shortcoming of producing this technology of chromium sesquioxide (claiming chrome green again) is that efficient is low, the material consumption height, liquid waste disposal is not thorough, causes pollution of chromium easily.Anshan Thermal Energy Inst. succeeded in developing in 1985 and builds up the new vitamin K of a cover in Anshan animal pharmaceutical factory
3Production equipment, this process using chromic trioxide and sulfuric acid are oxygenant, and beta-methylnaphthalene is oxidized to the Beta-methyl naphthoquinones, can get vitamin K after sulfonation is handled
3Waste liquid after the oxidation adopts electrolysis process regeneration, all oxidation liquid closed cycles, and technology does not have chromate waste water substantially and effluxes.Electrolyzer is the square groove structure that polyvinyl chloride panel is made, and selects homemade F for use
101Film is an ionic membrane, and anode is φ 50 a ceramic matrixs plating plumbic oxide, and negative electrode is a stereotype.The shortcoming of this technology mainly contains 2 points, and the 1st, oxidization time is long, the oxidizing temperature height, Beta-methyl naphthoquinones yield is low, and is of poor quality.The 2nd, because of positive plate is the garden rod, negative plate is tabular, and the cathode-anode plate spacing is big and inhomogeneous, and in addition, electrolysis procedure is a batch operation, and anode and cathode liquid is in stationary state substantially, so current efficiency is low, vitamin K per ton
3Power consumption reaches 5.5 ten thousand Kwh.
In view of the variety of problems of above-mentioned existence, purpose of the present invention just provides a kind of new method for oxidation, and promptly the phase transfer catalytic oxidation method provides a kind of new cell construction and electrolysis process, thereby increases substantially oxidation recovery rate and current efficiency, reduces vitamin K
3Production cost, improve vitamin K
3Quality.
Describe the present invention in detail.
Vitamin K
3Production divide three steps by chemical reaction:
1. beta-methylnaphthalene oxidation:
2. Beta-methyl-1.4-naphthoquinones (C
11H
8O
2) sulfonation:
3. oxidation waste liquid electrolytic regeneration:
Wherein the 1st step and the 3rd step are keys of the present invention, and the 2nd step sulfonation (or addition) reaction is conventional sulfonation reaction.The production technique in the 1st step and the 3rd step is described in detail in detail below.
Vitamin K
3Production be the principle that adopts phase transfer catalytic oxidation, contain CrO in the oxidation liquid
3130g/l, H
2SO
4, H
2O, the poly-ethyl ether of alkyl phenyl (OP series emulsifying agent) 200ppm, (beta-methylnaphthalene) adds 50～500ppmOP series emulsifying agent in the conventional oxidizing reaction material of oxidation liquid, above material together adds in the stills for air blowing, and 30～55 ℃ of controlled temperature make it to react 5 hours, put into the suction filter suction filtration then, waste liquid enters medial launder, can receive from suction filter top the Beta-methyl naphthoquinones, wash with water repeatedly, drain and can get the Beta-methyl naphthoquinones, again through sulfonation handle vitamin K
3
Waste liquid after the oxidation contains Cr
2(SO
4)
3, H
2SO
4, H
2O enters in the electrolysis elevated dosing vessel again, controls certain speed, puts into electrolyzer and carries out electrolysis, and the oxidation liquid after the electrolysis reaches Cr
+ 6After the concentration of 70～130g/l, sulfuric acid 330g/l, can pump into stills for air blowing again and carry out oxidizing reaction again.This technological reaction temperature is adjusted to 30～55 ℃ by original 30～70 ℃, reaction times shortened to 5 hours by original 12 hours, the weight yield of Beta-methyl naphthoquinones brings up to 72% by original 40%, and gained Beta-methyl naphthoquinones can reach 101～104 ℃ of fusing points without organic solvent extraction.
Waste liquid after the oxidation enters in the electrolyzer through the electrolysis elevated dosing vessel, electrolyzer is a flange-type structure, each groove is made up of a plurality of single grooves, between single groove the viton flange gasket is arranged, have ionic membrane to separate between anolyte compartment and the cathode compartment, positive plate is a titanium plating plumbic oxide expanded metals, negative plate is a stainless steel plate mesh, cathode-anode plate spacing＜30mm, electrolysis temperature are controlled at 60～70 ℃, and catholyte and anolyte all recycle.
Waste liquid at first enters electrolyzer anode chamber after the oxidation, Cr in the waste liquid
3+Oxidizing reaction promptly takes place and forms Cr in ejected electron voluntarily on positive plate
2O
2-
7, then obtain electronics on the negative plate, make H
+Be reduced into oxygen, from electrolyzer, overflow.The anolyte compartment separates the Cr that the cationic membrane that this groove adopts can stop the anolyte compartment to form effectively with cathode compartment is middle with ionic membrane
2O
2-
7Go to cathode compartment, thereby reached the effect of waste liquid oxidation regeneration.For preventing that cathode-anode plate two sides from forming the charged ion layer, the way of this process using pump circulation is destroyed the charged ion layer, thereby has improved current efficiency effectively.The oxidation waste liquid has been become dynamically by original static state in electrolyzer, thereby has improved electrolytic speed, presses Cr in the waste liquid
6+Concentration brings up to 90% by 20%, and current efficiency reaches 50～60%, improves 30～50% than former electrolytic cell currents efficient.
Accompanying drawings the present invention.
Accompanying drawing 1 is a schematic flow sheet of the present invention.Oxidation liquid, beta-methylnaphthalene, catalyzer are joined in the stills for air blowing (1), 30～55 ℃ of controlled temperature, reacted 5 hours, reactant is put into suction filter (2) and under reduced pressure entered medial launder (3), can obtain the Beta-methyl naphthoquinones from suction filter (2) top, wash with water repeatedly drain after, promptly get the Beta-methyl naphthoquinones, handle to get vitamin K again through sulfonation
3Waste liquid after the oxidation is put into electrolysis elevated dosing vessel (4), control certain speed, put into electrolyzer (5) again, electrolyzer is cascaded by the groove of five same spline structures, same shape, and waste liquid one side in these five grooves flows, and one side is by electrolysis, after five electrolyzers electrolysis successively, flow in the circulation groove (6), return electrolysis elevated dosing vessel (4) through recycle pump (7), when oxidation liquid reaches Cr
6+After the concentration of 70～130g/l, sulfuric acid 330g/l, then become regenerating oxidation liquid, return stills for air blowing (1) and carry out oxidizing reaction again.
Accompanying drawing 2 is cell construction synoptic diagram of the present invention.Electrolyzer is by the use that is together in series of five single electrolyzers, and each electrolyzer is made up of a plurality of single grooves, between single groove viton flange gasket (11) is arranged, ionic membrane (12) is Japanese Asahi Chemical Industry or du pont company Nafion427 film, positive plate is a titanium plating plumbic oxide expanded metals (13), negative plate is stainless steel plate mesh (14), single groove has 4～6, negative electrode and positive plate spacing＜30mm, 60～70 ℃ of electrolysis temperatures, the whole circular flows of catholyte and anolyte, the oxidation waste liquid is changed over dynamically by static state in electrolyzer, thereby has improved electrolytic speed widely.
Characteristics of the present invention are to adopt the phase transfer catalytic oxidation method, and the temperature of oxidation is low, and the reaction times is short, the yield height of Beta-methyl naphthoquinones, and the whole circular flows of catholyte and anolyte in the electrolyzer, electrolytic speed is fast, current efficiency height, vitamin K
3Production cost low, the quality height, yield is big.
Embodiment.
Press 2M
3Stills for air blowing (1) meter is with 1.7M
3Oxidation liquid (Cr
6++ 90%, total acid 330g/l) in the stills for air blowing of packing into (1), drops into 95% beta-methylnaphthalene 44kg, alkyl phenyl gathers ethyl ether 0.6kg, and 30～55 ℃ of control reaction temperature make it to react 4.5 hours, be cooled to 40 ℃, reactant is put in the suction filter (2), vacuumizes, the oxidation waste liquid flows into medial launder (3), obtain the Beta-methyl naphthoquinones from the suction filter sieve plate, send into then in the sulfonation still (8) and carry out sulfonation reaction,, can obtain C from whizzer (9) through frozen centrifugation
11H
8O
2NaHSO
33H
2O, i.e. vitamin K
3The oxidation waste liquid enters in the electrolysis elevated dosing vessel (4) lentamente, and enters first electrolyzer simultaneously, then successively through 2,3,4,5 electrolyzers, the groove temperature control between 60～70 ℃, current density 300A/M
2, electrolytic oxidation liquid flows into circulation groove (6), and partial oxidation liquid is returned elevated dosing vessel (4), works as Cr
6+Concentration reaches 90g/l, squeezes into stills for air blowing (1) again, current efficiency 60%, and oxidation gets smart Beta-methyl naphthoquinones 31.5kg.
6 single grooves are arranged in the electrolyzer, form by viton flange gasket (11) connection between single groove (15,16).Separate with ionic membrane (12) between anolyte compartment (15) and the cathode compartment (16), this ionic membrane (12) is a du pont company Nafion427 film, positive plate is a titanium plating plumbic oxide expanded metals (13), and negative plate is stainless steel plate mesh (14), positive plate and negative plate spacing＜30mm.Its electrolysis process is that catholyte and anolyte all are in flow state, thereby has improved electrolytic efficiency greatly, at current density 300A/M
2Under the situation, current efficiency reaches 60%.
Claims (2)
1, a kind of processing through the oxidation sulfonation by beta-methylnaphthalene generates vitamin K
3Method, it is characterized in that: method for oxidation is the phase transfer catalytic oxidation method, is oxygenant with chromic trioxide and sulfuric acid, OP series emulsifying agent is a catalyzer, the waste liquid after the oxidation uses after electrolytic tank electrolysis regeneration repeatedly.
2, a kind of processing through the oxidation sulfonation by beta-methylnaphthalene generates vitamin K
3Electrolyzer, it is characterized in that electrolyzer is a flange arrangement, each groove is made up of 6 single grooves, and the viton flange gasket is arranged between single groove, between anolyte compartment and the cathode compartment ionic membrane is arranged, the cathode and anode distance between plates is less than 30mm, electrolytic solution is pump circulation in electrolyzer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92112018A CN1038604C (en) | 1992-10-07 | 1992-10-07 | Method for producing vitamine K3 and electrolytic apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92112018A CN1038604C (en) | 1992-10-07 | 1992-10-07 | Method for producing vitamine K3 and electrolytic apparatus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1085266A true CN1085266A (en) | 1994-04-13 |
| CN1038604C CN1038604C (en) | 1998-06-03 |
Family
ID=4945697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92112018A Expired - Fee Related CN1038604C (en) | 1992-10-07 | 1992-10-07 | Method for producing vitamine K3 and electrolytic apparatus |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1038604C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1316108C (en) * | 2002-01-11 | 2007-05-16 | Lg电子株式会社 | Washing machine |
| CN101289227B (en) * | 2008-06-18 | 2010-04-14 | 代汉松 | Process for recovering chromium from waste liquid of vitamin K3 production |
| CN1837172B (en) * | 2006-03-16 | 2010-05-12 | 中钢集团鞍山热能研究院 | Use of separating agent used in preparation of vitamin K3 |
| CN105506668A (en) * | 2015-12-23 | 2016-04-20 | 四川省银河化学股份有限公司 | Electrolytic comprehensive utilization method of naphthoquinone raffinate |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100341834C (en) * | 2006-03-16 | 2007-10-10 | 中钢集团鞍山热能研究院 | Process for preparing vitamin K3 by extraction method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57134581A (en) * | 1981-02-13 | 1982-08-19 | Shigeru Torii | Production of 1, 4-naphthoquinone derivative |
-
1992
- 1992-10-07 CN CN92112018A patent/CN1038604C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1316108C (en) * | 2002-01-11 | 2007-05-16 | Lg电子株式会社 | Washing machine |
| CN1837172B (en) * | 2006-03-16 | 2010-05-12 | 中钢集团鞍山热能研究院 | Use of separating agent used in preparation of vitamin K3 |
| CN101289227B (en) * | 2008-06-18 | 2010-04-14 | 代汉松 | Process for recovering chromium from waste liquid of vitamin K3 production |
| CN105506668A (en) * | 2015-12-23 | 2016-04-20 | 四川省银河化学股份有限公司 | Electrolytic comprehensive utilization method of naphthoquinone raffinate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1038604C (en) | 1998-06-03 |
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