CN1038604C

CN1038604C - Method for producing vitamine K3 and electrolytic apparatus

Info

Publication number: CN1038604C
Application number: CN92112018A
Authority: CN
Inventors: 李文藩
Original assignee: ANSHAN THERMAL ENERGY INST MINISTRY OF METALLURGICAL INDUSTRY
Current assignee: ANSHAN THERMAL ENERGY INST MINISTRY OF METALLURGICAL INDUSTRY
Priority date: 1992-10-07
Filing date: 1992-10-07
Publication date: 1998-06-03
Anticipated expiration: 2007-10-07
Also published as: CN1085266A

Abstract

The present invention relates to a preparation method of vitamin K3 and an electrolysis device. The vitamin K3 is medicinal hemostatic and a feed additive used in livestock and poultry breeding. The vitamin K3 is prepared by the way that beta-methylnaphthalene and an oxidation solution have a catalytic oxidation reaction in an oxidation vessel by adding catalysts and enter an intermediate tank after the pressure is reduced by a suction filter, beta-methyl naphthoquinone can be obtained from the upper part of the suction filter and then carry out conventional sulphonation treatment to prepare the vitamin K3. The oxidized waste solution is electrolytically regenerated through an electrolysis tank. The present invention has the characteristics of phase-transfer catalytic oxidation method adopted in oxidation, low oxidation temperature, short reaction time and high yield, electrolytic regeneration of all oxidized waste solution, high speed of electrolysis and high current efficiency. The vitamin K3 has low cost and high quality.

Description

Production method of vitamin K3 and electrolysis device

Vitamin K3 also known as 2-methyl-1, 4-naphthoquinone sodium bisulfite with molecular formula C₁₁H₈O₂.NaHSO₃.3H₂O, a hemostatic belonging to the medicine category, a feed additive in the livestock and poultry raising industry.

The Shanghai public pharmaceutical factory, originally the largest vitamin K3 factory in China, adopts sodium dichromate and sulfuric acid as oxidants, and simultaneously adds acetone for extraction to generate β -methyl naphthoquinone, and after sulfonation treatment, vitamin K3 can be obtained, the oxidized waste liquid is treated by a neutralization, sedimentation and calcination method to prepare chromium sesquioxide (also called chrome green), the process has the disadvantages of low efficiency, high material consumption, incomplete waste liquid treatment and easy chromium pollution, the Mingshan heat energy research institute successfully develops in 1985 and builds a set of new vitamin K3 production device in Mingshan veterinary pharmaceutical factory, the process adopts chromic anhydride and sulfuric acid as oxidants to oxidize β -methyl naphthalene into β -methyl naphthoquinone, the waste liquid after sulfonation treatment, which can be oxidized by vitamin K3., is regenerated by an electrolysis method, all the oxidation liquid is in closed cycle, the process basically has no waste water, an electrolytic tank is made of polyvinyl chloride plates, the domestic F101 membrane is selected as an ionic membrane, Wh phi is 50 cathode lead dioxide, the anode plate is a second anode plate, the anode plate is in a stable anode plate, the cathode plate is in a stable anode plate, the cathode plate is operated at a stable anode plate, the temperature is low, the cathode plate is not uniform, the cathode plate is operated, the anode plate is operated at a stable anode plate, the stable anode plate is not stable anode plate, the cathode plate is not used in the stable anode plate, the stable anode plate is not used, the stable anode.

In view of the above problems, it is an object of the present invention to provide a novel oxidation method, i.e., a catalytic oxidation method, and to provide a novel electrolytic cell structure and an electrolytic process, which can significantly improve the oxidation yield and the current efficiency, reduce the production cost of vitamin K3, and improve the quality of vitamin K3.

Detailed description of the invention:

the production of vitamin K3 is divided into three steps according to the chemical reaction:

oxidation of 1, β -methylnaphthalene:

2, β -methyl-1, 4-naphthoquinone (C)₁₁H₈O₂) Sulfonation of (2):

(vitamin K3)

3. Electrolytic regeneration of oxidation waste liquid:

wherein the 1 st step and the 3 rd step are the key points of the invention, and the 2 nd step sulfonation reaction is a conventional sulfonation reaction. The production processes of the steps 1 and 3 are described in detail below.

The vitamin K3 is prepared from β -methylnaphthalene as raw material, alkylphenyl polyethyl ether (OP series emulsifier) as catalyst in an amount of 50-500ppm, and chromic anhydride (CrO)₃) And sulfuric acid (H)₂SO₄) As an oxidizing agent, (CrO)₃130g/l，H₂SO₄320-350g/l), controlling the temperature to be 30-55 ℃ in a sugar porcelain oxidation reaction kettle with a stirrer, reacting for 5.0 hours, performing suction filtration on reactants through a suction filter, feeding filtrate into an intermediate tank, obtaining an intermediate product β -methyl-1.4-naphthoquinone (β -methylnaphthoquinone for short) from the upper part of the suction filter, repeatedly washing with water until the intermediate product is neutral, performing suction drying, performing sulfonation reaction on β -methylnaphthoquinone and sodium bisulfite to obtain crude vitamin K3. and crude vitamin K3, recrystallizing and drying to obtain an refined vitamin K3. product, and performing comprehensive analysis and test by Liaoning veterinary drug monitoring, wherein each index completely reaches the quality requirements of Chinese veterinary drug Standard and GB7294-87 feed additive vitamin K3 Standard, and issuing a production license and a drug approval number of vitamin K3.

The oxidized waste liquid contains Cr₂(SO₄)₃、H₂SO₄、H₂And O, and then entering an electrolysis high-level metering tank. Controlling a certain speed, putting the mixture into an electrolytic cell for electrolysis, and enabling the electrolyzed oxidizing solution to reach CrO₃70-130g/l and 330g/l sulfuric acid, pumping into the oxidation kettle again for oxidation reaction, adjusting the reaction temperature of the process from the original 30-70 ℃ to 30-55 ℃, shortening the reaction time from the original 12 hours to 5 hours, increasing the weight yield of β -menaquinone from the original 40% to 72%, and obtaining β -menaquinone which can reach the melting point of 101-104 ℃ without organic solvent extraction.

The waste liquid after oxidation enters an electrolytic bath through an electrolytic high-position metering tank, the electrolytic bath is of a flange type structure, each bath consists of 5 single baths, the single baths are connected by fluororubber flange gaskets to form two anode chambers and three cathode chambers, ionic membranes are arranged between the anode chambers and the cathode chambers to separate the anode chambers from the cathode chambers, cathode plates are arranged in the anode chambers, anode plates are titanium-plated lead dioxide plate nets, the cathode plates in the cathode chambers are stainless steel plate nets, the distance between the cathode plates and the anode plates is less than 30mm, and the electrolytic temperature is controlled to be 60-70 ℃.

The waste liquid after oxidation firstly enters an anode chamber of an electrolytic cell, and Cr in the waste liquid³⁺Electrons are released on the anode plate, namely, the oxidation reaction occurs automatically to form Cr₂O₇ ^2-Electrons are obtained on the cathode plate to make H⁺Reduced to hydrogen and escaped from the electrolytic bath. The anode chamber and the cathode chamber are separated by an ionic membrane, and the cationic membrane adopted by the tank can effectively prevent Cr formed in the anode chamber₂O₇ ^2-And the waste liquid runs to the cathode chamber, thereby achieving the effect of oxidizing and regenerating the waste liquid. In order to prevent the charged ion layers from being formed on the two sides of the cathode plate and the anode plate, the process adopts a forced circulation method to destroy the charged ion layers, thereby effectively improving the current efficiency. The oxidation waste liquid is changed from original static state to dynamic state in the electrolytic bath, thereby improving the electrolytic speed according to CrO in the waste liquid₃The concentration is increased from 20% to 90%, the current efficiency reaches 50-60%, and is increased by 30-50% compared with the current efficiency of the original electrolytic cell.

The invention is described in connection with the accompanying drawings.

Adding an oxidizing solution, β -methylnaphthalene and a catalyst into an oxidation kettle 1, controlling the temperature to be 30-55 ℃, reacting for 5 hours, putting reactants into a suction filter 2, putting the reactants into an intermediate tank 3 under reduced pressure, obtaining β -methyl-1.4-naphthoquinone from the upper part of the suction filter 2, repeatedly washing and draining the reactants by water to obtain β -methyl-1.4-naphthoquinone, putting the waste liquid oxidized by vitamin K3. into an electrolysis high-level metering tank 4 after sulfonation treatment, controlling a certain speed, putting the waste liquid into an electrolysis tank 5, connecting the electrolysis tanks in series by five tanks with the same structure and the same shape, enabling the waste liquid to flow in the five tanks, electrolyzing the waste liquid in sequence by the five electrolysis tanks, flowing into a circulating tank 6, and circulating the waste liquidThe pump 7 is pumped back to the electrolysis high-level metering tank 4, and when the oxidizing solution reaches CrO₃70-130g/l and 330g/l sulfuric acid, and returning the regenerated oxidizing solution to the oxidizing kettle 1 for oxidation reaction.

FIG. 2 is a schematic view of the structure of the electrolytic cell of the present invention. The electrolytic bath is of a flange type structure, each electrolytic bath consists of 5 single baths, a fluororubber flange gasket 11 and an ionic membrane 12 are arranged between the single baths, the ionic membrane 12 is a Nafion427 membrane of Asahi chemical or DuPont, USA, an anode plate is a titanium-plated lead dioxide plate mesh 13, a cathode plate is a stainless steel plate mesh 14, the distance between a cathode plate and the anode plate is less than 30mm, the electrolytic temperature is 60-70 ℃, the catholyte and the anolyte are all circularly operated, and the oxidation waste liquid is changed fromstatic state to dynamic state in the electrolytic bath, so the electrolytic speed is greatly improved.

The invention is characterized in that a catalytic oxidation method is adopted, the oxidation temperature is low, the reaction time is short, the yield of β -methyl-1.4-naphthoquinone is high, the catholyte and the anolyte in the electrolytic bath are all circularly operated, the electrolytic speed is high, the current efficiency is high, the production cost of vitamin K3 is low, the quality is high, and the yield is high.

Example (b):

press 2M³1.7M of the oxidation kettle³Oxidizing liquid (CrO)₃90 percent of total acid 330g/l) is put into an oxidation kettle 1, 95 percent of β -methylnaphthalene 44Kg and alkyl phenyl polyethyl ether 0.6Kg are put into the oxidation kettle, the reaction temperature is controlled to be 30-55 ℃ for reaction for 4.5 hours, the reaction product is cooled to 40 ℃, the reaction product is put into a suction filter 2 and is vacuumized, the oxidation waste liquid flows into an intermediate tank 3, β -methyl naphthoquinone is obtained from a sieve plate of the suction filter, then the oxidation waste liquid is sent into a sulfonation kettle 8 for sulfonation reaction, and C can be obtained from a centrifuge 9 through refrigerated centrifugation₁₁H₈O₂.NaHSO₃.3H₂O, i.e. crude vitamin K3. (crude K3 is recrystallized by using ethanol as a solvent, and is dried to obtain refined vitamin K3, all indexes of the product reach the vitamin K3 standard in Chinese veterinary drug Specifications and also reach the vitamin K3 standard of GB7294-87 feed additive, and the oxidation waste liquid slowly enters an electrolysis high-level metering tank 4 and simultaneously enters a first electrolytic tankThen sequentially passing through 2, 3, 4 and 5 electrolytic tanks, controlling the temperature of the electrolytic tanks between 60 and 70 ℃ and the current density of 300A/M²The electrolytic oxidation liquid flows into a circulating tank 6, part of the oxidation liquid is pumped back to a high-level metering tank 4, when CrO₃The concentration reaches 90g/l, and then the mixture is pumped into an oxidation kettle 1, the current efficiency is 60 percent, and the refined β -methyl-1.4-naphthoquinone 31.5Kg is obtained by oxidation.

The electrolytic bath has 5 single baths, and the single baths 15 and 16 are connected by a fluororubber flange gasket 11. The anode chamber 15 and the cathode chamber 16 are separated by an ionic membrane 12, the ionic membrane 12 is a Nafion427 membrane of DuPont, the anode plate is a titanium-plated lead dioxide plate mesh 13, the cathode plate is a stainless steel plate mesh 14, and the distance between the anode plate and the cathode plate is less than 30 mm. The electrolysis process is that the catholyte and the anolyte are all in a flowing state, thereby greatly improving the electrolysis efficiency and ensuring that the current density is 300A/M²In the case, the current efficiency reaches 60%.

Claims

1. A process for preparing vitamin K3 from β -methylnaphthalene by oxidizing and sulfonating features that the oxidizing method is liquid-phase catalytic oxidizing method, which uses β -methylnaphthalene as raw material, chromic anhydride and sulfuric acid as oxidizing agent, OP series emulsifier as catalyst, reaction temp is 30-55 deg.C, and the oxidized waste liquid is regenerated by electrolysis in electrolyzer and reused.

2. An electrolyzer for oxidizing the waste liquid generated by oxidizing β -methylnaphthalene features that its electrolyzer has flange structure, each electrolyzer is composed of 5 single electrolyzer units, a fluororubber flange pad, ionic membrane, and negative or positive plate, the distance between said negative and positive plates is less than 30mm, the electrolyzing temp is 60-70 deg.C, and the cathode and anode are circulated in said electrolyzer.