CN111892490A - Ce4+Method for preparing beta-menadione and its derivative menadione sodium bisulfite as oxidant - Google Patents
Ce4+Method for preparing beta-menadione and its derivative menadione sodium bisulfite as oxidant Download PDFInfo
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- 229940041603 vitamin k 3 Drugs 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 66
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 26
- 239000007800 oxidant agent Substances 0.000 title claims abstract description 24
- 229960004051 menadione sodium bisulfite Drugs 0.000 title claims description 48
- XDPFHGWVCTXHDX-UHFFFAOYSA-M menadione sodium sulfonate Chemical compound [Na+].C1=CC=C2C(=O)C(C)(S([O-])(=O)=O)CC(=O)C2=C1 XDPFHGWVCTXHDX-UHFFFAOYSA-M 0.000 title description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 95
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- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
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- USJXWXWQXACJEA-UHFFFAOYSA-J cerium(4+);methanesulfonate Chemical compound [Ce+4].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O USJXWXWQXACJEA-UHFFFAOYSA-J 0.000 description 5
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- 230000015572 biosynthetic process Effects 0.000 description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 4
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 3
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- 125000000985 2-methyl-1,4-naphthoquinonyl group Chemical group CC=1C(C2=CC=CC=C2C(C1*)=O)=O 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
- C07C46/04—Preparation of quinones by oxidation giving rise to quinoid structures of unsubstituted ring carbon atoms in six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/10—Separation; Purification; Stabilisation; Use of additives
Abstract
The invention relates to Ce4+A method for preparing beta-menadione by using the beta-menadione as an oxidant, which comprises the following steps: step 1, preparing an electrolyzed high cerium methanesulfonic acid solution, and dissolving beta-methylnaphthalene in a first organic solvent to obtain a beta-methylnaphthalene organic solution; step 2, adding part of the high cerium methane sulfonate solution into a reaction kettle to be used as a base solution; step 3, carrying out constant temperature reaction for three times, and step 4, filtering to obtain a beta-menadione filter cake after the reaction is finished; layering the filtrate to obtain an organic solvent oil phase layer and a cerium methanesulfonate water phase layer; and 5, extracting the beta-menadione filter cake by using a first organic solvent, filtering, and layering the filtrate to obtain an oil phase layer of the beta-menadione organic solution and a cerium methanesulfonate water phase layer. In the method, a high-speed shearing emulsifying machine is adopted to strengthen mass transfer in the oxidation processThe use of emulsifier is avoided, and the problems of foam in the post-treatment and electrolysis processes of the oxidation residual liquid, the electrolysis efficiency and the enrichment in long-term cyclic application are solved.
Description
Technical Field
The invention relates to a chemical synthesis method, in particular to Ce4+A method for preparing beta-menadione and derivative thereof, namely menadione sodium bisulfite as an oxidant, which belongs to the field of chemical synthesisIn the technical field of chemical synthesis.
Background
The chemical name of the beta-menadione is 2-methyl-1, 4-naphthoquinone. The pure product is bright yellow crystal or crystalline powder, and has special pungent odor. Insoluble in water, soluble in ethanol, benzene, chloroform, carbon tetrachloride and vegetable oils. Is stable in air and is easy to deteriorate and decompose when being exposed to light, alkali and reducing agent. The compound is used as a feed additive raw material, and has the main functions of promoting the liver of livestock and poultry to synthesize prothrombin and promoting the synthesis of plasma coagulation factors in the liver to prepare a blood stopping agent.
MSB (menadione sodium bisulfite) obtained by the addition reaction of beta-menadione and sodium bisulfite. MSB is white crystalline powder, is easily soluble in water and hot ethanol, is insoluble in benzene and diethyl ether, has a pH of about 4.7-7, is stable at normal temperature, is easily decomposed by light, and can be used for treating bleeding diseases.
Currently, β -menadione is synthesized mainly by three different synthetic methods:
(1) sodium dichromate (potassium dichromate) oxidation process
The method is a synthesis technology which is most applied at present, namely a chromium method process, sodium dichromate or potassium dichromate is adopted as an oxidant, beta-methylnaphthalene is oxidized in the presence of sulfuric acid to obtain beta-menadione, and the yield is about 51%. The chromium method uses high-toxicity hexavalent chromium, generates a large amount of chromium-containing wastewater, has serious environmental pollution and has great harm to the health of operators.
(2) Hydrogen peroxide oxidation process
The method has the advantages that hydrogen peroxide (with the concentration of about 30 percent) is used as an oxidant, acetic acid is used as a solvent, and methyl trioxymethylene or Pd (II) -sulfate polystyrene resin is used as a catalyst, so that the method has high yield, but the hydrogen peroxide has large usage amount, the catalyst is difficult to recycle, the generated wastewater is more, and the environmental pollution is large.
(3) High-valence cerium salt oxidation method
The method uses Ce under the acidic condition of methanesulfonic acid or sulfuric acid4+Oxidizing beta-methylnaphthalene to obtain beta-menadione, and separating menadione containing Ce3+Oxidation of the residual liquidFiltering, oxidizing to remove organic matters, decolorizing, and electrolyzing and oxidizing to obtain Ce again4+Thereby realizing cyclic application. However, the emulsifier is added in the oxidation process to enhance mass transfer and accelerate reaction rate, but the emulsifier cannot be thoroughly and effectively decomposed and removed in the post-treatment and electrolysis processes of the oxidation residual liquid, a large amount of foam is generated in the electrolysis process in the post-treatment process due to the existence of the emulsifier, the problems of difficult normal operation, low electrolysis efficiency and the like exist, and the emulsifier can be gradually accumulated in the long-term cyclic application process and finally the cerium liquid cannot be continuously applied.
Therefore, by combining all factors, the synthesis process generally adopted by the current industrial production is a 'chromium method' route, but in order to solve the problem that a large amount of chromium-containing wastewater is generated by chromium-series oxidant processes, the research on the synthesis technology of the green and environment-friendly beta-menadione with high yield at home and abroad is not interrupted, but the success rate is not high.
Disclosure of Invention
The object of the present invention is to provide Ce4+The method for preparing beta-menadione and derivative thereof, namely the sodium bisulfite menadione, by using the cerium methanesulfonate as an oxidant instead of sodium dichromate avoids the use of high-toxicity hexavalent chromium and the generation of a large amount of chromium-containing wastewater, and can furthest reduce the harm to operators and the environment.
The technical scheme adopted by the invention for solving the technical problems is as follows:
ce4+A method for preparing beta-menadione by using the beta-menadione as an oxidant, which comprises the following steps:
step 1, preparing electrolytic high cerium methane sulfonate solution,
dissolving beta-methylnaphthalene in a first organic solvent to obtain a beta-methylnaphthalene organic solution;
step 2, adding part of the high cerium methane sulfonate solution into a reaction kettle to be used as a base solution;
step 3, carrying out constant temperature reaction: continuously dripping the beta-methylnaphthalene organic solution and the high cerium methane sulfonate solution into a reaction kettle at the same time, and reacting at constant temperature after finishing dripping, wherein the temperature is controlled to be 0-25 ℃, and the constant temperature time is 0.5-2 hours;
and (2) constant-temperature reaction: after the constant temperature reaction is finished, raising the temperature to continue the constant temperature reaction, wherein the temperature is controlled to be 25-45 ℃, and the constant temperature time is 0.5-2 hours;
and (3) constant-temperature reaction: after the constant-temperature reaction II is finished, raising the temperature to continue the constant-temperature reaction, wherein the temperature is controlled to be 45-75 ℃, and the constant-temperature time is 0.5-2 hours;
step 4, filtering to obtain a beta-menadione filter cake after the reaction is finished; layering the filtrate to obtain an organic solvent oil phase layer and a cerium methanesulfonate water phase layer, wherein the organic solvent layer is used for later use, and the cerium methanesulfonate water phase layer is used for later use;
and 5, extracting the beta-menadione filter cake by using a first organic solvent, filtering, and then layering the filtrate to obtain a beta-menadione organic solution oil phase layer and a cerium methanesulfonate water phase layer, mixing the beta-menadione organic solution oil phase layer and the organic solvent oil phase layer in the step 4 to obtain a beta-menadione organic solution, washing the beta-menadione organic solution with water, mixing the cerium methanesulfonate water phase layer and the cerium methanesulfonate water phase layer in the step 4 to obtain a cerium methanesulfonate solution, and recycling the cerium methanesulfonate solution after electrolysis.
In the method, a high-speed shearing emulsifying machine is adopted to strengthen mass transfer in the oxidation process, so that the use of an emulsifying agent is avoided, the problems of post-treatment of oxidation residual liquid, foaming in the electrolysis process, electrolysis efficiency and enrichment in long-term cyclic application are solved, and the problem of industrialization is solved; the mass transfer is enhanced in the oxidation process, and the yield is improved by matching with the temperature control of different stages in the reaction process, and the yield of menadione can reach more than 63 percent.
In the process of the invention, the oxidant is Ce4+Methanesulfonic acid solution of, Ce4+Is obtained by electrolyzing Ce3 +; the electrolysis method is a better method for cleanly obtaining the high-valence oxidant, and can avoid using inorganic oxidant.
Preferably, in the step 1, the concentration of the high cerium methanesulfonate solution is 0.1-1.2 mol/L, and the mass ratio of the beta-methylnaphthalene to the first organic solvent is 1: 1-10, preferably 1: 4-6.
Preferably, in the step 2, the priming amount of the high cerium methanesulfonate solution is 1 wt% to 10 wt% of the total amount of the high cerium methanesulfonate solution.
Preferably, in the step 3, the dropping time of the beta-methylnaphthalene organic solution and the cerous methanesulfonate solution is controlled to be 0.5-2 h, preferably 1-1.5 h.
Preferably, in the step 3, reacting at constant temperature, namely, controlling the temperature to be 10-20 ℃ and keeping the temperature for 1-1.5 hours; controlling the temperature of the constant-temperature reaction II to be 30-40 ℃ and keeping the temperature for 1-1.5 h; the temperature of the constant-temperature reaction is controlled to be 55-65 ℃, and the constant-temperature time is 1-1.5 h.
Preferably, in the step 4, the material temperature is controlled to be 10-60 ℃ during filtering, and preferably 20-40 ℃.
Preferably, in the step 5, the temperature of the material is controlled to be 40-90 ℃ during extraction, and preferably 60-70 ℃; the mass ratio of menadione (including beta-menadione and hexa-position quinone, pure amount) to the first organic solvent is 1: 1-20, preferably 1: 5-15.
Preferably, in the step 5, the temperature of the material is controlled to be preferably 40-90 ℃ when the beta-menadione organic solution is washed by water, and more preferably 60-70 ℃; the mass ratio of the beta-menadione organic solution to the washing water is preferably 1-20: 1, and more preferably 5-15: 1.
Ce4+A method for preparing beta-menadione derivative menadione sodium bisulfite as an oxidant, which comprises the following steps:
step 1, preparing electrolytic high cerium methane sulfonate solution,
dissolving beta-methylnaphthalene in a first organic solvent to obtain a beta-methylnaphthalene organic solution;
step 2, adding part of the high cerium methane sulfonate solution into a reaction kettle to be used as a base solution;
step 3, carrying out constant temperature reaction: continuously dripping the beta-methylnaphthalene organic solution and the high cerium methane sulfonate solution into a reaction kettle at the same time, and reacting at constant temperature after finishing dripping, wherein the temperature is controlled to be 0-25 ℃, and the constant temperature time is 0.5-2 hours;
and (2) constant-temperature reaction: after the constant temperature reaction is finished, raising the temperature to continue the constant temperature reaction, wherein the temperature is controlled to be 25-45 ℃, and the constant temperature time is 0.5-2 hours;
and (3) constant-temperature reaction: after the constant-temperature reaction II is finished, raising the temperature to continue the constant-temperature reaction, wherein the temperature is controlled to be 45-75 ℃, and the constant-temperature time is 0.5-2 hours;
step 4, filtering to obtain a beta-menadione filter cake after the reaction is finished; layering the filtrate to obtain an organic solvent oil phase layer and a cerium methanesulfonate water phase layer, wherein the organic solvent layer is used for later use, and the cerium methanesulfonate water phase layer is used for later use;
step 5, extracting the beta-menadione filter cake with a first organic solvent, filtering, and then layering the filtrate to obtain a beta-menadione organic solution oil phase layer and a cerium methanesulfonate water phase layer, wherein the beta-menadione organic solution oil phase layer and the organic solvent oil phase layer in the step 4 are mixed into a beta-menadione organic solution and washed with water, and the cerium methanesulfonate water phase layer in the step 4 are mixed into a cerium methanesulfonate solution and recycled after being electrolyzed;
step 6, carrying out addition reaction on the beta-menadione organic solution and the sodium metabisulfite solution to obtain MSB reaction liquid, layering to obtain an MSB solution water phase layer and an organic solvent oil phase layer, wherein the organic solvent oil phase layer is sleeved for dissolving beta-methylnaphthalene in the step 1 and extracting beta-menadione in the step 5;
the concentration of the sodium pyrosulfite solution is 10-45 wt%, and the mass ratio of menadione (including beta-menadione and hexa-quinone, pure amount) to sodium pyrosulfite is 1: 0.5 to 3;
the temperature of the addition reaction is 20-70 ℃;
step 7, adding a second organic solvent into the MSB solution water phase layer, cooling, crystallizing, centrifuging and washing, wherein the washing agent is the second organic solvent to obtain an MSB filter cake, and drying to obtain an MSB finished product; and mixing the filtrate with the washing liquid, and recovering the solvent to obtain a second organic solvent for MSB crystallization and washing.
In the method, the menadione and the derivative MSB obtained by the extraction separation method have no cerium metal residue; the first organic solvent is recovered and reused directly by oil-water layering after sulfonation reaction, so that purification procedures such as rectification and the like are not needed, the solvent loss is low, and the energy consumption is low.
Preferably, in step 6, the concentration of the sodium metabisulfite solution is 20 to 35 weight percent; the mass ratio of menadione (including beta-menadione and hexa-position quinone, pure amount) to sodium metabisulfite is 1:1 to 2.
Preferably, in step 6, the temperature of the addition reaction is 35 to 55 ℃.
Preferably, in the step 7, the crystallization temperature is controlled to be-5-10 ℃, and preferably 0-5 ℃; the mass ratio of the washing amount of the second organic solvent to the centrifugal filter cake is 1: 0.5 to 3, preferably 1:1 to 2.
Preferably, in the step 7, the temperature of the MSB drying material is controlled to be 30-90 ℃, and preferably 40-70 ℃.
Preferably, the first organic solvent is selected from one or more of n-butanol, n-hexane, cyclohexane, n-heptane and acetonitrile, and the second organic solvent is selected from one or more of n-butanol, methanol, ethanol, isopropanol and isobutanol.
Compared with the prior art, the invention has the beneficial effects that:
(1) in the method, the non-hexavalent chromium is used as the oxidant, so that the problem of generating a large amount of chromium-containing wastewater is avoided, and the yield of the prepared menadione and the derivative thereof is not reduced.
(2) The invention adopts Ce4+Oxidizing agent, oxidized Ce3+Obtaining Ce by electrolytic regeneration4+The method can be used repeatedly, and lossless is realized.
(3) According to the invention, the use of an emulsifier is avoided in the oxidation process, a liquid-liquid mass transfer effect better than that of the emulsifier is obtained by adopting a high-speed shearing emulsifying machine, the problems of foaming, electrolysis efficiency and enrichment in long-term cyclic application in the oxidation residual liquid post-treatment and electrolysis process are solved, and the problem of industrialization is solved.
(4) The mass transfer is enhanced in the oxidation process, and the yield is improved by matching with the temperature control of different stages in the reaction process, and the yield of menadione can reach more than 63 percent.
(5) The separation of menadione is extracted by a first organic solvent, only beta-menadione and hexa-position quinone in the oxidation reaction liquid are dissolved, and the purity of menadione is ensured; after being washed by water, the menadione does not contain cerium.
(6) The first organic solvent is recovered and applied mechanically, oil and water are layered after sulfonation reaction, no new impurities and no component accumulation are generated after tens of times of cyclic application detection, and the technical requirements of raw and auxiliary materials are met, so that purification procedures such as rectification and the like are not needed, the solvent loss is low, and the energy consumption is low.
(7) The obtained derivative MSB had no cerium metal remaining.
Drawings
In order to more clearly illustrate the embodiments or technical solutions of the present invention, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
FIG. 1 is Ce provided by the invention4+The process flow schematic diagram of a specific embodiment of the method for preparing the beta-menadione and the derivative thereof, namely the menadione sodium bisulfite, serving as the oxidant.
FIG. 2 is a schematic view of an oxidation process apparatus in the process of the present invention.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.
In the present invention, all parts and percentages are by weight, unless otherwise specified, and the equipment and materials used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1:
ce4+The process for preparing beta-menadione and its derivative sodium bisulfite menadione with oxidant, the process flow schematic diagram is shown in figure 1, the oxidation process in the method is carried out by using the device of figure 2, the concrete steps are as follows:
1. 13.6kg of electrolytic high-cerium methanesulfonic acid solution is prepared, and the molar concentration is 0.4 mol/L;
in a 200ml beaker, 70g of beta-methylnaphthalene is put into 105g of a first organic solvent at room temperature, and stirred until the beta-methylnaphthalene is completely dissolved, thereby obtaining a beta-methylnaphthalene organic solution.
2. 1600g of high cerium methane sulfonate solution is added into a 20L high-speed shearing emulsifying machine, and low-temperature water is introduced into a jacket to control the temperature of the materials to be about 10 ℃.
3. Under the condition of stirring rotating speed of 1600-2000 rpm, respectively dripping from two feed inlets: the remaining 12kg of the ceric methanesulfonate solution and the prepared organic solution of β -methylnaphthalene were added dropwise over a controlled period of about 1.5 hours (simultaneously).
After the dropwise addition is finished, entering a constant-temperature reaction stage: controlling the temperature of the system to be 10 ℃, and carrying out heat preservation reaction for 1 hour; then entering a constant temperature reaction stage: heating to 25 ℃ within 30min, and reacting for 1 hour under the condition of heat preservation; and (3) constant-temperature reaction: heating to 40 ℃ within 30min, and reacting for 2 hours under the condition of heat preservation;
4. and after the reaction is finished, cooling to 15-20 ℃, filtering the reaction liquid to obtain about 136g of filter cake, and layering the filtrate to obtain an oil phase layer and a water phase layer.
5. Adding 850g of a first organic solvent into a 3000ml reaction bottle (with a filter screen at a discharge port), and heating to 75 ℃ under stirring; putting the filter cake into a first organic solvent, and dissolving and stirring for 30-45 minutes at the temperature of 75 ℃; discharging the feed liquid, filtering off a small amount of solid between the water phase and the oil phase, and layering the discharged feed liquid to obtain a water phase layer and an oil phase layer, wherein the oil phase layer is mixed with the oil phase layer in the previous step.
Cleaning a 3000ml reactor, adding the mixed oil phase layer, controlling the temperature to be 75 ℃, washing the oil phase layer twice by using 120g of 75 ℃ hot water, layering to obtain a cerium-free menadione organic solution, detecting menadione by using a liquid chromatography detection method, detecting that the content of menadione is 54.3g, and the yield is 64% (the yield is the final yield and is calculated by mol); the menadione organic solution was thermostatted at 37 ℃.
6. 200g of water is added into a 2000ml reaction bottle, 57g of sodium metabisulfite is added, stirring is carried out at the temperature of 40 ℃ until the sodium metabisulfite is completely dissolved, and then heat preservation is carried out, thus obtaining the sodium metabisulfite solution.
And (3) quickly putting the menadione organic solution obtained in the last step into a sodium metabisulfite solution, carrying out heat preservation reaction for 1 hour at the temperature of 40 ℃, standing for 30 minutes, layering to obtain an upper organic solvent phase layer and an MSB aqueous phase layer 265g, and reusing the organic solvent in oxidation extraction operation.
7. Adding 265g of the aqueous phase layer into a 1000ml reaction bottle, adding 250g of a 40 ℃ second organic solvent, and carrying out gradient cooling under a stirring state: 30 ℃ (1 hour hold), 20 ℃ (1 hour hold), 10 ℃ (1 hour hold), 0 ℃ (1 hour hold); and filtering after the heat preservation is finished, and washing a filter cake by using a second organic solvent to obtain wet MSB.
And (3) putting the wet MSB into a 50 ℃ oven for drying for 5 hours to obtain dry MSB, and detecting that the MSB does not contain metal cerium by ICP-Mass spectrometry.
Example 2
Ce4+The method for preparing beta-menadione and derivative thereof, namely menadione sodium bisulfite, by using the beta-menadione as an oxidant comprises the following specific steps:
1. 13.6kg of electrolytic high-cerium methanesulfonic acid solution is prepared, and the molar concentration is 0.4 mol/L;
in a 200ml beaker, 70g of beta-methylnaphthalene is put into 105g of a first organic solvent at room temperature, and stirred until the beta-methylnaphthalene is completely dissolved, thereby obtaining a beta-methylnaphthalene organic solution.
2. 1600g of high cerium methane sulfonate solution is added into a 20L high-speed shearing emulsifying machine, and low-temperature water is introduced into a jacket to control the temperature of the materials to be about 0 ℃.
3. Under the condition of stirring rotating speed of 1600-2000 rpm, respectively dripping from two feed inlets: the remaining 12kg of the ceric methanesulfonate solution and the prepared organic solution of β -methylnaphthalene were added dropwise over a controlled period of about 1.5 hours (simultaneously).
After the dropwise addition is finished, entering a constant-temperature reaction stage: controlling the temperature of the system to be 0 ℃, and carrying out heat preservation reaction for 2 hours; then entering a constant temperature reaction stage: heating to 25 ℃ within 30min, and reacting for 2 hours under the condition of heat preservation; and (3) constant-temperature reaction: heating to 45 ℃ within 30min, and reacting for 2 hours under the condition of heat preservation;
4. and after the reaction is finished, cooling to 15-20 ℃, filtering the reaction liquid to obtain about 102g of filter cake, and layering the filtrate to obtain an oil phase layer and a water phase layer.
5. Adding 850g of a first organic solvent into a 3000ml reaction bottle (with a filter screen at a discharge port), and heating to 75 ℃ under stirring; putting the filter cake into a first organic solvent, and dissolving and stirring for 30-45 minutes at the temperature of 75 ℃; discharging the feed liquid, filtering off a small amount of solid between the water phase and the oil phase, and layering the discharged feed liquid to obtain a water phase layer and an oil phase layer, wherein the oil phase layer is mixed with the oil phase layer in the previous step.
Cleaning a 3000ml reactor, adding the mixed oil phase layer, controlling the temperature to be 75 ℃, washing the oil phase layer twice by using 120g of 75 ℃ hot water, layering to obtain a cerium-free menadione organic solution, and detecting that the content of menadione is 36.5g and the yield is 43%; the menadione organic solution was thermostatted at 37 ℃.
6. 200g of water is added into a 2000ml reaction bottle, 50g of sodium metabisulfite is added, the mixture is stirred at the temperature of 45 ℃ until the sodium metabisulfite is completely dissolved, and then the temperature is kept to obtain a sodium metabisulfite solution.
And (3) quickly putting the menadione organic solution obtained in the last step into a sodium metabisulfite solution, carrying out heat preservation reaction for 1 hour at the temperature of 40 ℃, standing for 30 minutes, layering to obtain an upper organic solvent phase layer and an MSB aqueous phase layer of 255g, and reusing the organic solvent in oxidation extraction operation.
7. Adding the 255g of water phase layer into a 1000ml reaction bottle, adding 250g of 40 ℃ second organic solvent, and reducing the temperature in a gradient way under the stirring state: 30 ℃ (1 hour for holding), 20 ℃ (1 hour for holding), 10 ℃ (1 hour for holding), -5 ℃ (1 hour for holding); and filtering after the heat preservation is finished, and washing a filter cake by using a second organic solvent to obtain wet MSB.
And (3) putting the wet MSB into a 50 ℃ oven for drying for 5 hours to obtain dry MSB, and detecting that the MSB does not contain metal cerium.
Example 3
Ce4+The method for preparing beta-menadione and derivative thereof, namely menadione sodium bisulfite, by using the beta-menadione as an oxidant comprises the following specific steps:
1. 13.6kg of electrolytic high-cerium methanesulfonic acid solution is prepared, and the molar concentration is 0.4 mol/L;
in a 200ml beaker, 70g of beta-methylnaphthalene is put into 105g of a first organic solvent at room temperature, and stirred until the beta-methylnaphthalene is completely dissolved, thereby obtaining a beta-methylnaphthalene organic solution.
2. 1600g of high cerium methane sulfonate solution is added into a 20L high-speed shearing emulsifying machine, and low-temperature water is introduced into a jacket to control the temperature of the materials to be about 10 ℃.
3. Under the condition of stirring rotating speed of 1600-2000 rpm, respectively dripping from two feed inlets: the remaining 12kg of the ceric methanesulfonate solution and the prepared organic solution of β -methylnaphthalene were added dropwise over a controlled period of about 1.5 hours (simultaneously).
After the dropwise addition is finished, entering a constant-temperature reaction stage: controlling the temperature of the system to be 25 ℃, and carrying out heat preservation reaction for 0.5 hour; then entering a constant temperature reaction stage: heating to 45 ℃ within 30min, and reacting for 1 hour under the condition of heat preservation; and (3) constant-temperature reaction: heating to 75 ℃ within 30min, and reacting for 0.5 hour under the condition of heat preservation;
4. and after the reaction is finished, cooling to 15-20 ℃, filtering the reaction liquid to obtain about 115g of filter cake, and layering the filtrate to obtain an oil phase layer and a water phase layer.
5. Adding 850g of a first organic solvent into a 3000ml reaction bottle (with a filter screen at a discharge port), and heating to 75 ℃ under stirring; putting the filter cake into a first organic solvent, and dissolving and stirring for 30-45 minutes at the temperature of 75 ℃; discharging the feed liquid, filtering off a small amount of solid between the water phase and the oil phase, and layering the discharged feed liquid to obtain a water phase layer and an oil phase layer, wherein the oil phase layer is mixed with the oil phase layer in the previous step.
Cleaning a 3000ml reactor, adding the mixed oil phase layer, controlling the temperature to be 75 ℃, washing the oil phase layer twice by using 120g of 75 ℃ hot water, layering to obtain a cerium-free menadione organic solution, and detecting that the content of menadione is 41.5g and the yield is 49%; the menadione organic solution was thermostatted at 37 ℃.
6. 200g of water is added into a 2000ml reaction bottle, 70g of sodium metabisulfite is added, and the mixture is stirred at the temperature of 40 ℃ until the sodium metabisulfite is completely dissolved, and then the temperature is kept to obtain a sodium metabisulfite solution.
And (3) quickly putting the menadione organic solution obtained in the last step into a sodium metabisulfite solution, carrying out heat preservation reaction for 0.5 hour at the temperature of 45 ℃, standing for 30 minutes, layering to obtain an upper organic solvent phase layer and 275g of an MSB aqueous phase layer, and reusing the organic solvent in oxidation extraction operation.
7. Adding 275g of the aqueous phase layer into a 1000ml reaction bottle, adding 250g of a 40 ℃ second organic solvent, and carrying out gradient cooling under a stirring state: 30 ℃ (1 hour hold), 20 ℃ (1 hour hold), 10 ℃ (1 hour hold), 5 ℃ (1 hour hold); and filtering after the heat preservation is finished, and washing a filter cake by using a second organic solvent to obtain wet MSB.
And (3) putting the wet MSB into a 50 ℃ oven for drying for 5 hours to obtain dry MSB, and detecting that the MSB does not contain metal cerium.
Example 4
Ce4+The method for preparing beta-menadione and derivative thereof, namely menadione sodium bisulfite, by using the beta-menadione as an oxidant comprises the following specific steps:
1. 13.6kg of electrolytic high-cerium methanesulfonic acid solution is prepared, and the molar concentration is 0.4 mol/L;
in a 200ml beaker, 70g of beta-methylnaphthalene is put into 105g of a first organic solvent at room temperature, and stirred until the beta-methylnaphthalene is completely dissolved, thereby obtaining a beta-methylnaphthalene organic solution.
2. 1600g of high cerium methane sulfonate solution is added into a 20L high-speed shearing emulsifying machine, and low-temperature water is introduced into a jacket to control the temperature of the materials to be about 5 ℃.
3. Under the condition of stirring rotating speed of 1600-2000 rpm, respectively dripping from two feed inlets: the remaining 12kg of the ceric methanesulfonate solution and the prepared organic solution of β -methylnaphthalene were added dropwise over a controlled period of about 1.5 hours (simultaneously).
After the dropwise addition is finished, entering a constant-temperature reaction stage: controlling the temperature of the system to be 5 ℃, and carrying out heat preservation reaction for 2 hours; then entering a constant temperature reaction stage: heating to 30 ℃ within 30min, and reacting for 1 hour under the condition of heat preservation; and (3) constant-temperature reaction: heating to 50 ℃ within 30min, and reacting for 1.5 hours under the condition of heat preservation;
4. and after the reaction is finished, cooling to 15-20 ℃, filtering the reaction liquid to obtain about 117g of filter cake, and layering the filtrate to obtain an oil phase layer and a water phase layer.
5. Adding 850g of a first organic solvent into a 3000ml reaction bottle (with a filter screen at a discharge port), and heating to 75 ℃ under stirring; putting the filter cake into a first organic solvent, and dissolving and stirring for 30-45 minutes at the temperature of 75 ℃; discharging the feed liquid, filtering off a small amount of solid between the water phase and the oil phase, and layering the discharged feed liquid to obtain a water phase layer and an oil phase layer, wherein the oil phase layer is mixed with the oil phase layer in the previous step.
Cleaning a 3000ml reactor, adding the mixed oil phase layer, controlling the temperature to be 75 ℃, washing the oil phase layer twice by using 120g of 75 ℃ hot water, layering to obtain a cerium-free menadione organic solution, and detecting that the content of menadione is 45.36g and the yield is 53.5%; the menadione organic solution was thermostatted at 37 ℃.
6. 200g of water is added into a 2000ml reaction bottle, 60g of sodium metabisulfite is added, and the temperature is kept after stirring at 40 ℃ till complete dissolution, so as to obtain sodium metabisulfite solution.
And (3) quickly putting the menadione organic solution obtained in the last step into a sodium metabisulfite solution, carrying out heat preservation reaction for 0.5 hour at the temperature of 40 ℃, standing for 30 minutes, layering to obtain an upper organic solvent phase layer and an MSB aqueous phase layer 257g, and reusing the organic solvent for oxidation extraction operation.
7. Adding 257g of the aqueous phase layer into a 1000ml reaction bottle, adding 250g of a 40 ℃ second organic solvent, and carrying out gradient cooling under a stirring state: 30 ℃ (1 hour hold), 20 ℃ (1 hour hold), 10 ℃ (1 hour hold), 5 ℃ (1 hour hold); and filtering after the heat preservation is finished, and washing a filter cake by using a second organic solvent to obtain wet MSB.
And (3) putting the wet MSB into a 50 ℃ oven for drying for 5 hours to obtain dry MSB, and detecting that the MSB does not contain metal cerium.
Example 5
Ce4+The method for preparing beta-menadione and derivative thereof, namely menadione sodium bisulfite, by using the beta-menadione as an oxidant comprises the following specific steps:
1. 13.6kg of electrolytic high-cerium methanesulfonic acid solution is prepared, and the molar concentration is 0.4 mol/L;
in a 200ml beaker, 70g of beta-methylnaphthalene is put into 105g of a first organic solvent at room temperature, and stirred until the beta-methylnaphthalene is completely dissolved, thereby obtaining a beta-methylnaphthalene organic solution.
2. 1600g of high cerium methane sulfonate solution is added into a 20L high-speed shearing emulsifying machine, and low-temperature water is introduced into a jacket to control the temperature of the materials to be about 10 ℃.
3. Under the condition of stirring rotating speed of 1600-2000 rpm, respectively dripping from two feed inlets: the remaining 12kg of the ceric methanesulfonate solution and the prepared organic solution of β -methylnaphthalene were added dropwise over a controlled period of about 1.5 hours (simultaneously).
After the dropwise addition is finished, entering a constant-temperature reaction stage: controlling the temperature of the system to be 15 ℃, and carrying out heat preservation reaction for 1.5 hours; then entering a constant temperature reaction stage: heating to 35 ℃ within 30min, and reacting for 1 hour under the condition of heat preservation; and (3) constant-temperature reaction: heating to 60 ℃ within 30min, and reacting for 1 hour under the condition of heat preservation;
4. and after the reaction is finished, cooling to 15-20 ℃, filtering the reaction liquid to obtain about 120g of filter cake, and layering the filtrate to obtain an oil phase layer and a water phase layer.
5. Adding 850g of a first organic solvent into a 3000ml reaction bottle (with a filter screen at a discharge port), and heating to 75 ℃ under stirring; putting the filter cake into a first organic solvent, and dissolving and stirring for 30-45 minutes at the temperature of 75 ℃; discharging the feed liquid, filtering off a small amount of solid between the water phase and the oil phase, and layering the discharged feed liquid to obtain a water phase layer and an oil phase layer, wherein the oil phase layer is mixed with the oil phase layer in the previous step.
Cleaning a 3000ml reactor, adding the mixed oil phase layer, controlling the temperature to be 75 ℃, washing the oil phase layer twice by using 120g of 75 ℃ hot water, layering to obtain a cerium-free menadione organic solution, and detecting that 47g of menadione is contained and the yield is 55%; the menadione organic solution was thermostatted at 37 ℃.
6. 200g of water is added into a 2000ml reaction bottle, 80g of sodium metabisulfite is added, the mixture is stirred at the temperature of 40 ℃ until the sodium metabisulfite is completely dissolved, and then the temperature is kept to obtain a sodium metabisulfite solution.
And (3) quickly putting the menadione organic solution obtained in the last step into a sodium metabisulfite solution, carrying out heat preservation reaction for 0.5 hour at the temperature of 45 ℃, standing for 30 minutes, layering to obtain an upper organic solvent phase layer and an MSB aqueous phase layer 284g, and reusing the organic solvent for oxidation extraction operation.
7. And (2) adding 284g of the aqueous phase layer into a 1000ml reaction bottle, adding 250g of a 40 ℃ second organic solvent, and reducing the temperature in a gradient manner under the stirring state: 30 ℃ (1 hour hold), 20 ℃ (1 hour hold), 10 ℃ (1 hour hold), 5 ℃ (1 hour hold); and filtering after the heat preservation is finished, and washing a filter cake by using a second organic solvent to obtain wet MSB.
And (3) putting the wet MSB into a 50 ℃ oven for drying for 5 hours to obtain dry MSB, and detecting that the MSB does not contain metal cerium.
The embodiments are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same or similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The above is for the Ce provided by the present invention4+The method for preparing beta-menadione and its derivative menadione sodium bisulfite as oxidant is described in detail. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. Ce4+The method for preparing beta-menadione by using the beta-menadione as an oxidant is characterized by comprising the following steps of:
step 1, preparing electrolytic high cerium methane sulfonate solution,
dissolving beta-methylnaphthalene in a first organic solvent to obtain a beta-methylnaphthalene organic solution;
step 2, adding part of the high cerium methane sulfonate solution into a reaction kettle to be used as a base solution;
step 3, carrying out constant temperature reaction: continuously dripping the beta-methylnaphthalene organic solution and the high cerium methane sulfonate solution into a reaction kettle at the same time, and reacting at constant temperature after finishing dripping, wherein the temperature is controlled to be 0-25 ℃, and the constant temperature time is 0.5-2 hours;
and (2) constant-temperature reaction: after the constant temperature reaction is finished, raising the temperature to continue the constant temperature reaction, wherein the temperature is controlled to be 25-45 ℃, and the constant temperature time is 0.5-2 hours;
and (3) constant-temperature reaction: after the constant-temperature reaction II is finished, raising the temperature to continue the constant-temperature reaction, wherein the temperature is controlled to be 45-75 ℃, and the constant-temperature time is 0.5-2 hours;
step 4, filtering to obtain a beta-menadione filter cake after the reaction is finished; layering the filtrate to obtain an organic solvent oil phase layer and a cerium methanesulfonate water phase layer, wherein the organic solvent layer is used for later use, and the cerium methanesulfonate water phase layer is used for later use;
and 5, extracting the beta-menadione filter cake by using a first organic solvent, filtering, and then layering the filtrate to obtain a beta-menadione organic solution oil phase layer and a cerium methanesulfonate water phase layer, mixing the beta-menadione organic solution oil phase layer and the organic solvent oil phase layer in the step 4 to obtain a beta-menadione organic solution, washing the beta-menadione organic solution with water, mixing the cerium methanesulfonate water phase layer and the cerium methanesulfonate water phase layer in the step 4 to obtain a cerium methanesulfonate solution, and recycling the cerium methanesulfonate solution after electrolysis.
2. The method of claim 1, wherein: in the step 1, the concentration of the high cerium methanesulfonate solution is 0.1-1.2 mol/L, and the mass ratio of beta-methylnaphthalene to the first organic solvent is 1: 1-10;
in the step 2, the priming amount of the high cerium methanesulfonate solution is 1-10 wt% of the total amount of the high cerium methanesulfonate solution; in the step 3, the dripping time of the beta-methylnaphthalene organic solution and the methanesulfonic acid ceric solution is controlled to be 0.5-2 h.
3. The method of claim 1, wherein: in the step 3, reacting at constant temperature, namely controlling the temperature to be 10-20 ℃ and keeping the temperature for 1-1.5 hours; controlling the temperature of the constant-temperature reaction II to be 30-40 ℃ and keeping the temperature for 1-1.5 h; the temperature of the constant-temperature reaction is controlled to be 55-65 ℃, and the constant-temperature time is 1-1.5 h.
4. The method of claim 1, wherein: in the step 5, the material temperature is controlled to be 40-90 ℃ during extraction; the mass ratio of menadione (including beta-menadione and hexa-position quinone, pure amount) to the first organic solvent is 1: 1-20; controlling the material temperature to be 40-90 ℃ when the beta-menadione organic solution is washed by water; the mass ratio of the beta-menadione organic solution to the washing water is 1-20: 1.
5. Ce4+A method for preparing beta-menadione derivative menadione sodium bisulfite as an oxidant is characterized by comprising the following steps:
step 1, preparing electrolytic high cerium methane sulfonate solution,
dissolving beta-methylnaphthalene in a first organic solvent to obtain a beta-methylnaphthalene organic solution;
step 2, adding part of the high cerium methane sulfonate solution into a reaction kettle to be used as a base solution;
step 3, carrying out constant temperature reaction: continuously dripping the beta-methylnaphthalene organic solution and the high cerium methane sulfonate solution into a reaction kettle at the same time, and reacting at constant temperature after finishing dripping, wherein the temperature is controlled to be 0-25 ℃, and the constant temperature time is 0.5-2 hours;
and (2) constant-temperature reaction: after the constant temperature reaction is finished, raising the temperature to continue the constant temperature reaction, wherein the temperature is controlled to be 25-45 ℃, and the constant temperature time is 0.5-2 hours;
and (3) constant-temperature reaction: after the constant-temperature reaction II is finished, raising the temperature to continue the constant-temperature reaction, wherein the temperature is controlled to be 45-75 ℃, and the constant-temperature time is 0.5-2 hours;
step 4, filtering to obtain a beta-menadione filter cake after the reaction is finished; layering the filtrate to obtain an organic solvent oil phase layer and a cerium methanesulfonate water phase layer, wherein the organic solvent layer is used for later use, and the cerium methanesulfonate water phase layer is used for later use;
step 5, extracting the beta-menadione filter cake with a first organic solvent, filtering, and then layering the filtrate to obtain a beta-menadione organic solution oil phase layer and a cerium methanesulfonate water phase layer, wherein the beta-menadione organic solution oil phase layer and the organic solvent oil phase layer in the step 4 are mixed into a beta-menadione organic solution and washed with water, and the cerium methanesulfonate water phase layer in the step 4 are mixed into a cerium methanesulfonate solution and recycled after being electrolyzed;
step 6, carrying out addition reaction on the beta-menadione organic solution and the sodium metabisulfite solution to obtain MSB reaction liquid, layering to obtain an MSB solution water phase layer and an organic solvent oil phase layer, wherein the organic solvent oil phase layer is sleeved for dissolving beta-methylnaphthalene in the step 1 and extracting beta-menadione in the step 5;
the concentration of the sodium pyrosulfite solution is 10-45 wt%, and the mass ratio of menadione (including beta-menadione and hexa-quinone, pure amount) to sodium pyrosulfite is 1: 0.5 to 3;
the temperature of the addition reaction is 20-70 ℃;
step 7, adding a second organic solvent into the MSB solution water phase layer, cooling, crystallizing, centrifuging and washing, wherein the washing agent is the second organic solvent to obtain an MSB filter cake, and drying to obtain an MSB finished product; and mixing the filtrate with the washing liquid, and recovering the solvent to obtain a second organic solvent for MSB crystallization and washing.
6. The method of claim 5, wherein: in step 6, the concentration of the sodium metabisulfite solution is 20-35 wt%; the mass ratio of menadione (including beta-menadione and hexa-position quinone, pure amount) to sodium metabisulfite is 1:1 to 2.
7. The method of claim 5, wherein: in the step 6, the temperature of the addition reaction is 35-55 ℃.
8. The method of claim 5, wherein: in the step 7, the crystallization temperature is controlled to be-5-10 ℃; the mass ratio of the washing amount of the second organic solvent to the centrifugal filter cake is 1: 0.5 to 3.
9. The method of claim 5, wherein: in the step 7, the temperature of the MSB dried material is controlled to be 30-90 ℃.
10. The method according to claim 1 or 5, characterized in that: the first organic solvent is selected from one or more of n-butanol, n-hexane, cyclohexane, n-heptane and acetonitrile, and the second organic solvent is selected from one or more of n-butanol, methanol, ethanol, isopropanol and isobutanol.
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| CN112778112A (en) * | 2021-01-04 | 2021-05-11 | 兄弟科技股份有限公司 | Method and device for synthesizing vitamin K3 |
| CN115246768A (en) * | 2021-04-28 | 2022-10-28 | 四川飞楼环保科技有限公司 | Method for extracting menadione from wastewater generated in vitamin K3 production |
| CN117534555A (en) * | 2024-01-05 | 2024-02-09 | 潍坊通润化工有限公司 | Synthesis method of alkyl p-benzoquinone |
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| CN112778112A (en) * | 2021-01-04 | 2021-05-11 | 兄弟科技股份有限公司 | Method and device for synthesizing vitamin K3 |
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| CN115246768B (en) * | 2021-04-28 | 2023-08-22 | 四川飞楼环保科技有限公司 | Method for extracting menaquinone from wastewater from vitamin K3 production |
| CN117534555A (en) * | 2024-01-05 | 2024-02-09 | 潍坊通润化工有限公司 | Synthesis method of alkyl p-benzoquinone |
| CN117534555B (en) * | 2024-01-05 | 2024-04-02 | 潍坊通润化工有限公司 | Synthesis method of alkyl p-benzoquinone |
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