Method for preparing beta-menadione by using compound emulsifier

Abstract

The invention discloses a method for preparing beta-menadione by using a compound emulsifier, which comprises the following steps: step 1, uniformly mixing high-molecular-weight alkanol and high-molecular alkyl sodium sulfonate to obtain the compound emulsifier; step 2, mixing beta-methylnaphthalene, water and a compound emulsifier to form an emulsion; step 3, mixing sodium dichromate with chromic anhydride, adding the mixture into water, and adding sulfuric acid to adjust the concentration of hexavalent chromium so as to form an oxidation solution; and 4, dropwise adding the oxidation liquid into the emulsion, carrying out a curing reaction on the reacted material, filtering, washing, and carrying out centrifugal dehydration to obtain the beta-menadione product. The invention has the following beneficial effects: the emulsion can be uniformly dispersed, the stability is better, the reaction speed with materials is high, the temperature range of reaction control is wider, and the side reaction is less; meanwhile, the compound emulsifier is better in stability and basically does not react with the oxidizing agent in the later period, the reaction process is more stable and continuous, and the obtained beta-menadione material is high in purity.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a method for preparing beta-menadione by using a composite emulsifier. Background Art

[0002] Menadione is an organic compound with the chemical formula C 11 H 8 O 2 , is an important intermediate for the production of vitamin K2 and K3. Vitamins are clinically classified as procoagulants and can be used to treat hemorrhagic diseases caused by vitamin K deficiency, such as neonatal hemorrhage, vitamin K deficiency caused by intestinal malabsorption, and hypoprothrombinemia. Vitamin K is an essential substance for the liver to synthesize proenzyme (factor B), and participates in the synthesis of coagulation factors VII, IX and X, maintaining the physiological process of blood coagulation in animals. Lack of vitamin K can cause the synthesis of the above coagulation factors, affect the coagulation process and cause bleeding. Vitamin K is also necessary for the vitamin K-dependent carboxylation system in the animal body (mainly in tissues and organs such as the liver, bones, testicles, skin and kidneys), and is an indispensable factor in the synthesis of bone glomerulonephrase (BGP). In addition, it plays an important role in the metabolism of high-energy compounds and oxidative phosphorylation, as well as in the metabolism of other fat-soluble vitamins, and has the functions of diuresis, enhancing liver detoxification function, participating in membrane structure, and lowering blood pressure.

[0003] At present, the main large-scale synthetic process of menadione is to use chromium-based oxidants to react with β-methylnaphthalene. The use of chromic anhydride as an oxidant has high production costs and many pre-processes. The traditional OP series emulsifier process for preparing menadione has a low yield of β-menadione. For example, the preparation method of a vitamin K3 intermediate disclosed in patent CN117209371A, when OP-10 is used as an emulsifier, the product yield is only 38.60%. The use of sodium chromium as an oxidant has problems such as difficult control of the reaction temperature, more side reactions, low main content of the finished product β-menadione, and more impurities. For example, the method for preparing β-menadione in a tubular continuous manner disclosed in patent CN105481673B uses sodium chromium as an oxidant, and the main content of the prepared β-menadione is low. Summary of the invention

[0004] An object of the present invention is to solve at least the above problems and / or disadvantages and to provide at least the advantages which will be described hereinafter.

[0005] In order to achieve these purposes and other advantages according to the present invention, a method for preparing β-menadione using a composite emulsifier is provided, comprising the following steps:

[0006] Step 1, uniformly mixing high molecular weight alkanol and high molecular weight sodium alkyl sulfonate to obtain a composite emulsifier;

[0007] Step 2: Mix β-methylnaphthalene, water and a composite emulsifier to form an emulsion;

[0008] Step 3: Mix sodium dichromate and chromic anhydride and dissolve them in water, then add water and sulfuric acid to adjust the concentration of hexavalent chromium and sulfuric acid to form an oxidizing solution;

[0009] Step 4: Add the oxidizing liquid droplets into the emulsion, and the reacted material is subjected to a aging reaction, filtered, washed, and then centrifuged and dehydrated to obtain the β-menadione product.

[0010] Preferably, in the step 1, the mass ratio of the high molecular weight alkanol to the high molecular weight sodium alkyl sulfonate is 1:5 to 5:1, the high molecular weight alkanol is hexadecanol, and the high molecular weight sodium alkyl sulfonate is sodium hexadecyl sulfonate.

[0011] Preferably, in step 2, the mass ratio of β-methylnaphthalene, water and composite emulsifier is 1:4-10:0.1-0.6.

[0012] Preferably, in step 3, the mass ratio of sodium dichromate to chromic anhydride is 1-5:5-1, water and sulfuric acid are added until the hexavalent chromium concentration is adjusted to 130 g / L-280 g / L, and the sulfuric acid concentration is adjusted to 450-720 g / L.

[0013] Preferably, in step 4, the mass ratio of the oxidizing liquid to the emulsified liquid is 15-25:1-1.4.

[0014] Preferably, in step 4, the dropping time is 0.5 to 4.5 hours, the reaction temperature is 38 to 62° C., and the aging reaction time is 2 to 6 hours.

[0015] Preferably, in step 4, after the oxidation liquid is added dropwise to the emulsion, a composite catalyst may be added, and a aging reaction is carried out under 40-80KHz ultrasound, and the amount of the composite catalyst used is 3-5% of the mass of β-methylnaphthalene in the emulsion.

[0016] Preferably, the preparation method of the composite catalyst is as follows: adding silica sol to 4A molecular sieve, stirring evenly and then calcining for the first time to obtain the composite molecular sieve, then adding ethanol to dilute the tetrabutylammonium perrhenate solution, then adding dicyandiamide, continuing to stir evenly, then adding the composite molecular sieve to the diluted solution, stirring in an oil bath pot for reaction, evaporating the solvent after the reaction is completed, and then heating in N 2 The composite catalyst was obtained by calcining for the second time under atmosphere.

[0017] Preferably, after adding ethanol, the concentration of the tetrabutylammonium perrhenate solution is diluted to 1 mol / L, the amount of 4A molecular sieve is 50 to 100 times the mass of rhenium element in the tetrabutylammonium perrhenate solution, the amount of dicyandiamide is 0.1 to 0.2% of the mass of the 4A molecular sieve, and the amount of silica sol is 10 to 20% of the 4A molecular sieve.

[0018] Preferably, the first calcination temperature is 300-500°C, the calcination time is 1-2h, the oil bath temperature is 50-60°C, the reaction time is 12-24h, the drying temperature is 40-50°C, the calcination temperature is 600-800°C, and the calcination time is 2-4h.

[0019] The present invention at least includes the following beneficial effects: compared with the traditional process for preparing menadione by using an OP series emulsifier, the present invention uses a composite emulsifier with better stability, so that the emulsion can be evenly dispersed, has better stability, reacts with materials quickly, has a wider temperature range for reaction control, and has fewer side reactions; at the same time, the composite emulsifier has better stability, basically does not react with an oxidant in the later stage, the reaction process is more stable and continuous, and the obtained β-menadione material has high purity; the present invention also further improves the yield of the product and the purity of the β-menadione material in the product by preparing a composite catalyst.

[0020] Other advantages, objectives and features of the present invention will be embodied in part through the following description, and in part will be understood by those skilled in the art through study and practice of the present invention. DETAILED DESCRIPTION

[0021] The present invention is described in further detail below so that those skilled in the art can implement it according to the description.

[0022] Example 1

[0023] A method for producing β-menadione using a composite chromium-containing oxidant comprises the following steps:

[0024] Step 1: Evenly mix 10 g of hexadecanol and 10 g of sodium hexadecyl sulfonate to obtain a composite emulsifier;

[0025] Step 2: Mix 10g of β-methylnaphthalene, 70g of water, and 1.5g of a composite emulsifier to form an emulsion;

[0026] Step 3: Mix and dissolve 240 g of sodium dichromate and 80 g of chromic anhydride in water, then add water and sulfuric acid to adjust the hexavalent chromium concentration of the material to 260 g / L and the sulfuric acid concentration to 510 g / L to form an oxidizing solution;

[0027] Step 4: Add 180g of oxidizing solution to 10g of emulsion, the adding time is controlled at 2.5h, the temperature during the adding is controlled at 50°C, the reacted material is matured for 2.5h, filtered, washed, and centrifuged to obtain a menadione product with a main content of 93.84% and a β-menadione yield of 74%.

[0028] Example 2

[0029] A method for producing β-menadione using a composite chromium-containing oxidant comprises the following steps:

[0030] Step 1: Evenly mix 10 g of hexadecanol and 40 g of sodium hexadecyl sulfonate to obtain a composite emulsifier;

[0031] Step 2: Mix 10g of β-methylnaphthalene, 55g of water and 2g of composite emulsifier to form an emulsion;

[0032] Step 3: Mix and dissolve 120g of sodium dichromate and 180g of chromic anhydride in water, then add water and sulfuric acid to adjust the hexavalent chromium concentration of the material to 210g / L and the sulfuric acid concentration to 550g / L to form an oxidizing solution;

[0033] Step 4: Add 230g of oxidizing solution to 10g of emulsion, the adding time is controlled at 2.5h, the temperature during the adding is controlled at 50°C, the reacted material is matured for 2.5h, filtered, washed, and centrifuged to obtain a menadione product with a main content of 94.52% and a β-menadione yield of 75.2%.

[0034] Example 3

[0035] A method for producing β-menadione using a composite chromium-containing oxidant comprises the following steps:

[0036] Step 1: Evenly mix 40 g of hexadecanol and 10 g of sodium hexadecyl sulfonate to obtain a composite emulsifier;

[0037] Step 2: Mix 10g of β-methylnaphthalene, 80g of water, and 18g of a composite emulsifier to form an emulsion;

[0038] Step 3: Mix and dissolve 70g of sodium dichromate and 350g of chromic anhydride in water, then add water and sulfuric acid to adjust the hexavalent chromium concentration of the material to 240g / L and the sulfuric acid concentration to 520g / L to form an oxidizing solution;

[0039] Step 4: Add 230g of oxidizing solution to 10g of emulsion, the adding time is controlled at 2.5h, the temperature during the adding is controlled at 50°C, the reacted material is matured for 2.5h, filtered, washed, and centrifuged to obtain a menadione product with a main content of 95.46% and a β-menadione yield of 76.74%.

[0040] Example 4

[0041] A method for producing β-menadione with a composite chromium-containing oxidant. The difference between this embodiment and embodiment 1 is that step 4 is: first prepare a composite catalyst, add 20g of silica sol to 186g of 4A molecular sieve, stir evenly, and calcine at 400°C for 2h to obtain a composite molecular sieve, then add ethanol to a tetrabutylammonium perrhenate solution to dilute it to 0.1mol / L, take 1L of tetrabutylammonium perrhenate solution, add 2g of dicyandiamide thereto, continue to stir evenly, then add the composite molecular sieve to the tetrabutylammonium perrhenate solution, stir and react in an oil bath at 60°C for 12h, after the reaction is completed, evaporate the solvent in a vacuum drying oven at 50°C, and then place in N 2 The composite catalyst was calcined at 600°C for 4 hours under an atmosphere. Then 180g of the oxidizing solution was added dropwise to 10g of the emulsion. The dropping time was controlled at 2.5h and the temperature during the dropping was controlled at 50°C. Then 0.3g of the prepared composite catalyst was added thereto. The mixture was subjected to ultrasonic aging reaction at 45KHz for 2.5h. After filtration and washing, the product was centrifuged and dehydrated to obtain a menadione product with a main content of 97.24% and a β-menadione yield of 81.22%.

[0042] The other steps of this embodiment are consistent with those of Embodiment 1.

[0043] Comparative Example 1

[0044] A method for producing β-menadione using a composite chromium-containing oxidant comprises the following steps:

[0045] Step 1: 10 g of β-methylnaphthalene, 70 g of water, and 1.5 g of hexadecanol as an emulsifier are mixed evenly to form an emulsion;

[0046] Step 2: Mix and dissolve 240g of sodium dichromate and 80g of chromic anhydride in water, then add water and sulfuric acid to adjust the hexavalent chromium concentration of the material to 260g / L and the sulfuric acid concentration to 510g / L to form an oxidizing solution;

[0047] Step 3: Add 180g of oxidizing solution to 10g of emulsion, the adding time is controlled at 2.5h, the temperature during the adding is controlled at 50°C, the reacted material is matured for 2.5h, filtered, washed, and centrifuged to obtain a menadione product with a main content of 85.62% and a β-menadione yield of 65.14%.

[0048] Comparative Example 2

[0049] A method for producing β-menadione using a composite chromium-containing oxidant comprises the following steps:

[0050] Step 1: 10 g of β-methylnaphthalene, 70 g of water, and 1.5 g of sodium hexadecyl sulfate as an emulsifier are mixed evenly to form an emulsion;

[0051] Step 2: Mix and dissolve 240g of sodium dichromate and 80g of chromic anhydride in water, then add water and sulfuric acid to adjust the hexavalent chromium concentration of the material to 260g / L and the sulfuric acid concentration to 510g / L to form an oxidizing solution;

[0052] Step 3: Add 180g of oxidizing solution to 10g of emulsion, the adding time is controlled at 2.5h, the temperature during the adding is controlled at 50°C, the reacted material is ripened for 2.5h, filtered, washed and centrifuged to obtain a menadione product with a main content of 87.54% and a β-menadione yield of 66.08%.

[0053] Comparative Example 3

[0054] A method for producing β-menadione using a composite chromium-containing oxidant comprises the following steps:

[0055] Step 1: Mix 10 g of β-methylnaphthalene and 71.5 g of water to form a mixed solution;

[0056] Step 2: Mix and dissolve 240g of sodium dichromate and 80g of chromic anhydride in water, then add water and sulfuric acid to adjust the hexavalent chromium concentration of the material to 260g / L and the sulfuric acid concentration to 510g / L to form an oxidizing solution;

[0057] Step 3: Add 180g of the oxidizing solution to 10g of the mixed solution, the dropping time is controlled at 2.5h, the temperature during the dropping is controlled at 50°C, the reacted material is matured for 2.5h, filtered, washed, and centrifuged to obtain a menadione product with a main content of 62.33% and a β-menadione yield of 45.24%.

[0058] Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the specification and the implementation modes, and they can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to the specific details and the illustrations shown and described herein.

Claims

1. A method for preparing β-menadione using a composite emulsifier, characterized in that: The following steps are involved: Step 1, uniformly mixing high molecular weight alkanol and high molecular weight sodium alkyl sulfonate to obtain a composite emulsifier; Step 2: Mix β-methylnaphthalene, water and a composite emulsifier to form an emulsion; Step 3: Mix sodium dichromate and chromic anhydride and dissolve them in water, then add water and sulfuric acid to adjust the concentration of hexavalent chromium and sulfuric acid to form an oxidizing solution; Step 4: Add the oxidizing liquid droplets into the emulsion, and the reacted material is subjected to a aging reaction, filtered, washed, and then centrifuged and dehydrated to obtain the β-menadione product.

2. The method for preparing β-menadione using the composite emulsifier according to claim 1, characterized in that: In the step 1, the mass ratio of the high molecular weight alkanol to the high molecular weight sodium alkyl sulfonate is 1:5 to 5:1, the high molecular weight alkanol is hexadecanol, and the high molecular weight sodium alkyl sulfonate is sodium hexadecyl sulfonate.

3. The method for preparing β-menadione using the composite emulsifier according to claim 1, characterized in that: In the step 2, the mass ratio of β-methylnaphthalene, water and composite emulsifier is 1:4-10:0.1-0.

6.

4. The method for preparing β-menadione using the composite emulsifier according to claim 1, characterized in that: In the step 3, the mass ratio of sodium dichromate to chromic anhydride is 1-5:5-1, water and sulfuric acid are added until the hexavalent chromium concentration is adjusted to 130 g / L-280 g / L, and the sulfuric acid concentration is adjusted to 450-720 g / L.

5. The method for preparing β-menadione using the composite emulsifier according to claim 1, characterized in that: In the step 4, the mass ratio of the oxidizing liquid to the emulsified liquid is 15-25:1-1.

4.

6. The method for preparing β-menadione using the composite emulsifier according to claim 1, characterized in that: In the step 4, the dropping time is 0.5 to 4.5 hours, the reaction temperature is 38 to 62° C., and the aging reaction time is 2 to 6 hours.

7. The method for preparing β-menadione using the composite emulsifier according to claim 1, characterized in that: In the step 4, after the oxidation liquid is added dropwise into the emulsion, a composite catalyst may be added, and a aging reaction is carried out under 40-80KHz ultrasound. The amount of the composite catalyst used is 3-5% of the mass of β-methylnaphthalene in the emulsion.

8. The method for preparing β-menadione using the composite emulsifier according to claim 7, characterized in that: The preparation method of the composite catalyst is as follows: adding silica sol to 4A molecular sieve, stirring evenly and then calcining for the first time to obtain the composite molecular sieve, then adding ethanol to dilute the tetrabutylammonium perrhenate solution, then adding dicyandiamide, continuing to stir evenly, then adding the composite molecular sieve to the diluted solution, stirring in an oil bath pot for reaction, evaporating the solvent after the reaction is completed, and then calcining for the second time under N2 atmosphere to obtain the composite catalyst.

9. The method for preparing β-menadione using the composite emulsifier according to claim 8, characterized in that: After adding ethanol, the concentration of the tetrabutylammonium perrhenate solution is diluted to 1 mol / L, the amount of 4A molecular sieve used is 50 to 100 times the mass of rhenium element in the tetrabutylammonium perrhenate solution, the amount of dicyandiamide used is 0.1 to 0.2% of the mass of the 4A molecular sieve, and the amount of silica sol used is 10 to 20% of the 4A molecular sieve.

10. The method for preparing β-menadione using the composite emulsifier according to claim 8, characterized in that: The first calcination temperature is 300-500°C, the calcination time is 1-2h, the oil bath temperature is 50-60°C, the reaction time is 12-24h, the drying temperature is 40-50°C, the calcination temperature is 600-800°C, and the calcination time is 2-4h.