阅读说明：本技术 一种a环降解物母液料处理方法 (Method for treating A-ring degradation product mother liquor ) 是由 孟浩 杨芳 赵小娟 王敬华 曾春玲 刘喜荣 于 2021-07-30 设计创作，主要内容包括：本发明属于一种甾体激素处理技术领域,具体是涉及到一种A环降解物母液料处理方法,包括如下步骤,将A环降解物母液料、水和豆油混合,加热,分层,将其中的水相调节pH值至小于3,加入氯仿萃取,分层,将氯仿层进行浓缩,然后加入甲苯,浓缩,冷却至0-4℃,析晶,回收得到A环降解物晶体；本发明将A环降解物母液料和豆油混合,并通过酸化闭环,氯仿萃取富集,甲苯精制出料等工序,顺利提取得到A环降解物结晶；该方法相对普通母液料处理方法,更高效经济,回收率更高。(The invention belongs to the technical field of steroid hormone treatment, and particularly relates to a method for treating A-ring degradation mother liquor, which comprises the following steps of mixing the A-ring degradation mother liquor, water and soybean oil, heating, layering, adjusting the pH value of a water phase to be less than 3, adding chloroform for extraction, layering, concentrating a chloroform layer, adding toluene, concentrating, cooling to 0-4 ℃, crystallizing, and recovering to obtain A-ring degradation product crystals; mixing the mother liquor material of the degradation product of the ring A with soybean oil, and smoothly extracting to obtain the degradation product crystal of the ring A through the working procedures of acidification, closed loop, chloroform extraction and enrichment, toluene refining and discharging and the like; compared with the common mother liquor treatment method, the method has the advantages of higher efficiency, higher economy and higher recovery rate.)

1. A method for treating A-ring degradation product mother liquor is characterized by comprising the following steps,

mixing the mother liquor material of the A-ring degradation product, water and soybean oil, heating, layering, adjusting the pH value of the water phase to be less than 3, adding chloroform for extraction, layering, concentrating the chloroform layer, adding toluene, concentrating, cooling to 0-4 ℃, crystallizing, and recovering to obtain the A-ring degradation product crystal.

2. The method for treating a mother liquor of a-ring degradation product according to claim 1, wherein the heating temperature is 80 ℃.

3. The method according to claim 1, wherein the weight ratio of the A-ring degradation mother liquor to the soybean oil is 10: 1.

4. The method according to claim 1, wherein the weight ratio of the A-ring degradation product mother liquor to water is 1: 10.

5. The method for treating mother liquor of A-ring degradation product according to any of claims 1 to 4, wherein the pH adjusting substance is sulfuric acid.

6. The method for treating a mother liquor of a-ring degradation product according to any of claims 1 to 4, wherein the concentration is carried out by concentrating under reduced pressure at 60 ℃ after adding toluene.

7. The method according to any one of claims 1 to 4, wherein the weight/volume ratio of the A-ring degradation product mother liquor to chloroform is 1g:4 mL.

8. The method according to any one of claims 1 to 4, wherein the weight/volume ratio of the A-ring degradation product mother liquor to toluene is 1g:2 mL.

9. The method for treating mother liquor of A-ring degradation product according to any of claims 1 to 4, wherein the recovery is carried out by filtering and drying at 70 ℃.

10. The method for treating mother liquor of A-ring degradation product as claimed in any of claims 1 to 4, wherein the pH of the aqueous phase is adjusted to 2.

Technical Field

The invention belongs to the technical field of steroid hormone treatment, and particularly relates to a method for treating an A-ring degradation product mother liquor material.

Background

Phytosterol is an important raw material for preparing steroid hormone, can be used for preparing steroid hormone of various traditional Chinese medicines or intermediates thereof, such as A-ring degradation product (silolactone) obtained by degradation, and has the following route:

in the process of producing the A-ring degradation product by fermenting the phytosterol, a large amount of mother liquor material is generated in one step of product refining, the composition of the mother liquor material is complex, and besides a certain amount of A-ring degradation product, the mother liquor material also contains a large amount of steroid intermediates, soybean oil and chemical substances related to the composition of thalli for production, so the recovery and refining of the material in the mother liquor material are very difficult and are difficult to operate.

Chinese patent application publication No. CN 109836405 a discloses a method for recovering a-ring degradation product from mother liquor, comprising the steps of: (1) adding water into the mother liquor containing the A-ring degradation product, adding alkali to adjust the pH value to 8-14, and extracting; (2) adding acid to the aqueous phase to adjust the pH to 4-7; (3) adding toluene into the water phase to extract and remove impurities; (4) adding activated carbon into the water phase with the impurities removed for decoloration and impurity removal; (5) adding acid into the decolored water phase to adjust the pH value to 1-2; (6) adding chloroform, dichloromethane or toluene into the water phase for extraction; (7) concentrating the organic phase; (8) toluene is added into the organic phase for recrystallization, and the A-ring degradation product is obtained by filtration. The invention firstly uses alkali to adjust the pH value to 8-14, to salify the degradation product of the A ring, and then uses acid to adjust the pH value to 4-7, to separate out impurities and oily matters. The separated impurities and oily substances are extracted by adding toluene, so that the impurities such as oil, protein, amino acid, polysaccharide and the like brought and generated in the fermentation process are effectively separated and removed, the recovery rate of the A-ring degradation product is improved, the recovery rate is over 75 percent, and the production cost is reduced. The recovery rate of the scheme can only reach 80 percent at most, and the space for further rising is provided.

The patent application with the Chinese patent application publication number of CN 104496958A discloses a method for extracting A-ring degradation products by a membrane method, which comprises the following steps: A) preparing A-ring degradation product by fermentation method to obtain fermentation liquor containing A-ring degradation product, standing for layering, and separating two-phase feed liquid; B) adjusting the pH value of the water phase feed liquid to a process value by using alkali, and then filtering the water phase feed liquid by using an ultrafiltration membrane to remove most of mycelium and macromolecular impurities, wherein the permeation side is ultrafiltration membrane purified liquid; C) feeding the ultrafiltration membrane purified liquid into a nanofiltration membrane for concentration, and obtaining a nanofiltration membrane concentrated liquid from the interception side; D) adjusting the pH value of the concentrated solution to a process value by using acid, then extracting by using chloroform, standing and layering to obtain a chloroform layer; E) concentrating chloroform, adding toluene, pulping, crystallizing, precipitating, centrifuging, and oven drying to obtain A ring degradation product dry powder. Above-mentioned scheme needs to adopt filtration membrane to carry out filtration operation, and the cost is higher.

Disclosure of Invention

The invention aims to solve the technical problem of providing a method for treating the mother liquor of the A-ring degradation product, and the recovery rate of the A-ring degradation product is high.

The invention relates to a method for treating A-ring degradation product mother liquor, which comprises the following steps,

mixing the mother liquor material of the A-ring degradation product, water and soybean oil, heating, layering, adjusting the pH value of the water phase to be less than 3, adding chloroform for extraction, layering, concentrating the chloroform layer, adding toluene, concentrating, cooling to 0-4 ℃, crystallizing, and recovering to obtain the A-ring degradation product crystal.

Preferably, the heating temperature is 80 ℃.

Preferably, the weight ratio of the A-ring degradation product mother liquor material to the soybean oil is 10: 1.

Preferably, the weight ratio of the A-ring degradation product mother liquor material to the water is 1: 10.

Preferably, the substance for adjusting the pH is sulfuric acid.

Preferably, after toluene is added, the concentration is carried out at 60 ℃ under reduced pressure.

Preferably, the weight-to-volume ratio of the A-ring degradation mother liquor material to the chloroform is 1g:4 mL.

Preferably, the weight-to-volume ratio of the A-ring degradation mother liquor material to the toluene is 1g:2 mL.

Preferably, the recovery is carried out by filtering and drying at 70 ℃.

Preferably, the aqueous phase is adjusted to a pH of 2.

The invention has the beneficial effects that the invention provides a simple and rapid method, the target substance in the mother liquor of the A-ring degradation product is extracted and crystallized, the overall yield of the process for producing the A-ring degradation product by fermenting phytosterol is improved, and the production cost is reduced.

Mixing the mother liquor material of the degradation product of the ring A with soybean oil, and smoothly extracting to obtain the degradation product crystal of the ring A through the working procedures of acidification, closed loop, chloroform extraction and enrichment, toluene refining and discharging and the like; compared with the common mother liquor treatment method, the method has the advantages of higher efficiency, higher economy and higher recovery rate. Compared with the method without using a solvent, the method of the invention directly adds water for extraction and obviously improves the recovery rate.

Detailed Description

Example 1

Taking 50 g of A-ring degradation product mother liquor, adding 5 g of soybean oil, heating to 80 ℃, adding water for extraction for 2 times, adding 500 ml of water each time, stirring for extraction for 30 minutes, preserving heat, standing for 2 hours, and layering. The aqueous phases obtained by the two demixing are combined, the pH value is adjusted to 2.0 by using sulfuric acid with the mass concentration of 20%, chloroform is used for extracting for 2 times, 100 ml of chloroform is added for each time, the mixture is stirred and extracted for 30 minutes, and the mixture is kept stand and demixed for 1 hour. And combining the obtained chloroform layers, concentrating and drying under reduced pressure, adding a proper amount of water to dry the residual chloroform, concentrating and drying, adding 100 ml of toluene, concentrating under reduced pressure at 60 ℃ to about 50 ml, cooling to 0-4 ℃, crystallizing overnight, filtering, and drying at 70 ℃ to obtain 7.1 g of light yellow crystals. The HPLC normalized content is 95.62 percent, and the external standard content is 91.29 percent.

Comparative example 1

50 g of mother liquor material is added with 50 ml of water for decompression concentration, residual solvent is carried out, dry water is concentrated, 100 ml of toluene is added, the temperature is heated to 60 ℃, the stirring is carried out for 1 hour, the temperature is reduced to 0-4 ℃, the standing is carried out for 24 hours, black solution is obtained, no solid is separated out, and the extraction fails.

Comparative example 2

Heating 50 g of mother liquor to 80 ℃, adding water for extraction for 2 times, adding 500 ml of water for each time, stirring and extracting for 30 minutes, preserving heat and standing for 2 hours, and layering. The aqueous phases obtained by the two layers were combined, the pH was adjusted to 2.0 with 20% strength sulfuric acid, and the mixture was extracted 2 times with chloroform, 100 ml of chloroform was added each time, extracted for 30 minutes with stirring, and allowed to stand for 1 hour. And combining the obtained chloroform layers, concentrating under reduced pressure to dry, adding an appropriate amount of water to dry the residual chloroform, concentrating to dry, adding 100 ml of toluene, concentrating under reduced pressure to about 50 ml at 60 ℃, cooling to 0-4 ℃, crystallizing overnight, filtering, digging out and drying crystals obtained at 70 ℃ to obtain 8.2 g of yellow crystals. The HPLC normalization content is 90.52%, and the external standard content is 80.16%.

Those of ordinary skill in the art will understand that: the discussion of any embodiment above is meant to be exemplary only, and is not intended to intimate that the scope of the disclosure, including the claims, is limited to these examples; within the spirit of the present disclosure, features from the above embodiments or from different embodiments may also be combined, steps may be implemented in any order, and there are many other variations of different aspects of one or more embodiments in this application as described above, which are not provided in detail for the sake of brevity.

It is intended that the one or more embodiments of the present application embrace all such alternatives, modifications and variations as fall within the broad scope of the appended claims. Therefore, any omissions, modifications, substitutions, improvements, and the like that may be made without departing from the spirit and principles of one or more embodiments of the present disclosure are intended to be included within the scope of the present disclosure.