阅读说明：本技术 一种处理16α-甲基雄甾-4，9（11）-二烯-3，17-二酮母液物的方法 (Method for treating 16 α -methylandrostane-4, 9(11) -diene-3, 17-diketone mother liquor ) 是由 杨明军 孙福锁 米奇 崔玉国 王玉帅 于 2019-10-30 设计创作，主要内容包括：本发明实施例提供了一种处理16α-甲基雄甾-4,9(11)-二烯-3,17-二酮母液物的方法,所述方法包括：向母液物加入足量碳酸盐进行沉淀反应,待反应完全后取出沉淀,得到粗制碳酸锂；将取出沉淀后的溶液蒸馏至稠状,然后对稠状液进行过滤,得到滤渣及滤液；将所述滤渣投入强碱溶液中,混匀后静置,得到分层溶液；取分层溶液的上层液进行蒸馏,得到二异丙胺；取分层溶液的下层液通入氯气并加入有机溶剂进行萃取反应,得到溴素；将萃取反应后得到的水溶液与所述滤液一同进行蒸馏处理,得到含有机磷的固废。本发明实施例可有效回收16α-甲基雄甾-4,9(11)-二烯-3,17-二酮母液物中的二异丙胺、锂、溴及水,并能高效去除母液物中的有机磷。(The embodiment of the invention provides a method for treating a 16 α -methylandrostane-4, 9(11) -diene-3, 17-diketone mother liquor, which comprises the steps of adding sufficient carbonate into the mother liquor to perform precipitation reaction, taking out precipitate after the reaction is completed to obtain crude lithium carbonate, distilling the solution obtained after the precipitation is taken out to be thick, filtering the thick solution to obtain filter residue and filtrate, putting the filter residue into a strong alkali solution, uniformly mixing and standing to obtain a layered solution, distilling the upper layer solution of the layered solution to obtain diisopropylamine, introducing chlorine into the lower layer solution of the layered solution, adding an organic solvent to perform extraction reaction to obtain bromine, distilling the aqueous solution obtained after the extraction reaction and the filtrate together to obtain solid waste containing organic phosphorus.)

1. A method of processing a 16 α -methylandrosta-4, 9(11) -diene-3, 17-dione mother liquor comprising:

adding sufficient carbonate into the mother liquor to carry out precipitation reaction, and taking out the precipitate after the reaction is completed to obtain crude lithium carbonate;

distilling the solution after taking out the precipitate to be thick, and then filtering the thick liquid to obtain filter residue and filtrate;

putting the filter residue into a strong alkali solution, uniformly mixing, and standing to obtain a layered solution;

distilling the supernatant of the layered solution to obtain diisopropylamine; introducing chlorine into the lower layer solution of the layered solution, and adding an organic solvent for extraction reaction to obtain bromine;

and (3) distilling the aqueous solution obtained after the extraction reaction and the filtrate to obtain the solid waste containing the organic phosphorus.

2. The method of claim 1, further comprising:

and recovering the distilled water generated in the process of distilling the solution after the precipitate is taken out to be thick.

3. The method of claim 1, further comprising:

and washing and drying the crude lithium carbonate to obtain refined lithium carbonate, and adding a cleaning solution generated in the washing process into the solution after the precipitate is taken out.

4. The method of claim 1, wherein the strong alkaline solution is sodium hydroxide and/or potassium hydroxide.

5. The method as claimed in claim 1, wherein the strong alkaline solution is sodium hydroxide or potassium hydroxide solution with mass concentration of 23-35%.

6. The method according to claim 1, wherein the organic solvent is any one of n-hexane, cyclohexane, heptane, dichloromethane and carbon tetrachloride.

7. The method of claim 1, wherein prior to adding sufficient carbonate solution to the mother liquor to effect the precipitation reaction, further comprising: preheating the mother liquor.

8. The method according to claim 7, wherein the preheating temperature is 30 to 35 ℃.

9. The method according to claim 1, wherein the carbonate is added in a molar amount of 1.1 times that of the lithium element in the mother liquor, and the molar amount of lithium is calculated according to the molar amount of the lithium metal charged in the process.

10. The method of claim 1, wherein the carbonate is sodium carbonate or potassium carbonate, and the carbonate is added to the mother liquor in the form of an aqueous solution.

Technical Field

The invention relates to the technical field of environmental protection, in particular to a method for treating a 16 α -methylandrostane-4, 9(11) -diene-3, 17-diketone mother liquor.

Background

16 α -methyl androstane-4, 9(11) -diene-3, 17-diketone is an important intermediate for synthesizing betamethasone and dexamethasone.

Disclosure of Invention

The technical problem to be solved by the embodiment of the invention is to provide a method for treating a 16 α -methylandrostane-4, 9(11) -diene-3, 17-dione mother liquor, so as to solve the technical problems that the treatment method for the 16 α -methylandrostane-4, 9(11) -diene-3, 17-dione mother liquor in the prior art is easy to cause environmental pollution and resource waste.

In order to solve the problems, the invention is realized by the following technical scheme:

a method of processing a 16 α -methylandrosta-4, 9(11) -diene-3, 17-dione mother liquor comprising:

adding sufficient carbonate into the mother liquor to carry out precipitation reaction, and taking out the precipitate after the reaction is completed to obtain crude lithium carbonate;

distilling the solution after taking out the precipitate to be thick, and then filtering the thick liquid to obtain filter residue and filtrate;

putting the filter residue into a strong alkali solution, uniformly mixing, and standing to obtain a layered solution;

distilling the supernatant of the layered solution to obtain diisopropylamine; introducing chlorine into the lower layer solution of the layered solution, and adding an organic solvent for extraction reaction to obtain bromine;

and (3) distilling the aqueous solution obtained after the extraction reaction and the filtrate to obtain the solid waste containing the organic phosphorus.

Optionally, the method further comprises:

and recovering the distilled water generated in the process of distilling the solution after the precipitate is taken out to be thick.

Optionally, the method further comprises:

and washing and drying the crude lithium carbonate to obtain refined lithium carbonate, and adding a cleaning solution generated in the washing process into the solution after the precipitate is taken out.

Optionally, in the method, the temperature of the drying is greater than 90 ℃.

Optionally, in the method, the strong alkaline solution is sodium hydroxide and/or potassium hydroxide.

Optionally, in the method, the strong alkali solution is a sodium hydroxide or potassium hydroxide solution with a mass concentration of 23% to 35%;

optionally, in the method, the organic solvent is any one of n-hexane, cyclohexane, heptane, dichloromethane and carbon tetrachloride.

Optionally, before adding a sufficient carbonate solution to the mother liquor to perform the precipitation reaction, the method further comprises: preheating the mother liquor.

Optionally, in the method, the preheating temperature is 30-35 ℃.

Optionally, in the method, the number of moles of the carbonate added is 1.1 times of the number of moles of lithium element in the mother liquor, and the number of moles of lithium is calculated according to the number of moles of the lithium metal charged in the process.

Optionally, in the method, the carbonate is sodium carbonate or potassium carbonate, and the carbonate is added to the mother liquor in the form of an aqueous solution.

Compared with the prior art, the embodiment of the invention has the following advantages:

according to the embodiment of the invention, carbonate is added into a mother liquor to recover lithium element, then the solution from which the lithium element is removed is distilled, the thick liquid generated after distillation is filtered, filter residues are put into a strong alkali solution to react, a mixed system with diisopropylamine at the upper layer and aqueous solution at the lower layer is formed, the upper layer liquid is distilled to recover the diisopropylamine, chlorine is introduced into the lower layer liquid to replace bromine, an organic solvent is added to extract the bromine, so that bromine is recovered, and simultaneously the aqueous solution obtained after extraction reaction and the filtrate are distilled to obtain solid waste containing organic phosphorus, so that the organic phosphorus is removed.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the application.

Drawings

FIG. 1 is a flow chart of a method for treating a 16 α -methylandrosta-4, 9(11) -diene-3, 17-dione mother liquor according to an embodiment of the invention.

Detailed Description

In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below.

Fig. 1 is a flow chart of a method for processing a 16 α -methylandrosta-4, 9(11) -diene-3, 17-dione mother liquor according to an embodiment of the present invention, and as shown in fig. 1, the method may include steps S100 to S500:

step S100, adding sufficient carbonate into the mother liquor to perform precipitation reaction, and taking out the precipitate after the reaction is completed to obtain crude lithium carbonate;

step S200, distilling the solution after the precipitate is taken out to be thick and thick, and then filtering the thick liquid to obtain filter residue and filtrate;

step S300, putting the filter residue into a strong alkali solution, uniformly mixing, and standing to obtain a layered solution;

s400, distilling the supernatant of the layered solution to obtain diisopropylamine; introducing chlorine into the lower layer solution of the layered solution, and adding an organic solvent for extraction reaction to obtain bromine;

and S500, distilling the aqueous solution obtained after the extraction reaction and the filtrate to obtain the solid waste containing the organic phosphorus.

According to the embodiment of the invention, carbonate is added into a mother liquor to recover lithium in the mother liquor, then the mother liquor without the lithium is distilled, thick liquid generated after distillation is filtered, filter residue is put into strong alkali solution, strong alkali is utilized to react with diisopropylamine hydrochloride to obtain diisopropylamine, a mixed system with an upper layer of diisopropylamine and a lower layer of aqueous solution is formed, distillation is continuously carried out on the upper layer of solution to realize recovery of the diisopropylamine, chlorine is introduced into the lower layer of solution to replace bromine, and an organic solvent is added to extract the bromine, so that bromine is recovered, and meanwhile, the aqueous solution obtained after extraction reaction and the filtrate are distilled to obtain solid waste containing organic phosphorus, so that the organic phosphorus is removed.

Specifically, in step S100, 16 α -methylandrost-4, 9(11) -diene-3, 17-dione mother liquor generated in a workshop is pumped into a kettle, carbonate is added, carbonate ions react with lithium ions in the mother liquor to generate lithium carbonate precipitate, and the precipitate is taken out to obtain crude lithium carbonate, so that the crude lithium carbonate can be recovered.

The main reaction equation in the above step S100 is as follows: 2LiBr + CO₃ ^2-＝Li₂CO₃+2Br^-。

In step S100, in order to sufficiently recover the lithium ions in the mother liquor, a sufficient amount of carbonate should be added so that the lithium ions can be completely reacted. Optionally, the mole number of the added carbonate is 1.1 times of the mole number of the lithium element in the mother liquor, so that the added carbonate ions can neutralize the unreacted hydrochloric acid in the mother liquor and completely combine the lithium ions, and excessive carbonate ions are avoided. Wherein, the mole number of the lithium element in the mother liquor can be calculated according to the mole number of the metallic lithium charged in the process.

Wherein, in order to facilitate the carbonate ions to combine with the lithium ions to generate precipitates, the carbonate may be a water-soluble carbonate. Optionally, the carbonate is sodium carbonate and/or potassium carbonate. Preferably, in order to facilitate the contact of the carbonate ions and the lithium ions, the carbonate is added dropwise to the mother liquor in the form of an aqueous solution to react, and the mother liquor is stirred to accelerate the contact collision of the carbonate ions and the lithium ions. Preferably, the carbonate water solution contains 15 to 20 mass% of carbonate.

More preferably, in order to further accelerate the contact collision of carbonate ions with lithium ions, so that the lithium ions in the solution can be sufficiently recovered, the mother liquor may be subjected to a preheating treatment in advance. For example, the mother liquor may be preheated to 30 to 35 ℃. The preset temperature is not too high, and lithium carbonate is easily dissolved in water due to too high temperature, so that the recovery of the lithium carbonate is influenced; and the combination rate of carbonate ions and lithium ions cannot be effectively improved when the temperature is too low.

Optionally, after step S100, the method further includes: and (5) washing and drying the crude lithium carbonate prepared in the step (S100) to obtain refined lithium carbonate, and adding a cleaning solution generated in the washing process into the solution after the precipitate is taken out to further recover the water, bromide ions and diisopropylamine hydrochloride in the cleaning solution. In the step, the washing process is repeated twice, the drying temperature is higher than 90 ℃, the lithium carbonate can be placed into a double cone for drying, the content of the prepared lithium carbonate reaches more than 98 percent, and the lithium carbonate can be directly sold.

In step S200, the solution after the precipitation in step S100 is pumped into a multi-effect evaporator for reduced pressure distillation, at this time, white crystals are continuously precipitated due to the evaporation of water, and the main components of the white crystals are diisopropylamine hydrochloride, bromate and hydrochloride, wherein the cations of the bromate and hydrochloride are the cations in the carbonate added in step S100. For example, if sodium carbonate is added in step S100, the main components of the white crystal are diisopropylamine hydrochloride, sodium bromate and sodium chloride. When the solution is distilled under reduced pressure until the solution is thick, white crystals are taken out as a filter residue by filtration or centrifugation, and phenylethane, unreacted styrene, hexamethylphosphoric triamide and the like remain in the filtrate.

In the step S300, the filter residue, mainly containing diisopropylamine hydrochloride and bromate, generated in the step S200 is added into a strong alkali solution, and a strong alkali is used to react with diisopropylamine hydrochloride therein under a stirring condition to generate diisopropylamine and hydrochloride, but since diisopropylamine is insoluble in water and the density of diisopropylamine is less than that of water, a layering phenomenon occurs when the solution after reaction is left to stand, the upper layer is diisopropylamine, and the lower layer is an aqueous solution in which hydrochloride and bromate are dissolved.

The main reaction equation of step S300 is as follows:

in the step S300, the alkali solution should be excessive to ensure that the diisopropylamine hydrochloride in the filter residue is reacted completely. Optionally, in step S300, the alkali solution is sodium hydroxide and/or potassium hydroxide, and correspondingly, the generated hydrochloride is sodium chloride and/or potassium chloride.

Preferably, the strong alkali solution is a sodium hydroxide or potassium hydroxide solution with a mass concentration of 23-35%, for example, a 30% sodium hydroxide solution. The strong base solution with too high concentration is not beneficial to the dissolution of diisopropylamine hydrochloride and bromate, namely, the reaction of strong base and diisopropylamine hydrochloride, and the reaction is too slow due to the too high concentration of the strong base solution, so that excessive moisture in the product is easily caused, and the subsequent reaction is not beneficial;

preferably, when the filter residue is put into the strong alkali solution, the mole number of hydroxide ions in the strong alkali is 0.77 times of the mole number of the diisopropylamine put in the process. Not only can the diisopropylamine hydrochloride in the filter residue react completely, but also excessive sodium ions and/or potassium ions can not be introduced.

In the step S400, the supernatant of the layered solution obtained in the step S300 is distilled to obtain diisopropylamine; the purity of the diisopropylamine obtained in the step is more than 99%. Preferably, the diisopropylamine may be dehydrated by a drying agent to remove water from the produced diisopropylamine, so that a pure diisopropylamine raw material can be obtained.

In the step S400, sufficient chlorine gas is introduced into the lower layer solution of the layered solution obtained in the step S300, and chlorine is used to replace bromide ions to obtain an aqueous solution containing bromine and hydrochloride, and then sufficient organic solvent is added to the aqueous solution containing bromine to perform an extraction reaction, so as to extract bromine from the solution containing bromine by using the organic solvent, thereby obtaining bromine and realizing the recovery of liquid bromine. Wherein, the introduced chlorine gas is enough to completely replace bromide ions as much as possible; wherein the organic solvent is added in an amount sufficient to ensure complete extraction of bromine from the bromine-containing solution.

In the step S500, the aqueous solution obtained after the extraction reaction in the step S400 and the filtrate in the step S200 are pumped into a reaction kettle for distillation, and after the water in the filtrate is evaporated, solid waste containing organic phosphorus is obtained, so that the organic phosphorus in the mother liquor is removed. The solid waste can be further subjected to solid waste treatment.

In the step, because the boiling points of the phenylethane, the unreacted styrene and the hexamethylphosphoric triamide are higher than that of water, the phenylethane, the unreacted styrene and the hexamethylphosphoric triamide can be separated from the water by distillation and are left in the reaction kettle in the form of a small amount of residue, so that the phenylethane, the unreacted styrene and the hexamethylphosphoric triamide in the mother liquor can be efficiently removed, and the problem that the COD (chemical oxygen demand) and the organic phosphorus in the mother liquor are seriously overproof is solved. Meanwhile, the metal cations introduced by the carbonate in the above step S100 and the metal cations introduced by the strong alkali solution in the step S300 exist in the final residue in the form of hydrochloride. The hydrochloride of the above step includes sodium chloride and/or potassium chloride depending on the carbonate and the strong base added.

Alternatively, in the step S200, the distilled water generated in the process of distilling the solution after the precipitate is taken out to be thick is recovered, and in the step S500, the distilled water generated in the process of distilling the aqueous solution obtained after the extraction reaction together with the filtrate is recovered. Through the above steps, most of the moisture in the mother liquor can be recovered.

The present invention will be described in detail below with reference to examples.