CN105541949A - Method for extracting 4-androstenedione from production residues of 17 alpha-hydroxyl-17 alpha-cyano-androstane-4-alkene-3-ketone - Google Patents
Method for extracting 4-androstenedione from production residues of 17 alpha-hydroxyl-17 alpha-cyano-androstane-4-alkene-3-ketone Download PDFInfo
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- CN105541949A CN105541949A CN201610052477.3A CN201610052477A CN105541949A CN 105541949 A CN105541949 A CN 105541949A CN 201610052477 A CN201610052477 A CN 201610052477A CN 105541949 A CN105541949 A CN 105541949A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J1/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, not substituted in position 17 beta by a carbon atom, e.g. estrane, androstane
- C07J1/0003—Androstane derivatives
- C07J1/0011—Androstane derivatives substituted in position 17 by a keto group
Abstract
The invention provides a method for extracting 4-androstenedione from production residues of 17 alpha-hydroxyl-17 alpha-cyano-androstane-4-alkene-3-ketone. The method comprises the ten steps of ultrasonic leaching, solid-liquid separation, depolymerization, distillation, solid-liquid separation, dissolving and adsorbing, solid-liquid separation, crystallizing, solid-liquid separation and drying. According to the method in an embodiment, qualified 4-androstenedione with the purity of 98.5 or above and an individual impurity of 0.3% or below can be extracted from the production residues of 17 alpha-hydroxyl-17 alpha-cyano-androstane-4-alkene-3-ketone, and the recovery rate of 4-androstenedione reaches 90% or above. Meanwhile, by means of the ultrasonic leaching technology, the leaching efficiency of 4-androstenedione is further improved, and the leaching yield of 4-androstenedione reaches 96% or above. In addition, raw materials adopted in the embodiment are low in price, equipment is simple, an organic solvent can be cyclically utilized, and therefore process cost is reduced. Meanwhile, the advantages of being reasonable in process, simple in method, environmentally friendly, high in product yield and good in production quality, saving energy and the like are achieved.
Description
Technical field
The invention belongs to medical environment chemical field, particularly relate to a kind of method extracting 4-AD from the production waste residue of 17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one.
Background technology
In actual production, with 4-AD and prussic acid for raw material, under alkalescence effect, 17 carbonyls and prussic acid generation carbonyl addition, obtain 17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one.
In the last handling process of above-mentioned reaction, 17 beta-hydroxyl-17 alphas-cyano group-androstane-4-alkene-3-one and a small amount of 17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one are converted into 4-AD, add unreacted raw material completely, cause producing the 4-AD containing 10% ~ 20% in waste residue.In addition, in reaction system, there is water and alkali, and under water and the simultaneous condition of alkali, the easy polymerization reaction take place of prussic acid, causes producing the prussic acid polymkeric substance also containing 50% ~ 60% in waste residue.
The market value of 4-AD is high, if directly abandoned by the production waste residue of 17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one, then can cause the wasting of resources, strengthens productive expense; If 4-AD can be extracted from the production waste residue of 17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one, then can reduce raw material consumption to a certain extent, reduce production cost, alleviate environmental pollution.Therefore, a kind of effective ways extracting 4-AD from the production waste residue of 17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one are badly in need of.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method extracting 4-AD from the production waste residue of 17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one, solves the problems of the technologies described above with all or part of.
In order to solve the problem, the invention discloses a kind of method extracting 4-AD from the production waste residue of 17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one, said method comprising the steps of:
Step (1), supersonic leaching: in the reaction vessel that described production waste residue is housed, add boiling point lower than first organic solvent of 100 DEG C, described reaction vessel is positioned in supersonic leaching equipment, at 0 ~ 70 DEG C, ultrasonic 0.5 ~ 4.0h, 4-AD in described production waste residue is gone out to make described organic solvent soaking extraction, until leaching terminates, in described reaction vessel, obtain the first material;
Step (2), solid-liquid separation: joined in solid-liquid separating equipment by described first material and carry out solid-liquid separation, the first solid phase after separation is waste residue, containing required 4-AD in the first liquid phase;
Step (3), depolymerization: in described first liquid phase obtained, add alkaline reagents, to make the prussic acid polymkeric substance solution coalescence salify in described production waste residue soluble in water, obtain the second material;
Step (4), distillation: described second material is added in distillation plant and distills, to distill out described first organic solvent, and water-fast described 4-AD is separated out along with the separation of described first organic solvent, after distillation terminates, remaining described second material is 3 material, described 3 material is solidliquid mixture, and the first organic solvent distilled out is back to described step (1) to be continued to use;
Step (5), solid-liquid separation: described 3 material is joined in described solid-liquid separating equipment and carries out solid-liquid separation, the 3rd liquid phase after separation is waste liquid, containing required 4-AD in the 3rd solid phase;
Step (6), dissolving and absorption: in described 3rd solid phase, add the second organic solvent, temperature rising reflux 0.5 ~ 2.0h, to make described 3rd solid-solution, after dissolving, add sorbent material decolouring and adsorbing contaminant, be cooled to 20 ~ 35 DEG C, obtain 4 materials;
Step (7), solid-liquid separation: described 4 materials is added in described solid-liquid separating equipment, the 4th solid phase after separation is waste residue, containing required 4-AD in the 4th liquid phase;
Step (8), crystallization: temperature rising reflux is carried out to described 4th liquid phase, is cooled to-15 ~ 0 DEG C more afterwards, insulation 3.0 ~ 5.0h, to make described 4-AD separate out, obtain the 5th material, described 5th material is solidliquid mixture;
Step (9), solid-liquid separation: described 5th material is joined in described solid-liquid separating equipment, containing required 4-AD in the 5th solid phase after separation, the 5th liquid phase is back to described step (6) and continues to use;
Step (10), drying: described 5th solid phase is added in drying plant and carries out drying treatment, obtain required 4-AD.
Alternatively, in described step (1), described first organic solvent is at least one in methyl alcohol, acetone, tetrahydrofuran (THF), methylene dichloride and ethyl acetate, and the ratio of the volume of described first organic solvent and the quality of described production waste residue is 2.0 ~ 6.0:1.0.
Alternatively, in described step (3), described alkaline reagents is at least one in sodium hydroxide, potassium hydroxide, ammoniacal liquor and sodium carbonate, the mass percent concentration of described alkaline reagents is 10% ~ 25%, the ratio of the quality of described alkaline reagents neutral and alkali solute and the quality of described production waste residue is 0.1 ~ 0.5:1.0, backflow 1.0 ~ 4.0h.
Alternatively, in described step (6), described second organic solvent is at least one in methyl alcohol, acetone, toluene, methylene dichloride, tetrahydrofuran (THF), chloroform, ethyl acetate and butylacetate, the ratio of the volume of described second organic solvent and the quality of described production waste residue is 0.2 ~ 2.0:1.0, and the quality of described sorbent material and the mass ratio of described production waste residue are 0.002 ~ 0.02:1.0.
Alternatively, in described step (7), described sorbent material is at least one in gac, silica gel and molecular sieve.
Alternatively, in described step (2), described step (5), described step (8) and described step (10), described solid-liquid separating equipment is sedimentation type soil-liquid separator, filtering type equipment for separating liquid from solid, centrifugal equipment for separating liquid from solid or vane-type equipment for separating liquid from solid.
Alternatively, in described step (10), described drying plant is Vacuumdrier, rotary drying machine, rotating drum dryer, fluidized bed dryer, spray-dryer or pneumatic moisture eliminator.
Compared with prior art, the present invention includes following advantage:
(1) adopt the method for the embodiment of the present invention can extract from the production waste residue of 17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one purity reaches more than 98.5%, single assorted content reach less than 0.3% up-to-standard 4-AD, the rate of recovery of 4-AD reaches more than 90%.
The production waste residue of (2) 17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one is harder, tradition leaching technologies can not meet processing requirement, and the supersonic leaching technology that the embodiment of the present invention adopts further increases the leaching yield of 4-AD, the leaching yield of 4-AD is made to reach more than 96%.
(3) simple, the organic solvent of the low in raw material price, the equipment that adopt of the embodiment of the present invention can recycle, thus reduces process costs; Have that rational technology, method are simple simultaneously, the advantage such as the high and good product quality of environmental protection and energy saving, product yield.
Accompanying drawing explanation
Fig. 1 is a kind of schema extracting the method for 4-AD from the production waste residue of 17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one described in the embodiment of the present invention.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, and below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation.
Be described in detail below by the realization flow of embodiment to the method for the invention.
Embodiments provide a kind of method extracting 4-AD from the production waste residue of 17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one.
With reference to Fig. 1, it illustrates a kind of schema extracting the method for 4-AD from the production waste residue of 17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one described in the embodiment of the present invention, said method comprising the steps of:
Step (1), supersonic leaching: in the reaction vessel that described production waste residue is housed, add boiling point lower than first organic solvent of 100 DEG C, described reaction vessel is positioned in supersonic leaching equipment, at 0 ~ 70 DEG C, ultrasonic 0.5 ~ 4.0h, 4-AD in described production waste residue is gone out to make described organic solvent soaking extraction, until leaching terminates, in described reaction vessel, obtain the first material.
The production waste residue of 17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one is harder, tradition leaching technologies can not meet processing requirement, and the supersonic leaching technology that the embodiment of the present invention adopts can make the leaching yield of 4-AD reach more than 96%, yield is higher.
Step (2), solid-liquid separation: joined in solid-liquid separating equipment by described first material and carry out solid-liquid separation, the first solid phase after separation is waste residue, containing required 4-AD in the first liquid phase.
Step (3), depolymerization: to the described first liquid phase neutral and alkali reagent obtained, backflow 1.0 ~ 4.0h, to make the prussic acid polymkeric substance solution coalescence salify in described production waste residue soluble in water, obtains the second material.
Step (4), distillation: described second material is added in distillation plant and distills, to distill out described first organic solvent, and water-fast described 4-AD is separated out along with the separation of described first organic solvent, after distillation terminates, remaining described second material is 3 material, described 3 material is solidliquid mixture, and the first organic solvent distilled out is back to described step (1) to be continued to use.
Step (5), solid-liquid separation: joined in described solid-liquid separating equipment by described 3 material and carry out solid-liquid separation, the 3rd liquid phase after separation is waste liquid, containing required 4-AD in the 3rd solid phase.
Step (6), dissolving and absorption: in described 3rd solid phase, add the second organic solvent, temperature rising reflux 0.5 ~ 2.0h, to make described 3rd solid-solution, after dissolving, add sorbent material decolouring and imurity-removal, be cooled to 20 ~ 35 DEG C, obtain 4 materials.
Step (7), solid-liquid separation: add in described solid-liquid separating equipment by described 4 materials, the 4th solid phase after separation is waste residue, containing required 4-AD in the 4th liquid phase.
Step (8), crystallization: carry out temperature rising reflux to described 4th liquid phase, be cooled to-15 ~ 0 DEG C more afterwards, freezing 3.0 ~ 5.0h, to make described 4-AD separate out, obtain the 5th material, and described 5th material is solidliquid mixture.
Step (9), solid-liquid separation: join in described solid-liquid separating equipment by described 5th material, containing required 4-AD in the 5th solid phase after separation, the 5th liquid phase is back to described step (6) and continues to use.
Step (10), drying: described 5th solid phase is added in drying plant and carries out drying treatment, obtain required 4-AD.
Adopt the method for the embodiment of the present invention can extract from the production waste residue of 17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one purity reaches more than 98.5%, single assorted content reach less than 0.3% up-to-standard 4-AD, the rate of recovery of 4-AD reaches more than 90%.The supersonic leaching technology that the embodiment of the present invention adopts simultaneously further increases the leaching yield of 4-AD, makes the leaching yield of 4-AD reach more than 96%.In addition, the low in raw material price that the embodiment of the present invention adopts, equipment are simple, organic solvent can recycle, thus reduce process costs; Have that rational technology, method are simple simultaneously, the advantage such as the high and good product quality of environmental protection and energy saving, product yield.
In the embodiment of the present invention, preferably, in described step (1), described first organic solvent is at least one in methyl alcohol, acetone, tetrahydrofuran (THF), methylene dichloride and ethyl acetate, and the ratio of the volume of described first organic solvent and the quality of described production waste residue is 2.0 ~ 6.0:1.0.
In the embodiment of the present invention, preferably, in described step (3), described alkali reagent is at least one in sodium hydroxide, potassium hydroxide, ammoniacal liquor and sodium carbonate, the mass percent concentration of described alkaline reagents is 10% ~ 25%, the quality of described alkaline reagents neutral and alkali solute and the ratio of described production slag quality are 0.1 ~ 0.5:1.0, backflow 1.0 ~ 4.0h.
In the embodiment of the present invention, preferably, in described step (6), described second organic solvent is at least one in methyl alcohol, acetone, toluene, methylene dichloride, tetrahydrofuran (THF), chloroform, ethyl acetate and butylacetate, the ratio of described second consumption of organic solvent and waste residue is 0.2 ~ 2.0:1.0, and the quality of described sorbent material and the mass ratio of described production waste residue are 0.002 ~ 0.02:1.0.
In the embodiment of the present invention, preferably, in described step (6), described sorbent material is at least one in gac, silica gel and molecular sieve.
In the embodiment of the present invention, preferably, in described step (2), described step (5), described step (8) and described step (10), described solid-liquid separating equipment is sedimentation type soil-liquid separator, filtering type equipment for separating liquid from solid, centrifugal equipment for separating liquid from solid or vane-type equipment for separating liquid from solid.
In the embodiment of the present invention, preferably, in described step (10), described drying plant is Vacuumdrier, rotary drying machine, rotating drum dryer, fluidized bed dryer, spray-dryer or pneumatic moisture eliminator.
For making those skilled in the art understand the present invention better, the method extracting 4-AD from the production waste residue of 17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one of the embodiment of the present invention is described below by way of multiple specific embodiment.
Embodiment 1
After testing, in the production waste residue of 17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one, the content of 4-AD is 20%.
The production waste residue getting 200g17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one is placed in four-hole boiling flask, adds 400mL methylene dichloride, maintains the temperature at 0 DEG C, supersonic leaching 0.5h; After filtration under diminished pressure, in mother liquor, add the aqueous sodium hydroxide solution that 200g mass percent concentration is 10%, backflow 4h; Distill out methylene dichloride, after filtering, solid material added in 400mL toluene, heat up clearly molten, backflow 0.5h, adds 0.4g gac, is cooled to 30 DEG C, filters, washing; Mother liquor reflux 0.5h, decrease temperature crystalline ,-5 DEG C of freezing 3.0h, filter, washing, vacuum drying oven is dry, obtain 4-AD finished product 36.4g, the rate of recovery of 4-AD is 91%, and high performance liquid chromatography (HPLC) detects that the purity of 4-AD is 98.5%.
Embodiment 2
After testing, in the production waste residue of 17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one, the content of 4-AD is 15%.
The production waste residue getting 400g17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one is placed in four-hole boiling flask, adds 2400mL acetone, maintains the temperature at 40 DEG C, supersonic leaching 4h; After filtration under diminished pressure, in mother liquor, add the aqueous sodium carbonate that 800g mass percent concentration is 25%, backflow 1h; Distill out acetone, after filtering, solid material added in 40mL methylene dichloride and 40mL chloroform, temperature rising reflux 2.0h, adds 8.0g silica gel, is cooled to 20 DEG C, filters, washing; Mother liquor reflux 2.0h, decrease temperature crystalline ,-15 DEG C of freezing 5.0h, centrifugal, washing, with nitrogen drying in pneumatic moisture eliminator, obtain 4-AD finished product 54.0g, the 4-AD rate of recovery is that 90%, HPLC detects that the purity of 4-AD is 98.5%.
Embodiment 3
After testing, in the production waste residue of 17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one, the content of 4-AD is 10%.
The production waste residue getting 800g17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one is placed in four-hole boiling flask, adds 2400mL ethyl acetate, maintains the temperature at 70 DEG C, supersonic leaching 2.0h; After filtration under diminished pressure, in mother liquor, add the potassium hydroxide aqueous solution that 800g mass percent concentration is 15%, backflow 2h; Distill out ethyl acetate, after centrifugal, solid material added in 600mL acetone and 200mL tetrahydrofuran (THF), heat up clearly molten, backflow 1.0h, adds 8.0g gac, is cooled to 25 DEG C, centrifugal, washing; Mother liquor reflux 1.0h, decrease temperature crystalline, 0 DEG C of freezing 4.0h, centrifugal, washing, vacuum-drying, obtains 4-AD finished product 72.0g, and the 4-AD rate of recovery is that 90%, HPLC detects that the purity of 4-AD is 98.5%.
Embodiment 4
After testing, in the production waste residue of 17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one, the content of 4-AD is 15%.
The production waste residue getting 400g17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one is placed in four-hole boiling flask, adds 1200mL tetrahydrofuran (THF), maintains the temperature at 35 DEG C, supersonic leaching 3.0h; After filtration under diminished pressure, in mother liquor, add the aqueous sodium carbonate that 1000g mass percent concentration is 15%, backflow 1h; Distill out tetrahydrofuran (THF), after filtering, solid material added in 120mL ethyl acetate and 120mL butylacetate, heat up clearly molten, backflow 2.0h, adds 6.0g molecular sieve, is cooled to 35 DEG C, filters, washing; Mother liquor reflux 2.0h, decrease temperature crystalline ,-10 DEG C of freezing 4h, centrifugal, washing, with nitrogen drying in pneumatic moisture eliminator, obtain 4-AD finished product 54g, the 4-AD rate of recovery is that 90%, HPLC detects that the purity of 4-AD is 98.5%.
Embodiment 5
After testing, in the production waste residue of 17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one, the content of 4-AD is 12%.
The production waste residue getting 800g17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one is placed in four-hole boiling flask, adds 2400mL methyl alcohol, maintains the temperature at 60 DEG C, supersonic leaching 3.0h; After filtration under diminished pressure, in mother liquor, add the ammonia soln that 400g mass percent concentration is 20%, backflow 3.0h; Distill out methyl alcohol, after centrifugal, solid material added in 600mL methyl alcohol, heat up clearly molten, backflow 1.5h, adds 3.0g gac and 2.0g molecular sieve, is cooled to 28 DEG C, centrifugal, washing; Mother liquor reflux 1.0h, decrease temperature crystalline, 0 DEG C of freezing 5.0h, centrifugal, washing, vacuum-drying, obtains 4-AD finished product 86.4g, and the 4-AD rate of recovery is that 90%, HPLC detects that the purity of 4-AD is 98.5%.
Above a kind of method extracting 4-AD from the production waste residue of 17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one provided by the present invention is described in detail, apply specific case herein to set forth principle of the present invention and embodiment, the explanation of above embodiment just understands method of the present invention and core concept thereof for helping; Meanwhile, for one of ordinary skill in the art, according to thought of the present invention, all will change in specific embodiments and applications, in sum, this description should not be construed as limitation of the present invention.
Claims (7)
1. from the production waste residue of 17 Alpha-hydroxy-17 beta-cyanos-androstane-4-alkene-3-one, extract a method for 4-AD, it is characterized in that, said method comprising the steps of:
Step (1), supersonic leaching: in the reaction vessel that described production waste residue is housed, add boiling point lower than first organic solvent of 100 DEG C, described reaction vessel is positioned in supersonic leaching equipment, at 0 ~ 70 DEG C, ultrasonic 0.5 ~ 4.0h, 4-AD in described production waste residue is gone out to make described organic solvent soaking extraction, until leaching terminates, in described reaction vessel, obtain the first material;
Step (2), solid-liquid separation: joined in solid-liquid separating equipment by described first material and carry out solid-liquid separation, the first solid phase after separation is waste residue, containing required 4-AD in the first liquid phase;
Step (3), depolymerization: in described first liquid phase obtained, add alkaline reagents, to make the prussic acid polymkeric substance solution coalescence salify in described production waste residue soluble in water, obtain the second material;
Step (4), distillation: described second material is added in distillation plant and distills, to distill out described first organic solvent, and water-fast described 4-AD is separated out along with the separation of described first organic solvent, after distillation terminates, remaining described second material is 3 material, described 3 material is solidliquid mixture, and the first organic solvent distilled out is back to described step (1) to be continued to use;
Step (5), solid-liquid separation: described 3 material is joined in described solid-liquid separating equipment and carries out solid-liquid separation, the 3rd liquid phase after separation is waste liquid, containing required 4-AD in the 3rd solid phase;
Step (6), dissolving and absorption: in described 3rd solid phase, add the second organic solvent, temperature rising reflux 0.5 ~ 2.0h, to make described 3rd solid-solution, after dissolving, add sorbent material decolouring and adsorbing contaminant, be cooled to 20 ~ 35 DEG C, obtain 4 materials;
Step (7), solid-liquid separation: described 4 materials is added in described solid-liquid separating equipment, the 4th solid phase after separation is waste residue, containing required 4-AD in the 4th liquid phase;
Step (8), crystallization: temperature rising reflux is carried out to described 4th liquid phase, is cooled to-15 ~ 0 DEG C more afterwards, insulation 3.0 ~ 5.0h, to make described 4-AD separate out, obtain the 5th material, described 5th material is solidliquid mixture;
Step (9), solid-liquid separation: described 5th material is joined in described solid-liquid separating equipment, containing required 4-AD in the 5th solid phase after separation, the 5th liquid phase is back to described step (6) and continues to use;
Step (10), drying: described 5th solid phase is added in drying plant and carries out drying treatment, obtain required 4-AD.
2. method according to claim 1, it is characterized in that, in described step (1), described first organic solvent is at least one in methyl alcohol, acetone, tetrahydrofuran (THF), methylene dichloride and ethyl acetate, and the ratio of the volume of described first organic solvent and the quality of described production waste residue is 2.0 ~ 6.0:1.0.
3. method according to claim 1, it is characterized in that, in described step (3), described alkaline reagents is at least one in sodium hydroxide, potassium hydroxide, ammoniacal liquor and sodium carbonate, the mass percent concentration of described alkaline reagents is 10% ~ 25%, the ratio of the quality of described alkaline reagents neutral and alkali solute and the quality of described production waste residue is 0.1 ~ 0.5:1.0, backflow 1.0 ~ 4.0h.
4. method according to claim 1, it is characterized in that, in described step (6), described second organic solvent is at least one in methyl alcohol, acetone, toluene, methylene dichloride, tetrahydrofuran (THF), chloroform, ethyl acetate and butylacetate, the ratio of the volume of described second organic solvent and the quality of described production waste residue is 0.2 ~ 2.0:1.0, and the quality of described sorbent material and the mass ratio of described production waste residue are 0.002 ~ 0.02:1.0.
5. method according to claim 1, is characterized in that, in described step (7), described sorbent material is at least one in gac, silica gel and molecular sieve.
6. method according to claim 1, it is characterized in that, in described step (2), described step (5), described step (8) and described step (10), described solid-liquid separating equipment is sedimentation type soil-liquid separator, filtering type equipment for separating liquid from solid, centrifugal equipment for separating liquid from solid or vane-type equipment for separating liquid from solid.
7. method according to claim 1, is characterized in that, in described step (10), described drying plant is Vacuumdrier, rotary drying machine, rotating drum dryer, fluidized bed dryer, spray-dryer or pneumatic moisture eliminator.
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| CN201610052477.3A CN105541949B (en) | 2016-01-26 | 2016-01-26 | A kind of method that 4 androstenedione are extracted from the production waste residue of the ketone of 17 α hydroxyls, 17 β cyano group androstane-14s alkene 3 |
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| CN105541949B (en) | 2017-11-10 |
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