CN101717422A - Method for producing dehydroepiandros-sterone - Google Patents
Method for producing dehydroepiandros-sterone Download PDFInfo
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- CN101717422A CN101717422A CN200910273027A CN200910273027A CN101717422A CN 101717422 A CN101717422 A CN 101717422A CN 200910273027 A CN200910273027 A CN 200910273027A CN 200910273027 A CN200910273027 A CN 200910273027A CN 101717422 A CN101717422 A CN 101717422A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 80
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 69
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 54
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 38
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002351 wastewater Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 230000007935 neutral effect Effects 0.000 claims abstract description 5
- 150000001993 dienes Chemical class 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims abstract description 4
- 238000006146 oximation reaction Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 16
- 208000005156 Dehydration Diseases 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 9
- 235000015320 potassium carbonate Nutrition 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 7
- 239000002699 waste material Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000007710 freezing Methods 0.000 claims description 6
- 230000008014 freezing Effects 0.000 claims description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 230000006911 nucleation Effects 0.000 claims description 3
- 238000010899 nucleation Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 230000002269 spontaneous effect Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 abstract description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 3
- 238000006073 displacement reaction Methods 0.000 abstract description 3
- 239000011780 sodium chloride Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 abstract 1
- 238000010025 steaming Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003317 industrial substance Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910019213 POCl3 Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- -1 diene alcohol ketone oxime Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 230000035935 pregnancy Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000003270 steroid hormone Substances 0.000 description 1
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- Pyridine Compounds (AREA)
Abstract
The invention provides a method for producing dehydroepiandros-sterone, comprising the following steps of: drying ketoxime substance obtained after the oximation reaction of diene till water content is not more than 0.5 percent; adding into benzene dehydrated with edible salt for raising the temperature and dissolving; after complete dissolving, reducing the temperature by 38+/-2 DEG C and adding pyridine; reducing the temperature by 5-8 DEG C with saline water; dropwise adding mixed solution of phosphorus oxychloride and benzene and controlling the temperature within 15 DEG C during dropping; keeping the temperature of the mixed solution within 16-18 DEG C for three hours; rapidly adding dilute acid liquid and then raising the temperature to 58+/-1 DEG C; keeping the temperature and reacting for 2 hours within 58+/-1 DEG C; and feeding wastewater into a storage tank, washing three times till the wastewater is neutral, filtering materials, adding water, steaming and distilling for hydrolysis reaction. The invention effectively reduces the consumption of phosphorus oxychloride and hydrochloric acid, simultaneously recovers the wastewater, carries out displacement reaction by using caustic soda to displace pyridinium in the wastewater into pyridine, purifies and recycles the pyridine, greatly reduces the cost of products while ensuring the quality of the product and improves the market competitiveness.
Description
Technical field
The present invention relates to a kind of method of producing dehydroepiandros-sterone.
Background technology
Dehydroepiandros-sterone is a steroid hormone class bulk drug, uses very extensive.The processing compound of producing at present dehydroepiandros-sterone is the ketoxime thing: benzene: phosphorus oxychloride: pyridine: hydrochloric acid=1: 6.5: 0.88: 0.48: 1.8, the acid-hydrolyzed processing method of hydrolyzing process be 12 ℃ of temperature controls with interior slow dropping, length consuming time, the waste liquid of generation is drained.The higher industrial chemicals processing compound height such as phosphorus oxychloride of market value in the above production technique, the waste liquid that contains pyridinium salt does not have recycling, and the production cycle is longer, waste liquid is acidity and enters in the environment, treatment cost is big, causes dehydroepiandros-sterone products production cost higher, and the market competitiveness is not high.
Summary of the invention
Higher in order to solve the dehydroepiandros-sterone cost, long and waste liquor contamination problem of environment of production cycle, the present invention proposes a kind of method of producing dehydroepiandros-sterone.
Technical scheme of the present invention for this reason is, a kind of method of producing dehydroepiandros-sterone, and its steps characteristic is:
At first in retort with diene through the 120kg of oximation reaction ketoxime thing, oven dry moisture content≤0.5% joins rising temperature for dissolving in the 780kg benzene after edible salt dehydration, treat that the ketoxime thing is cooled to 38 ℃ ± 2 ℃ after molten entirely, add the 57.6kg pyridine again, the content of pyridine 〉=98%, moisture content＜0.2%;
Secondly lead to 5～8 ℃ of salt water for cooling in the chuck in retort, the mixing solutions of Dropwise 5 8kg phosphorus oxychloride and 98kg benzene, the content of phosphorus oxychloride 〉=98% drips temperature control in 15 ℃, drips behind the mixing solutions of phosphorus oxychloride and benzene insulation reaction in 16 ℃-18 ℃;
Next reacts the solution after 3 hours again, add 227kg hydrogenchloride diluted acid water fast, the content of hydrogenchloride is 10%, is warming up to 58 ℃ ± 1 ℃ then, and insulation reaction is after 2 hours in this temperature range, the waste water of solution bottom is told, telling solution behind the waste water to storage tank, wash three times to neutral, PH=7-8, the solution of washing three times is filtered back dashing with steam heat up in a steamer, and centrifugal dehydration treatment;
Suction content 〉=92% ethanol 1000kg in retort more at last, drop into centrifugal good material, be warming up to 60 ℃ ± 2 ℃ with steam, stirred 30 minutes, the 80kg alkali Shui sodium hydroxide that suction prepares in advance, the content of sodium hydroxide is 30-40%, alkali Shui temperature is between 80-90 ℃, and the salt of wormwood that adds 30kg again stirs, and the content of salt of wormwood is 99%-103%, salt of wormwood is all dissolved, reflux after 2 hours, above-mentioned blended solution concentration to the 400L, was discharged in the stainless bucket spontaneous nucleation 8 hours, put to the freezing tank freezing 12 hours, the recentrifuge oven dry is dehydroepiandros-sterone again.
The recovery technology of pyridine:
At first detach waste acid water 300L after the heart dehydration to retort, add 50kg solid caustic soda sodium hydroxide, sodium hydrate content 〉=95% is neutralized to PH=8, divides the lixiviating water layer, and the solution that contains pyridine is collected in distillation, carries out first time and dewaters;
Secondly in containing the solution of pyridine, divide secondary to add solid caustic soda sodium hydroxide, each add-on is 5～8kg, divides the lixiviating water layer in the rest solution standing groove, adds the benzene of 1.5～2 times of pyridine solutions once more in containing the solution of pyridine, steam benzene and dewater for the second time, and from water trap, moisture is walked;
At last the water that contains pyridine solution is taken off most back and go up rectifying tower rectifying, the temperature of rectifying is got 110～118 ℃, and rectification and purification goes out to meet the pyridine that raw materials quality requires in this scope.
Effective effect:
Innovative point of the present invention is that one is the processing compound of innovation dehydroepiandros-sterone, improves the working method of hydrolyzing process, guarantees quality product; The 2nd, displacement, separation, the purifying process of pyridinium salt make the pyridine of recovery can reach raw material functional quality standard in the discovery waste water, and recovery set is used; The 3rd, by the innovation of above two aspects, produce 1 ton of dehydroepiandros-sterone, phosphorus oxychloride ton consumption drops to 0.75 ton by present 1.24 tons, hydrochloric acid ton consumption drops to 0.889 ton by present 2.5 tons, and the ton consumption of pyridine drops to 0.7 ton by present 1.2 tons, reclaims in the pyridine, the waste water pH value that produces is neutral, alleviate pollution treatment pressure greatly, the dehydroepiandros-sterone quality product is not affected, ton cost decline 20-35%.Analyze the dehydroepiandros-sterone production technology characteristic, find that oxidation operation uses the industrial chemicals marketable value higher, processing compound is big, and technical difficulty is higher relatively.By research to oxidation operation, experiment, effectively reduce the usage quantity of phosphorus oxychloride, hydrochloric acid, innovated Technology, reclaim waste water simultaneously, carry out replacement(metathesis)reaction with sheet alkali, pyridinium salt in the waste water is replaced into pyridine, and the recovery pyrido of purifying recycles, when guaranteeing quality product, reduce the cost of product greatly, improve the market competitiveness.
Reduce the processing compound usage quantity of phosphorus oxychloride, hydrochloric acid, the working method of innovation hydrolyzing process by the slow dripping method of original low temperature, changes nature quick heating addition into, adds 58 ℃ of insulation reaction of back intensification; The pyridinium salt that produces in the waste water reclaims the pyridine that conforms to quality requirements and applies mechanically aborning by materializing procedures such as separation by displacement, purifying, and the actual usage quantity of pyridine is reduced greatly.
Description of drawings
Fig. 1 is technological process of production figure of the present invention.
Embodiment
As shown in Figure 1,
At first in retort with diene through the 120kg of oximation reaction ketoxime thing, oven dry moisture content≤0.5% joins rising temperature for dissolving in the 780kg benzene after edible salt dehydration, treat that the ketoxime thing is cooled to 38 ℃ ± 2 ℃ after molten entirely, add the 57.6kg pyridine again, the content of pyridine 〉=98%, moisture content＜0.2%;
Secondly lead to 5～8 ℃ of salt water for cooling in the chuck in retort, the mixing solutions of Dropwise 5 8kg phosphorus oxychloride and 98kg benzene, the content of phosphorus oxychloride 〉=98% drips temperature control in 15 ℃, drips behind the mixing solutions of phosphorus oxychloride and benzene insulation reaction in 16 ℃-18 ℃;
Next reacts the solution after 3 hours again, add 227kg hydrogenchloride diluted acid water fast, the content of hydrogenchloride is 10%, is warming up to 58 ℃ ± 1 ℃ then, and insulation reaction is after 2 hours in this temperature range, the waste water of solution bottom is told, telling solution behind the waste water to storage tank, wash three times to neutral, PH=7-8, add water after the solution of washing three times filtered and dash with steam and heat up in a steamer, and centrifugal dehydration treatment;
Suction content 〉=92% ethanol 1000kg in retort more at last, drop into centrifugal good material, be warming up to 60 ℃ ± 2 ℃ with steam, stirred 30 minutes, the 80kg alkali Shui sodium hydroxide that suction prepares in advance, the content of sodium hydroxide is 30-40%, alkali Shui temperature is between 80-90 ℃, and the salt of wormwood that adds 30kg again stirs, and the content of salt of wormwood is 99%-103%, salt of wormwood is all dissolved, reflux after 2 hours, above-mentioned blended solution concentration to the 400L, was discharged in the stainless bucket spontaneous nucleation 8 hours, put to the freezing tank freezing 12 hours, the recentrifuge oven dry is dehydroepiandros-sterone again.
The recovery technology of pyridine:
At first detach waste acid water 300L after the heart dehydration to retort, add 50kg solid caustic soda sodium hydroxide, sodium hydrate content 〉=95% is neutralized to PH=8, divides lixiviating water water layer, and pyridine solution is collected in distillation, carries out first time and dewaters;
Secondly in pyridine solution, divide secondary to add solid caustic soda sodium hydroxide, each add-on is 5～8kg, divides the lixiviating water layer in the rest solution standing groove, adds the benzene of 1.5～2 times of pyridine solutions once more in pyridine solution, steam benzene and dewater for the second time, and from water trap, moisture is walked;
At last the water of pyridine solution is taken off most back and go up rectifying tower rectifying, the temperature of rectifying is got 110～118 ℃, and rectification and purification goes out to meet the pyridine that raw materials quality requires in this scope.
Wherein starting material are:
Ketoxime thing: chemical name: acetic acid gestation diene alcohol ketone oxime, content 〉=98%, fusing point: 199 ℃-200 ℃, moisture content≤0.5%; Pyridine: content 〉=98%, moisture content＜0.2%;
Salt solution is the NaCl aqueous solution of 50-68%;
Phosphorus oxychloride: molecular formula: POCl3, content 〉=98%;
Diluted acid water is 10% hydrochloride aqueous solution;
Solid caustic soda sodium hydroxide: industrial solid piece alkali, content 〉=95%.
Claims (2)
1. method of producing dehydroepiandros-sterone is characterized in that:
Production stage comprises:
At first in retort with diene through the 120kg of oximation reaction ketoxime thing, oven dry moisture content≤0.5% joins rising temperature for dissolving in the 780kg benzene after edible salt dehydration, treat that the ketoxime thing is cooled to 38 ℃ ± 2 ℃ after molten entirely, add the 57.6kg pyridine again, the content of pyridine 〉=98%, moisture content＜0.2%;
Secondly lead to 5～8 ℃ of salt water for cooling in the chuck in retort, the mixing solutions of Dropwise 5 8kg phosphorus oxychloride and 98kg benzene, the content of phosphorus oxychloride 〉=98% drips temperature control in 15 ℃, drips behind the mixing solutions of phosphorus oxychloride and benzene insulation reaction in 16 ℃-18 ℃;
Next reacts the solution after 3 hours again, add 227kg hydrogenchloride diluted acid water fast, the content of hydrogenchloride is 10%, is warming up to 58 ℃ ± 1 ℃ then, and insulation reaction is after 2 hours in this temperature range, the waste water of solution bottom is told, telling solution behind the waste water to storage tank, wash three times to neutral, PH=7-8, the solution of washing three times is filtered back dashing with steam heat up in a steamer, and centrifugal dehydration treatment;
Suction content 〉=92% ethanol 1000kg in retort more at last, drop into centrifugal good material, be warming up to 60 ℃ ± 2 ℃ with steam, stirred 30 minutes, the 80kg alkali Shui sodium hydroxide that suction prepares in advance, the content of sodium hydroxide is 30-40%, alkali Shui temperature is between 80-90 ℃, and the salt of wormwood that adds 30kg again stirs, and the content of salt of wormwood is 99%-103%, salt of wormwood is all dissolved, reflux after 2 hours, above-mentioned blended solution concentration to the 400L, was discharged in the stainless bucket spontaneous nucleation 8 hours, put to the freezing tank freezing 12 hours, the recentrifuge oven dry is dehydroepiandros-sterone again.
2. the recovery method of pyridine is characterized in that:
Production stage comprises:
At first detach waste acid water 300L after the heart dehydration to retort, add 50kg solid caustic soda sodium hydroxide, sodium hydrate content 〉=95% is neutralized to PH=8, divides the lixiviating water layer, and the solution that contains pyridine is collected in distillation, carries out first time and dewaters;
Secondly in containing the solution of pyridine, divide secondary to add solid caustic soda sodium hydroxide, each add-on is 5～8kg, divides the lixiviating water layer in the rest solution standing groove, adds the benzene of 1.5～2 times of pyridine solutions once more in containing the solution of pyridine, steam benzene and dewater for the second time, and from water trap, moisture is walked;
At last the water that contains pyridine solution is taken off most back and go up rectifying tower rectifying, the temperature of rectifying is got 110～118 ℃, and rectification and purification goes out to meet the pyridine that raw materials quality requires in this scope.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910273027A CN101717422A (en) | 2009-11-29 | 2009-11-29 | Method for producing dehydroepiandros-sterone |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910273027A CN101717422A (en) | 2009-11-29 | 2009-11-29 | Method for producing dehydroepiandros-sterone |
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| Publication Number | Publication Date |
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| CN101717422A true CN101717422A (en) | 2010-06-02 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212099A (en) * | 2011-04-02 | 2011-10-12 | 邵阳市科瑞化学品有限公司 | Synthesis method for dehydroepiandrosterone |
| CN102603839A (en) * | 2012-01-13 | 2012-07-25 | 宜城市共同药业有限公司 | Preparation method of dehydroepiandrosterone |
| US9879045B2 (en) | 2013-05-21 | 2018-01-30 | Dr. Reddy's Laboratories Limited | Processes for the preparation of dehydroepiandrosterone and its intermediates |
-
2009
- 2009-11-29 CN CN200910273027A patent/CN101717422A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212099A (en) * | 2011-04-02 | 2011-10-12 | 邵阳市科瑞化学品有限公司 | Synthesis method for dehydroepiandrosterone |
| CN102603839A (en) * | 2012-01-13 | 2012-07-25 | 宜城市共同药业有限公司 | Preparation method of dehydroepiandrosterone |
| US9879045B2 (en) | 2013-05-21 | 2018-01-30 | Dr. Reddy's Laboratories Limited | Processes for the preparation of dehydroepiandrosterone and its intermediates |
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Open date: 20100602 |