CN103709103A - Recycling process of aminoantipyrine mother liquor - Google Patents
Recycling process of aminoantipyrine mother liquor Download PDFInfo
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- CN103709103A CN103709103A CN201310681631.XA CN201310681631A CN103709103A CN 103709103 A CN103709103 A CN 103709103A CN 201310681631 A CN201310681631 A CN 201310681631A CN 103709103 A CN103709103 A CN 103709103A
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- aminoantipyrene
- mother liquor
- oil
- aminoantipyrine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
- C07D231/46—Oxygen atom in position 3 or 5 and nitrogen atom in position 4
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Abstract
The invention relates to a recycling process of aminoantipyrine mother liquor. The recycling process comprises the following steps: mixing the aminoantipyrine mother liquor with ammonium sulfate saturated liquor, stewing and separating out upper-layer aminoantipyrine salting-out oil; adding water into the aminoantipyrine salting-out oil, stirring, and dropwise adding concentrated sulfuric acid to regulate the pH of the liquor; adding chloroform for chlorine extraction, stewing and layering, and preserving a supernatant; heating the supernatant, adding active carbon, continuously heating and discoloring, filtering and getting a filtrate; cooling the filtrate, ventilating liquid ammonia to regulate the pH of the liquor, heating up, and adding the ammonium sulfate saturated liquor to regulate the liquor density, and stewing and layering to obtain aminoantipyrine oil; adding water into the aminoantipyrine oil, uniformly stirring, adding the mixture into tap water, cooling and centrifuging to obtain solid aminoantipyrine crystal and recycling the aminoantipyrine mother liquor. The recycling process disclosed by the invention is simple, and mother liquor containing the aminoantipyrine can be directly utilized after being recycled, so that the yield is improved, the cost is reduced and environment friendliness is achieved; besides, materials are saved, and the discharge amount of wastewater is lowered.
Description
Technical field
The invention belongs to field of medicine and chemical technology, particularly a kind of utilization process of aminoantipyrene mother liquor.
Background technology
During pyramidon hydrogenation, required aminoantipyrene crystallization is by aminoantipyrene oil, to add water to refine by decrease temperature crystalline, hydrogenation is that aminoantipyrene crystallization generates pyramidon with hydrogen, formaldehyde direct reaction after water-soluble under the effect of catalyzer, and the quality of aminoantipyrene crystallization is very large on the speed of hydrogenation, degree impact.The mother liquor of manufacturing aminoantipyrene crystallization generation all cannot be applied to rear operation and produce.The content of aminoantipyrene crystalline mother solution recovery article is generally between 60-67%, being continued the crystalline content that decrease temperature crystalline obtains is only 80%, and with aminoantipyrene crystallization required in normal production, content is greater than 94% quality and differs larger, cannot apply and produce, can only be as three waste discharge.
Summary of the invention
The utilization process that the object of this invention is to provide a kind of aminoantipyrene mother liquor, technique is simple, can be by directly utilization of recovery containing the mother liquor of aminoantipyrene, yield improves, and reduces cost, and protection of the environment, saves material, and reduces the quantity discharged of waste water.
The utilization process of aminoantipyrene mother liquor of the present invention, concrete technology is as follows:
(1) by aminoantipyrene mother liquor and ammonium sulfate saturated solution mix and blend 15-20 minute, the more standing upper strata aminoantipyrene oil of saltouing that separates;
(2) in aminoantipyrene is saltoutd oil, add water to stir, drip vitriol oil regulator solution pH and obtain mixed solution to acidity;
(3) in mixed solution, add chloroform, control temperature at 50-55 ℃, chlorine is carried 15-25min, and stratification retains upper strata liquid;
(4) upper strata liquid step (3) being obtained is heated to 60-80 ℃, adds after gac, continues to be warming up to 50-90 ℃ and decolours, and after 35-45min, filters, and gets filtrate;
(5) filtrate is cooled to below 60-80 ℃, passes into liquefied ammonia regulator solution pH to neutral, be warming up to 85-90 ℃, add ammonium sulfate saturated solution regulator solution density, pour in separating funnel, stratification obtains aminoantipyrene oil;
(6) in aminoantipyrene oil, add water, after stirring, put into after tap water is cooled to 35 ℃ and add ice block cooling to 10-25 ℃, centrifugal, obtain the crystallization of solid aminoantipyrene, aminoantipyrene mother liquor is back to use step (1).
The aminoantipyrene mother liquor of described step (1) and the volume ratio of ammonium sulfate saturated solution are 0.2-0.6:1, and preferred volume ratio is 0.3:1.
In step (1), mixing temperature is 40-70 ℃.
The saltout volume ratio of oil, water and the vitriol oil of described aminoantipyrene is 1:1-2.5:0.03-0.28.
Described step (2) is mixed rear pH value of solution=1.0-6.0.
The saltout ratio of oil, water and vitriol oil three cumulative volume of the volume of chloroform and aminoantipyrene is 1:0.6-1.4.
The saltout ratio of oil, water and vitriol oil three cumulative volume of the quality of gac and aminoantipyrene is 0.005-0.013:1.
After described step (5) neutralization, PH is 7.0-7.7.
In step (5), adding Auto-regulating System of Density of Heavy Medium after ammonium sulfate saturated solution is 1.15-1.30g/cm
3, preferred density is 1.235g/cm
3.
The present invention is by reclaiming the material in mother liquor to the processing of aminoantipyrene mother liquor, make material reach the requirement of aminoantipyrene crystallization salable product simultaneously, can reach the requirement of hydrogenation, resulting crystalline quality can be directly used in the hydro-reduction reaction of rear operation.
The present invention, by using the organic impurity in chloroform extraction aminoantipyrene mother liquor, uses activated carbon filtration decolouring to remove the inorganic impurity in aminoantipyrene mother liquor, and the impurity in aminoantipyrene mother liquor is effectively removed.
The present invention compared with prior art, has following beneficial effect:
Technique of the present invention is simple, containing aminoantipyrene mother liquor, can utilize by reclaiming directly, and 600 tons of year recovered material, yield improves, and reduces cost, protection of the environment; Technique of the present invention, recyclable the recycling of mother liquor of original direct discharge, 2160 tons of year minimizing quantity dischargeds.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
The utilization process of aminoantipyrene mother liquor is as follows:
(1) get aminoantipyrene mother liquor 240ml and ammonium sulfate saturated solution 1200ml, stir after 15 minutes standing 15 minutes, upper strata aminoantipyrene salt separating oil is gone out to metering volume 107ml;
(2) gained aminoantipyrene is saltoutd oil and the water of 263ml, put into reactor and stir, and slowly drips the 30ml vitriol oil, and temperature is raised to 50 ℃, survey pH=1.0;
(3) add 525ml chloroform, control temperature at 52 ± 2 ℃, chlorine is carried 20min, pour in 1000ml separating funnel, and stratification, minute sub-cloud chloroform, gets upper strata liquid;
(4) upper strata liquid is heated to 60 ℃, adds 5g gac, be warming up to 80 ℃ of decolourings, timing 40min, filters;
(5) get filtrate, be cooled to 60 ℃, logical liquefied ammonia is neutralized to pH=7.0, is warming up to 90 ℃, adds ammonium sulfate saturated solution and adjusts density to 1.273g/cm
3, pour in separating funnel, stratification, minute oil, obtains 149.6ml aminoantipyrene oil;
(6) in aminoantipyrene oil, add 12ml water, stir, put into tap water decrease temperature crystalline to 35 ℃, add afterwards ice block cooling to 15 ℃, centrifugal, obtain aminoantipyrene crystallization and aminoantipyrene mother liquor, aminoantipyrene mother liquor is back to use step (1).
Sampling analysis is surveyed aminoantipyrene content 94.77%, colorimetric 8ml.
Embodiment 2
The utilization process of aminoantipyrene mother liquor is as follows:
(1) get aminoantipyrene mother liquor 720ml and ammonium sulfate liquor 1200ml, stir after 15 minutes standing 20 minutes, upper strata aminoantipyrene salt separating oil is gone out to metering volume 356ml;
(2) gained aminoantipyrene is saltoutd oil and the water of 463ml, put into reactor and stir, and slowly drips the vitriol oil of 60ml, and temperature is raised to 50 ℃, survey pH=1.2;
(3) add 825ml chloroform, control temperature and carry 15min at 52 ± 2 ℃ of chlorine, pour in 1000ml separating funnel, stratification, minute sub-cloud chloroform, gets upper strata liquid;
(4) upper strata liquid is heated to 60 ℃, adds 5g gac, be warming up to 80 ℃ of decolourings, timing 40min, filters;
(5) get filtrate, be cooled to 60 ℃, logical liquefied ammonia is neutralized to pH=7.0, is warming up to 87 ℃, adds ammonium sulfate saturated solution and adjusts density to 1.182g/cm
3, pour in separating funnel, stratification, minute oil, obtains 149.6ml aminoantipyrene oil;
(6) in aminoantipyrene oil, add 12ml water, stir, put into tap water decrease temperature crystalline to 35 ℃, add afterwards ice block cooling to 15 ℃, centrifugal, obtain aminoantipyrene crystallization and aminoantipyrene mother liquor, aminoantipyrene mother liquor is back to use step (1).
Sampling analysis surveys that aminoantipyrene content is 94.86%, colorimetric 8ml.
Embodiment 3
The utilization process of aminoantipyrene mother liquor is as follows:
(1) get aminoantipyrene mother liquor 400ml and ammonium sulfate liquor 1200ml, stir 18 minutes, stop stirring standing 15 minutes, upper strata aminoantipyrene salt separating oil is gone out to metering volume 189ml;
(2) gained aminoantipyrene is saltoutd oil and the water of 463ml, put into reactor, slowly drips the vitriol oil of 10ml, and temperature is raised to 50 ℃, survey PH=6.0;
(3) add 525ml chloroform, control temperature and carry 20min at 50-55 ℃ of chlorine, pour in 1000ml separating funnel stratification into.Divide sub-cloud chloroform, get upper strata liquid;
(4) upper strata liquid is heated to 80 ℃, adds 5g gac, be warming up to 50 ℃ of decolourings, timing 40min, filters;
(5) get filtrate, be cooled to 60 ℃, logical liquefied ammonia is neutralized to pH=7.0, is warming up to 90 ℃, adds ammonium sulfate saturated solution and adjusts density to 1.273g/cm
3, pour in separating funnel, stratification, minute oil, obtains 149.6ml aminoantipyrene oil;
(6) in aminoantipyrene oil, add 12ml water, stir, put into tap water decrease temperature crystalline, put into tap water decrease temperature crystalline to 35 ℃, add afterwards ice block cooling to 15 ℃, centrifugal, obtain aminoantipyrene crystallization and aminoantipyrene mother liquor, aminoantipyrene mother liquor is back to use step (1).
Sampling analysis surveys that aminoantipyrene content is 95.13%, colorimetric 8ml.
Embodiment 4
The utilization process of aminoantipyrene mother liquor is as follows:
(1) get aminoantipyrene mother liquor 400ml and ammonium sulfate liquor 1200ml, stir after 20 minutes standing 12 minutes, upper strata aminoantipyrene salt separating oil is gone out to metering volume 189ml;
(2) gained aminoantipyrene is saltoutd oil and the water of 463ml, put into reactor, slowly drips the vitriol oil of 25ml, and temperature is raised to 50 ℃, survey pH=2.0;
(3) add 525ml chloroform, temperature is controlled at 50-55 ℃, and chlorine is carried 25min, pour in 1000ml separating funnel, and stratification, minute sub-cloud chloroform, gets upper strata liquid;
(4) upper strata liquid is heated to 60 ℃, adds 5g gac, be warming up to 60 ℃ of decolourings, timing 40min, filters;
(5) get filtrate, be cooled to 60 ℃, logical liquefied ammonia is neutralized to pH=7.6, is warming up to 85 ℃, adds ammonium sulfate saturated solution and adjusts density to 1.203g/cm
3, pour in separating funnel, stratification, minute oil, obtains 149.6ml aminoantipyrene oil;
(6) in aminoantipyrene oil, add 12ml water, stir, put into tap water decrease temperature crystalline to 35 ℃, add afterwards ice block cooling to 15 ℃, centrifugal, obtain aminoantipyrene crystallization and aminoantipyrene mother liquor, aminoantipyrene mother liquor is back to use step (1).
Sampling analysis is surveyed aminoantipyrene content 94.79%, colorimetric 8ml.
Claims (9)
1. a utilization process for aminoantipyrene mother liquor, is characterized in that, processing step is as follows:
(1) by aminoantipyrene mother liquor and ammonium sulfate saturated solution mix and blend 15-20 minute, the more standing upper strata aminoantipyrene oil of saltouing that separates;
(2) in aminoantipyrene is saltoutd oil, add water to stir, drip vitriol oil regulator solution pH and obtain mixed solution to acidity;
(3) in mixed solution, add chloroform, control temperature at 50-55 ℃, chlorine is carried 15-25min, and stratification retains upper strata liquid;
(4) upper strata liquid step (3) being obtained is heated to 60-80 ℃, adds after gac, continues to be warming up to 50-90 ℃ and decolours, and after 35-45min, filters, and gets filtrate;
(5) filtrate is cooled to below 60-80 ℃, passes into liquefied ammonia regulator solution pH to neutral, be warming up to 85-90 ℃, add ammonium sulfate saturated solution regulator solution density, pour in separating funnel, stratification obtains aminoantipyrene oil;
(6) in aminoantipyrene oil, add water, after stirring, put into after tap water is cooled to 35 ℃ and add ice block cooling to 10-25 ℃, centrifugal, obtain the crystallization of solid aminoantipyrene, aminoantipyrene mother liquor is back to use step (1).
2. the utilization process of aminoantipyrene mother liquor according to claim 1, is characterized in that, the aminoantipyrene mother liquor of described step (1) and the volume ratio of ammonium sulfate saturated solution are 0.2-0.6:1.
3. the utilization process of aminoantipyrene mother liquor according to claim 1, is characterized in that, in step (1), mixing temperature is 40-70 ℃.
4. the utilization process of aminoantipyrene mother liquor according to claim 1, is characterized in that, the saltout volume ratio of oil, water and the vitriol oil of described aminoantipyrene is 1:1-2.5:0.03-0.28.
5. the utilization process of aminoantipyrene mother liquor according to claim 1, is characterized in that, described step (2) is mixed rear pH value of solution=1.0-6.0.
6. the utilization process of aminoantipyrene mother liquor according to claim 1, is characterized in that, the saltout ratio of oil, water and vitriol oil three cumulative volume of the volume of chloroform and aminoantipyrene is 1:0.6-1.4.
7. the utilization process of aminoantipyrene mother liquor according to claim 1, is characterized in that, the saltout ratio of oil, water and vitriol oil three cumulative volume of the quality of gac and aminoantipyrene is 0.005-0.013:1.
8. the utilization process of aminoantipyrene mother liquor according to claim 1, is characterized in that, after described step (5) neutralization, PH is 7.0-7.7.
9. the utilization process of aminoantipyrene mother liquor according to claim 1, is characterized in that, in step (5), adding Auto-regulating System of Density of Heavy Medium after ammonium sulfate saturated solution is 1.15-1.30g/cm
3.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4334076A (en) * | 1976-08-03 | 1982-06-08 | Hoechst Aktiengesellschaft | Process for the preparation of sulfuric acid semiester ethylsulfonyl compounds of aminophenols, aminobenzanilides or phenylpyrazolones by esterification with sulfuric acid and/or sulfur trioxide in a kneader |
| CN101357903A (en) * | 2008-09-05 | 2009-02-04 | 山东新华制药股份有限公司 | Novel technique for preparing 4-formyl amino antipyrine |
| CN101891683A (en) * | 2010-07-22 | 2010-11-24 | 河北冀衡（集团）药业有限公司 | Aminopyrine production method |
| CN102603639A (en) * | 2012-01-18 | 2012-07-25 | 河北冀衡（集团）药业有限公司 | Production method of 4-amino-antipyrine oil |
-
2013
- 2013-12-13 CN CN201310681631.XA patent/CN103709103B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4334076A (en) * | 1976-08-03 | 1982-06-08 | Hoechst Aktiengesellschaft | Process for the preparation of sulfuric acid semiester ethylsulfonyl compounds of aminophenols, aminobenzanilides or phenylpyrazolones by esterification with sulfuric acid and/or sulfur trioxide in a kneader |
| CN101357903A (en) * | 2008-09-05 | 2009-02-04 | 山东新华制药股份有限公司 | Novel technique for preparing 4-formyl amino antipyrine |
| CN101891683A (en) * | 2010-07-22 | 2010-11-24 | 河北冀衡（集团）药业有限公司 | Aminopyrine production method |
| CN102603639A (en) * | 2012-01-18 | 2012-07-25 | 河北冀衡（集团）药业有限公司 | Production method of 4-amino-antipyrine oil |
Non-Patent Citations (1)
| Title |
|---|
| 杨成顺，等: "4-氨基安替比林中杂质分离初步研究", 《山东化工》, vol. 39, 31 December 2010 (2010-12-31), pages 12 - 14 * |
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Effective date of registration: 20220128 Address after: 255086 No. 1, Lutai Avenue, high tech Zone, Zibo City, Shandong Province Patentee after: Shandong Xinhua Pharmaceutical Chemical Design Co.,Ltd. Address before: 255086 Chemical Zone of Technology Industry Development Zone, Zibo High-tech Zone, Shandong Province Patentee before: SHANDONG XINHUA PHARMACEUTICAL Co.,Ltd. |
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