CN103709103B - The utilization process of aminoantipyrene mother liquor - Google Patents
The utilization process of aminoantipyrene mother liquor Download PDFInfo
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- CN103709103B CN103709103B CN201310681631.XA CN201310681631A CN103709103B CN 103709103 B CN103709103 B CN 103709103B CN 201310681631 A CN201310681631 A CN 201310681631A CN 103709103 B CN103709103 B CN 103709103B
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- aminoantipyrene
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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
Abstract
The present invention relates to a kind of utilization process of aminoantipyrene mother liquor, step is: by aminoantipyrene mother liquor and the mixing of ammonium sulfate saturated solution, leaves standstill to separate upper strata aminoantipyrene and to saltout oil; In aminoantipyrene saltouts oil, add water stir, drip vitriol oil regulator solution pH; Add chloroform chlorine to carry, stratification, retain upper liquid; Upper liquid is heated, adds gac, continue the decolouring that heats up, filter, get filtrate; Filtrate lowered the temperature, pass into liquefied ammonia regulator solution pH, heat up, add ammonium sulfate saturated solution regulator solution density, stratification obtains aminoantipyrene oil; Add water in aminoantipyrene oil, put into tap water after stirring and lower the temperature, centrifugal, obtain the crystallization of solid aminoantipyrene, the reuse of aminoantipyrene mother liquor.Present invention process is simple, and containing the mother liquor of aminoantipyrene by reclaiming direct utilization, yield improves, and reduces cost, protection of the environment; Save material, reduce the quantity discharged of waste water.
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
Aminoantipyrene crystallization required during pyramidon hydrogenation be by aminoantipyrene oil add water by decrease temperature crystalline refine, hydrogenation be aminoantipyrene crystallization water-soluble after under the effect of catalyzer, generate pyramidon with hydrogen, formaldehyde direct reaction, the quality of aminoantipyrene crystallization is very large on the speed of hydrogenation, degree impact.The mother liquor 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%, continued the crystalline content that decrease temperature crystalline obtains and be only 80%, with normally produces in needed for aminoantipyrene crystallization, it is larger that content is greater than 94% mass difference, cannot apply and produce, can only as three waste discharge.
Summary of the invention
The object of this invention is to provide a kind of utilization process of aminoantipyrene mother liquor, technique is simple, and containing the mother liquor of aminoantipyrene by reclaiming direct utilization, yield improves, and reduce cost, 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, then leave standstill and separate upper strata aminoantipyrene and to saltout oil;
(2) in aminoantipyrene saltouts oil, add water stir, drip vitriol oil regulator solution pH and obtain mixed solution to acidity;
(3) add chloroform in mixed solution, control temperature is at 50-55 DEG C, and chlorine carries 15-25min, stratification, retains upper liquid;
(4) upper liquid that step (3) obtains is heated to 60-80 DEG C, after adding gac, continues to be warming up to 50-90 DEG C and decolour, filter after 35-45min, get filtrate;
(5) filtrate is cooled to less than 60-80 DEG C, pass into liquefied ammonia regulator solution pH to neutral, be warming up to 85-90 DEG C, add ammonium sulfate saturated solution regulator solution density, pour in separating funnel, stratification obtains aminoantipyrene oil;
(6) add water in aminoantipyrene oil, put into after tap water is cooled to 35 DEG C and add ice block cooling to 10-25 DEG C after stirring, centrifugal, obtain the crystallization of solid aminoantipyrene, aminoantipyrene mother liquor is back to use step (1).
The described aminoantipyrene mother liquor of 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 DEG C.
The saltout volume ratio of oil, water and the vitriol oil of described aminoantipyrene is 1:1-2.5:0.03-0.28.
PH value of solution=1.0-6.0 after described step (2) mixing.
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.
After adding ammonium sulfate saturated solution in step (5), Auto-regulating System of Density of Heavy Medium 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 process of aminoantipyrene mother liquor, make material reach the requirement of aminoantipyrene crystallization salable product simultaneously, can reach the requirement of hydrogenation, the crystalline quality obtained 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 the inorganic impurity in activated carbon filtration decolouring removal aminoantipyrene mother liquor, is effectively removed by the impurity in aminoantipyrene mother liquor.
The present invention compared with prior art, has following beneficial effect:
Present invention process is simple, containing aminoantipyrene mother liquor by reclaiming direct utilization, year recovered material 600 tons, yield improves, and reduces cost, protection of the environment; Technique of the present invention, the mother liquor of original direct discharge is recyclable to be recycled, year emissions reduction amount 2160 tons.
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 and leave standstill 15 minutes, upper strata aminoantipyrene salt separating oil is gone out, metered volume 107ml;
(2) saltoutd by gained aminoantipyrene oil and the water of 263ml, put into reactor and stir, slowly drip the 30ml vitriol oil, temperature is raised to 50 DEG C, survey pH=1.0;
(3) add 525ml chloroform, control temperature is at 52 ± 2 DEG C, and chlorine carries 20min, pours in 1000ml separating funnel, stratification, and point sub-cloud chloroform, gets upper liquid;
(4) upper liquid is heated to 60 DEG C, adds 5g gac, be warming up to 80 DEG C of decolourings, timing 40min, filter;
(5) get filtrate, be cooled to 60 DEG C, logical liquefied ammonia is neutralized to pH=7.0, is warming up to 90 DEG C, adds ammonium sulfate saturated solution and adjusts density to 1.273g/cm
3, pour in separating funnel, stratification, point oil, obtain 149.6ml aminoantipyrene oil;
(6) in aminoantipyrene oil, add 12ml water, stir, put into tap water decrease temperature crystalline to 35 DEG C, add ice block cooling to 15 DEG C afterwards, centrifugal, obtain aminoantipyrene crystallization and aminoantipyrene mother liquor, aminoantipyrene mother liquor is back to use step (1).
Sampling analysis surveys 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 and leave standstill 20 minutes, upper strata aminoantipyrene salt separating oil is gone out, metered volume 356ml;
(2) saltoutd by gained aminoantipyrene oil and the water of 463ml, put into reactor and stir, slowly drip the vitriol oil of 60ml, temperature is raised to 50 DEG C, survey pH=1.2;
(3) add 825ml chloroform, control temperature carries 15min at 52 ± 2 DEG C of chlorine, pours in 1000ml separating funnel, stratification, and point sub-cloud chloroform, gets upper liquid;
(4) upper liquid is heated to 60 DEG C, adds 5g gac, be warming up to 80 DEG C of decolourings, timing 40min, filter;
(5) get filtrate, be cooled to 60 DEG C, logical liquefied ammonia is neutralized to pH=7.0, is warming up to 87 DEG C, adds ammonium sulfate saturated solution and adjusts density to 1.182g/cm
3, pour in separating funnel, stratification, point oil, obtain 149.6ml aminoantipyrene oil;
(6) in aminoantipyrene oil, add 12ml water, stir, put into tap water decrease temperature crystalline to 35 DEG C, add ice block cooling to 15 DEG C afterwards, 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, metered volume 189ml;
(2) saltoutd by gained aminoantipyrene oil and the water of 463ml, put into reactor, slowly drip the vitriol oil of 10ml, temperature is raised to 50 DEG C, survey PH=6.0;
(3) add 525ml chloroform, control temperature carries 20min at 50-55 DEG C of chlorine, pours in 1000ml separating funnel, stratification.Divide sub-cloud chloroform, get upper liquid;
(4) upper liquid is heated to 80 DEG C, adds 5g gac, be warming up to 50 DEG C of decolourings, timing 40min, filter;
(5) get filtrate, be cooled to 60 DEG C, logical liquefied ammonia is neutralized to pH=7.0, is warming up to 90 DEG C, adds ammonium sulfate saturated solution and adjusts density to 1.273g/cm
3, pour in separating funnel, stratification, point oil, obtain 149.6ml aminoantipyrene oil;
(6) in aminoantipyrene oil, 12ml water is added, stir, put into tap water decrease temperature crystalline, put into tap water decrease temperature crystalline to 35 DEG C, add ice block cooling to 15 DEG C afterwards, 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 and leave standstill 12 minutes, upper strata aminoantipyrene salt separating oil is gone out, metered volume 189ml;
(2) saltoutd by gained aminoantipyrene oil and the water of 463ml, put into reactor, slowly drip the vitriol oil of 25ml, temperature is raised to 50 DEG C, survey pH=2.0;
(3) add 525ml chloroform, temperature controls at 50-55 DEG C, and chlorine carries 25min, pours in 1000ml separating funnel, stratification, and point sub-cloud chloroform, gets upper liquid;
(4) upper liquid is heated to 60 DEG C, adds 5g gac, be warming up to 60 DEG C of decolourings, timing 40min, filter;
(5) get filtrate, be cooled to 60 DEG C, logical liquefied ammonia is neutralized to pH=7.6, is warming up to 85 DEG C, adds ammonium sulfate saturated solution and adjusts density to 1.203g/cm
3, pour in separating funnel, stratification, point oil, obtain 149.6ml aminoantipyrene oil;
(6) in aminoantipyrene oil, add 12ml water, stir, put into tap water decrease temperature crystalline to 35 DEG C, add ice block cooling to 15 DEG C afterwards, centrifugal, obtain aminoantipyrene crystallization and aminoantipyrene mother liquor, aminoantipyrene mother liquor is back to use step (1).
Sampling analysis surveys aminoantipyrene content 94.79%, colorimetric 8ml.
Claims (1)
1. a utilization process for aminoantipyrene mother liquor, is characterized in that, processing step 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, metered volume 189ml;
(2) saltoutd by gained aminoantipyrene oil and the water of 463ml, put into reactor, slowly drip the vitriol oil of 10ml, temperature is raised to 50 DEG C, survey pH=6.0;
(3) add 525ml chloroform, control temperature carries 20min at 50-55 DEG C of chlorine, pours in 1000ml separating funnel, stratification; Divide sub-cloud chloroform, get upper liquid;
(4) upper liquid is heated to 80 DEG C, adds 5g gac, be warming up to 50 DEG C of decolourings, timing 40min, filter;
(5) get filtrate, be cooled to 60 DEG C, logical liquefied ammonia is neutralized to pH=7.0, is warming up to 90 DEG C, adds ammonium sulfate saturated solution and adjusts density to 1.273g/cm
3, pour in separating funnel, stratification, point oil, obtain 149.6ml aminoantipyrene oil;
(6) in aminoantipyrene oil, add 12ml water, stir, put into tap water decrease temperature crystalline to 35 DEG C, add ice block cooling to 15 DEG C afterwards, 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.
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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》.2010,第39卷第12-14页. * |
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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. |