CN103232402B - A kind of method of Hydrolysis kinetics azophenlyene from 4-aminodiphenylamine waste material - Google Patents
A kind of method of Hydrolysis kinetics azophenlyene from 4-aminodiphenylamine waste material Download PDFInfo
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Abstract
The method of a kind of Hydrolysis kinetics azophenlyene from 4-aminodiphenylamine waste material of the present invention belongs to azophenlyene technical field of refinement; Technical problem to be solved can obtain highly purified azophenlyene crystal for providing one, and solvent for use is all recovery solvent, without the method for purification of waste liquor contamination; The technical scheme adopted is: 4-aminodiphenylamine waste material obtains refining azophenlyene through twice extraction, twice recrystallization, drying, solvent recuperation, fusion-crystallization, adopt the azophenlyene that present method is produced, purity Absorbable organic halogens is more than 99.8%, far away higher than pharmaceutical grade requirement, can meet the need of market completely, the present invention is widely used in Hydrolysis kinetics azophenlyene field from 4-aminodiphenylamine waste material.
Description
Technical field
The method of a kind of Hydrolysis kinetics azophenlyene from 4-aminodiphenylamine waste material of the present invention belongs to azophenlyene technical field of refinement.
Background technology
Produce in the process of 4-aminodiphenylamine at nitrobenzene method, aniline under the catalysis of the Tetramethylammonium hydroxide of alkalescence with oil of mirbane generation nucleophilic addition, the contraposition of nucleophilic reagent attack oil of mirbane, through reducing final generation main reaction product 4-aminodiphenylamine, the ortho position of attack oil of mirbane then generates the by product azophenlyene of this reaction.As can be seen from reaction mechanism we, azophenlyene is the by product that will inevitably produce in 4-aminodiphenylamine production process, therefore fully utilizes it, is the important topic of pendulum in face of RT manufacturing enterprise.
But, in the process for raw material production 4-aminodiphenylamine with oil of mirbane and aniline, the by product azophenlyene produced is difficult to effectively be separated by current production technique, waste material is mixed into a small amount of aniline, 4-ADPA, nitrogen benzide, direct discharge or burn not only contaminate environment, and cause resource significant wastage.The existing method extracting azophenlyene from RT waste material is as described in patent (CN200810099916.1), take the technological operation of dissolution extraction, solid-liquid separation, recrystallization, drying, distillation, rectifying, but the azophenlyene product purity obtained is lower, and adopt rectificating method to reclaim distillation residue aniline, 4-ADPA, nitrogen benzide etc., operational cycle is long, and cost recovery is high.
Summary of the invention
The present invention is in order to overcome the deficiencies in the prior art, and provide one can obtain highly purified azophenlyene crystal, solvent for use is all recovery solvent, without the method for purification of waste liquor contamination.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of method of Hydrolysis kinetics azophenlyene from 4-aminodiphenylamine waste material is carried out according to following steps:
The first step, single extraction
Added by 4-aminodiphenylamine waste material in reextraction mother liquor, the ratio of described 4-aminodiphenylamine waste material and reextraction mother liquor is 1:5-9(g:mL), temperature rising reflux 30-60min, then be cooled to 25 DEG C of centrifugations, obtain filter cake and single extraction mother liquor;
Second step, fusion-crystallization
Described single extraction mother liquor distills at 80 DEG C, collects 77-80 DEG C of cut and is recycled ethanol, after the raffinate after distillation is incubated 30min at 80 DEG C, pours fast filtering in the suction funnel and filter flask being preheating to 80 DEG C into and obtains thick azophenlyene and fusion-crystallization mother liquor;
3rd step, reextraction
Added by described filter cake in primary crystallization mother liquor, the ratio of described filter cake and primary crystallization mother liquor is 1:8-12(g:mL), temperature rising reflux 45-90min, suction filtration when being cooled to 25 DEG C, obtains reextraction filter cake and described reextraction mother liquor;
4th step, primary crystallization
Described reextraction filter cake is added in secondary crystal mother liquor, the ratio of described reextraction filter cake and secondary crystal mother liquor is 1:5-9(g:mL), temperature rising reflux 30-60min, heat filtering removes insoluble slag, filtrate, at room temperature after slow cooling 120-180min, obtains primary crystallization filter cake and described primary crystallization mother liquor through centrifugation;
5th step, secondary crystal
Described primary crystallization filter cake is added in described recovery ethanol, the ratio of described primary crystallization filter cake and described recovery ethanol is 1:7-10(g:mL), temperature rising reflux 30-60min, heat filtering removes insoluble slag, filtrate, at room temperature after slow cooling 120-180min, obtains refining azophenlyene and described secondary crystal mother liquor through centrifugation.
The described thick azophenlyene that second step obtains is mixed in described 4-aminodiphenylamine waste material and enters single extraction step together, further refines; Described fusion-crystallization mother liquor returns in 4-aminodiphenylamine production.
Carry out in described 5th step secondary crystal step leaving standstill the refining azophenlyene product that can obtain large crystalline form near ctystallizing point.
The present invention compared with prior art has following beneficial effect.
1, according to the process ration of separation and purification azophenlyene from RT waste material reported, this technique adopts twice solvent extraction, twice recrystallization process, and all solvents are all recovery solvent, has route science, simple to operate, can the advantages such as continuity is strong.
2, this technique only carries out a solvent distillation recycling step to single extraction mother liquor after single extraction, gained recycling design is used as the solvent of secondary crystal, the solvent of all the other single extractions, reextraction, primary crystallization is all the filtrated stock of next step, greatly reduce solvent recuperation cost, reduce energy consumption, decrease the consumption to solvent simultaneously.
3, product purity is high, and the commercialization pharmaceutical grade azophenlyene product purity the highest to purity requirement requires >=99.5%, and adopt the azophenlyene of this explained hereafter, purity Absorbable organic halogens, more than 99.8%, far away higher than pharmaceutical grade requirement, can be met the need of market completely.
4, product good crystalline and controlled, product is solvent recrystallization gained, there is crystalline form even, grain size is controlled, dispersity advantages of higher, and can according to customer demand, control crystal growing process, produce the product of different grain size, the pollution that feeds intake because dust causes can be avoided completely, facilitate suitability for industrialized production.When recrystallization, if do not stir near ctystallizing point, the larger product of crystalline form can be obtained; If stir near ctystallizing point, crystalline form comparatively miscellaneous goods can be obtained.The larger product purity of crystalline form generally can reach more than 99.8%; And crystalline form comparatively miscellaneous goods purity mostly between 99.7 ~ 99.8%.Consider downstream client in addition in use, the wetting property of the larger product of crystalline form, the accessibility fed intake may be better.
5, by gained raffinate after single extraction disposing mother liquor through fusion-crystallization, in solid-liquid separation gained filter cake, azophenlyene content can reach 89.61%, can refine as thick azophenlyene completely.And directly carry out rectifying, be then difficult to obtain the very high azophenlyene of purity because azophenlyene boiling point (360 DEG C) and fusing point (171 DEG C) all very high, rectifying difficulty is very large.The main following points of reason of fusion-crystallization: the different melting points 1) between material is very big, and azophenlyene fusing point is 171 DEG C; Nitrogen benzide is 71 DEG C; 4-aminodiphenylamine is 75 DEG C; Aniline is-6.2 DEG C, and therefore utilize storeroom fusing point difference that the mode of fusion-crystallization can be adopted to be separated, controlling raffinate is 80 DEG C, and except azophenlyene, all the other organism are all liquid, therefore can be separated; 2) fusion-crystallization employing when carrying out solvent recuperation, contained organic content except ethanol itself just less (its main component is still ethanol), is not too suitable for carrying out rectifying production; 3) raffinate obtained after carrying out solvent recuperation, wherein material component is very complicated, and organism kinds is a lot, and content is relatively all few, and rectifying difficulty is very big, so raffinate to be carried out fusion-crystallization, and does not carry out distillation operation.
Mother liquid obtained middle material consists of nitrogen benzide 38.83%, azophenlyene 21.42%, 4-aminodiphenylamine 2.62% simultaneously, can return RT production system, and can not increase system burden as raw material.
6, adopt this technique purification azophenlyene, solvent is recovery all, and without residue contamination, liquid residue can be used as raw material and returns RT production system and do not produce waste liquor contamination, and whole process is separating-purifying process, does not produce exhaust emission.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
A kind of method of Hydrolysis kinetics azophenlyene from 4-aminodiphenylamine waste material is carried out according to following steps:
The first step, single extraction
Added by 4-aminodiphenylamine waste material in reextraction mother liquor, the ratio of described 4-aminodiphenylamine waste material and reextraction mother liquor is 1:5(g:mL), temperature rising reflux 60min, then be cooled to 25 DEG C of centrifugations, obtain filter cake and single extraction mother liquor;
Second step, fusion-crystallization
Described single extraction mother liquor distills at 80 DEG C, collects 77-80 DEG C of cut and is recycled ethanol, after the raffinate after distillation is incubated 30min at 80 DEG C, pours fast filtering in the suction funnel and filter flask being preheating to 80 DEG C into and obtains thick azophenlyene and fusion-crystallization mother liquor;
3rd step, reextraction
Added by described filter cake in primary crystallization mother liquor, the ratio of described filter cake and primary crystallization mother liquor is 1:12(g:mL), temperature rising reflux 45min, suction filtration when being cooled to 25 DEG C, obtains reextraction filter cake and described reextraction mother liquor;
4th step, primary crystallization
Described reextraction filter cake is added in secondary crystal mother liquor, the ratio of described reextraction filter cake and secondary crystal mother liquor is 1:9(g:mL), temperature rising reflux 30min, heat filtering removes insoluble slag, filtrate, at room temperature after slow cooling 120min, obtains primary crystallization filter cake and described primary crystallization mother liquor through centrifugation;
5th step, secondary crystal
Described primary crystallization filter cake is added in described recovery ethanol, the ratio of described primary crystallization filter cake and described recovery ethanol is 1:7(g:mL), temperature rising reflux 30min, heat filtering removes insoluble slag, filtrate, at room temperature after slow cooling 180min, obtains refining azophenlyene and described secondary crystal mother liquor through centrifugation.
The described thick azophenlyene that second step obtains is mixed in described 4-aminodiphenylamine waste material and enters single extraction step together, further refines; Described fusion-crystallization mother liquor returns in 4-aminodiphenylamine production.
Embodiment 2
Solvent extraction process: join in 700mL reextraction mother liquor by 100gRT training department waste material, temperature rising reflux 1h, is then placed in cold water chilling and lowers the temperature about 1h, suction filtration when being chilled to 25 DEG C, fully be filtered dry, obtain weight in wet base and be about 70g single extraction filter cake, single extraction mother liquor is about 700mL.To once slightly go filter cake to join in 700mL primary crystallization mother liquor, temperature rising reflux 1h, then be placed in cold water chilling and to lower the temperature about 1h, suction filtration when being chilled to 25 DEG C, be fully filtered dry, obtain weight in wet base and be about 62g reextraction filter cake, reextraction mother liquor be about 700mL.
Recrystallization process: reextraction filter cake is joined in 800mL secondary crystal mother liquor, temperature rising reflux 30min, after leaving standstill 3min again, supernatant liquid is inclined and about 2/3 and enter in filter flask, pour lower floor's liquid in the suction funnel and filter flask being preheating to 80 DEG C fast filtering, mother liquid obtained in filter flask slow cooling to 25 DEG C, filter, obtain the primary crystallization filter cake that weight in wet base is about 60g, primary crystallization mother liquor is about 740mL.Gained primary crystallization filter cake is joined 800mL dehydrated alcohol or reclaim in ethanol, temperature rising reflux 15min, gained solution is left standstill visual the wanted crystallite size of about 2.4h(in room temperature, carry out swaying and obtain crystalline form comparatively miscellaneous goods) after precipitation solid, filter after being chilled to 25 DEG C, weight in wet base is about 50g and refines azophenlyene, secondary crystal mother liquor is about 800mL.
Product is dried: secondary crystal gained solid is placed in 80 DEG C of baking ovens and dries 6h, obtain refining dry azophenlyene and be about 43g.
Solvent recuperation: by 2000mL single extraction mother liquor at 80 DEG C, collect 77 ~ 80 DEG C of cuts, must reclaim ethanol 1820mL, the rate of recovery is about 91.0%, can be used for substituting dehydrated alcohol in secondary crystal.After gained raffinate is incubated 30min at 80 DEG C, pour fast filtering in the suction funnel and filter flask being preheating to 80 DEG C into.In gained filter cake, azophenlyene content is 89.61%, can refine together with thick azophenlyene, and mother liquid obtained middle nitrogen benzide content is 38.31%, azophenlyene content is 21.42%, can return condensation workshop section.
Embodiment 3
A kind of method of Hydrolysis kinetics azophenlyene from 4-aminodiphenylamine waste material is carried out according to following steps:
The first step, single extraction
Added by 4-aminodiphenylamine waste material in reextraction mother liquor, the ratio of described 4-aminodiphenylamine waste material and reextraction mother liquor is 1:9(g:mL), temperature rising reflux 60min, then be cooled to 25 DEG C of centrifugations, obtain filter cake and single extraction mother liquor;
Second step, fusion-crystallization
Described single extraction mother liquor distills at 80 DEG C, collects 77-80 DEG C of cut and is recycled ethanol, after the raffinate after distillation is incubated 30min at 80 DEG C, pours fast filtering in the suction funnel and filter flask being preheating to 80 DEG C into and obtains thick azophenlyene and fusion-crystallization mother liquor;
3rd step, reextraction
Added by described filter cake in primary crystallization mother liquor, the ratio of described filter cake and primary crystallization mother liquor is 1:8(g:mL), temperature rising reflux 45min, suction filtration when being cooled to 25 DEG C, obtains reextraction filter cake and described reextraction mother liquor;
4th step, primary crystallization
Described reextraction filter cake is added in secondary crystal mother liquor, the ratio of described reextraction filter cake and secondary crystal mother liquor is 1:9(g:mL), temperature rising reflux 30min, heat filtering removes insoluble slag, filtrate, at room temperature after slow cooling 180min, obtains primary crystallization filter cake and described primary crystallization mother liquor through centrifugation;
5th step, secondary crystal
Described primary crystallization filter cake is added in described recovery ethanol, the ratio of described primary crystallization filter cake and described recovery ethanol is 1:10(g:mL), temperature rising reflux 60min, heat filtering removes insoluble slag, filtrate, at room temperature after slow cooling 120min, obtains refining azophenlyene and described secondary crystal mother liquor through centrifugation.
The described thick azophenlyene that second step obtains is mixed in described 4-aminodiphenylamine waste material and enters single extraction step together, further refines; Described fusion-crystallization mother liquor returns in 4-aminodiphenylamine production.
Embodiment 4
A kind of method of Hydrolysis kinetics azophenlyene from 4-aminodiphenylamine waste material is carried out according to following steps:
The first step, single extraction
Added by 4-aminodiphenylamine waste material in reextraction mother liquor, the ratio of described 4-aminodiphenylamine waste material and reextraction mother liquor is 1:7(g:mL), temperature rising reflux 50min, then be cooled to 25 DEG C of centrifugations, obtain filter cake and single extraction mother liquor;
Second step, fusion-crystallization
Described single extraction mother liquor distills at 80 DEG C, collects 77-80 DEG C of cut and is recycled ethanol, after the raffinate after distillation is incubated 30min at 80 DEG C, pours fast filtering in the suction funnel and filter flask being preheating to 80 DEG C into and obtains thick azophenlyene and fusion-crystallization mother liquor;
3rd step, reextraction
Added by described filter cake in primary crystallization mother liquor, the ratio of described filter cake and primary crystallization mother liquor is 1:10(g:mL), temperature rising reflux 60min, suction filtration when being cooled to 25 DEG C, obtains reextraction filter cake and described reextraction mother liquor;
4th step, primary crystallization
Described reextraction filter cake is added in secondary crystal mother liquor, the ratio of described reextraction filter cake and secondary crystal mother liquor is 1:6(g:mL), temperature rising reflux 45min, heat filtering removes insoluble slag, filtrate, at room temperature after slow cooling 120-180min, obtains primary crystallization filter cake and described primary crystallization mother liquor through centrifugation;
5th step, secondary crystal
Described primary crystallization filter cake is added in described recovery ethanol, the ratio of described primary crystallization filter cake and described recovery ethanol is 1:8(g:mL), temperature rising reflux 50min, heat filtering removes insoluble slag, filtrate, at room temperature after slow cooling 150min, obtains refining azophenlyene and described secondary crystal mother liquor through centrifugation.
The described thick azophenlyene that second step obtains is mixed in described 4-aminodiphenylamine waste material and enters single extraction step together, further refines; Described fusion-crystallization mother liquor returns in 4-aminodiphenylamine production.
The present invention can summarize with other the specific form without prejudice to spirit of the present invention or principal character.Therefore, no matter from that, above-mentioned embodiment of the present invention all can only be thought explanation of the present invention and can not limit invention, claims indicate scope of the present invention, and scope of the present invention is not pointed out in above-mentioned explanation, therefore, any change in the implication suitable with claims of the present invention and scope, all should think to be included in the scope of claims.
Claims (3)
1. the method for Hydrolysis kinetics azophenlyene from 4-aminodiphenylamine waste material, is characterized in that carrying out according to following steps:
The first step, single extraction
Added by 4-aminodiphenylamine waste material in reextraction mother liquor, the ratio of described 4-aminodiphenylamine waste material and reextraction mother liquor is 1:5-9 by mass volume ratio g:mL, temperature rising reflux 30-60min, then is cooled to 25 DEG C of centrifugations, obtains filter cake and single extraction mother liquor;
Second step, fusion-crystallization
Described single extraction mother liquor distills at 80 DEG C, collects 77-80 DEG C of cut and is recycled ethanol, after the raffinate after distillation is incubated 30min at 80 DEG C, pours fast filtering in the suction funnel and filter flask being preheating to 80 DEG C into and obtains thick azophenlyene and fusion-crystallization mother liquor;
3rd step, reextraction
Added by described filter cake in primary crystallization mother liquor, the ratio of described filter cake and primary crystallization mother liquor is 1:8-12 by mass volume ratio g:mL, temperature rising reflux 45-90min, and suction filtration when being cooled to 25 DEG C, obtains reextraction filter cake and described reextraction mother liquor;
4th step, primary crystallization
Described reextraction filter cake is added in secondary crystal mother liquor, the ratio of described reextraction filter cake and secondary crystal mother liquor is 1:5-9 by mass volume ratio g:mL, temperature rising reflux 30-60min, heat filtering removes insoluble slag, filtrate, at room temperature after slow cooling 120-180min, obtains primary crystallization filter cake and described primary crystallization mother liquor through centrifugation;
5th step, secondary crystal
Described primary crystallization filter cake is added in described recovery ethanol, the ratio of described primary crystallization filter cake and described recovery ethanol is 1:7-10 by mass volume ratio g:mL, temperature rising reflux 30-60min, heat filtering removes insoluble slag, filtrate, at room temperature after slow cooling 120-180min, obtains refining azophenlyene and described secondary crystal mother liquor through centrifugation.
2. the method for a kind of Hydrolysis kinetics azophenlyene from 4-aminodiphenylamine waste material according to claim 1, is characterized in that described thick azophenlyene that second step obtains is mixed in described 4-aminodiphenylamine waste material and enters single extraction step together, further refine; Described fusion-crystallization mother liquor returns in 4-aminodiphenylamine production.
3. the method for a kind of Hydrolysis kinetics azophenlyene from 4-aminodiphenylamine waste material according to claim 1, is characterized in that carrying out in described 5th step secondary crystal step leaving standstill the refining azophenlyene product that can obtain large crystalline form near ctystallizing point.
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| CN106316969A (en) * | 2015-06-19 | 2017-01-11 | 中国石油化工股份有限公司 | Separation method of RT base production wastes |
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| KR100621310B1 (en) * | 2005-05-16 | 2006-09-06 | 금호석유화학 주식회사 | Method for preparing 4-aminodiphenylamine |
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