CN1629131A - Process for comprehensive utilization of waste sulfuric acid from 3,3'-dichloro benzidine hydrochloride - Google Patents
Process for comprehensive utilization of waste sulfuric acid from 3,3'-dichloro benzidine hydrochloride Download PDFInfo
- Publication number
- CN1629131A CN1629131A CN 200410050361 CN200410050361A CN1629131A CN 1629131 A CN1629131 A CN 1629131A CN 200410050361 CN200410050361 CN 200410050361 CN 200410050361 A CN200410050361 A CN 200410050361A CN 1629131 A CN1629131 A CN 1629131A
- Authority
- CN
- China
- Prior art keywords
- acid
- toluene
- dichlorobenzidine
- filter
- hydrochloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000002699 waste material Substances 0.000 title claims abstract description 14
- HXFNXEIKMAEASE-UHFFFAOYSA-N 4-(4-amino-3-chlorophenyl)-2-chloroaniline;hydrochloride Chemical compound Cl.C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HXFNXEIKMAEASE-UHFFFAOYSA-N 0.000 title claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000002253 acid Substances 0.000 claims abstract description 34
- 238000000605 extraction Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 40
- 239000000047 product Substances 0.000 claims description 17
- 230000017105 transposition Effects 0.000 claims description 17
- 239000012452 mother liquor Substances 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 14
- 230000008025 crystallization Effects 0.000 claims description 14
- 239000012065 filter cake Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- IWKMQNKKYZERHI-UHFFFAOYSA-N 1,2-bis(2-chlorophenyl)hydrazine Chemical compound ClC1=CC=CC=C1NNC1=CC=CC=C1Cl IWKMQNKKYZERHI-UHFFFAOYSA-N 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000006227 byproduct Substances 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical compound C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 claims description 8
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 239000000284 extract Substances 0.000 claims description 3
- LLZQOYGUEJLTSB-UHFFFAOYSA-N formaldehyde hydrazine hydrate Chemical compound O.NN.C=O LLZQOYGUEJLTSB-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000003672 processing method Methods 0.000 claims description 2
- 230000005945 translocation Effects 0.000 claims description 2
- OMKBWNZUEYDVLC-UHFFFAOYSA-N CC1=CC=CC=C1.ClN(NC1=CC=CC=C1)C1=C(C=CC=C1)Cl Chemical compound CC1=CC=CC=C1.ClN(NC1=CC=CC=C1)C1=C(C=CC=C1)Cl OMKBWNZUEYDVLC-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 abstract 1
- 238000011110 re-filtration Methods 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 238000007599 discharging Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 101100489867 Mus musculus Got2 gene Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a process for comprehensive utilization of waste sulfuric acid from 33'-dichloro benzidine hydrochloride, which comprises preparing 2,2'-dichlorin hydrazobenzene toluene reduction liquid by means of catalytic hydrogenation reduction method, then carrying out filtration, salt producing, extraction, crystallizing, re-filtration, and drying. The process can reduce the discharge of waste acid by 80%.
Description
Technical field the present invention relates to a kind of important pigment and dyestuff intermediate 3, the sulfur waste acid comprehensive utilization novel process of 3 '-dichlorobenzidine hydrochloride.
3,3 '-dichlorobenzidine that background technology the present invention narrated (being called for short DCB) is a kind of crucial pigment and dyestuff intermediate, and its commodity generally exist with the form of hydrochloride, and its structure is as follows:
The production technique that DCB is traditional is to be main starting raw material with o-Nitrochlorobenzene, in NaOH solution, be reduced into 2 with formaldehyde, 2 '-dichloro zinin, be reduced into 2 with hydrazine hydrate then, 2 '-dichlorohydrazobenzene becomes 3 with 55% sulfuric acid transposition again, the vitriol of 3 '-dichlorobenzidine, because vitriol is thick, can not form good crystallization, being sorry leaches commodity, so also need thin up at last, use the hydrochloric acid salify, crystallization, centrifuging goes out commodity again, promptly 3, the hydrochloride of 3 '-dichlorobenzidine:
This technical process is long, and produces three step waste water or spent acid discharging.Especially the hydrochloric acid that contains about 25% sulfuric acid and 3-5% in the spent acid of final step discharging, and about 1% organism, contain 3 of 30-40% in the organism approximately, 3 '-dichlorobenzidine target product, not only cause waste, and the improvement of this step spent acid is very difficult, the cost that cost a lot of money, need with a large amount of alkali neutralizations, and other many treatment process.
At present, industrial, most of producer has adopted the shortening method to produce 3,3 '-dichlorobenzidine, and method is with the water-soluble immiscible organic solvent of o-Nitrochlorobenzene (as toluene), at tensio-active agent and noble metal catalyst (as Pt/C, Pd/C) under the existence, hydrogenation in water and organic solvent two-phase directly is reduced into 2,2 '-dichlorohydrazobenzene, become 3, the vitriol of 3 '-dichlorobenzidine, thin up with 55% sulfuric acid transposition again, isolate organic solvent, use the hydrochloric acid salify, crystallization, centrifuging goes out commodity again, promptly 3, the hydrochloride of 3 '-dichlorobenzidine:
Though this technology has reduced by a step process, also reduced by a step discharge of wastewater, the serious spent acid discharging of final step still exists.
Though, once there was report to remove organism in the spent acid with the method for ultra-filtration membrane, concentrate, apply mechanically spent acid again, be difficult to realization industrial, concentrated vitriol will consume a large amount of energy.
Purpose of the present invention is with 2, and direct filtration after the transposition of 2 '-dichlorohydrazobenzene reduces very little sulfur waste acid with concentration, through adjusting, the sulfuric acid of using when cover is used for the next batch transposition is again eliminated the most of spent acid of discharging in the DCB production technique, reduce the spent acid discharging thereby reach, save the vitriolic target.
Summary of the invention the present invention 3, the spent acid comprehensive utilization process method of 3 '-dichlorobenzidine hydrochloric acid (DCB) is a process: (1) 2, the producing of 2 '-dichlorohydrazobenzene reduced liquid, (2) transposition, (3) filter (4) salify, (5) extraction, (6) crystallization, (7) refilter (8) drying, (9) product, (10) separate, operations such as (11) complex acid are finished.
Concrete enforcement 3, the processing method of 3 '-dichlorobenzidine hydrochloride spent acid comprehensive utilization is: (referring to accompanying drawing 1)
At first, in toluene solvant, o-Nitrochlorobenzene is got 2 with the catalytic hydrogenating reduction legal system, 2 '-dichlorohydrazobenzene toluene reducing solution, then, under-10-20 ℃, the 50-60% aqueous sulfuric acid that the vitriol oil and water are made into is added drop-wise in the toluene reduced liquid, 2,2 '-dichlorohydrazobenzene and 50-60% vitriolic weight ratio are 1: 2-10, continue to react 24 hours under this temperature, 2, the transposition of 2 '-dichlorohydrazobenzene becomes 3,3 '-dichlorobenzidine vitriol; Again with after the transposition in 50-60% sulfuric acid solubleness very little 3,3 '-dichlorobenzidine vitriol directly carries out the first time and filters; Filtrate is divided into two-layer the separation, and the upper strata is the toluene solvant phase, delivers to extraction, and lower floor is transmitted back to complex acid for reducing the aqueous sulfuric acid phase of 3-10%, adds the vitriol oil, is made into and uses when 50-60% sulfuric acid cover is used for the next batch translocation reaction; To filter for the first time the filter cake 3 that obtains, 3 '-dichlorobenzidine vitriol adds entry (perhaps add last consignment of with the mother liquor that obtains is filtered in the crystallization of hydrochloric acid salify for the second time) and 22% hydrochloric acid, heats, and makes filter cake vitriol be transformed into hydrochloride and all dissolves; At last, the mother liquor that filters out with transposition is through separating, and the toluene that obtains extracts dissolved 3,3 '-dichlorobenzidine hydrochloride, the toluene layer of telling after the extraction is sent to distillation and is reclaimed toluene, and the water layer of telling through the cooling, crystallization separates out 3,3 '-dichlorobenzidine hydrochloride, through filtering for the second time, the filter cake drying obtains product again; Filter the filtrate that obtains for the second time, be back to salify, thereby, finish 3, the sulfur waste acid comprehensive utilization process process of 3 '-dichlorobenzidine hydrochloride.
The present invention is applicable to the o-Nitrochlorobenzene to be raw material, in sodium hydroxide solution, adopt traditional formaldehyde---hydrazine hydrate secondary reduction method produce 2,2 '-dichlorohydrazobenzene, because without toluene solvant, save in the technical process and separate and extraction process, make whole process flow of the present invention more simple.
In addition, in the transposition process, can produce by product 3,3 '-two chloro-2 of minute quantity, 4 '-benzidine (is called for short 2,4 isomer) enter the sulfuric acid layer of applying mechanically, considering the constantly accumulation of this by product, is the quality that guarantees product, sulfur waste acid apply mechanically batch, to control 2, the content of 4-isomer by product in the finished product exceeds less than 0.1%.
The present invention reduces very little and 2 owing to made full use of the sulfuric acid concentration that transposition uses, very little these two characteristics of the vitriol that generates after the transposition of 2 '-dichlorohydrazobenzene solubleness in the sulfuric acid of 50-60%, direct filtration after the employing transposition, then sulfur waste acid is applied mechanically continuously, make the quantity discharged of spent acid reduce 80% significantly, product per ton is used about 3 tons of sulfuric acid and a part of hydrochloric acid less simultaneously, has formed core innovative point of the present invention and superiority.
Description of drawings
1, reduced liquid---can produce through catalytic hydrogenating reduction method or formaldehyde-hydrazine hydrate secondary reduction method from o-Nitrochlorobenzene;
2, transposition---with 2,2 '-dichlorohydrazobenzene is transformed into 3,3 '-dichlorobenzidine vitriol;
3, filter 1---can tell 3,3 '-dichlorobenzidine vitriol filter cake and filtrate, filtrate is sent to separation: toluene is told on the upper strata, delivers to extraction, lower floor's sulfuric acid layer, send to complex acid after, use transposition;
4, salify---with 3,3 '-dichlorobenzidine vitriol is transformed into 3,3 '-dichlorobenzidine hydrochloride;
5, extraction---extract 3 with separating the toluene that comes, 3 '-dichlorobenzidine hydrochloride, toluene is reclaimed in the toluene layer distillation;
6, crystallization---water layer is through cooling, and crystallization goes out 3,3 '-dichlorobenzidine hydrochloride;
7, filter 2---tell 3,3 '-dichlorobenzidine hydrochloride filter cake, filtrate is recycled to salify;
8, drying---oven dry 3,3 '-dichlorobenzidine hydrochloride;
9, product---3,3 '-dichlorobenzidine hydrochloride.
Embodiment
Embodiment 1
First:
Under 0-5 ℃, with 88 grams, 55% aqueous sulfuric acid, be added drop-wise to the 66ml 2 that hydrogenation method makes, in the toluene solution of 2 '-dichlorohydrazobenzene (contain 2,2 '-dichlorohydrazobenzene 12 gram), continue 0-5 ℃ of insulation reaction 24 hours.Filter, the mother liquor layering gets toluene layer and acid layer, and the acid layer weighs 65 and restrains sulfuric acid content 50.5%.Filter cake adds in the 200ml water, adds toluene layer and 35ml 22% aqueous hydrochloric acid that layering obtains again, and being heated to refluxes all dissolves solid, layering is with water layer naturally cooling, crystallization, filter, mother liquor is treated reuse, and the crystal oven dry gets 15.1g 3,3 '-dichlorobenzidine hydrochloride, content 99.86%, 2,4 content of isomer 0.035%.
Second batch:
The sulfuric acid of the acid layer of last consignment of 65 gram 50.5% and 23 grams 67.7% is made into 88 restrains 55% sulfuric acid, under 0-5 ℃, this sulfuric acid is added drop-wise to the 66ml 2 that hydrogenation method makes, the toluene solution of 2 '-dichlorohydrazobenzene (contains 12 grams 2,2 '-dichlorohydrazobenzene) in, continues 0-5 ℃ of insulation reaction 24 hours.Filter, the mother liquor layering gets toluene layer and acid layer, and the acid layer weighs 66 and restrains sulfuric acid content 50.2%.Filter cake is added in the mother liquor of criticizing and adds water to volume 200ml, adds toluene layer and 35ml 22% aqueous hydrochloric acid that layering obtains again, and being heated to refluxes all dissolves solid, layering is with water layer naturally cooling, crystallization, filter, mother liquor is treated reuse, and the crystal oven dry gets 15.5g 3,3 '-dichlorobenzidine hydrochloride, content 99.54%, 2,4 content of isomer 0.043%.
Third and fourth, five batches:
According to second batch of identical method, apply mechanically the sulfuric acid layer and the mother liquor of last consignment of respectively, the product result of gained is as follows:
The 3rd batch 15.3 the gram products, content 99.60%, 2,4 isomer by-products contents 0.067%;
The 4th batch 15.6 the gram products, content 99.70%, 2,4 isomer by-products contents 0.075%;
The 5th batch 15.2 the gram products, content 99.56%, 2,4 isomer by-products contents 0.092%;
Embodiment 2
First:
Under 0-5 ℃, with 12 grams 2,2 '-dichlorohydrazobenzene adds in 55% aqueous sulfuric acids of 88 grams, continues 0-5 ℃ of insulation reaction 24 hours.Filter, mother liquor weighs 65 grams, sulfuric acid content 50.5%.Filter cake adds in the 200ml water, adds 22% aqueous hydrochloric acid 35ml again, and being heated to refluxes all dissolves solid, naturally cooling, crystallization, filter, mother liquor is treated reuse, and the crystal oven dry gets 15.1g 3,3 '-dichlorobenzidine hydrochloride, content 99.86%, 2,4 content of isomer 0.042%.
Second batch: 67.7 sulfuric acid of last consignment of 65 gram 50.5% sulfate liquors and 23 grams is made into 55% sulfuric acid of 88 grams, and under 0-5 ℃, with 12 grams 2,2 '-dichlorohydrazobenzene adds in this sulfuric acid, and continuation was 0-5 ℃ of insulation reaction 24 hours.Filter, mother liquor weighs 65 grams, sulfuric acid content 50.5%.Filter cake adds in supreme batch the mother liquor, and adds water to volume 200ml, adds 22% aqueous hydrochloric acid 35ml again, being heated to refluxes all dissolves solid, naturally cooling, crystallization, filter, mother liquor is treated reuse, and the crystal oven dry gets 15.1g 3,3 '-dichlorobenzidine hydrochloride, content 99.86%, 2,4 content of isomer 0.053%.
Third and fourth, five batches:
According to second batch of identical method, apply mechanically the sulfuric acid layer and the mother liquor of last consignment of respectively, the product result of gained is as follows:
The 3rd batch 15.3 the gram products, content 99.60%, 2,4 isomer by-products contents 0.071%;
The 4th batch 15.6 the gram products, content 99.70%, 2,4 isomer by-products contents 0.083%;
The 5th batch 15.2 the gram products, content 99.56%, 2,4 isomer by-products contents 0.096%;
Claims (3)
1, a kind of is raw material with the o-Nitrochlorobenzene, through reduction, transposition, salify, crystallization, filtration, dry preparation 3, the processing method of 3 '-dichlorobenzidine hydrochloride, it is characterized in that 3, the spent acid comprehensive utilization process method of 3 '-dichlorobenzidine hydrochloride is through (1) 2, the producing of 2 '-dichlorohydrazobenzene reduced liquid, (2) transposition, filter (3), (4) salify, (5) extraction, (6) crystallization, filter (7), (8) drying, (9) product, separate (10), and (11) complex acid operation is finished; Specific implementation method is: at first, with the catalytic hydrogenating reduction method produce 2,2 '-dichlorohydrazobenzene toluene reduced liquid, under-10-20 ℃, the 50-60% aqueous sulfuric acid that complex acid is obtained is added drop-wise in the toluene reduced liquid 2,2 '-dichlorohydrazobenzene and 50-60% vitriolic are heavy than being 1: 2-10, and remain under this temperature reaction 24 hours, and making 2, the transposition of 2 '-dichlorohydrazobenzene becomes 3,3 '-dichlorobenzidine vitriol, then, directly carry out the first time and filter, gained filtrate is divided into the two-layer separation of delivering to, the upper strata is the toluene phase, deliver to extraction, lower floor is transmitted back to complex acid for reducing the aqueous sulfuric acid phase of 3-10%, through adding the vitriol oil, be made into 50-60% sulfuric acid again, usefulness when cover is used for the next batch translocation reaction is applied mechanically for several times continuously; Add 22% hydrochloric acid and water in the filter cake of filtration gained, heating makes filter cake vitriol be transformed into hydrochloride and all dissolves; At last, the mother liquor that filters out with transposition is through separating, the toluene that obtains extracts dissolved 3, and 3 '-dichlorobenzidine hydrochloride, the toluene layer of telling after the extraction are sent to distillation and reclaimed toluene, the water layer of telling is through cooling, crystallization separates out 3,3 '-dichlorobenzidine hydrochloride, carry out the second time and filter, the filter cake drying obtains product; Filter the filtrate that obtains for the second time, be back to salify, finish 3, the sulfur waste acid comprehensive utilization process process of 3 '-dichlorobenzidine hydrochloride.
2, according to claim 1 described 3, the sulfur waste acid comprehensive utilization process method of 3 '-dichlorobenzidine hydrochloride, it is characterized in that it is raw material that this method is applicable to the o-Nitrochlorobenzene, in sodium hydroxide solution, use formaldehyde---hydrazine hydrate secondary reduction method produce 2,2 '-dichlorohydrazobenzene is owing to without toluene solvant, can save in the technical process and separate and extraction process.
3, described 3 according to claim 1, the sulfur waste acid comprehensive utilization process method of 3 '-dichlorobenzidine hydrochloride is characterized in that the number of times that sulfur waste acid is applied mechanically, and to control 2, the content of 4-isomer by product in the finished product exceeds less than 0.1%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410050361 CN1280255C (en) | 2004-08-31 | 2004-08-31 | Process for comprehensive utilization of waste sulfuric acid from 3,3'-dichloro benzidine hydrochloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410050361 CN1280255C (en) | 2004-08-31 | 2004-08-31 | Process for comprehensive utilization of waste sulfuric acid from 3,3'-dichloro benzidine hydrochloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1629131A true CN1629131A (en) | 2005-06-22 |
| CN1280255C CN1280255C (en) | 2006-10-18 |
Family
ID=34846050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410050361 Expired - Fee Related CN1280255C (en) | 2004-08-31 | 2004-08-31 | Process for comprehensive utilization of waste sulfuric acid from 3,3'-dichloro benzidine hydrochloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1280255C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100354250C (en) * | 2006-06-19 | 2007-12-12 | 常州市佳森化工有限公司 | Tech. of separating purifying 3,3-dichlorobenzidine hydrochloride |
| CN1752032B (en) * | 2005-08-17 | 2010-07-28 | 夏念冉 | Treatment and recovery technology for mixed acid from industrial waste water 3,3-dichlorobenzidine hydrochloride |
| CN103880685A (en) * | 2012-12-20 | 2014-06-25 | 江苏道博化工有限公司 | Comprehensive recovery utilization method for 3,3-dichlorobenzidine |
| CN108218711A (en) * | 2018-01-12 | 2018-06-29 | 浙江鼎龙科技有限公司 | A kind of preparation method of 3,3 ', 4,4 '-tetra-amino-biphenyl |
| CN111807995A (en) * | 2020-07-31 | 2020-10-23 | 山东泓瑞医药科技股份公司 | Method for resource utilization of waste acid in amantadine production |
| CN113024385A (en) * | 2021-03-16 | 2021-06-25 | 西安瑞联新材料股份有限公司 | Preparation method of 2,2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl |
| CN113548972A (en) * | 2021-07-13 | 2021-10-26 | 济宁祥泰和新材料科技有限公司 | Production process of 3, 3' -dichlorobenzidine hydrochloride |
-
2004
- 2004-08-31 CN CN 200410050361 patent/CN1280255C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1752032B (en) * | 2005-08-17 | 2010-07-28 | 夏念冉 | Treatment and recovery technology for mixed acid from industrial waste water 3,3-dichlorobenzidine hydrochloride |
| CN100354250C (en) * | 2006-06-19 | 2007-12-12 | 常州市佳森化工有限公司 | Tech. of separating purifying 3,3-dichlorobenzidine hydrochloride |
| CN103880685A (en) * | 2012-12-20 | 2014-06-25 | 江苏道博化工有限公司 | Comprehensive recovery utilization method for 3,3-dichlorobenzidine |
| CN103880685B (en) * | 2012-12-20 | 2015-08-19 | 江苏道博化工有限公司 | 3, the recovery method of comprehensive utilization of 3 '-dichlorobenzidine |
| CN108218711A (en) * | 2018-01-12 | 2018-06-29 | 浙江鼎龙科技有限公司 | A kind of preparation method of 3,3 ', 4,4 '-tetra-amino-biphenyl |
| CN111807995A (en) * | 2020-07-31 | 2020-10-23 | 山东泓瑞医药科技股份公司 | Method for resource utilization of waste acid in amantadine production |
| CN113024385A (en) * | 2021-03-16 | 2021-06-25 | 西安瑞联新材料股份有限公司 | Preparation method of 2,2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl |
| CN113024385B (en) * | 2021-03-16 | 2022-08-16 | 西安瑞联新材料股份有限公司 | Preparation method of 2,2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl |
| CN113548972A (en) * | 2021-07-13 | 2021-10-26 | 济宁祥泰和新材料科技有限公司 | Production process of 3, 3' -dichlorobenzidine hydrochloride |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1280255C (en) | 2006-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2009130387A2 (en) | A process for preparation of formate salt | |
| CN1736969A (en) | Method for separating and preparing mono, bis-pentaerythritol and its by-product using high temperature condensation and concatenate recrystallization | |
| CN1280255C (en) | Process for comprehensive utilization of waste sulfuric acid from 3,3'-dichloro benzidine hydrochloride | |
| CN1804148A (en) | Method for recovering copper and nickel nitrate by electrolysis of electroplating waste water | |
| CN112441926B (en) | Method for co-producing m-methylbenzoic acid nitride and m-phthalic acid | |
| CN101941901A (en) | Method for recycling mother solid in PTA-refining wastewater | |
| CN1088055C (en) | Process for extracting alpha-or omege-alkadicarboxylic acid from fermented liquid and refining it | |
| EP1399231A2 (en) | Method for removing formic acid from aqueous solutions | |
| CN1050356C (en) | Process for preparing sodium (or potassium) L-ascorbate | |
| CN108754162A (en) | A kind of green reclaim method recycling noble metal in wet method waste water | |
| CN1207267C (en) | Liquid-phase hydrogenation new technological process for preparation of P-aminophenol by using P-nitrophenol | |
| CN1124268C (en) | Process for preparing aminopyrimidine sulfate by reducing pyrimidine derivative containing nitroso | |
| CN108191868A (en) | A kind of processing method of the molten refinement mother liquor of riboflavin acid | |
| CN109400555B (en) | Process for α -acetyl-gamma-butyrolactone sodium salt free acetamidine hydrochloride | |
| CN114314929A (en) | Comprehensive treatment method for printing and dyeing wastewater of reactive dye | |
| CN1772722A (en) | Methyl heptenone preparing and refining process | |
| CN108328638B (en) | method for preparing ammonium aluminum sulfate from FCC spent catalyst | |
| CN1033618A (en) | Produce the method for phenol | |
| CZ261395A3 (en) | Process for preparing pure solutions of alkali aluminates | |
| CN1284759C (en) | Method for producing tetrahydro isomerized alpha acid | |
| CN111704272B (en) | Method for treating hydroquinone-containing sewage and recovering resources | |
| CN1042919C (en) | Method of wet-extraction for arsenic | |
| CN1062347A (en) | The method of separation and Extraction L-tyrosine, Gelucystine from the recovery mother liquor of producing Gelucystine | |
| CN1039435C (en) | Conversion and separation method for extracting glycerin from fermentation liquid | |
| CN210419811U (en) | Amine alcohol compound reaction system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20061018 Termination date: 20090930 |