CN107540077A - A kind for the treatment of by catalytic oxidation in 3,3 '-dichlorobenzidine hydrochloride with waste water - Google Patents
A kind for the treatment of by catalytic oxidation in 3,3 '-dichlorobenzidine hydrochloride with waste water Download PDFInfo
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Abstract
In 3,3 ' dichlorobenzidine hydrochlorides and waste water treatment by catalytic oxidation, including：（1）Mixing, suction strainer：It is in faintly acid that salkali waste, which is added dropwise in neutralization waste water to pH, and clear filtrate is obtained after suction strainer；（2）Catalysis oxidation：Activated-carbon catalyst is loaded in catalyst oxidation reactor, running water, distilled water or deionized water are added, by step（1）After obtained filtrate mixes in proportion with running water, distilled water or deionized water, continuously squeeze at the top of catalyst oxidation reactor, oxidation reaction occurs under normal temperature condition.The oxidized waste water part generated after reaction is applied mechanically, and continues to carry out oxidation reaction in catalyst oxidation reactor after mixing in proportion with filtrate, remaining oxidized waste water carries out biochemical treatment.The organic constitution that the present invention can be destroyed effectively in waste water, larger molecular organicses is become the small organic molecule of paired Biochemical Effect very little, make the biochemical processing of waste water；Catalytic oxidation is normal-temperature reaction, and energy consumption is low；Technological process is relatively simple, has preferable industrial prospect.
Description
Technical field
The present invention relates to one kind 3, in 3 '-dichlorobenzidine hydrochloride and waste water treatment by catalytic oxidation, belonging to
Work processing, chemical technology field.
Background technology
3,3 '-dichloro-benzidine, abbreviation DCB, be the double chlordiphenyl amine system organic pigments of production important intermediate, using its as
The serial organic pigment yield of main manufacture accounts for the 25% of organic pigment total amount, is widely used in ink, paint, rubber, plastics etc.
Coloring and the production of pigment printing slurries pigment dyeing slurry.Its commodity typically exists with hydrochloride form, and structural formula is：
3, the production of 3 '-dichlorobenzidine hydrochloride is the raw material based on o-nitrochlorobenzene, is reduced in alkaline medium,
Generation 2,2’- dichlorohydrazobenzene（DHB）, then 2,2’- dichlorohydrazobenzene carries out indexing and obtained in acid medium
3,3’- dichloro-benzidine.In reducing process, catalytic hydrogenation method has the advantages that product yield is high, quality is good, the three wastes are few, mesh
Before be industrialized production main flow.Indexable technique has two kinds of sulfuric acid indexing and hydrochloric acid indexing, and wherein sulfuric acid indexing advantage is reaction
Hurry up, can stratification, be easy to further purify, but because the sulfuric acid salt solubility of 3,3 '-dichloro-benzidine is big, also after rearrangement
Hydrochloride is converted into, therefore complex process, yield are low；Hydrochloric acid indexing technique is simpler, easily operated, yield is higher, and shortcoming is thing
Expect that sticky, resistance to mass tranfer is big, reaction is slower, but can improve the sticky problem of material by adding the method for auxiliary agent, it is ensured that reaction
It is carried out continuously and is not interrupted.Two kinds of indexable techniques have application in industrialized production.
Using catalytic hydrogenation method, hydrochloric acid indexing technique productions 3, the process of 3 '-dichlorobenzidine hydrochloride includes hydrogenation, divided
From, indexing, the step such as dissolving is decolourized, saltouts, filters, neutralized, two filter product reclaim.Caused waste water includes hydrogenation in production process
Caused neutralization waste water after the spent lye isolated afterwards and neutralization, wherein spent lye pH value is about 14, neutralizes pH value of waste water and is about
2, both COD values are 15000 ppm or so.It is organic containing the macromolecular that mass fraction is 1~2% in waste water due to neutralizing
Thing, mainly including 3,3 '-dichloro-benzidine and reduction accessory substance o-chloraniline etc., therefore can not direct biochemical treatment.The waste water
It is extremely difficult to one of industrial organic waste water of processing.
The country reports the processing method of several sulfuric acid indexing production 3,3 '-dichlorobenzidine hydrochloride waste water at present.Specially
Sharp CN 1629131A, 3, the Waste Sulfuric Acid comprehensive utilization process method of 3 '-dichlorobenzidine hydrochloride, utilize 2,2’- dichloro hydrogen
Change the sulfate generated after azobenzene indexing and the characteristics of solubility very little, directly filter in mother liquor, then continuously apply mechanically spent acid,
Make the discharge capacity of spent acid reduce 80%.But the organic matter of by-product can be accumulated gradually when applying mechanically spent acid, so as to influence product quality.
Patent CN 1752032A, industrial wastewater 3,3- dichlorobenzidine hydrochlorides produce treatment and recovery technology for mixed acid, using containing magnesium elements
Ore reacted with sulfuric acid, be extracted magnesium sulfate while reducing waste water acidity, but this method can not effectively reduce waste water
In content of organics；Patent CN 101372381A, one kind 3,3 '-dichlorobenzidine hydrochloride waste water reclaiming processing method
And its device, waste water is handled by steps such as evaporation, rectifying, decolouring, filtering, cooling, crystallization, separation, it is recyclable its
In hydrochloric acid and sulfuric acid, and obtain o-chloraniline sulfate byproduct.But this method process is complicated, and the unit such as evaporation, rectifying
There is larger energy consumption, from the viewpoint of economy, the difficulty of its industrial applications is higher.
The content of the invention
It is an object of the invention to provide a kind of catalysis oxygen being used in 3,3 '-dichlorobenzidine hydrochloride with wastewater treatment
Change method.For hydrochloric acid indexing technique productions 3, caused neutralization waste water during 3 '-dichlorobenzidine hydrochloride, in catalyst
In the presence of, oxidant is used air as to destroy the organic constitution in waste water, larger molecular organicses is become biochemical in pairs
The small organic molecule of very little is influenceed, makes the biochemical processing of waste water, qualified discharge.Concrete technology flow process figure is as shown in Figure 1.
Catalysed oxidation processes in the present invention 3,3 '-dichlorobenzidine hydrochloride of processing with waste water are carried out as follows：
（1）Mixing, suction strainer：Alkali lye is added dropwise in the neutralization waste water of acidity, stirred, stop drop when pH reaches 4~5
Add, stirring maintains suction strainer after 10~15 min, obtains clear filtrate；
（2）Catalysis oxidation：Load activated-carbon catalyst in catalyst oxidation reactor, add running water, distilled water or go from
Sub- water is concordant with catalyst face to liquid level.By step（1）Obtained filtrate is with running water, distilled water or deionized water by 1：2
After~3 ratio mixing, continuously squeeze at the top of catalyst oxidation reactor.Air is continuously passed through from reactor bottom, in catalyst
In the presence of, gas-liquid counter current contact, oxidation reaction occurs under normal temperature condition.The oxidized waste water generated after reaction applies mechanically 1/2~
3/4, continue to carry out oxidation reaction in catalyst oxidation reactor after mixing in proportion with filtrate, remaining oxidized waste water is given birth to
Change is handled.
Described step（1）In, alkali lye 3, that is isolated after being hydrogenated with 3 '-dichlorobenzidine hydrochloride production process is useless
Alkali lye；
Described step（2）In, Catalyst packing volume is the 1/2~2/3 of catalyst oxidation reactor volume；
Described step（2）In, the volume flow rate for the air that the unit interval passes through catalyst（GHSV）For 20~40 h-1；
Described step（2）In, the ratio between composite waste flow velocity and air velocity are 1：130~170；
Described step（2）In, filtrate and the ratio for applying mechanically oxidized waste water are 1 in composite waste：2~3.
The present invention and 3, the existing processing method of 3 '-dichlorobenzidine hydrochloride waste water is compared, and has advantages below：（1）
The organic constitution neutralized in waste water can be effectively destroyed using catalysed oxidation processes, larger molecular organicses is become biochemical shadow in pairs
Ring the small organic molecule of very little.After oxidized, the COD value of waste water is reduced to 1000 below ppm, waste water by about 15000 ppm
Middle larger molecular organicses（Mainly 3,3 '-dichloro-benzidine and o-chloraniline）Shared mass fraction is reduced to 0.01 by 1 ~ 2%~
0.02%, make the biochemical processing of waste water；（2）The present invention carries out catalytic oxidation under normal temperature condition, without heating, rectifying etc.
Unit operates, and energy consumption is low；（3）Present invention process flow is relatively simple, and catalytic oxidation stage using continuous operation by the way of,
With preferable industrial prospect.
Brief description of the drawings
Fig. 1 is that catalytic oxidation of the embodiment of the present invention handles the technique stream with waste water in 3,3 '-dichlorobenzidine hydrochloride
Cheng Tu.
Embodiment
The technological process of following examples method is referring to accompanying drawing 1.
Embodiment 1
Stirred in being added in four-hole boiling flask with waste water, unlatching, alkali lye is added dropwise to dropping funel and neutralized in waste water, stirring is equal
Its pH value is surveyed after even.Stop being added dropwise when pH reaches 4, moved to after 15 min of stirring maintenance and suction strainer is carried out in filter flask, it is heavy to filter off
Clear filtrate is obtained behind shallow lake.
Activated-carbon catalyst is loaded in catalyst oxidation reactor, Catalyst packing volume is the 1/2 of reactor volume, is added
It is concordant with catalyst face to liquid level to enter running water.Filtrate and running water are pressed 1：Catalysis oxidation is continuously squeezed into after 3 ratio mixing
Reactor head, air are continuously passed through from reactor bottom.The volume flow rate for the air that unit interval passes through catalyst（GHSV）
For 40 h-1, the ratio between composite waste flow velocity and air velocity are 1：170.In the presence of catalyst, gas-liquid counter current contact, normal
Oxidation reaction occurs under the conditions of temperature, generates oxidized waste water.After testing, COD ﹤ 1000 ppm of oxidized waste water, 3,3 '-dichlorobenzene
Amine content ﹤ 0.005%, o-chloraniline content ﹤ 0.005%, colourity ﹤ 50, meets the requirement of biochemical treatment.Oxidized waste water is applied mechanically 3/
4, after being mixed with filtrate（Filtrate and the ratio for applying mechanically oxidized waste water are 1：3）Continue oxidation reaction, remaining oxidized waste water
Carry out biochemical treatment.
Embodiment 2
Stirred in being added in four-hole boiling flask with waste water, unlatching, salkali waste is added dropwise to dropping funel and neutralized in waste water, stirring is equal
Its pH value is surveyed after even.Stop being added dropwise when pH reaches 5, moved to after 10 min of stirring maintenance and suction strainer is carried out in filter flask, it is heavy to filter off
Clear filtrate is obtained behind shallow lake.
Activated-carbon catalyst is loaded in catalyst oxidation reactor, Catalyst packing volume is the 1/2 of reactor volume, is added
It is concordant with catalyst face to liquid level to enter distilled water.Filtrate and distilled water are pressed 1：Catalysis oxidation is continuously squeezed into after 2 ratio mixing
Reactor head, air are continuously passed through from reactor bottom.The volume flow rate for the air that unit interval passes through catalyst（GHSV）
For 20 h-1, the ratio between composite waste flow velocity and air velocity are 1：130., in the presence of catalyst, gas-liquid counter current contact, normal
Oxidation reaction occurs under the conditions of temperature, generates oxidized waste water.After testing, COD ﹤ 1000 ppm of oxidized waste water, 3,3 '-dichlorobenzene
Amine content ﹤ 0.005%, o-chloraniline content ﹤ 0.005%, colourity ﹤ 50, meets the requirement of biochemical treatment.Oxidized waste water is applied mechanically 1/
2, after being mixed with filtrate（Filtrate and the ratio for applying mechanically oxidized waste water are 1：2）Continue oxidation reaction, remaining oxidized waste water
Carry out biochemical treatment.
Embodiment 3
Stirred in being added in four-hole boiling flask with waste water, unlatching, salkali waste is added dropwise to dropping funel and neutralized in waste water, stirring is equal
Its pH value is surveyed after even.Stop being added dropwise when pH reaches 4, moved to after 10 min of stirring maintenance and suction strainer is carried out in filter flask, it is heavy to filter off
Clear filtrate is obtained behind shallow lake.
Activated-carbon catalyst is loaded in catalyst oxidation reactor, Catalyst packing volume is the 2/3 of reactor volume, is added
It is concordant with catalyst face to liquid level to enter deionized water.By filtrate with pressing 1 with deionized water：Continuously squeeze into and urge after 3 ratio mixing
At the top of oxidation device, air is continuously passed through from reactor bottom.The volume flow rate for the air that unit interval passes through catalyst
（GHSV）For 25 h-1, the ratio between composite waste flow velocity and air velocity are 1：140., in the presence of catalyst, gas-liquid counter current connects
Touch, oxidation reaction occurs under normal temperature condition, generate oxidized waste water.After testing, COD ﹤ 1000 ppm of oxidized waste water, 3,3 '-
Dichlorobenzene amine content ﹤ 0.005%, o-chloraniline content ﹤ 0.005%, colourity ﹤ 50, meets the requirement of biochemical treatment.Oxidation is useless
Water jacket is with 3/4, after being mixed with filtrate（Filtrate and the ratio for applying mechanically oxidized waste water are 1：3）Continue oxidation reaction, it is remaining
Oxidized waste water carries out biochemical treatment.
Embodiment 4
Stirred in being added in four-hole boiling flask with waste water, unlatching, salkali waste is added dropwise to dropping funel and neutralized in waste water, stirring is equal
Its pH value is surveyed after even.Stop being added dropwise when pH reaches 5, moved to after 15 min of stirring maintenance and suction strainer is carried out in filter flask, it is heavy to filter off
Clear filtrate is obtained behind shallow lake.
Activated-carbon catalyst is loaded in catalyst oxidation reactor, Catalyst packing volume is the 2/3 of reactor volume, is added
It is concordant with catalyst face to liquid level to enter running water.Filtrate and running water are pressed 1：Catalysis oxidation is continuously squeezed into after 2 ratio mixing
Reactor head, air are continuously passed through from reactor bottom.The volume flow rate for the air that unit interval passes through catalyst（GHSV）
For 30 h-1, the ratio between composite waste flow velocity and air velocity are 1：170., in the presence of catalyst, gas-liquid counter current contact, normal
Oxidation reaction occurs under the conditions of temperature, generates oxidized waste water.After testing, COD ﹤ 1000 ppm of oxidized waste water, 3,3 '-dichlorobenzene
Amine content ﹤ 0.005%, o-chloraniline content ﹤ 0.005%, colourity ﹤ 50, meets the requirement of biochemical treatment.Oxidized waste water is applied mechanically 1/
2, after being mixed with filtrate（Filtrate and the ratio for applying mechanically oxidized waste water are 1：2）Continue oxidation reaction, remaining oxidized waste water
Carry out biochemical treatment.
Claims (6)
1. one kind 3, in 3 '-dichlorobenzidine hydrochloride and waste water treatment by catalytic oxidation, it is characterised in that including following
Step：
（1）Mixing, suction strainer：Alkali lye is added dropwise in the neutralization waste water of acidity, stirred, stop drop when pH reaches 4~5
Add, stirring maintains suction strainer after 10~15 min, obtains clear filtrate；
（2）Catalysis oxidation：Load activated-carbon catalyst in catalyst oxidation reactor, add running water, distilled water or go from
Sub- water is concordant with catalyst face to liquid level；By step（1）Obtained filtrate is with running water, distilled water or deionized water by 1：2
After~3 ratio mixing, continuously enter at the top of catalyst oxidation reactor, air is continuously passed through from reactor bottom；In catalyst
In the presence of, gas-liquid counter current contact, oxidation reaction occurs under normal temperature condition, oxidized waste water is generated after reaction；By oxidized waste water
1/2~3/4 is applied mechanically, continues to carry out oxidation reaction, remaining oxidation in catalyst oxidation reactor after mixing in proportion with filtrate
Waste water carries out biochemical treatment.
2. according to claim 13, in 3 '-dichlorobenzidine hydrochloride and waste water treatment by catalytic oxidation, it is special
Sign is：Described step（1）In, alkali lye 3, that is isolated after being hydrogenated with 3 '-dichlorobenzidine hydrochloride production process is useless
Alkali lye.
3. according to claim 13, in 3 '-dichlorobenzidine hydrochloride and waste water treatment by catalytic oxidation, it is special
Sign is：Described step（2）In, Catalyst packing volume is the 1/2~2/3 of catalyst oxidation reactor volume.
4. according to claim 13, in 3 '-dichlorobenzidine hydrochloride and waste water treatment by catalytic oxidation, its
It is characterised by：Described step（2）In, the volume flow rate for the air that the unit interval passes through catalyst is 20~40 h-1。
5. 3 according to claim 1 or 4, in 3 '-dichlorobenzidine hydrochloride and waste water treatment by catalytic oxidation,
It is characterized in that：Described step（2）In, the ratio between composite waste flow velocity and air velocity are 1：130~170.
6. according to claim 13, in 3 '-dichlorobenzidine hydrochloride and waste water treatment by catalytic oxidation, it is special
Sign is：Described step（2）In, filtrate and the ratio for applying mechanically oxidized waste water are 1 in composite waste：2~3.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113371881A (en) * | 2021-06-22 | 2021-09-10 | 中石化南京化工研究院有限公司 | Treatment method of process wastewater generated in one-step synthesis of N-phenylmaleimide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102765801A (en) * | 2012-08-09 | 2012-11-07 | 山东聊城中盛蓝瑞化工有限公司 | Air catalytic oxidation treatment benzyl cyanide waste water method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102765801A (en) * | 2012-08-09 | 2012-11-07 | 山东聊城中盛蓝瑞化工有限公司 | Air catalytic oxidation treatment benzyl cyanide waste water method |
Non-Patent Citations (1)
| Title |
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| 姜刚村等: "湿式氧化工艺处理苯胺类废水技术研究", 《染料与染色》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113371881A (en) * | 2021-06-22 | 2021-09-10 | 中石化南京化工研究院有限公司 | Treatment method of process wastewater generated in one-step synthesis of N-phenylmaleimide |
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Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee after: China Petroleum & Chemical Corp. Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee before: China Petroleum & Chemical Corp. Patentee before: Nanhua Group Research Institute |