CN1015272B - Electrolytic preparation method and equipment of 3, 3 '-dichloro 4, 4' -diaminobenzidine - Google Patents
Electrolytic preparation method and equipment of 3, 3 '-dichloro 4, 4' -diaminobenzidineInfo
- Publication number
- CN1015272B CN1015272B CN90109751.9A CN90109751A CN1015272B CN 1015272 B CN1015272 B CN 1015272B CN 90109751 A CN90109751 A CN 90109751A CN 1015272 B CN1015272 B CN 1015272B
- Authority
- CN
- China
- Prior art keywords
- electrolyzer
- electrolytic
- dichloro
- diaminobenzidine
- negative electrode
- 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.)
- Expired
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- KTRQCNQFWHWLDW-UHFFFAOYSA-N 2-chloro-4-(4,4-diamino-3-chlorocyclohexa-2,5-dien-1-ylidene)cyclohexa-2,5-diene-1,1-diamine Chemical compound ClC1=CC(C=CC1(N)N)=C1C=C(C(N)(C=C1)N)Cl KTRQCNQFWHWLDW-UHFFFAOYSA-N 0.000 title abstract 2
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 13
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006462 rearrangement reaction Methods 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 230000009467 reduction Effects 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 230000004888 barrier function Effects 0.000 claims description 4
- 239000003637 basic solution Substances 0.000 claims description 4
- 210000005056 cell body Anatomy 0.000 claims description 3
- 229910003460 diamond Inorganic materials 0.000 claims description 3
- 239000010432 diamond Substances 0.000 claims description 3
- SXEHKFHPFVVDIR-UHFFFAOYSA-N [4-(4-hydrazinylphenyl)phenyl]hydrazine Chemical compound C1=CC(NN)=CC=C1C1=CC=C(NN)C=C1 SXEHKFHPFVVDIR-UHFFFAOYSA-N 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000004080 punching Methods 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 28
- 230000008569 process Effects 0.000 abstract description 7
- BVPHWSDABGXRQD-UHFFFAOYSA-N 1,2-bis(4-chlorophenyl)hydrazine Chemical compound C1=CC(Cl)=CC=C1NNC1=CC=C(Cl)C=C1 BVPHWSDABGXRQD-UHFFFAOYSA-N 0.000 abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010935 stainless steel Substances 0.000 abstract description 4
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 4
- 238000011946 reduction process Methods 0.000 abstract description 3
- 239000012670 alkaline solution Substances 0.000 abstract description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010931 gold Substances 0.000 abstract description 2
- 229910052737 gold Inorganic materials 0.000 abstract description 2
- 229910052697 platinum Inorganic materials 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 239000007772 electrode material Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 10
- IWKMQNKKYZERHI-UHFFFAOYSA-N 1,2-bis(2-chlorophenyl)hydrazine Chemical compound ClC1=CC=CC=C1NNC1=CC=CC=C1Cl IWKMQNKKYZERHI-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 125000003963 dichloro group Chemical group Cl* 0.000 description 4
- 230000017105 transposition Effects 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000003929 acidic solution Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- LYTNSPPNOOYAAJ-UHFFFAOYSA-N ClC1=C(C(=CC=C1N)C1=CC(=C(C=C1)N)Cl)N Chemical compound ClC1=C(C(=CC=C1N)C1=CC(=C(C=C1)N)Cl)N LYTNSPPNOOYAAJ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- -1 aromatic nitro compound Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000037237 body shape Effects 0.000 description 1
- RFAFBXGYHBOUMV-UHFFFAOYSA-N calcium chromate Chemical compound [Ca+2].[O-][Cr]([O-])(=O)=O RFAFBXGYHBOUMV-UHFFFAOYSA-N 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention relates to a method and equipment for electrolyzing and reducing ortho-nitrochlorobenzene into dichlorohydrazobenzene by a one-step electrolysis method, and further generating 3, 3 '-dichloro-4, 4' -diaminobenzidine by a rearrangement reaction. The one-step electrolysis method is to complete two reduction processes in alkaline solution in one electrolytic cell, thus reducing equipment, simplifying process, and having high yield and stable product quality. The electrode material of the required electrolytic cell adopts carbon steel-stainless steel and hard lead, which replaces gold and platinum electrodes, greatly saves the cost and is a preparation method suitable for industrial production.
Description
The present invention relates to the electrolysis production of organic compound, relate to the o-nitrochlorobenzene electrolytic reduction specifically, generate 2,2 '-dichlorohydrazobenzene, and then produce 3,3 '-dichloro-4,4,4 '-method of diaminobenzidine.
3,3 '-dichloro-4,4,4 '-diaminobenzidine (being called for short DCB) is a kind of important pigment dyestuff intermediate.With it is organic face (dying) material that main body is made, and occupies about 30% of machine face (dying) material, is the international standard yellow ultramarine.
The synthetic of DCB is to be basic material with the o-Nitrochlorobenzene, reduction generation earlier 2,2 '-dichlorohydrazobenzene.Then with 2,2 '-dichlorohydrazobenzene carries out transposition, generates DCB salt in acidic medium.Entire reaction course is as follows:
(1) reduction:
The method of producing DCB has multiple.Early the method for usefulness is the zinc powder reduction method, the DCB quality instability that this method prepares, and the zinc powder that wherein contains is difficult for separating, and it also need consume a large amount of zinc powders, causes cost to increase greatly.After this developed the formaldehyde reduction method, this method and zinc powder reduction method are similar, earlier through the reduction of two steps o-nitrochlorobenzene is changed into 2,2 '-dichlorohydrazobenzene, make its transposition again and saltout with generation DCB.Two step reduction processes of this method are as follows: the raw material o-nitrochlorobenzene, at catalyzer 2, under the catalytic condition of 3-dichloro 1,4 naphthoquinones, in alkaline medium, reduce lentamente with formaldehyde, generation 2,2 '-the dichloro zinin, then in acidic medium, with iron powder reducing become 2,2 '-dichlorohydrazobenzene.The advantage of this method is not consume non-ferrous metal zinc, but has increased combustible and explosive articles-formaldehyde, and the three wastes are handled also complicated simultaneously.The seventies is not, early eighties, the U.S. etc. have developed the catalytic hydrogenating reduction method again and have produced DCB, this method does not consume advantages such as metal, turnout are big, steady quality, but needs to consume highly purified hydrogen and use expensive catalysts, and needs use high-pressure hydrogenation process, cause technical process long, production unit is numerous and jumbled and the operational condition requirement is harsh, has increased greatly and has produced investment, and the three wastes are handled also complexity.A kind of method of producing aromatic series hydrazo-compound with the electrolysis method of reducing is disclosed in U.S. Pat 4345978 documents.This patent is still continued to use zinc powder and the used two-step process of formaldehyde reduction, be that the first step becomes 2 with aromatic nitro compound electrolytic reduction in basic solution earlier, 2 '-the dichloro zinin, second step became 2,2 to the dichloro zinin electrolytic reduction in acidic solution after refining '-dichlorohydrazobenzene.The purpose of refining zinin is to separate because of reducing the excessive byproduct dichlorohydrazobenzene that generates.The easy transposition in acidic solution of this product becomes other byproducts, thereby influences the quality of product.The electrode that adopts in this method is gold and platinum.As seen from above-mentioned, this method is complex process not only, and the cost height, and yield is also low simultaneously, only
Have 45～52%, the operational condition harshness.
It is short that the object of the invention provides a kind of technical process, simplified control, and cost is low, the method and apparatus of the electrolytic preparation DCB of yield height and constant product quality.
The present invention has adopted single stage method to finish two chemical reduction processes.Promptly become the dichloro zinin and further be reduced into dichlorohydrazobenzene and an electrolyzer, carry out from the o-nitrochlorobenzene electrolytic reduction, because its two reduction processes are all carried out in basic solution, therefore can change groove, and in a kind of basic solution, reduce, need not isolate the excessive byproduct of reduction, thereby simplified control, and operational condition is not harsh yet.Trough reduces to one by two, so facility investment also significantly reduces.The electrode that the present invention adopts is with stainless steel and antimonial lead material, greatly reduces production cost again.Because flow process has reduced many middle-chains, and yield also improves, and can reach 75～80%, quality product is also stable in addition.
Fig. 1 is the synoptic diagram of the circular electrolyzer of the present invention.
Fig. 2 is the A-A schematic cross-section of circular electrolyzer.
Fig. 3 is oval electrolyzer synoptic diagram.
Fig. 4 is a rectangle electrolyzer synoptic diagram.
From Fig. 1-Fig. 4 as seen, the cell construction that adopts of the present invention and general electrolytic cell is identical. It is made up of cell body 1, anode 2, negative electrode 3, barrier film 4 and agitator 5. Barrier film 4 of the present invention adopts the diamond spar material to fire and forms, can be tubulose or tabular, is abound with micropore in its body, and the aperture is 0.5 μ～80 μ. These film characteristics are that resistance is little, so power consumption is little, have greatly saved electric energy, and it can be separated negative electrode liquid and anode liquid preferably, in order to avoid interpenetrate, the electroreduction product can be limited in the negative electrode liquid simultaneously. Negative electrode of the present invention adopts carbon steel or stainless steel, and perforate 6 on negative electrode, can increase the convection current of negative electrode liquid, and pore size is 2～10 millimeters, and percent opening is 25～40%. In order further to increase cathodic surface area, when punching, the hole sheet that sweeps away still is connected the hole along upper. Cathode shape is consistent with groove shape, and it is arranged to greatest extent. Anode material selection antimonial lead, its shape are also consistent with the cell body shape. Groove shape can be circular, ellipse and rectangle.
Negative electrode liquid and anode liquid that the present invention adopts are the same alkaline solution, and commonly used is the NaOH aqueous solution. Anode solution concentration is 20～60%, and cathode liquid concentration is 5～15%. Electrolytic potential is 3～25 volts, and the better electrical position is 4～6 volts. Current density is 0.1～10 ampere every square decimeter. The electroreduction temperature is 30～100 ℃, and preferred temperature is 70～90 ℃.
The product that makes from electrolyzer is a dichlorohydrazobenzene, and this product separates through separator again, and isolated dichlorohydrazobenzene is sent into the rearrangement reactor transposition and saltoutd, and obtains the DCB product.Isolated anolyte and catholyte are capable of circulation to be used in electrolyzer.
Embodiment one.
Electrolyzer is that diameter is 0.9 meter, and height is 1.3 meters a reactor (seeing Fig. 1 and Fig. 2).The barrier film of electrolyzer is a round shape, and diameter is 0.3 meter, and material is to fire the diamond spar that forms.Cathode area is 300 square decimeters, and the aperture on the negative electrode is 8 millimeters, and percentage of open area is 30%, and cathode material is the 0Cr13 stainless steel.Annode area is 90 square decimeters, and material is an antimonial lead.Catholyte is the 10%NaOH aqueous solution, and anolyte is the 30%NaOH aqueous solution.Faradaic current is 400 amperes, and voltage is 5 volts, and electrolysis temperature is 80 ℃.Drop into the o-nitrochlorobenzene of 200 kilograms electrolyzers, electric weight inputs to 1.3 times of dischargings of Theoretical Calculation amount during electrolysis.Obtain 156 kilogram 2,2 '-dichlorohydrazobenzene, move to then in the rearrangement reactor, obtain 150 kilogram 3,3 '-dichlorobenzidine.
Embodiment two.
Electrolyzer is that major axis is that 0.5 meter, minor axis are 0.3 meter, and height is 1 meter an oval reactor (see figure 3).Electrode diaphragm is that 2 diameters are 0.1 meter round tube, and cathode area is 30 square decimeters, ovalize, and anode is 10 square decimeters, is annular.Anode, catholyte are with embodiment one, and current density, temperature and embodiment are together.Drop into the material of 40 kilograms of o-Nitrochlorobenzenes in the groove, electric weight inputs to 1.28 times of dischargings of Theoretical Calculation amount during electrolysis, obtain 31.52 kilogram 2,2 '-dichlorohydrazobenzene.
Embodiment three.
Electrolyzer is 0.6 meter * 0.2 meter * 0.4 meter a rectangular reactor (see figure 4), and material is a glass reinforced plastic.Cathode area is 24 square decimeters.Anode is 8 square decimeters, and other conditions are with embodiment one.The material amount that drops into electrolyzer is 15 kilograms of o-nitrochlorobenzenes, and electric weight inputs to 1.35 times of Theoretical Calculation amount during electrolysis, obtains 11.46 kilograms of dichlorohydrazobenzenes.
Its amino value of the product that is made by aforesaid method is greater than 70%, acid number about 21%, and moisture content is less than 9%, and yield reaches 80%.With this products production benzidine yellow pigment, every index such as color and luster all meets international standards.
In sum as seen, the present invention is than two one-step electrolysis reduction method yield height, and electrolysis is low, and the facility investment expense is few, and technological operation is simple, and processing condition are not harsh, thereby are applicable to suitability for industrialized production.
Claims (8)
1, a kind of 3,3 '-dichloro-4,4,4 '-electrolytic preparation method of diaminobenzidine, it comprises electrolytic reduction and two steps of position rotaring rearrangement reaction, it is characterized in that being reduced to 2 by o-nitrochlorobenzene, 2 '-dichlorohydrazobenzene be in diaphragm sell in basic solution an one-step electrolysis form, its anolyte is 20～60% the NaOH aqueous solution, catholyte is 5～15%NaOH aqueous solution, electrolytic potential is 3～25 volts, current density is 0.1～10 ampere every square decimeter, and electrolysis temperature is 30～100 ℃.
2, electrolytic preparation method as claimed in claim 1 is characterized in that electrolytic potential is 4～6 volts.
3, electrolytic preparation method as claimed in claim 1 or 2 is characterized in that electrolysis temperature is 70～90 ℃.
4, a kind of in order to prepare 3,3 '-dichloro-4,4,4 '-diaminobenzidine is at electrolyzer, this electrolyzer is made up of cell body 1, anode 2, negative electrode 3, barrier film 4 and agitator 5, it is characterized in that having on the negative electrode 3 aperture 6, anode material is an antimonial lead, and membrane pore size is 0.5 μ～80 μ.
5, electrolyzer as claimed in claim 4 is characterized in that diaphragm material is a diamond spar.
6, electrolyzer as claimed in claim 4 is characterized in that the aperture on the negative electrode is 2～10 millimeters, and percentage of open area is 30～40%.
7, electrolyzer as claimed in claim 4 is characterized in that the circle that is shaped as, ellipse or the rectangle of groove.
8, electrolyzer as claimed in claim 4, the hole that it is characterized in that cathode aperture along on the hole sheet that stays when being connected with punching.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90109751.9A CN1015272B (en) | 1990-12-11 | 1990-12-11 | Electrolytic preparation method and equipment of 3, 3 '-dichloro 4, 4' -diaminobenzidine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90109751.9A CN1015272B (en) | 1990-12-11 | 1990-12-11 | Electrolytic preparation method and equipment of 3, 3 '-dichloro 4, 4' -diaminobenzidine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1051402A CN1051402A (en) | 1991-05-15 |
| CN1015272B true CN1015272B (en) | 1992-01-01 |
Family
ID=4881580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90109751.9A Expired CN1015272B (en) | 1990-12-11 | 1990-12-11 | Electrolytic preparation method and equipment of 3, 3 '-dichloro 4, 4' -diaminobenzidine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1015272B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105102682A (en) * | 2013-03-07 | 2015-11-25 | 赢创德固赛有限公司 | Electrochemical coupling of anilines |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597765B (en) * | 2008-06-02 | 2012-12-19 | 汉能科技有限公司 | 2,2'-dichlorohydrazobenzene preparation method and special electrolytic tank thereof |
| CN102329242A (en) * | 2011-07-13 | 2012-01-25 | 盐城市瓯华化学工业有限公司 | Method for salifying to prepare 3, 3'-dichlorobenzidine hydrochloride by using inorganic chloride |
| CN102321891A (en) * | 2011-09-19 | 2012-01-18 | 北京化工大学 | High-yield electrochemical method for synthesizing 2,2'-dichlorohydrazobenzene |
| CN103938220B (en) * | 2014-04-29 | 2016-08-24 | 北京化工大学 | Electrolysis prepares method and the electrolysis unit of hydrodiazo benzene-like compounds |
| CN112501641B (en) * | 2020-11-30 | 2021-09-03 | 苏州大学张家港工业技术研究院 | Method for preparing azobenzene and azoxybenzene compounds through electrocatalysis |
-
1990
- 1990-12-11 CN CN90109751.9A patent/CN1015272B/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105102682A (en) * | 2013-03-07 | 2015-11-25 | 赢创德固赛有限公司 | Electrochemical coupling of anilines |
| TWI588298B (en) * | 2013-03-07 | 2017-06-21 | 贏創德固賽有限責任公司 | Electrochemical coupling of anilines |
| CN105102682B (en) * | 2013-03-07 | 2017-07-04 | 赢创德固赛有限公司 | The galvanic coupling of amino benzenes compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1051402A (en) | 1991-05-15 |
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