CN103266329A - Electrochemical method for synthesizing 2,2'-dichlorohydrazobenzene by use of supported catalyst ionic membrane - Google Patents
Electrochemical method for synthesizing 2,2'-dichlorohydrazobenzene by use of supported catalyst ionic membrane Download PDFInfo
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Abstract
The invention relates to an electrochemical method for synthesizing 2,2'-dichlorohydrazobenzene by use of a supported catalyst ionic membrane. The method is used for preparing a catalyst which is supported on an ionic exchange membrane, so that the membrane has a higher hydrogen generation rate, the ionic exchange capacity is increased, and the electrochemical performance of the ionic exchange membrane is optimized. The ionic exchange membrane is applied to a reaction of electrochemical synthesis of 2,2'-dichlorohydrazobenzene from o-chloronitrobenzene; an electrolytic tank is separated into a cathode chamber and an anode chamber by the supported catalyst ionic exchange membrane; a sodium hydroxide solution is added into the cathode chamber and the anode chamber; the raw material o-chloronitrobenzene generates a reduction reaction in the cathode chamber; the supported catalyst ionic membrane realizes a great effect on promoting the increase of the hydrogen generation rate in the reducing process, and the reaction efficiency is improved; and the method provided by the invention has the characteristics of short technological process and high product yield.
Description
Technical field
The present invention relates to a kind of employing supported catalyst ionic membrane synthetic 2, the electrochemical method of 2 '-dichlorohydrazobenzene, belong to the synthetic field of organic electrochemistry, be specifically related to adopt supported catalyst electrolysis with ion-exchange film reduction o-chloronitrobenzene to generate 2, the electrochemical method of 2 '-dichlorohydrazobenzene.
Background technology
2,2 '-dichlorohydrazobenzene (DHB) is in the strongly-acid medium, intramolecular rearrangement takes place generate 3,3 '-dichlorobenzidine (DCB), this material is the intermediate of serial yellow dyess such as permanent yellow HR, diarylide yellow and benzidine yellow G, and this serial organic dye occupies about 25% of organic dye total amount, because it is widely used, moderate cost, so development prospect is very wide.3,3 '-synthetic route of dichlorobenzidine is relatively clearer and more definite, by o-chloronitrobenzene hydrogenating reduction synthetic 2 in alkaline medium, 2 '-dichlorohydrazobenzene, the latter under the effect of inorganic acid (hydrochloric acid or sulfuric acid), position rotaring rearrangement takes place generate 3,3 '-dichlorobenzidine.
The preparation method of DHB mainly contains zinc/iron powder method, the shortening method, electrolytic reduction etc., along with the environmental problem that becomes increasingly conspicuous and the labor cost that rises steadily, preparation method originally exists seriously polluted, complicated operation, and potential safety hazard is many, shortcomings such as noble metal catalyst cost height, its application and development are more and more limited to.Electrochemical reducing based on ionic membrane has clean environment firendly, and the three wastes produce few, and advantages such as reaction conditions gentleness more and more are subjected to investigator's favor.
The zinc powder method is to be applied in the method that industrial reduction o-chloronitrobenzene is produced DHB the earliest.At first o-chloronitrobenzene is reduced to DOB in alkaline medium, conditions such as the concentration of re-adjustment alkali and temperature further are reduced into DHB with DOB.At last product D HB is separated, produces DHB technology comparative maturity in this way, and processing simple relatively, but the problem that exists is long reaction time, labour intensity is big; And developed with cheap iron powder replacement zinc powder, this process application is extensive, technology maturation, and raw material is cheap and easy to get.But this method labour intensity is big, and toxicity is big, and three wastes discharge capacity is big, difficult solvent recovery, and environmental pollution is serious, and the result is also not really desirable.
The shortening method mainly is to use precious metal to make catalyzer, and autoclave is made reaction vessel, and solvent is benzene, toluene etc., and reductive agent is hydrogen.Patent US4217307 thinks that adding the naphthoquinone derivative in reaction makes reduction accelerator, and toluene is solvent, and the DHB yield is 80%～90%.It is catalyzer that patent CN1594286A adopts the nickel system, is reaction medium with alkaline condition, alcohols and aromatic hydrocarbons mixed solvent, and hydrogenating reduction prepares 2,2 '-dichlorohydrazobenzene.This invention replaces noble metal catalyst with common nickel system, reduced production cost, but the total recovery of resultant is lower, unsuitable industrial applications.The shortening method has many advantages: not with an organic solvent, product is easy to separate; Hydrogen is pollution-free, the product yield height.But its technical requirements is higher, and because using noble metal catalyst, cost is higher.
Patent CN1051402A discloses a kind of usefulness one one-step electrolysis method the o-nitrochlorobenzene electrolytic reduction has been become the method and apparatus of dichlorohydrazobenzene, and then generates 3 with rearrangement reaction, 3 '-dichloro-4,4,4 '-diaminobenzidine.Its electrolytic preparation method comprises two-step reaction, be respectively two steps of electrolytic reduction and position rotaring rearrangement reaction, it is characterized in that by the o-nitrochlorobenzene reductase 12,2 '-dichlorohydrazobenzene be in the diaphragm electrolyzer in basic solution an one-step electrolysis form, its anolyte is 20～60% sodium hydroxide solution, catholyte is 5～15% sodium hydroxide solution, electrolytic potential is 3～25V, current density is every square decimeter of 0.1～10A, electrolysis temperature is 30～100 ℃, and preferred temperature is 70～90 ℃.Its diaphragm for electrolytic cell that adopts is round shape, and material is to fire the diamond spar that forms, and the material of cathode-anode plate is respectively stainless steel and antimonial lead; Though diamond spar is more heat-resisting and strength and toughness is high, its chemical property is poor slightly, and ion sees through ability and selective power all not as ion-exchange membrane, and internal resistance is bigger; Secondly because stainless steel plate hydrogen-evolution overpotential in the electrolytic reduction reaction is high and easily generate metal oxide thereby be attached on the pole plate and be dissolved in the solution, reduce current efficiency, increased power consumption, improved production cost.
It is a kind of 2 that patent CN101597765A discloses, and the preparation method of 2 '-dichlorohydrazobenzene mainly may further comprise the steps: cathode can alkali lye is preheating 15-35min under 30-60 ℃ of condition, feeds electric current 1-2.5A/dm earlier
2The current activation pole plate, and then reactant o-chloronitrobenzene, toluene and promotor joined in the cathode can, stir, connecting voltage is the power supply of 1.42-2.65V, electrolytic current density is 1-5A, electrolysis temperature is 50-80 ℃.It adopts the time-dependent current method on industrial application power-supply unit to be had relatively high expectations, and has increased production cost; It is very little to the product yield influence to add promotor in reaction, purifies for the volume increase product and has added difficulty; Adopt the method that feeds electric current earlier, have bubble at the cathode-anode plate place and produce, if the untimely discharge of bubble can increase the transport resistance of proton, strengthened reaction mechanism, reduce current efficiency, bath voltage is raise; Design of electrolysis cells is open system, and to add toluene at high temperature volatile in institute, contaminate environment and increased material cost; Cathode material is selected the nickel plate for use, is unfavorable for catalyst cupport and less with the reactant real contact area, and production efficiency reduces.
Patent CN102321891A discloses a kind of with o-nitrochlorobenzene reduction generation 2, the electrochemical method of 2 '-dichlorohydrazobenzene.The perfluorinated sulfonic acid ionic membrane that this method will only allow positively charged ion to pass through is separated the negative and positive district, catalyst P bO is attached on the electrode with the coating form, select the good pole plate of electric property for use, optimize the electrochemical synthesis condition, in cathodic area o-nitrochlorobenzene generation reduction reaction, generate 2,2 '-dichlorohydrazobenzene.Negative plate is selected nickel foam for use, and positive plate adopts sintering iridium titanium plate, and the cathode-anode plate spacing is selected 2mm, current density 500A/m
2, 80 ℃ of electrolysis temperatures are taked pump Recycle design dispersing and mixing liquid in closed system.Shortened reaction mechanism greatly, reduced production cost, the product purity height.This method have than conventional chemical reduction method simplify technology, cut down the consumption of energy, advantages such as product yield height and stable in properties.It adopts with the pump Recycle design and replaces mechanical stirring very little to the product yield influence; And negative plate selection use nickel foam working life is shorter, for realizing difficulty of industrialization; Current density is higher in the reaction process, and these have all increased power consumption, have improved production cost.
Summary of the invention
The electrochemical method of synthetic 2, the 2 '-dichlorohydrazobenzene of advantage such as the object of the present invention is to provide that a kind of technical process is short, product yield is high and production cost is low.
A kind of employing supported catalyst ionic membrane synthesizes 2, and the electrochemical method of 2 '-dichlorohydrazobenzene is characterized in that step is as follows:
At first graphite is prepared into graphene oxide Graphene, with sodium ascorbate VC the mixing solutions of graphene oxide and Platinic chloride is reduced, the ratio that is prepared into Pt and Graphene quality is the Pt/Graphene catalyzer of 2-4:10; Be perfluorinated sulfonic resin and the N of 5:1 with mass ratio, dinethylformamide mixing solutions and ultrasonic the mixing of Pt/Graphene catalyzer for preparing, described mixing solutions is that 50:1 no longer includes bubble and produces with the mass ratio of the Pt/Graphene catalyzer for preparing in solution; Next adopts the casting method knifing; Tetrafluoroethylene screen cloth after the removal of impurities is tiled on the sheet glass, utilizes the mixing solutions that configures to carry out knifing; Be prepared into the metal platinum charge capacity at last and be 20～40% graphene-supported platinum ion exchange membrane;
The supported catalyst ionic membrane is applied to electrochemical synthesis 2, and in 2 '-dichlorohydrazobenzene technology, ion-exchange membrane is close on the positive plate, and separates with silicagel pad between the negative plate; Selecting cathode compartment sodium hydroxide solution mass percent concentration is 5～15%, and anolyte compartment's sodium hydroxide solution mass percent concentration is 25～30%; Catalyzer is yellow lead oxide, bismuthous oxide bismuth trioxide, antimonous oxide or tindioxide, is attached on the negative plate in the electrostatic adhesion mode; Add raw material o-chloronitrobenzene and toluene in cathode compartment, the negative plate material is the titanium plate, and positive plate is stainless steel plate; Current density is 500～1000A/m
2, electrolysis temperature is 70～90 ℃, the time is 5～6 hours; Adopt mechanical stirring to disperse the negative electrode mixed solution.
What the present invention adopted is the ion-exchange membrane of supported catalyst, be that 30% graphene-supported platinum ion exchange membrane is applied to electrochemical synthesis 2 with the metal platinum charge capacity, in 2 '-dichlorohydrazobenzene technology, ion-exchange membrane is close on the positive plate, and separating with silicagel pad between the negative plate, is 12.5% and 30% sodium hydroxide solution at the indoor massfraction that adds respectively of cathode and anode; The catalyzer yellow lead oxide is attached on the cathode titanium plates in the electrostatic adhesion mode, and positive plate is stainless steel plate; In cathode compartment, add raw material o-chloronitrobenzene (o-CNB) and toluene solvant, current density 250A/m
2, 80 ℃ of electrolysis temperatures adopt mechanical stirring to disperse the negative electrode mixed solution, and the DHB yield reaches 96.1%.
Embodiment
Embodiment 1
The preparation of perfluorinated sulfonic acid ion exchange membrane:
Be perfluorinated sulfonic resin and the N of 5:1 with the 5g mass ratio at first, the dinethylformamide mixing solutions is ultrasonic to mix, and no longer includes bubble and produce in solution.With specification be the polytetrafluoroethylene (PTFE) screen cloth of 8cm * 10cm under 80 ℃ water bath condition, be earlier 3% H with massfraction
2O
2Solution soaking 30min uses the H of 0.5mol/L again
2SO
4Solution soaking 30min puts into loft drier at last and carries out drying treatment.Next adopts the casting method knifing, and pretreated PTFE screen cloth is tiled on the sheet glass, utilizes the mixing solutions that configures to carry out knifing.Be prepared into perfluorinated sulfonic acid ion exchange membrane at last.
Perfluorinated sulfonic acid ion exchange membrane is applied to electrochemical synthesis 2, in 2 '-dichlorohydrazobenzene technology, ion-exchange membrane is close on the positive plate, and separates with silicagel pad between the negative plate, is 5% and 25% sodium hydroxide solution at the indoor massfraction that adds respectively of cathode and anode; Catalyzer yellow lead oxide (1.64g) is attached on the cathode titanium plates in the electrostatic adhesion mode, and positive plate is stainless steel plate; In cathode compartment, add raw material o-chloronitrobenzene (o-CNB) 10.90g and 44ml toluene solvant, current density 250A/m
2, 80 ℃ of electrolysis temperatures adopt mechanical stirring to disperse the negative electrode mixed solution, and the DHB yield reaches 91.96%.
Embodiment 2
The modification of perfluorinated sulfonic acid ion exchange membrane:
At first graphite is prepared into graphene oxide (Graphene), use sodium ascorbate (VC) that the mixing solutions of graphene oxide and Platinic chloride is reduced again, the ratio that is prepared into Pt and Graphene quality is the Pt/Graphene catalyzer of 3:10, and its size is 1.99nm; Be perfluorinated sulfonic resin and the N of 5:1 with the 5g mass ratio, ultrasonic the mixing of Pt/Graphene catalyzer that dinethylformamide mixing solutions and 0.1g prepare no longer includes bubble and produces in solution.Next adopts the casting method knifing.Tetrafluoroethylene screen cloth after the removal of impurities is tiled on the sheet glass, utilizes the mixing solutions that configures to carry out knifing.Be prepared into the metal platinum charge capacity at last and be 30% graphene-supported platinum ion exchange membrane.
Graphene-supported platinum ion exchange membrane is applied to electrochemical synthesis 2, in 2 '-dichlorohydrazobenzene technology, is 5% and 25% sodium hydroxide solution at the indoor massfraction that adds respectively of cathode and anode; Catalyzer yellow lead oxide (1.64g) is attached on the cathode titanium plates in the electrostatic adhesion mode, and the DHB yield reaches 96.1%.
Embodiment 3
The modification of perfluorinated sulfonic acid ion exchange membrane:
At first graphite is prepared into graphene oxide (Graphene), use sodium ascorbate (VC) that the mixing solutions of graphene oxide and Platinic chloride is reduced again, the ratio that is prepared into Pt and Graphene quality is the Pt/Graphene catalyzer of 2:10, and its size is 4.58nm; Be perfluorinated sulfonic resin and the N of 5:1 with the 5g mass ratio, ultrasonic the mixing of Pt/Graphene catalyzer that dinethylformamide mixing solutions and 0.1g prepare no longer includes bubble and produces in solution.Next adopts the casting method knifing.Tetrafluoroethylene screen cloth after the removal of impurities is tiled on the sheet glass, utilizes the mixing solutions that configures to carry out knifing.Be prepared into the metal platinum charge capacity at last and be 20% graphene-supported platinum ion exchange membrane.Graphene-supported platinum ion exchange membrane is applied to electrochemical synthesis 2, and in 2 '-dichlorohydrazobenzene technology, the DHB yield reaches 95.4%.
Embodiment 4
The modification of perfluorinated sulfonic acid ion exchange membrane:
At first graphite is prepared into graphene oxide (Graphene), use sodium ascorbate (VC) that the mixing solutions of graphene oxide and Platinic chloride is reduced again, the ratio that is prepared into Pt and Graphene quality is the Pt/Graphene catalyzer of 4:10, and its size is 6.17nm; Be perfluorinated sulfonic resin and the N of 5:1 with the 5g mass ratio, ultrasonic the mixing of Pt/Graphene catalyzer that dinethylformamide mixing solutions and 0.1g prepare no longer includes bubble and produces in solution.Next adopts the casting method knifing.Tetrafluoroethylene screen cloth after the removal of impurities is tiled on the sheet glass, utilizes the mixing solutions that configures to carry out knifing.Graphene-supported platinum ion exchange membrane is applied to electrochemical synthesis 2, and in 2 '-dichlorohydrazobenzene technology, the DHB yield reaches 94.83%.
Embodiment 5
Be that 30% graphene-supported platinum ion exchange membrane is applied to electrochemical synthesis 2 with the metal platinum charge capacity, in 2 '-dichlorohydrazobenzene technology, ion-exchange membrane is close on the positive plate, and separating with silicagel pad between the negative plate, is 12.5% and 25% sodium hydroxide solution at the indoor massfraction that adds respectively of cathode and anode; Catalyzer yellow lead oxide (1.64g) is attached on the cathode titanium plates in the electrostatic adhesion mode, and positive plate is stainless steel plate; In cathode compartment, add raw material o-chloronitrobenzene (o-CNB) 10.90g and 44ml toluene solvant, current density 250A/m
2, 80 ℃ of electrolysis temperatures adopt mechanical stirring to disperse the negative electrode mixed solution, and the DHB yield reaches 93.57%.
Embodiment 6
Be that 30% graphene-supported platinum ion exchange membrane is applied to electrochemical synthesis 2 with the metal platinum charge capacity, in 2 '-dichlorohydrazobenzene technology, ion-exchange membrane is close on the positive plate, and separating with silicagel pad between the negative plate, is 7.5% and 30% sodium hydroxide solution at the indoor massfraction that adds respectively of cathode and anode; Catalyzer yellow lead oxide (1.64g) is attached on the cathode titanium plates in the electrostatic adhesion mode, and positive plate is stainless steel plate; In cathode compartment, add raw material o-chloronitrobenzene (o-CNB) 10.90g and 44ml toluene solvant, current density 250A/m
2, 80 ℃ of electrolysis temperatures adopt mechanical stirring to disperse the negative electrode mixed solution, and the DHB yield reaches 95.55%.
The electrochemical synthesis experiment of table 1 embodiment 1-4
Above-mentioned synthetic 2 with reference to the electrochemical reducing of embodiment, the detailed description that 2 '-dichlorohydrazobenzene carries out is illustrative rather than determinate, therefore in the variation and the modification that do not break away under the general plotting of the present invention, should belong within protection scope of the present invention.
Claims (1)
1. one kind is adopted the supported catalyst ionic membrane to synthesize 2, and the electrochemical method of 2 '-dichlorohydrazobenzene is characterized in that step is as follows:
At first graphite is prepared into graphene oxide Graphene, with sodium ascorbate VC the mixing solutions of graphene oxide and Platinic chloride is reduced, the ratio that is prepared into Pt and Graphene quality is the Pt/Graphene catalyzer of 2-4:10; With perfluorinated sulfonic resin and N, dinethylformamide mixing solutions and ultrasonic the mixing of Pt/Graphene catalyzer for preparing no longer include bubble and produce in solution; Next adopts the casting method knifing; Tetrafluoroethylene screen cloth after the removal of impurities is tiled on the sheet glass, utilizes the mixing solutions that configures to carry out knifing; Be prepared into the metal platinum charge capacity at last and be 20～40% graphene-supported platinum ion exchange membrane;
The supported catalyst ionic membrane is applied to electrochemical synthesis 2, and in 2 '-dichlorohydrazobenzene technology, ion-exchange membrane is close on the positive plate, and separates with silicagel pad between the negative plate; Selecting cathode compartment sodium hydroxide solution mass percent concentration is 5～15%, and anolyte compartment's sodium hydroxide solution mass percent concentration is 25～30%; Catalyzer is yellow lead oxide, bismuthous oxide bismuth trioxide, antimonous oxide or tindioxide, is attached on the negative plate in the electrostatic adhesion mode; Add raw material o-chloronitrobenzene and toluene in cathode compartment, the negative plate material is the titanium plate, and positive plate is stainless steel plate; Current density is 200～1000A/m
2, electrolysis temperature is 70～90 ℃, the time is 5～8 hours; Adopt mechanical stirring to disperse the negative electrode mixed solution.
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Cited By (3)
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| CN104646042A (en) * | 2015-03-05 | 2015-05-27 | 吉首大学 | Pt@BiPO4/GR high-efficiency visible light catalysis composite nano fiber and preparation method thereof |
| CN104846395A (en) * | 2015-06-02 | 2015-08-19 | 淮阴工学院 | Synthesis method of 3,4-dichloroaniline |
| CN112126940A (en) * | 2019-06-24 | 2020-12-25 | 天津大学 | Electrochemical selective reduction method of nitrobenzene |
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| WO2012088681A1 (en) * | 2010-12-29 | 2012-07-05 | 海洋王照明科技股份有限公司 | Pt/graphene catalyst, preparation method and use thereof |
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| WO2012088681A1 (en) * | 2010-12-29 | 2012-07-05 | 海洋王照明科技股份有限公司 | Pt/graphene catalyst, preparation method and use thereof |
| CN102274724A (en) * | 2011-05-16 | 2011-12-14 | 浙江大学 | High-activity catalyst used in hydrogenation reaction of aromatic nitro-compound and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104646042A (en) * | 2015-03-05 | 2015-05-27 | 吉首大学 | Pt@BiPO4/GR high-efficiency visible light catalysis composite nano fiber and preparation method thereof |
| CN104646042B (en) * | 2015-03-05 | 2015-10-28 | 吉首大学 | Pt@BiPO 4/ GR efficient visible light catalysis composite nano fiber and preparation method thereof |
| CN104846395A (en) * | 2015-06-02 | 2015-08-19 | 淮阴工学院 | Synthesis method of 3,4-dichloroaniline |
| CN112126940A (en) * | 2019-06-24 | 2020-12-25 | 天津大学 | Electrochemical selective reduction method of nitrobenzene |
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Application publication date: 20130828 |