CN1817455A - Production of 3,4-dichloroaniline catalyst with 3,4-mirbane oil dichloride hydrogenation - Google Patents
Production of 3,4-dichloroaniline catalyst with 3,4-mirbane oil dichloride hydrogenation Download PDFInfo
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- CN1817455A CN1817455A CN 200610049942 CN200610049942A CN1817455A CN 1817455 A CN1817455 A CN 1817455A CN 200610049942 CN200610049942 CN 200610049942 CN 200610049942 A CN200610049942 A CN 200610049942A CN 1817455 A CN1817455 A CN 1817455A
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Abstract
A catalyst for preparing 3,4-dichlorophenylamine from 3,4-dichloronitrobenzene by hydrogenating is prepared through immersing activated carbon in the aqueous solution of potassium (or sodium) halide, washing until no halogen ions, immersing it in the aqueous solution of H2PdCl4, regulating pH value, filtering, washing filtered cake, reducing to obtain neutral product, and drying. It has high catalytic activity and selectivity.
Description
(1) technical field
The present invention relates to a kind ofly be used for 3,4-dichloronitrobenzene catalytic hydrogenation preparation 3, the palladium carbon catalyst preparation method of 4-dichloroaniline particularly is applicable to 3,4-dichloronitrobenzene catalytic hydrogenation preparation 3, the processing method of the palladium activated-carbon catalyst of 4-dichloroaniline.
(2) background technology
3, the 4-dichloroaniline is a kind of important agricultural chemicals and dyestuff intermediate, is widely used in herbicide such as synthetic Stam F-34, linuron, diuron, swep and azo dyes etc., also is the raw material of producing bacteriostatic agent 3,4,4 '-trichlorocarbanilide.Usually pass through 3 by chemical reduction method, electrolytic reduction, catalytic hydrogenating reduction method, 4-dichloronitrobenzene reduction preparation 3,4-dichloroaniline.Adopt iron powder reducing method or the preparation of the chemical reduction methods such as sodium sulfide reducing method under alkali condition 3 under the acid condition, though 4-dichloroaniline cost is lower, but produce a large amount of amine toxic metals residue or hydrochloric high concentrated organic wastewaters of containing, handle very difficult, serious environment pollution.Electrolytic reduction can not be realized industrialization because the restriction of factors such as electrode material, electrolysis installation, cost rests on conceptual phase always.
The catalytic hydrogenating reduction method has eco-friendly characteristics, is considered to a kind of green chemical industry production technology.But, 3,4-dichloronitrobenzene catalytic hydrogenation synthetic 3, in the 4-dichloroaniline course of reaction, the side reaction of C-Cl key hydrogenolysis-dehalogenation may take place also, generate accessory substances such as monochloro-benzene amine and aniline, reduce the quality of product, the hydrogen chloride meeting etching apparatus that dehalogenation side reaction simultaneously generates etc.As Lin Shuzhi report [Lin Shuzhi, dye industry, 2002 (6): vol39 (3): 23-25] use Raney's nickel catalyst, at 3-4MPa, 60-70 ℃, catalyst amount is 7.5% of a nitrobenzene, the ratio of dichloronitrobenzene and ethanol is 1: reacts under the condition of 1-1.5 (weight ratio), and 3, the conversion ratio of 4-dichloronitrobenzene is 100%, but total amine content is 96%, 3 in the product, the content of 4-dichloroaniline＜90%.Therefore, the key of catalytic hydrogenating reduction method is to improve product 3, the selectivity of 4-dichloroaniline.Generally adopt at present in the catalytic hydrogenation system to add and reach the purpose that suppresses dechlorination such as dechlorination inhibitor such as the organic amine of morpholine, pKb＜3 or triphenyl phosphate, triphenyl phosphorous acid, alkalinity additive, formamidine salt, thiazoles.[Hu drags flat, Chen Hongbo, petrochemical industry to drag the equality report recklessly, 31 (1) (2002) 6-9] use Raney's nickel catalyst and methyl alcohol to be solvent, add dechlorination inhibitor 0.1g, at 1.0MPa, 80 ℃, catalyst amount is 10% of a nitrobenzene, dissolves in 3 of 5g in 30ml methyl alcohol, react 90min under the condition of 4-dichloronitrobenzene, in the product 3, the selectivity of 4-dichloroaniline is greater than 99%, and the mass percent of dechlorination amount is less than 2%, yield is greater than 96%, and conversion ratio is 100%.Japan Patent [JP 48-49729 (1973)] adopts Ru-Pt/C adding under the dechlorination inhibitor situation as catalyst, and in the product 3, the selectivity of 4-dichloroaniline can reach 96.3%.European patent [Eur EP0421878 (1991)] report adopts Pt/Al
2O
3Adding under the dechlorination inhibitor situation as catalyst, in the product 3, the selectivity of 4-dichloroaniline is 99.5%.When Deutsche Bundespatent [Ger.DE 392,8329] report adopts Pt-Ni/C as catalyst under the situation of adding the dechlorination inhibitor, 3, the selectivity of 4-dichloroaniline is 99%.United States Patent (USP) [US 5120875 (1992)] report adopts Pt-Ni-Co/C as catalyst, under the situation of adding the dechlorination inhibitor, and 3, the selectivity of 4-dichloroaniline is 99%.Adding dehalogenation inhibitor can improve the selectivity of reaction, but has reduced the quality of product in reaction system behind the introducing dechlorination inhibitor, has improved production cost.
Therefore, industrial exploitation high-selectivity catalyst suppresses 3,4-dichloronitrobenzene hydrogenation preparing 3, and the dehalogenation in the 4-dichloroaniline course of reaction is very important.Under the situation of not adding the dechlorination inhibitor, by 3, the also existing report of the technology of the synthetic aniline of 4-dichloronitrobenzene highly selective.United States Patent (USP) [US 4760187 (1988)] report adopts Ru-Pt-Ni-Cr/C as catalyst, and 3, the selectivity of 4-dichloroaniline is 98%.But this patented technology adopts quaternary active component, the catalyst preparation process complexity, and also the recovery of precious metals pt, Ru is very difficult.Chinese patent [CN200510050594.8] is with Ru-Fe/Al
2O
3As catalyst, 3, the selectivity of 4-dichloroaniline is 99.3%.But this patented technology is used the two-element active component, equally also exists the preparation process complexity; Owing to use three oxygen, two aluminium to cause the cost recovery of noble metal Ru to be increased as carrier.Chinese patent [CN02148509.7] respectively with Pd/NCT and Pt/NCT as catalyst, 3, the selectivity of 4-dichloroaniline is respectively 99.2% and 99%, but use carbon nanotube as carrier, costing an arm and a leg etc. of carrier, this patented technology will depend on the cost of carbon nanotube in industrial application prospect.
(3) summary of the invention
The purpose of this invention is to provide and a kind ofly be used for 3,4-dichloronitrobenzene hydrogenation preparing 3, the preparation method of the palladium carbon catalyst of 4-dichloroaniline, treated palladium activated-carbon catalyst is specially adapted to 3,4-dichloronitrobenzene hydrogenation preparing 3,4-dichloroaniline, not only has the selectivity height, and preparation is simple and environmental friendliness, and precious metal palladium reclaims easily, is applicable to commercial Application.
The technical solution used in the present invention is as follows: a kind of 3,4-dichloronitrobenzene catalytic hydrogenation preparation 3, the Preparation of catalysts method of 4-dichloroaniline, described catalyst is the palladium activated-carbon catalyst, described palladium activated-carbon catalyst preparation method is: earlier with active carbon with potassium halide or sodium halide aqueous solution impregnation process, filtration washing is to halogen-free ion, again with above active carbon palladium-impregnated compound H then
2PdCl
4The aqueous solution, regulator solution pH value preferably transfers to alkalescent with the pH value to alkalescence, filters, and filter cake is washed to neutrality, and filter cake is reduced with reducing agent, the neutral products that obtains, drying promptly gets the palladium activated-carbon catalyst, and the halogen ion in described potassium halide or the sodium halide is F
-, Cl
-, Br
-Or I
-The most palladium grain diameter of the palladium activated-carbon catalyst of treated mistake is 20～30nm.
Further, described active carbon washs to halogen-free ion with potassium halide or sodium halide aqueous solution impregnation process, is that active carbon is made into slurries, is that 1-10wt% adds palladium compound H by the palladium loading
2PdCl
4The aqueous solution.
Further, the specific area of the carrier active carbon of described palladium activated-carbon catalyst is 1300-1700m
2/ g.
Further, described potassium halide solution is liquor kalii iodide, and concentration is 0.125-10mol/l.
Further, described reducing agent is a hydrazine hydrate solution, preferred 85% hydrazine hydrate solution, and described reduction is that filter cake is made into slurries, drips hydrazine hydrate solution, stirs, and filters, and obtains filter cake.
Further, described palladium activated-carbon catalyst specifically adopts laxative remedy to make: active carbon washs to there not being iodide ion with KI or sodium iodide aqueous solution impregnation process, active carbon is made into slurries, is that 1-10wt% is with above active carbon slurry palladium compound H by the palladium loading
2PdCl
4The aqueous solution, the regulator solution alkalescent as the pH value is transferred to 7.1～9, is filtered, and the filter cake water washing is reduced filter cake to neutral with hydrazine hydrate solution, the neutral products that obtains, drying promptly gets the palladium activated-carbon catalyst.
More specifically, described palladium activated-carbon catalyst adopts laxative remedy to make: take by weighing active carbon, the specific area of active carbon is 1600m
2/ g, active carbon are immersed in the KI solution that concentration is 2.5mol/l 4～8 hours, filter, and spend deionised water and do not detect to there being iodide ion, and above-mentioned active carbon is mixed with the slurries of 60～90 ℃ of temperature, are that 1～5wt% slowly drips H by the palladium loading
2PdCl
4Solution stirs, again with 10%NaOH solution regulator solution pH value to 7.1～9, and cool the temperature to room temperature, filter, filter cake spends deionised water to neutral, again filter cake is configured to slurries under 30 ℃, drip 85% hydrazine hydrate solution, stir, filter, filter cake spends deionised water to neutral, at last in room temperature in air through preliminarily dried, get wet sample and promptly get described palladium activated-carbon catalyst.Palladium activated-carbon catalyst through handling like this more than 90% the palladium grain diameter be 20～30nm, preferably the palladium grain diameter of palladium activated-carbon catalyst more than 90% is 25nm.
Above-described 3,4-dichloronitrobenzene catalytic hydrogenation preparation 3, the 4-dichloroaniline is meant with 3, the 4-dichloronitrobenzene is a raw material, under the effect of palladium activated-carbon catalyst and hydrogen, in the fatty alcohol organic solvent of C1～C2, in 60～130 ℃ reaction temperature, 0.8 reaction generates 3 under the～2.0MPa reaction pressure, the 4-dichloroaniline.Usually described 3, the mass volume ratio of 4-dichloronitrobenzene and fatty alcohol is 1: 1.5～15, and described palladium activated-carbon catalyst consumption is 3,0.5～5% of 4-dichloronitrobenzene quality, described fatty alcohol organic solvent methyl alcohol or ethanol.
Be noted that main points of the present invention are that the palladium activated-carbon catalyst is that to make the most palladium grain diameter of palladium activated-carbon catalyst after treatment be 20～30nm.Such palladium activated-carbon catalyst is specially adapted to 3,4-dichloronitrobenzene catalytic hydrogenation preparation 3,4-dichloroaniline.
Described 3,4-dichloronitrobenzene catalytic hydrogenation preparation 3, the method of 4-dichloroaniline is specific as follows: add through the present invention in autoclave and handle the palladium activated-carbon catalyst that makes, amount is 3,1% of 4-dichloronitrobenzene quality, with raw material 3, the mass ratio of 4-dichloronitrobenzene and solvent methanol is that 0.3: 1 mixing material joins in the described reactor, the off-response device, go out air in the reactor with nitrogen replacement, then with hydrogen exchange nitrogen and to adjust reaction temperature be 80 ℃, reaction pressure is 1.0MPa, begin to stir, isothermal reaction stops reaction till not inhaling hydrogen, take out the product liquid that described reaction obtains, filter out catalyst and remove excessive methyl alcohol and promptly obtain 3, the 4-dichloroaniline.
The present invention compared with prior art, the present invention can't have influence on the quality of product owing to do not add the dehalogenation inhibitor, and single active constituent catalyst preparation process of palladium active carbon is simple, adopt active carbon to do carrier, just be easy to reclaim noble metal by burning the charcoal carrier.The present invention simultaneously uses the potassium halide or the sodium halide aqueous solution, and particularly KI is handled active carbon, and potassium iodide aqueous solution can recycle, and has overcome the shortcoming that common employing nitric acid pretreatment absorbent charcoal carrier produces a large amount of spent acid.Simultaneously, it is also very little to physical arrangement influences such as the specific surface of active carbon and pore structures to handle active carbon with potassium iodide aqueous solution.Use potassium iodide aqueous solution to handle active carbon, introduce the anionic part or the group of inorganic agent self at activated carbon surface, therefore the kind of group is single, and can control the quantity of the group of introducing on the activated carbon surface exactly by the concentration that changes liquor kalii iodide.Interaction by these functional ions or group and palladium presoma has determined the dispersity of Metal Palladium at activated carbon surface.Therefore, the present invention can introduce functional ion or the group that needs at activated carbon surface exactly, structure meets 3,4-dichloronitrobenzene catalytic preparation 3, the Metal Palladium decentralized environment that 4-dichloroaniline catalystic converter system requires, the controlled activated carbon supported palladium catalyst of preparation active component particle size satisfies the requirement of this catalystic converter system.The most palladium grain diameter of palladium activated-carbon catalyst of the present invention is 20～30nm.And use nitric acid pretreatment active carbon, be to introduce all kinds of oxy radicals at activated carbon surface, interact by oxy radical and palladium compound presoma and to regulate the size of control Metal Palladium particle size, therefore use oxidisability wet treatment method such as nitric acid to be difficult to control exactly the kind and the quantity of activated carbon surface oxy radical.
The prepared catalyst of the present invention is 3, and 4-dichloronitrobenzene catalytic preparation 3 has obtained to be higher than 99.5% product selectivity in the reaction of 4-dichloroaniline.
In addition, catalyst reusable reduced the use cost of catalyst, also reduces pollution and energy consumption in catalyst recovery, the regenerative process, has important economic value and Significance for Environment.
(4) specific embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment one
Take by weighing the 10g active carbon, the specific area of active carbon is 1600m
2/ g, active carbon are immersed in the KI solution that 120 ml concns are 2.5mol/l 6 hours, filter, and spend deionised water and do not detect to there being iodide ion.Then the active carbon of handling is mixed with the 100ml slurries of 80 ℃ of temperature, slowly drips 4 milliliters H
2PdCl
4Solution (Pd content is 0.05g/ml) stirs 6h, again with 10% NaOH solution regulator solution pH value to alkalescent (pH=8), and cool the temperature to room temperature, filter, the deionized water washing is to neutrality.Unreduced catalyst is configured to the slurries of 150ml under 30 ℃, slowly drips 2 milliliters 85% hydrazine hydrate solution then, continue to stir 2 hours.Catalyst after the reduction after filtration, deionized water washing is to neutral, at last in room temperature in air through preliminarily dried, get wet sample sealing and preserve.Mean size through high power transmissioning electric mirror determining palladium particulate is 26.5nm.
Embodiment two
Take by weighing the 10g active carbon, the specific area of active carbon is 1600m
2/ g, active carbon are immersed in the KI solution that 120 ml concns are 2.5mol/l 6 hours, filter, and spend deionised water and do not detect to there being iodide ion.Then the active carbon of handling is mixed with the 100ml slurries of 80 ℃ of temperature, slowly drips 2 milliliters H
2PdCl
4Solution (Pd content is 0.05g/ml) stirs 6h, and the NaOH solution regulator solution pH value with 10% is to alkalescent (pH=8), and cools the temperature to room temperature, filters, and the deionized water washing is to neutrality.Unreduced catalyst is configured to the slurries of 150ml under 30 ℃, slowly drips 85% hydrazine hydrate solution of 2ml then, continue to stir 2 hours.Catalyst after the reduction after filtration, deionized water washing is to neutral, at last in room temperature in air through preliminarily dried, get wet sample sealing and preserve.Mean size through high power transmissioning electric mirror determining palladium particulate is 23nm.
Embodiment three
Take by weighing the 10g active carbon, the specific area of active carbon is 1600m
2/ g, active carbon are immersed in the KI solution that 120 ml concns are 2.5mol/l 6 hours, filter, and spend deionised water and do not detect to there being iodide ion.Then the active carbon of handling is mixed with the 100ml slurries of 80 ℃ of temperature, slowly drips 6 milliliters H
2PdCl
4Solution (Pd content is 0.05g/ml) stirs 6h, and the NaOH solution regulator solution pH value with 10% is to alkalescent (pH=8), and cools the temperature to room temperature, filters, and the deionized water washing is to neutrality.Unreduced catalyst is configured to the slurries of 150ml under 30 ℃, slowly drips 85% hydrazine hydrate solution of 2ml then, continue to stir 2 hours.Catalyst after the reduction after filtration, deionized water washing is to neutral, at last in room temperature in air through preliminarily dried, get wet sample sealing and preserve.Mean size through high power transmissioning electric mirror determining palladium particulate is 27.1nm.
Embodiment four
Take by weighing the 10g active carbon, the specific area of active carbon is 1400m
2/ g, active carbon are immersed in the KI solution that 120 ml concns are 2.5mol/l 6 hours, filter, and spend deionised water and do not detect to there being iodide ion.Then the active carbon of handling is mixed with the 100ml slurries of 80 ℃ of temperature, slowly drips 4 milliliters H
2PdCl
4Solution (Pd content is 0.05g/ml) stirs 6h, and the NaOH solution regulator solution pH value with 10% is to alkalescent (pH=8), and cools the temperature to room temperature, filters, and the deionized water washing is to neutrality.Unreduced catalyst is configured to the slurries of 150ml under 30 ℃, slowly drips 85% hydrazine hydrate solution of 2ml then, continue to stir 2 hours, catalyst after the reduction after filtration, deionized water washing is to neutral, at last in room temperature in air through preliminarily dried, get wet sample sealing and preserve.Mean size through high power transmissioning electric mirror determining palladium particulate is 26.8nm.
Embodiment five
Take by weighing the 10g active carbon, the specific area of active carbon is 1500m
2/ g, active carbon are immersed in the KI solution that 120 ml concns are 0.625mol/l 6 hours, filter, and spend deionised water and do not detect to there being iodide ion, then the active carbon of handling are mixed with the 100ml slurries of 80 ℃ of temperature, slowly drip 4 milliliters H
2PdCl
4Solution (Pd content is 0.05g/ml) stirs 6h, and the NaOH solution regulator solution pH value with 10% is to alkalescent (pH=8), and cool the temperature to room temperature, filter, the deionized water washing is configured to unreduced catalyst the slurries of 150ml to neutral under 30 ℃, slowly drip 85% hydrazine hydrate solution of 2ml then, continue to stir 2 hours, the catalyst after the reduction after filtration, the deionized water washing is to neutral, at last in room temperature in air through preliminarily dried, get wet sample sealing and preserve.Mean size through high power transmissioning electric mirror determining palladium particulate is 26.5nm.
Embodiment six
Take by weighing the 10g active carbon, the specific area of active carbon is 1600m
2/ g, active carbon are immersed in the KI solution that 120 ml concns are 5.0mol/l 6 hours, filter, and spend deionised water and do not detect to there being iodide ion, then the active carbon of handling are mixed with the 100ml slurries of 80 ℃ of temperature, slowly drip 4 milliliters H
2PdCl
4Solution (Pd content is 0.05g/ml) stirs 6h, and the NaOH solution regulator solution pH value with 10% is to alkalescent (pH=8), and cool the temperature to room temperature, filter, the deionized water washing is configured to unreduced catalyst the slurries of 150ml to neutral under 30 ℃, slowly drip 85% hydrazine hydrate solution of 2ml then, continue to stir 2 hours, the catalyst after the reduction after filtration, the deionized water washing is to neutral, at last in room temperature in air through preliminarily dried, get wet sample sealing and preserve.Mean size through high power transmissioning electric mirror determining palladium particulate is 25.7nm.
Embodiment seven
Take by weighing the 10g active carbon, the specific area of active carbon is 1600m
2/ g, active carbon are immersed in the NaI solution that 120 ml concns are 10.0mol/l 6 hours, filter, and spend deionised water and do not detect to there being iodide ion, then the active carbon of handling are mixed with the 100ml slurries of 80 ℃ of temperature, slowly drip 4 milliliters H
2PdCl
4Solution (Pd content is 0.05g/ml) stirs 6h, and the NaOH solution regulator solution pH value with 10% is to alkalescent (pH=8), and cool the temperature to room temperature, filter, the deionized water washing is configured to unreduced catalyst the slurries of 150ml to neutral under 30 ℃, slowly drip 85% hydrazine hydrate solution of 2ml then, continue to stir 2 hours, the catalyst after the reduction after filtration, the deionized water washing is to neutral, at last in room temperature in air through preliminarily dried, get wet sample sealing and preserve.Mean size through high power transmissioning electric mirror determining palladium particulate is 25.5nm.
Embodiment eight
Take by weighing the 10g active carbon, the specific area of active carbon is 1600m
2/ g, active carbon are immersed in the aqueous solution of nitric acid that 90 ℃ 120 ml concns are 40wt% and refluxed 6 hours, filter, and spend deionised water to neutral, then the active carbon of handling are mixed with the 100ml slurries of 80 ℃ of temperature, slowly drip 4 milliliters H
2PdCl
4Solution (Pd content is 0.05g/ml) stirs 6h, and the NaOH solution regulator solution pH value with 10% is to alkalescent (pH=8), and cool the temperature to room temperature, filter, the deionized water washing is configured to unreduced catalyst the slurries of 150ml to neutral under 30 ℃, slowly drip 85% hydrazine hydrate solution of 2ml then, continue to stir 2 hours, the catalyst after the reduction after filtration, the deionized water washing is to neutral, at last in room temperature in air through preliminarily dried, get wet sample sealing and preserve.Mean size through high power transmissioning electric mirror determining palladium particulate is 13.5nm.
Embodiment nine to embodiment 33 is used for catalytic hydrogenation 3 with the Pd/C catalyst that above-mentioned method for making makes, 4-dichloronitrobenzene preparation 3, and the example of 4-dichloroaniline:
Embodiment nine
In the stainless steel autoclave, add the Pd/C catalyst 0.1g of embodiment one preparation, 3,4-dichloronitrobenzene 10g, absolute methanol 100ml, off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in the reactor, be warming up to 80 ℃, reaction pressure is 1.0MPa, begins to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 30min stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas-chromatography-spectrometer analysis, and each components contents is: 3, and 4-dichloroaniline 100%, monochloro-benzene amine 0%, aniline 0%, 3,4-dichloronitrobenzene 0%.
Embodiment ten
In the stainless steel autoclave, add the Pd/C catalyst 0.1g of embodiment one preparation, 3,4-dichloronitrobenzene 10g, absolute methanol 100ml, off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in the reactor, be warming up to 90 ℃, reaction pressure is 1.0MPa, begins to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 30min stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas-chromatography-spectrometer analysis, and each components contents is: 3, and 4-dichloroaniline 100%, monochloro-benzene amine 0%, aniline 0%, 3,4-dichloronitrobenzene 0%.
Embodiment 11
In the stainless steel autoclave, add the Pd/C catalyst 0.1g of embodiment one preparation, 3,4-dichloronitrobenzene 10g, absolute methanol 100ml, off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in the reactor, be warming up to 100 ℃, reaction pressure is 1.0MPa, begins to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 30min stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas-chromatography-spectrometer analysis, and each components contents is: 3, and 4-dichloroaniline 99.80%, monochloro-benzene amine 0.20%, aniline 0%, 3,4-dichloronitrobenzene 0%.
Embodiment 12
In the stainless steel autoclave, add the Pd/C catalyst 0.2g of embodiment one preparation, 3,4-dichloronitrobenzene 10g, absolute methanol 100ml, off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in the reactor, be warming up to 100 ℃, reaction pressure is 1.0MPa, begins to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 30min stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas-chromatography-spectrometer analysis, and each components contents is: 3, and 4-dichloroaniline 99.78%, monochloro-benzene amine 0.22%, aniline 0%, 3,4-dichloronitrobenzene 0%.
Embodiment 13
In the stainless steel autoclave, add the Pd/C catalyst 0.1g of embodiment one preparation, 3,4-dichloronitrobenzene 10g, absolute methanol 100ml, off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in the reactor, be warming up to 110 ℃, reaction pressure is 1.0MPa, begins to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 30min stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas-chromatography-spectrometer analysis, and each components contents is: 3, and 4-dichloroaniline 99.63%, monochloro-benzene amine 0.32%, aniline 0.03%, 3,4-dichloronitrobenzene 0%.
Embodiment 14
In the stainless steel autoclave, add the Pd/C catalyst 0.1g of embodiment one preparation, 3,4-dichloronitrobenzene 10g, absolute methanol 100ml, off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in the reactor, be warming up to 80 ℃, reaction pressure is 1.2MPa, begins to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 30min stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is analyzed with the gas chromatography and mass spectromentry instrument, and each components contents is: 3, and 4-dichloroaniline 99.85%, monochloro-benzene amine 0.15%, aniline 0%, 3,4-dichloronitrobenzene 0%.
Embodiment 15
In the stainless steel autoclave, add the Pd/C catalyst 0.1g of embodiment one preparation, 3,4-dichloronitrobenzene 10g, absolute methanol 100ml, off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in the reactor, be warming up to 80 ℃, reaction pressure is 1.4MPa, begins to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 30min stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas-chromatography-spectrometer analysis, and each components contents is: 3, and 4-dichloroaniline 99.63%, monochloro-benzene amine 0.27%, aniline 0.10%, 3,4-dichloronitrobenzene 0%.
Embodiment 16
In the stainless steel autoclave, add the Pd/C catalyst 0.5g of embodiment one preparation, 3,4-dichloronitrobenzene 50g, absolute methanol 100ml, off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in the reactor, be warming up to 80 ℃, reaction pressure is 1.0MPa, begins to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 70min stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas-chromatography-spectrometer analysis, and each components contents is: 3, and 4-dichloroaniline 99.95%, monochloro-benzene amine 0.05%, aniline 0%, 3,4-dichloronitrobenzene 0%.
Embodiment 17
In the stainless steel autoclave, add the Pd/C catalyst 2.5g of embodiment one preparation, 3,4-dichloronitrobenzene 50g, absolute methanol 100ml, off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in the reactor, be warming up to 80 ℃, reaction pressure is 1.0MPa, begins to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 110min stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas-chromatography-spectrometer analysis, and each components contents is: 3, and 4-dichloroaniline 99.72%, monochloro-benzene amine 0.23%, aniline 0.05%, 3,4-dichloronitrobenzene 0%.
Embodiment 18
In the stainless steel autoclave, add the Pd/C catalyst 1.5g of embodiment one preparation, 3,4-dichloronitrobenzene 50g, absolute methanol 100ml, off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in the reactor, be warming up to 80 ℃, reaction pressure is 1.0MPa, begins to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 160min stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas-chromatography-spectrometer analysis, and each components contents is: 3, and 4-dichloroaniline 99.75%, monochloro-benzene amine 0.25%, aniline 0%, 3,4-dichloronitrobenzene 0%.
Embodiment 19
In the stainless steel autoclave, add the Pd/C catalyst 0.06g of embodiment one preparation, 3,4-dichloronitrobenzene 6g, absolute methanol 100ml, off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in the reactor, be warming up to 80 ℃, reaction pressure is 1.0MPa, begins to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 10min stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas-chromatography-spectrometer analysis, and each components contents is: 3, and 4-dichloroaniline 99.88%, monochloro-benzene amine 0.12%, aniline 0%, 3,4-dichloronitrobenzene 0%.
Embodiment 20
In the stainless steel autoclave, add the Pd/C catalyst 0.3g of embodiment one preparation, 3,4-dichloronitrobenzene 30g, absolute methanol 100ml, off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in the reactor, be warming up to 80 ℃, reaction pressure is 1.0MPa, begins to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 45min stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas-chromatography-spectrometer analysis, and each components contents is: 3, and 4-dichloroaniline 99.89%, monochloro-benzene amine 0.11%, aniline 0%, 3,4-dichloronitrobenzene 0%.
Embodiment 21
In the stainless steel autoclave, add the Pd/C catalyst 0.5g of embodiment one preparation, 3,4-dichloronitrobenzene 50g, absolute methanol 100ml, off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in the reactor, be warming up to 80 ℃, reaction pressure is 1.0MPa, begins to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 70min stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas-chromatography-spectrometer analysis, and each components contents is: 3, and 4-dichloroaniline 99.95%, monochloro-benzene amine 0.05%, aniline 0%, 3,4-dichloronitrobenzene 0%.
Embodiment 22
In the stainless steel autoclave, add the Pd/C catalyst 0.6g of embodiment one preparation, 3,4-dichloronitrobenzene 60g, absolute methanol 100ml, off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in the reactor, be warming up to 80 ℃, reaction pressure is 1.0MPa, begins to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 85min stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas-chromatography-mass spectral analysis, and each components contents is: 3, and 4-dichloroaniline 99.67%, monochloro-benzene amine 0.33%, aniline 0%, 3,4-dichloronitrobenzene 0%.
Embodiment 23
In the stainless steel autoclave, add the Pd/C catalyst 0.15g of embodiment two preparations, 3,4-dichloronitrobenzene 10g, absolute methanol 100ml, off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in the reactor, be warming up to 80 ℃, reaction pressure is 1.0MPa, begins to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 53min stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas-chromatography-spectrometer analysis, and each components contents is: 3, and 4-dichloroaniline 99.32%, monochloro-benzene amine 0.68%, aniline 0%, 3,4-dichloronitrobenzene 0%.
Embodiment 24
In the stainless steel autoclave, add the Pd/C catalyst 0.1g of embodiment three preparations, 3,4-dichloronitrobenzene 10g, absolute methanol 100ml, off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen three times of hydrogen exchange reactor and keep pressure in the reactor, be warming up to 80 ℃, reaction pressure is 1.0MPa, begins to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 25min stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas-chromatography-spectrometer analysis, and each components contents is: 3, and 4-dichloroaniline 98.96%, monochloro-benzene amine 1.04%, aniline 0%, 3,4-dichloronitrobenzene 0%.
Embodiment 25
In the stainless steel autoclave, add the Pd/C catalyst 0.1g of embodiment four preparations, 3,4-dichloronitrobenzene 10g, absolute methanol 100ml, off-response device, go out the nitrogen three times in the reactor with hydrogen exchange then three times and keep pressure in the reactor with the air in the nitrogen replacement reactor, be warming up to 80 ℃, reaction pressure is 1.0MPa, begins to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 30min stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas-chromatography-spectrometer analysis, and each components contents is: 3, and 4-dichloroaniline 99.65%, monochloro-benzene amine 0.35%, aniline 0%, 3,4-dichloronitrobenzene 0%.
Embodiment 26
In the stainless steel autoclave, add the Pd/C catalyst 0.1g of embodiment five preparations, 3,4-dichloronitrobenzene 10g, absolute methanol 100ml, off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in the reactor, be warming up to 80 ℃, reaction pressure is 1.0MPa, begins to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 30min stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas-chromatography-spectrometer analysis, and each components contents is: 3, and 4-dichloroaniline 99.84%, monochloro-benzene amine 0.16%, aniline 0%, 3,4-dichloronitrobenzene 0%.
Embodiment 27
In the stainless steel autoclave, add the Pd/C catalyst 0.1g of embodiment one preparation, 3,4-dichloronitrobenzene 10g, absolute methanol 100ml, off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in the reactor, be warming up to 80 ℃, reaction pressure is 1.0MPa, begins to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 30min stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas-chromatography-spectrometer analysis, and each components contents is: 3, and 4-dichloroaniline 99.95%, monochloro-benzene amine 0.05%, aniline 0%, 3,4-dichloronitrobenzene 0%.
Embodiment 28
In the stainless steel autoclave, add the Pd/C catalyst 0.1g of embodiment six preparations, 3,4-dichloronitrobenzene 10g, absolute methanol 100ml, off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in the reactor, be warming up to 80 ℃, reaction pressure is 1.0MPa, begins to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 30min stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas-chromatography-spectrometer analysis, and each components contents is: 3, and 4-dichloroaniline 99.93%, monochloro-benzene amine 0.07%, aniline 0%, 3,4-dichloronitrobenzene 0%.
Embodiment 29
In the stainless steel autoclave, add the Pd/C catalyst 0.1g of embodiment seven preparations, 3,4-dichloronitrobenzene 10g, absolute ethyl alcohol 100ml, off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in the reactor, be warming up to 80 ℃, reaction pressure is 1.0MPa, begins to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 30min stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas-chromatography-spectrometer analysis, and each components contents is: 3, and 4-dichloroaniline 99.95%, monochloro-benzene amine 0.05%, aniline 0%, 3,4-dichloronitrobenzene 0%.
Embodiment 30
In the stainless steel autoclave, add the Pd/C catalyst 0.1g of embodiment eight preparations, 3,4-dichloronitrobenzene 10g, absolute methanol 100ml, off-response device, with the air in the nitrogen replacement reactor three times then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in the reactor, be warming up to 80 ℃, reaction pressure is 1.0MPa, begins to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction 30min stops reaction, takes out reactant liquor, remove by filter catalyst, filtrate is used gas-chromatography-spectrometer analysis, and each components contents is: 3, and 4-dichloroaniline 99.95%, monochloro-benzene amine 1.33%, aniline 4.57%, 3,4-dichloronitrobenzene 0%.
Embodiment 31
In the stainless steel autoclave, the Pd/C catalyst 0.5g that adds embodiment one preparation, 3,4-dichloronitrobenzene 50g, methyl alcohol 100ml, the off-response device then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in the reactor, is warming up to 80 ℃ with the air in the nitrogen replacement reactor three times, reaction pressure is 1.0MPa, begin to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction stops reaction until not inhaling hydrogen, take out reactant liquor, filter out and remove catalyst, filtrate is used gas-chromatography-spectrometer analysis, and each components contents is shown in Table 1.The amount of adding catalyst according to table 1 is applied mechanically experiment subsequently.
Table 1Pd/C catalyst is applied mechanically the experiment catalyst Catalytic Hydrogenation Properties
| Apply mechanically number of times | Reaction time (min) | Conversion ratio (%) | Selectivity of product | ||
| 3,4-dichloroaniline (%) | Monochloro-benzene amine (%) | Aniline (%) | |||
| Fresh 1234 (adding 20 %) 56 | 70 90 100 110 90 100 110 | 100 100 100 100 100 100 100 | 99.76 99.81 99.78 99.77 99.75 99.65 99.50 | 0.24 0.19 0.22 0.23 0.25 0.35 0.50 | 0 0 0 0 0 0 0 |
| 7 (adding 20 %) 89 10 (adding 20 %) 11 12 13 (adding 20 %) | 120 120 130 100 100 120 100 | 100 100 100 100 100 100 100 | 99.71 99.75 99.78 99.55 99.63 99.52 99.67 | 0.29 0.25 0.22 0.45 0.37 0.44 0.33 | 0 0 0 0 0 0.04 0 |
Embodiment 32
In the stainless steel autoclave, the Pd/C catalyst 0.5g that adds embodiment one preparation, 3 of technical grade, 4-dichloronitrobenzene raw material (adopt Luo Huaxue Co., Ltd and produce by Bangbu nine, technical grade 3, the 4-dichloronitrobenzene, content 99.5%) 50g, methyl alcohol 100ml, the off-response device, then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in the reactor, be warming up to 80 ℃ with the air in the nitrogen replacement reactor three times, reaction pressure is 1.0MPa, begin to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction stops reaction until not inhaling hydrogen, takes out reactant liquor, remove by filter catalyst, filtrate is used gas-chromatography-spectrometer analysis, each components contents: 3, and 4-dichloroaniline 99.95%, monochloro-benzene amine 0.05%, aniline 0%, 3,4-dichloronitrobenzene 0%.
Embodiment 33
In the stainless steel autoclave, add the Pd/C catalyst 0.5g of embodiment one preparation,
3,4-dichloronitrobenzene 50g, methyl alcohol 100ml (the methyl alcohol moisture content is shown in Table 2), the off-response device then with the nitrogen in the hydrogen exchange reactor three times and keep pressure in the reactor, is warming up to 80 ℃ with the air in the nitrogen replacement reactor three times, reaction pressure is 1.0MPa, begin to stir, 600 rev/mins of stir speed (S.S.)s, isothermal reaction stops reaction until not inhaling hydrogen, take out reactant liquor, remove by filter catalyst, filtrate is used gas-chromatography-spectrometer analysis, and each components contents is shown in Table 2.
Table 2 solvent methanol moisture content is to 3 of Pd/C catalyst, the influence of 4-dichloronitrobenzene catalytic hydrogenation reaction
| Solvent comprises water rate (%) | Reaction time (min) | Conversion ratio (%) | Selectivity of product | ||
| 3,4-dichloroaniline (%) | Monochloro-benzene amine (%) | Aniline (%) | |||
| 0 2 5 | 70 90 115 | 100 100 100 | 99.95 99.92 99.84 | 0.05 0.07 0.13 | 0 0.01 0.03 |
Claims (10)
1. one kind 3,4-dichloronitrobenzene catalytic hydrogenation preparation 3, the Preparation of catalysts method of 4-dichloroaniline, described catalyst is the palladium activated-carbon catalyst, it is characterized in that described palladium activated-carbon catalyst preparation method is: active carbon washs to halogen-free ion, with above active carbon palladium-impregnated compound H with potassium halide or sodium halide aqueous solution impregnation process
2PdCl
4The aqueous solution, regulator solution pH value filter to alkalescence, and the filter cake water washing is reduced filter cake to neutral with reducing agent, the neutral products that obtains, and drying promptly gets the palladium activated-carbon catalyst, and the halogen ion in described potassium halide or the sodium halide is F
-, Cl
-, Br
-Or I
-
2. as claimed in claim 13,4-dichloronitrobenzene catalytic hydrogenation preparation 3, the Preparation of catalysts method of 4-dichloroaniline, it is characterized in that described active carbon washs to halogen-free ion with potassium halide or sodium halide aqueous solution impregnation process, active carbon is made into slurries, is that 1-10wt% adds palladium compound H by the palladium loading
2PdCl
4The aqueous solution.
3. as claimed in claim 23,4-dichloronitrobenzene catalytic hydrogenation preparation 3, the Preparation of catalysts method of 4-dichloroaniline, the specific area that it is characterized in that the carrier active carbon of described palladium activated-carbon catalyst is 1300-1700m
2/ g.
4. as claimed in claim 13,4-dichloronitrobenzene catalytic hydrogenation preparation 3, the Preparation of catalysts method of 4-dichloroaniline is characterized in that described potassium halide solution is liquor kalii iodide, its concentration is 0.125-10mol/l.
5. as claimed in claim 13,4-dichloronitrobenzene catalytic hydrogenation preparation 3, the Preparation of catalysts method of 4-dichloroaniline, it is characterized in that described reducing agent is a hydrazine hydrate solution, described reduction is that filter cake is made into slurries, drips hydrazine hydrate solution, stir, filter, obtain filter cake.
6. as claimed in claim 13,4-dichloronitrobenzene catalytic hydrogenation preparation 3, the Preparation of catalysts method of 4-dichloroaniline, the preparation method who it is characterized in that described palladium activated-carbon catalyst is: active carbon washs to there not being iodide ion with KI or sodium iodide aqueous solution impregnation process, active carbon is made into slurries, is that 1-10wt% is with above active carbon slurry palladium compound H by the palladium loading
2PdCl
4The aqueous solution, filter regulator solution pH value to 7.1～9, and the filter cake water washing is reduced filter cake to neutral with hydrazine hydrate solution, the neutral products that obtains, drying promptly gets the palladium activated-carbon catalyst.
7. as claimed in claim 63,4-dichloronitrobenzene catalytic hydrogenation preparation 3, the Preparation of catalysts method of 4-dichloroaniline is characterized in that the preparation method of described palladium activated-carbon catalyst is specially: take by weighing active carbon, the specific area of active carbon is 1600m
2/ g, active carbon are immersed in the KI solution that concentration is 2.5mol/l 4～8 hours, filter, and spend deionised water and do not detect to there being iodide ion, and above-mentioned active carbon is mixed with the slurries of 60～90 ℃ of temperature, are that 1-5wt% slowly drips H by the palladium loading
2PdCl
4Solution stirs, again with NaOH solution regulator solution pH value to 7.1～9 alkalescence, and cool the temperature to room temperature, and filtering, filter cake spends deionised water to neutral, again filter cake is configured to slurries under 30 ℃, drip 85% hydrazine hydrate solution, stir, filter, filter cake spends deionised water to neutral, at last in room temperature in air through preliminarily dried, get wet sample and promptly get described palladium activated-carbon catalyst, described palladium activated-carbon catalyst more than 90% the palladium grain diameter be 20～30nm.
8. as claimed in claim 73,4-dichloronitrobenzene catalytic hydrogenation preparation 3, the Preparation of catalysts method of 4-dichloroaniline is characterized in that the palladium grain diameter of described palladium activated-carbon catalyst more than 90% is 25nm.
9. as one of claim 1～8 described 3,4-dichloronitrobenzene catalytic hydrogenation preparation 3, the Preparation of catalysts method of 4-dichloroaniline is characterized in that described 3,4-dichloronitrobenzene catalytic hydrogenation preparation 3, the 4-dichloroaniline is meant that with 3 the 4-dichloronitrobenzene is a raw material, under the effect of palladium activated-carbon catalyst and hydrogen, in the fatty alcohol organic solvent of C1～C2, in 60～130 ℃ reaction temperature, reaction generates 3, the 4-dichloroaniline under 0.8～2.0MPa reaction pressure.
10. as claimed in claim 83,4-dichloronitrobenzene catalytic hydrogenation preparation 3, the Preparation of catalysts method of 4-dichloroaniline, it is characterized in that 3, the mass volume ratio of 4-dichloronitrobenzene and fatty alcohol is 1: 1.5～15, described palladium activated-carbon catalyst consumption is 3,0.5～5% of 4-dichloronitrobenzene quality, and described fatty alcohol organic solvent is methyl alcohol or ethanol.
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| CN109759109A (en) * | 2018-11-28 | 2019-05-17 | 浙江工业大学 | The preparation and the application in nitrobenzene compounds hydrogenation reaction that nitrogen modifies charcoal supported noble metal hydrogenation catalyst |
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| CN114478315B (en) * | 2022-02-25 | 2023-10-31 | 山东艾孚特科技有限公司 | Method for catalytic reduction of irosartan biphenyl waste residues by using halogen-modified Pd/C catalyst |
| CN115555051A (en) * | 2022-10-08 | 2023-01-03 | 江苏快达农化股份有限公司 | Pd/CuMOF-x composite material catalyst, preparation method and application thereof |
| CN115555051B (en) * | 2022-10-08 | 2023-09-15 | 江苏快达农化股份有限公司 | Pd/CuMOF-x composite material catalyst, preparation method and application thereof |
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Assignee: Guangzhou Yabang Shenlian Chemical Co., Ltd. Assignor: Zhejiang University of Technology Contract record no.: 2010320000673 Denomination of invention: Production of 3,4-dichloroaniline catalyst with 3,4-mirbane oil dichloride hydrogenation Granted publication date: 20080220 License type: Exclusive License Open date: 20060816 Record date: 20100521 |
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