CN1775351A - Catalyst for preparing aromatic amine by catalytic hydrogenation of nitrobenzene compounds and its use method - Google Patents
Catalyst for preparing aromatic amine by catalytic hydrogenation of nitrobenzene compounds and its use method Download PDFInfo
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- CN1775351A CN1775351A CN 200510200593 CN200510200593A CN1775351A CN 1775351 A CN1775351 A CN 1775351A CN 200510200593 CN200510200593 CN 200510200593 CN 200510200593 A CN200510200593 A CN 200510200593A CN 1775351 A CN1775351 A CN 1775351A
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- catalyst
- catalytic hydrogenation
- aromatic amine
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- nitrobenzene compounds
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Abstract
The present invention relates to a catalyst for preparing arylamine by utilizing catalytic hydrogenation of nitrobenzene compound and its application method, belonging to the field of catalytic synthesis technology in application chemistry. Said catalyst is formed from carrier and active component, its carrier can be metal oxide; carbon materials of active carbon, carbon nano tube and porous carbon, etc.; micropore molecular sieve with different compositions or silica-base material into which one or several kinds of hetero-atoms are added, also can be organic high-molecular polymer. The active component can be double-component (multicomponent) metal formed from metal silver and gold or silver gold and palladium, platinum and copper, etc. in which the weight percentage of active metal component and carrie.r is 0.5-30%.
Description
Technical field
The invention belongs to the catalytic synthetic techniques field in the applied chemistry.The catalyst that relates to unsaturated group nitro in a kind of catalytic reduction aromatic, specifically a kind of Nano Silver, nano catalyst based on support type.
Background technology
The catalytic reduction of the unsaturated group-nitro in the aromatic is an important channel of realizing that Organic Ingredients transforms mutually.At present, the catalyst of industrial employing mainly is based on Pd, Pt, Ru, Ir and Raney Ni catalyst.But there is shortcoming such as cost an arm and a leg, poor selectivity and preparation process are loaded down with trivial details in existing these catalyst.Loading type silver catalyst is widely studied in catalytic oxidation, as Ag/Al
2O
3Be applied to the suitability for industrialized production of oxirane.But the catalytic reduction performance of loading type silver catalyst fails to cause people's attention always.Along with the development of nanometer science and technology, the preparation of load-type nanometer metal catalyst has obtained very big progress, and these carrier nanometer catalysts reveal excellent performance to a lot of reaction tables, and wherein typical example is a nano catalyst.For a long time, gold be it is believed that there is not catalytic activity always, since the last century the nineties, it is found that nano catalyst has the catalytic performance of a lot of excellences, has become the focus of people's research at present.Innovation part of the present invention is loaded nano silver, Au catalyst are applied to unsaturated group nitro in the catalytic reduction aromatic, and has obtained good effect.
Summary of the invention
The object of the present invention is to provide a kind ofly be easy to prepare, price is lower, have the catalyst that is used for preparing aromatic amine by catalytic hydrogenation of nitrobenzene compounds and the using method of better industrial application prospect.
Technical solution of the present invention is, a kind of catalyst that is used for preparing aromatic amine by catalytic hydrogenation of nitrobenzene compounds is made up of carrier and active metal component, and the percentage by weight of active metal component and carrier is 0.5-30%; The carrier of catalyst is metal oxide, carbon material, micro porous molecular sieve, silica-base material or organic high molecular polymer; Active metal component is a silver and golden, and by weight percentage, the ratio that silver, gold account for active component is silver-colored 0-100%, golden 0-100%.
Metal oxide as catalyst carrier is SiO
2, Al
2O
3, CeO
2, TiO
2, MnO
2, ZnO, Fe
2O
3And Co
3O
4, by weight percentage, SiO
2, Al
2O
3, CeO
2, TiO
2, MnO
2, ZnO, Fe
2O
3Or Co
3O
4The ratio that accounts for metal oxide is SiO
20-100%, Al
2O
30-100%, CeO
20-100%, TiO
20-100%, MnO
20-100%, ZnO0-100%, Fe
2O
30-100%, Co
3O
40-100%.
Carbon material as catalyst carrier is active carbon, carbon nanotube and porous charcoal, and by weight percentage, the ratio that active carbon, carbon nanotube or porous charcoal account for carbon material is active carbon 0-100%, carbon nanotube 0-100%, porous charcoal 0-100%.
The micro porous molecular sieve of forming by Si, Al, Ti, P, B, Ga as the micro porous molecular sieve of catalyst carrier, by weight percentage, the mass percent that Si, Al, Ti, P, B, Ga account for composition is: Si 0-100%, Al 0-100%, Ti 0-100%, P 0-100%, B 0-100%, Ga 0-100%.
Silica-base material as catalyst carrier is by weight percentage, to be mixed with the heteroatomic silica-base material of 0-80%, wherein, hetero atom is cerium, zirconium, titanium, aluminium, iron, lanthanum and phosphorus, and by weight percentage, the ratio that cerium, zirconium, titanium, aluminium, iron, lanthanum or phosphorus account for the hetero atom total amount is, cerium 0-100%, zirconium 0-100%, titanium 0-100%, aluminium 0-100%, iron 0-100%, lanthanum 0-100%, phosphorus 0-100%.
Machine high molecular polymer as catalyst carrier is cationic, anionic exchange resin or polypyrrole alkane ketone.
The precursor of metal is AgNO in the active component
3, Ag (Ph
3P) NO
3, Ag (NH
3)
2NO
3Or HAuCl
4Deng silver-colored, golden salt.
Active component is: the argent of one pack system, gold.Bi-component Yin-Jin, silver-palladium, silver-platinum, silver-copper, wherein silver accounts for the 40-100% of whole component; Bi-component gold-palladium, gold-platinum, gold-copper, wherein gold accounts for the 40-100% of whole component.
Use a kind of method that is used for the catalyst of preparing aromatic amine by catalytic hydrogenation of nitrobenzene compounds to be, in the catalytic reduction reaction process, reducing agent is H
2, the reaction temperature of catalytic reaction is 60-150 ℃, reaction pressure is 0.2-4.0MPa, reaction time 0.5-20 hour; By mass percentage, catalyst consumption is the 1%-40% of nitrobenzene compounds.
The Application of Catalyst scope is meant nitrobenzene compounds; Contain substituting group in the nitrobenzene: the Cl in the halogen, Br, I, in the alkyl-CH3 ,-CH2CH3, or hydroxyl-OH.
The Preparation of catalysts method that wherein said activity of such catalysts component is argent, golden one pack system has:
1. infusion process: its concrete preparation process is: at first with the precursor dissolving of argent or gold, incipient impregnation is on carrier; Room temperature was dried in the shade 8-16 hour then, 80-120 ℃ of oven dry; Handled in oxygen, hydrogen 2-6 hour then, temperature is 30-400 ℃.
2. micro emulsion method: its concrete preparation process is: surfactant (as: polyoxyethylene (n=2-20) lauryl ether, five ethene glycol lauryl ethers, polyoxyethylene nonyl phenylate etc.) be dissolved in the mixed solution of cyclohexane and n-butanol, the volume ratio of n-butanol and cyclohexane is 1 in the described mixed solution: 4-6, the aqueous solution that under vigorous stirring, adds the slaine of a certain amount of one pack system slaine, stir and form micro emulsion, regulate the mol ratio W=1-15 of water and surfactant simultaneously, to obtain the metallic of different size; Stir and add hydrazine hydrate after 1-2 hour, stirred 2-3 hour, adding proper ammonia, to regulate pH value be 8.5-11, adds TEOS (just tetraethyl orthosilicate) and cyclohexane at last, and the weight ratio that makes TEOS and cyclohexane is 1: 1-6, mixture stirring 2-5 hour; After filtration, the washing, sample is dried under 80-120 ℃ of air, at 300-700 ℃ of roasting 2-5 hour.Salt used in the described micro emulsion method can be: AgNO
3Or HAuCl
4
3. local reduction way: on silica-base material or other material, introduce the complexing group as-CH by functionalisation of surfaces
2CH
2CH
2NH
2,-CH
2CH
2CH
2NR
3 +X
-(R=(CH
2)
nCH
3, n=0-5, X=Br, Cl), thereby with the Ag in the aqueous solution
+, AuCl
4 -Be incorporated into the surface of carrier material, again at 40-500 ℃ of following roasting, hydrogen reducing.Perhaps on silica-base material or other material, introduce reproducibility functional group as CH by functionalisation of surfaces
2CH
2CH
2NHCH
2OH, with it at Ag
+, Ag (NH
3)
2 +, AuCl
4 -The aqueous solution in stir after 1-5 hour, just can obtain Nano Silver, nm of gold loaded catalyst.
4. ion-exchange, the carrier that is suitable for this method comprises: anion and cation exchange resin (has on the macromolecular scaffold-SO
3H or-N (CH
3)
3The Cl group), Si-Al molecular sieve etc.
Coprecipitation, deposition-precipitation method and sol-gel process can adopt the universal method of reporting in the present document to carry out.
The Preparation of catalysts method that described activity of such catalysts component is the bi-component metal.Operating process is: with the aqueous solution of the bi-component slaine of solubility, load on the carrier with the method for dipping.
Beneficial effect and benefit that the present invention reached are:
1. the catalyst cost is lower, is easy to preparation, can adopt multiple organic or inorganic carrier.
2. the catalytic performance of catalyst is good.Catalyst of the present invention can carry out selective catalytic hydrogenation to multiple nitrobenzene compounds under relatively mild condition, thereby obtains the corresponding aroma aminated compounds.
Following table is Ag/SiO
2The reaction result of catalyst reduction distinct fragrance nitro compound.
The invention will be further described below in conjunction with the drawings and specific embodiments.
Fig. 1 is the Ag/SiO of in-situ reducing method preparation
2Change the transmission electron microscope photo of agent.
The specific embodiment
Embodiment 1
Adopt equi-volume impregnating to prepare SiO
2The nano-silver catalyst of load.Be dissolved in the 8mL distilled water by the part by weight of active component and carrier silver nitrate, to wherein adding 5.0g SiO 0.1575g
2Carrier is at room temperature placed 12h after the stirring, 80 ℃ of oven dry down, handle 2h down in 500 ℃ at last in helium-atmosphere afterwards, and the load capacity that promptly obtains silver is the loaded catalyst of 2wt%, and wherein active component mainly exists with the form of argent.
Embodiment 2
Adopt prepared with microemulsion reactor Ag/SiO
2Catalyst.Take by weighing 6.0g (after the concentration of salting liquid was determined, promptly the molal quantity of water was definite, and its value changes according to the W value) surfactant (C
16H
33(OCH
2CH
2)
nOH n=2-20), to wherein adding the dissolving of 20mL cyclohexane and 5mL n-butanol, adds afterwards and contains 0.06g AgNO
3The 3.6mL aqueous solution (w=4), stir to form microemulsion; Add two hydrazine hydrates (85%), reduction AgNO
3Add ammoniacal liquor, regulate pH=9; Add 3.57g TEOS subsequently, the mixture of 4mL cyclohexane and water stirs and makes TEOS hydrolysis formation SiO
2, aging, to filter, washing forms Ag/SiO
2Sample.In addition, after forming microemulsion, can add ready-made SiO
2Carrier stirs 2h, adds two hydrazine hydrates afterwards, makes deposition of silver at SiO
2On the carrier, all the other operations are the same.
Embodiment 3
Adopt local reduction way to prepare Ag/SiO
2Catalyst.At first, with 2g SiO
2And the 3-aminopropyl silane of 6ml is scattered in the toluene.Stir and to be warming up to 80 ℃ and down at 80 ℃ of maintenance 8h down.Cooling, filtration, toluene and ethanol washing back are in 80 ℃ of oven for drying.Secondly, 5ml formaldehyde, 80ml deionized water and 20ml ethanol are mixed.The functionalized SiO of 1.0g
2Add above-mentioned solution, stir 30min down at 40 ℃.Filter, after a large amount of deionized water washings.Put into 50 ℃ of oven dryings.At last, 1.0g is contained reduce the SiO of functional group
2Add 0.069g AgNO
3In the 90ml silver ammino solution of preparation, stir 30min down at 40 ℃.Then, the yellow solution that obtains is filtered, and wash with a large amount of deionized waters.The gained solid can obtain carrying capacity and be the nanometer Ag/SiO of 4% high dispersive after 50 ℃ of oven for drying
2Its projection electromicroscopic photograph is seen Fig. 1.
Embodiment 4
According to silver, the weight ratio of platinum takes by weighing a certain amount of H respectively
2PtCl
6H
2O is dissolved in the 3.2mL water, to wherein adding 2.0gSiO
2, the AgNO of 0.5039g is flooded in 120 ℃ of oven dry again
3The aqueous solution, 80 ℃ of oven dry, 500 ℃ of roasting 4h in Muffle furnace reduce 90min under 400 ℃ of nitrogen atmosphere.Silver, platinum mass ratio are 16: 2,4,6,8.Bimetallic silver, the platinum loaded catalyst can pass through graded impregnation, as elder generation's silver back platinum, or silver behind the first platinum, also can use co-impregnation.
Embodiment 5
0.5g o-chloronitrobenzene and 50 milliliters of ethanol added in 100 milliliters the autoclave, add 0.2g 4%Ag/SiO
2, charging into the hydrogen of 2MPa, 140 ℃ of reactions are after 3 hours, and the conversion ratio of o-chloronitrobenzene is 100%, and the selectivity of product o-chloraniline is 100%.
Embodiment 6
0.5g parachloronitrobenzene and 50 milliliters of ethanol added in 100 milliliters the autoclave, add 0.2g 4%Ag/SiO
2, charge into the hydrogen of 2.0MPa, 100 ℃ of reactions 3 hours down, the conversion ratio of parachloronitrobenzene is 80%, the selectivity of product o-chloraniline reaches 92%.
Embodiment 7
0.5g parachloronitrobenzene and 50 milliliters of ethanol added in 100 milliliters the autoclave, add 0.2g 1%Au/TiO
2, charge into the hydrogen of 2.0MPa, 100 ℃ of reactions 3 hours down, the conversion ratio of parachloronitrobenzene is 100%, the selectivity of product o-chloraniline reaches 95%.
Embodiment 8
0.5g o-chloronitrobenzene and 50 milliliters of ethanol added in 100 milliliters the autoclave, add 0.2g 4%Ag/SiO
2, charge into the hydrogen of 0.5MPa, 140 ℃ of reactions 3 hours down, the conversion ratio of o-chloronitrobenzene is 30%, the selectivity of product o-chloraniline reaches 100%.
Embodiment 9
0.5g o-chloronitrobenzene and 50 milliliters of ethanol added in 100 milliliters the autoclave, add 0.2g 4%Ag/ resin, charge into the hydrogen of 2.0MPa, 140 ℃ were reacted 3 hours down, the conversion ratio of o-chloronitrobenzene is 100%, and the selectivity of product o-chloraniline reaches 100%.
Embodiment 10
0.5g ortho-methylnitrobenzene and 50 milliliters of ethanol added in 100 milliliters the autoclave, add 0.2g 4%Ag/ZSM-5 (Si-Al molecular sieve), charge into the hydrogen of 2.0MPa, 140 ℃ were reacted 3 hours down, the conversion ratio of ortho-methylnitrobenzene is 100%, and the selectivity of product o-toluidine reaches 100%.
Embodiment 11
0.5g o-nitrophenol and 50 milliliters of ethanol added in 100 milliliters the autoclave, add 0.2g 4%Ag/ active carbon, charge into the hydrogen of 2.0MPa, 140 ℃ were reacted 3 hours down, the conversion ratio of o-nitrophenol is 100%, and the selectivity of product ortho-aminophenol reaches 100%.
Claims (9)
1. a catalyst that is used for preparing aromatic amine by catalytic hydrogenation of nitrobenzene compounds is characterized in that, is made up of carrier and active metal component, and the percentage by weight of active metal component and carrier is 0.5-30%; The carrier of catalyst is metal oxide, carbon material, micro porous molecular sieve, silica-base material or organic high molecular polymer; Active metal component is a silver and golden, and by weight percentage, the ratio that silver, gold account for active component is silver-colored 0-100%, golden 0-100%.
2. a kind of catalyst that is used for preparing aromatic amine by catalytic hydrogenation of nitrobenzene compounds according to claim 1, it is characterized in that, metal oxide as catalyst carrier is SiO2, Al2O3, CeO2, TiO2, MnO2, ZnO, Fe2O3 and Co3O4, by weight percentage, the ratio that SiO2, Al2O3, CeO2, TiO2, MnO2, ZnO, Fe2O3 or Co3O4 account for metal oxide is SiO20-100%, Al2O30-100%, CeO20-100%, TiO20-100%, MnO20-100%, ZnO0-100%, Fe2O30-100%, Co3O40-100%.
3. a kind of catalyst that is used for preparing aromatic amine by catalytic hydrogenation of nitrobenzene compounds according to claim 1, it is characterized in that, carbon material as catalyst carrier is active carbon, carbon nanotube and porous charcoal, by weight percentage, the ratio that active carbon, carbon nanotube or porous charcoal account for carbon material is active carbon 0-100%, carbon nanotube 0-100%, porous charcoal 0-100%.
4. a kind of catalyst that is used for preparing aromatic amine by catalytic hydrogenation of nitrobenzene compounds according to claim 1, it is characterized in that, the micro porous molecular sieve of forming by Si, Al, Ti, P, B, Ga as the micro porous molecular sieve of catalyst carrier, by weight percentage, Si, Al, Ti, P, B, Ga account for the mass percent of composition and are: Si 0-100%, Al0-100%, Ti 0-100%, P 0-100%, B 0-100%, Ga 0-100%.
5. a kind of catalyst that is used for preparing aromatic amine by catalytic hydrogenation of nitrobenzene compounds according to claim 1, it is characterized in that, silica-base material as catalyst carrier is, by weight percentage, be mixed with the heteroatomic silica-base material of 0-80%, wherein, hetero atom is cerium, zirconium, titanium, aluminium, iron, lanthanum and phosphorus, and by weight percentage, the ratio that cerium, zirconium, titanium, aluminium, iron, lanthanum or phosphorus account for the hetero atom total amount is, cerium 0-100%, zirconium 0-100%, titanium 0-100%, aluminium 0-100%, iron 0-100%, lanthanum 0-100%, phosphorus 0-100%.
6. a kind of catalyst that is used for preparing aromatic amine by catalytic hydrogenation of nitrobenzene compounds according to claim 1 is characterized in that, is cationic, anionic exchange resin or polypyrrole alkane ketone as the machine high molecular polymer of catalyst carrier.
7. a kind of catalyst that is used for preparing aromatic amine by catalytic hydrogenation of nitrobenzene compounds according to claim 1 is characterized in that, the precursor of metal is AgNO3, Ag (Ph3P) NO3, Ag (NH3) 2NO3 or HAuCl4 in the active component.
8. use the described a kind of method that is used for the catalyst of preparing aromatic amine by catalytic hydrogenation of nitrobenzene compounds of claim 1, it is characterized in that, in the catalytic reduction reaction process, reducing agent is H2, the reaction temperature of catalytic reaction is 60-150 ℃, reaction pressure is 0.2-4.0MPa, reaction time 0.5-20 hour; By mass percentage, catalyst consumption is the 1%-40% of nitrobenzene compounds.
9. a kind of using method that is used for the catalyst of preparing aromatic amine by catalytic hydrogenation of nitrobenzene compounds according to claim 8 is characterized in that the Application of Catalyst scope is meant nitrobenzene compounds; Contain substituting group in the nitrobenzene: halogen (Cl, Br, I), alkyl (as-CH3 ,-CH2CH3) or hydroxyl (OH).
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