CN103691478B - A kind of preparation of Ni/Ag/Cu/SBA-15 composite catalyst and application thereof - Google Patents
A kind of preparation of Ni/Ag/Cu/SBA-15 composite catalyst and application thereof Download PDFInfo
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Abstract
The present invention relates to the preparation of a kind of Ni/Ag/Cu/SBA-15 composite catalyst and application thereof, belong to nanocatalyst preparation and catalyticing research field.Carry out according to following step: first with copper nitrate, silver nitrate, nickel nitrate for raw material, SBA-15 is carrier, adopts equi-volume impregnating to prepare the Ni/Ag/Cu/SBA-15 Compound Negative supported catalyst of different loads amount.Then with p-nitrophenol, absolute ethyl alcohol for raw material, adopt Ni/Ag/Cu/SBA-15 compound as catalyst, p-aminophenol prepared by selective catalysis hydrogenation paranitrophenol.Ni/Ag/Cu/SBA-15 composite catalyst prepared by the present invention, consumption is few, has high catalytic activity and stability, has higher selective for specific reaction.Adopt Ni/Ag/Cu/SBA-15 compound simple as the method technological requirement of catalyst preparing p-aminophenol, be applicable to industrial requirement.
Description
Technical field
The present invention relates to a kind of preparation method and application thereof of Ni/Ag/Cu/SBA-15 composite catalyst, belong to nanocatalyst preparation and catalyticing research field.
Background technology
In recent years, nano science and nanometer technology cause at numerous areas such as catalysis, medicine, communication, biology, environmental protection and pay close attention to widely, become and research and develop one of most active field in the world.Nanoparticle due to size little, the percentage by volume shared by surface is large, and the key state on surface is different from granule interior with electronic state, the not congruent activity site increase causing surface of surface atom coordination, and this just makes it possess primary condition as catalyst.It is reported, compared with conventional metals catalyst, nano-metal particle, as: palladium, platinum, rhodium, ruthenium, gold and nickel, all show higher catalytic activity in catalytic hydrogenation, catalytic oxidation.Such as: the activity of Nano Silver (2-4 nm) catalytic oxidation ethylene making oxirane is more than 4 times of commercial silver catalyst (30-150 nm); When nano nickel (30 nm) catalyst cyclo-octadiene hydrogenation generates cyclo-octene reaction, the catalytic activity of nano nickel is 2-7 times of traditional skeleton nickel activity, and the high 5-10 of selectivity ratios skeleton nickel doubly.
The selective catalysis hydrogenation reduction of nitro-aromatic is the important organic reaction of a class; its corresponding product aromatic amine; as alkyl; acyl group; hydroxyl; nitro and halogen family aromatic amine compound, be important chemical raw material and chemical intermediate, have very important application in fields such as pharmacy, dyestuff, spices, polyurethane rubber, agricultural chemicals and nonlinear optical materials.Such as, in medical industry, para-aminophenol prepared by p-nitrophenol catalytic hydrogenation is the intermediate producing anodyne and antipyretic.At present, in the industrial production of aromatic amine compound, catalytic hydrogenation method used catalyst is mainly the rare precious metal such as Raney-Ni and Pt, Pd, Ru, Rh.
Metallic catalyst, particularly precious metal, due to expensive, and be often dispersed into small particle and be attached on high surface and macroporous carrier, which reduce the content of active component, reduce catalyst cost.Loaded catalyst has certain shape, and large active surface and suitable pore structure, and mechanical strength is also enhanced.In order to adapt to the industrial needs putting by force (suction) thermal response, carrier generally should have larger thermal capacitance and good thermal conductivity, reaction heat energy is passed rapidly (coming in), avoid hot-spot and cause sintering and the inactivation of catalyst, or device damage, also can avoid the side reaction under high temperature, thus improve the selective of catalyst.Nickel catalyst carriedly to be applied in many hydrogenation reactions, if MDNB is at Ni/SiO
2liquid-phase hydrogenatin synthesis m-phenylene diamine (MPD), MDNB conversion ratio and m-phenylene diamine (MPD) is selective reaches more than 99.9% and 99.6% respectively.Therefore, p-aminophenol prepared by research Ni/Ag/Cu/SBA-15 composite catalyst selective catalysis hydrogenation paranitrophenol, significant to the selective catalysis hydrogenation research of nitro-aromatic.
Summary of the invention
The present invention has prepared a kind of Ni/Ag/Cu/SBA-15 support type composite catalyst, and prepares p-aminophenol for selective catalysis hydrogenation paranitrophenol.This catalyst amount is few, high activity, high selectivity, and has good stability in use.
Technical scheme of the present invention is as follows:
A kind of Ni/Ag/Cu/SBA-15 composite catalyst, with silver nitrate, copper nitrate, nitric acid acid nickel, SBA-15, adopts equi-volume impregnating preparation.
Preparation process is:
(1) SBA-15 of 200 mesh sieve dryings was taken, and measure the dipping volume of carrier S BA-15, take copper nitrate, preparation copper nitrate aqueous solution, equi-volume impregnating is adopted to be flooded by carrier S BA-15 copper nitrate aqueous solution, stirred at ambient temperature 24 h, makes copper nitrate solution and the full and uniform dipping of carrier S BA-15; First gained mixture is constantly stirred to drying at 60 DEG C, then dry 12 h at 110 DEG C, finally roasting 4 h at 450 DEG C, ground 200 mesh sieves, in resulting composite, the load capacity of copper is 1wt%-10wt%.
(2) take silver nitrate and prepare silver nitrate aqueous solution, flooded by step (1) gained compound silver nitrate aqueous solution, wherein the volume of silver nitrate aqueous solution is equal with the dipping volume of carrier S BA-15, at room temperature stirs 24 h; At 60 DEG C, be constantly stirred to drying, then dry 12 h at 110 DEG C, finally roasting 4 h at 450 DEG C, ground 200 mesh sieves, in compound, the load capacity of silver is 1wt%-10 wt %.
(3) take nickel nitrate and prepare nickel nitrate aqueous solution, flooded by step (2) gained compound nickel nitrate aqueous solution, wherein the volume of nickel nitrate aqueous solution is equal with the dipping volume of carrier S BA-15, at room temperature stirs 24 h.At 60 DEG C, be constantly stirred to drying, then dry 12 h at 110 DEG C, finally roasting 4 h at 450 DEG C, ground 200 mesh sieves, in compound, the load capacity of nickel is 5wt%-20 wt %.
(4) step (3) gained compound is placed in stainless steel reaction pipe, first rises to 300 DEG C with the programming rate of 2-5 DEG C/min from room temperature, use H simultaneously
2-N
2gaseous mixture carries out purging reduction, wherein H
2and N
2volume ratio be 1:9, gas flow rate is 30-50 mL/min, subsequently, is warming up to 450 DEG C with the programming rate of 5-10 DEG C/min, simultaneously slowly improves gaseous mixture H
2content, final H
2volume fraction is stablized to 30-40%, and reduces 6-10 h at this temperature, finally at N
2namely the Ni/Ag/Cu/SBA-15 agent of different loads amount is obtained after being down to room temperature in air-flow.
According to the Ni/Ag/Cu/SBA-15 composite catalyst prepared by above-mentioned steps, it is characterized in that, in this composite catalyst, the load capacity of active component Cu, Ag, Ni is respectively 1%-10%, 1%-10%, 5%-20%.
A method for Ni/Ag/Cu/SBA-15 agent catalytic hydrogenation paranitrophenol, carries out according to following step: (1) gets paranitrophenol and absolute ethyl alcohol is placed in reactor, then adds Ni/Ag/Cu/SBA-15 compound
Catalyst, wherein, the ratio of paranitrophenol, absolute ethyl alcohol and Ni/Ag/Cu/SBA-15 composite catalyst is: 2 g:150 mL:0.02g;
(2) install reaction unit, pass into nitrogen and purge about 15 minutes, the air in removing reactor, then passes into High Purity Hydrogen and makes pressure increase to 0.8 Mpa, being slowly warming up to 80-160 DEG C, lower reaction 8 h of insulation, and stir speed (S.S.) is 600 r/min;
(3), after reaction terminates, reaction mass is cooled to room temperature.Sample gas chromatograph is analyzed.
Beneficial effect of the present invention:
In nickel prepared by the present invention, silver, copper support type composite catalyst, the size, structure, pattern etc. of different key component nano nickel, Nano Silver, Nanometer Copper have significant impact to the catalytic activity of composite catalyst, the selective of product.Simultaneously, self intrinsic property such as its hydrothermal stability of carrier S BA-15 is high, aperture is large makes it be applicable to need the reaction of long response time in duct, and carrier S BA-15 and key component Ni, interaction between Ag, Cu, also have material impact to the catalytic activity of catalyst.Compare with single metal load type catalyst with single metallic catalyst, polynary nanometer metal load type catalyst consumption in catalytic reaction process of preparation is few, and there is good catalytic activity and stability, make reaction condition gentle, avoid high-temperature high-voltage reaction, thus avoid the generation of a large amount of accessory substance, improve the selective of catalyst, make product purity high, profit is worth and raises, and manufacturing technique requirent is simple, is applicable to industrial requirement.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described.
embodiment 1:
1. catalyst preparing:
Ni/Ag/Cu/SBA-15 composite catalyst is prepared by equi-volume impregnating, and raw material is copper nitrate, silver nitrate, nickel nitrate, and carrier is SBA-15.
(1) take the SBA-15 of 9.3g, the dipping volume recording SBA-15 is 1.82 mL/g.Take copper nitrate configuration copper nitrate aqueous solution, wherein the concentration of copper nitrate aqueous solution is 0.093 mol/L, and by copper nitrate aqueous solution 12.926mL and carrier incipient impregnation, stirred at ambient temperature 24 h, makes copper nitrate solution and carrier S BA-15 homogeneous impregnation.First constantly being stirred at 60 DEG C by gained mixture makes moisture evaporate completely, then dry 12 h at 110 DEG C, finally roasting 4 h at 450 DEG C.
(2) take silver nitrate preparation silver nitrate aqueous solution, wherein the concentration of silver nitrate aqueous solution is 0.0548 mol/L, by the resulting composite 12.926mL silver nitrate aqueous solution dipping obtained in step (1), and stirred at ambient temperature 24 h.Constantly stirring at 60 DEG C makes moisture evaporate completely, then dry 12 h at 110 DEG C, finally roasting 4 h at 450 DEG C.
(3) take nickel nitrate preparation nickel nitrate aqueous solution, wherein the concentration of nickel nitrate aqueous solution is 0.5033 mol/L, by the resulting composite 12.926mL nickel nitrate aqueous solution dipping obtained in step (2), and stirred at ambient temperature 24 h.Constantly stirring at 60 DEG C makes moisture evaporate completely, then dry 12 h at 110 DEG C, finally roasting 4 h at 450 DEG C, ground 200 mesh sieves.
(4) step (3) gained compound is placed in stainless steel reaction pipe, first to rise to 300 DEG C with the programming rate of 2-5 DEG C/min from room temperature, uses H simultaneously
2-N
2gaseous mixture (1:9/V:V) carries out purging reduction, and gas flow rate is 30-50 mL/min, subsequently, is warming up to 450 DEG C with the programming rate of 5-10 DEG C/min, slowly improves gaseous mixture H simultaneously
2content, final H
2volume fraction is stablized to 30-40%, and reduces 6-10 h at this temperature, finally at N
2room temperature is down in air-flow.Final acquisition Ni/Ag/Cu/SBA-15 composite catalyst, in catalyst, the load capacity of active component Cu, Ag, Ni is respectively 1 wt%, 1 wt% and 5 wt%.
2. paranitrophenol selective catalysis Hydrogenation reacts for p-aminophenol:
Get 2 g paranitrophenols and 150 ml absolute ethyl alcohols are placed in reactor, then add 0.02 g catalyst; Install reaction unit, pass into nitrogen and purge about 15 minutes, the air in removing reactor, then passes into High Purity Hydrogen and makes pressure increase to 0.8 Mpa, being slowly warming up to 120 DEG C, lower reaction 8 h of insulation, and stir speed (S.S.) is 600 r/min; After reaction terminates, reaction mass is cooled to room temperature.Sample passes through chromatographic.
embodiment 2:
With embodiment 1, the temperature only changing reactor is respectively 80 DEG C, 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C, and carry out paranitrophenol selective hydrogenation reaction, acquired results is in table 1.
Table 1. is at 0.8MP H
2under, when catalyst amount is 0.02 g, at differential responses temperature, under insulation, react 8h, the conversion ratio of the selective and raw material of Ni/Ag/Cu/SBA-15 agent selective catalysis paranitrophenol hydrogenation reaction product p-aminophenol
embodiment 3:
With embodiment 1, the load capacity only changing active component Cu in catalyst is: 5 wt%, 10 wt%, namely the concentration of copper nitrate is respectively: 0.5404 mol/L and 1.4411 mol/L, carry out paranitrophenol selective hydrogenation reaction, acquired results is in table 2.
Table 2. is at 0.8MP H
2under, paranitrophenol consumption is 2 g, and reaction temperature is 120 DEG C, and the reaction time is 8h, the conversion ratio of the selective and raw material of the Ni/Ag/Cu/SBA-15 catalyst choice catalysis paranitrophenol hydrogenation reaction product p-aminophenol of different Cu load capacity
embodiment 4:
With embodiment 1, the load capacity only changing active component A g in catalyst is: 5 wt%, 10 wt%, namely the concentration of silver nitrate is respectively: 0.3184 mol/L and 0.8490 mol/L, carry out paranitrophenol selective hydrogenation reaction, acquired results is in table 3.
Table 3. is at 0.8MP H
2under, paranitrophenol consumption is 2 g, and reaction temperature is 120 DEG C, and the reaction time is 8h, the conversion ratio of the selective and raw material of the Ni/Ag/Cu/SBA-15 composite catalyst selective catalysis paranitrophenol hydrogenation reaction product p-aminophenol prepared under different silver-colored load capacity
embodiment 5:
With embodiment 1, the load capacity only changing active component Ni in catalyst is: 10wt%, 20 wt%, namely the concentration of nickel nitrate is respectively: 1.1702 mol/L and 3.1205 mol/L, carry out paranitrophenol selective hydrogenation reaction, acquired results is in table 4.
Table 4. is at 0.8MP H
2under, paranitrophenol consumption is 2 g, and reaction temperature is 120 DEG C, and the reaction time is 8h, the conversion ratio of the selective and raw material of the Ni/Ag/Cu/SBA-15 catalyst choice catalysis paranitrophenol hydrogenation reaction product p-aminophenol of the lower preparation of different nickel loading
Claims (3)
1. a preparation method for Ni/Ag/Cu/SBA-15 composite catalyst, is characterized in that, prepares according to following steps:
(1) SBA-15 of 200 mesh sieve dryings was taken, and measure the dipping volume of carrier S BA-15, take copper nitrate, preparation copper nitrate aqueous solution, equi-volume impregnating is adopted to be flooded by carrier S BA-15 copper nitrate aqueous solution, stirred at ambient temperature 24 h, makes copper nitrate solution and the full and uniform dipping of carrier S BA-15; First gained mixture is constantly stirred to drying at 60 DEG C, then dry 12 h at 110 DEG C, finally roasting 4 h at 450 DEG C, ground 200 mesh sieves obtain compound;
(2) take silver nitrate and prepare silver nitrate aqueous solution, flooded by step (1) gained compound silver nitrate aqueous solution, wherein the volume of silver nitrate aqueous solution is equal with the dipping volume of carrier S BA-15, at room temperature stirs 24 h; At 60 DEG C, be constantly stirred to drying, then dry 12 h at 110 DEG C, finally roasting 4 h at 450 DEG C, ground 200 mesh sieves obtain compound;
(3) take nickel nitrate and prepare nickel nitrate aqueous solution, flooded by step (2) gained compound nickel nitrate aqueous solution, wherein the volume of nickel nitrate aqueous solution is equal with the dipping volume of carrier S BA-15, at room temperature stirs 24 h; At 60 DEG C, be constantly stirred to drying, then dry 12 h at 110 DEG C, finally roasting 4 h at 450 DEG C, ground 200 mesh sieves obtain compound;
(4) step (3) gained compound is placed in stainless steel reaction pipe, first rises to 300 DEG C with the programming rate of 2-5 DEG C/min from room temperature, use H simultaneously
2-N
2gaseous mixture carries out purging reduction, wherein H
2and N
2volume ratio be 1:9, gas flow rate is 30-50 mL/min, subsequently, is warming up to 450 DEG C with the programming rate of 5-10 DEG C/min, simultaneously slowly improves H in gaseous mixture
2content, final H
2volume fraction is stablized to 30-40%, and reduces 6-10 h at this temperature, finally at N
2namely the Ni/Ag/Cu/SBA-15 catalyst of different loads amount is obtained after being down to room temperature in air-flow;
1wt%-10wt%, 1wt%-10wt%, 5wt%-20wt% is respectively according to the load capacity of active component Cu, Ag, Ni in the Ni/Ag/Cu/SBA-15 composite catalyst prepared by above-mentioned steps.
2. the preparation method of a kind of Ni/Ag/Cu/SBA-15 composite catalyst according to claim 1, it is characterized in that, prepared Ni/Ag/Cu/SBA-15 composite catalyst is applied to selective catalysis hydrogenation paranitrophenol and prepares p-aminophenol, carries out according to following step:
(1) get paranitrophenol and absolute ethyl alcohol is placed in reactor, then add Ni/Ag/Cu/SBA-15 composite catalyst;
(2) install reaction unit, pass into nitrogen and purge 15 minutes, the air in removing reactor, then passes into High Purity Hydrogen and makes pressure increase to 0.8 Mpa, being slowly warming up to 80-160 DEG C, lower reaction 8 h of insulation, and stir speed (S.S.) is 600 r/min;
(3), after reaction terminates, reaction mass is cooled to room temperature.
3. the preparation method of a kind of Ni/Ag/Cu/SBA-15 composite catalyst according to claim 2, it is characterized in that, wherein the ratio of the paranitrophenol described in step (1), absolute ethyl alcohol and Ni/Ag/Cu/SBA-15 composite catalyst is: 2 g:150 mL:0.02g.
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Citations (4)
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|---|---|---|---|---|
| GB1150277A (en) * | 1965-07-31 | 1969-04-30 | Nagynyomasu Kiserleti Intezet | Process for Producing Catalysts and Catalyst Carriers. |
| CN101041623A (en) * | 2007-04-26 | 2007-09-26 | 上海华谊丙烯酸有限公司 | Method for preparation of (substituted radical containted) aminophenol by catalytic hydrogenation of (substituted radical containted) nitrophenol |
| CN101301608A (en) * | 2008-06-26 | 2008-11-12 | 南京大学 | Silicon dioxide supported nano-silver catalyst, preparation and use thereof |
| WO2009016141A1 (en) * | 2007-07-31 | 2009-02-05 | Shell Internationale Research Maatschappij B.V. | Catalyst composition, its preparation and use |
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2013
- 2013-12-09 CN CN201310651269.1A patent/CN103691478B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1150277A (en) * | 1965-07-31 | 1969-04-30 | Nagynyomasu Kiserleti Intezet | Process for Producing Catalysts and Catalyst Carriers. |
| CN101041623A (en) * | 2007-04-26 | 2007-09-26 | 上海华谊丙烯酸有限公司 | Method for preparation of (substituted radical containted) aminophenol by catalytic hydrogenation of (substituted radical containted) nitrophenol |
| WO2009016141A1 (en) * | 2007-07-31 | 2009-02-05 | Shell Internationale Research Maatschappij B.V. | Catalyst composition, its preparation and use |
| CN101301608A (en) * | 2008-06-26 | 2008-11-12 | 南京大学 | Silicon dioxide supported nano-silver catalyst, preparation and use thereof |
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