CN103638948B - A kind of Ni/Ag/Cu/Al 2o 3the preparation of composite catalyst and application thereof - Google Patents
A kind of Ni/Ag/Cu/Al 2o 3the preparation of composite catalyst and application thereof Download PDFInfo
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- CN103638948B CN103638948B CN201310651281.2A CN201310651281A CN103638948B CN 103638948 B CN103638948 B CN 103638948B CN 201310651281 A CN201310651281 A CN 201310651281A CN 103638948 B CN103638948 B CN 103638948B
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Abstract
The present invention relates to a kind of Ni/Ag/Cu/Al
2o
3the preparation of composite catalyst and application thereof, belong to nanocatalyst preparation and catalyticing research field.Belonging to catalyst carry out according to following step: first with copper nitrate, silver nitrate, nickel nitrate for raw material, Al
2o
3for carrier, equi-volume impregnating is adopted to prepare the Ni/Ag/Cu/Al of different loads amount
2o
3composite catalyst.Then with p-nitrophenol, absolute ethyl alcohol for raw material, adopt this catalyst to carry out catalytic hydrogenation reaction, high-purity p-aminophenol can be obtained.This catalyst amount is few, high activity, high selectivity, and has good stability in use; Use the method technological requirement of this catalyst preparing p-aminophenol simple, be applicable to industrial requirement.
Description
Technical field
The present invention relates to a kind of Ni/Ag/Cu/Al
2o
3the preparation method of composite catalyst and application thereof, 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, Ni/Ag/Cu/Al is studied
2o
3p-aminophenol prepared by support type 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/Al
2o
3support type composite catalyst, and prepare 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/Al
2o
3composite catalyst, with silver nitrate, copper nitrate, nitric acid acid nickel, Al
2o
3for raw material, adopt equi-volume impregnating preparation.
Preparation process is:
(1) Al of 200 mesh sieve dryings was taken
2o
3, and measure carrier A l
2o
3dipping volume, take copper nitrate and prepare copper nitrate aqueous solution, adopt equi-volume impregnating by carrier A l
2o
3with copper nitrate aqueous solution dipping, stirred at ambient temperature 24 h, makes copper nitrate solution and carrier A l
2o
3full and uniform dipping; First gained mixture is constantly stirred to drying under 60 DEG C of conditions, 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%-10 wt%.
(2) take silver nitrate and prepare silver nitrate aqueous solution, step (1) gained compound silver nitrate aqueous solution is flooded, wherein the volume of silver nitrate aqueous solution and carrier A l
2o
3dipping volume equal, at room temperature stir 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, step (2) gained compound nickel nitrate aqueous solution is flooded, wherein the volume of nickel nitrate aqueous solution and carrier A l
2o
3dipping volume equal, at room temperature stir 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/Al of different loads amount is obtained after being down to room temperature in air-flow
2o
3composite catalyst.
According to the Ni/Ag/Cu/Al prepared by above step
2o
3composite catalyst, 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%.
According to the Ni/Ag/Cu/Al prepared by above step
2o
3composite catalyst, is applied to catalytic hydrogenation paranitrophenol and prepares p-aminophenol, specifically carry out according to following step:
(1) get paranitrophenol and absolute ethyl alcohol is placed in reactor, then add Ni/Ag/Cu/Al
2o
3composite catalyst, wherein paranitrophenol, absolute ethyl alcohol, Ni/Ag/Cu/Al
2o
3the ratio of composite catalyst is: 2 g:150 mL:0.01-0.1 g;
(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 0.6-1.2 Mpa, being slowly warming up to 80-160 DEG C, insulation lower reaction 2-8 h, and stir speed (S.S.) is 600 rpm;
(3), after reaction terminates, reaction mass is cooled to room temperature.Sample gas chromatograph is analyzed.
The invention has the advantages that:
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.Carrier A l
2o
3for amphoteric oxide, himself inherent characteristic and Al
2o
3and active component Ni, interaction between Ag, Cu, to catalytic activity, the selectivity of product important 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, selective 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/Al
2o
3composite catalyst is prepared by equi-volume impregnating, and raw material is copper nitrate, silver nitrate, nickel nitrate and Al
2o
3.
(1) 9.3g carrier A l is taken
2o
3, measure carrier A l
2o
3dipping volume be 0.8mL/g, take copper nitrate configuration copper nitrate aqueous solution, wherein the concentration of copper nitrate aqueous solution is 0.7243 mol/L, by 7.44mL copper nitrate aqueous solution and carrier A l
2o
3incipient impregnation, stirred at ambient temperature 24 h, makes copper nitrate solution and carrier A l
2o
3full and uniform dipping.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.
(2) take silver nitrate configuration silver nitrate aqueous solution, wherein the concentration of silver nitrate aqueous solution is 0.2115 mol/L, by step (1) gained compound 7.44mL silver nitrate aqueous solution dipping, and stirred at ambient temperature 24 h.Constantly drying is stirred to, then dry 12 h at 110 DEG C, finally roasting 4 h at 450 DEG C at 60 DEG C.
(3) take nickel nitrate configuration nickel nitrate aqueous solution, wherein the concentration of nickel nitrate aqueous solution is 1.1450 mol/L, by step (1) gained compound 7.44mL nickel nitrate aqueous solution dipping, and stirred at ambient temperature 24 h.Constantly drying is stirred to, then dry 12 h at 110 DEG C, finally roasting 4 h at 450 DEG C, ground 200 mesh sieves at 60 DEG C.
(4) step (3) gained compound is placed in stainless steel reaction pipe, first rises to 300 DEG C with the programming rate of 2 DEG C/min from room temperature, use H simultaneously
2-N
2gaseous mixture (1:9/V:V) carries out purging reduction, subsequently, is warming up to 450 DEG C with the programming rate of 5 DEG C/min, slowly improves gaseous mixture H simultaneously
2content, final H
2volume fraction is stablized to 30%, and reduces 8 h at this temperature, finally at N
2room temperature is down in air-flow.Final gained Ni/Ag/Cu/Al
2o
3in composite catalyst, the load capacity of active component Cu, Ag, Ni is respectively 1wt%, 1wt%, 5wt%.
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 rpm; After reaction terminates, reaction mass is cooled to room temperature.Sample passes through chromatographic.
embodiment 2:
With embodiment 1, only changing catalyst amount is: 0.01,0.02,0.06,0.1g, carry out paranitrophenol selective hydrogenation reaction.Products therefrom selective with feed stock conversion in table 1.
Table 1. is at 0.8MP H
2under, reaction temperature is 120 DEG C, reacts 8h under insulation, during different catalysts consumption, and Ni/Ag/Cu/Al
2o
3the conversion ratio of the selective and raw material of composite catalyst selective catalysis paranitrophenol hydrogenation reaction product p-aminophenol
embodiment 3:
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 2.
Table 2. is at 0.8MP H
2under, when catalyst amount is 0.08 g, at differential responses temperature, react 8h under insulation, Ni/Ag/Cu/Al
2o
3the conversion ratio of the selective and raw material of composite catalyst selective catalysis paranitrophenol hydrogenation reaction product p-aminophenol
embodiment 4:
With embodiment 1, only the change reaction time is respectively 2h, 4h, 6h, and carry out paranitrophenol selective hydrogenation reaction, acquired results is in table 3.
Table 3. is at 0.8MP H
2under, catalyst amount is 0.08 g, and reaction temperature is 120 DEG C, under the differential responses time, and Ni/Ag/Cu/Al
2o
3the conversion ratio of the selective and raw material of composite catalyst selective catalysis paranitrophenol hydrogenation reaction product p-aminophenol
embodiment 5:
With embodiment 1, the load capacity only changing active component Cu in catalyst is 5 wt%, 10wt%, and namely the concentration of copper nitrate changes into 1.2294 mol/L and 3.2785 mol/L respectively, and 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 the Ni/Ag/Cu/Al of 8h, different Cu load capacity
2o
3the conversion ratio of the selective and raw material of composite catalyst selective catalysis paranitrophenol hydrogenation reaction product p-aminophenol
embodiment 6:
With embodiment 1, the load capacity only changing active component A g in catalyst is 5 wt%, 10wt%, and namely the concentration of silver nitrate changes into 0.7243 mol/L and 1.9314 mol/L respectively, and carry out paranitrophenol selective hydrogenation reaction, acquired results is in table 5.
Table 5. 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 Ni/Ag/Cu/Al of different silver-colored load capacity
2o
3the conversion ratio of the selective and raw material of composite catalyst selective catalysis paranitrophenol hydrogenation reaction product p-aminophenol
embodiment 7:
With embodiment 1, only changing the load capacity of active component Ni in catalyst is 10 wt%, 20wt%, and namely the concentration of copper nitrate changes into 2.6621 mol/L and 7.0991 mol/L carry out paranitrophenol selective hydrogenation reaction respectively, and acquired results is in table 6.
Table 6. 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 Ni/Ag/Cu/Al of the lower preparation of different nickel loading
2o
3the conversion ratio of the selective and raw material of composite catalyst selective catalysis paranitrophenol hydrogenation reaction product p-aminophenol
embodiment 8:
With embodiment 1, only change reaction pressure be 0.6,0.8,1.2MP H
2carry out paranitrophenol selective hydrogenation reaction, acquired results is in table 7.
Table 7. is at different H
2under pressure, paranitrophenol consumption is 2 g, and reaction temperature is 120 DEG C, and the reaction time is 8h, Ni/Ag/Cu/Al
2o
3the conversion ratio of the selective and raw material of composite catalyst selective catalysis paranitrophenol hydrogenation reaction product p-aminophenol
Claims (4)
1. a Ni/Ag/Cu/Al
2o
3the preparation method of composite catalyst, is characterized in that, according to following steps system
Standby:
(1) Al of 200 mesh sieve dryings was taken
2o
3, and measure carrier A l
2o
3dipping volume, take copper nitrate and prepare copper nitrate aqueous solution, adopt equi-volume impregnating by carrier A l
2o
3with copper nitrate aqueous solution dipping, stirred at ambient temperature 24 h, makes copper nitrate solution and carrier A l
2o
3full and uniform dipping; 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 this step gained compound, the load capacity of copper is 1wt%-10 wt%;
(2) take silver nitrate and prepare silver nitrate aqueous solution, step (1) gained compound silver nitrate aqueous solution is flooded, wherein the volume of silver nitrate aqueous solution and carrier A l
2o
3dipping volume equal, at room temperature stir 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 this step gained compound, the load capacity of silver is 1wt%-10 wt %;
(3) take nickel nitrate and prepare nickel nitrate aqueous solution, step (2) gained compound nickel nitrate aqueous solution is flooded, wherein the volume of nickel nitrate aqueous solution and carrier A l
2o
3dipping volume equal, at room temperature stir 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 this step gained 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/Al of different loads amount is obtained after being down to room temperature in air-flow
2o
3composite catalyst.
2. a kind of Ni/Ag/Cu/Al according to claim 1
2o
3the preparation method of composite catalyst, is characterized in that, prepared Ni/Ag/Cu/Al
2o
3in composite catalyst, the load capacity of active component Cu, Ag, Ni is respectively 1%-10%, 1%-10%, 5%-20%.
3. a kind of Ni/Ag/Cu/Al according to claim 1
2o
3the preparation method of composite catalyst, is characterized in that, prepared Ni/Ag/Cu/Al
2o
3composite 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/Al
2o
3composite catalyst;
(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 0.6-1.2 Mpa, being slowly warming up to 80-160 DEG C, insulation lower reaction 2-8 h, and stir speed (S.S.) is 600 rpm;
(3), after reaction terminates, reaction mass is cooled to room temperature.
4. a kind of Ni/Ag/Cu/Al according to claim 3
2o
3the preparation method of composite catalyst, is characterized in that, wherein paranitrophenol, absolute ethyl alcohol, the Ni/Ag/Cu/Al described in step (1)
2o
3the ratio of composite catalyst is: 2 g:150 mL:0.01-0.1 g.
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| CN105294459B (en) * | 2015-11-30 | 2018-03-06 | 辽宁石油化工大学 | A kind of Ag Cu/CuFe2O4The preparation and its application of magnetic coupling catalyst |
| CN112337481B (en) * | 2020-09-14 | 2021-08-24 | 昆明理工大学 | Application of catalyst capable of removing hydrogen cyanide and ammonia gas simultaneously in treatment of tail gas containing hydrogen cyanide and ammonia gas |
| CN113278238A (en) * | 2021-05-20 | 2021-08-20 | 广东恩泰环保新材料科技有限公司 | Low-temperature water-soluble film |
| CN113694936A (en) * | 2021-08-13 | 2021-11-26 | 江苏大学 | Copper-silver-gold nano alloy catalyst and preparation method and application thereof |
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| CN101007275B (en) * | 2007-01-25 | 2010-04-07 | 南京工业大学 | Catalyst used in the catalytic hydrogenation of p-nitrophenol and its preparation method |
| CN100554243C (en) * | 2007-04-26 | 2009-10-28 | 上海华谊丙烯酸有限公司 | The method of a kind of (containing substituent) nitrophenols shortening preparation (containing substituent) amino-phenol |
| US20110250122A1 (en) * | 2008-11-07 | 2011-10-13 | The Regents Of The University Of California | Core-Shell Nanocatalyst For High Temperature Reactions |
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