CN103623861B - A kind of preparation of Ni/Ag/MCM-41 composite catalyst and application thereof - Google Patents
A kind of preparation of Ni/Ag/MCM-41 composite catalyst and application thereof Download PDFInfo
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Abstract
The present invention relates to preparation and the application thereof of Ni-Ag-MCM-41 composite catalyst, belong to nanocatalyst preparation and catalyticing research field.Carry out according to following step: first with silver nitrate, nickel nitrate for raw material, the MAM-41 of preparation is carrier, adopts equi-volume impregnating to prepare the Ni/Ag/MCM-41 Compound Negative supported catalyst of different loads amount.Then with p-nitrophenol, absolute ethyl alcohol for raw material, adopt Ni/Ag/MCM-41 compound as catalyst, at 0.8MPaH
2under pressure, reaction temperature is made to be warming up to 80-160 DEG C, and insulation reaction 8h, obtain high-purity p-aminophenol.Ni/Ag/MCM-41 composite catalyst prepared by the present invention, consumption is few, has high catalytic activity and stability.The method technological requirement preparing p-aminophenol with this catalyst is simple, is applicable to industrial requirement.
Description
Technical field
The present invention relates to preparation and the application thereof of Ni/Ag/MCM-41 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/MCM-41 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/MCM-41 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/MCM-41 composite catalyst, with silver nitrate, nickel nitrate for raw material, MCM-41 is carrier, adopts equi-volume impregnating preparation.
Preparation process is:
(1) take the MCM-41 of 200 mesh sieve dryings, and measure the dipping volume of carrier MCM-41; Take silver nitrate and prepare silver nitrate aqueous solution, adopt equi-volume impregnating to be flooded by carrier MCM-41 silver nitrate aqueous solution, stirred at ambient temperature 24 h, makes liquor argenti nitratis ophthalmicus and the full and uniform dipping of carrier MCM-41.First gained compound 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 compound, the load capacity of silver is 1wt%-10 wt %.
(2) take nickel nitrate and prepare nickel nitrate aqueous solution, flooded by step (1) gained compound nickel nitrate aqueous solution, wherein nickel nitrate aqueous solution volume is equal with the dipping volume of carrier MCM-41, stirred at ambient temperature 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 %.
(3) step (2) 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
2be down to room temperature in air-flow, obtain the Ni/Ag/MCM-41 composite catalyst of different loads amount.
According to the Ni/Ag/MCM-41 composite catalyst prepared by above step, it is characterized in that, in this composite catalyst, the load capacity of active component A g, Ni is respectively 1%-10%, 5%-20%.
According to the Ni/Ag/MCM-41 composite catalyst prepared by above step, be applied to catalytic hydrogenation paranitrophenol and prepare p-aminophenol, carry out according to following step:
(1) get paranitrophenol and absolute ethyl alcohol is placed in reactor, then add Ni/Ag/MCM-41 composite catalyst, wherein, the ratio of paranitrophenol, absolute ethyl alcohol and Ni/Ag/MCM-41 composite catalyst is: 2 g:150 mL:0.02g-0.1g;
(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.
The invention has the advantages that:
In nickel prepared by the present invention, silver-colored support type composite catalyst, different key component nickel, silver have significant impact to the catalytic activity of composite catalyst, the selective of product.Meanwhile, characteristic and the interactions between carrier MCM-41 and Ni, Ag such as carrier MCM-41 specific area is large, aperture is little, also have material impact to the catalytic activity of catalyst.Compare with single metal load type catalyst with single metallic catalyst, the polynary nanometer metal load type catalyst of preparation has good catalytic activity and stability in catalytic reaction process, 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/MCM-41 composite catalyst is prepared by equi-volume impregnating, and raw material is silver nitrate, nickel nitrate and MCM-41.
(1) take 9.3g carrier MCM-41, the dipping volume recording MCM-41 is 1.31 mL/g.Preparation concentration is the silver nitrate aqueous solution of 0.0753 mol/L, and with 12.183mL silver nitrate aqueous solution and carrier MCM-41 incipient impregnation, stirred at ambient temperature 24 h, makes liquor argenti nitratis ophthalmicus and the full and uniform dipping of carrier MCM-41.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) nickel nitrate aqueous solution that concentration is 0.6918 mol/L is prepared, by step (1) gained compound 12.183mL nickel nitrate aqueous solution dipping, 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.
(3) step (2) 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 (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 Ag/Ni/MCM-41 composite catalyst, wherein in composite catalyst, the load capacity of active component A g, Ni is respectively 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, only changing catalyst amount is: 0.02,0.04,0.06,0.1g, 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 the conversion ratio of the selective and raw material of Ni/Ag/MCM-41 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 1.
Table 2. 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/MCM-41 composite catalyst selective catalysis paranitrophenol hydrogenation reaction product p-aminophenol
embodiment 4:
With embodiment 1, the load capacity only changing active component A g in catalyst is respectively 5 wt% and 10 wt%, and namely the concentration of silver nitrate is respectively: 0.4163 mol/L and 1.0110 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/MCM-41 composite catalyst selective catalysis paranitrophenol hydrogenation reaction product p-aminophenol prepared under different silver-colored load capacity
embodiment 5:
With embodiment 1, only change load capacity 10 wt% of active component Ni in catalyst, 20 wt%, namely the concentration of nickel nitrate is respectively: 1.5301 mol/L and 3.7160 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/MCM-41 composite catalyst selective catalysis paranitrophenol hydrogenation reaction product p-aminophenol of the lower preparation of different nickel loading
Claims (2)
1. a preparation method for Ni/Ag/MCM-41 composite catalyst, is characterized in that, prepares according to following steps:
(1) take the MCM-41 of 200 mesh sieve dryings, and measure the dipping volume of carrier MCM-41;
Take silver nitrate and prepare silver nitrate aqueous solution, adopt equi-volume impregnating to be flooded by carrier MCM-41 silver nitrate aqueous solution, stirred at ambient temperature 24h, makes liquor argenti nitratis ophthalmicus and the full and uniform dipping of carrier MCM-41; First gained compound is constantly stirred to drying under 60 DEG C of conditions, then dry 12h at 110 DEG C, finally roasting 4h at 450 DEG C, ground 200 mesh sieves, in compound, the load capacity of silver is 1wt%-10wt%;
(2) take nickel nitrate and prepare nickel nitrate aqueous solution, flooded by step (1) gained compound nickel nitrate aqueous solution, wherein nickel nitrate aqueous solution volume is equal with the dipping volume of carrier MCM-41, stirred at ambient temperature 24h; At 60 DEG C, be constantly stirred to drying, then dry 12h at 110 DEG C, finally roasting 4h at 450 DEG C, ground 200 mesh sieves, in compound, the load capacity of nickel is 5wt%-20wt%;
(3) step (2) 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 30-50mL/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 6-10h at this temperature, finally at N
2be down to room temperature in air-flow, obtain the Ni/Ag/MCM-41 composite catalyst of different loads amount;
1%-10%, 5%-20% is respectively according to the load capacity of active component A g, Ni in the Ni/Ag/MCM-41 composite catalyst prepared by above step.
2. the application of p-aminophenol prepared by the Ni/Ag/MCM-41 composite catalyst that according to claim 1 prepared by method as catalytic hydrogenation paranitrophenol, it is characterized in that, described application is carried out according to following step:
(1) get paranitrophenol and absolute ethyl alcohol is placed in reactor, then add Ni/Ag/MCM-41 composite catalyst;
(2) install reaction unit, pass into nitrogen and purge about 15 minutes, the air in removing reactor, then pass into High Purity Hydrogen and make pressure increase to 0.8Mpa, being slowly warming up to 80-160 DEG C, reacting 8h under insulation, stir speed (S.S.) is 600r/min;
(3), after reaction terminates, reaction mass is cooled to room temperature;
Wherein the ratio of the paranitrophenol described in step (1), absolute ethyl alcohol and Ni/Ag/MCM-41 composite catalyst is: 2g:150mL:0.02g-0.1g.
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| CN105126869A (en) * | 2015-08-26 | 2015-12-09 | 辽宁石油化工大学 | Method for preparing p-aminophenol by adopting Ni/Ag/Fe3O4 complex catalyst |
| CN112275323B (en) * | 2020-11-15 | 2022-06-28 | 南开大学 | Preparation method and application of nickel-based Ni-MOF-Ni/MCM-41 composite material |
| CN115634697B (en) * | 2022-10-21 | 2024-03-29 | 宁夏大学 | Bimetallic catalyst for dry reforming reaction of methane and carbon dioxide and preparation thereof |
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| CN101007275A (en) * | 2007-01-25 | 2007-08-01 | 南京工业大学 | Catalyst used in the catalytic hydrogenation of p-nitrophenol and its preparation method |
| CN101007277A (en) * | 2006-01-26 | 2007-08-01 | 中国科学院大连化学物理研究所 | Catalyst for synthesis of indole and its preparation method |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101007277A (en) * | 2006-01-26 | 2007-08-01 | 中国科学院大连化学物理研究所 | Catalyst for synthesis of indole and its preparation method |
| CN101007275A (en) * | 2007-01-25 | 2007-08-01 | 南京工业大学 | Catalyst used in the catalytic hydrogenation of p-nitrophenol and its preparation method |
| 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 |
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