CN103623861A - Preparation of Ni/Ag/MCM-41 composite catalyst and application thereof - Google Patents
Preparation of Ni/Ag/MCM-41 composite catalyst and application thereof Download PDFInfo
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- CN103623861A CN103623861A CN201310651270.4A CN201310651270A CN103623861A CN 103623861 A CN103623861 A CN 103623861A CN 201310651270 A CN201310651270 A CN 201310651270A CN 103623861 A CN103623861 A CN 103623861A
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Abstract
The invention relates to preparation of Ni/Ag/MCM-41 composite catalyst and application thereof, and belongs to the fields of nano-catalyst preparation and catalysis research. The preparation can be implemented through the following steps: firstly, preparing Ni/Ag/MCM-41 composite supported catalysts with different loading capacities by using silver nitrate and nickel nitrate as raw materials and prepared MAM-41 as a carrier and adopting an equivalent-volume impregnation method; then by using p-nitrophenol and absolute ethyl alcohol as raw materials and adopting a Ni/Ag/MCM-41 compound as a catalyst, adopting H2 under the pressure of 0.8Mpa, enabling the reaction temperature to rise to 80-160 DEG C, and performing thermal reaction for 2-8 h, so as to obtain high-purity p-aminophenol. The prepared Ni/Ag/MCM-41 composite catalyst disclosed by the invention is small in use amount, and has high catalytic activity and stability; the method for preparing the p-aminophenol by adopting the catalyst is simple in technological requirement, and meets the 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 have caused widely and have paid close attention at numerous areas such as catalysis, medicine, communication, biology, environmental protection, become one of the most active field of researching and developing in the world.Nanoparticle is because size is little, and surperficial shared percentage by volume is large, and the key state on surface is different from granule interior with electronic state, and surface atom coordination is not congruent causes surperficial activity site to increase, and this just makes it possess the primary condition as catalyst.It is reported, compare with traditional metal catalyst, nano-metal particle, as: palladium, platinum, rhodium, ruthenium, gold and nickel all show higher catalytic activity in catalytic hydrogenation, catalytic oxidation.For example: the activity that Nano Silver (2-4 nm) catalytic oxidation ethene is prepared 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, in fields such as pharmacy, dyestuff, spices, polyurethane rubber, agricultural chemicals and nonlinear optical materials, has very important application.For example, in medical industry, para-aminophenol prepared by p-nitrophenol catalytic hydrogenation is the intermediate of producing anodyne and antipyretic.At present, in the industrial production of aromatic amine compound, catalytic hydrogenation method used catalyst is mainly the rare precious metals such as Raney-Ni and Pt, Pd, Ru, Rh.
Metallic catalyst, particularly precious metal, due to expensive, be attached on high surface and macroporous carrier and be often dispersed into small particle, reduced like this content of active component, reduced 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 of putting by force (suction) thermal response, carrier generally should have larger thermal capacitance and good thermal conductivity, make to react heat energy and pass 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, thereby improve the selective of catalyst.Nickel catalyst carriedly in many hydrogenation reactions, be applied, if MDNB is at Ni/SiO
2m-phenylene diamine (MPD) is synthesized in liquid-phase hydrogenatin, and MDNB conversion ratio and m-phenylene diamine (MPD) selectively reach respectively more than 99.9% and 99.6%.Therefore, research Ni/Ag/MCM-41 support type composite catalyst selective catalysis hydrogenation paranitrophenol is prepared p-aminophenol, 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, and high selectivity, and there is good stability in use.
Technical scheme of the present invention is as follows:
A Ni/Ag/MCM-41 composite catalyst, take silver nitrate, nickel nitrate is raw material, MCM-41 is carrier, adopts equi-volume impregnating preparation.
Preparation process is:
(1) take the dry MCM-41 of 200 mesh sieves, and measured the dipping volume of carrier MCM-41; Take silver nitrate and prepare silver nitrate aqueous solution, adopt equi-volume impregnating that carrier MCM-41 is flooded with silver nitrate aqueous solution, under room temperature, stir 24 h, make liquor argenti nitratis ophthalmicus and the full and uniform dipping of carrier MCM-41.First gained compound is constantly stirred under 60 ℃ of conditions dry, dry 12 h at 110 ℃ then, finally roasting 4 h at 450 ℃, 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, step (1) gained compound is flooded with nickel nitrate aqueous solution, wherein nickel nitrate aqueous solution volume equates with the dipping volume of carrier MCM-41, stirs 24 h under room temperature.At 60 ℃, be constantly stirred to dry, dry 12 h at 110 ℃ then, finally roasting 4 h at 450 ℃, ground 200 mesh sieves, in compound, the load capacity of nickel is 5wt%-20 wt %.
(3) step (2) gained compound is placed in to stainless steel reaction pipe, first the programming rate with 2-5 ℃/min rises to 300 ℃ from room temperature, uses H simultaneously
2-N
2gaseous mixture purges reduction, wherein H
2and N
2volume ratio be 1:9, gas flow rate is 30-50 mL/min, subsequently, with the programming rate of 5-10 ℃/min, is warming up to 450 ℃, slowly improves gaseous mixture H simultaneously
2content, final H
2volume fraction is stablized to 30-40%, and at this temperature, reduces 6-10 h, finally at N
2in air-flow, be down to room temperature, obtain the Ni/Ag/MCM-41 composite catalyst of different loads amount.
According to the prepared Ni/Ag/MCM-41 composite catalyst of 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 prepared Ni/Ag/MCM-41 composite catalyst of above step, be applied to catalytic hydrogenation paranitrophenol and prepare p-aminophenol, according to following step, carry out:
(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 blowing approximately 15 minutes, remove the air in reactor, then pass into High Purity Hydrogen and make pressure increase to 0.8 Mpa, be slowly warming up to 80-160 ℃, lower reaction 8 h of insulation, stir speed (S.S.) is 600 r/min;
(3) after reaction finishes, reaction mass is cooled to room temperature.Sample is analyzed with gas chromatograph.
The invention has the advantages that:
In the prepared nickel of the present invention, silver-colored support type composite catalyst, different key component nickel, silver selectively have a significant impact to the catalytic activity of composite catalyst, product.Meanwhile, the interaction between the characteristic such as carrier MCM-41 specific area is large, aperture is little and carrier MCM-41 and Ni, Ag, also has 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, thereby avoided the generation of a large amount of accessory substances, improved the selective of catalyst, make product purity high, profit is worth and raises, and manufacturing technique requirent is simple, is applicable to industrial requirement.
The specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described.
embodiment 1:
1. catalyst preparation:
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 that records MCM-41 is 1.31 mL/g.Preparation concentration is the silver nitrate aqueous solution of 0.0753 mol/L, with 12.183mL silver nitrate aqueous solution and carrier MCM-41 incipient impregnation, stirs 24 h under room temperature, makes liquor argenti nitratis ophthalmicus and the full and uniform dipping of carrier MCM-41.First gained mixture is constantly stirred at 60 ℃ dry, then dry 12 h, finally roasting 4 h at 450 ℃ at 110 ℃.
(2) prepare the nickel nitrate aqueous solution that concentration is 0.6918 mol/L, by 12.183mL nickel nitrate aqueous solution dipping for step (1) gained compound, under room temperature, stir 24 h.At 60 ℃, be constantly stirred to dry, dry 12 h at 110 ℃ then, finally roasting 4 h at 450 ℃, ground 200 mesh sieves.
(3) step (2) gained compound is placed in to stainless steel reaction pipe, first the programming rate with 2-5 ℃/min rises to 300 ℃ from room temperature, uses H simultaneously
2-N
2gaseous mixture (1:9/V:V) purges reduction, and gas flow rate is 30-50 mL/min, subsequently, with the programming rate of 5-10 ℃/min, is warming up to 450 ℃, slowly improves gaseous mixture H simultaneously
2content, final H
2volume fraction is stablized to 30-40%, and at this temperature, reduces 6-10 h, finally at N
2in air-flow, be down to room temperature.The final Ag/Ni/MCM-41 composite catalyst that obtains, 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 blowing approximately 15 minutes, remove the air in reactor, then pass into High Purity Hydrogen and make pressure increase to 0.8 Mpa, be slowly warming up to 120 ℃, lower reaction 8 h of insulation, stir speed (S.S.) is 600 r/min; After reaction finishes, reaction mass is cooled to room temperature.Sample is analyzed by gas chromatograph.
embodiment 2:
0.02,0.04,0.06,0.1g with embodiment 1, only change catalyst amount and be:, carry out paranitrophenol selective hydrogenation reaction.Selective and the feed stock conversion of products therefrom is in Table 1.
Table 1. is at 0.8MP H
2under, reaction temperature is 120 ℃, the lower reaction 8h of insulation, and during different catalysts consumption, 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 that only changes reactor is respectively 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, carries out paranitrophenol selective hydrogenation reaction, and 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, the lower reaction 8h of insulation, 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 that only changes active component A g in catalyst is respectively 5 wt% and 10 wt%, and the concentration of silver nitrate is respectively: 0.4163 mol/L and 1.0110 mol/L, carry out paranitrophenol selective hydrogenation reaction, and acquired results is in Table 3.
Table 3 is at 0.8MP H
2under, paranitrophenol consumption is 2 g, and reaction temperature is 120 ℃, 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 preparing 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%, 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 ℃, 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 loadings
Claims (4)
1. a preparation method for Ni/Ag/MCM-41 composite catalyst, is characterized in that, according to following steps system
Standby:
Take the dry MCM-41 of 200 mesh sieves, and measured the dipping volume of carrier MCM-41;
Take silver nitrate and prepare silver nitrate aqueous solution, adopt equi-volume impregnating that carrier MCM-41 is flooded with silver nitrate aqueous solution, under room temperature, stir 24 h, make liquor argenti nitratis ophthalmicus and the full and uniform dipping of carrier MCM-41; First gained compound is constantly stirred under 60 ℃ of conditions dry, dry 12 h at 110 ℃ then, finally roasting 4 h at 450 ℃, 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, step (1) gained compound is flooded with nickel nitrate aqueous solution, wherein nickel nitrate aqueous solution volume equates with the dipping volume of carrier MCM-41, stirs 24 h under room temperature; At 60 ℃, be constantly stirred to dry, dry 12 h at 110 ℃ then, finally roasting 4 h at 450 ℃, ground 200 mesh sieves, in compound, the load capacity of nickel is 5wt%-20 wt %;
(3) step (2) gained compound is placed in to stainless steel reaction pipe, first the programming rate with 2-5 ℃/min rises to 300 ℃ from room temperature, uses H simultaneously
2-N
2gaseous mixture purges reduction, wherein H
2and N
2volume ratio be 1:9, gas flow rate is 30-50 mL/min, subsequently, with the programming rate of 5-10 ℃/min, is warming up to 450 ℃, slowly improves gaseous mixture H simultaneously
2content, final H
2volume fraction is stablized to 30-40%, and at this temperature, reduces 6-10 h, finally at N
2in air-flow, be down to room temperature, obtain the Ni/Ag/MCM-41 composite catalyst of different loads amount.
2. the preparation method of a kind of Ni/Ag/MCM-41 composite catalyst according to claim 1, is characterized in that, according to the prepared Ni/Ag/MCM-41 composite catalyst of above step, the load capacity of middle active component A g, Ni is respectively 1%-10%, 5%-20%.
3. the preparation method of a kind of Ni/Ag/MCM-41 composite catalyst according to claim 1, it is characterized in that, according to the prepared Ni/Ag/MCM-41 composite catalyst of above step, be applied to catalytic hydrogenation paranitrophenol and prepare p-aminophenol, according to following step, carry out:
(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 blowing approximately 15 minutes, remove the air in reactor, then pass into High Purity Hydrogen and make pressure increase to 0.8 Mpa, be slowly warming up to 80-160 ℃, lower reaction 8 h of insulation, stir speed (S.S.) is 600 r/min;
(3) after reaction finishes, reaction mass is cooled to room temperature.
4. the preparation method of a kind of Ni/Ag/MCM-41 composite catalyst according to claim 3, it is characterized in that, wherein the ratio of the paranitrophenol described in step (1), absolute ethyl alcohol and Ni/Ag/MCM-41 composite catalyst is: 2 g:150 mL:0.02g-0.1g.
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Cited By (3)
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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 |
| CN112275323A (en) * | 2020-11-15 | 2021-01-29 | 南开大学 | Preparation method and application of nickel-based Ni-MOF-Ni/MCM-41 composite material |
| CN115634697A (en) * | 2022-10-21 | 2023-01-24 | 宁夏大学 | Bimetallic catalyst for dry reforming reaction of methane and carbon dioxide and preparation thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN112275323A (en) * | 2020-11-15 | 2021-01-29 | 南开大学 | Preparation method and application of nickel-based Ni-MOF-Ni/MCM-41 composite material |
| 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 |
| CN115634697A (en) * | 2022-10-21 | 2023-01-24 | 宁夏大学 | Bimetallic catalyst for dry reforming reaction of methane and carbon dioxide and preparation thereof |
| 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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