CN103691478A - Preparation and application of Ni/Ag/Cu/SBA-15 compound catalyst - Google Patents
Preparation and application of Ni/Ag/Cu/SBA-15 compound catalyst Download PDFInfo
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Abstract
The invention relates to preparation and application of an Ni/Ag/Cu/SBA-15 compound catalyst, belonging to the field of preparation and catalysis research of a nano catalyst. The preparation is carried out according to the following step of firstly, by adopting cupric nitrate, silver nitrate and nickel nitrate as raw materials and SBA-15 as a carrier, preparing the Ni/Ag/Cu/SBA-15 compound load type catalyst with different loading capacities by adopting an equivalent-volume impregnation method, then by using paranitrophenol and absolute ethyl alcohol as raw materials and an Ni/Ag/Cu/SBA-15 composite as a catalyst, performing selective catalytic hydrogenation on paranitrophenol to prepare p-aminophenol. The Ni/Ag/Cu/SBA-15 compound catalyst prepared by adopting the preparation method is less in consumption, high in catalysis activity and stability, and high in selectivity for a specific reaction. According to the method for preparing the p-aminophenol by using the Ni/Ag/Cu/SBA-15 composite as the catalyst, the process requirement is simple, and the catalyst is suitable for industrialized 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 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/Cu/SBA-15 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/Cu/SBA-15 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/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) took the dry SBA-15 of 200 mesh sieves, and measure the dipping volume of carrier S BA-15, take copper nitrate, preparation copper nitrate aqueous solution, adopt equi-volume impregnating that carrier S BA-15 is flooded with copper nitrate aqueous solution, under room temperature, stir 24 h, make copper nitrate solution and the full and uniform dipping of carrier S BA-15; First gained mixture is constantly stirred at 60 ℃ dry, dry 12 h at 110 ℃ then, finally roasting 4 h at 450 ℃, 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, step (1) gained compound is flooded with silver nitrate aqueous solution, wherein the volume of silver nitrate aqueous solution equates with the dipping volume of carrier S BA-15, at room temperature stirs 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, 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 is flooded with nickel nitrate aqueous solution, wherein the volume of nickel nitrate aqueous solution equates with the dipping volume of carrier S BA-15, at room temperature stirs 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, in compound, the load capacity of nickel is 5wt%-20 wt %.
(4) step (3) 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 the Ni/Ag/Cu/SBA-15 agent that obtains different loads amount after room temperature.
According to the prepared Ni/Ag/Cu/SBA-15 composite catalyst of 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 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.
Beneficial effect of the present invention:
In the prepared nickel of the present invention, silver, copper support type composite catalyst, the size of different key component nano nickels, Nano Silver, Nanometer Copper, structure, pattern etc. selectively have a significant impact to the catalytic activity of composite catalyst, product.Simultaneously, its hydrothermal stability of carrier S BA-15 is high, aperture is large etc. self intrinsic property makes its be applicable to need to be in duct the reaction of long response time, and the interaction between carrier S BA-15 and key component Ni, Ag, Cu, the catalytic activity of catalyst is also had to material impact.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, and 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, made product purity high, profit is worth and raises, and manufacturing technique requirent is simple, be 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/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 that records 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, by copper nitrate aqueous solution 12.926mL and carrier incipient impregnation, stirs 24 h under room temperature, and copper nitrate solution and carrier S BA-15 are evenly flooded.First gained mixture is constantly stirred moisture is evaporated completely at 60 ℃, then dry 12 h, finally roasting 4 h at 450 ℃ at 110 ℃.
(2) take silver nitrate preparation silver nitrate aqueous solution, wherein the concentration of silver nitrate aqueous solution is 0.0548 mol/L, by 12.926mL silver nitrate aqueous solution dipping for the resulting composite obtaining in step (1), stirs 24 h under room temperature.At 60 ℃, constantly stir moisture is evaporated completely, then dry 12 h, finally roasting 4 h at 450 ℃ at 110 ℃.
(3) take nickel nitrate preparation nickel nitrate aqueous solution, wherein the concentration of nickel nitrate aqueous solution is 0.5033 mol/L, by 12.926mL nickel nitrate aqueous solution dipping for the resulting composite obtaining in step (2), stirs 24 h under room temperature.At 60 ℃, constantly stir moisture is evaporated completely, then at 110 ℃, be dried 12 h, finally roasting 4 h at 450 ℃, ground 200 mesh sieves.
(4) step (3) gained compound is placed in to stainless steel reaction pipe, first with the programming rate with 2-5 ℃/min, from room temperature, rises to 300 ℃, use 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 Ni/Ag/Cu/SBA-15 composite catalyst that obtains, 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 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:
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 1. 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/Cu/SBA-15 agent selective catalysis paranitrophenol hydrogenation reaction product p-aminophenol
embodiment 3:
With embodiment 1, the load capacity that only changes active component Cu in catalyst is: 5 wt%, and 10 wt%, 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 ℃, and the reaction time is 8h, the conversion ratio of the selective and raw material of the Ni/Ag/Cu/SBA-15 catalyst selective catalysis paranitrophenol hydrogenation reaction product p-aminophenol of different Cu load capacity
embodiment 4:
With embodiment 1, the load capacity that only changes active component A g in catalyst is: 5 wt%, and 10 wt%, 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 ℃, 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 of preparing under different silver-colored load capacity
embodiment 5:
With embodiment 1, the load capacity that only changes active component Ni in catalyst is: 10wt%, and 20 wt%, 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 ℃, and the reaction time is 8h, the conversion ratio of the selective and raw material of the Ni/Ag/Cu/SBA-15 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/Cu/SBA-15 composite catalyst, is characterized in that, according to following steps, prepares:
(1) took the dry SBA-15 of 200 mesh sieves, and measure the dipping volume of carrier S BA-15, take copper nitrate, preparation copper nitrate aqueous solution, adopt equi-volume impregnating that carrier S BA-15 is flooded with copper nitrate aqueous solution, under room temperature, stir 24 h, make copper nitrate solution and the full and uniform dipping of carrier S BA-15; First gained mixture is constantly stirred at 60 ℃ dry, dry 12 h at 110 ℃ then, finally roasting 4 h at 450 ℃, 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, step (1) gained compound is flooded with silver nitrate aqueous solution, wherein the volume of silver nitrate aqueous solution equates with the dipping volume of carrier S BA-15, at room temperature stirs 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, 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 is flooded with nickel nitrate aqueous solution, wherein the volume of nickel nitrate aqueous solution equates with the dipping volume of carrier S BA-15, at room temperature stirs 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, in compound, the load capacity of nickel is 5wt%-20 wt %;
(4) step (3) 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 the Ni/Ag/Cu/SBA-15 catalyst that obtains different loads amount after room temperature.
2. the preparation method of a kind of Ni/Ag/Cu/SBA-15 composite catalyst according to claim 1, it is characterized in that, according to the load capacity of active component Cu, Ag, Ni in the prepared Ni/Ag/Cu/SBA-15 composite catalyst of above-mentioned steps, be respectively 1%-10%, 1%-10%, 5%-20%.
3. 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, according to following step, carries out:
(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 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/Cu/SBA-15 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/Cu/SBA-15 composite catalyst is: 2 g:150 mL:0.02g.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289697A (en) * | 2014-07-17 | 2016-02-03 | 中国石油天然气集团公司 | Micro-NiO-doped CuO-NiO/SBA-15 catalyst and preparation method |
| CN105289697B (en) * | 2014-07-17 | 2018-06-01 | 中国石油天然气集团公司 | The CuO-NiO/SBA-15 catalyst and preparation method of micro NiO doping |
| CN109806904A (en) * | 2019-03-01 | 2019-05-28 | 中北大学 | A kind of Ni-Ag/SBA-15 load type bimetal catalyst and its preparation method and application |
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 |
| 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 |
-
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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289697A (en) * | 2014-07-17 | 2016-02-03 | 中国石油天然气集团公司 | Micro-NiO-doped CuO-NiO/SBA-15 catalyst and preparation method |
| CN105289697B (en) * | 2014-07-17 | 2018-06-01 | 中国石油天然气集团公司 | The CuO-NiO/SBA-15 catalyst and preparation method of micro NiO doping |
| CN109806904A (en) * | 2019-03-01 | 2019-05-28 | 中北大学 | A kind of Ni-Ag/SBA-15 load type bimetal catalyst and its preparation method and application |
| CN109806904B (en) * | 2019-03-01 | 2021-11-19 | 中北大学 | Ni-Ag/SBA-15 supported bimetallic catalyst and preparation method and application thereof |
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