CN1539553A - Method for preparing polymolecularity metal catalyst in load type from plasma - Google Patents
Method for preparing polymolecularity metal catalyst in load type from plasma Download PDFInfo
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- CN1539553A CN1539553A CNA2003101067208A CN200310106720A CN1539553A CN 1539553 A CN1539553 A CN 1539553A CN A2003101067208 A CNA2003101067208 A CN A2003101067208A CN 200310106720 A CN200310106720 A CN 200310106720A CN 1539553 A CN1539553 A CN 1539553A
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Abstract
A process for preparing the high-dispersing carried catalyst by plasma includes carrying active components by dipping method or ion exchange method, drying, putting the catalyst in discharging tube, vacuumizing to 10-20 Pa, filling N2, O2, H2, or inertial gas to 10-1000 Pa, applying 200-5000 V across two electrodes for plasma treating for 10-500 min, and calcining at 300-600 deg.C for 3-7 hrs.
Description
Technical field
The invention belongs to catalysis technical field, particularly a kind of plasma prepares the method for polymolecularity load type metal catalyst.
Background technology
Loaded catalyst is a catalyst commonly used in the chemical industry, and it can make the metal active constituent of comparison costliness be distributed to the surface of catalyst uniformly, thereby saves the consumption of metal, can also improve activity of such catalysts.Prepare loaded catalyst method commonly used and comprise infusion process, ion-exchange, sol-gal process and coprecipitation etc., what these methods were all successful is applied in the middle of the industrial production.But along with the attention to environmental protection, to the demand of the energy etc., active catalyst high, that price is low more and more comes into one's own, and therefore increasing new catalyst preparation method emerges.As 1998, mention in 14 (9): 769 " Acta PhySico-Chimica Sinica ": micro-reduction method commonly used has prepared the catalyst of high dispersive, but this method is also just at laboratory stage, choosing of microorganism is very loaded down with trivial details, the Preparation of catalysts cycle is also very long, therefore the Preparation of catalysts cost is just than higher, and the catalyst of their preparation at present is not also through roasting be used for catalytic activity and test in addition.The preparation process of patent CN02138658.7 " carrier loading platinum and platinum Quito unit metallic catalyst organosol preparation method " is: (alcohol compound) utilizes SnCl in organic media
2Reduce platinum and platinum Quito the unit metal salt or acid compounds, obtain metal-sol; Thereby again carrier is added colloidal sol and obtain loaded catalyst.But also will pass through alkali cleaning in the subsequent process of this catalyst, certain heat treatment is carried out in pickling or washing again after the drying, and this just makes and is difficult to the preparation process more complicated grasp.Paper Mahata N., Vishwanathan V., Journal of Catalysis, 196 (2000), 262-270 has discussed Pd precursor (Pd (OOCCH
3)
2, PdCl
2, Pd (NH
3)
4Cl
2) be supported on the influence of Pyrogentisinic Acid's hydrogenation reaction catalytic activity on aluminium oxide or the magnesia, find to adopt Pd (OOCCH
3)
2Best as metal dispersity in the catalyst of Pd precursor, activity is also the highest.But in actual applications, be similar to Pd (OOCCH
3)
2Metal-organic price very high, this can increase production cost greatly.Paper Philippe Serp, Plilippe Kalck, Roselyne Feurer, Chemistry Review, 102 (2002), 3085-3128, summarize the employing chemical vapour deposition technique and prepared loaded catalyst, be called gas phase impregnation-decomposition method (GPI-D) again, be deposited on again on the carrier after just making metal active precursor vaporization, add thermal bake-out at last and make precursors decompose.Compare with conventional liquid impregnation method, it is more even that this method can make metal active constituent distribute, and activity also improves a lot.But the selection of metal precursor is a big problem, it requires gasification easily, Heat stability is good in the transportation, be easy to preparation, also want the purity height, easily thoroughly, the most frequently used metal precursor is metal carbonyl (M (CO) x) now, also is difficult at present be applied in the actual industrial production process again in thermal decomposition.
Summary of the invention
The purpose of this invention is to provide a kind of novel method for preparing catalyst, Zhi Bei catalyst like this, its metal active constituent decentralization improves a lot.This method is a method the most frequently used in the catalyst process industry---on the basis of liquid impregnation method and ion-exchange, before high-temperature roasting, catalyst carried out simple plasma treatment, just can improve catalytic activity greatly.
Technical scheme of the present invention is achieved in that
Metal active constituent adopts infusion process or ion-exchange to load on the catalyst, and is dry then; Put into discharge tube and carry out plasma treatment.
The concrete operations step is as follows:
1. dried catalyst is put into discharge tube, be evacuated to 10～20Pa, feed N
2, O
2, H
2Or inert gas, make the pressure of discharge tube reach 10～1000Pa, between two electrodes, add the voltage of 200～5000V, carried out plasma treatment 10～500 minutes;
2. after plasma treated catalyst takes out, 300～600 ℃ of following roastings 3～7 hours.If bicomponent catalyst, second component also supports according to step 1,2.
Metal ion generally loads on the catalyst by 0.01～10% metering.Metal active constituent adopts noble metal, Ferrious material, Cu, Zn, Mo, W etc.
Above-mentioned plasma is generally cold plasma.Cold plasma comprises glow discharge plasma, rf (discharge) plasma, microwave plasma.
Described plasma working gas is N
2, O
2, Ar, He, H
2Deng.
Described plasma prepares the method for polymolecularity load type metal catalyst, and the catalyst type of processing is a load type metal catalyst, and catalyst carrier is a molecular sieve, aluminium oxide, silica, active carbon etc.
Through the catalyst of plasma method preparation, metal active constituent is evenly distributed in catalyst surface, and decentralization increases, but also can improve the interaction of carrier and active component.
The present invention has opened up new approach for the preparation effective catalyst.This method is very easy to drop into suitability for industrialized production, under existing working condition, only needs to add one plasma treatment operation and just can improve catalytic activity greatly, thereby save cost, improves economic effect.
The specific embodiment
Embodiment 1.
Adopt infusion process that 2% palladium is loaded to the HZSM-5 molecular sieve, and then following dry 4 hours at 110 ℃.Catalyst is put between glow discharge plasma device two electrodes.Begin to be evacuated down to 10Pa after airtight, regulate argon flow amount and make vacuum system pressure maintain 100Pa, continue to add the DC voltage of 1000V then between electrode, the processing time is 60 minutes.After the catalyst taking-up, put into 500 ℃ of roastings of roaster 4 hours, promptly get Pd/HZSM-5.Can see that by height explanation transmission electron microscope the particle diameter of active component Pd is about 5nm.
Embodiment 2.
Adopt infusion process that 4%Mo is loaded to activated alumina, dry then.Catalyst is put between glow discharge plasma device two electrodes.Begin to be evacuated down to 10Pa after airtight, regulate nitrogen flow and make vacuum system pressure maintain 50Pa, continue to add the DC voltage of 500V then between electrode, the processing time is 50 minutes.After the catalyst taking-up, put into 500 ℃ of roastings of roaster 7 hours, promptly get Mo/Al
2O
3, can see that by height explanation transmission electron microscope the particle diameter of active component Mo is about 1～10nm.
Embodiment 3.
To the catalyst of embodiment 2 gained, add cobalt nitrate solution, make that Co content is 3% on the catalyst, stirs to leave standstill 12 hours after 30 minutes, then drying.Catalyst is put between glow discharge plasma device two electrodes.Begin to be evacuated down to 10Pa after airtight, regulate nitrogen flow and make vacuum system pressure maintain 50Pa, continue to add the DC voltage of 500V then between electrode, the processing time is 50 minutes.After the catalyst taking-up, put into 500 ℃ of roastings of roaster 7 hours, promptly get CoMo/Al
2O
3, can see that by height explanation transmission electron microscope the particle diameter of active component Mo and Co is about 1～10nm.
Embodiment 4.
Identical with embodiment 1 condition, but adopt ion-exchange that platinum is supported on the molecular sieve, the Pt loading is 0.01%, the plasma generation mode is radio frequency discharge, working gas is a helium, the system vacuum degree is 1000Pa, can see that by height explanation transmission electron microscope the particle diameter of active component Pt is about 3nm.
Embodiment 5.
Identical with embodiment 4, be rhodium chloride solution but support on the molecular sieve, the plasma generation mode is a microwave plasma, can see that by height explanation transmission electron microscope the particle diameter of active component rhodium Rh is about 1～10nm.
Embodiment 6.
Identical with embodiment 5, but catalyst carrier is SiO
2, the plasma working gas is H
2, the system vacuum degree is 10Pa, and two interpolar voltages are 200V, and the processing time is 10 minutes, 300 ℃ of roastings 3 hours, can see that by height explanation transmission electron microscope the particle diameter of active component Pd is about 1～10nm.
Embodiment 7.
Substantially the same manner as Example 4, but catalyst carrier is an active carbon, and the plasma working gas is O
2, can see that by height explanation transmission electron microscope the particle diameter of active component rhodium is about 1～10nm.
Embodiment 8.
Substantially the same manner as Example 2, but active component is W, two interpolar voltages are 5000V, the processing time is 500 minutes, can see that by height explanation transmission electron microscope the particle diameter of active component Mo is about 1～10nm.
Embodiment 9
To the catalyst of embodiment 8 gained, support the second active component Ni under the same terms, make the content of Ni reach 10%, then, dry then.Catalyst is put between glow discharge plasma device two electrodes.Begin to be evacuated down to 20Pa after airtight, regulate nitrogen flow and make vacuum system pressure maintain 50Pa, continue to add the DC voltage of 2500V then between electrode, the processing time is 150 minutes.After the catalyst taking-up, put into 500 ℃ of roastings of roaster 7 hours, promptly get Mo-Ni-Al
2O
3, can see that by height explanation transmission electron microscope the particle diameter of active component Mo and Ni is about 1～10nm.
Embodiment 10.
Substantially the same manner as Example 2, but the content of active component Mo is 6% in body, and catalyst carrier is the HZSM-5 molecular sieve, can see that by height explanation transmission electron microscope the particle diameter of active component Mo is about 1～10nm.
Embodiment 11
To supporting the second active component Fe under embodiment 10 the same terms, content is 1%, 600 ℃ of roastings 4 hours, can see that by height explanation transmission electron microscope the particle diameter of active component is about 1～10nm, can see that by height explanation transmission electron microscope the particle diameter of active component is about 5nm.
Embodiment 12
Substantially the same manner as Example 4, but support the second active component Zn under the same conditions, can see that by height explanation transmission electron microscope the particle diameter of active component is about 1～10nm.
Embodiment 13
Substantially the same manner as Example 8, but support the second active component Cu under the same terms, can see that by height explanation transmission electron microscope the particle diameter of active component is about 1～10nm.
Claims (8)
1. a plasma prepares the method for polymolecularity load type metal catalyst, may further comprise the steps:
Metal active constituent is loaded on the catalyst with infusion process or ion-exchange, dry then, put into discharge tube and carry out plasma treatment.
2. a kind of plasma as claimed in claim 1 prepares the method for polymolecularity load type metal catalyst, it is characterized in that the concrete operations step is as follows:
A. dried catalyst is put into discharge tube, be evacuated to 10 ~ 20Pa, feed N
2, O
2, H
2Or inert gas, make the pressure of discharge tube reach 10 ~ 1000Pa, between two electrodes, add the voltage of 200 ~ 5000V, carried out plasma treatment 10 ~ 500 minutes;
B. after plasma treated catalyst takes out, 300 ~ 600 ℃ of following roastings 3 ~ 7 hours; If bicomponent catalyst, second component also supports according to step a and b.
3. a kind of plasma as claimed in claim 1 or 2 prepares the method for polymolecularity load type metal catalyst, it is characterized in that: the general metering by 0.01 ~ 10% of described metal ion loads on the catalyst.
4. a kind of plasma as claimed in claim 1 or 2 prepares the method for polymolecularity load type metal catalyst, it is characterized in that: described metal active constituent adopts noble metal, Ferrious material, Cu, Zn, Mo, W.
5. a kind of plasma as claimed in claim 1 or 2 prepares the method for polymolecularity load type metal catalyst, it is characterized in that: described plasma is generally cold plasma.
6. a kind of plasma as claimed in claim 5 prepares the method for polymolecularity load type metal catalyst, it is characterized in that: described cold plasma is a glow discharge plasma, rf (discharge) plasma, microwave plasma.
7. a kind of plasma as claimed in claim 1 or 2 prepares the method for polymolecularity load type metal catalyst, it is characterized in that: described plasma working gas is N
2, O
2, Ar, He, H
2
8. a kind of plasma as claimed in claim 1 or 2 prepares the method for polymolecularity load type metal catalyst, it is characterized in that: described catalyst type is the load metallic catalyst, and catalyst carrier is a molecular sieve, aluminium oxide, silica, active carbon.
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| CNA2003101067208A CN1539553A (en) | 2003-10-28 | 2003-10-28 | Method for preparing polymolecularity metal catalyst in load type from plasma |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604209A (en) * | 2012-02-20 | 2012-07-25 | 金发科技股份有限公司 | Thermal-oxidizing-aging resisting polypropylene composite |
| CN103394347A (en) * | 2013-07-23 | 2013-11-20 | 河海大学 | Preparation method of high-activity palladium-carbon catalyst |
| CN106311222A (en) * | 2016-09-09 | 2017-01-11 | 广西大学 | Double-transition metal-based silkworm excrement porous carbon catalyst and preparation method thereof |
| CN106423167A (en) * | 2016-09-09 | 2017-02-22 | 广西大学 | Double transition metal based carbonized silkworm excrement catalyst and preparation method thereof |
| CN109876819A (en) * | 2019-01-23 | 2019-06-14 | 重庆理工大学 | A kind of the V-Ce-Ni catalyst preparation and application of unconventional SCR |
| CN110585864A (en) * | 2019-08-15 | 2019-12-20 | 杭州电子科技大学 | Reaction process suitable for low-temperature plasma concerted catalytic degradation of VOCs and membrane catalyst preparation process |
| CN112275284A (en) * | 2020-10-20 | 2021-01-29 | 大连海事大学 | Method for regulating interaction between metal nanoparticles and carrier by using plasma |
| CN113318795A (en) * | 2021-06-24 | 2021-08-31 | 大连海事大学 | Device and method for preparing liquid metal catalyst by using plasma |
| CN113731471A (en) * | 2021-09-03 | 2021-12-03 | 盐城工学院 | Ni-based catalyst and preparation method and application thereof |
| CN114797464A (en) * | 2022-06-01 | 2022-07-29 | 宁波工程学院 | Device and method for online elimination of CO based on plasma technology |
-
2003
- 2003-10-28 CN CNA2003101067208A patent/CN1539553A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604209A (en) * | 2012-02-20 | 2012-07-25 | 金发科技股份有限公司 | Thermal-oxidizing-aging resisting polypropylene composite |
| CN102604209B (en) * | 2012-02-20 | 2014-06-18 | 金发科技股份有限公司 | Thermal-oxidizing-aging resisting polypropylene composite |
| CN103394347A (en) * | 2013-07-23 | 2013-11-20 | 河海大学 | Preparation method of high-activity palladium-carbon catalyst |
| CN106311222A (en) * | 2016-09-09 | 2017-01-11 | 广西大学 | Double-transition metal-based silkworm excrement porous carbon catalyst and preparation method thereof |
| CN106423167A (en) * | 2016-09-09 | 2017-02-22 | 广西大学 | Double transition metal based carbonized silkworm excrement catalyst and preparation method thereof |
| CN109876819A (en) * | 2019-01-23 | 2019-06-14 | 重庆理工大学 | A kind of the V-Ce-Ni catalyst preparation and application of unconventional SCR |
| CN110585864A (en) * | 2019-08-15 | 2019-12-20 | 杭州电子科技大学 | Reaction process suitable for low-temperature plasma concerted catalytic degradation of VOCs and membrane catalyst preparation process |
| CN112275284A (en) * | 2020-10-20 | 2021-01-29 | 大连海事大学 | Method for regulating interaction between metal nanoparticles and carrier by using plasma |
| CN112275284B (en) * | 2020-10-20 | 2023-06-20 | 大连海事大学 | Method for regulating interaction between metal nano particles and carrier by plasma |
| CN113318795A (en) * | 2021-06-24 | 2021-08-31 | 大连海事大学 | Device and method for preparing liquid metal catalyst by using plasma |
| CN113318795B (en) * | 2021-06-24 | 2023-07-14 | 大连海事大学 | Device and method for preparing liquid metal catalyst by using plasma |
| CN113731471A (en) * | 2021-09-03 | 2021-12-03 | 盐城工学院 | Ni-based catalyst and preparation method and application thereof |
| CN113731471B (en) * | 2021-09-03 | 2023-11-24 | 盐城工学院 | Ni-based catalyst and preparation method and application thereof |
| CN114797464A (en) * | 2022-06-01 | 2022-07-29 | 宁波工程学院 | Device and method for online elimination of CO based on plasma technology |
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