CN103769163A - Method for preparing load type double-metal catalyst by reducing atmospheric cold plasmas - Google Patents
Method for preparing load type double-metal catalyst by reducing atmospheric cold plasmas Download PDFInfo
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- CN103769163A CN103769163A CN201410010033.4A CN201410010033A CN103769163A CN 103769163 A CN103769163 A CN 103769163A CN 201410010033 A CN201410010033 A CN 201410010033A CN 103769163 A CN103769163 A CN 103769163A
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Abstract
The invention relates to a method for preparing a load type double-metal catalyst by reducing atmospheric cold plasmas. Integrated-immersion reducing preparation or stepwise immersion reducing preparation can be adopted. According to the first scheme of an integrated-immersion method, the method specifically comprises the steps of loading a double-metal component on a carrier through the integrated-immersion method, drying, then putting the carrier into a reactor, and reducing the atmospheric cold plasmas to obtain the catalyst. According to the second scheme of a stepwise immersion preparation method, the method comprises the steps of loading a certain component of double metal on the carrier through the immersion method, drying, and reducing the atmospheric cold plasmas; then loading another metal component on the carrier through the immersion method, drying, and reducing the atmospheric cold plasmas to prepare the catalyst. If necessary, the catalysts prepared by the two schemes are subjected to thermal treatment. The process for preparing the load type double-metal catalyst by combining the atmospheric cold plasmas and the simple immersion method is simple and is environmentally friendly; the performance of the catalyst can be obviously improved; a new way can be created for the preparation of the load type double-metal catalyst.
Description
Technical field
The present invention relates to a kind of atmosphere cold plasma reduction and prepare the method for load type bimetal catalyst, it belongs to material preparation and catalytic science technical field.
Background technology
With respect to support type single-metal reforming catalyst, load type bimetal catalyst has electronic structure, surface nature and chemical property special and can modulation, has important application prospect at chemical industry, environmental protection and energy field.Simple and effective method for preparing catalyst is the key of producing high efficiency load type bimetal catalyst.The preparation method of load type bimetal catalyst, mainly adopts chemical reduction method and deposition-precipitation method etc. at present.Chemical reduction method need to use a large amount of poisonous and hazardous reducing agents, wayward loading, and environment is unfriendly.Deposition-the precipitation method conventionally can the higher load type bimetal catalyst of processability, but it is not suitable for the carrier of low isoelectric point, and is difficult for realizing completely deposition, needs comparatively harsh reaction condition simultaneously.Infusion process is to prepare the method a kind of simple, that easily go of load type metal catalyst, can control well metal loading.But the metal particle diameter of its load type bimetal catalyst of preparing is large, dispersed poor, thereby makes its activity poor.
Therefore,, if the presoma of the load type metal catalyst that can obtain infusion process carries out simple process, obtain high performance catalyst and there is important using value.Cold plasma is a kind of method of preparing load type metal catalyst, have simple to operate, the processing time is short, advantages of environment protection, can obviously improve the performance of catalyst.
The people such as Diamy (Chemical Physics Letters, 1997,269(3-4): 327-332) published employing microwave plasma and prepared support type Au bimetallic catalyst.Its advantage is to reduce at low temperatures, has avoided the noble metal granule that fuel factor causes to reunite change greatly.But it is not easy to scale and amplifies under low pressure.The people such as Liu Changjun have reported and have adopted plasma deoxidization in low termprature to prepare the method for load type metal catalyst, metal ion can be reduced into metal simple-substance in patent (patent publication No.: CN1539553, CN1647858, CN1739854, CN102151586).But it carries out conventionally under low pressure, and emphasize electron reduction in its patent, be difficult to realize reducing metal ion under atmospheric pressure.
Summary of the invention
In view of the problem of prior art existence, the object of the invention is to provide a kind of atmosphere cold plasma reduction to prepare the method for load type bimetal catalyst, it is fast restore bimetallic presoma under atmospheric pressure, obtains high-performance supported type bimetallic catalyst.
To achieve these goals, the technical solution adopted in the present invention is: the method for load type bimetal catalyst is prepared in atmosphere cold plasma reduction, and it comprises two kinds of methods: first method: it comprises the following steps:
(1) adopt co-impregnation that the presoma of bimetallic component is loaded on carrier, room temperature is placed 2-24 h, 50-120
oc is dried 2-24 h,
(2) product of step (1) is put into plasma reactor, pass into working gas, be to carry out atmosphere cold plasma reduction under the condition of 1-40 kV at alternating current discharge voltage peak-to-peak value, the recovery time is 6-60 min, obtains load type bimetal catalyst;
(3) if needed, load type bimetal catalyst roasting 0.5-6 h in hydrogen or inert gas that also step (2) can be obtained, temperature is 200-500
oc;
Second method: it comprises the following steps:
(1) adopt step impregnation method that the presoma of a component in bimetallic is loaded on carrier, room temperature is placed 2-24 h, 50-120
oc is dried 2-24 h;
(2) step (1) products therefrom being put into plasma reactor, pass into working gas, is to carry out atmosphere cold plasma reduction under the condition of 1-40 kV at alternating current discharge voltage peak-to-peak value, and the recovery time is 6-60 min;
(3) take step (2) products therefrom as carrier, adopt infusion process that the presoma of another component in bimetallic is loaded on carrier, room temperature is placed 2-24 h, 50-120
oc is dried 2-24 h;
(4) step (3) products therefrom being put into plasma reactor, pass into working gas, is to carry out atmosphere cold plasma reduction under the condition of 1-40 kV at alternating current discharge voltage peak-to-peak value, and the recovery time is 6-60 min;
(5) if needed, load type bimetal catalyst roasting 0.5-6 h in hydrogen or inert gas that also step (4) can be obtained, temperature is 200-500
oc;
Described bimetallic is any two kinds in Pd, Pt, Cu, Ag and Au.
Described carrier is TiO
2, CeO
2, Fe
2o
3, Co
3o
4, SiO
2, Al
2o
3with the one in molecular sieve.
Described bimetallic component loads on carrier by the loading of 0.1-10%, and two kinds of metal components are arbitrary proportion.
Described atmosphere cold plasma is atmospheric dielectric barrier discharge cold plasma, the one in atmospheric radio-frequency discharging cold plasma or Atomospheric pressure glow discharge cold plasma.
Described plasma working gas is pure hydrogen, hydrogen and argon gas, or the mist of hydrogen and helium.
The invention has the advantages that employing cold plasma, under atmospheric pressure, the load type metal ion fast restore that simple infusion process is obtained is prepared high-performance supported type bimetallic catalyst.Reactive hydrogen particle in atmospheric pressure hydrogen cold plasma, has very strong reducing power, can be at a lower temperature by the metal ion fast restore of load.Device is simple, and processing ease is pollution-free, environmental friendliness.
Accompanying drawing explanation
Fig. 1. the XRD spectra of embodiment 1-3 gained sample;
Fig. 2. the Oxidation of Carbon Monoxide active testing curve of embodiment 1-3 gained sample.
The specific embodiment
embodiment 1:
By γ-Al
2o
3for carrier, 500
oroasting 3 h under C, dipping Cu (NO
3)
2solution, leaves standstill 24 h, 100
oc is dried 2 h.Obtain the presoma of carried copper catalyst.Get this precursor samples of 0.3 g and put into plasma reactor, take the mist of hydrogen and argon gas as working gas (total gas flow rate 100 mlmin
-1, the ratio of hydrogen and argon gas is 1:1), adopt atmospheric dielectric barrier discharge cold plasma to reduce, regulating simple alternating current discharge voltage peak-to-peak value is 32 kV, the recovery time is 15 min, obtains 2%Cu/Al
2o
3catalyst.Its XRD spectra as shown in Figure 1.As shown in Figure 1, the load type gold ion that plasma method can be prepared infusion process is reduced to Cu simple substance.Get this sample of 10 mg, put into the reaction tube that internal diameter is 4 mm, pass into 20 mlmin
-1cO calibrating gas (CO:O
2 : N
2 =1:20:79), carry out the test of CO oxidation activity, result represents as Fig. 2.As seen from Figure 2, plasma method is prepared 2%Cu/Al
2o
3sample is 160
oc does not have catalyzing carbon monoxide oxidation activity below substantially.
embodiment 2:
By γ-Al
2o
3for carrier, 500
oroasting 3 h under C, dipping Pd (NO
3)
2solution, leaves standstill 24 h, 100
oc is dried 2 h.Obtain the presoma of load type palladium catalyst.Get this precursor samples of 0.3 g and put into plasma reactor, adopt the condition identical with embodiment 1, carry out plasma deoxidization 15 min, obtain 2%Pd/Al
2o
3catalyst.Its XRD spectra as shown in Figure 1.As shown in Figure 1, the load type gold ion that plasma method can be prepared infusion process is reduced to Pd simple substance.Get this sample of 10 mg, adopt the condition identical with embodiment 1, carry out the test of CO oxidation activity, result represents as Fig. 2.As seen from Figure 2, plasma method is prepared 2%Pd/Al
2o
3sample is 145
ounder C condition, can be carbon dioxide by carbon monoxide complete oxidation.
embodiment 3:
By γ-Al
2o
3for carrier, 500
oroasting 3 h under C, dipping Cu (NO
3)
2with Pd (NO
3)
2mixed solution, leave standstill 24 h, 100
oc is dried 2 h.Obtain the presoma of load type bimetal catalyst.Get this precursor samples of 0.3 g and put into plasma reactor, adopt the condition identical with embodiment 1, carry out plasma deoxidization 15 min, obtain 2%Pd-Cu/Al
2o
3catalyst.Its XRD spectra as shown in Figure 1.As shown in Figure 1, the load type gold ion that plasma method can be prepared infusion process is reduced to Pd and Cu simple substance.Get this sample of 10 mg, adopt the condition identical with embodiment 1, carry out the test of CO oxidation activity, result represents as Fig. 2.As seen from Figure 2, plasma method is prepared 2%Pd-Cu/Al
2o
3sample is 130
ounder C condition, can be carbon dioxide by carbon monoxide complete oxidation, compared with single-metal reforming catalyst, activity obviously improves.
Claims (7)
1. the method for load type bimetal catalyst is prepared in atmosphere cold plasma reduction, and it comprises two kinds of methods: first method: it comprises the following steps:
(1) adopt co-impregnation that the presoma of bimetallic component is loaded on carrier, room temperature is placed 2-24 h, 50-120
oc is dried 2-24 h,
(2) product of step (1) is put into plasma reactor, pass into working gas, be to carry out atmosphere cold plasma reduction under the condition of 1-40 kV at alternating current discharge voltage peak-to-peak value, the recovery time is 6-60 min, obtains load type bimetal catalyst;
Second method: it comprises the following steps:
(1) adopt step impregnation method that the presoma of a component in bimetallic is loaded on carrier, room temperature is placed 2-24 h, 50-120
oc is dried 2-24 h;
(2) step (1) products therefrom being put into plasma reactor, pass into working gas, is to carry out atmosphere cold plasma reduction under the condition of 1-40 kV at alternating current discharge voltage peak-to-peak value, and the recovery time is 6-60 min;
(3) take step (2) products therefrom as carrier, adopt infusion process that the presoma of another component in bimetallic is loaded on carrier, room temperature is placed 2-24 h, 50-120
oc is dried 2-24 h;
(4) step (3) products therefrom being put into plasma reactor, pass into working gas, is to carry out atmosphere cold plasma reduction under the condition of 1-40 kV at alternating current discharge voltage peak-to-peak value, and the recovery time is 6-60 min; Obtain load type bimetal catalyst.
2. the method for load type bimetal catalyst is prepared in atmosphere cold plasma reduction according to claim 1, it is characterized in that: described the first method and the second method also comprise: by the load type bimetal catalyst roasting 0.5-6 h in hydrogen or inert gas obtaining, temperature is 200-500
oc.
3. the method for load type bimetal catalyst is prepared in atmosphere cold plasma reduction according to claim 1, it is characterized in that: described bimetallic is any two kinds in Pd, Pt, Cu, Ag and Au.
4. the method for load type bimetal catalyst is prepared in atmosphere cold plasma reduction according to claim 1, it is characterized in that: described carrier is TiO
2, CeO
2, Fe
2o
3, Co
3o
4, SiO
2, Al
2o
3with the one in molecular sieve.
5. the method for load type bimetal catalyst is prepared in atmosphere cold plasma reduction according to claim 1, it is characterized in that: bimetallic component loads on carrier by the loading of 0.1-10%, and two kinds of metal components are arbitrary proportion.
6. the method for load type bimetal catalyst is prepared in atmosphere cold plasma reduction according to claim 1, it is characterized in that: described atmosphere cold plasma is atmospheric dielectric barrier discharge cold plasma the one in atmospheric radio-frequency discharging cold plasma or Atomospheric pressure glow discharge cold plasma.
7. the method for load type bimetal catalyst is prepared in atmosphere cold plasma reduction according to claim 1, it is characterized in that: described plasma working gas is pure hydrogen hydrogen and argon gas, or the mist of hydrogen and helium.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105032408A (en) * | 2015-09-07 | 2015-11-11 | 黑龙江省科学院石油化学研究院 | Preparation method of load type nano catalyst for catalyzing Suzuki coupling reaction |
| CN106179290A (en) * | 2016-06-24 | 2016-12-07 | 杭州众材科技有限公司 | A kind of method preparing load type gold metal nano-particle |
| CN106334587A (en) * | 2016-10-14 | 2017-01-18 | 大连大学 | Method for preparing supported metal catalyst through cold plasma-alcohol synergetic reduction under atmospheric pressure |
| CN108031287A (en) * | 2017-08-30 | 2018-05-15 | 大连民族大学 | A kind of plasma enhancing Ag/Al2O3The method of catalyst removal nitrogen oxides |
| CN108144605A (en) * | 2016-12-05 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of preparation of loaded alloy catalyst and catalyst and application |
| CN109012674A (en) * | 2018-08-03 | 2018-12-18 | 西北大学 | A kind of high efficiency load type bimetal or multimetal reforming catalyst and preparation method thereof |
| CN116253365A (en) * | 2022-12-14 | 2023-06-13 | 中国科学院大连化学物理研究所 | Preparation method and application of ferric oxide catalyst |
| CN116273123A (en) * | 2023-03-20 | 2023-06-23 | 洛阳师范学院 | Large-scale preparation method of supported single-atom catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1647858A (en) * | 2004-12-01 | 2005-08-03 | 天津大学 | Method for reducing loaded metal catalyst using low temperature plasma |
| CN102600854A (en) * | 2012-02-16 | 2012-07-25 | 四川大学 | Catalyst for carbon dioxide methanation and preparation method thereof |
-
2014
- 2014-01-09 CN CN201410010033.4A patent/CN103769163A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1647858A (en) * | 2004-12-01 | 2005-08-03 | 天津大学 | Method for reducing loaded metal catalyst using low temperature plasma |
| CN102600854A (en) * | 2012-02-16 | 2012-07-25 | 四川大学 | Catalyst for carbon dioxide methanation and preparation method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105032408A (en) * | 2015-09-07 | 2015-11-11 | 黑龙江省科学院石油化学研究院 | Preparation method of load type nano catalyst for catalyzing Suzuki coupling reaction |
| CN106179290A (en) * | 2016-06-24 | 2016-12-07 | 杭州众材科技有限公司 | A kind of method preparing load type gold metal nano-particle |
| CN106334587A (en) * | 2016-10-14 | 2017-01-18 | 大连大学 | Method for preparing supported metal catalyst through cold plasma-alcohol synergetic reduction under atmospheric pressure |
| CN106334587B (en) * | 2016-10-14 | 2020-10-09 | 大连大学 | Method for preparing supported metal catalyst by co-reduction of cold plasma-alcohol under atmospheric pressure |
| CN108144605A (en) * | 2016-12-05 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of preparation of loaded alloy catalyst and catalyst and application |
| CN108031287A (en) * | 2017-08-30 | 2018-05-15 | 大连民族大学 | A kind of plasma enhancing Ag/Al2O3The method of catalyst removal nitrogen oxides |
| CN109012674A (en) * | 2018-08-03 | 2018-12-18 | 西北大学 | A kind of high efficiency load type bimetal or multimetal reforming catalyst and preparation method thereof |
| CN116253365A (en) * | 2022-12-14 | 2023-06-13 | 中国科学院大连化学物理研究所 | Preparation method and application of ferric oxide catalyst |
| CN116273123A (en) * | 2023-03-20 | 2023-06-23 | 洛阳师范学院 | Large-scale preparation method of supported single-atom catalyst |
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Application publication date: 20140507 |