CN101007280A - Preparation method of a novel hydrogenation and dechlorination catalyst - Google Patents
Preparation method of a novel hydrogenation and dechlorination catalyst Download PDFInfo
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- CN101007280A CN101007280A CN 200710056636 CN200710056636A CN101007280A CN 101007280 A CN101007280 A CN 101007280A CN 200710056636 CN200710056636 CN 200710056636 CN 200710056636 A CN200710056636 A CN 200710056636A CN 101007280 A CN101007280 A CN 101007280A
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- nipd
- dechlorination
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Abstract
The invention involves a new preparation method of hydrogenation dechlorination accelerant, it loads high scattering Pd atom cluster on nanometer amorphous alloy or nanometer Ni powder through replacement reaction, then prepares new surface NiPd alloy accelerant through crystallization treatment. The accelerant prepared through the invention has characteristics of small dimension of active components, good dispersion degree and high activity, and it applies to catalytic hydrogenation dechlorination reaction.
Description
Technical field
The present invention relates to a kind of preparation method of novel hydrogenation and dechlorination catalyst, and a kind of preparation of saying so more specifically has the method for the non-loading type and the support type NiPd alloy catalyst of high catalytic activity.
Background technology
Chloro organic cpd is the product after one or several hydrogen atoms in a class aliphatic hydrocarbon, aromatic hydrocarbon and the derivative thereof are replaced by the chlorine atom.It is of a great variety, comprise chlorinated aliphatic hydrocarbon, chlorobenzene class (CBs), chloro phenols (CPs), polychlorinated biphenyl (PCBs) compound, be important chemical material, organic synthesis intermediate and organic solvent, for a long time, be widely used in industries such as chemical industry, medicine, agricultural chemicals, dyestuff, electronics.Organochlorine has also caused the serious environmental pollution simultaneously for the extensive use of thing.This pollution problem has caused people's extensive concern.Calendar year 2001,127 country manager are had a meeting at Stockholm, SWE, and the signature forbidding comprises the agreement of 12 kinds of persistence organic pollutants of PCBs, bioxin.Therefore, in conjunction with China's national situation, drawing domestic and international advanced achievement in research, will be the important topic in China Research of Environmental Sciences field from now on to organochlorine for the thing Research on degradation.
The heterogeneous catalytic hydrogenation dechlorination has been widely used in the elimination of organochlorine for thing, is considered to effective and promising improvement technology.Catalyst activity component comprises Ni, Mo, Cu, Fe, Au, Pd, Rh, Pt grade in an imperial examination VIII group 4 transition metal and noble metal, and carrier comprises inorganic material such as silica gel (SiO
2), aluminium oxide (Al
2O
3), molecular sieve and other some inorganic oxides such as TiO
2, MgO, ZrO
2With the organic material active carbon.
At present, CN 1460547, CN 1460549, CN 1460670 and CN 1351903 have disclosed a class catalysis fluorinated refrigerant CFC-113 hydrogenation-dechlorination and have prepared CTFE and trifluoro-ethylene catalyst for reaction.Such catalyst is an active component with precious metals pt, Pd, Ru and transition metal Cu, is carrier with aluminium oxide or coconut husk charcoal, has embodied high activity and high stability in the hydrogenation-dechlorination reaction.1060649 of CN 1701846, CN 1350885 and CN have reported that hydrogenation-dechlorination of carbon tetrachloride prepares the Pt Preparation of catalysts method of chloroform.Pt/Al
2O
3Catalyst embodies excellent hydrogenation-dechlorination performance in this reaction.In addition, lot of documents report bimetallic catalyst has incomparable hydrogenation activity of single-metal reforming catalyst and selectivity.2005, M.O.Nutt reported a kind of novel Hydrodechlorinating catalyst the preparation method (Environ.Sci.Technol.2005,39:1346-1353).The author is by deposition part metals Pd atom on nanometer Au cluster, and design has prepared PdAu bimetallic Hydrodechlorinating catalyst, and the gained catalyst embodies in the reaction of trichloro-ethylene hydrogenation-dechlorination and is better than conventional P d activity of such catalysts.The work of Nutt shows that the design bimetallic catalyst has important in theory and practical significance to developing a kind of highly effective hydrogenation dechlorination catalyst.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing novel hydrogenation and dechlorination catalyst, it is the method for preparing non-loading type and support type NiPd catalyst, this catalyst can form the NiPd alloy at NiB or Ni cluster surface, and then has improved the hydrogenation-dechlorination performance of catalyst.
In the NiPd catalyst that characteristics of the present invention are to be developed, precious metals pd and metal Ni are main active component, and with Al
2O
3Or the coconut husk charcoal is carrier, Ni: Pd=19~999 (weight ratio); For support type NiPd catalyst, Ni account for catalyst gross weight 1%~40%.
The Preparation of catalysts step is as follows:
With the NiB amorphous alloy of non-loading type (10~250nm) and (5~100nm) join PdCl at the nano-nickel powder end
2In the solution (Pd accounts for catalyst weight 0.01%~5%), stir until the Pd ion by simple substance Ni displacement fully, to neutral, dry back is at 100 ℃~400 ℃ following crystallization 2.0h through the deionized water washing for product.Loaded catalyst then is at PdCl
2Adding NiB amorphous alloy or nano-nickel powder are last in the solution, add carrier immediately, stir until the Pd ion by simple substance Ni displacement fully, and product is extremely neutral through the centrifugal water washing, and dry back is at 200 ℃~400 ℃ following crystallization 2.0h.
Described NiB amorphous alloy cluster size is in 10~250nm, and the cluster size at nano-nickel powder end is in 5~100nm, and preferred cluster is of a size of 25nm NiB amorphous alloy and 10nm nano-nickel powder end.
The crystallization temperature of described NiPd and support type NiPd catalyst is 100 ℃~400 ℃ and 200~400 ℃, preferred 200 ℃.
The specific embodiment
Comparative Examples 1
This Comparative Examples explanation Preparation of catalysts process.
Embodiment 1~12
These embodiment illustrate the preparation process of non-loading type NiPd bimetallic catalyst.
PdCl with 0.05g
2Be dissolved in the NaCI solution of 50ml 4mol/L, add then cluster be of a size of 25nm the NiB amorphous alloy (control Pd account for catalyst weight 1%), stirring is replaced fully by simple substance Ni until the Pd ion, and to neutral, the drying back is at 200 ℃ of following crystallization 2.0h through the centrifugal water washing for product.Obtain catalyst A.
The same with the catalyst A preparation process, make the NiB amorphous alloy about 25nm into the nano-nickel powder end of 10nm NiB amorphous alloy, 250nmNiB amorphous alloy, 5nm and the nano-nickel powder end of 100nm, obtain catalyst B-E.
The same with the catalyst A preparation process, change PdCl
2Addition, control Pd accounts for catalyst weight and is respectively 0.1% and 5%, obtains catalyst F and G.
The same with the catalyst A preparation process, changing crystallization temperature is 100 ℃ and 400 ℃, obtains catalyst H and I.
The same with the catalyst A preparation process, the addition of change NiB amorphous alloy, control Ni: Pd (weight ratio) is respectively 19 and 999, obtains catalyst J and K.
Embodiment 13~15
These embodiment illustrate the preparation process of support type NiPd bimetallic catalyst.
In the catalyst A preparation process, add 9gAl
2O
3After carrier stirred, to neutral, dry back was at 200 ℃ of following crystallization 2.0h through the centrifugal water washing for product.Obtain catalyst L.
The same with catalyst L preparation process, changing carrier is the coconut husk charcoal, obtains catalyst M.
The same with catalyst L preparation process, change the carrier consumption, control Ni accounts for 1% and 40% of catalyst loadings, obtains catalyst n and O.
Comparative Examples 2
This Comparative Examples is used for illustrating the catalytic performance of catalyst at oxygen benzene hydrogenation dechlorination reaction, and reaction is carried out in 100ml compressive reaction still, and reaction condition is: 70 ℃ of temperature, pressure 1.0MPa, catalyst amount 6% (weight ratio), the ethanolic solution of 60ml chlorobenzene (4.2g), 1.2gNaOH.
Table 1
Catalyst | Benzene productive rate (%) |
Skeleton nickel | 17.5 |
Pd(4nm) | 40.2 |
A | 85.3 |
C | 40.2 |
D | 70.2 |
H | 40.6 |
I | 17.6 |
L | 60.6 |
N | 70.2 |
Claims (6)
1. the purpose of this invention is to provide a kind of method for preparing novel hydrogenation and dechlorination catalyst, it is the method for preparing non-loading type and support type NiPd catalyst, this catalyst can form the NiPd alloy at NiB or Ni cluster surface, and then has improved the hydrogenation-dechlorination performance of catalyst.
In the NiPd catalyst that characteristics of the present invention are to be developed, precious metals pd and metal Ni are main active component, and with Al
2O
3Or the coconut husk charcoal is carrier, Ni: Pd=19~999 (weight ratio); For support type NiPd catalyst, Ni account for catalyst gross weight 1%~40%.
The Preparation of catalysts step is as follows:
With the NiB amorphous alloy of non-loading type (10~250nm) and (5~100nm) join PdCl at the nano-nickel powder end
2In the solution (Pd accounts for catalyst weight 0.01%~5%), stir until the Pd ion by simple substance Ni displacement fully, to neutral, dry back is at 100 ℃~400 ℃ following crystallization 2.0h through the deionized water washing for product.Loaded catalyst then is at PdCl
2Adding NiB amorphous alloy or nano-nickel powder are last in the solution, add carrier immediately, stir until the Pd ion by simple substance Ni displacement fully, and product is extremely neutral through the centrifugal water washing, and dry back is at 200 ℃~400 ℃ following crystallization 2.0h.
2, according to the described NiB amorphous alloy of claim 1 cluster size in 10~250nm, the cluster size at nano-nickel powder end is in 5~100nm, preferred cluster is of a size of the nano-nickel powder end of 25nm NiB amorphous alloy and 10nm.
3, the crystallization temperature according to described NiPd of claim 1 and support type NiPd catalyst is 100 ℃~400 ℃ and 200~400 ℃, preferred 200 ℃.
4, according to the described NiPd catalyst of claim 1, Ni: Pd=19~999 (weight ratio), preferred 99.
5, according in the described support type NiPd of claim 1 catalyst, Ni account for catalyst gross weight 1%~40%, preferred 5%.
6, the catalyst of claim 1 preparation is applied to the reaction of chlorobenzene hydrogenation-dechlorination.
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101406835B (en) * | 2008-12-08 | 2011-05-25 | 西安近代化学研究所 | Hydrogenation and dechlorination catalyst |
CN101632931B (en) * | 2009-08-14 | 2012-06-27 | 西安近代化学研究所 | Hydrodechlorination catalyst |
CN101229515B (en) * | 2008-01-17 | 2012-08-29 | 南开大学 | Method of preparing highly effective hydrogenation amorphous alloy catalyst |
CN103894209A (en) * | 2014-03-18 | 2014-07-02 | 巨化集团技术中心 | Catalyst applicable to dechlorination and hydrogenation of chlorination aromatic hydrocarbon, preparation method and application method of catalyst |
CN103910598A (en) * | 2014-03-18 | 2014-07-09 | 巨化集团技术中心 | Method of preparing cyclohexane by dechlorinating and hydrogenating chlorinated aromatic hydrocarbon |
CN106492856A (en) * | 2016-10-18 | 2017-03-15 | 中国科学院深圳先进技术研究院 | NiP Pd catalyst and its preparation method and application |
CN109824473A (en) * | 2019-03-04 | 2019-05-31 | 浙江工业大学 | A kind of method that Pd-M alloy loaded catalyst prepares a fluoromethane |
CN114984935A (en) * | 2022-05-17 | 2022-09-02 | 杭州灰弘环保科技有限公司 | Low-consumption and high-efficiency treatment method for carbon adsorption of dioxin in fly ash |
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2007
- 2007-01-26 CN CN2007100566368A patent/CN101007280B/en not_active Expired - Fee Related
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101229515B (en) * | 2008-01-17 | 2012-08-29 | 南开大学 | Method of preparing highly effective hydrogenation amorphous alloy catalyst |
CN101406835B (en) * | 2008-12-08 | 2011-05-25 | 西安近代化学研究所 | Hydrogenation and dechlorination catalyst |
CN101632931B (en) * | 2009-08-14 | 2012-06-27 | 西安近代化学研究所 | Hydrodechlorination catalyst |
CN103894209A (en) * | 2014-03-18 | 2014-07-02 | 巨化集团技术中心 | Catalyst applicable to dechlorination and hydrogenation of chlorination aromatic hydrocarbon, preparation method and application method of catalyst |
CN103910598A (en) * | 2014-03-18 | 2014-07-09 | 巨化集团技术中心 | Method of preparing cyclohexane by dechlorinating and hydrogenating chlorinated aromatic hydrocarbon |
CN103894209B (en) * | 2014-03-18 | 2016-04-13 | 巨化集团技术中心 | A kind of catalyst for chlorination aromatic hydrocarbon dechlorination hydrogenation and preparation and application |
CN103910598B (en) * | 2014-03-18 | 2016-05-18 | 巨化集团技术中心 | A kind of chlorination aromatic hydrocarbon dechlorination Hydrogenation is for the method for cyclohexane |
CN106492856A (en) * | 2016-10-18 | 2017-03-15 | 中国科学院深圳先进技术研究院 | NiP Pd catalyst and its preparation method and application |
CN106492856B (en) * | 2016-10-18 | 2019-02-26 | 中国科学院深圳先进技术研究院 | NiP-Pd catalyst and its preparation method and application |
CN109824473A (en) * | 2019-03-04 | 2019-05-31 | 浙江工业大学 | A kind of method that Pd-M alloy loaded catalyst prepares a fluoromethane |
CN109824473B (en) * | 2019-03-04 | 2022-03-01 | 浙江工业大学 | Method for preparing monofluoromethane by Pd-M alloy supported catalyst |
CN114984935A (en) * | 2022-05-17 | 2022-09-02 | 杭州灰弘环保科技有限公司 | Low-consumption and high-efficiency treatment method for carbon adsorption of dioxin in fly ash |
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