CN104056621A - Preparation method of noble metal catalyst - Google Patents
Preparation method of noble metal catalyst Download PDFInfo
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- CN104056621A CN104056621A CN201410252757.XA CN201410252757A CN104056621A CN 104056621 A CN104056621 A CN 104056621A CN 201410252757 A CN201410252757 A CN 201410252757A CN 104056621 A CN104056621 A CN 104056621A
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- noble metal
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000012265 solid product Substances 0.000 claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 239000012153 distilled water Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000012266 salt solution Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 238000006722 reduction reaction Methods 0.000 claims description 10
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000010970 precious metal Substances 0.000 claims description 4
- 238000009938 salting Methods 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 15
- 239000002184 metal Substances 0.000 abstract description 15
- 239000006185 dispersion Substances 0.000 abstract description 7
- 238000005406 washing Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 2
- 230000005855 radiation Effects 0.000 abstract description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 6
- 239000002923 metal particle Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention relates to a preparation method of a noble metal catalyst. The method comprises the following steps: (1) mixing a carrier, a salt solution of noble metal, and a dispersant, and performing dispersion in the presence of ultrasonic wave to obtain a mixture; (2) adding the mixture in a reductant and performing reduction under microwave radiation to obtain a solid product; and (3) washing the solid product with distilled water, and drying the solid product to obtain the noble metal catalyst. The preparation method is simple and easy to operate; metal is dispersed uniformly on the carrier, the particle size of the metal is small, the reaction time is short and the energy consumption in reaction is low.
Description
Technical field
The invention belongs to catalyst field, relate in particular to a kind of preparation method of noble metal catalyst.
Background technology
Loaded noble metal catalyst, due to its catalytic activity can not be substituted and selective, has extremely important status in the fields such as oil, chemical industry, medicine, agricultural chemicals, food.In the reactions such as the hydro-reduction of noble metal catalyst in oil and chemical industry, oxidative dehydrogenation, hydrocrack, hydrodesulfurization, have a wide range of applications.Aspect environmental protection, noble metal catalyst is widely used in vehicle exhaust is processed.Aspect new forms of energy, noble metal catalyst is the part of most critical in new fuel cell exploitation.But Precious Metals Resources shortage, expensive, causes noble metal catalyst cost greatly to increase.So, the activity of raising noble metal catalyst, the consumption of minimizing noble metal, improving noble metal dispersion degree is the effective way that reduces noble metal dosage.
Prior art has been reported the method for preparing polymolecularity metal catalyst in load type from plasma, and metal active constituent is loaded on catalyst with soaking duty method or ion-exchange, then dry, puts into discharge tube and carries out isoelectronic species processing.The catalyst that the method using plasma is processed before roasting has certain novelty, but does not explain the effect essence of plasma.CN101502798A has reported the preparation method of the carbon-supported metal hydrogenation catalyst of a kind of nanometer ruthenium, and this catalyst is made with being carried on active carbon and through the metal Ru of reduction activation processing by absorbent charcoal carrier.By active carbon after the ultrasonic processing of salpeter solution, extremely neutral by washed with de-ionized water, join and in the water-soluble precursor solution of metal Ru, stir dipping, then with the aqueous solution of alkali compounds, regulate pH, by adding chemical reducing agent to carry out liquid-phase reduction ruthenium C catalyst, the carbon-supported metal hydrogenation catalyst of nanometer ruthenium will be obtained after product washing and drying, but the decentralization of metallic catalyst prepared by use the method is lower, metal is difficult to be distributed to carrier surface, and operating process is complicated.
Summary of the invention
The object of the invention is to overcome noble metal in existing carrier metal catalyst and be difficult to be distributed to equably carrier surface, shortcoming that noble metal granule is large, a kind of preparation method of noble metal catalyst is provided, makes that noble metal can be distributed to carrier surface equably, noble metal granule is little.
For this reason, the invention provides a kind of preparation method of noble metal catalyst, said method comprising the steps of:
(1) by the salting liquid of carrier, noble metal and dispersant, under ul-trasonic irradiation, disperse, obtain mixture;
(2) mixture added to reducing agent and reduce under microwave, obtaining solid product;
(3) solid product is washed with distilled water, after oven dry, obtain noble metal catalyst.
According to the present invention, in step (1), carrier consumption is 1-5g, and precious metal salt solution concentration is 0.01-0.5mol/L, and consumption is 1-15mL, and dispersant mass fraction is 1%-10%, and consumption is 1-5mL.
According to the present invention, in step (1), carrier comprises SiO
2, Al
2o
3, ZrO
2, TiO
2, active carbon or CNT.Described carrier is preferably active carbon, and is that specific area is 1200-1400m
2the active carbon of/g.The specific area of active carbon than large, hole is many, noble metal can better be dispersed on absorbent charcoal carrier.
According to the present invention, in step (1), noble metal comprises Pt, Au, Ru, Re, Rd or Pd.
According to the present invention, in step (1), the salting liquid of noble metal comprises solution of chlorate, nitrate solution or sulfate liquor.
According to the present invention, in step (1), dispersant comprises neopelex, dodecyl sodium sulfate or gelatin.
According to the present invention, in step (1), supersonic frequency is 20-80KHz, and ultrasonic time is 0.5-1h.Under ul-trasonic irradiation, metal can be uniformly dispersed, and metallic particles can be less.
According to the present invention, in step (2), microwave irradiation power is 5-30w, and microwave irradiation time is 0.5-2h, and reduction reaction temperature is 60-80 ℃.Carry out microwave radiation heating is even, and microwave can make molecule produce resonance, and key active force is destroyed, can reduce the required energy of reaction, thereby Reaction time shorten reduces energy consumption of reaction.Microwave can also make the simple substance noble metal dispersion that obtains of reduction improve, and disperses more evenly, and particle diameter is less.
According to the present invention, in step (2), reducing agent comprises sodium borohydride, hydrazine hydrate, KBr, formic acid, sodium acetate or natrium citricum, and reductant concentration is 0.01-1mol/L, and reducing agent consumption is 20-100mL.The reproducibility of above-mentioned substance can be reduced to simple substance noble metal by the high price noble metal in precious metal salt solution.
According to the present invention, in step (3), bake out temperature is 80-120 ℃, and drying time is 4-10h.
There is following advantage in the method for preparing noble metal catalyst of the present invention: preparation method is simple, easy operating; Noble metal is uniformly dispersed on carrier, and noble metal particle diameter is little; Reaction time is short, and energy consumption of reaction is low.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the Ru/C catalyst of embodiment 1 preparation.
Fig. 2 is the stereoscan photograph of the Pd/C catalyst of embodiment 2 preparations.
Fig. 3 is the stereoscan photograph of the Pt/C catalyst of embodiment 3 preparations.
Fig. 4 is the stereoscan photograph of the Pt/C catalyst of embodiment 4 preparations.
The specific embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, the specific embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
Embodiment 1
By 5g active carbon, 13ml, 0.2mol/L RuCl
3solution and 4mL, 5% dodecyl sodium sulfate mixes, and under ul-trasonic irradiation, disperses, and it is 40KHz that supersonic frequency is set, and ultrasonic time is 0.5h.The mixture obtaining after ultrasonic is added to 20ml, and 0.25mol/L sodium borohydride solution reduces under microwave, and it is 20w that microwave irradiation power is set, and the time is 1h, and reduction reaction temperature is 70 ℃.By distilled water washing 5 times for the solid product obtaining, then at 80 ℃, dry 10h, obtain 5%Ru/C catalyst.
Can output from Fig. 1, the metal Ru good dispersion of Ru/C catalyst, disperses comparatively evenly, and metal particle diameter is less.
Embodiment 2
By 1g active carbon, 5ml, 0.0376mol/L Pd (NO
3)
2solution and 2mL, 3% neopelex mixes, and under ul-trasonic irradiation, disperses, and it is 60KHz that supersonic frequency is set, and ultrasonic time is 0.5h.The mixture obtaining after ultrasonic is added to 10ml, and 0.3mol/L sodium borohydride solution reduces under microwave, and it is 25w that microwave irradiation power is set, and the time is 1h, and reduction reaction temperature is 70 ℃.By distilled water washing 5 times for the solid product obtaining, then at 80 ℃, dry 10h, obtain 2%Pd/C catalyst.
Can output from Fig. 2, the metal Pd good dispersion of Pd/C catalyst, disperses comparatively evenly, and metal particle diameter is less.
Embodiment 3
By 1g active carbon, 2ml, 0.0125mol/L K
2ptCl
4solution and 5mL, 4% dodecyl sodium sulfate mixes, and under ul-trasonic irradiation, disperses, and it is 80KHz that supersonic frequency is set, and ultrasonic time is 1h.The mixture obtaining after ultrasonic is added to 10ml, and 0.15mol/L sodium borohydride solution reduces under microwave, and it is 25w that microwave irradiation power is set, and the time is 1.5h, and reduction reaction temperature is 80 ℃.By distilled water washing 5 times for the solid product obtaining, then at 80 ℃, dry 10h, obtain 0.5%Pt/C catalyst.
Can output from Fig. 3, the Pt metal good dispersion of Pt/C catalyst, disperses comparatively evenly, and metal particle diameter is less.
Embodiment 4
By 1g active carbon, 8ml, 0.0125mol/L K
2ptCl
4solution and 4mL, 5% dodecyl sodium sulfate mixes, and under ul-trasonic irradiation, disperses, and it is 80KHz that supersonic frequency is set, and ultrasonic time is 1h.The mixture obtaining after ultrasonic is added to 10ml, and 0.25mol/L sodium borohydride solution reduces under microwave, and it is 25w that microwave irradiation power is set, and the time is 1.5h, and reduction reaction temperature is 80 ℃.By distilled water washing 5 times for the solid product obtaining, then at 80 ℃, dry 10h, obtain 2%Pt/C catalyst.
Can output from Fig. 4, the Pt metal good dispersion of Pt/C catalyst, disperses comparatively evenly, and metal particle diameter is less.
Claims (10)
1. a preparation method for noble metal catalyst, is characterized in that, said method comprising the steps of:
(1) by the salting liquid of carrier, noble metal and dispersant, under ul-trasonic irradiation, disperse, obtain mixture;
(2) mixture added to reducing agent and reduce under microwave, obtaining solid product;
(3) solid product is washed with distilled water, after oven dry, obtain noble metal catalyst.
2. the preparation method of noble metal catalyst as claimed in claim 1, is characterized in that, in described step (1), carrier consumption is 1-5g, precious metal salt solution concentration is 0.01-0.5mol/L, consumption is 1-15mL, and dispersant mass fraction is 1%-10%, and consumption is 1-5mL.
3. the preparation method of noble metal catalyst as claimed in claim 1, is characterized in that, in described step (1), carrier comprises SiO
2, Al
2o
3, ZrO
2, TiO
2, active carbon or CNT.
4. the preparation method of noble metal catalyst as claimed in claim 1, is characterized in that, in described step (1), noble metal comprises Pt, Au, Ru, Re, Rd or Pd.
5. the preparation method of noble metal catalyst as claimed in claim 1, is characterized in that, in described step (1), the salting liquid of noble metal comprises solution of chlorate, nitrate solution or sulfate liquor.
6. the preparation method of noble metal catalyst as claimed in claim 1, is characterized in that, in described step (1), dispersant comprises neopelex, dodecyl sodium sulfate or gelatin.
7. the preparation method of noble metal catalyst as claimed in claim 1, is characterized in that, in described step (1), ultrasonic frequency is 20-80KHz, and ultrasonic time is 0.5-1h.
8. the preparation method of noble metal catalyst as claimed in claim 1, is characterized in that, in described step (2), microwave irradiation power is 5-30w, and microwave irradiation time is 0.5-2h, and reduction reaction temperature is 60-80 ℃.
9. the preparation method of noble metal catalyst as claimed in claim 1, it is characterized in that, in described step (2), reducing agent comprises sodium borohydride, hydrazine hydrate, KBr, formic acid, sodium acetate or natrium citricum, and reductant concentration is 0.01-1mol/L, and reducing agent consumption is 5-50mL.
10. the preparation method of noble metal catalyst as claimed in claim 1, is characterized in that, in described step (3), bake out temperature is 80-120 ℃, and drying time is 4-10h.
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|---|---|---|---|
| CN201410252757.XA CN104056621A (en) | 2014-06-09 | 2014-06-09 | Preparation method of noble metal catalyst |
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|---|---|---|---|
| CN201410252757.XA CN104056621A (en) | 2014-06-09 | 2014-06-09 | Preparation method of noble metal catalyst |
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|---|---|
| CN104056621A true CN104056621A (en) | 2014-09-24 |
Family
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| CN201410252757.XA Pending CN104056621A (en) | 2014-06-09 | 2014-06-09 | Preparation method of noble metal catalyst |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104667909A (en) * | 2015-03-07 | 2015-06-03 | 刘平 | Preparation method of high-activity long-acting platinum-carbon catalyst |
| CN104801298A (en) * | 2014-10-15 | 2015-07-29 | 青岛科技大学 | Method for preparing platinum-carbon catalyst |
| CN104959142A (en) * | 2015-05-25 | 2015-10-07 | 安徽海德石油化工有限公司 | Catalyst for preparation of ethylene and propylene through naphtha cracking |
| CN105214653A (en) * | 2015-08-28 | 2016-01-06 | 北京化工大学 | A kind of preparation method of carbon nanotube loaded nanoparticle catalyst |
| CN106475094A (en) * | 2015-09-02 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of selective acetylene hydrocarbon hydrogenation catalyst and its preparation method and application and C-2-fraction are except the method for alkynes |
| CN106607020A (en) * | 2016-11-29 | 2017-05-03 | 南京东焱氢能源科技有限公司 | Preparation method for high-activity palladium-carbon catalyst |
| CN106732566A (en) * | 2017-02-07 | 2017-05-31 | 西北师范大学 | A kind of preparation method of carbon nanotube loaded metal Ru nano-particle catalyst |
| CN107511150A (en) * | 2017-09-18 | 2017-12-26 | 吉林大学 | A kind of preparation method of the heterogeneous catalyst of formic acid decomposing hydrogen-production |
| CN109745969A (en) * | 2018-12-20 | 2019-05-14 | 西安交通大学 | A kind of carbon carries super-small precious metal nano-particle catalyst and preparation method |
| CN110380069A (en) * | 2019-07-22 | 2019-10-25 | 中国科学技术大学 | A kind of noble metal catalyst of active carbon confinement and preparation method thereof and application |
| CN110841634A (en) * | 2019-10-24 | 2020-02-28 | 西安凯立新材料股份有限公司 | Preparation method of rhodium-carbon catalyst for synthesizing minocycline hydrochloride |
| CN117816153A (en) * | 2024-02-29 | 2024-04-05 | 黎明化工研究设计院有限责任公司 | Preparation method and application of supported Pd-based catalyst |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104801298A (en) * | 2014-10-15 | 2015-07-29 | 青岛科技大学 | Method for preparing platinum-carbon catalyst |
| CN104667909A (en) * | 2015-03-07 | 2015-06-03 | 刘平 | Preparation method of high-activity long-acting platinum-carbon catalyst |
| CN104959142B (en) * | 2015-05-25 | 2017-07-14 | 安徽海德石油化工有限公司 | A kind of naphtha pyrolysis prepares ethene and propylene catalyst |
| CN104959142A (en) * | 2015-05-25 | 2015-10-07 | 安徽海德石油化工有限公司 | Catalyst for preparation of ethylene and propylene through naphtha cracking |
| CN105214653A (en) * | 2015-08-28 | 2016-01-06 | 北京化工大学 | A kind of preparation method of carbon nanotube loaded nanoparticle catalyst |
| CN106475094A (en) * | 2015-09-02 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of selective acetylene hydrocarbon hydrogenation catalyst and its preparation method and application and C-2-fraction are except the method for alkynes |
| CN106607020A (en) * | 2016-11-29 | 2017-05-03 | 南京东焱氢能源科技有限公司 | Preparation method for high-activity palladium-carbon catalyst |
| CN106732566A (en) * | 2017-02-07 | 2017-05-31 | 西北师范大学 | A kind of preparation method of carbon nanotube loaded metal Ru nano-particle catalyst |
| CN107511150A (en) * | 2017-09-18 | 2017-12-26 | 吉林大学 | A kind of preparation method of the heterogeneous catalyst of formic acid decomposing hydrogen-production |
| CN109745969A (en) * | 2018-12-20 | 2019-05-14 | 西安交通大学 | A kind of carbon carries super-small precious metal nano-particle catalyst and preparation method |
| CN110380069A (en) * | 2019-07-22 | 2019-10-25 | 中国科学技术大学 | A kind of noble metal catalyst of active carbon confinement and preparation method thereof and application |
| CN110841634A (en) * | 2019-10-24 | 2020-02-28 | 西安凯立新材料股份有限公司 | Preparation method of rhodium-carbon catalyst for synthesizing minocycline hydrochloride |
| CN117816153A (en) * | 2024-02-29 | 2024-04-05 | 黎明化工研究设计院有限责任公司 | Preparation method and application of supported Pd-based catalyst |
| CN117816153B (en) * | 2024-02-29 | 2024-05-10 | 黎明化工研究设计院有限责任公司 | Preparation method and application of supported Pd-based catalyst |
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Application publication date: 20140924 |