CN104084194A - Method for preparing high-selectivity platinum-carbon catalyst through vacuum impregnation - Google Patents
Method for preparing high-selectivity platinum-carbon catalyst through vacuum impregnation Download PDFInfo
- Publication number
- CN104084194A CN104084194A CN201410323021.7A CN201410323021A CN104084194A CN 104084194 A CN104084194 A CN 104084194A CN 201410323021 A CN201410323021 A CN 201410323021A CN 104084194 A CN104084194 A CN 104084194A
- Authority
- CN
- China
- Prior art keywords
- platinum
- preparation
- active carbon
- reducing agent
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing a high-selectivity platinum-carbon catalyst through vacuum impregnation, relating to the technical field of catalysis. The method comprises the following steps: (1) preparing a platinum precursor solution; (2) pretreating activated carbon; (3) performing vacuum impregnation; (4) performing liquid-phase inversion reduction; and (5) aging, filtering, washing and drying. According to the preparation method, energy-saving and environment-friendly effects are achieved, the control is easy, the stability is high, and the prepared platinum-carbon catalyst is wide in active ingredient particle range, small in particle size, uniform to distribute, high in activity, high in selectivity and long in service life.
Description
Technical field
The present invention relates to catalysis technical field, in particular a kind of preparation method of vacuum impregnation high selectivity platinum carbon catalyst.
Background technology
Platinum metal catalysts has good catalytic performance, occupies extremely important status in petrochemical industry and organic synthesis, is widely used in the reactions such as hydrogenation, dehydrogenation, oxidation, reduction, isomerization, aromatisation, cracking.The catalytic performance of catalyst, except depending on the composition and content of catalyst, also closely related with the preparation method of catalyst and process conditions etc., same raw material, identical composition and content, preparation method is different, and the activity of catalyst and heat endurance may have very large difference.Therefore, the preparation method of research high selectivity platinum carbon catalyst has very important meaning.
The tradition precipitation method or infusion process in preparing the process of platinum carbon catalyst, the particle diameter of active component, decentralization and catalyst selective be all subject to the physico-chemical property of carrier charcoal, the temperature of the speed of stirring, reaction, effect of complicate factors such as the concentration of the concentration of reaction system, reducing agent and kinds thereof.As platinum nucleus in precipitation-reduction process can be grown up, be reunited in liquid phase or on carrier surface, the active component granulometric range of prepared catalyst is wide, particle diameter large, skewness, decentralization are low, is difficult to prepare the long-life platinum carbon catalyst of high selectivity high activity.
Though the standby platinum carbon catalyst of colloidal solution legal system can solve particle diameter, reunion and three problems of decentralization of active component platinum, but platinum carbon catalyst active component prepared by the method is the exposed carrier carbon surface that is deposited on of large number absolutely, seldom infiltrate in the nearly outer surface of carrier charcoal, this method cannot solve active component Platinum Nanoparticles and carrier charcoal adhesion-tight problem, in catalytic reaction, catalyst initial activity does very well, but there is no reserve strength, repeat to apply mechanically that number of times is few, service life is short.
In Chinese patent ZL200810031255.9, introduce a kind of preparation method of nano-crystalline platinum carbon catalyst, comprised the preparation of platinum complex, the configuration of the absorption of platinum complex, reducing agent, microwave reduction and drying and other steps.Colloidal platinum catalyst cupport is to overcome these deficiencies and keep one of effective way of colloidal platinum catalyst high selectivity, high activity and reaction condition gentleness.
Summary of the invention
Technical problem to be solved by this invention is the deficiency existing for prior art, and a kind of preparation method of vacuum impregnation high selectivity platinum carbon catalyst is provided.
Technical scheme of the present invention is as follows:
A preparation method for vacuum impregnation high selectivity platinum carbon catalyst, its step is as follows:
(1) preparation of platinum precursor solution
Take chloroplatinic acid, add deionized water dilution platinum to 20-50g/L, and add lubricant in platinum acid chloride solution, under agitation, regulate pH to 1-5, make platinum precursor solution;
(2) pretreatment of active carbon
At normal temperatures, the nitric acid treatment 4h by active carbon with the 0.5mol/L of 5 times of volumes, filters, and by the deionized water of 2-5 times of quality, soaks, and under agitation, regulates pH to 1-5, soaks 4-12h, filtration, dry;
(3) vacuum impregnation
Good active carbon of pretreatment in (2) is put into the platinum precursor solution that special plastic bucket neutralization (1) prepares and be placed in together gloves vacuum tank, inflated with nitrogen, vacuumize 3-5 time repeatedly, platinum precursor solution is kept to temperature 30-50 ℃, then it is slowly joined in active carbon, limit edged stirs, particle is ground, pass into nitrogen protection, normal pressure 4-24h;
(4) liquid phase inversion reduction
Vacuum-impregnated platinum active carbon in (3) is slowly joined in reducing agent, and the temperature of reducing agent is controlled as 40-80 ℃;
(5) ageing, filtration, washing and dry
By the material in (4) through 15-35 ℃ of ageing 1-10h, it is 2-6 with 0.05-1.5mol/L hydrochloric acid or acetic acid tune pH that ageing finishes rear material, then with deionized water filtration washing, extremely with silver nitrate, detect without till white precipitate, dry in 80-120 ℃ of drying box, the load capacity that makes platinum is the high selectivity platinum carbon catalyst of 0.5-10%wt (load capacity of platinum is the mass percent of platinum and active carbon).
Described preparation method, in step (1), described lubricant is that one or more of castor oil, silicone oil, fatty acid amide, grease, oleic acid and carboxylic acid are formulated; The consumption of lubricant is 0.01-5 times of platinum quality.
Described preparation method, in step (1) and (2), regulating the solvent of pH is Na
2cO
3, sodium acetate, EDTA or NaHCO
3in one or both, the mass fraction of solution is 5-20%.
Described preparation method, in step (4), described reducing agent is one or more formulated mixtures of formaldehyde, formic acid, sodium acetate, natrium citricum, hydrazine hydrate, sodium borohydride; The concentration of reducing agent is 0.05-2mol/L, and the consumption of reducing agent is that 1 gram of active carbon adds 5-30 milliliter reducing agent.
Preparation method of the present invention, has not only solved that traditional precipitation method and infusion process activity are low, poor selectivity and the problem such as service life is short, and has kept the particle diameter similar to colloidal platinum catalyst to distribute and particle size.The vacuum impregnation that preparation method of the present invention adopts makes active component platinum can fully be distributed to carrier inside, and nano platinum particle decentralization is even; The liquid phase inversion reduction adopting, the adhesive force of maintenance nano platinum particle, enhancing nano platinum particle.
Preparation method's energy-conserving and environment-protective of the present invention, be easy to control, good stability, the platinum carbon catalyst active component granulometric range of preparation is narrow, particle diameter is little, be evenly distributed, active high, selective good, long service life.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
One, the preparation of platinum precursor solution
Accurately take chloroplatinic acid 394.74g (in chloroplatinic acid, platinum content 38.0%), add deionized water dilution platinum to 50g/L, and add 150g castor oil (lubricant) in platinum acid chloride solution, under stirring, the Na that service property (quality) mark is 5%
2cO
3solution regulates its pH to 1, makes platinum precursor solution;
Two, the pretreatment of active carbon
At normal temperatures, take the nitric acid treatment 4h that 5.5kg active carbon adds the 0.5mol/L of 5 times of volumes, filter, immerse in 11kg deionized water the Na that service property (quality) mark is 5%
2cO
3solution regulates pH to 1, soaks 12h, filters, is dried;
Three, vacuum impregnation
Accurately taking the good active carbon 4.85kg of pretreatment in step (two) puts into the platinum precursor solution that special plastic bucket neutralization procedure () prepares and is placed in together gloves vacuum tank, inflated with nitrogen, vacuumize 3-5 time repeatedly, keep 30 ℃ of temperature slowly to join in active carbon platinum precursor solution, limit edged stirs, with spoon, particle is ground, pass into nitrogen protection, normal pressure 4h;
Four, liquid phase inversion reduction
Compound concentration is the formic acid solution 97L (reducing agent) of 1mol/L, and heating and thermal insulation to 80 ℃ slowly joins in reducing agent by the active carbon of vacuum impregnation platiniferous in step (three);
Five, ageing, filtration, washing and dry
Acetic acid adjustment pH to 6 by the material in step (four) through 25 ℃ of ageings 2 hours, use 0.1mol/L, filter, wash, with deionized water filtration washing, extremely with silver nitrate, detect without till white precipitate, dry in 80 ℃ of drying boxes, the high selectivity platinum carbon catalyst that the load capacity that makes platinum is 3%.
Embodiment 2
Aphox, has and tags, and stifling and blade face osmosis is selective strong aphicide; Can effectively prevent and treat all aphids except cotten aphid, the aphid that organophosphor is produced to resistance is also effective; Desinsection is rapid, but the longevity of residure is short; To crop safety, do not hinder natural enemy, be the desirable medicament of integrated control.
The presoma of synthetic pirimicarb pesticidal intermediate has C=C and two unsaturated bonds of C=O, from the two keys of thermodynamics C=O than the easier hydrogenation of C=C, and pirimicarb pesticidal intermediate will retain C=C double-bond hydrogenation the two keys of C=O, the synthetic pirimicarb pesticidal intermediate of the platinum carbon catalyst of preparation application in embodiment 1, the yield that obtains pirimicarb pesticidal intermediate is 99.4%.
Embodiment 3
O-chloraniline, is a kind of important fine-chemical intermediate, is widely used in the fine chemicals such as agricultural chemicals, dyestuff, medicine.At present, chloro aminobenzen is generally made by reducing aromatic nitro compound, industrial main employing akali sulphide, iron powder, hydrazine hydrate reduction or liquid phase catalytic hydrogenation reducing process.Wherein, the three wastes are few, post processing simple, good product quality because producing for catalytic hydrogenating reduction legal system chloro aminobenzen, and more approach Green Chemistry.
To o-chloronitrobenzene preparing o-chloroaniline by catalytic hydrogenation, reaction has good catalytic performance to the platinum carbon catalyst of embodiment 1 preparation, at o-chloronitrobenzene, be 1.6g, isopropyl alcohol is 15mL, catalyst amount is 15.0mg, reaction temperature is at 40 ℃, synthesis under normal pressure 1h, obtains o-chloronitrobenzene conversion ratio and o-chloraniline and is selectively respectively 100% and 96.8%, still keeps good catalytic activity after reusing 8 times.
Embodiment 4
One, the preparation of platinum precursor solution
Accurately take chloroplatinic acid 394.74g (in chloroplatinic acid, platinum content 38.0%), add deionized water dilution platinum to 30g/L, and add 300g fatty acid amide (lubricant) in platinum acid chloride solution, under agitation, the NaHCO that service property (quality) mark is 15%
3solution regulates its pH to 2.5, makes platinum precursor solution;
Two, the pretreatment of active carbon
At normal temperatures, take the nitric acid treatment 4h that 8.5kg active carbon adds the 0.5mol/L of 5 times of volumes, filter, immerse in 17kg deionized water the NaHCO that service property (quality) mark is 20%
3solution regulates pH to 2.5, soaks 8h, filters, is dried;
Three, vacuum impregnation
Accurately taking the good active carbon 7.35kg of pretreatment in step (two) puts into the platinum precursor solution that special plastic bucket neutralization procedure () prepares and is placed in together gloves vacuum tank, inflated with nitrogen, vacuumize 3-5 time repeatedly, keep 40 ℃ of temperature slowly to join in active carbon platinum precursor solution, limit edged stirs, with spoon, particle is ground, pass into nitrogen protection, normal pressure 12h;
Four, liquid phase inversion reduction
Compound concentration is the sodium borohydride solution 220.5L (reducing agent) of 0.5mol/L, and heating and thermal insulation to 60 ℃ slowly joins in reducing agent by the active carbon of vacuum impregnation platiniferous in step (three);
Five, ageing, filtration, washing and dry
Acetic acid adjustment pH to 4 by the material in step (four) through 25 ℃ of ageings 2 hours, use 1mol/L, filter, wash, with deionized water filtration washing, extremely with silver nitrate, detect without till white precipitate, dry in 90 ℃ of drying boxes, the high selectivity platinum carbon catalyst that the load capacity that makes platinum is 2%.
Embodiment 5
The synthetic pirimicarb pesticidal intermediate of the platinum carbon catalyst of preparation application in embodiment 4, the yield that obtains pirimicarb pesticidal intermediate is 99.5%.
To o-chloronitrobenzene preparing o-chloroaniline by catalytic hydrogenation, reaction has good catalytic performance to the platinum carbon catalyst of embodiment 4 preparations, at o-chloronitrobenzene, be 1.6g, isopropyl alcohol is 15mL, catalyst amount is 22.5mg, reaction temperature is at 40 ℃, synthesis under normal pressure 1h, obtains o-chloronitrobenzene conversion ratio and o-chloraniline and is selectively respectively 100% and 97.3%, still keeps good catalytic activity after reusing 10 times.
Embodiment 6
One, the preparation of platinum precursor solution
Accurately take chloroplatinic acid 394.74g (in chloroplatinic acid, platinum content 38.0%), add deionized water dilution platinum to 20g/L, and add 450g oleic acid (lubricant) in platinum acid chloride solution, under agitation, service property (quality) mark is that 20% SAS regulates its pH to 5, makes platinum precursor solution;
Two, the pretreatment of active carbon
At normal temperatures, take the nitric acid treatment 4h that 11.5kg active carbon adds the 0.5mol/L of 5 times of volumes, filter, immerse in 34.5kg deionized water, the SAS that service property (quality) mark is 20% regulates pH to 5, soaks 4h, filtration, dry;
Three, vacuum impregnation
Accurately taking the good active carbon 9.85kg of pretreatment in step (two) puts into the platinum precursor solution that special plastic bucket neutralization procedure () prepares and is placed in together gloves vacuum tank, inflated with nitrogen, vacuumize 3-5 time repeatedly, keep temperature 50 C slowly to join in active carbon platinum precursor solution, limit edged stirs, with spoon, particle is ground, pass into nitrogen protection, normal pressure 24h;
Four, liquid phase inversion reduction
Compound concentration is the hydrazine hydrate solution 49.25L (reducing agent) of 0.05mol/L, and heating and thermal insulation to 40 ℃ slowly joins in reducing agent by the active carbon of vacuum impregnation platiniferous in step (three);
Five, ageing, filtration, washing and dry
Acetic acid adjustment pH to 2 by the material in step (four) through 25 ℃ of ageings 2 hours, use 1.5mol/L, filter, wash, with deionized water filtration washing, extremely with silver nitrate, detect without till white precipitate, dry in 120 ℃ of drying boxes, the high selectivity platinum carbon catalyst that the load capacity that makes platinum is 1.5%.
Embodiment 7
The synthetic pirimicarb pesticidal intermediate of the platinum carbon catalyst of preparation application in embodiment 6, the yield that obtains pirimicarb pesticidal intermediate is 99.7%.
To o-chloronitrobenzene preparing o-chloroaniline by catalytic hydrogenation, reaction has good catalytic performance to the platinum carbon catalyst of embodiment 6 preparations, at o-chloronitrobenzene, be 1.6g, isopropyl alcohol is 15mL, catalyst amount is 30.0mg, reaction temperature is at 40 ℃, synthesis under normal pressure 1h, obtains o-chloronitrobenzene conversion ratio and o-chloraniline and is selectively respectively 100% and 97.8%, still keeps good catalytic activity after reusing 14 times.
Should be understood that, for those of ordinary skills, can be improved according to the above description or convert, and all these improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (4)
1. a preparation method for vacuum impregnation high selectivity platinum carbon catalyst, is characterized in that, its step is as follows:
(1) preparation of platinum precursor solution
Take chloroplatinic acid, add deionized water dilution platinum to 20-50g/L, and add lubricant in platinum acid chloride solution, under agitation, regulate pH to 1-5, make platinum precursor solution;
(2) pretreatment of active carbon
At normal temperatures, the nitric acid treatment 4h by active carbon with the 0.5mol/L of 5 times of volumes, filters, and by the deionized water of 2-5 times of quality, soaks, and under agitation, regulates pH to 1-5, soaks 4-12h, filtration, dry;
(3) vacuum impregnation
Good active carbon of pretreatment in (2) is put into the platinum precursor solution that special plastic bucket neutralization (1) prepares and be placed in together gloves vacuum tank, inflated with nitrogen, vacuumize 3-5 time repeatedly, platinum precursor solution is kept to temperature 30-50 ℃, then it is slowly joined in active carbon, limit edged stirs, particle is ground, pass into nitrogen protection, normal pressure 4-24h;
(4) liquid phase inversion reduction
Vacuum-impregnated platinum active carbon in (3) is slowly joined in reducing agent, and the temperature of reducing agent is controlled as 40-80 ℃;
(5) ageing, filtration, washing and dry
By the material in (4) through 15-35 ℃ of ageing 1-10h, it is 2-6 with 0.05-1.5mol/L hydrochloric acid or acetic acid tune pH that ageing finishes rear material, then with deionized water filtration washing, extremely with silver nitrate, detect without till white precipitate, dry in 80-120 ℃ of drying box, the high selectivity platinum carbon catalyst that the load capacity that makes platinum is 0.5-10%wt.
2. preparation method according to claim 1, is characterized in that, in step (1), described lubricant is that one or more of castor oil, silicone oil, fatty acid amide, grease, oleic acid and carboxylic acid are formulated; The consumption of lubricant is 0.01-5 times of platinum quality.
3. preparation method according to claim 1, is characterized in that, in step (1) and (2), regulating the solvent of pH is Na
2cO
3, sodium acetate, EDTA or NaHCO
3in one or both, the mass fraction of solution is 5-20%.
4. preparation method according to claim 1, is characterized in that, in step (4), described reducing agent is one or more formulated mixtures of formaldehyde, formic acid, sodium acetate, natrium citricum, hydrazine hydrate, sodium borohydride; The concentration of reducing agent is 0.05-2mol/L, and the consumption of reducing agent is that 1 gram of active carbon adds 5-30 milliliter reducing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410323021.7A CN104084194A (en) | 2014-07-08 | 2014-07-08 | Method for preparing high-selectivity platinum-carbon catalyst through vacuum impregnation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410323021.7A CN104084194A (en) | 2014-07-08 | 2014-07-08 | Method for preparing high-selectivity platinum-carbon catalyst through vacuum impregnation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104084194A true CN104084194A (en) | 2014-10-08 |
Family
ID=51632011
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410323021.7A Pending CN104084194A (en) | 2014-07-08 | 2014-07-08 | Method for preparing high-selectivity platinum-carbon catalyst through vacuum impregnation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104084194A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104624185A (en) * | 2015-01-12 | 2015-05-20 | 鲁奎 | Method for preparing carbon-supported platinum catalyst by precipitation transformation |
| CN109225258A (en) * | 2018-10-19 | 2019-01-18 | 郴州高鑫铂业有限公司 | A kind of Pt-Fe/C catalyst and its preparation method and application |
| CN111013574A (en) * | 2019-11-13 | 2020-04-17 | 北京博雅合众环保科技有限公司 | Preparation method of noble metal/carbon sphere composite catalytic material for removing formaldehyde from air |
| CN111068666A (en) * | 2019-11-18 | 2020-04-28 | 天津博雅大地新材料科技有限公司 | Sepiolite supported noble metal formaldehyde room-temperature oxidation catalyst and preparation method thereof |
| CN111974383A (en) * | 2020-08-25 | 2020-11-24 | 浙江工业大学 | Coconut shell activated carbon supported platinum catalyst and preparation method and application thereof |
| CN108126694B (en) * | 2017-12-26 | 2020-12-29 | 赣南师范大学 | Platinum-carbon catalyst for azithromycin production and preparation method thereof |
| CN112174831A (en) * | 2020-11-06 | 2021-01-05 | 西安凯立新材料股份有限公司 | Method for synthesizing o-chloroaniline by using platinum carbon catalyst |
| CN112517001A (en) * | 2020-12-16 | 2021-03-19 | 上海济平新能源科技有限公司 | Preparation method of platinum black catalyst and platinum black catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101502797A (en) * | 2008-12-30 | 2009-08-12 | 西安凯立化工有限公司 | Platinum-based selective hydrogenation catalyst as well as preparation method and use thereof |
-
2014
- 2014-07-08 CN CN201410323021.7A patent/CN104084194A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101502797A (en) * | 2008-12-30 | 2009-08-12 | 西安凯立化工有限公司 | Platinum-based selective hydrogenation catalyst as well as preparation method and use thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王尚弟等: "《催化剂工程导论》", 31 August 2001, article "-", pages: 54 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104624185A (en) * | 2015-01-12 | 2015-05-20 | 鲁奎 | Method for preparing carbon-supported platinum catalyst by precipitation transformation |
| CN108126694B (en) * | 2017-12-26 | 2020-12-29 | 赣南师范大学 | Platinum-carbon catalyst for azithromycin production and preparation method thereof |
| CN109225258A (en) * | 2018-10-19 | 2019-01-18 | 郴州高鑫铂业有限公司 | A kind of Pt-Fe/C catalyst and its preparation method and application |
| CN111013574A (en) * | 2019-11-13 | 2020-04-17 | 北京博雅合众环保科技有限公司 | Preparation method of noble metal/carbon sphere composite catalytic material for removing formaldehyde from air |
| CN111068666A (en) * | 2019-11-18 | 2020-04-28 | 天津博雅大地新材料科技有限公司 | Sepiolite supported noble metal formaldehyde room-temperature oxidation catalyst and preparation method thereof |
| CN111974383A (en) * | 2020-08-25 | 2020-11-24 | 浙江工业大学 | Coconut shell activated carbon supported platinum catalyst and preparation method and application thereof |
| CN112174831A (en) * | 2020-11-06 | 2021-01-05 | 西安凯立新材料股份有限公司 | Method for synthesizing o-chloroaniline by using platinum carbon catalyst |
| CN112174831B (en) * | 2020-11-06 | 2022-08-05 | 西安凯立新材料股份有限公司 | Method for synthesizing o-chloroaniline by using platinum carbon catalyst |
| CN112517001A (en) * | 2020-12-16 | 2021-03-19 | 上海济平新能源科技有限公司 | Preparation method of platinum black catalyst and platinum black catalyst |
| CN112517001B (en) * | 2020-12-16 | 2023-04-07 | 广东济平新能源科技有限公司 | Preparation method of platinum black catalyst and platinum black catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104084194A (en) | Method for preparing high-selectivity platinum-carbon catalyst through vacuum impregnation | |
| CN106753549B (en) | A kind of method that the phenolic product hydrotreating of lignin depolymerization lightweight prepares HC fuel | |
| Sarmah et al. | Effect of substrates on catalytic activity of biogenic palladium nanoparticles in C–C cross-coupling reactions | |
| CN104324761B (en) | The Synthesis and applications that a kind of porous rare earth organic coordination compound is catalyst based | |
| CN105536779B (en) | A kind of preparation method of Pd/TiO2 nano-wire catalyst, catalyst obtained and its application | |
| CN103418421B (en) | A kind of Catalysts and its preparation method synthesizing paraxylene for coking benzene and methanol alkylation | |
| CN102218321B (en) | Method for preparing heterogeneous phase Fenton catalyst used for methyl orange wastewater treatment | |
| CN111085241B (en) | Method for preparing aniline by nitrobenzene hydrogenation and preparation method of catalyst thereof | |
| CN104399535B (en) | The preparation method and application that a kind of magnetic partner is catalyst based | |
| CN103664524B (en) | The method of 1,4 cyclohexanedicarboxylic acid Hydrogenation 1,4 cyclohexane dimethanol | |
| CN103394348A (en) | Method for preparing catalyst for hydrogenating pyridine compound and application thereof | |
| CN100594978C (en) | Process for preparing catalyst Pd/TiO2 for hydrogenation of p-carboxybenzaldehyde | |
| CN103464195A (en) | Method for preparing catalyst for methane oxidation-based methanol preparation by introduction of active component into pore-enlarging agent | |
| CN103769088A (en) | Preparation method of size-controllable nano Pd/C catalyst | |
| CN104801299A (en) | Plant reduction preparation method of ruthenium-on-carbon catalyst, ruthenium-on-carbon catalyst and application | |
| CN107029764B (en) | A kind of preparation method and application of support type P Modification palladium catalyst | |
| CN106944075B (en) | A method of nitro reducing catalyst is prepared by reduced iron powder waste residue | |
| CN105251488A (en) | Dehydrogenation catalyst capable of loading copper nanoparticles on surface of CNT (carbon nanotube) with high dispersion and preparation method of dehydrogenation catalyst | |
| CN103433059A (en) | Catalyst used in hydrogenation reaction of m-dinitrobenzene to synthesize m-phenylenediamine and application of catalyst | |
| CN104971738A (en) | Preparation method of magnetic nano palladium catalyst | |
| CN100408179C (en) | Transition metal catalyst for gas phase synthesis of N-alkylaniline by aniline and alcohol | |
| CN111604060A (en) | Preparation method of hydrogenation catalyst carrier and product | |
| CN100443172C (en) | Accelerating agent and its application in synthesizing carbolic acid using benzene and hydrogen dioxide | |
| CN104324758A (en) | Preparation and applications of magnetic metal organic polymer-supported noble metal catalyst | |
| CN107715870A (en) | A kind of preparation method and application for preparing L aminopropanol ruthenium Pd/carbon catalysts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20141008 |