CN101954278A - Palladium-based catalyst used for synthesis of high-saturation nitrile butadiene rubber and preparation method thereof - Google Patents
Palladium-based catalyst used for synthesis of high-saturation nitrile butadiene rubber and preparation method thereof Download PDFInfo
- Publication number
- CN101954278A CN101954278A CN2010102821279A CN201010282127A CN101954278A CN 101954278 A CN101954278 A CN 101954278A CN 2010102821279 A CN2010102821279 A CN 2010102821279A CN 201010282127 A CN201010282127 A CN 201010282127A CN 101954278 A CN101954278 A CN 101954278A
- Authority
- CN
- China
- Prior art keywords
- palladium
- preparation
- nitrile rubber
- highly saturated
- saturated nitrile
- 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
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a palladium-based catalyst used for the synthesis of high-saturation nitrile butadiene rubber and a preparation method thereof. The method comprises the following steps of: infrared solution preparation, vacuum adsorption, liquid phase reduction, washing, drying and the like. In the nano palladium-based catalyst prepared by the method of the invention, the average grain diameter of an active ingredient palladium is 1 to 2nm, the dispersion degree of the active ingredient palladium is more than or equal to 40 percent, and the specific surface area of the active ingredient palladium is more than or equal to 138m<2>/g. The catalyst is applied to the synthesis of the high-saturation nitrile butadiene rubber, a carbon-carbon double bond instead of a carbon-nitrogen triple bond is directionally selected during hydrogenation, and the hydrogenation rate of the nitrile butadiene rubber is over 99.5 percent, so the problems of high cost and difficult separation, recovery and regeneration of the catalyst are solved, and the catalyst has the advantages of simple process, environmental protection, high efficiency, small grain diameter, narrow grain diameter distribution, high selectivity and the like.
Description
Technical field
The invention belongs to catalysis technical field, be specifically related to the synthetic highly saturated nitrile rubber Catalysts and its preparation method of a kind of palladium base.
Background technology
Along with going deep into of nanometer area research, the researcher finds that the noble metal of Nano grade has higher researching value on catalytic performance.The physical property of precious metal palladium uniqueness and high catalytic activity cause researchers' interest greatly equally, because Pd nano particle fabulous catalytic performance in various reactions obtains extensive studies, palladium is used for liquid phase catalytic hydrogenation usually as a kind of hydrogenation catalyst in academia and industry, especially the hydrogenation of the two keys of C=C, the hydrocarbon conversion, selective hydrogenation, and important course of reaction such as selective oxidation in obtained to use widely.The needs that the activated centre particle diameter is big, shortcomings such as particle size distribution range is wide, poor selectivity can not satisfy Industrial Catalysis that present traditional preparation method obtains, wherein synthetic highly saturated nitrile rubber synthetic catalyst is exactly one of them.
Hydrogenated nitrile-butadiene rubber (HNBR) is the novel elastomer of a kind of high-tech, high added value.In recent years, external many to the research of HNBR, German Bayer company, Japanese Zeon company and Canadian Polysar company successively found the factory and produce HNBR.Domesticly set foot in laterly, and mainly concentrate in the utilization again to the exploitation of novel cheap catalyst and expensive catalyst.The rhodium series catalysts remains the emphasis of research, and Beijing University of Chemical Technology has developed Rh – Ru bimetallic list ligand catalyst, and its hydrogenation rate reaches more than 98%.On this basis, they have also developed the two part hydrogenation catalysts of a kind of new rhodium ruthenium bimetallic, are used for the NBR hydrogenation, have higher activity, good selectivity and lower cost.Domestic and international main use rhodium base catalyst and homogeneous catalysis are come synthesizing hydrogenated acrylonitrile-butadiene rubber, can not fundamentally solve synthesizing hydrogenated acrylonitrile-butadiene rubber catalyst cost height, difficult separation, be difficult for problems such as recovery and regeneration.
Summary of the invention
The purpose of this invention is to provide the synthetic highly saturated nitrile rubber Catalysts and its preparation method of a kind of palladium base.The nanometer palladium-based catalyst of the inventive method preparation, the average grain diameter 1～2nm of active component palladium, the decentralization of active component palladium 〉=40%, the specific area of active component palladium
Be applied to synthetic highly saturated nitrile rubber, the directed C=C that selects of hydrogenation, and to C ≡ N hydrogenation not, the hydrogenation ratio of acrylonitrile-butadiene rubber is greater than 99.5%.This method solved catalyst cost height, difficultly separate, be difficult for reclaiming and the difficult problem of regeneration, and have that technological process is simple, environment-friendly high-efficiency, particle diameter are little, narrow diameter distribution, good selective.
In order to reach above purpose, technical scheme of the present invention is by following design:
A kind of palladium base synthesizes the highly saturated nitrile rubber Catalysts and its preparation method, it is characterized in that this method may further comprise the steps: infrared liquid making, vacuum suction, liquid-phase reduction, washing and drying.
A kind of palladium base synthesizes the highly saturated nitrile rubber Catalysts and its preparation method, it is characterized in that, infrared liquid making is to take by weighing 1.78g PdCl
2Add 0.1～5mL hydrochloric acid, and add deionized water, 200W on the far infrared electronic oven～800W heating for dissolving also concentrates and catches up with acid, and it is standby to be settled to 5～20g/L at last.
A kind of palladium base synthesizes the highly saturated nitrile rubber Catalysts and its preparation method, it is characterized in that, vacuum suction is add stabilizing agent in palladium liquid after, in vacuum tank, slowly join in the carrier, and use infrared pressure to adsorb 20～80 ℃ of adsorption temps, adsorption time 6～24h.
A kind of palladium base synthesizes the highly saturated nitrile rubber Catalysts and its preparation method, it is characterized in that, reducing agent can be one or both in formaldehyde, formic acid, sodium acetate, sodium borohydride, the hydrazine hydrate, and the mol ratio of itself and Metal Palladium is 1: 0.1～10.Concentration is 0.01～5mol/L, and the liquid-phase reduction temperature is 50～100 ℃.
A kind of palladium base synthesizes the highly saturated nitrile rubber Catalysts and its preparation method, it is characterized in that, washing process detects to silver nitrate with deionized water cyclic washing palladium-based catalyst not to be had
Till.
A kind of palladium base synthesizes the highly saturated nitrile rubber Catalysts and its preparation method, it is characterized in that, baking temperature is 40～110 ℃, and the time is 0.5～6h.
A kind of palladium base synthesizes the highly saturated nitrile rubber Catalysts and its preparation method, it is characterized in that, the vacuum of vacuum suction is 0.05～0.1MPa.
A kind of palladium base synthesizes the highly saturated nitrile rubber Catalysts and its preparation method, it is characterized in that, stabilizing agent can be one or both in natrium citricum, polyvinylpyrrolidone, polyvinyl alcohol, the polyethylene glycol etc., and wherein the mol ratio of stabilizing agent and palladium is 1: 1～100.
A kind of palladium base synthesizes the highly saturated nitrile rubber Catalysts and its preparation method, it is characterized in that, carrier is the mixture that one or more components in silica, active carbon, aluminium oxide, the alkali carbonate combine by any mass ratio.
The important technological parameters table that nanometer Pd is catalyst based
Description of drawings
Accompanying drawing is the IR Characterization figure of hydrogenated nitrile-butadiene rubber in the performance evaluation of the present invention.
The specific embodiment
Below in conjunction with embodiment the present invention being made and to further specify, is not limitation of the present invention.
The performance evaluation of this catalyst realizes by the synthetic highly saturated nitrile rubber of acrylonitrile-butadiene rubber catalytic hydrogenation.Concrete evaluating is as follows: the catalyst based and 50g chlorobenzene of NBR 25g, 2.5 g nanometer Pd joins in the autoclave together, extract earlier the air in the autoclave repeatedly, with hydrogen exchange for several times, fill hydrogen to 4MPa, stir also and slowly be heated to 80 ℃, reaction 10h, the cooling naturally of reaction back, the hydrogenation ratio of infrared spectrum analysis HNBR, accompanying drawing are the analysis result of embodiment 5.
Embodiment 1
Take by weighing 1.78g PdCl
2Powder dissolution is in 0.1～5mL hydrochloric acid, add deionized water, 200W on the far infrared electronic oven～800W heating for dissolving and concentrated catching up with sour 2 times, one or both in interpolation 0.02g natrium citricum, polyvinylpyrrolidone, polyvinyl alcohol, the polyethylene glycol etc., and constant volume is to 10g/L.In vacuum tank, above-mentioned palladium liquid is slowly joined in the 20.14g active carbon, infrared pressure absorption, 20～80 ℃ of adsorption temps, adsorption time are 10h; Then, one or both reduction in the formaldehyde of adding 0.01～5mol/L, formic acid, sodium acetate, sodium borohydride, the hydrazine hydrate, the mol ratio of addition and Metal Palladium is 1: 0.1～10, the liquid-phase reduction temperature is 50～100 ℃; Filter, wash to silver nitrate detection nothing
, place 40～110 ℃ of drying 0.5～6h of drying box.Through performance test, the conversion ratio 99.5% of NBR, the hydrogenation ratio of HNBR reaches 99.5%.
Embodiment 2
Take by weighing 1.78g PdCl
2Powder dissolution is in 0.1～5mL hydrochloric acid, add deionized water, 200W on the far infrared electronic oven～800W heating for dissolving and concentrated catching up with sour 2 times, one or both in interpolation 0.05g natrium citricum, polyvinylpyrrolidone, polyvinyl alcohol, the polyethylene glycol etc., and constant volume is to 10g/L.In vacuum tank, above-mentioned palladium liquid is slowly joined in the 20.14g active carbon, infrared pressure absorption, 20～80 ℃ of adsorption temps, adsorption time are 10h; Then, add one or both reduction in the formaldehyde, formic acid, sodium acetate, sodium borohydride, hydrazine hydrate of 0.01～5mol/L, addition and Metal Palladium mol ratio be 1: 0.1～10, the liquid-phase reduction temperature is 50～100 ℃; Filter, wash to silver nitrate detection nothing
, place 40～110 ℃ of drying 0.5～6h of drying box.Through performance test, the conversion ratio 99.5% of NBR, the hydrogenation ratio of HNBR reaches 99.6%.
Embodiment 3
Take by weighing 1.78g PdCl
2Powder dissolution is in 0.1～5mL hydrochloric acid, add deionized water, 200W on the far infrared electronic oven～800W heating for dissolving and concentrated catching up with sour 2 times, one or both in interpolation 0.02g natrium citricum, polyvinylpyrrolidone, polyvinyl alcohol, the polyethylene glycol etc., and constant volume is to 5g/L.In vacuum tank, above-mentioned palladium liquid is slowly joined in the 20.14g active carbon, infrared pressure absorption, 20～80 ℃ of adsorption temps, adsorption time are 10h; Then, add one or both reduction in the formaldehyde, formic acid, sodium acetate, sodium borohydride, hydrazine hydrate of 0.01～5mol/L, addition and Metal Palladium mol ratio be 1: 0.1～10, the liquid-phase reduction temperature is 50～100 ℃; Filter, wash to silver nitrate detection nothing
, place 40～110 ℃ of drying 0.5～6h of drying box.Through performance test, the conversion ratio 99.6% of NBR, the hydrogenation ratio of HNBR reaches 99.7%.
Embodiment 4
Take by weighing 1.78g PdCl
2Powder dissolution is in 0.1～5mL hydrochloric acid, add deionized water, 200W on the far infrared electronic oven～800W heating for dissolving and concentrated catching up with sour 2 times, one or both in interpolation 0.02g natrium citricum, polyvinylpyrrolidone, polyvinyl alcohol, the polyethylene glycol etc., and constant volume is to 10g/L.In vacuum tank, above-mentioned palladium liquid is slowly joined in the 20.14g active carbon, infrared pressure absorption, 20～80 ℃ of adsorption temps, adsorption time are 20h; Then, add one or both reduction in the formaldehyde, formic acid, sodium acetate, sodium borohydride, hydrazine hydrate of 0.01～5mol/L, addition and Metal Palladium mol ratio be 1: 0.1～10, the liquid-phase reduction temperature is 50～100 ℃; Filter, wash to silver nitrate detection nothing
, place 40～110 ℃ of drying 0.5～6h of drying box.Through performance test, the conversion ratio 99.7% of NBR, the hydrogenation ratio of HNBR reaches 99.6%.
Embodiment 5
Take by weighing 1.78g PdCl
2Powder dissolution is in 0.1～5mL hydrochloric acid, add deionized water, 200W on the far infrared electronic oven～800W heating for dissolving and concentrated catching up with sour 2 times, one or both in interpolation 0.05g natrium citricum, polyvinylpyrrolidone, polyvinyl alcohol, the polyethylene glycol etc., and constant volume is to 5g/L.In vacuum tank, above-mentioned palladium liquid is slowly joined in the 20.14g active carbon, infrared pressure absorption, 20～80 ℃ of adsorption temps, adsorption time are 20h; Then, add one or both reduction in the formaldehyde, formic acid, sodium acetate, sodium borohydride, hydrazine hydrate of 0.01～5mol/L, addition and Metal Palladium mol ratio be 1: 0.1～10, the liquid-phase reduction temperature is 50～100 ℃; Filter, wash to silver nitrate detection nothing
, place 40～110 ℃ of drying 0.5～6h of drying box.Through performance test, the conversion ratio 99.8% of NBR, the hydrogenation ratio of HNBR reaches 99.8%.
Claims (9)
1. a palladium base synthesizes the highly saturated nitrile rubber Catalysts and its preparation method, and it is characterized in that: this method may further comprise the steps: infrared liquid making, vacuum suction, liquid-phase reduction, washing and drying.
2. a kind of palladium base according to claim 1 synthesizes the highly saturated nitrile rubber Catalysts and its preparation method, and it is characterized in that: infrared liquid making is to take by weighing 1.78g PdCl
2Add 0.1～5mL hydrochloric acid, and add deionized water, 200W on the far infrared electronic oven～800W heating for dissolving also concentrates and catches up with acid, and it is standby to be settled to 5～20g/L at last.
3. a kind of palladium base according to claim 1 synthesizes the highly saturated nitrile rubber Catalysts and its preparation method, it is characterized in that: vacuum suction is add stabilizing agent in palladium liquid after, in vacuum tank, slowly join in the carrier, and use infrared pressure to adsorb, 20～80 ℃ of adsorption temps, adsorption time 6～24h.
4. a kind of palladium base according to claim 1 synthesizes the highly saturated nitrile rubber Catalysts and its preparation method, it is characterized in that: reducing agent can be one or both in formaldehyde, formic acid, sodium acetate, sodium borohydride, the hydrazine hydrate, the mol ratio of itself and Metal Palladium is 1: 0.1～10, concentration is 0.01～5mol/L, and the liquid-phase reduction temperature is 50～100 ℃.
5. a kind of palladium base according to claim 1 synthesizes the highly saturated nitrile rubber Catalysts and its preparation method, it is characterized in that: washing process detects to silver nitrate with deionized water cyclic washing palladium-based catalyst not to be had
Till.
6. a kind of palladium base according to claim 1 synthesizes the highly saturated nitrile rubber Catalysts and its preparation method, and it is characterized in that: baking temperature is 40～110 ℃, and the time is 0.5～6h.
7. according to claim 1 or the synthetic highly saturated nitrile rubber Catalysts and its preparation method of 3 described a kind of palladium bases, it is characterized in that the vacuum of vacuum suction is 0.05～0.1MPa.
8. a kind of palladium base according to claim 3 synthesizes the highly saturated nitrile rubber Catalysts and its preparation method, it is characterized in that: stabilizing agent can be one or both in natrium citricum, polyvinylpyrrolidone, polyvinyl alcohol, the polyethylene glycol etc., and wherein the mol ratio of stabilizing agent and palladium is 1: 1～100.
9. a kind of palladium base according to claim 3 synthesizes the highly saturated nitrile rubber Catalysts and its preparation method, it is characterized in that: carrier is the mixture that one or more components in silica, active carbon, aluminium oxide, the alkali carbonate combine by any mass ratio.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102821279A CN101954278A (en) | 2010-09-15 | 2010-09-15 | Palladium-based catalyst used for synthesis of high-saturation nitrile butadiene rubber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102821279A CN101954278A (en) | 2010-09-15 | 2010-09-15 | Palladium-based catalyst used for synthesis of high-saturation nitrile butadiene rubber and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101954278A true CN101954278A (en) | 2011-01-26 |
Family
ID=43482011
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102821279A Pending CN101954278A (en) | 2010-09-15 | 2010-09-15 | Palladium-based catalyst used for synthesis of high-saturation nitrile butadiene rubber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101954278A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911293A (en) * | 2012-11-13 | 2013-02-06 | 北京化工大学 | Method for normal-pressure hydrogenation of unsaturated polymer using magnetic nano ferroferric oxide catalyst |
| CN103073683A (en) * | 2013-02-26 | 2013-05-01 | 郴州高鑫铂业有限公司 | Method for synthesizing hydrogenated butadiene-acrylonitrile rubber by nano-Pd/C catalyst |
| CN108778503A (en) * | 2016-03-31 | 2018-11-09 | 日本瑞翁株式会社 | The manufacturing method of the dispersion liquid of particle containing metal and the manufacturing method of hydrogenating conjugated diene polymers |
| CN109265581A (en) * | 2018-08-31 | 2019-01-25 | 北京化工大学 | A kind of nitrification nitrile rubber and its preparation method and application |
| CN110449151A (en) * | 2019-09-03 | 2019-11-15 | 福州大学 | A kind of loading type Pd/ZrO2The preparation method and applications of catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1167775A (en) * | 1997-04-22 | 1997-12-17 | 中国石油化工总公司 | Process for hydrogenation of NBR |
| US20070287806A1 (en) * | 2006-06-01 | 2007-12-13 | Ong Christopher M | Process for preparing hydrogenated nitrile rubbers |
| CN101157029A (en) * | 2007-11-12 | 2008-04-09 | 中国海洋石油总公司 | A dicyclopentadiene hydrogenation special-purpose catalyzer and its preparing method |
| CN101269324A (en) * | 2008-05-08 | 2008-09-24 | 郴州高鑫铂业有限公司 | Preparation method of high-activity nanocrystalline platinum carbon catalyst |
-
2010
- 2010-09-15 CN CN2010102821279A patent/CN101954278A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1167775A (en) * | 1997-04-22 | 1997-12-17 | 中国石油化工总公司 | Process for hydrogenation of NBR |
| US20070287806A1 (en) * | 2006-06-01 | 2007-12-13 | Ong Christopher M | Process for preparing hydrogenated nitrile rubbers |
| CN101157029A (en) * | 2007-11-12 | 2008-04-09 | 中国海洋石油总公司 | A dicyclopentadiene hydrogenation special-purpose catalyzer and its preparing method |
| CN101269324A (en) * | 2008-05-08 | 2008-09-24 | 郴州高鑫铂业有限公司 | Preparation method of high-activity nanocrystalline platinum carbon catalyst |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911293A (en) * | 2012-11-13 | 2013-02-06 | 北京化工大学 | Method for normal-pressure hydrogenation of unsaturated polymer using magnetic nano ferroferric oxide catalyst |
| CN102911293B (en) * | 2012-11-13 | 2014-06-25 | 北京化工大学 | Method for normal-pressure hydrogenation of unsaturated polymer using magnetic nano ferroferric oxide catalyst |
| CN103073683A (en) * | 2013-02-26 | 2013-05-01 | 郴州高鑫铂业有限公司 | Method for synthesizing hydrogenated butadiene-acrylonitrile rubber by nano-Pd/C catalyst |
| CN108778503A (en) * | 2016-03-31 | 2018-11-09 | 日本瑞翁株式会社 | The manufacturing method of the dispersion liquid of particle containing metal and the manufacturing method of hydrogenating conjugated diene polymers |
| EP3437737A4 (en) * | 2016-03-31 | 2019-12-04 | Zeon Corporation | Method for preparing dispersion of metal-containing particles and method for producing hydrogenated conjugated diene polymer |
| US11266978B2 (en) | 2016-03-31 | 2022-03-08 | Zeon Corporation | Method for preparing dispersion of metal-containing particles and method for producing hydrogenated conjugated diene polymer |
| CN109265581A (en) * | 2018-08-31 | 2019-01-25 | 北京化工大学 | A kind of nitrification nitrile rubber and its preparation method and application |
| CN110449151A (en) * | 2019-09-03 | 2019-11-15 | 福州大学 | A kind of loading type Pd/ZrO2The preparation method and applications of catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104998659B (en) | It is a kind of to be used to be catalyzed furfural or furfuryl alcohol rearrangement Hydrogenation for the catalyst of cyclopentanol and its preparation method and application method | |
| CN103316704B (en) | A kind of stable acetylene hydrochlorination catalysts and preparation method thereof | |
| CN103691451B (en) | Catalyst for synthesizing methyl formate by virtue of gas-phase methanol carbonylation as well as preparation method and application of catalyst | |
| CN101954278A (en) | Palladium-based catalyst used for synthesis of high-saturation nitrile butadiene rubber and preparation method thereof | |
| CN101875016A (en) | Catalyst for preparing methane by low-temperature oxidization of methane and preparation method and application thereof | |
| CN105562009B (en) | A kind of layer structure copper-based catalysts and its preparation method and application | |
| CN102274724B (en) | High-activity catalyst used in hydrogenation reaction of aromatic nitro-compound and preparation method thereof | |
| CN102259007A (en) | Method for preparing mercury-free catalyst for synthesis of chloroethylene by acetylene process | |
| CN110694618B (en) | Method for hydrodeoxygenation of lignin by ruthenium-based catalyst under deep eutectic solvent condition | |
| CN102728380B (en) | Application of catalyst used for preparing 1,3-propylene glycol through glycerin hydrogenolysis | |
| CN105355935A (en) | Preparation method and application of precious metal electrocatalyst | |
| CN105148917B (en) | A kind of method and its formaldehyde catalyst for improving formaldehyde catalyst catalytic efficiency | |
| CN109453762B (en) | Preparation method and application of modified clay mineral supported palladium catalyst | |
| CN103694116A (en) | Method for synthesizing methyl formate by gas-phase carbonylation of methyl alcohol | |
| CN106622224B (en) | Application of the nanometer Au-based catalyst in formic acid or formates synthesis | |
| CN103252241A (en) | Catalyst for synthesising methanol by hydrogenation of carbon dioxide as well as preparation method and application thereof | |
| CN102380380A (en) | Mercury-free catalyst system for acetylene hydrochlorination and use thereof | |
| CN105289603A (en) | Method for preparing high-dispersibility gold-loading catalyst | |
| CN103464195A (en) | Method for preparing catalyst for methane oxidation-based methanol preparation by introduction of active component into pore-enlarging agent | |
| CN105013492A (en) | Methanol catalyst synthesized by carbon dioxide hydrogenation, preparation method and application thereof | |
| CN101716508A (en) | Catalyst used for synthesizing chloroethylene by acetylene and preparation method thereof | |
| CN108993595A (en) | A kind of copper-based catalysts and its preparation method and application for acetylene hydrochlorination synthesis vinyl chloride thereof | |
| CN105344357A (en) | Catalyst for preparing 1,3-propanediol through glycerine hydrogenolysis | |
| WO2024078051A1 (en) | Biomass skeleton carbon-metal composite micro-nano structure catalytic material, and preparation method and use | |
| CN104174411B (en) | A kind of method improving VOCs catalyst oxidation activity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110126 |