CN101670301B - Method for preparing loaded catalyst for hydrogenation - Google Patents
Method for preparing loaded catalyst for hydrogenation Download PDFInfo
- Publication number
- CN101670301B CN101670301B CN2009100353500A CN200910035350A CN101670301B CN 101670301 B CN101670301 B CN 101670301B CN 2009100353500 A CN2009100353500 A CN 2009100353500A CN 200910035350 A CN200910035350 A CN 200910035350A CN 101670301 B CN101670301 B CN 101670301B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- preparation
- alcohol
- carrier
- solution
- 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.)
- Expired - Fee Related
Links
Images
Abstract
The invention relates to a method for preparing a loaded catalyst for hydrogenation. The method comprises the steps of taking low-price crystalline type silicon dioxide as a carrier and transition metal as an active component, and reducing and activating a thermally treated catalyst precursor by adopting a dipping-chemical reduction method under an organic system. The loaded catalyst prepared by the method has the characteristics of high active metal dispersion degree, good catalyst activity, low preparation cost, and the like and is suitable for p-nitrophenol catalytic hydrogenation reactions.
Description
Technical field
The present invention relates to a kind of preparation method of loaded catalyst for hydrogenation, relate in particular to and be used for p-nitrophenol hydrogenation Preparation of catalysts method, belong to catalyst preparation technology.
Background technology
Catalytic hydrogenation reaction is a kind of technical process that is widely used in chemical field.The catalyst that is used for hydrogenation reaction at present is mainly metallic catalyst, comprises loaded catalyst, as Pd/C, Pt/C, Ni/Al
2O
3Deng, and unsupported catalyst, as skeleton nickel, nanometer nickel etc.The mature production technology of these catalyst, in industrial application for many years, never alternative catalysts comes into operation for a long time.The loaded catalyst with the preparation of dipping-chemical reduction method of report all is improved largely than traditional catalyst on catalytic activity and stability in recent years, and the trend that replaces traditional catalyst is arranged greatly.
Infusion process is one of main method of producing loaded catalyst, owing to be directly to adopt the outsourcing carrier, has that treating capacity is big, efficient is high, low cost and other advantages, in industrial extensive use.The production process of infusion process mainly comprises dipping, drying, roasting, four steps of activation, and wherein roasting and activation step are bigger for catalyst final structure and catalytic performance influence.Roasting and activation step in the general preparation process carry out under hot environment usually, and sintering at high temperature may take place in reactive metal, cause reactive metal crystal grain to become big, the specific activity surface area reduces, and therefore reduces the active component sintering, increases the catalytic performance that the specific activity surface area can further improve catalyst.With hydrazine class, polyalcohol, boron hydride etc. is reducing agent, by chemical reduction method catalyst is activated and can operate at a lower temperature, can avoid catalyst that sintering takes place in reduction process like this, more help the dispersion of active component, help to improve the catalytic performance of catalyst at carrier surface.
Report showed in recent years, and the load type metal catalyst of chemical reduction method preparation has characteristics such as high degree of dispersion, high activity and selectivity.Patent CN1709572 discloses a kind of aryl halide to load type bimetal catalyst of alkene arylation and preparation method thereof, this method adopts infusion process that active component palladium and alkali metal are loaded to carrier surface, after 80-105 ℃ of drying, directly with boron hydride as reducing agent, under water solution system, the gained catalyst precursor is carried out electronation and prepares the bimetallic loaded catalyst.This catalyst has catalytic activity height, advantage that noble metal dosage is few.Patent CN1714932 discloses a kind of carried non-crystal alloy catalyst of preparing cyclohexene from benzene added with hydrogen, this catalyst is carrier with the zirconium dioxide, with metal Ru and light rare earth is raw material, in the aqueous solution, prepare the homogeneous suspension according to a certain percentage, by drip boron hydride with metal Ru and nonmetal boron with the form uniform load of Ru-M-B in carrier surface, this catalyst has increased substantially the yield of cyclohexene, and has reduced the generation of by-product cyclic hexane.Patent CN101259414 discloses a kind of new method for preparing supported nanometer nickel catalyst, it is that material with the load derivant is a carrier, in the plating bath of forming with water soluble nickel salt, hydrazine hydrate, NaOH, induce the hydrazine hydrate reduction nickel salt, make nanometer nickel in the carrier surface orientated deposition, preparation high dispersive, highly active supported nanometer nickel catalyst.Patent CN101157034 discloses a kind of preparation method of load type palladium series non-crystalline state alloy catalyst, and this method utilizes means such as ultrasonic dispersion, vacuum impregnation with divalence palladium salt and the abundant hybrid infusion of carrier, drips then and contains BH
4 -The aqueous solution active component is carried out electronation, active high, low, the technology characteristic of simple of preparation cost that prepared catalyst has.Patent CN101239318 discloses a kind of catalyst that is used for hydrogenation on cinnamic aldehyde, it is to be reducing agent with hydrazine hydrate or boron hydride, the cobalt chloride, the nickel chloride that are dissolved in water, ethanol or contain in the aqueous surfactant solution are carried out electronation, the preparation bimetallic catalyst.The catalyst of this method preparation has advantages such as the active component size is little, good dispersion degree, catalytic activity height, good reaction selectivity.Patent CN1376537 discloses a kind of Pd/C hydrogenation catalyst that is used to produce caprolactam, and it is with PdCl
2Or Pd (NO
3)
2Dipping carries out electronation with hydrazine hydrate or formaldehyde etc. after drying through the material with carbon element carrier after the oxidation processes, and prepared catalyst has characteristics such as high degree of dispersion, small particle diameter, shows very high activity and stable in producing caprolactam.Chin.J.Chem.Eng., 2007, reported support type Ni/Al among the 15:884
2O
3The Preparation of catalysts method, it is to flood good catalyst precursor through directly carrying out electronation with hydrazine hydrate in the aqueous solution after the super-dry, the catalyst of this method preparation has shown very high activity and selectivity in the p-nitrophenol hydrogenation reaction.
The loaded catalyst of reporting in the above document does not all carry out other processing before carrying out electronation, promptly finish or just carry out catalyst after drying activating reduction reaction at dipping.The catalyst of this method preparation, active component mainly is to load on carrier surface with sedimentation state, and the interaction force between carrier is strong and disperse inhomogeneously, can cause loss of active component after repeatedly using, catalytic performance descends, and its stability also needs further to strengthen.In addition, the chemical reduction reaction of reporting in the patent mostly occurs in the aqueous solution, is free in the active component collision mutually in reduction process in the aqueous solution, causes catalyst size bigger, is unfavorable for making full use of of active component.The preparation nano material can prevent that nano particle from assembling in organic system, and the nano particle of acquisition size homogeneous prepares load type metal catalyst and yet there are no report and carry out electronation in organic system.
Summary of the invention
The present invention seeks to exist the lower deficiency of active component decentralization that a kind of loaded catalyst for hydrogenation preparation method is provided for improving existing loaded catalyst for hydrogenation preparation method.
Technical scheme of the present invention is: a kind of preparation method of loaded catalyst for hydrogenation, and concrete steps are:
(1) carrier preprocessing process: with bronsted lowry acids and bases bronsted lowry solution the powdered quartz carrier is carried out preliminary treatment, spend deionised water to pH=6.5～8.5, dry roasting;
(2) dipping process: the soluble transition metal salting liquid is mixed with the pretreated carrier of process, and wherein reactive metal amount and carrier mass ratio are 0.05～1: 1, leave standstill after the ultrasonic processing, get mixture;
(3) drying and heat treatment process: said mixture is stirred drying, heat-treat after removing moisture;
(4) reduction activation process: with hydrazine hydrate and solvent preparation reduction reaction solution, wherein hydrazine hydrate concentration is 0.01～1.0g/ml, the pH value of regulator solution is 10～14, add through heat treated catalyst precursor, addition is the control hydrazine hydrate: the mol ratio of reactive metal is 2～10: 1, stirs under the control temperature and carries out reduction reaction;
(5) filtration washing process: above-mentioned reaction solution is filtered, and washing is in 80～150 ℃ of dry down catalyst that get.
Wherein said powdered quartz carrier is quartz sand, silica flour or silicon powder; Particle size is 80～300 orders.
The ultrasonic processing time is 5～60min in the preferred steps (2), and time of repose is 1～8h.Heat treatment temperature is 100～500 ℃ in the preferred steps (3); Preferred 150～350 ℃; Heat treatment time is 1～12h.
Reaction dissolvent in the preferred steps (4) in the reduction reaction system is the mixed solution of alcohol or alcohol and water; To account for reaction dissolvent cumulative volume percentage composition be 20%-100% to alcohol in the wherein said solvent; Wherein said alcohol is any in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol or the butanols.Reduction reaction temperature is 20～100 ℃, and the reduction reaction time is 5～60min.
Above-mentioned soluble transition metal salt is chloride, acetate, nitrate or the sulfate of soluble transition metal; Its concentration is 0.1mol/l～1mol/l.Wherein said soluble transition metal is nickel, cobalt, palladium, platinum, ruthenium or rhodium.
Product washs respectively 3～4 times with deionized water and absolute ethyl alcohol in the preferred steps (5); Baking temperature is 80～150 ℃, and be 1～5h drying time.
The consumption of transition metal salt calculates according to the theoretical negative carrying capacity in the obtained catalyst of the present invention, and the reactive metal quality is 1%～50% of a catalyst gross mass.
The present invention adopts following condition to carry out activity rating.
Be reflected in the 25ml stainless steel autoclave and carry out.Ethanol 8ml, deionized water 2ml, p-nitrophenol 0.3g and catalyst 0.1g are added in the still together, feed nitrogen, the interior air of hydrogen exchange still after the sealing respectively 4～5 times, feed the hydrogen and the intensification of certain pressure at last; When temperature reaches setting value, feed hydrogen and boost to 1.5MPa, under magnetic agitation, carry out hydrogenation reaction.Behind the reaction certain hour, stop reaction and be cooled to room temperature, catalyst is filtered, negate is used efficient liquid phase chromatographic analysis after answering product to dilute 20 times, calculates feed stock conversion and selectivity of product according to calibration curve.
Beneficial effect:
1. the present invention introduces heat treatment process before catalyst carries out the electronation activation, strengthens the interaction force between metal and carrier, and promotes metal to disperse at the carrier surface secondary, improves catalyst stability.
2. the present invention carries out chemical reduction reaction and prevents that active component from reuniting under organic system, reduces the active component size, improves the reactive metal utilization rate.
3. the present invention uses cheap carrier material, and method for preparing catalyst has low, the characteristic of simple process of production cost.The catalyst that adopts the present invention's preparation characterizes as can be known through XRD and ESEM, and reactive metal has very high decentralization at carrier surface.
Description of drawings
Fig. 1 is the X-ray diffractogram of 20% loading type nickel-based catalyst; Fig. 2 is the stereoscan photograph of 20% loading type nickel-based catalyst.
The specific embodiment
Further specify the result of use of the inventive method and catalyst below by embodiment and Comparative Examples.The specific embodiment
The preparation of embodiment 1 support type Ni/ silica flour
Industrial silica flour with 0.1mol/L hydrochloric acid and 0.1mol/L sodium hydroxide solution immersion treatment, is spent deionised water to pH=7, stand-by after the roasting.Under the room temperature 5g is passed through pretreated industrial silica flour and 50ml0.4mol/l NiCl
2Solution mixes, and behind the ultrasonic processing 30min, leaves standstill 1h.Stir drying and remove excessive moisture, be transferred to dry 12h in 100 ℃ of baking ovens.The catalyst precursor that drying is good changes in the Muffle furnace heat-treats 3h under 250 ℃, mix under alkali condition with hydrazine hydrate after being cooled to room temperature, and wherein the amount of each material is than being N
2H
4: Ni
2+=4, NaOH: Ni
2+=2, the reduction reaction solvent is a 20ml alcohol-water mixed solution, and volume ratio is 1: 1, and 80 ℃ of following stirring reactions are to finishing, and product filters back water and ethanol washing 3 times, 80 ℃ down dry 4h get the catalyst finished product.Accompanying drawing 1 is the X-ray diffractogram of 20% loading type nickel-based catalyst, does not find tangible metal Ni crystal diffraction peak from figure, and this explanation metal Ni there is no agglomeration in the carrier surface high degree of dispersion.Accompanying drawing 2 is stereoscan photographs of 20% loading type nickel-based catalyst, the metallic nickel particle of can having seen the carrier surface uniform load from photo.Catalyst numbering A
Comparative Examples 1
Employing is with the identical preparation method of embodiment 1, just without heat treatment process.Catalyst numbering B Comparative Examples 2
Employing is with the identical preparation method of embodiment 1, and just the reduction reaction solvent is a water.Catalyst numbering C Comparative Examples 3
Employing is with the identical preparation method of embodiment 1, and just without heat treatment process, and the reduction reaction solvent is a water.Catalyst numbering D
Above catalyst is used for the p-nitrophenol catalytic hydrogenation reaction, sample analysis behind the reaction 1h, relatively feed stock conversion and selectivity of product.The catalytic performance of above-mentioned several catalyst relatively sees Table 1.Relatively the performance of different catalysts as can be seen, without heat treatment process and in the aqueous solution, carry out the catalyst of reduction reaction, its catalytic performance is the poorest, and adds heat treatment process simultaneously and carry out the catalyst of reduction reaction in organic solvent, its catalytic performance the best.Only quote one of them factor in two factors, its catalytic performance falls between.
The different preparation conditions of table 1 are to the influence of catalyst performance
The preparation of embodiment 2 load type Cos/silica flour
Industrial silica flour with bronsted lowry acids and bases bronsted lowry solution immersion treatment, is spent deionised water to pH=6.5, stand-by after the roasting.Under the room temperature 5g is passed through pretreated silica flour and 50ml 0.5mol/l CoSO
4Solution mixes, and behind the ultrasonic processing 20min, leaves standstill 2h.Stir drying and remove excessive moisture, be transferred to dry 6h in 100 ℃ of baking ovens.The catalyst precursor that drying is good changes in the Muffle furnace heat-treats 2h under 150 ℃, mix under alkali condition with hydrazine hydrate after being cooled to room temperature, and wherein the amount of each material is than being N
2H
4: Ni
2+=8, NaOH: Ni
2+=3, the reduction reaction solvent is 20ml butanols-water mixed solution, and volume ratio is 4: 1, and 90 ℃ of following stirring reactions are to finishing, and product filters back water and ethanol washing 3 times, 80 ℃ down dry 5h get the catalyst finished product.Catalytic performance test shows that the p-nitrophenol conversion ratio is higher than 70%, and selectivity is higher than 75%.
The preparation of embodiment 3 loading type Pds/silicon powder
The industrial silicon micro mist with 0.05mol/L nitric acid and 0.1mol/L sodium hydroxide solution, is spent deionised water to pH=7.5, stand-by after the roasting.Under the room temperature 5g is passed through pretreated silicon powder and 50ml 0.1mol/l PdCl
2Solution mixes, and behind the ultrasonic processing 40min, leaves standstill 5h.Stir drying and remove excessive moisture, be transferred to dry 16h in 100 ℃ of baking ovens.The catalyst precursor that drying is good changes in the Muffle furnace heat-treats 6h under 300 ℃, mix under alkali condition with hydrazine hydrate after being cooled to room temperature, and wherein the amount of each material is than being N
2H
4: Ni
2+=3, NaOH: Ni
2+=6, the reduction reaction solvent is a 20ml ethanol, and 80 ℃ of following stirring reactions are to finishing, and product filters back water and ethanol washing 4 times, 90 ℃ down dry 4h get the catalyst finished product.Catalytic performance test shows that the p-nitrophenol conversion ratio is higher than 99%, and selectivity is higher than 99%.
The preparation of embodiment 4 support type Ru/ silica flours
Industrial silica flour with 0.05mol/L hydrochloric acid and 0.05mol/L sodium hydroxide solution, is spent deionised water to pH=7, stand-by after the roasting.Under the room temperature 5g is passed through pretreated silica flour and 50ml 0.8mol/l RuCl
3Solution mixes, and behind the ultrasonic processing 50min, leaves standstill 6h.Stir drying and remove excessive moisture, be transferred to dry 10h in 100 ℃ of baking ovens.The catalyst precursor that drying is good changes in the Muffle furnace heat-treats 5h under 350 ℃, mix under alkali condition with hydrazine hydrate after being cooled to room temperature, and wherein the amount of each material is than being N
2H
4: Ni
2+=8, NaOH: Ni
2+=8, the reduction reaction solvent is a 20ml methyl alcohol, and 70 ℃ of following stirring reactions are to finishing, and product filters back water and ethanol washing 3 times, 100 ℃ down dry 4h get the catalyst finished product.Catalytic performance test shows that the p-nitrophenol conversion ratio is higher than 97%, and selectivity is higher than 95%.
The preparation of embodiment 5 support type Ni/ silicon powders
The industrial silicon micro mist with 0.1mol/L hydrochloric acid and 0.1mol/L sodium hydroxide solution, is spent deionised water to pH=8, stand-by after the roasting.Under the room temperature 5g is passed through pretreated silicon powder and 50ml 0.6mol/l NiSO
4Solution mixes, and behind the ultrasonic processing 15min, leaves standstill 1h.Stir drying and remove excessive moisture, be transferred to dry 12h in 100 ℃ of baking ovens.The catalyst precursor that drying is good changes in the Muffle furnace heat-treats 2h under 400 ℃, mix under alkali condition with hydrazine hydrate after being cooled to room temperature, and wherein the amount of each material is than being N
2H
4: Ni
2+=10, NaOH: Ni
2+=4, the reduction reaction solvent is 20ml propyl alcohol-water mixed solution, and volume ratio is 2: 1, and 40 ℃ of following stirring reactions are to finishing, and product filters back water and ethanol washing 3 times, 110 ℃ down dry 3h get the catalyst finished product.Catalytic performance test shows that the p-nitrophenol conversion ratio is higher than 87%, and selectivity is higher than 85%.
The preparation of embodiment 6 support type Ni/ crystal powders
The industry water crystalline flour with 0.1mol/L hydrochloric acid and 0.1mol/L sodium hydroxide solution, is spent deionised water to pH=6.5, stand-by after the roasting.Under the room temperature 5g is passed through pretreated crystal powder and 50ml 1mol/l Ni (NO
3)
2Solution mixes, and behind the ultrasonic processing 30min, leaves standstill 4h.Stir drying and remove excessive moisture, be transferred to dry 24h in 100 ℃ of baking ovens.The catalyst precursor that drying is good changes in the Muffle furnace heat-treats 6h under 500 ℃, mix under alkali condition with hydrazine hydrate after being cooled to room temperature, and wherein the amount of each material is than being N
2H
4: Ni
2+=4, NaOH: Ni
2+=2, the reduction reaction solvent is 20ml isopropyl alcohol-water mixed solution, and volume ratio is 1: 4, and 20 ℃ of following stirring reactions are to finishing, and product filters back water and ethanol washing 4 times, 80 ℃ down dry 4h get the catalyst finished product.Catalytic performance test shows that the p-nitrophenol conversion ratio is higher than 85%, and selectivity is higher than 80%.
Claims (7)
1. the preparation method of a loaded catalyst for hydrogenation, concrete steps are:
(1) carrier preprocessing process: with bronsted lowry acids and bases bronsted lowry solution the powdered quartz carrier is carried out preliminary treatment, spend deionised water to pH=6.5～8.5, dry roasting; Wherein said powdered quartz carrier is quartz sand, silica flour or silicon powder; Particle size is 80～300 orders;
(2) dipping process: the soluble transition metal salting liquid is mixed with the pretreated carrier of process, and wherein reactive metal amount and carrier mass ratio are 0.05～1: 1, leave standstill after the ultrasonic processing, get mixture; Wherein soluble transition metal salt is chloride, acetate, nitrate or the sulfate of soluble transition metal; Its concentration is 0.1mol/l～1mol/l; Described soluble transition metal is nickel, cobalt, palladium, platinum, ruthenium or rhodium;
(3) drying and heat treatment process: said mixture is stirred drying, heat-treat after removing moisture;
(4) reduction activation process: with hydrazine hydrate and solvent preparation reduction reaction solution, wherein hydrazine hydrate concentration is 0.01～1.0g/ml, the pH value of regulator solution is 10～14, add through heat treated catalyst precursor, addition is the control hydrazine hydrate: the mol ratio of reactive metal is 2～10: 1, stirs under the control temperature and carries out reduction reaction;
(5) filtration washing process: above-mentioned reaction solution is filtered, and washing is in 80～150 ℃ of dry down catalyst that get.
2. according to the described preparation method of claim 1, it is characterized in that the ultrasonic processing time is 5～60min in the step (2); Time of repose is 1～8h.
3. according to the described preparation method of claim 1, it is characterized in that heat treatment temperature is 100～500 ℃ in the step (3); Heat treatment time is 1～12h.
4. according to the described preparation method of claim 3, it is characterized in that heat treatment temperature is 150～350 ℃ in the step (3).
5. according to the described preparation method of claim 1, it is characterized in that the reaction dissolvent in the reduction reaction system is alcoholic solution or alcohol and water mixed solution in the step (4); Described reduction reaction temperature is 20～100 ℃, and the reduction reaction time is 5～60min.
6. according to the described preparation method of claim 5, it is characterized in that in the reaction dissolvent described in the step (4) that it is 20%-100% that alcohol accounts for reaction dissolvent cumulative volume percentage composition; Wherein alcohol is any in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol or the butanols.
7. according to the described preparation method of claim 1, it is characterized in that product washs respectively 3～4 times with deionized water and absolute ethyl alcohol in the step (5); Baking temperature is 80～150 ℃, and be 1～5h drying time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100353500A CN101670301B (en) | 2009-09-25 | 2009-09-25 | Method for preparing loaded catalyst for hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100353500A CN101670301B (en) | 2009-09-25 | 2009-09-25 | Method for preparing loaded catalyst for hydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101670301A CN101670301A (en) | 2010-03-17 |
| CN101670301B true CN101670301B (en) | 2011-07-20 |
Family
ID=42017844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100353500A Expired - Fee Related CN101670301B (en) | 2009-09-25 | 2009-09-25 | Method for preparing loaded catalyst for hydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101670301B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102091625B (en) * | 2010-12-24 | 2012-10-17 | 南京工业大学 | Nickel-based catalyst prepared through solid-phase thermal dispersion and preparation method thereof |
| CN102649690A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for improving selectivity of ethylene glycol prepared through hydrogenation reaction by oxalic ester |
| CN103521169B (en) * | 2013-10-30 | 2015-07-08 | 吉林大学 | Preparing method of potassium permanganate modified manganese removing filter materials |
| CN104001557B (en) * | 2014-06-09 | 2016-01-20 | 山东公泉化工股份有限公司 | Loaded catalyst and preparation method thereof |
| CN104190414B (en) * | 2014-08-29 | 2016-03-23 | 中国科学院福建物质结构研究所 | A kind of sodium borohydride reduction that adopts prepares Pd/ α-Al 2o 3the preparation method of catalyst |
| CN104841421B (en) * | 2015-04-15 | 2018-06-15 | 北京旭阳科技有限公司 | A kind of carbon monoxide-olefin polymeric, preparation method and prepare the method for o-phenyl phenol using it |
| CN106582709B (en) * | 2016-11-23 | 2020-05-19 | 西安凯立新材料股份有限公司 | Catalyst for synthesizing aromatic primary amine by hydrogenation of aromatic nitrile and preparation method thereof |
| CN115501886B (en) * | 2022-03-31 | 2023-10-24 | 西南民族大学 | Preparation method of catalyst for synthesizing aniline by hydrogenating nitrobenzene at low temperature |
| CN115212927A (en) * | 2022-07-19 | 2022-10-21 | 江南大学 | Soluble organic molecular cage composite material for packaging platinum-rhodium alloy nanoclusters and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544145A (en) * | 2003-11-26 | 2004-11-10 | 蔡万煜 | Preparation method for charcoal loading noble metal nanometer crystal hydrogenation catalyst and platinum charcoal catalyst produced by the method |
| CN101195090A (en) * | 2006-12-04 | 2008-06-11 | 中国科学院大连化学物理研究所 | Catalyst for benzene catalysis selective hydrogenation reaction, production method and application thereof |
-
2009
- 2009-09-25 CN CN2009100353500A patent/CN101670301B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544145A (en) * | 2003-11-26 | 2004-11-10 | 蔡万煜 | Preparation method for charcoal loading noble metal nanometer crystal hydrogenation catalyst and platinum charcoal catalyst produced by the method |
| CN101195090A (en) * | 2006-12-04 | 2008-06-11 | 中国科学院大连化学物理研究所 | Catalyst for benzene catalysis selective hydrogenation reaction, production method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| Nikolaos Dimitratos,et.al.Effect of particle size on monometallic and bimetallic (Au,Pd)/C on the liquid phase oxidation of glycerol.《Catalysis Letters》.2006,第108卷(第3-4期),147-153. * |
| NikolaosDimitratos et.al.Effect of particle size on monometallic and bimetallic (Au |
| 任飞等.乙腈加氢制乙胺催化剂的研究.《工业催化》.2007,第15卷(第6期), * |
| 孙昱等.化学还原新体系制备负载Ni-B非晶态催化剂及其催化加氢性能.《应用化学》.2006,第23卷(第9期),第1047-1051页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101670301A (en) | 2010-03-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101670301B (en) | Method for preparing loaded catalyst for hydrogenation | |
| CN110743544B (en) | Palladium-carbon catalyst for preparing alpha-phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof | |
| WO2016173285A1 (en) | Supported catalyst having core-shell structure, preparation method therefor, and application thereof | |
| CN106748813B (en) | A kind of synthesis N, the method for N '-dibenzyl-ethylenediamin | |
| CN105498756B (en) | The catalyst of hydrogenation of carbon dioxide methanol | |
| CN106391001B (en) | Activated carbon supported ruthenium-platinum double-metal composite catalyst and preparation method and application | |
| CN102728380B (en) | Application of catalyst used for preparing 1,3-propylene glycol through glycerin hydrogenolysis | |
| CN102091625A (en) | Nickel-based catalyst prepared through solid-phase thermal dispersion and preparation method thereof | |
| CN105268433A (en) | Highly-dispersed catalyst for hydrogen peroxide synthesis and preparation method thereof | |
| CN110947382B (en) | Catalyst for preparing methanol and co-producing ethylene glycol by ethylene carbonate hydrogenation and preparation method thereof | |
| CN111905755B (en) | Catalyst for hydrogenation of 2,2,4, 4-tetramethyl-1, 3-cyclobutanedione and preparation method and application thereof | |
| CN110961110A (en) | Catalyst and application thereof in hydrodechlorination of 2,3, 6-trichloropyridine | |
| CN105859610A (en) | Synthesis method of 2,2'-dipyridine by using supported bimetal nano catalyst | |
| CN107497448B (en) | Rhodium/copper alloy nano catalyst and preparation method and application thereof | |
| CN104610199B (en) | The method of tetrahydrofurfuryl alcohol and the catalyst of use thereof are prepared in a kind of liquid-phase hydrogenatin | |
| CN109046379A (en) | A kind of perovskite composite oxides load platinum catalyst and its preparation and application | |
| CN104028267B (en) | A kind of method for making of benzene selective Hydrogenation cyclohexene noble metal Ru catalyst | |
| CN102416325A (en) | Preparation method of isobutyl ketone synthesis catalyst | |
| CN108970632A (en) | A kind of load type bimetal catalyst and preparation method thereof efficiently synthesizing DBE | |
| CN102319562A (en) | The Preparation of catalysts method of producing cyclohexene with benzene selective hydrogenation and the catalyst for preparing through this method | |
| CN102974342B (en) | Catalyst for preparing cyclohexene from benzene by selective hydrogenation and preparation method thereof | |
| CN116440899A (en) | Noble metal supported catalyst with low loss rate, preparation method and application thereof | |
| CN112337474B (en) | High-activity nickel-based acetone hydrogenation catalyst and preparation method thereof | |
| CN113578346A (en) | Copper/silver alloy nano catalyst and preparation method and application thereof | |
| CN114130416A (en) | Preparation method of carbon-supported multi-metal catalyst and application of carbon-supported multi-metal catalyst in N-alkylation reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110720 Termination date: 20150925 |
|
| EXPY | Termination of patent right or utility model |