CN108993484A - A method of palladium carbon catalyst is prepared with chloronitrobenzene selective hydrogenation - Google Patents
A method of palladium carbon catalyst is prepared with chloronitrobenzene selective hydrogenation Download PDFInfo
- Publication number
- CN108993484A CN108993484A CN201810716879.8A CN201810716879A CN108993484A CN 108993484 A CN108993484 A CN 108993484A CN 201810716879 A CN201810716879 A CN 201810716879A CN 108993484 A CN108993484 A CN 108993484A
- Authority
- CN
- China
- Prior art keywords
- palladium
- carbon catalyst
- selective hydrogenation
- palladium carbon
- chloronitrobenzene
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of methods for preparing palladium carbon catalyst with chloronitrobenzene selective hydrogenation, it mainly solves the problems, such as active component palladium being uniformly distributed on absorbent charcoal carrier, and improves palladium carbon catalyst in chloronitrobenzene selective hydrogenation to the selective problems of chloro aminobenzen.The present invention is co-precipitated by using by palladium presoma and iron presoma sodium hydroxide on absorbent charcoal carrier surface, after to be restored, then the technical solution for being dissolved out iron with organic acid, obtain the active and preferable palladium carbon catalyst of selectivity.In chloronitrobenzene selective hydrogenation, the conversion ratio of chloronitrobenzene may be up to 100%, and the selectivity of primary product chloro aminobenzen is up to 95%.
Description
Technical field
It is especially a kind of to prepare palladium with chloronitrobenzene selective hydrogenation the present invention relates to a kind of preparation method of catalyst
The method of Pd/carbon catalyst.
Background technique
Industrially preparing o-chloraniline all with catalytic hydrogenation method at present is using platinum based catalyst, but the rare valence of platinum
Lattice are expensive, and severe reaction conditions.It is cheap as the palladium carbon catalyst in activated centre using homogeneous noble metal palladium, have and adds hydrogen
Activity it is high, selectivity is good, performance is stable, use when feed ratio it is small the advantages that.But commercial palladium carbon catalyst adds in chloronitrobenzene
Can not be widely used in hydrogen since dechlorination reaction easily occurs, if a kind of palladium carbon catalyst can be designed, on the one hand weaken hydrogen with
On the other hand the interaction of palladium activated centre changes suction type of the o-chloronitrobenzene in palladium activated centre, so that it may effectively
Inhibit dechlorination side reaction to occur, improves selectivity.
The preparation method of palladium carbon catalyst is varied, and common and more popular method has chemical reduction method and receives at present
Rice Metal Supported method.Nano metal load method is the Technique of Nano Pd that the protection of Metal Palladium stabilizer is first prepared into high degree of dispersion, so
It is supported on absorbent charcoal carrier surface again afterwards, this method is that current most study is also most popular method, but is prepared in this method
There may be the unnecessary substances being difficult to clean off to be attached on carrier in the process, and preparation process is complicated, is giving birth on a large scale
It is difficult being consistent property in production.It is often used addition dispersing agent in chemical reduction method and has the function that dispersed active metal palladium,
This method is relatively easy, easily controllable, can guarantee the consistency of product.Some high-molecular compounds, organic acid and organic acid
Salt is often used as the dispersing agent of metallic catalyst.
Summary of the invention
In view of the above shortcomings of the prior art, palladium charcoal is prepared with chloronitrobenzene selective hydrogenation the present invention provides a kind of
The method of catalyst, it is the technical problem to be solved is that making palladium better dispersion degree on carrier, and the trace residue of iron mentions
High palladium carbon catalyst adds the selectivity in hydrogen to chloro aminobenzen in chloronitrobenzene.
To achieve the above object, the technical solution adopted by the present invention is that:
A method of palladium carbon catalyst, specific steps are prepared with chloronitrobenzene selective hydrogenation are as follows:
Step 1: the modification of absorbent charcoal carrier: first pre-processing powdered activated carbon: by active carbon in hydrochloric acid solution
After middle immersion for 24 hours, it is washed with deionized to neutrality, drying for standby at 120 DEG C, then by pretreated powdered activated high-area carbon
It impregnates in deionized water, stirring is uniformly mixed it and basically reaches adsorption equilibrium for 1 hour, obtains modified powdered activated
Charcoal water solution system A；
Step 2: dipping process: by precursor solution containing palladium and auxiliary agent iron precursor solution be added drop-wise to system A respectively
In, stirring dipping obtained system B after 24 hours, and the weight percent of palladium is 1~10% in system B；
Step 3: coprecipitation process: being co-precipitated system B with coprecipitator, it is ensured that the pH of last system is 8-10
Left and right, obtains system C；
Step 4: first time reduction process: reducing agent solution being slowly dropped in system C, is stirred when being added dropwise, is added dropwise
In stirring 2 hours after completely, system D is obtained；
Step 5: separation of solid and liquid process: system D being separated by solid-liquid separation, black colloidal solid E is obtained；
Step 6: second of reduction process: black colloidal solid E being immersed in organic acid soln, after stirring 4h, is carried out
It is separated by solid-liquid separation, obtains black colloidal solid F, then impregnate black colloidal solid F in deionized water, after stirring 1h, with also
Former agent solution is restored；
Step 7: washing drying process: the slurry filtering and washing that the 6th step is restored, repeated washing 8-10 times, so
It dries at 80 DEG C in a vacuum drying oven afterwards, obtains the palladium carbon catalyst of required palladium content.
Preferably, the ratio that the additive amount of auxiliary agent iron precursor solution uses in the second step for the additive amount of iron with
The molar ratio of active component palladium is 0.05-0.1:1.
Preferably, the presoma containing palladium is chlorine palladium acid or palladium nitrate.
Preferably, the iron presoma is iron chloride or ferric nitrate.
Preferably, the coprecipitator sodium hydroxide solution.
Preferably, the reducing agent solution is the mixed solution of sodium borohydride and sodium hydroxide, sodium borohydride and hydrogen-oxygen
The weight ratio for changing sodium is 10:1.
Preferably, the organic acid is the oxalic acid of 0.05M.
Preferably, in the palladium carbon catalyst of preparation palladium content be total weight 1%-10%.
Preferably, the mass ratio of deionized water and powdered activated high-area carbon is 10:1 in the first step；Deionization in 6th step
The mass ratio of water and black colloidal solid F are 10:1.
Preferably, the concentration of hydrochloric acid is 0.2mol/L in the hydrochloric acid solution.
The present invention is a kind of by co-precipitation palladium presoma and iron presoma, then the preparation for the palladium carbon catalyst that iron is dissolved out
Method mainly solves the problems, such as active component palladium being uniformly distributed on absorbent charcoal carrier, and improves palladium carbon catalyst in chloro nitre
Base benzene selective adds the selective problems in hydrogen to chloro aminobenzen.The present invention is by using by palladium presoma and iron presoma hydrogen
Sodium oxide molybdena is co-precipitated on absorbent charcoal carrier surface, after to be restored, then with organic acid is dissolved out iron, obtained activity and selectivity compared with
Good palladium carbon catalyst.In chloronitrobenzene selective hydrogenation, the conversion ratio of chloronitrobenzene may be up to 100%, master
The selectivity of product chloro aminobenzen is wanted to be up to 95%.
Specific embodiment
Clearly, completely retouch below in conjunction with the embodiment of the present invention technical solution in the embodiment of the present invention
It states, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the present invention
In embodiment, every other implementation obtained by those of ordinary skill in the art without making creative efforts
Example, shall fall within the protection scope of the present invention.
The evaluation of catalyst activity:
Precise 0.1g catalyst (dry weight), 0.5g o-chloronitrobenzene and 50ml ethyl alcohol, the after agitation (revolving speed of stirring
Once be added in 100ml three-necked flask for 900r/min) (, heating water bath is controlled to 30 DEG C, opens hydrogen valve, and control is passed through
Hydrogen (intake velocity 20ml/min) starts timing, controls temperature at 30 DEG C or so, the duct entry for controlling gas is maintained at
1cm under liquid level carries out gas chromatographic analysis every sampling in 10 minutes, when selectively reaching highest, closes hydrogen valve, continues to stir
It mixes, reaction is cooled to room temperature, and terminates evaluation experimental.
Material source: powdered activated carbon (specific surface area 1450m2/g)；Chlorine palladium acid (congratulates Li Shi industrial technology material in Shanghai
Company)；Ferric trichloride is that analysis is pure；Sodium borohydride is that analysis is pure；Sodium hydroxide is that analysis is pure；Oxalic acid is that analysis is pure；Adjacent chlorine nitre
Base benzene is that analysis is pure；Dehydrated alcohol is that analysis is pure.
Example 1: it after 95g active carbon is impregnated for 24 hours in the hydrochloric acid solution of 0.2mol/L, is washed with deionized into
Pretreated powdered activated high-area carbon, is then immersed in the deionized water solution of 1000mL by property, drying for standby at 120 DEG C,
Stirring 1h is uniformly mixed it and basically reaches adsorption equilibrium, is then respectively adding 0.638g Iron(III) chloride hexahydrate and palladium containing 5g
Chlorine palladium acid solution 0.05mol/L sodium hydroxide solution is slowly added dropwise after stirring 15 hours, until pH=10, stirred when being added dropwise
It mixes, continues stirring 24 hours after dripping, prepared reducing agent solution is then added dropwise, and (its process for preparation is by 50g hydroboration
Sodium and 5g sodium hydroxide are dissolved in 500mL deionized water), it stirs, is stirred for after dripping 2 hours, then by it when being added dropwise
It is separated by solid-liquid separation.Solid portion is immersed in the oxalic acid solution of 1mol/L, after stirring 15 hours, is separated by solid-liquid separation again, and
After being washed with deionized 5 times, solid portion is immersed in the deionized water of 1000mL, prepared reducing agent solution is added dropwise
(its process for preparation is that 50g sodium borohydride and 5g sodium hydroxide are dissolved in 500mL deionized water) is stirred when being added dropwise, is added dropwise
It is stirred for after complete 2 hours, is then separated by solid-liquid separation, and after being washed with deionized 10 times, in a vacuum drying oven at 80 DEG C
Drying, obtains 5% palladium carbon catalyst of finished product.For the evaluation result after o-chloronitrobenzene hydrogenation reaction are as follows: conversion ratio is
100%, o-chloraniline yield is 96.2%, and selectivity is 96.2%.
Example 2: it after 95g active carbon is impregnated for 24 hours in the hydrochloric acid solution of 0.2mol/L, is washed with deionized into
Pretreated powdered activated high-area carbon, is then immersed in the deionized water solution of 1000mL by property, drying for standby at 120 DEG C,
Stirring 1h is uniformly mixed it and basically reaches adsorption equilibrium, is separately added into the chlorine of 0.766g Iron(III) chloride hexahydrate and the palladium containing 5g
0.05mol/L sodium hydroxide solution is slowly added dropwise after stirring 15 hours in palladium acid solution, until pH=9, is stirred when being added dropwise, is added dropwise
Continue stirring 24 hours after complete, prepared reducing agent solution is then added dropwise, and (its process for preparation is by 50g sodium borohydride and 5g hydrogen
Sodium oxide molybdena is dissolved in 500mL deionized water), it is stirred when being added dropwise, is stirred for after dripping 2 hours, is then separated by solid-liquid separation,
Then solid portion is immersed in the oxalic acid solution of 1mol/L, stirring 15 hours after, be separated by solid-liquid separation again, and spend from
After sub- water washing 5 times, solid portion is immersed in the deionized water of 1000mL, prepared reducing agent solution is added dropwise, and (it is matched
Process processed is that 50g sodium borohydride and 5g sodium hydroxide are dissolved in 500mL deionized water), it is stirred when being added dropwise, after dripping again
Stirring 2 hours, is then separated by solid-liquid separation, and after being washed with deionized 10 times, is dried at 80 DEG C, is obtained in a vacuum drying oven
To 5% palladium carbon catalyst of finished product.For the evaluation result after o-chloronitrobenzene hydrogenation reaction are as follows: conversion ratio 100%, adjacent chlorobenzene
Amine yield is 90.6%, and selectivity is 90.6%.
Example 3: it after 95g active carbon is impregnated for 24 hours in the hydrochloric acid solution of 0.2mol/L, is washed with deionized into
Pretreated powdered activated high-area carbon, is then immersed in the deionized water solution of 1000mL by property, drying for standby at 120 DEG C,
Stirring 1h is uniformly mixed it and basically reaches adsorption equilibrium, is separately added into the chlorine of 1.021g Iron(III) chloride hexahydrate and the palladium containing 5g
0.05mol/L sodium hydroxide solution is slowly added dropwise after stirring 15 hours in palladium acid solution, until pH=8, is stirred when being added dropwise, is added dropwise
Continue stirring 24 hours after complete, prepared reducing agent solution is then added dropwise, and (its process for preparation is by 50g sodium borohydride and 5g hydrogen
Sodium oxide molybdena is dissolved in 500mL deionized water), it is stirred when being added dropwise, is stirred for after dripping 2 hours, is then separated by solid-liquid separation,
Then solid portion is immersed in the oxalic acid solution of 1mol/L, stirring 15 hours after, be separated by solid-liquid separation again, and spend from
After sub- water washing 5 times, solid portion is immersed in the deionized water of 1000mL, prepared reducing agent solution is added dropwise, and (it is matched
Process processed is that 50g sodium borohydride and 5g sodium hydroxide are dissolved in 500mL deionized water), it is stirred when being added dropwise, after dripping again
Stirring 2 hours, is then separated by solid-liquid separation, and after being washed with deionized 10 times, is dried at 80 DEG C, is obtained in a vacuum drying oven
To 5% palladium carbon catalyst of finished product.For the evaluation result after o-chloronitrobenzene hydrogenation reaction are as follows: conversion ratio 100%, adjacent chlorobenzene
Amine yield is 88.3%, and selectivity is 88.3%.
Example 4: it after 95g active carbon is impregnated for 24 hours in the hydrochloric acid solution of 0.2mol/L, is washed with deionized into
Pretreated powdered activated high-area carbon, is then immersed in the deionized water solution of 1000mL by property, drying for standby at 120 DEG C,
Stirring 1h is uniformly mixed it and basically reaches adsorption equilibrium, is separately added into the chlorine of 1.276g Iron(III) chloride hexahydrate and the palladium containing 5g
0.05mol/L sodium hydroxide solution is slowly added dropwise after stirring 15 hours in palladium acid solution, until pH=8, is stirred when being added dropwise, is added dropwise
Continue stirring 24 hours after complete, prepared reducing agent solution is then added dropwise, and (its process for preparation is by 50g sodium borohydride and 5g hydrogen
Sodium oxide molybdena is dissolved in 500mL deionized water), it is stirred when being added dropwise, is stirred for after dripping 2 hours, is then separated by solid-liquid separation,
Then solid portion is immersed in the oxalic acid solution of 1mol/L, stirring 15 hours after, be separated by solid-liquid separation again, and spend from
After sub- water washing 5 times, solid portion is immersed in the deionized water of 1000mL, prepared reducing agent solution is added dropwise, and (it is matched
Process processed is that 50g sodium borohydride and 5g sodium hydroxide are dissolved in 500mL deionized water), it is stirred when being added dropwise, after dripping again
Stirring 2 hours, is then separated by solid-liquid separation, and after being washed with deionized 10 times, is dried at 80 DEG C, is obtained in a vacuum drying oven
To 5% palladium carbon catalyst of finished product.For the evaluation result after o-chloronitrobenzene hydrogenation reaction are as follows: conversion ratio 100%, adjacent chlorobenzene
Amine yield is 83.7%, and selectivity is 83.7%.
Example 5: it after 95g active carbon is impregnated for 24 hours in the hydrochloric acid solution of 0.2mol/L, is washed with deionized into
Pretreated powdered activated high-area carbon, is then immersed in the deionized water solution of 1000mL by property, drying for standby at 120 DEG C,
Stirring 1h is uniformly mixed it and basically reaches adsorption equilibrium, is separately added into the chlorine of 0.383g Iron(III) chloride hexahydrate and the palladium containing 3g
0.05mol/L sodium hydroxide solution is slowly added dropwise after stirring 15 hours in palladium acid solution, until pH=9, is stirred when being added dropwise, is added dropwise
Continue stirring 24 hours after complete, prepared reducing agent solution is then added dropwise, and (its process for preparation is by 50g sodium borohydride and 5g hydrogen
Sodium oxide molybdena is dissolved in 500mL deionized water), it is stirred when being added dropwise, is stirred for after dripping 2 hours, is then separated by solid-liquid separation,
Then solid portion is immersed in the oxalic acid solution of 1mol/L, stirring 15 hours after, be separated by solid-liquid separation again, and spend from
After sub- water washing 5 times, solid portion is immersed in the deionized water of 1000mL, prepared reducing agent solution is added dropwise, and (it is matched
Process processed is that 50g sodium borohydride and 5g sodium hydroxide are dissolved in 500mL deionized water), it is stirred when being added dropwise, after dripping again
Stirring 2 hours, is then separated by solid-liquid separation, and after being washed with deionized 10 times, is dried at 80 DEG C, is obtained in a vacuum drying oven
To 3% palladium carbon catalyst of finished product.For the evaluation result after o-chloronitrobenzene hydrogenation reaction are as follows: conversion ratio 100%, adjacent chlorobenzene
Amine yield is 86.2%, and selectivity is 86.2%.
Claims (10)
1. a kind of method for preparing palladium carbon catalyst with chloronitrobenzene selective hydrogenation, specific steps are as follows:
Step 1: the modification of absorbent charcoal carrier: first pre-processing powdered activated carbon: active carbon is soaked in hydrochloric acid solution
It after steeping for 24 hours, is washed with deionized to neutrality, drying for standby at 120 DEG C, then impregnates pretreated powdered activated high-area carbon
In deionized water, stirring 1 hour is uniformly mixed it and basically reaches adsorption equilibrium, obtains modified powdered activated carbon water
Solution system A；
Step 2: dipping process: by precursor solution containing palladium and auxiliary agent iron precursor solution be added drop-wise in system A respectively, stir
Dipping is mixed after 24 hours, obtains system B, the weight percent of palladium is 1~10% in system B；
Step 3: coprecipitation process: being co-precipitated system B with coprecipitator, it is ensured that the pH of last system is 8-10 or so,
Obtain system C；
Step 4: first time reduction process: reducing agent solution being slowly dropped in system C, is stirred when being added dropwise, is added dropwise complete
Afterwards in stirring 2 hours, system D is obtained；
Step 5: separation of solid and liquid process: system D being separated by solid-liquid separation, black colloidal solid E is obtained；
Step 6: second of reduction process: black colloidal solid E being immersed in organic acid soln, after stirring 4h, carries out solid-liquid
Separation, obtains black colloidal solid F, then impregnates in deionized water black colloidal solid F, after stirring 1h, uses reducing agent
Solution is restored；
Step 7: washing drying process: the slurry filtering and washing that the 6th step is restored, wash repeatedly 8-10 times, then in
It is dried at 80 DEG C in vacuum oven, obtains the palladium carbon catalyst of required palladium content.
2. a kind of method for preparing palladium carbon catalyst with chloronitrobenzene selective hydrogenation as described in claim 1, feature
Be: the ratio that the additive amount of auxiliary agent iron precursor solution uses in the second step is the additive amount of iron and active component palladium
Molar ratio be 0.05-0.1:1.
3. a kind of method for preparing palladium carbon catalyst with chloronitrobenzene selective hydrogenation as described in claim 1, feature
Be: the presoma containing palladium is chlorine palladium acid or palladium nitrate.
4. a kind of method for preparing palladium carbon catalyst with chloronitrobenzene selective hydrogenation as described in claim 1, feature
Be: the iron presoma is iron chloride or ferric nitrate.
5. a kind of method for preparing palladium carbon catalyst with chloronitrobenzene selective hydrogenation as described in claim 1, feature
It is: the coprecipitator sodium hydroxide solution.
6. a kind of method for preparing palladium carbon catalyst with chloronitrobenzene selective hydrogenation as described in claim 1, feature
Be: the reducing agent solution is the mixed solution of sodium borohydride and sodium hydroxide, the weight ratio of sodium borohydride and sodium hydroxide
For 10:1.
7. a kind of method for preparing palladium carbon catalyst with chloronitrobenzene selective hydrogenation as described in claim 1, feature
Be: the organic acid is the oxalic acid of 0.05M.
8. a kind of method for preparing palladium carbon catalyst with chloronitrobenzene selective hydrogenation as described in claim 1, feature
Be: palladium content is the 1%-10% of total weight in the palladium carbon catalyst of preparation.
9. a kind of method for preparing palladium carbon catalyst with chloronitrobenzene selective hydrogenation as described in claim 1, feature
Be: the mass ratio of deionized water and powdered activated high-area carbon is 10:1 in the first step；Deionized water and black glue in 6th step
The mass ratio of shape solid F is 10:1.
10. a kind of method for preparing palladium carbon catalyst with chloronitrobenzene selective hydrogenation as described in claim 1, feature
Be: the concentration of hydrochloric acid is 0.2mol/L in the hydrochloric acid solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810716879.8A CN108993484A (en) | 2018-07-03 | 2018-07-03 | A method of palladium carbon catalyst is prepared with chloronitrobenzene selective hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810716879.8A CN108993484A (en) | 2018-07-03 | 2018-07-03 | A method of palladium carbon catalyst is prepared with chloronitrobenzene selective hydrogenation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108993484A true CN108993484A (en) | 2018-12-14 |
Family
ID=64598915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810716879.8A Pending CN108993484A (en) | 2018-07-03 | 2018-07-03 | A method of palladium carbon catalyst is prepared with chloronitrobenzene selective hydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108993484A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109621992A (en) * | 2019-02-11 | 2019-04-16 | 陈欣 | A method of catalysis preparation treatment breast cancer medicines lapatinib intermediate |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817455A (en) * | 2006-03-21 | 2006-08-16 | 浙江工业大学 | Production of 3,4-dichloroaniline catalyst with 3,4-mirbane oil dichloride hydrogenation |
| CN103007962A (en) * | 2012-12-14 | 2013-04-03 | 北京格林凯默科技有限公司 | Metal oxide assisted palladium carbon catalyst and preparation method thereof |
| CN103349983A (en) * | 2013-07-27 | 2013-10-16 | 西安凯立化工有限公司 | Catalyst for preparing halogenated aniline through catalytic hydrogenation of halogenated nitrobenzene and application thereof |
| CN103357407A (en) * | 2013-07-29 | 2013-10-23 | 西安凯立化工有限公司 | Preparation method and application of catalyst for one-step preparation of p-aminophenol from nitrobenzene |
| CN103394347A (en) * | 2013-07-23 | 2013-11-20 | 河海大学 | Preparation method of high-activity palladium-carbon catalyst |
| CN103990468A (en) * | 2014-05-30 | 2014-08-20 | 中国科学院长春应用化学研究所 | Post-processing method for carbon-supported Pt-Fe catalyst |
| CN105312056A (en) * | 2014-06-26 | 2016-02-10 | Sk新技术株式会社 | Catalysts based on natural minerals and process for gasification using the same |
-
2018
- 2018-07-03 CN CN201810716879.8A patent/CN108993484A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817455A (en) * | 2006-03-21 | 2006-08-16 | 浙江工业大学 | Production of 3,4-dichloroaniline catalyst with 3,4-mirbane oil dichloride hydrogenation |
| CN103007962A (en) * | 2012-12-14 | 2013-04-03 | 北京格林凯默科技有限公司 | Metal oxide assisted palladium carbon catalyst and preparation method thereof |
| CN103394347A (en) * | 2013-07-23 | 2013-11-20 | 河海大学 | Preparation method of high-activity palladium-carbon catalyst |
| CN103349983A (en) * | 2013-07-27 | 2013-10-16 | 西安凯立化工有限公司 | Catalyst for preparing halogenated aniline through catalytic hydrogenation of halogenated nitrobenzene and application thereof |
| CN103357407A (en) * | 2013-07-29 | 2013-10-23 | 西安凯立化工有限公司 | Preparation method and application of catalyst for one-step preparation of p-aminophenol from nitrobenzene |
| CN103990468A (en) * | 2014-05-30 | 2014-08-20 | 中国科学院长春应用化学研究所 | Post-processing method for carbon-supported Pt-Fe catalyst |
| CN105312056A (en) * | 2014-06-26 | 2016-02-10 | Sk新技术株式会社 | Catalysts based on natural minerals and process for gasification using the same |
Non-Patent Citations (1)
| Title |
|---|
| 王彦恩 等: ""Fe对 Pt-Fe/C催化剂电催化氧还原反应活性的影响"", 《高等学校化学学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109621992A (en) * | 2019-02-11 | 2019-04-16 | 陈欣 | A method of catalysis preparation treatment breast cancer medicines lapatinib intermediate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7019813B2 (en) | Catalyst for producing α-phenylethanol by hydrogenation of acetophenone, its production method and application | |
| CN110302769B (en) | Catalyst carrier, supported catalyst, preparation method and application thereof | |
| CN109718806B (en) | Noble metal monoatomic catalyst and preparation method and application thereof | |
| CN110270348A (en) | A kind of monatomic catalyst of noble metal and its preparation and application | |
| CN107051420B (en) | N-butane isomerization catalyst and preparation method thereof | |
| CN106866349B (en) | Method for preparing vinyl chloride by low-temperature hydrochlorination of acetylene | |
| CN110813300B (en) | Cobalt-zinc-loaded bimetallic nano-carbon material, preparation method thereof and application thereof in catalytic oxidation of magnesium sulfite | |
| CN105126840A (en) | Efficiently supported palladium catalyst for hydrogenation process of H2O2 production with anthraquinone method and preparation method of efficiently supported palladium catalyst | |
| CN105322183B (en) | A kind of preparation method of Carbon dioxide electrochemical reduction reaction electrode | |
| CN111468163B (en) | Two-dimensional iron monatomic catalyst, preparation thereof and application thereof in production of ethylene by reducing 1,2-dichloroethane | |
| CN115254100A (en) | For CO 2 Preparation and application of metal oxide doped type monatomic catalyst for preparing ethanol by hydrogenation | |
| CN101947444B (en) | Attapulgite load nano Pd catalyst and method for preparing chloroaniline by catalyzing and deoxidating attapulgite load nano Pd catalyst | |
| CN107626329A (en) | A kind of platinum/aluminium oxide catalyst and its preparation method and application | |
| CN105457631A (en) | Catalyst for preparing ethyl alcohol acid ester through oxalic ester gas phase hydrogenation and preparation method | |
| CN108993484A (en) | A method of palladium carbon catalyst is prepared with chloronitrobenzene selective hydrogenation | |
| CN107670698B (en) | Preparation method of catalyst for methanation reaction of synthesis gas | |
| CN106732557A (en) | A kind of preparation method of HPO methods synthesizing azanol phosphate noble metal catalyst | |
| CN107413333A (en) | For producing the chloroacetic modified Hydrodechlorinating catalyst of high-purity and preparation method | |
| CN111054384B (en) | Catalyst for organic liquid hydrogen storage material dehydrogenation and preparation method thereof | |
| CN106693960A (en) | Supported palladium catalyst for synthesizing 1,4-cyclohexanedicarboxylic acid | |
| CN115970707A (en) | Preparation method and application method of hydrogenation catalyst | |
| CN111063902A (en) | Preparation method of nano metal intercalated hydrotalcite material electrode catalyst | |
| CN103816899B (en) | A kind of preparation method of Glucose Liquid phase oxidation Au catalyst | |
| CN107754802B (en) | Catalyst for ethylene carbonate hydrogenation, preparation method and application | |
| CN112452341B (en) | Supported gold-nickel catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181214 |
|
| RJ01 | Rejection of invention patent application after publication |