CN109939713A - A kind of preparation method of the loaded catalyst for chloronitrobenzene catalytic hydrogenation synthesis chloro aminobenzen - Google Patents
A kind of preparation method of the loaded catalyst for chloronitrobenzene catalytic hydrogenation synthesis chloro aminobenzen Download PDFInfo
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- CN109939713A CN109939713A CN201910212703.3A CN201910212703A CN109939713A CN 109939713 A CN109939713 A CN 109939713A CN 201910212703 A CN201910212703 A CN 201910212703A CN 109939713 A CN109939713 A CN 109939713A
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Abstract
The present invention relates to a kind of for synthesizing the preparation method of the catalyst of chloro aminobenzen.In particular to a kind of preparation method of nitrogen-doped carbon material load noble metal catalyst, and it is applied to catalytic hydrogenation synthesis chloro aminobenzen.The catalyst has many advantages, such as that catalytic activity is high, inhibits dechlorination, long service life, and obtained chloro aminobenzen product purity is high.
Description
Technical field
The present invention relates to a kind of for synthesizing the preparation method of the catalyst of chloro aminobenzen.In particular to a kind of nitrogen
The preparation method of carbon material supported noble metal catalyst is adulterated, and is applied to catalytic hydrogenation synthesis chloro aminobenzen.
Background technique
Chloro aminobenzen is a kind of important organic synthesis intermediate, can be widely applied to the fining such as medicine, pesticide, dyestuff
The production of work product.The industrial method of domestic and international chloro aminobenzen mainly has iron powder reducing method, sodium sulfide reducing method and catalytic hydrogenation
Three kinds of method.Iron powder reducing method and sodium sulfide reducing method are asked there are the three wastes environmental pollution that at high cost, yield is low, generates is larger etc.
Topic, has been eliminated substantially.Catalytic hydrogenation method has that reaction route is short, low energy consumption and advantages of environment protection, meets Green Chemistry
Demand for development and trend;But the problem of this friendly process generally existing hydrogenation-dechlorination, mainly the C-Cl on chloro aminobenzen exists
Under the action of catalyst, hydrogenolysis dechlorination side reaction occurs, chloro aminobenzen yield is caused to be lower, and the aniline and hydrochloric acid that generate can produce
The problems such as generating apparatus burn into catalyst inactivation.
For US4070401 using 5wt%Pt/C as catalyst, polyamine is dechlorination inhibitor, and catalytic hydrogenation method prepares adjacent chlorobenzene
Amine, 100 DEG C of temperature, pressure 5.0MPa, o-nitrochlorobenzene conversion ratio 100%, dechlorination rate 0.4%.
CN102757352A discloses a kind of production technology of parachloroanilinum, and using paranitrochlorobenzene as raw material, methanol is molten
Agent, Raney's nickel are catalyst, and dicyandiamide is dechlorination inhibitor, and obtained parachloroanilinum is selectively greater than 98.5%, and dechlorination amount is small
In 0.5%.These methods need to be continuously added dechlorination inhibitor, although dechlorination amount declines, also increase kettle residual, influence to produce
Product purity.
Summary of the invention
The present invention provides one kind can be with efficient catalytic chloronitrobenzene hydrogenation synthesis chloro aminobenzen, while inhibiting dechlorination
The preparation method of catalyst.The catalyst has many advantages, such as that catalytic activity is high, inhibits dechlorination, long service life, obtained chloro
Aniline product purity is high.
Technical scheme is as follows:
(1) Activated Carbon Pretreatment
Active carbon, hydrochloric acid solution are sequentially added into there-necked flask, are stirred at 50 DEG C -80 DEG C.Filtering, then add into filter cake
Enter nitric acid solution, 60-100 DEG C of stirring.Ammonium hydroxide is added and adjusts pH to neutrality, then washes twice, obtains active carbon slurry, N2Atmosphere
Lower drying, it is spare.
(2) preparation of catalyst
Take a certain amount of polymer with nitrogen, pretreated active carbon, precious metal salt, base metal salt, in organic solvent
Middle ultrasonic disperse 2h, later in N2Lower drying and processing, obtains yellowish-brown mill base material.After slurry is dried, it is being connected with N2、H2Gaseous mixture
900 DEG C of Muffle furnace high temperatures of body are calcined, and the Pt/Zn bimetallic catalyst of nitrogen-dopped activated carbon load is obtained.
The active carbon can be powdery carbo lignius or shell class charcoal, preferably powdered shell class charcoal, more preferable coconut husk, apricot
Shell or peach shell, specific surface area 800-2000m2/ g, 75 μm of granularity, ash content 2%.
The organic solvent can be N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, two
Methyl sulfoxide, preferably n,N-Dimethylformamide.
During step (1) Activated Carbon Pretreatment, affiliated concentration of hydrochloric acid be 1-35wt%, preferably 15-25wt%, it is described
Active carbon and hydrochloric acid weight ratio be 1:0.5-50, preferably 1:1-20, the concentration of nitric acid be 1-30wt%, preferably 5-
25wt%, the active carbon and nitric acid weight ratio are 1:0.5-50, preferably 1:1-10;
In step (2) catalyst loading process, the weight ratio of the polymer with nitrogen and active carbon is 10-80wt%,
The polymer with nitrogen can be polyacrylonitrile, chitosan, polyaniline, carbonitride, preferably polyacrylonitrile, and noble metal can be
Rhodium, palladium, platinum, ruthenium, silver, preferably platinum, the preferably preferred chloroplatinic acid of precious metal salt or potassium chloroplatinate, the base metal can
To be iron, zinc, copper, the preferably preferred zinc chloride of zinc zinc salt or zinc nitrate;The weight ratio of platinum salt, zinc salt and active carbon is 0.1-
5wt%, preferably 0.5-4.5wt%, more preferably 1-3wt%, mole of contained pt atom and the zinc atom in zinc salt in platinum salt
Than for 0.5:1-1.5:1, N2、H2Calcination temperature be preferably 600-1000 DEG C, the preferred 3-5h of calcination time.
Catalyst prepared by the present invention is mainly used in chloronitrobenzene preparing chloroaniline by catalysis hydrogenation, the chlorine
It is o-chloronitrobenzene, parachloronitrobenzene, 3,4- dichloronitrobenzenes, 2,5- dichloronitrobenzenes for nitrobenzene.
Compared with the prior art, the present invention has the following beneficial effects:
(1) present invention and the production technology of traditional noble-metal-supported catalyst are not much different, and technical process is simple.
(2) present invention is with polyacrylonitrile, and active carbon, platinum salt, zinc salt are primary raw material, will form greatly after high temperature cabonization is blended
The nitrogen-dopped activated carbon bimetallic catalyst of molecular structure.Its steady chemical structure, nitrogen-atoms, metallic atom are not easy to flow
It loses, catalyst hydrogenation activity is stablized, long service life, is recycled often.
(3) continuous macromolecular skeleton structure possessed by catalyst can effectively transmit electronics, and the nitrogen-atoms of doping has
Lone pair electrons can also effectively increase transfer of the electronics to Pt metal, so that catalytic activity is improved, so that chloronitrobenzene inhales hydrogen
Speed is fast, and the reaction time is short.
(4) nitrogen-atoms adulterated in catalyst, electronegativity are unfavorable in chloronitrobenzene and chloro aminobenzen compared with carbon atom height
C-Cl absorption, thus achieve the effect that inhibit dechlorination.
(5) base metal Zn is introduced, zinc salt is cheap, and the bimetallic of Pt and Zn acts synergistically so that Pt is in electron rich
State, can effectively inhibit C-Cl key adds hydrogen.
Specific embodiment
Embodiment 1
1.1 Activated Carbon Pretreatment
The 1000g hydrochloric acid solution of 50g active carbon, 20wt% are sequentially added into 2000mL there-necked flask, stir 3h at 60 DEG C.
It filters, then the nitric acid solution of 300g 25wt%, 80 DEG C of stirring 5h is added into filter cake.Ammonium hydroxide is added and adjusts pH to neutrality, then water
It washes twice, obtains active carbon slurry, N2It is dry under atmosphere, it is spare.
The preparation of 1.2 catalyst
Take 20g polyacrylonitrile, the pretreated active carbon of 30g, 0.4g chloroplatinic acid, 0.13g zinc chloride, in N, N- dimethyl
Ultrasonic disperse 2h in formamide, later in N2Lower drying and processing, obtains yellowish-brown mill base material.Slurry is being connected with N2、H2Mixed gas
900 DEG C of Muffle furnace high temperatures calcine 2h, obtain nitrogen-dopped activated carbon load Pt/Zn bimetallic catalyst.With ICP spectrometer
It is 9.2wt% that measuring and calculating Pt content 0.30wt%, Zn content 0.12wt%, EDS energy disperse spectroscopy, which measures nitrogen content,.
1.3 catalytic hydrogenation parachloronitrobenzenes synthesize parachloroanilinum
100g parachloronitrobenzene, 2g Pt/Zn N doping catalyst, 150g methanol, displacement are sequentially added into 1L autoclave
N2After 3 times, 60 DEG C are warming up to, after reaction, pours out reaction solution, is filtered, filter cake is catalyst, recycling, filtrate
Through rectifying, decoking, light yellow product o-chloraniline is obtained.Reaction time 2.5h, conversion ratio 99.8%, o-chloraniline liquid compose content
99.5%, dechlorination amount 0.03%.After circulation 20 times, catalytic performance is still without significant change.
Embodiment 2
2.1 Activated Carbon Pretreatment
The 1000g hydrochloric acid solution of 50g active carbon, 20wt% are sequentially added into 2000mL there-necked flask, stir 3h at 60 DEG C.
It filters, then the nitric acid solution of 300g 25wt%, 80 DEG C of stirring 5h is added into filter cake.Ammonium hydroxide is added and adjusts pH to neutrality, then water
It washes twice, obtains active carbon slurry, N2It is dry under atmosphere, it is spare.
The preparation of 2.2 catalyst
Take 20g polyacrylonitrile, the pretreated active carbon of 30g, 0.60g chloroplatinic acid, 0.15g zinc chloride, in N, N- diformazan
Ultrasonic disperse 2h in base formamide, later in N2Lower drying and processing, obtains yellowish-brown mill base material.Slurry is being connected with N2、H2Gaseous mixture
900 DEG C of Muffle furnace high temperature of body calcines 2h, obtains the Pt/Zn bimetallic catalyst of nitrogen-dopped activated carbon load.With ICP light
It is 9.0wt% that spectrometer measuring and calculating Pt content 0.45wt%, Zn content 0.16wt%, EDS energy disperse spectroscopy, which measures nitrogen content,.
2.3 catalytic hydrogenation parachloronitrobenzenes synthesize parachloroanilinum
100g parachloronitrobenzene, 2g Pt/Zn N doping catalyst, 150g methanol, displacement are sequentially added into 1L autoclave
N2After 3 times, 60 DEG C are warming up to, after reaction, pours out reaction solution, is filtered, filter cake is catalyst, recycling, filtrate
Through rectifying, decoking, light yellow product o-chloraniline is obtained.Reaction time 2h, conversion ratio 99.9%, o-chloraniline liquid compose content
99.6%, dechlorination amount 0.03%.Circulation 20 times, catalytic performance is without significant change.
Embodiment 3
3.1 Activated Carbon Pretreatment
The 1000g hydrochloric acid solution of 50g active carbon, 20wt% are sequentially added into 2000mL there-necked flask, stir 3h at 60 DEG C.
It filters, then the nitric acid solution of 300g 25wt%, 80 DEG C of stirring 5h is added into filter cake.Ammonium hydroxide is added and adjusts pH to neutrality, then water
It washes twice, obtains active carbon slurry, N2It is dry under atmosphere, it is spare.
The preparation of 3.2 catalyst
Take 20g polyacrylonitrile, the pretreated active carbon of 30g, 0.80g chloroplatinic acid, 0.30g zinc chloride, in N, N- diformazan
Ultrasonic disperse 2h in base formamide, later in N2Lower drying and processing, obtains yellowish-brown mill base material.Slurry is being connected with N2、H2Gaseous mixture
900 DEG C of Muffle furnace high temperature of body calcines 2h, obtains the Pt/Zn bimetallic catalyst of nitrogen-dopped activated carbon load.With ICP light
It is 8.5wt% that spectrometer measuring and calculating Pt content 0.6wt%, Zn content 0.28wt%, EDS energy disperse spectroscopy, which measures nitrogen content,.
3.3 catalysis parachloronitrobenzenes synthesize parachloroanilinum
100g parachloronitrobenzene, 2g Pt/Zn N doping catalyst, 150g methanol, displacement are sequentially added into 1L autoclave
N2After 3 times, 60 DEG C are warming up to, after reaction, pours out reaction solution, is filtered, filter cake is catalyst, recycling, filtrate
Through rectifying, decoking, light yellow product o-chloraniline is obtained.Reaction time 2h, conversion ratio 99.7%, o-chloraniline liquid compose content
99.5%, dechlorination amount 0.04%.Circulation 20 times, catalytic performance is without significant change.
Embodiment 4
4.1 Activated Carbon Pretreatment
The 1000g hydrochloric acid solution of 50g active carbon, 20wt% are sequentially added into 2000mL there-necked flask, stir 3h at 60 DEG C.
It filters, then the nitric acid solution of 300g 25wt%, 80 DEG C of stirring 5h is added into filter cake.Ammonium hydroxide is added and adjusts pH to neutrality, then water
It washes twice, obtains active carbon slurry, N2It is dry under atmosphere, it is spare.
4.2 the preparation of catalyst
Take 15g polyacrylonitrile, the pretreated active carbon of 35g, 0.80g chloroplatinic acid, 0.30g zinc chloride, in N, N- diformazan
Ultrasonic disperse 2h in base formamide, later in N2Lower drying and processing, obtains yellowish-brown mill base material.Slurry is being connected with N2、H2Gaseous mixture
900 DEG C of Muffle furnace high temperature of body calcines 2h, obtains the Pt/Zn bimetallic catalyst of nitrogen-dopped activated carbon load.With ICP light
It is 6.9wt% that spectrometer measuring and calculating Pt content 0.6wt%, Zn content 0.28wt%, EDS energy disperse spectroscopy, which measures nitrogen content,.
4.3 catalysis parachloronitrobenzenes synthesize parachloroanilinum
100g parachloronitrobenzene, 2g Pt/Zn N doping catalyst, 150g methanol, displacement are sequentially added into 1L autoclave
N2After 3 times, 60 DEG C are warming up to, after reaction, pours out reaction solution, is filtered, filter cake is catalyst, recycling, filtrate
Through rectifying, decoking, light yellow product o-chloraniline is obtained.Reaction time 2h, conversion ratio 98.7%, o-chloraniline liquid compose content
99.4%, dechlorination amount 0.08%.Circulation 20 times, catalytic performance is without significant change.
Embodiment 5
5.1 Activated Carbon Pretreatment
The 1000g hydrochloric acid solution of 50g active carbon, 20wt% are sequentially added into 2000mL there-necked flask, stir 3h at 60 DEG C.
It filters, then the nitric acid solution of 300g 25wt%, 80 DEG C of stirring 5h is added into filter cake.Ammonium hydroxide is added and adjusts pH to neutrality, then water
It washes twice, obtains active carbon slurry, N2It is dry under atmosphere, it is spare.
The preparation of 5.2 catalyst
Take 25g polyacrylonitrile, the pretreated active carbon of 25g, 0.80g chloroplatinic acid, 0.30g zinc chloride, in N, N- diformazan
Ultrasonic disperse 2h in base formamide, later in N2Lower drying and processing, obtains yellowish-brown mill base material.Slurry is being connected with N2、H2Gaseous mixture
900 DEG C of Muffle furnace high temperature of body calcines 2h, obtains the Pt/Zn bimetallic catalyst of nitrogen-dopped activated carbon load.With ICP light
It is 11.3wt% that spectrometer measuring and calculating Pt content 0.6wt%, Zn content 0.28wt%, EDS energy disperse spectroscopy, which measures nitrogen content,.
5.3 catalysis parachloronitrobenzenes synthesize parachloroanilinum
100g parachloronitrobenzene, 2g Pt/Zn N doping catalyst, 150g methanol, displacement are sequentially added into 1L autoclave
N2After 3 times, 60 DEG C are warming up to, after reaction, pours out reaction solution, is filtered, filter cake is catalyst, recycling, filtrate
Through rectifying, decoking, light yellow product o-chloraniline is obtained.Reaction time 2h, conversion ratio 98.7%, o-chloraniline liquid compose content
99.4%, dechlorination amount 0.08%.Circulation 20 times, catalytic performance is without significant change.
Comparative example 1
1.1 Activated Carbon Pretreatment
The 1000g hydrochloric acid solution of 50g active carbon, 20wt% are sequentially added into 2000mL there-necked flask, stir 3h at 60 DEG C.
It filters, then the nitric acid solution of 300g 25%, 80 DEG C of stirring 5h is added into filter cake.Ammonium hydroxide is added and adjusts pH to neutrality, then washes
Twice, active carbon slurry, N are obtained2It is dry under atmosphere, it is spare.
The preparation of 1.2 catalyst
The pretreated active carbon of 50g, 0.80g chloroplatinic acid are taken, zinc chloride 0.30g surpasses in n,N-Dimethylformamide
Sound disperses 2h, later in N2Lower drying and processing, obtains yellowish-brown mill base material.Slurry is being connected with N2、H2900 DEG C of mixed gas
Muffle furnace high temperature calcines 2h, obtains activated carbon supported Pt/Zn bimetallic catalyst.Pt content is calculated with ICP spectrometer
0.62wt%, Zn content 0.28wt%.
1.3 catalysis parachloronitrobenzenes synthesize parachloroanilinum
Sequentially add 100g parachloronitrobenzene into 1L autoclave, the activated carbon supported Pt/Zn catalyst of 2g, 150g methanol,
Replace N2After 3 times, 60 DEG C are warming up to, after reaction, pours out reaction solution, is filtered, filter cake is catalyst, recycling,
Filtrate obtains light yellow product parachloroanilinum through rectifying, decoking.Reaction time 2h, conversion ratio 97.5%, parachloroanilinum liquid spectrum contain
Amount 96.3%, dechlorination amount 0.6%.
Claims (8)
1. a kind of preparation method of the catalyst of efficient catalytic chloronitrobenzene hydrogenation synthesis chloro aminobenzen, which is characterized in that packet
Include following steps:
(1) Activated Carbon Pretreatment:
Active carbon, hydrochloric acid solution are sequentially added into there-necked flask, is stirred at 50 DEG C -80 DEG C, are filtered, then nitre is added into filter cake
Acid solution, 60-100 DEG C of stirring, addition ammonium hydroxide adjusting pH to neutrality, then wash twice, obtain active carbon slurry, N2It is done under atmosphere
It is dry, it is spare;
(2) preparation of catalyst:
A certain amount of polymer with nitrogen is taken, pretreated active carbon, precious metal salt, base metal salt are ultrasonic in organic solvent
Disperse 2h, later in N2Lower drying and processing, obtains yellowish-brown mill base material, after slurry is dried, is being connected with N2、H2Mixed gas
600-1000 DEG C of Muffle furnace high temperature calcining, obtains the bimetallic catalyst of nitrogen-dopped activated carbon load.
2. the preparation side of the catalyst of efficient catalytic chloronitrobenzene hydrogenation synthesis chloro aminobenzen according to claim 1
Method, which is characterized in that the active carbon is powdery carbo lignius or shell class charcoal, preferably powdered shell class charcoal, more preferable coconut husk,
Apricot shell or peach shell, specific surface area 800-2000m2/ g, 75 μm of granularity, ash content 2%.
3. the preparation side of the catalyst of efficient catalytic chloronitrobenzene hydrogenation synthesis chloro aminobenzen according to claim 1
Method, which is characterized in that the organic solvent be n,N-Dimethylformamide, n,N-dimethylacetamide, N-Methyl pyrrolidone,
Dimethyl sulfoxide, preferably n,N-Dimethylformamide.
4. the preparation side of the catalyst of efficient catalytic chloronitrobenzene hydrogenation synthesis chloro aminobenzen according to claim 1
Method, which is characterized in that during step (1) Activated Carbon Pretreatment, affiliated concentration of hydrochloric acid is 1-35wt%, preferably 15-
25wt%, the active carbon and hydrochloric acid weight ratio are 1:0.5-50, and preferably 1:1:20, the concentration of nitric acid is 1-
30wt%, preferably 5-25wt%, the active carbon and nitric acid weight ratio are 1:0.5-50, preferably 1:1-10.
5. the preparation side of the catalyst of efficient catalytic chloronitrobenzene hydrogenation synthesis chloro aminobenzen according to claim 1
Method, which is characterized in that in step (2) catalyst loading process, the weight ratio of the polymer with nitrogen and active carbon is 10-
80wt%, the polymer with nitrogen are polyacrylonitrile, chitosan, polyaniline, carbonitride, preferably polyacrylonitrile.
6. the preparation side of the catalyst of efficient catalytic chloronitrobenzene hydrogenation synthesis chloro aminobenzen according to claim 1
Method, which is characterized in that precious metal salt is rhodium salt, palladium salt, platinum salt, ruthenium salt, silver salt, preferably platinum salt, more preferable chloroplatinic acid or chlorine
Potassium platinate, the base metal are molysite, zinc salt, mantoquita, preferably zinc salt.More preferable zinc chloride or zinc nitrate;Precious metal salt,
The weight ratio of base metal salt and active carbon is 0.1-5wt%, preferably 0.5-4.5wt%, more preferably 1-3wt%.
7. the preparation side of the catalyst of efficient catalytic chloronitrobenzene hydrogenation synthesis chloro aminobenzen according to claim 6
Method, which is characterized in that the molar ratio of contained pt atom and the zinc atom in zinc salt is 0.5:1-1.5:1 in platinum salt.
8. the preparation side of the catalyst of efficient catalytic chloronitrobenzene hydrogenation synthesis chloro aminobenzen according to claim 1
Method, which is characterized in that N2、H2Calcination temperature be 900 DEG C, calcination time 3-5h.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4532350A (en) * | 1980-08-01 | 1985-07-30 | Rhone-Poulenc Agrochimie | Process for the selective preparation of meta-chloroanilines |
CN101049560A (en) * | 2007-05-09 | 2007-10-10 | 华东理工大学 | Catalyst for preparing dichloroaniline through hydrogenization for dichloronitrobenzene, and preparation method |
CN101195579A (en) * | 2006-12-04 | 2008-06-11 | 中国科学院大连化学物理研究所 | Method for synthesizing chloro-aniline by chloronitrobenzene selective hydrogenation in alcohol-water system |
CN103962150A (en) * | 2013-02-06 | 2014-08-06 | 中国中化股份有限公司 | Catalyst for preparation of chlorinated aromatic amine and preparation method thereof |
CN107970967A (en) * | 2017-11-21 | 2018-05-01 | 江苏扬农化工集团有限公司 | A kind of preparation method that chloro arylamine catalyst is prepared for catalytic hydrogenation |
CN107999116A (en) * | 2017-12-14 | 2018-05-08 | 湘潭大学 | For being catalyzed the catalyst of chloro virtue nitro compound selection hydrogenation |
CN109225258A (en) * | 2018-10-19 | 2019-01-18 | 郴州高鑫铂业有限公司 | A kind of Pt-Fe/C catalyst and its preparation method and application |
CN109433239A (en) * | 2018-10-23 | 2019-03-08 | 重庆师范大学 | A kind of preparation method and application for the platinum carbon catalyst that Fe-N is modified |
-
2019
- 2019-03-20 CN CN201910212703.3A patent/CN109939713A/en active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4532350A (en) * | 1980-08-01 | 1985-07-30 | Rhone-Poulenc Agrochimie | Process for the selective preparation of meta-chloroanilines |
CN101195579A (en) * | 2006-12-04 | 2008-06-11 | 中国科学院大连化学物理研究所 | Method for synthesizing chloro-aniline by chloronitrobenzene selective hydrogenation in alcohol-water system |
CN101049560A (en) * | 2007-05-09 | 2007-10-10 | 华东理工大学 | Catalyst for preparing dichloroaniline through hydrogenization for dichloronitrobenzene, and preparation method |
CN103962150A (en) * | 2013-02-06 | 2014-08-06 | 中国中化股份有限公司 | Catalyst for preparation of chlorinated aromatic amine and preparation method thereof |
CN107970967A (en) * | 2017-11-21 | 2018-05-01 | 江苏扬农化工集团有限公司 | A kind of preparation method that chloro arylamine catalyst is prepared for catalytic hydrogenation |
CN107999116A (en) * | 2017-12-14 | 2018-05-08 | 湘潭大学 | For being catalyzed the catalyst of chloro virtue nitro compound selection hydrogenation |
CN109225258A (en) * | 2018-10-19 | 2019-01-18 | 郴州高鑫铂业有限公司 | A kind of Pt-Fe/C catalyst and its preparation method and application |
CN109433239A (en) * | 2018-10-23 | 2019-03-08 | 重庆师范大学 | A kind of preparation method and application for the platinum carbon catalyst that Fe-N is modified |
Non-Patent Citations (1)
Title |
---|
XIAOXIANG HAN ET.AL: "Effect of transition metal (Cr, Mn, Fe, Co, Ni and Cu) on the hydrogenation properties of chloronitrobenzene over Pt/TiO2 catalysts", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
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CN112007657B (en) * | 2019-05-31 | 2022-04-29 | 浙江省化工研究院有限公司 | Method for controlling metal atomic ratio in supported Cu-Pd/AC alloy catalyst |
CN111250107A (en) * | 2020-03-11 | 2020-06-09 | 浙江晨和生物医药有限公司 | Biomass-derived recyclable metal catalyst and preparation method and application thereof |
CN111250107B (en) * | 2020-03-11 | 2023-02-28 | 浙江晨和生物医药有限公司 | Biomass-derived recyclable metal catalyst and preparation method and application thereof |
CN112108182A (en) * | 2020-03-16 | 2020-12-22 | 厦门大学 | Cyanimide compound-Pt-based nanocrystalline catalyst and preparation method and application thereof |
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