CN103664641A - Method for preparing o-chloroaniline by virtue of solvent-free catalytic hydrogenation - Google Patents
Method for preparing o-chloroaniline by virtue of solvent-free catalytic hydrogenation Download PDFInfo
- Publication number
- CN103664641A CN103664641A CN201210330392.9A CN201210330392A CN103664641A CN 103664641 A CN103664641 A CN 103664641A CN 201210330392 A CN201210330392 A CN 201210330392A CN 103664641 A CN103664641 A CN 103664641A
- Authority
- CN
- China
- Prior art keywords
- ortho
- nitrochlorobenzene
- solvent
- catalyzer
- reaction
- 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.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention belongs to the technical field of fine chemical engineering, and relates to a method for preparing o-chloroaniline by virtue of solvent-free catalytic hydrogenation ortho-nitrochlorobenzene. The method is characterized in that ortho-nitrochlorobenzene is adopted as a raw material to be reacted with hydrogen in the presence of a catalyst at the temperature of 70-120 DEG C and the pressure of 0.5-5.0 MPa so as to obtain o-chloroaniline through the processing after the reaction. By adopting the method, no solvent is added, the defect for adding the solvent can be overcome, the environmental pollution problem and the solvent recycling problem can be avoided, the equipment investment is reduced, the production cost is reduced, the conversion rate of the ortho-nitrochlorobenzene can reach 100 percent, the selectivity of the o-chloroaniline is more than 99.2 percent, and the dechlorinating rate is less than 0.09 percent.
Description
Technical field
The invention belongs to fine chemical technology field, relate to a kind of new Ortho-Chloro aniline preparation method, specifically the method for the solvent-free preparing o-chloroaniline by catalytic hydrogenation of ortho-nitrochlorobenzene.
Background technology
Ortho-Chloro aniline is the important intermediate of agricultural chemicals, medicine, spices, dyestuff, polyurethane industrial.In industrial production, the preparation of Ortho-Chloro aniline be take ortho-nitrochlorobenzene as raw material, carries out reduction reaction and obtains Ortho-Chloro aniline.Because existing with serious pollution problem, iron powder reducing method, sodium sulfide reducing method, hydrazine hydrate reduction method be eliminated, the technique that production Ortho-Chloro aniline is generally used is at present as catalyzer by skeleton nickel, methyl alcohol or ethanol are as solvent, and catalytic hydrogenating reduction ortho-nitrochlorobenzene makes Ortho-Chloro aniline.The shortcoming that this method exists is the problem that the use of solvent has brought solvent environmental pollution and solvent recuperation, has increased raw materials cost and equipment cost, and dechlorination reaction easily occurs in reduction process, cause equipment corrosion, the yield that reduces product, easily makes poisoning of catalyst, reduces catalyst activity.
In order to solve skeleton nickel catalyzed hydrodechlorination problem, people mainly take to improve skeletal nickel catalyst and add two kinds of methods of dechlorination inhibitor.
CN102050746A methyl alcohol is solvent, and skeleton nickel is catalyzer, and Dyhard RU 100 is dechlorination inhibitor, catalytic hydrogenating reduction ortho-nitrochlorobenzene, and the selectivity of Ortho-Chloro aniline is greater than 99%, and dechlorination rate is less than 0.1%.CN101774931A ethyl acetate solution is solvent, and nickelalloy is catalyzer, and Dyhard RU 100 is dechlorination inhibitor, catalytic hydrogenating reduction ortho-nitrochlorobenzene, and the selectivity of Ortho-Chloro aniline is greater than 99%, and dechlorination rate is less than 0.3%.The shortcoming of CN102050746A and CN101774931A is that selectivity of catalyst is not high, need to add dechlorination inhibitor, has increased production cost, has the processing of dechlorination inhibitor and the problem that alcoholic solvent reclaims simultaneously.
US4070401 polyamine is dechlorination inhibitor, and 5% platinum/carbon is catalyzer, catalytic hydrogenating reduction ortho-nitrochlorobenzene, and 100 ℃ of temperature of reaction, reaction pressure 5.0MPa, in reaction solution, the mass percent of aniline is 0.5%, dechlorination rate is 0.4%.Shortcoming is that dechlorination rate is high, generates hydrogen-chloride etching equipment, need to add dechlorination inhibitor, has increased production cost, the problem that simultaneously exists dechlorination inhibitor to process.
CN02148509.7 discloses that to take nano-carbon tube load Pt or Pd be catalyzer, and shortening halogenated nitrobenzene is prepared halogen aromatic amines.Nano-carbon tube load Pt is the reaction yield 99.0% of catalyzer, dechlorination rate 0.05%, and the reaction yield 99.2% that nano-carbon tube load Pd is catalyzer, dechlorination rate 0.1%, can suppress hydrodechlorination effectively.But due to CNT (carbon nano-tube) high cost, this method industrial application value is little.
CN1660774A be take ortho-nitrochlorobenzene as raw material, under alcohol solvent and catalyzer existence, reaction at 150 ℃～250 ℃, the aftertreatment that reacts completely obtains Ortho-Chloro aniline, wherein catalyzer is selected from one of following: Ru/C, amorphous state NiB, Ni-Fe-B, Ni-Co-B, catalyst levels is 10%～20% of raw materials quality, and the hydrogen obtaining with alcohol cracking, for hydrogenation reaction, reaches the object that suppresses dechlorination.But the consumption of reacting middle catalyst is very large, has increased production cost.
CN101333169 be take ortho-nitrochlorobenzene as raw material, under alcoholic solvent and catalyzer, auxiliary agent exist, under 10 ℃～120 ℃ and 0.3MPa～4.0MPa, with hydrogen successive reaction, complete aftertreatment and obtain Ortho-Chloro aniline, wherein catalyzer is selected from one of following: skeleton nickel, Ni/Al
2o
3, Pt/C, Pd/C, catalyst levels is 0.05%～20% of raw materials quality, adding one to three kind in hexahydroaniline, quadrol, thanomin, diethanolamine, trolamine, pyridine, liquefied ammonia, bicarbonate of ammonia, volatile salt, sodium bicarbonate, sodium carbonate, saleratus, salt of wormwood, sodium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC, potassium hydrogen phosphate, potassium primary phosphate is auxiliary agent, reaches the object that suppresses dechlorination.Shortcoming is to add multiple auxiliary agent to suppress dechlorination, has increased production cost, has the processing of dechlorination inhibitor and the problem that alcoholic solvent reclaims simultaneously.
Summary of the invention
The invention provides a kind of highly selective, high yield and prepare the novel method of Ortho-Chloro aniline.
Technical solution of the present invention is: take ortho-nitrochlorobenzene as raw material, under catalyzer exists, under 70 ℃～120 ℃ and 0.5MPa～5.0MPa pressure, with hydrogen reaction, reaction finishes aftertreatment and obtains Ortho-Chloro aniline.
Usually, catalyzer of the present invention is platinum/C catalyst, and wherein the quality percentage composition of platinum is 1%～5%; Platinum content preferably 3%;
Further, catalyzer of the present invention is for containing the platinum/C catalyst of vanadium, wherein platinum content be 1%～5%, content of vanadium is 0.1～2%, preferably platinum content is 3%, content of vanadium 0.5%.
Preferred catalyst levels is 0.02%～5% of raw material ortho-nitrochlorobenzene quality, further preferably 0.05%～0.5%, and preferred temperature of reaction is 80 ℃～110 ℃, reaction pressure is 2.0MPa～3.5MPa.
Compared with prior art, the present invention has the following advantages:
1) the Pt/C catalyzer that the present invention uses can effectively solve hydrogenolysis dechlorination problem in ortho-nitrochlorobenzene hydrogenating reduction process, and dechlorination rate is less than 0.09%, has reduced the corrosion of dechlorination to conversion unit, reduces maintenance of equipment nurse fees and uses.
2) the Pt/C catalyst component that the present invention uses is simple, and with respect to other multicomponent catalyst, cost recovery is low.
3) the Pt/C catalyst activity that the present invention uses is stable, and selectivity is high, and the time of applying mechanically is continuously long.
4) the Pt/C catalyzer that the present invention uses is safe.
5) the present invention does not use dechlorination inhibitor, has reduced the sepn process of dechlorination inhibitor, fundamentally eliminates the impact of dechlorination inhibitor on final product quality.
6) the present invention does not use solvent, fundamentally solves the difficult problem of alcoholic solvent to the pollution of environment and solvent recuperation, has reduced production cost, has improved throughput.
Because solventless method preparing o-chloroaniline by catalytic hydrogenation, saved the consumption of solvent, prevented the environmental pollution that solvent evaporates causes, the per unit area yield efficiency that has improved reaction vessel, has improved product purity, has reduced pollution, cost-saving, productive rate is higher, and technique is simpler, is more conducive to industrial application.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail
.
embodiment 1
By 60g ortho-nitrochlorobenzene and 0.36 g3%Pt/C(water content, being 59.98%) catalyzer joins in 100 milliliters of stainless steel autoclaves, enclosed high pressure still, with air in nitrogen replacement autoclave three times, then with nitrogen in hydrogen exchange still three times and keep certain pressure in still.Under stirring, be warming up to 95 ℃, maintain reaction pressure 2.25MPa, react 120 minutes, after reaction finishes, close hydrogen valve, the cooling rear disappointing autoclave discharging of opening, filter catalyzer, filtrate is through efficient liquid phase chromatographic analysis, ortho-nitrochlorobenzene transformation efficiency 100%, Ortho-Chloro aniline selectivity 99.3%, dechlorination rate 0.09%.
embodiment 2
By 60g ortho-nitrochlorobenzene and 0.36 g1%Pt/C(water content, being 59.78%) catalyzer joins in 100 milliliters of stainless steel autoclaves, enclosed high pressure still, with air in nitrogen replacement autoclave three times, then with nitrogen in hydrogen exchange still three times and keep certain pressure in still.Under stirring, be warming up to 95 ℃, maintain reaction pressure 2.25MPa, react 120 minutes, after reaction finishes, close hydrogen valve, the cooling rear disappointing autoclave discharging of opening, filter catalyzer, filtrate is through efficient liquid phase chromatographic analysis, ortho-nitrochlorobenzene transformation efficiency 96%, Ortho-Chloro aniline selectivity 99.5%, dechlorination rate 0.06%.
embodiment 3
By 60g ortho-nitrochlorobenzene and 0.36 g5%Pt/C(water content, being 60.12%) catalyzer joins in 100 milliliters of stainless steel autoclaves, enclosed high pressure still, with air in nitrogen replacement autoclave three times, then with nitrogen in hydrogen exchange still three times and keep certain pressure in still.Under stirring, be warming up to 95 ℃, maintain reaction pressure 2.25MPa, react 120 minutes, after reaction finishes, close hydrogen valve, the cooling rear disappointing autoclave discharging of opening, filter catalyzer, filtrate is through efficient liquid phase chromatographic analysis, ortho-nitrochlorobenzene transformation efficiency 100%, Ortho-Chloro aniline selectivity 98.9%, dechlorination rate 0.39%.
embodiment 4
By 60g ortho-nitrochlorobenzene and 0.36 g, containing the 3%Pt/C(water content of vanadium 0.5%, being 59.27%) catalyzer joins in 100 milliliters of stainless steel autoclaves, enclosed high pressure still, with air in nitrogen replacement autoclave three times, then with nitrogen in hydrogen exchange still three times and keep certain pressure in still.Under stirring, be warming up to 95 ℃, maintain reaction pressure 2.25MPa, react 120 minutes, after reaction finishes, close hydrogen valve, the cooling rear disappointing autoclave discharging of opening, filter catalyzer, filtrate is through efficient liquid phase chromatographic analysis, ortho-nitrochlorobenzene transformation efficiency 100%, Ortho-Chloro aniline selectivity 99.5%, dechlorination rate 0.07%.Comparing embodiment 1 and embodiment 4 are known, Pt/C catalyzer containing vanadium can effectively suppress the dechlorination of Ortho-Chloro aniline in ortho-nitrochlorobenzene reduction process, dechlorination rate drops to 0.07% from 0.09%, and the selectivity of Ortho-Chloro aniline is increased, and Ortho-Chloro aniline selectivity brings up to 99.5% from 99.3%.With the reduced liquid aftertreatment of the Pt/C catalyst reduction ortho-nitrochlorobenzene gained containing vanadium, be difficult for the danger of blasting simultaneously.
embodiment 5
By 60g ortho-nitrochlorobenzene and 0.36 g3%Pt/C(water content, being 59.98%) catalyzer joins in 100 milliliters of stainless steel autoclaves, enclosed high pressure still, with air in nitrogen replacement autoclave three times, then with nitrogen in hydrogen exchange still three times and keep certain pressure in still.Under stirring, be warming up to 120 ℃, maintain reaction pressure 2.25MPa, react 120 minutes, after reaction finishes, close hydrogen valve, the cooling rear disappointing autoclave discharging of opening, filter catalyzer, filtrate is through efficient liquid phase chromatographic analysis, ortho-nitrochlorobenzene transformation efficiency 100%, Ortho-Chloro aniline selectivity 98.3%, dechlorination rate 0.27%.
embodiment 6
By 60g ortho-nitrochlorobenzene and 0.36 g3%Pt/C(water content, being 59.98%) catalyzer joins in 100 milliliters of stainless steel autoclaves, enclosed high pressure still, with air in nitrogen replacement autoclave three times, then with nitrogen in hydrogen exchange still three times and keep certain pressure in still.Under stirring, be warming up to 100 ℃, maintain reaction pressure 2.25MPa, react 120 minutes, after reaction finishes, close hydrogen valve, the cooling rear disappointing autoclave discharging of opening, filter catalyzer, filtrate is through efficient liquid phase chromatographic analysis, ortho-nitrochlorobenzene transformation efficiency 100%, Ortho-Chloro aniline selectivity 99.0%, dechlorination rate 0.12%.
embodiment 7
By 60g ortho-nitrochlorobenzene and 0.36 g3%Pt/C(water content, being 59.98%) catalyzer joins in 100 milliliters of stainless steel autoclaves, enclosed high pressure still, with air in nitrogen replacement autoclave three times, then with nitrogen in hydrogen exchange still three times and keep certain pressure in still.Under stirring, be warming up to 90 ℃, maintain reaction pressure 2.25MPa, react 120 minutes, after reaction finishes, close hydrogen valve, the cooling rear disappointing autoclave discharging of opening, filter catalyzer, filtrate is through efficient liquid phase chromatographic analysis, ortho-nitrochlorobenzene transformation efficiency 99.8%, Ortho-Chloro aniline selectivity 99.4%, dechlorination rate 0.07%.
embodiment 8
By 60g ortho-nitrochlorobenzene and 0.36 g3%Pt/C(water content, being 59.98%) catalyzer joins in 100 milliliters of stainless steel autoclaves, enclosed high pressure still, with air in nitrogen replacement autoclave three times, then with nitrogen in hydrogen exchange still three times and keep certain pressure in still.Under stirring, be warming up to 70 ℃, maintain reaction pressure 2.25MPa, react 120 minutes, after reaction finishes, close hydrogen valve, the cooling rear disappointing autoclave discharging of opening, filter catalyzer, filtrate is through efficient liquid phase chromatographic analysis, ortho-nitrochlorobenzene transformation efficiency 82.3%, Ortho-Chloro aniline selectivity 99.6%, dechlorination rate 0.02%.
embodiment 9
By 60g ortho-nitrochlorobenzene and 0.36 g3%Pt/C(water content, being 59.98%) catalyzer joins in 100 milliliters of stainless steel autoclaves, enclosed high pressure still, with air in nitrogen replacement autoclave three times, then with nitrogen in hydrogen exchange still three times and keep certain pressure in still.Under stirring, be warming up to 95 ℃, maintain reaction pressure 2.0MPa, react 120 minutes, after reaction finishes, close hydrogen valve, the cooling rear disappointing autoclave discharging of opening, filter catalyzer, filtrate is through efficient liquid phase chromatographic analysis, ortho-nitrochlorobenzene transformation efficiency 99.8%, Ortho-Chloro aniline selectivity 99.4%, dechlorination rate 0.08%.
embodiment 10
By 60g ortho-nitrochlorobenzene and 0.36 g3%Pt/C(water content, being 59.98%) catalyzer joins in 100 milliliters of stainless steel autoclaves, enclosed high pressure still, with air in nitrogen replacement autoclave three times, then with nitrogen in hydrogen exchange still three times and keep certain pressure in still.Under stirring, be warming up to 95 ℃, maintain reaction pressure 3.0MPa, react 120 minutes, after reaction finishes, close hydrogen valve, the cooling rear disappointing autoclave discharging of opening, filter catalyzer, filtrate is through efficient liquid phase chromatographic analysis, ortho-nitrochlorobenzene transformation efficiency 100%, Ortho-Chloro aniline selectivity 99.1%, dechlorination rate 0.10%.
embodiment 11
By 60g ortho-nitrochlorobenzene and 0.30 g3%Pt/C(water content, being 59.98%) catalyzer joins in 100 milliliters of stainless steel autoclaves, enclosed high pressure still, with air in nitrogen replacement autoclave three times, then with nitrogen in hydrogen exchange still three times and keep certain pressure in still.Under stirring, be warming up to 95 ℃, maintain reaction pressure 2.25MPa, react 120 minutes, after reaction finishes, close hydrogen valve, the cooling rear disappointing autoclave discharging of opening, filter catalyzer, filtrate is through efficient liquid phase chromatographic analysis, ortho-nitrochlorobenzene transformation efficiency 98.9%, Ortho-Chloro aniline selectivity 99.4%, dechlorination rate 0.07%.
embodiment 12
By 60g ortho-nitrochlorobenzene and 0.45 g3%Pt/C(water content, being 59.98%) catalyzer joins in 100 milliliters of stainless steel autoclaves, enclosed high pressure still, with air in nitrogen replacement autoclave three times, then with nitrogen in hydrogen exchange still three times and keep certain pressure in still.Under stirring, be warming up to 95 ℃, maintain reaction pressure 2.25MPa, react 120 minutes, after reaction finishes, close hydrogen valve, the cooling rear disappointing autoclave discharging of opening, filter catalyzer, filtrate is through efficient liquid phase chromatographic analysis, ortho-nitrochlorobenzene transformation efficiency 100%, Ortho-Chloro aniline selectivity 98.7%, dechlorination rate 0.15%.
embodiment 13
By the condition of embodiment 1, carrying out 3%Pt/C(water content is 59.98%) catalyzer applies mechanically, and adds 0.018 g live catalyst at every turn, applies mechanically 60 times, and catalyst activity is stable, and reduction is in order.
The recycled result of table 3%Pt/C catalyzer
| Apply mechanically number of times | Transformation efficiency, % | Selectivity, % | Dechlorination rate, % |
| 1 | 100 | 99.2 | 0.09 |
| 2 | 100 | 99.2 | 0.09 |
| 3 | 100 | 99.2 | 0.09 |
| 4 | 100 | 99.2 | 0.08 |
| 5 | 100 | 99.3 | 0.08 |
| … | … | … | … |
| 26 | 100 | 99.3 | 0.08 |
| 27 | 100 | 99.3 | 0.08 |
| 28 | 100 | 99.3 | 0.08 |
| 29 | 100 | 99.4 | 0.08 |
| 30 | 100 | 99.3 | 0.08 |
| … | … | … | … |
| 56 | 100 | 99.4 | 0.08 |
| 57 | 100 | 99.3 | 0.07 |
| 58 | 100 | 99.4 | 0.08 |
| 59 | 100 | 99.4 | 0.08 |
| 60 | 100 | 99.5 | 0.07 |
Claims (9)
1. the method for a solvent-free preparing o-chloroaniline by catalytic hydrogenation, take ortho-nitrochlorobenzene as raw material, it is characterized in that: ortho-nitrochlorobenzene is under catalyzer exists, and under 70 ℃～120 ℃ and 0.5MPa～5.0MPa pressure, with hydrogen reaction, reaction finishes aftertreatment and obtains Ortho-Chloro aniline.
2. the method for claim 1, is characterized in that described catalyzer is platinum/C catalyst, and wherein the quality percentage composition of platinum is 1%～5%.
3. method as claimed in claim 2, is characterized in that the platinum quality percentage composition of described platinum/C catalyst is 3%.
4. method as claimed in claim 3, is characterized in that described platinum/C catalyst contains vanadium, and the quality percentage composition of vanadium is 0.1～2%.
5. method as claimed in claim 4, is characterized in that described platinum/C catalyst contains vanadium, and the quality percentage composition of vanadium is 0.5%.
6. the method as described in one of claim 1～5, is characterized in that described catalyst levels is 0.02%～5% of raw material ortho-nitrochlorobenzene quality.
7. method as claimed in claim 6, is characterized in that described catalyst levels is 0.05%～0.5% of raw material ortho-nitrochlorobenzene quality.
8. the method for claim 1, is characterized in that described temperature of reaction is 80 ℃～110 ℃.
9. the method for claim 1, is characterized in that described reaction pressure is 2.0MPa～3.5MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210330392.9A CN103664641B (en) | 2012-09-10 | 2012-09-10 | A kind of method of solvent-free preparing o-chloroaniline by catalytic hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210330392.9A CN103664641B (en) | 2012-09-10 | 2012-09-10 | A kind of method of solvent-free preparing o-chloroaniline by catalytic hydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103664641A true CN103664641A (en) | 2014-03-26 |
| CN103664641B CN103664641B (en) | 2016-01-20 |
Family
ID=50303531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210330392.9A Active CN103664641B (en) | 2012-09-10 | 2012-09-10 | A kind of method of solvent-free preparing o-chloroaniline by catalytic hydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103664641B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108821981A (en) * | 2018-05-03 | 2018-11-16 | 浙江解氏新材料股份有限公司 | A kind of catalytic hydrogenation process of the nitroaromatic containing chlorine |
| CN108911991A (en) * | 2018-08-17 | 2018-11-30 | 济南和润化工科技有限公司 | A kind of method of solvent-free catalytic hydrogenation production 2,3,4- trifluoromethyl aniline |
| CN108997138A (en) * | 2018-08-17 | 2018-12-14 | 济南和润化工科技有限公司 | A kind of method of solvent-free catalytic hydrogenation production para-fluoroaniline |
| CN114618504A (en) * | 2022-04-14 | 2022-06-14 | 大连理工大学 | Nickel-oxide composite catalyst for preparing iodoarylamine from iodoaromatic nitro compound at high selectivity and application of nickel-oxide composite catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3882048A (en) * | 1972-03-23 | 1975-05-06 | Bayer Ag | Supported vanadium-palladium-containing catalyst |
| US6096924A (en) * | 1995-05-19 | 2000-08-01 | Novartis Ag | Process for the catalytic hydrogeneration of aromatic nitro compounds |
| CN101811973A (en) * | 2010-04-23 | 2010-08-25 | 浙江工业大学 | Method for synthesizing halogen aromatic amines by high-selectivity liquid phase hydrogenation under the condition of no solvent |
| CN101875610A (en) * | 2009-04-29 | 2010-11-03 | 拜尔材料科学股份公司 | Process for preparing aromatic amines |
| CN102285891A (en) * | 2011-06-30 | 2011-12-21 | 浙江工业大学 | Method for preparing arylamine by catalytic hydrogenation of aromatic nitro compound |
-
2012
- 2012-09-10 CN CN201210330392.9A patent/CN103664641B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3882048A (en) * | 1972-03-23 | 1975-05-06 | Bayer Ag | Supported vanadium-palladium-containing catalyst |
| US6096924A (en) * | 1995-05-19 | 2000-08-01 | Novartis Ag | Process for the catalytic hydrogeneration of aromatic nitro compounds |
| CN101875610A (en) * | 2009-04-29 | 2010-11-03 | 拜尔材料科学股份公司 | Process for preparing aromatic amines |
| CN101811973A (en) * | 2010-04-23 | 2010-08-25 | 浙江工业大学 | Method for synthesizing halogen aromatic amines by high-selectivity liquid phase hydrogenation under the condition of no solvent |
| CN102285891A (en) * | 2011-06-30 | 2011-12-21 | 浙江工业大学 | Method for preparing arylamine by catalytic hydrogenation of aromatic nitro compound |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108821981A (en) * | 2018-05-03 | 2018-11-16 | 浙江解氏新材料股份有限公司 | A kind of catalytic hydrogenation process of the nitroaromatic containing chlorine |
| CN108911991A (en) * | 2018-08-17 | 2018-11-30 | 济南和润化工科技有限公司 | A kind of method of solvent-free catalytic hydrogenation production 2,3,4- trifluoromethyl aniline |
| CN108997138A (en) * | 2018-08-17 | 2018-12-14 | 济南和润化工科技有限公司 | A kind of method of solvent-free catalytic hydrogenation production para-fluoroaniline |
| CN108911991B (en) * | 2018-08-17 | 2021-03-23 | 济宁市金泰利华化工科技有限公司 | Method for producing 2,3, 4-trifluoroaniline by solvent-free catalytic hydrogenation method |
| CN114618504A (en) * | 2022-04-14 | 2022-06-14 | 大连理工大学 | Nickel-oxide composite catalyst for preparing iodoarylamine from iodoaromatic nitro compound at high selectivity and application of nickel-oxide composite catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103664641B (en) | 2016-01-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103664642B (en) | A kind of method adopting microchannel reaction unit to prepare Ortho-Chloro aniline | |
| CN103664641B (en) | A kind of method of solvent-free preparing o-chloroaniline by catalytic hydrogenation | |
| CN101333169A (en) | Method for producing o-chloroaniline | |
| CN103804242A (en) | Method for preparation of m-aminobenzenesulfonic acid by catalytic hydrogenation | |
| CN103694124B (en) | A kind of highly selective prepares the method for 3,4-dichlorphenamide bulk powder | |
| CN101774930A (en) | Method for preparing m-chloro aniline | |
| CN105566126A (en) | Method for preparing 2-amino-4-nitrophenol through liquid catalytic hydrogenation | |
| CN102050746A (en) | Method for preparing o-chloroaniline | |
| CN102633647A (en) | Environment-friendly preparation method of tert-butylamine | |
| CN1962608A (en) | Catalytic hydrogenation method for preparing 3,4-dichloroaniline | |
| WO2018133196A1 (en) | Phosphor-doped carbon material hydrogenation catalyst, preparation method therefor and use thereof | |
| CN102336673A (en) | Method for preparing 3,4-dichloroaniline through catalytic hydrogenation | |
| CN100418943C (en) | Production method of 3,4-dichloro aniline | |
| CN1199935C (en) | Production process of catalytically hydrogenating nitrobenzene halide to synthesize haloarylamine | |
| CN110054582B (en) | Preparation method of 3-amino-N-ethyl carbazole | |
| CN101434547B (en) | Method for preparing aniline from nitrobenzene | |
| CN100436403C (en) | Method for preparing o-chloroaniline | |
| CN102757352A (en) | Production process for preparing parachloroaniline by catalytic hydrogenation of para-nitrochlorobenzene | |
| CN109336770A (en) | A kind of method that solvent-free hydrogenating reduction method prepares 3,4- dichloroaniline | |
| CN101475488A (en) | Method for preparing aminotoluene by catalytic hydrogenation of 2,4-dinitrotoluene or/and 2,6-dinitrotoluene | |
| CN104292113A (en) | Preparation method of 3-chloro-4-fluoroaniline | |
| CN101434549A (en) | Method for preparing 1,4-3 diaminonaphthalene from 1,4-dinitronaphthalene | |
| CN104058933A (en) | Biodiesel based crude glycerol catalytic hydrogenolysis method for preparation of propylene glycol | |
| CN101475515A (en) | Method for preparing 5-amino-2-chloro-N-(2,4-xylyl)-benzene sulfonic amide in water phase | |
| CN106892829A (en) | The method that p-nitrophenol catalytic hydrogenation prepares para-aminophenol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | 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 | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee after: China Petroleum & Chemical Corp. Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee before: China Petroleum & Chemical Corp. Patentee before: Nanhua Group Research Institute |