CN102757352A - Production process for preparing parachloroaniline by catalytic hydrogenation of para-nitrochlorobenzene - Google Patents
Production process for preparing parachloroaniline by catalytic hydrogenation of para-nitrochlorobenzene Download PDFInfo
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- CN102757352A CN102757352A CN201210163472XA CN201210163472A CN102757352A CN 102757352 A CN102757352 A CN 102757352A CN 201210163472X A CN201210163472X A CN 201210163472XA CN 201210163472 A CN201210163472 A CN 201210163472A CN 102757352 A CN102757352 A CN 102757352A
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- para
- nitrochloro
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- acid amide
- chlorobenzoic acid
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- YFYWXINRFIZMRI-UHFFFAOYSA-N [O-][NH+](c(cc1)ccc1Cl)I Chemical compound [O-][NH+](c(cc1)ccc1Cl)I YFYWXINRFIZMRI-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a production process for preparing chloroaniline by catalytic hydrogenation of para-nitrochlorobenzene. The meta-chloroaniline is prepared by catalytic hydrogenation of para-nitrochlorobenzene as raw material in methanol as solvent in the presence of Raney-Ni catalyst and dicyandiamide as a dechlorination inhibotor at 55 DEG C under 1 MPa. According to the process, the selectivity of parachloroaniline is more than 98.5%, and the dechlorination rate is less than 0.5%.
Description
Technical field
The present invention relates to a kind of production technique of p-Chlorobenzoic acid amide, specifically is a kind of production technique that adopts hydrogenation technique to prepare p-Chlorobenzoic acid amide.
Background technology
P-Chlorobenzoic acid amide is a kind of important fine-chemical intermediate, is widely used in the production of fine chemicals such as agricultural chemicals, dyestuff, medicine.Traditional nitroreduction mainly contains iron powder reducing method, sodium sulfide reducing method, catalytic hydrogenating reduction method, electrochemical reducing.The iron powder reducing method produces a large amount of iron mud, serious environment pollution; Shortcomings such as the sodium sulfide reducing method exists the reduction route complicated, and product yield is low, and waste liquid amount is big; The electrochemical reducing energy consumption is too high; The shortening method route that responds is short, and energy consumption is low, advantages of environment protection.But, prepare in the process of p-Chlorobenzoic acid amide at the p-Nitrophenyl chloride shortening, because the C-Cl key is prone to the side reaction that the hydrogenolysis dechlorination generates aniline takes place on the phenyl ring, thereby reduced the yield of principal product in the presence of metal catalyst.Simultaneously, the hydrogenchloride of dechlorination generation also can cause corrosion to equipment.The method that addresses this problem has two kinds: (1) adds the dechlorination suppressor factor in reaction system; (2) performance of reduction catalyzer reaches the purpose that suppresses dechlorination.
Summary of the invention
The present invention provides a kind of can suppress hydrodechlorination, and the p-Nitrophenyl chloride shortening that can obtain high yield prepares the method for p-Chlorobenzoic acid amide.
In order to solve above technical problem; A kind of para-nitrochloro-benzene shortening of the present invention prepares the production technique of p-Chlorobenzoic acid amide; It is characterized in that: be raw material with the p-Nitrophenyl chloride; With the alcoholic solution is solvent; Raney-Ni is a catalyzer, and Dyhard RU 100 is the dechlorination suppressor factor, at 20-80 ℃; Shortening prepares p-Chlorobenzoic acid amide under the hydrogen pressure 0.5-2MPa, and reaction equation is following:
.
Wherein, described Raney-Ni catalyst levels is the 3%-20% of p-Nitrophenyl chloride, and it is 5% for good that this patent requires.
Described alcoholic solution is: it is best that a kind of in methyl alcohol, ethanol, the Virahol, the present invention require methyl alcohol.
Wherein methanol usage and para-nitrochloro-benzene mass ratio are between 1:1-1:5, and it is good that the present invention requires with 1:1.5.
Selected anti-dechlorination thing is generally organic amine, as: aniline, Monoethanolamine MEA BASF, diethylolamine, trolamine, diethylamine, triethylamine, pyridine and pyridines low molecular compound, piperidines and piperidines etc., the present invention requires Dyhard RU 100 to be advisable.
The consumption of dechlorination suppressor factor Dyhard RU 100 is the 10%-60% of Raney-Ni quality, and it is 30% that the present invention requires.
Described temperature of reaction can be at 20-80 ℃, and the present invention requires 50-60 ℃ for good.
Hydrogenation pressure can be between 0.5-2MPa, and it is good that the present invention requires 0.8-1.0MPa.
Reaction times can be between 4-8h, and requirement of following reaction times of condition of the present invention is good for 4h.
Advantage of the present invention:
This technology had both suppressed hydrodechlorination, also obtained high yield, yield be p-Nitrophenyl chloride content more than or equal to 98.15%, aniline is smaller or equal to 0.38%.
Specific examples:
Instance one:
P-Nitrophenyl chloride 100 g, methyl alcohol 150g are joined in the 1L autoclave, add Raney-Ni catalyzer 5 g simultaneously, Dyhard RU 100 1.5g; Airtight autoclave is opened the hydrogen valve, in autoclave, feeds hydrogen; Take a breath 3 times, regulate still and be depressed into 1.0 MPa, stir and be warming up to 55 ℃ of reaction 4h.Sampling is through gas chromatographic analysis p-Nitrophenyl chloride content 98.95% as a result, aniline 0.45%.
Instance two:
P-Nitrophenyl chloride 150 g, methyl alcohol 225g are joined in the 1L autoclave, add Raney-Ni catalyzer 7.5 g simultaneously, Dyhard RU 100 2.1g; Airtight autoclave is opened the hydrogen valve, in autoclave, feeds hydrogen; Take a breath 3 times, regulate still and be depressed into 1.0 MPa, stir and be warming up to 55 ℃ of reaction 4h.Sampling is through gas chromatographic analysis p-Nitrophenyl chloride content 99.03% as a result, aniline 0.48%.
Instance three:
P-Nitrophenyl chloride 200 g, methyl alcohol 300g are joined in the 1L autoclave, add Raney-Ni catalyzer 10 g simultaneously, Dyhard RU 100 3g; Airtight autoclave is opened the hydrogen valve, in autoclave, feeds hydrogen; Take a breath 3 times, regulate still and be depressed into 1.0 MPa, stir and be warming up to 55 ℃ of reaction 4h.Sampling is through gas chromatographic analysis p-Nitrophenyl chloride content 99.15% as a result, aniline 0.38%.
Instance four:
P-Nitrophenyl chloride 300 g, methyl alcohol 450g are joined in the 1L autoclave, add Raney-Ni catalyzer 15 g simultaneously, Dyhard RU 100 4.5g; Airtight autoclave is opened the hydrogen valve, in autoclave, feeds hydrogen; Take a breath 3 times, regulate still and be depressed into 1.0 MPa, stir and be warming up to 55 ℃ of reaction 4h.Sampling is through gas chromatographic analysis p-Nitrophenyl chloride content 99.05% as a result, aniline 0.41%.
Claims (13)
1. a para-nitrochloro-benzene shortening prepares the production technique of p-Chlorobenzoic acid amide; It is characterized in that: with the p-Nitrophenyl chloride is raw material, is solvent with the alcoholic solution, and Raney-Ni is a catalyzer; Dyhard RU 100 is the dechlorination suppressor factor; At 20-80 ℃, shortening prepares p-Chlorobenzoic acid amide under the hydrogen pressure 0.5-2MPa, and reaction equation is following:
2. a kind of para-nitrochloro-benzene shortening according to claim 1 prepares the production technique of p-Chlorobenzoic acid amide, it is characterized in that: the 3%-20% mass parts that described Raney-Ni catalyst levels is a p-Nitrophenyl chloride.
3. a kind of para-nitrochloro-benzene shortening according to claim 1 prepares the production technique of p-Chlorobenzoic acid amide, it is characterized in that: described Raney-Ni catalyst levels is 5% mass parts of p-Nitrophenyl chloride.
4. a kind of para-nitrochloro-benzene shortening according to claim 1 prepares the production technique of p-Chlorobenzoic acid amide, it is characterized in that: described alcoholic solution is: any one in methyl alcohol, ethanol, the Virahol.
5. a kind of para-nitrochloro-benzene shortening according to claim 1 prepares the production technique of p-Chlorobenzoic acid amide, it is characterized in that: said alcoholic solution is: methyl alcohol.
6. a kind of para-nitrochloro-benzene shortening according to claim 1 prepares the production technique of p-Chlorobenzoic acid amide, it is characterized in that: said methanol usage and para-nitrochloro-benzene mass ratio are between 1:1-1:5.
7. a kind of para-nitrochloro-benzene shortening according to claim 1 prepares the production technique of p-Chlorobenzoic acid amide, it is characterized in that: said methanol usage and para-nitrochloro-benzene mass ratio are at 1:1.5.
8. a kind of para-nitrochloro-benzene shortening according to claim 1 prepares the production technique of p-Chlorobenzoic acid amide, it is characterized in that: selected anti-dechlorination thing is generally organic amine: aniline, Monoethanolamine MEA BASF, diethylolamine, trolamine, diethylamine, triethylamine, pyridine and pyridines low molecular compound, piperidines and piperidines.
9. a kind of para-nitrochloro-benzene shortening according to claim 1 prepares the production technique of p-Chlorobenzoic acid amide, it is characterized in that: the consumption of dechlorination suppressor factor Dyhard RU 100 is the 10%-60% of Raney-Ni quality.
10. a kind of para-nitrochloro-benzene shortening according to claim 1 prepares the production technique of p-Chlorobenzoic acid amide, it is characterized in that: the consumption of dechlorination suppressor factor Dyhard RU 100 is 30% of a Raney-Ni quality.
11. a kind of para-nitrochloro-benzene shortening according to claim 1 prepares the production technique of p-Chlorobenzoic acid amide, it is characterized in that: described temperature of reaction 50-60 ℃.
12. a kind of para-nitrochloro-benzene shortening according to claim 1 prepares the production technique of p-Chlorobenzoic acid amide, it is characterized in that: hydrogenation pressure is between 0.5-2MPa.
13. a kind of para-nitrochloro-benzene shortening according to claim 1 prepares the production technique of p-Chlorobenzoic acid amide, it is characterized in that: hydrogenation pressure is between 0.8-1.0MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210163472XA CN102757352A (en) | 2012-05-24 | 2012-05-24 | Production process for preparing parachloroaniline by catalytic hydrogenation of para-nitrochlorobenzene |
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| CN201210163472XA CN102757352A (en) | 2012-05-24 | 2012-05-24 | Production process for preparing parachloroaniline by catalytic hydrogenation of para-nitrochlorobenzene |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113233A (en) * | 2013-01-11 | 2013-05-22 | 山东富原化工有限公司 | Production method for preparing chlorinated aniline via chlorination of nitrobenzene hydrogenation by utilizing solvent-free process |
| CN109627194A (en) * | 2018-12-28 | 2019-04-16 | 甘肃银光聚银化工有限公司 | A method of the synthesis chloro- toluenesulfonic acid of 2- amino -5- |
| CN110467533A (en) * | 2019-09-26 | 2019-11-19 | 辽宁顺通化工股份有限公司 | A kind of preparation method of parachloroanilinum hydrochloride |
| CN114349644A (en) * | 2020-10-13 | 2022-04-15 | 中石化南京化工研究院有限公司 | Method for preparing dichloroaniline from byproduct mixed dichlorobenzene |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3989756A (en) * | 1973-09-06 | 1976-11-02 | Nippon Kayaku Kabushiki Kaisha | Process for the production of halogenated aromatic primary amines |
| CN101774930A (en) * | 2010-02-10 | 2010-07-14 | 江苏康恒化工有限公司 | Method for preparing m-chloro aniline |
-
2012
- 2012-05-24 CN CN201210163472XA patent/CN102757352A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3989756A (en) * | 1973-09-06 | 1976-11-02 | Nippon Kayaku Kabushiki Kaisha | Process for the production of halogenated aromatic primary amines |
| CN101774930A (en) * | 2010-02-10 | 2010-07-14 | 江苏康恒化工有限公司 | Method for preparing m-chloro aniline |
Non-Patent Citations (1)
| Title |
|---|
| 姚蒙正等: "芳香族硝基化合物还原反应的若干进展", 《化工进展》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113233A (en) * | 2013-01-11 | 2013-05-22 | 山东富原化工有限公司 | Production method for preparing chlorinated aniline via chlorination of nitrobenzene hydrogenation by utilizing solvent-free process |
| CN109627194A (en) * | 2018-12-28 | 2019-04-16 | 甘肃银光聚银化工有限公司 | A method of the synthesis chloro- toluenesulfonic acid of 2- amino -5- |
| CN110467533A (en) * | 2019-09-26 | 2019-11-19 | 辽宁顺通化工股份有限公司 | A kind of preparation method of parachloroanilinum hydrochloride |
| CN114349644A (en) * | 2020-10-13 | 2022-04-15 | 中石化南京化工研究院有限公司 | Method for preparing dichloroaniline from byproduct mixed dichlorobenzene |
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Application publication date: 20121031 |