CN102633653A - Method for preparing o-phenylenediamine by catalytic hydrogenation of o-nitrophenylamine - Google Patents
Method for preparing o-phenylenediamine by catalytic hydrogenation of o-nitrophenylamine Download PDFInfo
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- CN102633653A CN102633653A CN2011100428881A CN201110042888A CN102633653A CN 102633653 A CN102633653 A CN 102633653A CN 2011100428881 A CN2011100428881 A CN 2011100428881A CN 201110042888 A CN201110042888 A CN 201110042888A CN 102633653 A CN102633653 A CN 102633653A
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- Prior art keywords
- nitraniline
- phenylene diamine
- reaction
- shortening
- phenylenediamine
- 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.)
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- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 title claims abstract description 32
- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006722 reduction reaction Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000004904 shortening Methods 0.000 claims description 12
- 230000001476 alcoholic effect Effects 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- 230000009467 reduction Effects 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000004821 distillation Methods 0.000 abstract description 2
- 239000000446 fuel Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 abstract 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 7
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 3
- 230000000994 depressogenic effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- IZUKQUVSCNEFMJ-UHFFFAOYSA-N 1,2-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1[N+]([O-])=O IZUKQUVSCNEFMJ-UHFFFAOYSA-N 0.000 description 2
- 238000004176 ammonification Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- TWFZGCMQGLPBSX-UHFFFAOYSA-N Carbendazim Natural products C1=CC=C2NC(NC(=O)OC)=NC2=C1 TWFZGCMQGLPBSX-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000006013 carbendazim Substances 0.000 description 1
- JNPZQRQPIHJYNM-UHFFFAOYSA-N carbendazim Chemical compound C1=C[CH]C2=NC(NC(=O)OC)=NC2=C1 JNPZQRQPIHJYNM-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- KOOMFXGDLMRWSN-UHFFFAOYSA-N n-phenylnitrous amide Chemical group O=NNC1=CC=CC=C1 KOOMFXGDLMRWSN-UHFFFAOYSA-N 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing o-phenylenediamine by catalytic hydrogenation of o-nitrophenylamine. The method is characterized in that: in the hydrogenation reaction of o-nitrophenylamine, alcohol is used as a solvent, nickel is used as a catalyst, reduction reaction is performed for 2 to 10 hours under the hydrogen pressure of 1.0 to 6 MPa at the temperature of between 40 and 80 DEG C, and the reaction product is rectified to form the while o-phenylenediamine. The method has the advantages that the alcohol is used as the solvent in the catalytic hydrogenation for producing o-phenylenediamine, the alcohol can be reclaimed and directly used for next reaction, and the waste residue produced by distillation can be used as an organic fuel, so that the problem that a large amount of waste water containing organic substances is produced in reduction of iron powder or sodium sulfide in the conventional process is solved; and thick acid and thick alkali used in the conventional process are avoided in the hydrogenation process, so that corrosion of equipment is greatly reduced, pollution is reduced, and almost zero pollution is realized. In addition, compared with the conventional iron powder or sodium sulfide reduction, the catalytic hydrogenation process has the advantages of low pollution, high yield, high quality, short production period and low energy consumption.
Description
Technical field
The present invention relates to a kind of o-Nitraniline shortening and produce the method for O-Phenylene Diamine.
Background technology
O-Phenylene Diamine is the important intermediate of dyestuff, agricultural chemicals, auxiliary agent, sensitive materials etc.Itself be the yellowish-brown M of dyestuff fur.Be used to make polymeric amide, urethane, fungicide carbendazim and mildethane, vat scarlet GG, levelling agent, antioxidant MB, also be used to prepare photographic developer, tensio-active agent etc.
Feasible route has following three types at present:
One: O-Phenylene Diamine is produced in the direct ammonification of orthodichlorobenzene
O-Phenylene Diamine is produced in the direct ammonification of orthodichlorobenzene because the amine impurity produced is many, exist follow-up when refining difficulty bigger, if solve this industriallization difficult problem, will have reasonable application prospect future.
Two: O-Phenylene Diamine is produced in the o-dinitrobenzene reduction
O-Phenylene Diamine is produced in o-dinitrobenzene reduction, mainly is the also by-product during the original production mphenylenediamine of mix dinitrobenzene in the industry, seriously receives the restriction of raw material.
Three: O-Phenylene Diamine is produced in the o-Nitraniline reduction
This is to use the widest industrialized route at present, and the product yield that obtains is high, quality better.
Summary of the invention
Main task of the present invention is to provide a kind of o-Nitraniline shortening to produce the method for O-Phenylene Diamine, and specifically a kind of on traditional technology, the improvement obtains.The traditional technology o-Nitraniline is iron powder or sodium sulphite in still, under the acidic conditions, and behind 80-90 ℃ of reaction 8-9h, alkalization, cooling obtains bullion, and rectifying obtains elaboration again, and yield is about 80%, and purity is poor generally about 90%.
In order to solve above technical problem, a kind of o-Nitraniline shortening of the present invention is produced the method for O-Phenylene Diamine, it is characterized in that: in the said o-Nitraniline hydrogenation reaction; Alcohol is made solvent; Nickel is made catalyzer, at the hydrogen pressure of 1.0-6 MPa, under 40-80 ℃ the temperature; Behind the reduction reaction 2-10h, rectifying obtains white O-Phenylene Diamine again.
Further, described nickel catalyzator is the Powdered nickel of at least 200 purposes, and its consumption is the 3%-10% mass percent of o-Nitraniline.
Further, described alcoholic solvent is a kind of in methyl alcohol, ethanol, the Virahol.
Further, the mass ratio of described alcoholic solvent consumption and o-Nitraniline: between 1:1-10:1.
Further, the mass ratio of described alcoholic solvent consumption and o-Nitraniline is 2:1-4:1.
Further, said reduction reaction temperature is 60-70 ℃; Reaction times is 2-3h.
Further, said hydrogen pressure is 1-2 MPa.
Reaction equation of the present invention is:
Owing to produce in the reaction of O-Phenylene Diamine at the o-Nitraniline hydrogenation, the main side reaction that exists is that the o-Nitraniline reduction generates adjacent nitrosoaniline, and the nitroso compound of generation is generating coupling compound with the O-Phenylene Diamine that generates.The homemade high order of my company is counted catalyzer with regard to good this problem that solved.
Advantage of the present invention is following: by the old and new's technology process comparative result be: shortening is produced O-Phenylene Diamine and is done can directly overlap after solvent and used alcohol reclaim with alcohol again and use the next batch reaction; The waste residue that distillation produces can be regarded organic-fuel; What solved that iron powder in the traditional technology or sodium sulphite reduction produce contains the organic waste water problem in a large number; Avoid using in the traditional technology concentrated acid, concentrated base in the hydrogenation technique simultaneously; Significantly reduced corrosion on Equipment, reduced pollution, accomplished that basic zero pollutes.In this; Hydrogenation technique is compared with traditional reducing process; Product yield rises to more than 90% from original 80%, and the quality of product rises to 99% from original 95%, greatly reduces material loss; High-quality O-Phenylene Diamine has improved the market competitiveness of my Company products simultaneously, has also solved the impurity problem in the derived product production process.Simultaneously, the reduction of hydrogenation technique only needs at 60 ℃, and 2h just can accomplish, and compares with 80-90 ℃ of maintenance 8h of traditional technology, the brief greatly reaction times, reduced the production cycle, and reduced production energy consumption, the call of the country of response " energy-saving consumption-reducing ".In a word, catalytic hydrogenation process and original iron powder or sodium sulphite reduction are compared, have pollute little, yield is high, quality is high, with short production cycle, advantage of low energy consumption.
Embodiment
Instance 1:
With o-Nitraniline 150g, methyl alcohol 300g joins in the autoclave, adds self-control 200 order Ni catalyzer 7.5g simultaneously; Airtight autoclave is opened the hydrogen valve, in autoclave, feeds hydrogen; Take a breath 3 times, regulate still and be depressed into 2.0 MPa, stir and be warming up to 60-70 ℃ of reaction; Cause pressure and do not changing (about 2-3h), take a sample, through gas chromatographic analysis O-Phenylene Diamine content 98.50% as a result.
Instance 2:
With o-Nitraniline 500 g, methyl alcohol 1000g joins in the autoclave, adds self-control Ni catalyzer 25g simultaneously, and airtight autoclave is opened the hydrogen valve; In autoclave, feed hydrogen, take a breath 3 times, regulate still and be depressed into 2.0 MPa, stir and be warming up to 60-70 ℃ of reaction; Cause pressure and do not changing (about 2-3h), take a sample, through gas chromatographic analysis O-Phenylene Diamine content 98.78% as a result, behind the reacting liquid filtering; Reclaim solvent, rectifying obtains white O-Phenylene Diamine 360g again, and GC detects 99.9%, yield 92.0%.
Instance 3:
With o-Nitraniline 2000 g, methyl alcohol 4000g joins in the autoclave, adds self-control Ni catalyzer 25g simultaneously, and airtight autoclave is opened the hydrogen valve; In autoclave, feed hydrogen, take a breath 3 times, regulate still and be depressed into 2.0 MPa, stir and be warming up to 60-70 ℃ of reaction; Cause pressure and do not changing (about 2-3h), take a sample, through gas chromatographic analysis O-Phenylene Diamine content 99.00% as a result, behind the reacting liquid filtering; Reclaim solvent, rectifying obtains white O-Phenylene Diamine 1455g again, and GC detects 99.9%, yield 92.95%.
Claims (7)
1. an o-Nitraniline shortening is produced the method for O-Phenylene Diamine, and it is characterized in that: in the said o-Nitraniline hydrogenation reaction, alcohol is made solvent; Nickel is made catalyzer, at the hydrogen pressure of 1.0-6 MPa, under 40-80 ℃ the temperature; Behind the reduction reaction 2-10h, rectifying obtains white O-Phenylene Diamine again.
2. produce the method for O-Phenylene Diamine according to claim 1 o-Nitraniline shortening, it is characterized in that: described nickel catalyzator is the Powdered nickel of at least 200 purposes, and its consumption is the 3%-10% mass percent of o-Nitraniline.
3. produce the method for O-Phenylene Diamine according to claim 1 o-Nitraniline shortening, it is characterized in that: described alcoholic solvent is a kind of in methyl alcohol, ethanol, the Virahol.
4. produce the method for O-Phenylene Diamine according to claim 1 o-Nitraniline shortening, it is characterized in that: the mass ratio of described alcoholic solvent consumption and o-Nitraniline: between 1:1-10:1.
5. produce the method for O-Phenylene Diamine according to claim 4 o-Nitraniline shortening, it is characterized in that: the mass ratio of described alcoholic solvent consumption and o-Nitraniline is 2:1-4:1.
6. produce the method for O-Phenylene Diamine according to claim 1 o-Nitraniline shortening, it is characterized in that: said reduction reaction temperature is 60-70 ℃; Reaction times is 2-3h.
7. produce the method for O-Phenylene Diamine according to claim 1 o-Nitraniline shortening, it is characterized in that: said hydrogen pressure is 1-2 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100428881A CN102633653A (en) | 2011-02-23 | 2011-02-23 | Method for preparing o-phenylenediamine by catalytic hydrogenation of o-nitrophenylamine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100428881A CN102633653A (en) | 2011-02-23 | 2011-02-23 | Method for preparing o-phenylenediamine by catalytic hydrogenation of o-nitrophenylamine |
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| Publication Number | Publication Date |
|---|---|
| CN102633653A true CN102633653A (en) | 2012-08-15 |
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| CN2011100428881A Pending CN102633653A (en) | 2011-02-23 | 2011-02-23 | Method for preparing o-phenylenediamine by catalytic hydrogenation of o-nitrophenylamine |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827008A (en) * | 2012-10-16 | 2012-12-19 | 江苏科圣化工机械有限公司 | Method and device for producing phenylenediamine by taking water as solvent through liquid phase continuous hydrogenation method |
| CN103787893A (en) * | 2013-11-20 | 2014-05-14 | 南通波涛化工有限公司 | O-phenylenediamine medium-pressure catalytic hydrogenation process |
| CN104086441A (en) * | 2014-06-10 | 2014-10-08 | 安徽华润涂料有限公司 | Novel preparation method of o-phenylenediamine |
| CN104744267A (en) * | 2015-04-15 | 2015-07-01 | 西安凯立化工有限公司 | Method for synthesizing o-phenylenediamine from ortho-nitroaniline by virtue of catalytic hydrogenation |
| CN105001097A (en) * | 2015-06-11 | 2015-10-28 | 安徽东至广信农化有限公司 | O-phenylenediamine mother solution deaminizing and ammonia gas removal method |
| CN105037171A (en) * | 2015-06-08 | 2015-11-11 | 江阴市华亚化工有限公司 | Method for synthesizing and preparing o-phenylenediamine from orthodichlorobenzene |
| CN106349081A (en) * | 2016-08-29 | 2017-01-25 | 江苏天嘉宜化工有限公司 | Synthesis method of 3,4-diaminotoluene |
| CN111217712A (en) * | 2020-01-21 | 2020-06-02 | 江苏扬农化工集团有限公司 | Method for preparing o-phenylenediamine from aniline |
-
2011
- 2011-02-23 CN CN2011100428881A patent/CN102633653A/en active Pending
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| 左东华等: "纳米镍在硝基苯加氢中催化性能的研究", 《分子催化》 * |
| 杜艳等: "纳米镍粉的制备及其对对硝基苯酚催化加氢的影响", 《精细石油化工》 * |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827008A (en) * | 2012-10-16 | 2012-12-19 | 江苏科圣化工机械有限公司 | Method and device for producing phenylenediamine by taking water as solvent through liquid phase continuous hydrogenation method |
| CN103787893A (en) * | 2013-11-20 | 2014-05-14 | 南通波涛化工有限公司 | O-phenylenediamine medium-pressure catalytic hydrogenation process |
| CN104086441A (en) * | 2014-06-10 | 2014-10-08 | 安徽华润涂料有限公司 | Novel preparation method of o-phenylenediamine |
| CN104744267A (en) * | 2015-04-15 | 2015-07-01 | 西安凯立化工有限公司 | Method for synthesizing o-phenylenediamine from ortho-nitroaniline by virtue of catalytic hydrogenation |
| CN105037171A (en) * | 2015-06-08 | 2015-11-11 | 江阴市华亚化工有限公司 | Method for synthesizing and preparing o-phenylenediamine from orthodichlorobenzene |
| CN105001097A (en) * | 2015-06-11 | 2015-10-28 | 安徽东至广信农化有限公司 | O-phenylenediamine mother solution deaminizing and ammonia gas removal method |
| CN106349081A (en) * | 2016-08-29 | 2017-01-25 | 江苏天嘉宜化工有限公司 | Synthesis method of 3,4-diaminotoluene |
| CN111217712A (en) * | 2020-01-21 | 2020-06-02 | 江苏扬农化工集团有限公司 | Method for preparing o-phenylenediamine from aniline |
| CN111217712B (en) * | 2020-01-21 | 2023-01-10 | 江苏扬农化工集团有限公司 | Method for preparing o-phenylenediamine from aniline |
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Application publication date: 20120815 |