CN104744267A - Method for synthesizing o-phenylenediamine from ortho-nitroaniline by virtue of catalytic hydrogenation - Google Patents
Method for synthesizing o-phenylenediamine from ortho-nitroaniline by virtue of catalytic hydrogenation Download PDFInfo
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- CN104744267A CN104744267A CN201510181266.5A CN201510181266A CN104744267A CN 104744267 A CN104744267 A CN 104744267A CN 201510181266 A CN201510181266 A CN 201510181266A CN 104744267 A CN104744267 A CN 104744267A
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- IYVGZMSKFQVFEK-OUPQRBNQSA-N C/C=C\C(\N)=C(/C)\N Chemical compound C/C=C\C(\N)=C(/C)\N IYVGZMSKFQVFEK-OUPQRBNQSA-N 0.000 description 1
- 0 CC([N+]([O-])=O)=*(C=CC=C)N Chemical compound CC([N+]([O-])=O)=*(C=CC=C)N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention provides a method for synthesizing o-phenylenediamine from ortho-nitroaniline by virtue of catalytic hydrogenation. The method comprises the following steps: firstly, adding ortho-nitroaniline and a palladium-carbon catalyst into a high-pressure reaction kettle, introducing nitrogen to exhaust air in the kettle, and then introducing hydrogen to exhaust nitrogen in the kettle; secondly, heating and introducing hydrogen, performing catalytic hydrogenation reduction reaction under the conditions that the temperature is 110 DEG C and the pressure is 1.0MPa, reacting for 7-8 hours, then stopping introducing hydrogen, water-cooling, then filtering to recycle the catalyst, and collecting a filtrate after filtration to obtain o-phenylenediamine. According to the method provided by the invention, a raw material namely ortho-nitroaniline is subjected to direct hydrogenation without using a solvent, so that the consumption of the solvent can be greatly reduced, the after-treatment energy consumption can be saved, and large-sized solvent steaming equipment can be saved; and by adopting the method, a separation process can be simplified, the equipment investment, separation energy consumption, material consumption and environmental pollution can be reduced, and the system productivity and production safety can be improved.
Description
Technical field
The invention belongs to technical field of catalytic hydrogenation, be specifically related to the method for a kind of o-Nitraniline shortening synthesis O-Phenylene Diamine.
Background technology
O-Phenylene Diamine is a kind of important chemical intermediate, is mainly used in synthetic pesticide colour additive sensitive materials etc., and tool has been widely used and wide market outlook.Its synthesis technique has sulfuration method, ammoniation process and shortening method etc., and shortening method generally generates product and water, can not generate other by product (except side reaction), has good development prospect.
The method of current production O-Phenylene Diamine mainly contains following several: (1) chemical reduction method; (2) electrolytic reduction; (3) palladium charcoal catalytic hydrogenating reduction method.Wherein, chemical reduction method iron powder, Sodium Sulphide, hydrazine hydrate, hydroborate etc. go back original production, early stage need react under strongly acidic conditions, follow-uply to neutralize with highly basic again, technical process is long, the generation three wastes are many, especially a large amount of iron mud containing amino substance and waste water is produced, big for environment pollution, eliminate this technique abroad.Electrolytic reduction, for the consideration of the aspects such as electrode materials, electrolyzer, cost, has no industrialization report so far at home.Palladium charcoal hydrogenating reduction method has good product quality, produces the few feature of the three wastes, but traditional technology generally adopts methanol as solvent, not only solvent load makes more greatly production cost raise, and solvent need be steamed by main equipment during aftertreatment, therefore aftertreatment technology energy consumption increases, facility investment, separating energy consumption, supplies consumption and environmental pollution increase, and impact system production capacity and production safety.
So far, not yet find that the correlative study that condition of no solvent produces O-Phenylene Diamine is seen in report.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned the deficiencies in the prior art, provides a kind of o-Nitraniline shortening to synthesize the method for O-Phenylene Diamine.The direct shortening of the method raw material o-Nitraniline, without the need to solvent, greatly can save solvent load, save aftertreatment energy consumption, steams solvent equipment without the need to large-scale.The method can simplify separating technology, reduces facility investment, separating energy consumption, supplies consumption and environmental pollution, improves system production capacity and production safety.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of method of o-Nitraniline shortening synthesis O-Phenylene Diamine, and it is characterized in that, the method comprises the following steps:
Step one, o-Nitraniline and palladium carbon catalyst are joined in autoclave, first adopt the method passing into nitrogen to get rid of air in autoclave, then adopt the method passing into hydrogen to get rid of nitrogen in autoclave; The add-on of described palladium carbon catalyst is 0.1% ~ 0.3% of o-Nitraniline quality;
Step 2, to heat getting rid of the autoclave after nitrogen in step one, continue to pass into hydrogen in autoclave simultaneously, it is 110 DEG C in temperature, pressure is make o-Nitraniline generation catalytic hydrogenating reduction react under the condition of 1.0MPa, stop passing into hydrogen after reaction 7h ~ 8h, filtering recovering catalyst after water-cooled, collects the filtrate after filtering, obtains O-Phenylene Diamine.
The method of above-mentioned a kind of o-Nitraniline shortening synthesis O-Phenylene Diamine, it is characterized in that, in palladium carbon catalyst described in step one, the mass percentage of palladium is 3%.
The method of above-mentioned a kind of o-Nitraniline shortening synthesis O-Phenylene Diamine, it is characterized in that, the add-on of palladium carbon catalyst described in step one is 0.15% of o-Nitraniline quality.
The present invention compared with prior art has the following advantages:
1, the present invention take o-Nitraniline as raw material, with palladium charcoal (Pd/C) for catalyzer, low pressure catalytic hydrogenating reduction synthesis O-Phenylene Diamine under condition of no solvent, the present invention uses solvent-free direct hydrogenation, aftertreatment is simply easy, good reaction selectivity, and does not produce other unmanageable three refuses, industrial production has good application and development prospect, and concrete reaction equation is:
2, transformation efficiency 100% of the present invention, yield is more than 96%, solve in traditional technology adopt the reduction such as iron powder or sodium sulphite to produce a large amount of and contain organic waste water problem, avoid in traditional technology, using concentrated acid, concentrated base in hydrogenation technique simultaneously, greatly reduce the corrosion of equipment, decrease pollution, accomplish basic no pollution.In addition, catalytic hydrogenation process of the present invention, compared with traditional technology, has and pollutes the advantage little, yield is high, quality is high, with short production cycle, energy consumption is low.
3, the present invention is without the need to solvent, and its feature is: 1) without the need to a large amount of methyl alcohol equal solvent, and methanol prices is expensive, and therefore the present invention can reduce production cost greatly; 2) save and steam methanol solvate equipment, reduce investment of production equipment expense; 3) making to produce more environmental protection, avoiding because using methyl alcohol, its easy volatile causes intoxicating, the safety problem such as inflammable, explosive occur.
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment
Embodiment 1
The method of the present embodiment o-Nitraniline shortening synthesis O-Phenylene Diamine comprises the following steps:
Step one, the palladium carbon catalyst being 3% by 50g o-Nitraniline and 0.05g palladium mass content join in autoclave, first employing passes into the air in the method eliminating autoclave of nitrogen, and then employing passes into the nitrogen in the method eliminating autoclave of hydrogen;
Step 2, to heat getting rid of the autoclave after nitrogen in step one, continue to pass into hydrogen in autoclave simultaneously, it is 110 DEG C in temperature, pressure is make o-Nitraniline generation catalytic hydrogenating reduction react under the condition of 1.0MPa, stop passing into hydrogen after reaction 8h, filtering recovering catalyst after water-cooled, collects the filtrate after filtering, obtains 37.9g O-Phenylene Diamine.
Through gas chromatographic detection, the feed stock conversion of the present embodiment is 100%, and product yield is more than 96%, and product purity is more than 99.5%.
Embodiment 2
The method of the present embodiment o-Nitraniline shortening synthesis O-Phenylene Diamine comprises the following steps:
Step one, the palladium carbon catalyst being 3% by 100g o-Nitraniline and 0.1g palladium mass content join in autoclave, first employing passes into the air in the method eliminating autoclave of nitrogen, and then employing passes into the nitrogen in the method eliminating autoclave of hydrogen;
Step 2, to heat getting rid of the autoclave after nitrogen in step one, continue to pass into hydrogen in autoclave simultaneously, it is 110 DEG C in temperature, pressure is make o-Nitraniline generation catalytic hydrogenating reduction react under the condition of 1.0MPa, stop passing into hydrogen after reaction 7.5h, filtering recovering catalyst after water-cooled, collects the filtrate after filtering, obtains 76.8g O-Phenylene Diamine.
Through gas chromatographic detection, the feed stock conversion of the present embodiment is 100%, and product yield is more than 96%, and product purity is more than 99.5%.
Embodiment 3
The method of the present embodiment o-Nitraniline shortening synthesis O-Phenylene Diamine comprises the following steps:
Step one, the palladium carbon catalyst being 3% by 50g o-Nitraniline and 0.15g palladium mass content join in autoclave, first employing passes into the air in the method eliminating autoclave of nitrogen, and then employing passes into the nitrogen in the method eliminating autoclave of hydrogen;
Step 2, to heat getting rid of the autoclave after nitrogen in step one, continue to pass into hydrogen in autoclave simultaneously, it is 110 DEG C in temperature, pressure is make o-Nitraniline generation catalytic hydrogenating reduction react under the condition of 1.0MPa, stop passing into hydrogen after reaction 8h, filtering recovering catalyst after water-cooled, collects the filtrate after filtering, obtains 38.1g O-Phenylene Diamine.
Through gas chromatographic detection, the feed stock conversion of the present embodiment is 100%, and product yield is more than 96%, and product purity is more than 99.5%.
Embodiment 4
The method of the present embodiment o-Nitraniline shortening synthesis O-Phenylene Diamine comprises the following steps:
Step one, the palladium carbon catalyst being 3% by 200g o-Nitraniline and 0.3g palladium mass content join in autoclave, first employing passes into the air in the method eliminating autoclave of nitrogen, and then employing passes into the nitrogen in the method eliminating autoclave of hydrogen;
Step 2, to heat getting rid of the autoclave after nitrogen in step one, continue to pass into hydrogen in autoclave simultaneously, it is 110 DEG C in temperature, pressure is make o-Nitraniline generation catalytic hydrogenating reduction react under the condition of 1.0MPa, stop passing into hydrogen after reaction 7h, filtering recovering catalyst after water-cooled, collects the filtrate after filtering, obtains 153.2g O-Phenylene Diamine.
Through gas chromatographic detection, the feed stock conversion of the present embodiment is 100%, and product yield is more than 96%, and product purity is more than 99.5%.
The above is only preferred embodiment of the present invention, not imposes any restrictions the present invention.Every above embodiment is done according to invention technical spirit any simple modification, change and equivalence change, all still belong in the protection domain of technical solution of the present invention.
Claims (3)
1. a method for o-Nitraniline shortening synthesis O-Phenylene Diamine, it is characterized in that, the method comprises the following steps:
Step one, o-Nitraniline and palladium carbon catalyst are joined in autoclave, first adopt the method passing into nitrogen to get rid of air in autoclave, then adopt the method passing into hydrogen to get rid of nitrogen in autoclave; The add-on of described palladium carbon catalyst is 0.1% ~ 0.3% of o-Nitraniline quality;
Step 2, to heat getting rid of the autoclave after nitrogen in step one, continue to pass into hydrogen in autoclave simultaneously, it is 110 DEG C in temperature, pressure is make o-Nitraniline generation catalytic hydrogenating reduction react under the condition of 1.0MPa, stop passing into hydrogen after reaction 7h ~ 8h, filtering recovering catalyst after water-cooled, collects the filtrate after filtering, obtains O-Phenylene Diamine.
2. the method for a kind of o-Nitraniline shortening synthesis O-Phenylene Diamine according to claim 1, it is characterized in that, in palladium carbon catalyst described in step one, the mass percentage of palladium is 3%.
3. the method for a kind of o-Nitraniline shortening synthesis O-Phenylene Diamine according to claim 1, it is characterized in that, the add-on of palladium carbon catalyst described in step one is 0.15% of o-Nitraniline quality.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107382792A (en) * | 2017-06-07 | 2017-11-24 | 盐城市瓯华化学工业有限公司 | The intermediate aminolysis thing hydrogenation reduction method of active blue 19 8 |
| CN107513022A (en) * | 2017-07-13 | 2017-12-26 | 安徽东至广信农化有限公司 | A kind of restoring method of intermediate o-phenylenediamine for carbendazim production |
| CN107519866A (en) * | 2017-07-13 | 2017-12-29 | 安徽东至广信农化有限公司 | A kind of renovation process for the catalyst that o-phenylenediamine is made for reducing process |
| CN107570215A (en) * | 2017-08-01 | 2018-01-12 | 安徽东至广信农化有限公司 | A kind of renovation process for being used to synthesize the catalyst of o-chloraniline |
| CN110694641A (en) * | 2019-10-10 | 2020-01-17 | 西安凯立新材料股份有限公司 | Method for preparing catalyst for nitro reduction and application |
| 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 |
| CN111662182A (en) * | 2020-07-17 | 2020-09-15 | 四川北方红光特种化工有限公司 | Method for producing phenylenediamine by dinitrobenzene solvent-free hydrogenation continuous reaction |
| CN114634418A (en) * | 2022-03-08 | 2022-06-17 | 安徽东至广信农化有限公司 | Green and efficient preparation method of high-purity o-phenylenediamine |
| CN114685282A (en) * | 2022-05-10 | 2022-07-01 | 安徽东至广信农化有限公司 | Production process for hydrogenation reduction of o-phenylenediamine |
| CN115232012A (en) * | 2022-08-02 | 2022-10-25 | 福建康峰新材料有限公司 | Method for producing m-amino benzotrifluoride by solvent-free hydrogenation process |
| CN115636752A (en) * | 2022-09-29 | 2023-01-24 | 宁夏瑞泰科技股份有限公司 | Method for preparing o-phenylenediamine by using jet loop reactor |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107382792A (en) * | 2017-06-07 | 2017-11-24 | 盐城市瓯华化学工业有限公司 | The intermediate aminolysis thing hydrogenation reduction method of active blue 19 8 |
| CN107513022A (en) * | 2017-07-13 | 2017-12-26 | 安徽东至广信农化有限公司 | A kind of restoring method of intermediate o-phenylenediamine for carbendazim production |
| CN107519866A (en) * | 2017-07-13 | 2017-12-29 | 安徽东至广信农化有限公司 | A kind of renovation process for the catalyst that o-phenylenediamine is made for reducing process |
| CN107570215A (en) * | 2017-08-01 | 2018-01-12 | 安徽东至广信农化有限公司 | A kind of renovation process for being used to synthesize the catalyst of o-chloraniline |
| CN110694641B (en) * | 2019-10-10 | 2022-08-16 | 西安凯立新材料股份有限公司 | Method for preparing catalyst for nitro reduction and application |
| CN110694641A (en) * | 2019-10-10 | 2020-01-17 | 西安凯立新材料股份有限公司 | Method for preparing catalyst for nitro reduction and application |
| 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 |
| CN111662182A (en) * | 2020-07-17 | 2020-09-15 | 四川北方红光特种化工有限公司 | Method for producing phenylenediamine by dinitrobenzene solvent-free hydrogenation continuous reaction |
| CN114634418A (en) * | 2022-03-08 | 2022-06-17 | 安徽东至广信农化有限公司 | Green and efficient preparation method of high-purity o-phenylenediamine |
| CN114685282A (en) * | 2022-05-10 | 2022-07-01 | 安徽东至广信农化有限公司 | Production process for hydrogenation reduction of o-phenylenediamine |
| WO2023216458A1 (en) * | 2022-05-10 | 2023-11-16 | 杨镭 | Production process for hydrogenation of o-phenylenediamine |
| CN115232012A (en) * | 2022-08-02 | 2022-10-25 | 福建康峰新材料有限公司 | Method for producing m-amino benzotrifluoride by solvent-free hydrogenation process |
| CN115636752A (en) * | 2022-09-29 | 2023-01-24 | 宁夏瑞泰科技股份有限公司 | Method for preparing o-phenylenediamine by using jet loop reactor |
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Application publication date: 20150701 |