CN105017028A - Improved synthetic method for preparing o-phenylenediamine by reducing o-nitroaniline - Google Patents
Improved synthetic method for preparing o-phenylenediamine by reducing o-nitroaniline Download PDFInfo
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Abstract
The invention relates to an improved synthetic method for preparing o-phenylenediamine by reducing o-nitroaniline. The method comprises adding o-nitroaniline and sodium sulfide according to the molar ratio of 1:1.5-2 into a reaction vessel, injecting water, controlling the weight ratio of sodium sulfide to water to be 1:1-20, controlling the reaction temperature to be 50-150 DEG C, reacting for 1-5 h, crystallizing and separating o-phenylenediamine, so as to obtain reaction waste water; concentrating the reaction waste water to obtain a solid residue; performing medium-temperature calcining on the residue, concretely adding an inorganic base into the residue and controlling the temperature of medium-temperature calcining to be 300-600 DEG C; performing high-temperature calcining on the residue, concretely mixing with carbon powder, and controlling the temperature of high-temperature calcining to be 900-1200 DEG C; and performing separation filtering, concretely using water to dissolve the post-calcined product, filtering and recovering superfluous carbon powder and obtaining a filtrate which is a sodium sulfide aqueous solution. The method realized continuous efficient wastewater processing, is beneficial for reducing discharge of ' three wastes (waste gas,waste water and industrial residue) ', reduces safe production risk, improves sodium sulfide recovery rate, and is relatively suitable for large-scale production of o-phenylenediamine in industry.
Description
Technical field
The present invention relates to the synthetic method of O-Phenylene Diamine, be specifically related to the synthetic method preparing O-Phenylene Diamine with o-Nitraniline reduction, the green safety circulation and stress of realization response product.
Background technology
O-Phenylene Diamine is a kind of important organic chemical industry's intermediate, except for except DYE PRODUCTION, or the main raw material of the systemic fungicide such as pesticide carbendazim, F-1991, (methyl) thiophanate, be also the important source material of photographic developer, levelling agent and tensio-active agent etc.
At present, the synthesis of O-Phenylene Diamine has several route, and wherein two outbalance routes are as follows:
One, patent CN 102633653 reports a kind of method that o-Nitraniline shortening produces O-Phenylene Diamine, take o-Nitraniline as raw material, alcohol is solvent, and nickel is catalyzer, at the hydrogen pressure of 1 ~ 6MPa, at the temperature of 40 ~ 80 DEG C, reduction reaction 2 ~ 10 hours, rectifying obtains white O-Phenylene Diamine, and reaction formula is as follows:
This operational path is ripe, with short production cycle, yield is high, is a feasible industrialized route.But this reaction uses the large usage quantity of catalyzer, and aftertreatment is loaded down with trivial details, causes production cost too high, be difficult to promote batch production.
They are two years old, patent CN1559886 reports a kind of method that o-Nitraniline and Sodium Sulphide produce O-Phenylene Diamine, and by product Sulfothiorine and sodium hydroxide are under the effect of carbon dust, microwave heat simultaneously, regenerate Sodium Sulphide, realize recycling of Sodium Sulphide, reduce environmental pollution.Reaction is as follows:
in this technique, the reduction reaction of o-Nitraniline is more ripe, but wastewater recycling process is not perfect, do not consider the complicacy (contains sodium sulfate of the actual content of Sodium Sulphide in industrial actual production lower (50 ~ 60%) and aniline reducing waste water composition, Sulfothiorine, S-WAT, Sodium Thiocyanate 99 and a small amount of phenyl amines organic compound) etc. factor, when waste water mixture directly and carbon dust reacts under the instantaneously heated hot environment of microwave, easy generation is made us suffocating, stench, the toxic gas of acid attack, gas absorbs through sodium hydroxide solution the solution composition formed and comprises: sodium carbonate, Sodium sulfhydrate, S-WAT and sodium cyanide, illustrate in waste gas containing hypertoxic gas vulcanization hydrogen and prussic acid, there is obvious potential safety hazard.In order to stop security risk in production process and secondary pollution, being further improved the above-mentioned recovery processing technique preparing O-Phenylene Diamine and corresponding waste water with sodium sulfide reducing o-Nitraniline is the difficult problem that those skilled in the art need to think deeply.
Summary of the invention
Technical problem to be solved by this invention provides a kind of sodium sulfide reducing o-Nitraniline of improvement to prepare the method for O-Phenylene Diamine for above-mentioned prior art, improve the rate of recovery of Sodium Sulphide and react security, the reliability of rear waste water recycling device, avoid the production of toxic gas, make continuous, the High-efficient Production that realize wastewater treatment reaction.
The present invention's adopted technical scheme that solves the problem is: the improvement synthetic method of O-Phenylene Diamine is prepared in a kind of o-Nitraniline reduction, o-Nitraniline and sodium sulphite are dropped in reactor with the mol ratio of 1:1.5 ~ 2, then in reactor, water is injected, the weight ratio of sodium sulphite and water is 1:1 ~ 20, control temperature of reaction at 50 ~ 150 DEG C, react 1 ~ 5 hour, Crystallization Separation O-Phenylene Diamine, obtains reaction waste; Reaction waste recycles via following steps:
(1) cryoconcentration: concentration response waste water at 50 ~ 150 DEG C of temperature, removes water and a small amount of organism obtains concentrated residue;
(2) temperature calcining in: add mineral alkali in concentrated residue, in control, warm calcining temperature is 300 ~ 600 DEG C, calcining 10 ~ 30min, after middle temperature calcining, the bulk composition of waste water and residue is sodium sulfate;
(3) high-temperature calcination: mixed with carbon dust by the waste water and residue after middle temperature calcining, controlling high-temperature calcination temperature is 900 ~ 1200 DEG C, calcining 10 ~ 30min;
(4) separating and filtering: by gained solid water dissolution after high-temperature calcination, the carbon dust that filtered and recycled is unnecessary, filtrate is the aqueous solution of sodium sulphite.
Aforesaid method has that operational safety is reliable, energy consumption is low, the sodium sulphite rate of recovery is high, and produce without harmful by-products, environmental protection, is suitable for extending to suitability for industrialized production.Reaction formula is as follows:
The object of middle temperature calcining guarantees that Sulfothiorine disproportionation reaction all occurs in the presence of an inorganic base and changes into sodium sulphite and sodium sulfate; High-temperature calcination makes the sodium sulfate of generation finally all change into useful sodium sulphite, realizes circulation.The mode that this segmentation reaction formula reclaims sodium sulphite can be avoided easily producing toxic and harmful and the not high defect of the rate of recovery because waste water and residue complicated component directly carries out pyroreaction.
As optimum condition of the present invention, described mineral alkali is one or more in sodium hydroxide, sodium carbonate or sodium bicarbonate.In concentrated residue, the mol ratio of the mineral alkali of Sulfothiorine and interpolation is 1:0.05 ~ 1.Described carbon dust is coal dust, coke, charcoal.In concentrated residue, the mol ratio of the carbon dust of Sulfothiorine and interpolation is 1:2.67 ~ 5.Heating installation is electric furnace, converter, kiln or microwave heater.
Compared with prior art, feature of the present invention is as follows:
The present invention with o-Nitraniline and Sodium Sulphide for raw material, O-Phenylene Diamine is prepared in aqueous phase reduction, reducing waste water is through concentrated, add mineral alkali, the calcining of middle temperature alkalescence and high temperature carbon dust calcining reduction prepare Sodium Sulphide, Appropriate application Sulfothiorine, the physico-chemical property of Sodium Sulphide and sodium sulfate, adopt more scientific, rational process means, time sharing segment ground is separated, conversion of waste water composition, avoid the potential safety hazard in various reaction process and pollute and occur, achieve continuously, efficient waste treatment capacity, contribute to reducing three waste discharge, reduce Safety Risk in Production, and improve the rate of recovery of sodium sulphite, be more suitable for industrial scale operation O-Phenylene Diamine.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
In the reactor of 20L, drop into 2.5 kilograms of o-Nitranilines, the water of 2.1 kilograms of sodium sulphite and 6.35 kilograms, mix, temperature in control reactor is between 96 ~ 102 DEG C, back flow reaction 1 ~ 1.5 hour, then crystallisation by cooling filters and obtains O-Phenylene Diamine crude product 1.84 kilograms (GC detects O-Phenylene Diamine content and is greater than 99.5%, productive rate is 94%), filtrate is done to reclaim sodium sulphite process as waste reaction solution, concentration response waste liquid in 80 ~ 120 DEG C of temperature ranges, remove the organism of most of water and portion of residual in waste liquid, obtain solid residue, main component is Sulfothiorine, sodium hydroxide and sodium sulphite not reacted on a small quantity, sulphur mainly exists with the form of Sulfothiorine.Mixed with 110g sodium hydroxide by solid residue, send into electric furnace furnace chamber, the Heating temperature arranging the calcining of middle temperature is between 450 ~ 460 DEG C, and calcination reaction 10 ~ 15min, in detection, the composition of warm calcinate is the mixture of sodium sulfate and sodium sulphite.Middle temperature is calcined the solid obtained to pulverize, mix with 500g excess coke powder, utilize the reductive action of coke powder that sodium sulfate high-temperature calcination is reduced into sodium sulphite, high-temperature calcination temperature is between 950 ~ 1000 DEG C, calcination reaction 10 ~ 15min, have a large amount of colorless and odorless gas to release in reaction process, analyzing and testing is carbonic acid gas and carbon monoxide, and high-temperature calcination product is detected as the mixture of coke powder and sodium sulphite.Then appropriate water dissolution is added, filter, filter residue is coke powder, dry reuse, solid mixture is obtained: sodium sulphate content is lower than 10%, and the content of sodium sulphite is greater than 80%, and all the other are sodium hydroxide after filtrate is concentrated, meet the quality standard of sodium sulphite completely, achieve the high-recovery of sodium sulphite and meet the processing requirement recycled.
Embodiment 2
In the reactor of 20L, drop into 2.5 kilograms of o-Nitranilines, the water of 2.5 kilograms of sodium sulphite and 10 kilograms, mix, temperature in control reactor is between 100 ~ 130 DEG C, back flow reaction 3.5 hours, then crystallisation by cooling filters and obtains O-Phenylene Diamine crude product 1.9 kilograms (GC detects O-Phenylene Diamine content and is greater than 99.3%, productive rate is 99.7%), filtrate is done to reclaim sodium sulphite process as waste reaction solution, concentration response waste liquid in 80 ~ 120 DEG C of temperature ranges, remove the organism of most of water and portion of residual in waste liquid, obtain solid residue, main component is Sulfothiorine, sodium hydroxide and sodium sulphite not reacted on a small quantity, sulphur mainly exists with the form of Sulfothiorine.Solid residue is mixed with 140g sodium carbonate, send into electric furnace furnace chamber, the Heating temperature arranging temperature calcining is between 450 ~ 460 DEG C, calcination reaction 10 ~ 15min, a large amount of colorless and odorless gas is had to release in reaction process, analyzing and testing is carbonic acid gas, and in detection, the composition of warm calcinate is the mixture of sodium sulfate and sodium sulphite.Middle temperature is calcined the solid obtained to pulverize, mix with the excessive wood charcoal powder of 500g, utilize the reductive action of wood charcoal powder that sodium sulfate high-temperature calcination is reduced into sodium sulphite, adopt the calcining manners of microwave heating, high-temperature calcination temperature is set between 1000 ~ 1100 DEG C, calcination reaction 25min, has a large amount of colorless and odorless gas to release in reaction process, analyzing and testing is carbonic acid gas and carbon monoxide, and high-temperature calcination product is detected as the mixture of wood charcoal powder and sodium sulphite.Then appropriate water dissolution is added, filter, filter residue is wood charcoal powder, dry reuse, solid mixture is obtained: sodium sulphate content is lower than 10%, and the content of sodium sulphite is greater than 80%, and all the other are sodium hydroxide after filtrate is concentrated, meet the quality standard of sodium sulphite completely, achieve the high-recovery of sodium sulphite and meet the processing requirement recycled.
Embodiment 3
In the reactor of 20L, drop into 2.5 kilograms of o-Nitranilines, the water of 2.1 kilograms of sodium sulphite and 8.3 kilograms, mix, temperature in control reactor is between 90 ~ 110 DEG C, back flow reaction 2 hours, then crystallisation by cooling filters and obtains O-Phenylene Diamine crude product 1.86 kilograms (GC detects O-Phenylene Diamine content and is greater than 99.3%, productive rate is 99.6%), filtrate is done to reclaim sodium sulphite process as waste reaction solution, concentration response waste liquid in 80 ~ 120 DEG C of temperature ranges, remove the organism of most of water and portion of residual in waste liquid, obtain solid residue, main component is Sulfothiorine, sodium hydroxide and sodium sulphite not reacted on a small quantity, sulphur mainly exists with the form of Sulfothiorine.Mixed with 120g sodium hydroxide by solid residue, send into electric furnace furnace chamber, the Heating temperature arranging the calcining of middle temperature is between 450 ~ 500 DEG C, and calcination reaction 15min, in detection, the composition of warm calcinate is the mixture of sodium sulfate and sodium sulphite.Middle temperature is calcined the solid obtained to pulverize, mix with the excessive wood charcoal powder of 500g, utilize the reductive action of wood charcoal powder that sodium sulfate high-temperature calcination is reduced into sodium sulphite, high-temperature calcination temperature is set between 1000 ~ 1100 DEG C, calcination reaction 15min, have a large amount of colorless and odorless gas to release in reaction process, analyzing and testing is carbonic acid gas and carbon monoxide, and high-temperature calcination product is detected as the mixture of wood charcoal powder and sodium sulphite.Then appropriate water dissolution is added, filter, filter residue is wood charcoal powder, dry reuse, solid mixture is obtained: sodium sulphate content is lower than 10%, and the content of sodium sulphite is greater than 80%, and all the other are sodium hydroxide after filtrate is concentrated, meet the quality standard of sodium sulphite completely, achieve the high-recovery of sodium sulphite and meet the processing requirement recycled.
Claims (6)
1. the improvement synthetic method of O-Phenylene Diamine is prepared in o-Nitraniline reduction, it is characterized in that: o-Nitraniline and sodium sulphite are dropped in reactor with the mol ratio of 1:1.5 ~ 2, then in reactor, water is injected, the weight ratio of sodium sulphite and water is 1:1 ~ 20, control temperature of reaction at 50 ~ 150 DEG C, react 1 ~ 5 hour, Crystallization Separation O-Phenylene Diamine, obtains reaction waste; Reaction waste recycles via following steps:
(1) cryoconcentration: concentration response waste water at 50 ~ 150 DEG C of temperature, removes water and a small amount of organism obtains concentrated residue;
(2) temperature calcining in: add mineral alkali in concentrated residue, in control, warm calcining temperature is 300 ~ 600 DEG C, calcining 10 ~ 30min, after middle temperature calcining, the bulk composition of waste water and residue is sodium sulfate;
(3) high-temperature calcination: mixed with carbon dust by the waste water and residue after middle temperature calcining, controlling high-temperature calcination temperature is 900 ~ 1200 DEG C, calcining 10 ~ 30min;
(4) separating and filtering: by gained solid water dissolution after high-temperature calcination, the carbon dust that filtered and recycled is unnecessary, filtrate is the aqueous solution of sodium sulphite.
2. the improvement synthetic method of O-Phenylene Diamine is prepared in o-Nitraniline according to claim 1 reduction, it is characterized in that: described mineral alkali is one or more in sodium hydroxide, sodium carbonate or sodium bicarbonate.
3. the improvement synthetic method of O-Phenylene Diamine is prepared in o-Nitraniline reduction according to claim 1, it is characterized in that: in concentrated residue, the mol ratio of the mineral alkali of Sulfothiorine and interpolation is 1:0.05 ~ 1.
4. the improvement synthetic method of O-Phenylene Diamine is prepared in o-Nitraniline reduction according to claim 1, it is characterized in that: described carbon dust is coal dust, coke, charcoal.
5. the improvement synthetic method of O-Phenylene Diamine is prepared in o-Nitraniline reduction according to claim 1, it is characterized in that: in concentrated residue, the mol ratio of the carbon dust of Sulfothiorine and interpolation is 1:2.67 ~ 5.
6. the improvement synthetic method of O-Phenylene Diamine is prepared in o-Nitraniline reduction according to claim 1, it is characterized in that: heating installation is electric furnace, converter, kiln or microwave heater.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106083664A (en) * | 2016-06-06 | 2016-11-09 | 王兴民 | A kind of nitro compounds method of reducing |
| CN106278906A (en) * | 2016-08-13 | 2017-01-04 | 安徽东至广信农化有限公司 | A kind of circulation ammonolysis process for o-phenylenediamine mother solution |
| CN106316863A (en) * | 2016-08-13 | 2017-01-11 | 安徽东至广信农化有限公司 | Efficient o-phenylenediamine recovery method |
| CN114769293A (en) * | 2022-04-11 | 2022-07-22 | 深圳星河环境股份有限公司 | Method for cooperative treatment of industrial solid waste and resource utilization of industrial waste salt |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109046246B (en) * | 2018-09-06 | 2021-03-16 | 青岛科技大学 | Resource utilization method of m-phenylenediamine hydrolysis waste residue |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106083664A (en) * | 2016-06-06 | 2016-11-09 | 王兴民 | A kind of nitro compounds method of reducing |
| CN106278906A (en) * | 2016-08-13 | 2017-01-04 | 安徽东至广信农化有限公司 | A kind of circulation ammonolysis process for o-phenylenediamine mother solution |
| CN106316863A (en) * | 2016-08-13 | 2017-01-11 | 安徽东至广信农化有限公司 | Efficient o-phenylenediamine recovery method |
| CN114769293A (en) * | 2022-04-11 | 2022-07-22 | 深圳星河环境股份有限公司 | Method for cooperative treatment of industrial solid waste and resource utilization of industrial waste salt |
| CN114769293B (en) * | 2022-04-11 | 2023-02-28 | 深圳星河环境股份有限公司 | Method for cooperative treatment of industrial solid waste and resource utilization of industrial waste salt |
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