CN105566121A - Method for reducing generation of nitrophenol in preparation process of nitroanisole - Google Patents
Method for reducing generation of nitrophenol in preparation process of nitroanisole Download PDFInfo
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- CN105566121A CN105566121A CN201410533185.2A CN201410533185A CN105566121A CN 105566121 A CN105566121 A CN 105566121A CN 201410533185 A CN201410533185 A CN 201410533185A CN 105566121 A CN105566121 A CN 105566121A
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- sodium hydroxide
- nitrophenol
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- methyl alcohol
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Abstract
A special feeding mode is adopted in the invention to reduce generation of nitrophenol, and is characterized in that a sodium methoxide solution prepared from methanol and sodium hydroxide is added to an autoclave in t he production process of nitroanisole from m-oil (o-nitrochlorobenzene, p-nitrochlorobenzene and m-nitrochlorobenzene) in the autoclave, so generation of nitrophenol is reduced, thereby the reaction time is greatly shortened, the raw material conversion rate is improved, the reaction selectivity and the yield of the above product are improved, the cost is reduced, and three wastes are reduced.
Description
Technical field
The invention belongs to technical field of fine, specifically, relate to a kind of mixing nitro-chlorobenzene that reduces in autoclave, react the method generating nitrophenol generation in Nitroanisole process.
Background technology
Nitroanisole (o-Nitrophenyl methyl ether, p-Nitromethoxybenzene) is the important intermediate of synthetic dyestuff, spices and medicine, is the important source material of synthesizing amino methyl-phenoxide (Ortho Anisidine, Para-Anisidine).
Traditional Ortho Anisidine or the production technique of Para-Anisidine be with ortho-nitrochlorobenzene or para-nitrochloro-benzene for raw material, obtain through processes such as etherificate, hydrogenation, separation, rectifying.This traditional preparation technology also exists the high shortcoming of raw materials cost.
Jiasen Chemical Industry Co., Ltd., Changzhou City discloses one chlorobenzene production o-Nitrophenyl methyl ether, the technique (Chinese patent CN200610085488.8) of p-Nitromethoxybenzene and m-nitrochlorobenzene, this technique take chlorobenzene as raw material, chlorobenzene obtains nitro-chlorobenzene mixture through nitration reaction, directly there is etherification reaction in nitro-chlorobenzene mixture, etherification product obtains o-Nitrophenyl methyl ether through separation and purification in etherifying agent, p-Nitromethoxybenzene and m-nitrochlorobenzene product, the feature of this etherification reaction is etherifying agent can be methyl alcohol, and also can be mixture or the compound of acid binding agent and methyl alcohol, acid binding agent can be sodium hydroxide, sodium carbonate, magnesium oxide, calcium oxide, volatile salt, magnesiumcarbonate, calcium carbonate, bicarbonate of ammonia, sodium bicarbonate etc., methyltertiarvbutyl ether reactor can adopt continuous tubular reactor, the continuous stirred tank reactor (CSTR) of multi-floating bodies, batch stirred tank reactor, static mixer, dynamic mixers etc. are methyl alcohol and sodium hydroxide and mixing nitro-chlorobenzene are dropped in autoclave when wherein reacting in reactor simultaneously, then airtight temperature reaction.
In addition, Yangzhou Ming Ruida Chemical Technology Co., Ltd. discloses a kind of nitro-chlorobenzene that mixes in water solvent, reacts the method (Chinese patent CN200910033501.9) of producing anisidine, this technique take water as solvent, under the katalysis of sodium hydroxide, mixing nitro-chlorobenzene and methyl alcohol are reacted, concrete steps are: add mixing nitro-chlorobenzene in the reactor, methyl alcohol and sodium hydroxide, stir, water is added after being heated to 70 DEG C, the mass ratio of mixing nitro-chlorobenzene and methyl alcohol is 1:0.2 ~ 1, the mass ratio of mixing nitro-chlorobenzene and water is 1:0.2 ~ 1.2, the mass ratio of mixing nitro-chlorobenzene and sodium hydroxide is 1:0.3 ~ 0.5, temperature of reaction 70-150 DEG C, pressure 0.1-1.6MPa, reaction 4-12 hour.
As everyone knows, because halogenated aryl hydrocarbon is difficult to hydrolysis, need under the condition of high temperature, high pressure, but when the ortho position of halogen atom or contraposition are connected with strong electron-withdrawing group group, hydrolysis reaction just carry out, and at this moment just easily produces nitrophenol than being easier to.But due to the feed way that autoclave is special, disposable material must be added, the mode of dropping can not be adopted, namely usually conventional method is that between handle, position oil adds in autoclave together with methyl alcohol and sodium hydroxide, this just make between position oil when there is etherification reaction in autoclave due under localized hyperthermia's high pressure and highly basic situation, generate in the process of Nitroanisole and especially easily produce nitrophenol, thus affect the yield of product.
Summary of the invention
In order to solve the existing problem producing nitrophenol in autoclave between utilization in position oil synthesizing nitryl methyl-phenoxide process, the present invention adopts a kind of special feeding mode to reduce the generation of nitrophenol, in autoclave, namely utilize the nitrated production of Benzene Chloride right, rectifying still liquid in ortho-nitrochlorobenzene process namely between position oil (ortho-nitrochlorobenzene, para-nitrochloro-benzene and a nitro chlorobenzene) produce in the process of anisidine, join again in autoclave after solvent methanol and sodium hydroxide being mixed with sodium methoxide solution during etherification reaction, thus reduce the generation of nitrophenol, so not only Reaction time shorten greatly, improve the transformation efficiency of raw material, also improve the selectivity of reaction and the yield of product, reduce cost, decrease the three wastes, because according to the characteristic of nitrophenol, exist with the form of phenol sodium in the basic conditions, mostly water-soluble, thus add the intractability of waste water.
The method that minimizing nitrophenol of the present invention generates is: generate in the process of Nitroanisole in a position oil etherificate, be added to again in autoclave after methyl alcohol and solid sodium hydroxide are first made into sodium methoxide solution, in order to avoid localized hyperthermia's high pressure and alkalescence are excessively strong, cause nitrophenol to produce in a large number, thus affect the yield of product.
For achieving the above object, the technical solution used in the present invention is as follows: in sodium methylate preparation, first add specified amount flake caustic and methyl alcohol, and the mol ratio of methyl alcohol and a position oil is 1 ~ 10:1; The mol ratio of sodium hydroxide and a position oil is 0.1 ~ 1.0:1; Stir, react 0.5 ~ 2 hour at 10 ~ 70 DEG C of temperature, then a position oil is placed in autoclave in the lump with the sodium methoxide solution prepared, stir and heat up, reaction pressure controls at 0.1-1.6MPa, and temperature controls at 70-150 DEG C, reaction 2-10 hour, then maintain insulation 1-3 hour, obtained the mixture of a nitro chlorobenzene, o-Nitrophenyl methyl ether and p-Nitromethoxybenzene by distillation, washing.The methyl alcohol collected after ether-based liquid distillation is recyclable to be applied mechanically, and continues to be made into sodium methoxide solution and recycles.
The preferred technical characteristic of method of the present invention:
A: in described etherification reaction, the mol ratio of methyl alcohol and a position oil is 6 ~ 9:1;
B: in described etherification reaction, the mol ratio of sodium hydroxide and a position oil is 0.5 ~ 0.8:1;
C: in described etherification reaction, the preparation temperature of sodium methylate is 30 ~ 45 DEG C;
D: the solvent particular methanol in described etherification reaction;
E: could drop in autoclave in the lump after methyl alcohol and sodium hydroxide must be made into sodium methoxide solution in described etherification reaction;
Advantage of the present invention:
(1) generation of nitrophenol in etherification reaction process can be reduced;
(2) can all apply mechanically after solvent distillation used in reaction process.
(3) improve the selectivity of reaction and the yield of product, reduce cost, decrease the three wastes.
Accompanying drawing explanation
Accompanying drawing 1 is the process flow diagram of embodiment of the present invention method.
Embodiment
Below by embodiment and accompanying drawing in detail the present invention is described in detail, but the invention is not restricted to following embodiment.
Shown in the technical process accompanying drawing 1 of following examples.
embodiment 1
1, sodium methylate preparation process
In sodium methylate preparation pot, add flake caustic and 240 ml methanol of 22 grams, stir, preparation pot temperature rises naturally, stirs, react after 0.5 ~ 2 hour when temperature no longer rises, cooling.
2, nitro-chlorobenzene etherificate operation
In stainless steel autoclave, add position oil and methyl alcohol between 116 grams prepare sodium methoxide solution in pot, pressure-controlling is at 0.5-0.6MPa, temperature controls at 70-150 DEG C, reaction 2-3 hour, then be incubated 2 hours, obtained the mixture of a nitro chlorobenzene, o-Nitrophenyl methyl ether and p-Nitromethoxybenzene by distillation, washing.
embodiment 2
Below in conjunction with specific embodiment (comparative example), the present invention is elaborated:
The oil of position between 116 grams, the flake caustic of 22 grams and 240 ml methanol are added in stainless steel autoclave, stir and heat up, pressure-controlling is at 0.5-0.6MPa, temperature controls at 70-150 DEG C, reaction 2-3 hour, then be incubated 2 hours, obtained the mixture of a nitro chlorobenzene, o-Nitrophenyl methyl ether and p-Nitromethoxybenzene by distillation, washing.
Conclusion: in the Nitroanisole adopting the present invention to produce, nitrophenol content is at below 200ppm, and in the Nitroanisole that embodiment 2 is produced the content of nitrophenol up to 0.1-0.3%.
Claims (7)
1. one kind is reduced the method that in Nitroanisole production process, nitrophenol generates, its feature with sodium hydroxide, methyl alcohol, position oil for raw material, at pressure 0.1-1.6MPa, 2-10 hour is reacted under the condition of temperature 70-150 DEG C, then be incubated 1-3 hour, obtained the mixture of a nitro chlorobenzene, o-Nitrophenyl methyl ether and p-Nitromethoxybenzene by distillation, washing; The mol ratio of methyl alcohol and a position oil is 1 ~ 10:1; The mol ratio of sodium hydroxide and a position oil is 0.1 ~ 1.0:1.
2. method according to claim 1, it is characterized in that methyl alcohol and sodium hydroxide be first made into sodium methoxide solution again and position oil react.
3. method according to claim 2, is characterized in that sodium hydroxide and methanol mixed, and at 10 ~ 70 DEG C of temperature, stirring reaction is after 0.5 ~ 2 hour, obtains sodium methoxide solution.
4. method according to claim 2, is characterized in that the preparation temperature of sodium methylate is 30 ~ 45 DEG C.
5. method according to claim 1, is characterized in that the mol ratio of methyl alcohol and a position oil is 6 ~ 9:1.
6. method according to claim 1, is characterized in that the mol ratio of sodium hydroxide and a position oil is 0.5 ~ 0.8:1.
7. method according to claim 1, the Methanol Recovery of collecting after it is characterized in that ether-based liquid distillation is applied mechanically, and continues to be made into sodium methoxide solution and recycles.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106336359A (en) * | 2016-09-30 | 2017-01-18 | 连云港泰盛化工有限公司 | Device for continuously producing nitroanisole through nitrochlorobenzene and production method |
| CN106496039A (en) * | 2016-09-28 | 2017-03-15 | 连云港泰盛化工有限公司 | Nitrochlorobenzene meta-position oil intermediate nitro Benzene Chloride and para-nitrochloro-benzene, the separation method of ortho-nitrochlorobenzene |
| CN106883129A (en) * | 2016-12-29 | 2017-06-23 | 安徽海华科技股份有限公司 | A kind of method that utilization meta oil prepares m-chloroaniline |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496039A (en) * | 2016-09-28 | 2017-03-15 | 连云港泰盛化工有限公司 | Nitrochlorobenzene meta-position oil intermediate nitro Benzene Chloride and para-nitrochloro-benzene, the separation method of ortho-nitrochlorobenzene |
| CN106496039B (en) * | 2016-09-28 | 2019-04-05 | 连云港泰盛化工有限公司 | The separation method of nitrochlorobenzene meta-position oil intermediate nitro Benzene Chloride and para-nitrochloro-benzene, ortho-nitrochlorobenzene |
| CN106336359A (en) * | 2016-09-30 | 2017-01-18 | 连云港泰盛化工有限公司 | Device for continuously producing nitroanisole through nitrochlorobenzene and production method |
| CN106883129A (en) * | 2016-12-29 | 2017-06-23 | 安徽海华科技股份有限公司 | A kind of method that utilization meta oil prepares m-chloroaniline |
| CN106883129B (en) * | 2016-12-29 | 2021-05-14 | 安徽海华科技集团有限公司 | Method for preparing m-chloroaniline by using meta-oil |
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