CN106883129B - Method for preparing m-chloroaniline by using meta-oil - Google Patents
Method for preparing m-chloroaniline by using meta-oil Download PDFInfo
- Publication number
- CN106883129B CN106883129B CN201611246576.1A CN201611246576A CN106883129B CN 106883129 B CN106883129 B CN 106883129B CN 201611246576 A CN201611246576 A CN 201611246576A CN 106883129 B CN106883129 B CN 106883129B
- Authority
- CN
- China
- Prior art keywords
- kettle
- tower
- chloronitrobenzene
- water
- temperature
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/16—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
Abstract
The invention relates to a method for preparing m-chloroaniline by using meta-position oil, belongs to the technical field of m-chloroaniline preparation, and specifically comprises the steps of batching reaction, washing, drying, three-stage vacuum distillation, crystallization, reduction, redistillation and the like. The method takes waste meta-position oil produced by para-nitro and ortho-nitro and industrial waste liquid sodium hydrosulfide as raw materials, prepares the m-chloroaniline by methoxylation, crystallization and reduction, and generates byproducts of o-anisidine and p-anisidine, thereby realizing low cost and high yield.
Description
Technical Field
The invention belongs to the technical field of preparation of m-chloroaniline, and particularly relates to a method for preparing m-chloroaniline by using meta-oil.
Background
M-chloroaniline, colorless liquid to light amber liquid, is toxic, is an important fine chemical intermediate, and is mainly used as an intermediate of azo dyes and pigments, drugs, insecticides and pesticide chemicals.
The meta-position oil mainly comprises meta-nitro, ortho-chloro nitrobenzene and para-chloro nitrobenzene, and is a general name of para-nitro and ortho-nitro products in a para-nitro production process and waste liquid rich in meta-nitrochlorobenzene and high-boiling-point organic matters.
The existing method for preparing m-chloroaniline is to prepare m-chloroaniline by nitro reduction of m-nitrochlorobenzene. The traditional nitro reduction mainly comprises an iron powder reduction method, a sodium sulfide reduction method, a catalytic hydrogenation reduction method and an electrochemical reduction method. The iron powder reduction method produces a large amount of iron mud, which seriously pollutes the environment; the sodium sulfide reduction method has the characteristics of complex reduction route, low product yield, large waste liquid amount and the like; the energy consumption of the electrochemical reduction method is too high; the catalytic hydrogenation method has the advantages of reaction route, low energy consumption, environmental friendliness and the like, but in the catalytic hydrogenation process of m-nitrochlorobenzene, the side reaction of generating aniline through hydrogenolysis and dechlorination of C-CL bonds can be increased due to the meta-position activation of nitro groups, so that the yield of a main product is reduced. At the same time, the hydrogen chloride produced by dechlorination can cause corrosion to the equipment.
In summary, the prior art has the problems that the cost of the m-nitrochlorobenzene is too high, the environment is polluted by the reduction of the iron powder serving as the auxiliary raw material, the reduction cost of the sodium sulfide is too high, dechlorination and equipment corrosion are easy to occur in hydrogenation reduction, and the like.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing m-chloroaniline by using cheap and easily available meta-position oil as a raw material, and the method has the characteristics of high recovery rate, low cost and suitability for large-scale production.
In order to realize the purpose of the invention, the following technical scheme is adopted:
a method for preparing m-chloroaniline by using meta-oil comprises the following steps:
(1) burdening reaction: adding meta-position oil into a methoxylation reaction kettle, metering and adding methanol from a methanol metering tank under a closed state, adding a catalyst ammonium chloride, stirring, simultaneously heating the reaction kettle to 58-63 ℃, adjusting the pressure of the reaction kettle to 0-0.2MPa, finally adding sodium hydroxide into the reaction kettle, keeping the temperature unchanged, and sampling and detecting after 5 hours of reaction; wherein, meta-oil: methanol: sodium hydroxide: the mass ratio of ammonium chloride is 1: 0.30: 0.32: 0.045, when the content of the p-nitrochlorobenzene is detected to be less than or equal to 0.1 percent and the content of the o-nitrochlorobenzene is detected to be less than or equal to 2 percent, recovering the methanol, and then transferring to the next washing procedure;
(2) washing with water: conveying the material obtained by the reaction in the step (1) to a workshop storage tank by a pump, pumping the material into a washing kettle from the workshop storage tank for washing, wherein the pumping amount of the material is two thirds of the volume of the washing kettle, then washing twice, wherein the adding amount of washing water is one fourth of the pumping amount of the material, stirring for 0.5h, and standing for 2 h; sending the waste water after washing into a waste water tank, and sending the material after washing into a dry front tank;
(3) and (3) drying: starting a vacuum pump, opening a vacuum valve of a water receiving tank and a water valve of a condenser, opening a material pumping valve, pumping the water-washed materials from a pre-drying tank into a dehydration kettle, wherein the pumped materials are two thirds of the volume of the dehydration kettle, then stirring, slightly opening steam for dehydration, finishing dehydration when the viewing mirror of the condenser is basically anhydrous, then closing the vacuum valve and an air outlet valve, and opening air pressure to press the dried materials into a post-drying tank;
(4) and (3) rectification: three-stage vacuum distillation is adopted to separate m-chloronitrobenzene and remove a small amount of chlorobenzene, and the specific process is as follows:
column # 1: introducing the dried material obtained in the step (3) into the 1# tower, simultaneously heating, starting a vacuum pump when the temperature of a tower kettle rises to 100 ℃, vacuumizing the 1# tower, the 2# tower and the 3# tower to-0.096 Mpa, simultaneously opening a circulating water pump, adjusting the water inlet and outlet of a condenser at the top of the tower, performing total reflux for 2-3h to ensure that the interior of the tower is balanced and then extracting when the temperature of the top of the tower is 50-60 ℃, adjusting the temperature of the kettle of the 1# tower to 145-155 ℃, and controlling the pressure to-0.1 Mpa, collecting low-boiling-point substances from the top of the tower, and continuously pumping the material in the tower kettle into the 2# tower;
2# tower: continuously pumping the material in the tower kettle No. 1 into a feed inlet of a tower No. 2, adjusting the temperature of the tower kettle No. 2 to be 170-180 ℃, and the pressure to be-0.1 Mpa, separating m-chloronitrobenzene from the tower top, wherein the content of the m-chloronitrobenzene is more than or equal to 90 percent, and then feeding the m-chloronitrobenzene into a crystallization kettle; continuously pumping the material in the tower kettle 2 into the tower kettle 3, and keeping the balance of the feeding amount and the extracted amount in the process so that the volume of the material in the tower kettle is always one third of the volume of the tower kettle;
3# tower: continuously pumping the material in the tower kettle 2 into the tower 3, adjusting the temperature of the tower kettle 3 to be 170-180 ℃, and the pressure to be-0.1 Mpa, separating the nitrobenzyl ether from the tower kettle, putting the nitrobenzyl ether into a No. 1 intermediate storage tank, and carrying out subsequent treatment; the material at the top of the tower is circularly and continuously pumped into a feed inlet of a No. 2 tower;
(5) and (3) crystallization: pumping m-chloronitrobenzene separated from the No. 2 tower into a crystallization kettle by a pump, stopping the pump after reflux exists in a reflux sight glass, starting a circulating pump, quickly cooling the crystallization kettle, adjusting a water valve of the circulating pump to slowly cool after the temperature is reduced to 45 ℃, completing crystallization when the temperature is lower than 27 ℃, and then detecting the content of the m-chloronitrobenzene; when the content of m-chloronitrobenzene is more than or equal to 99.5 percent, pumping the m-chloronitrobenzene into a No. 2 intermediate storage tank for subsequent preparation of m-chloroaniline or direct packaging for sale; the m-chloronitrobenzene content is between 93 percent and 99.5 percent and is crystallized for use again; when the content of m-chloronitrobenzene is less than 93 percent, uniformly collecting the m-chloronitrobenzene, pumping the m-chloronitrobenzene into a feed inlet of a No. 2 tower for further rectification and purification;
(6) reduction: adding 350g/L sodium hydrosulfide aqueous solution into a reduction kettle, gradually raising the temperature of the reduction kettle to 110 ℃, then adding m-chloronitrobenzene of a No. 2 intermediate storage tank into the reaction kettle through a metering tank, then adjusting the temperature in the kettle to be 135-145 ℃, and the pressure to be 0.25Mpa, carrying out reduction reaction with the sodium hydrosulfide, standing and layering after the reaction is finished, wherein the lower layer is a mixture of water, sodium thiosulfate, sodium hydrosulfide and sodium hydroxide, and conveying the mixture to a sodium bicarbonate preparation process through a pipeline, and the crude product reduction material on the upper layer is conveyed into an amino tank for the next process; the intermediate chloronitrobenzene: the mass ratio of the sodium hydrosulfide is 3: 5.5;
(7) and (3) distillation: introducing the crude product reduced material in the amino tank into a distillation kettle, raising the temperature of the kettle to 170 ℃, removing water and trace impurities in the crude product reduced material through vacuum distillation to obtain a finished product of m-chloroaniline, and leading out the material at the bottom of the kettle for solid waste treatment.
Preferably, the temperature of the two water washes in step (2) is 65-70 ℃.
Preferably, the stirring speed in the step (1) and the step (2) is 60 r/min.
Further, the materials obtained by the reaction in the step (1) comprise p-nitroanisole, o-nitroanisole, m-chloronitrobenzene, water, sodium p-nitrophenolate, sodium o-nitrophenolate, sodium chloride and low-boiling-point substances.
Preferably, the pressure of the dehydration kettle is-0.1-0 MPa, and the temperature is higher than 85 ℃.
Further, the low-boiling-point substances are nitrobenzene, water and chlorobenzene with the content of less than 1 percent.
In the invention, the nitroanisole in the No. 1 intermediate storage tank can also further react with a sodium hydrosulfide solution, then the nitroanisole is distilled to obtain the aminobenzene ether, and then the aminobenzene ether and the p-anisidine are rectified to obtain byproducts.
Compared with the prior art, the invention has the beneficial effects that:
the method takes waste meta-position oil produced by para-nitro and ortho-nitro and industrial waste liquid sodium hydrosulfide as raw materials, prepares the m-chloroaniline by methoxylation, crystallization and reduction, and generates byproducts of o-anisidine and p-anisidine, thereby realizing low cost and high yield.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Examples
A method for preparing m-chloroaniline by using meta-oil comprises the following steps:
(1) burdening reaction: adding meta-position oil into a methoxylation reaction kettle, metering and adding methanol from a methanol metering tank under a closed state, adding a catalyst ammonium chloride, stirring at the rotating speed of 60r/min, simultaneously heating the reaction kettle to 58-63 ℃, adjusting the pressure of the reaction kettle to 0-0.2MPa, finally adding sodium hydroxide into the reaction kettle, keeping the temperature unchanged, reacting for 5 hours, and then sampling and detecting; wherein, meta-oil: methanol: sodium hydroxide: the mass ratio of ammonium chloride is 1: 0.30: 0.32: 0.045, when the content of the p-nitrochlorobenzene is detected to be less than or equal to 0.1 percent and the content of the o-nitrochlorobenzene is detected to be less than or equal to 2 percent, recovering the methanol, and then transferring to the next washing procedure;
(2) washing with water: conveying the material obtained by the reaction in the step (1) to a workshop storage tank by a pump, wherein the material comprises p-nitroanisole, o-nitroanisole, m-chloronitrobenzene, water, sodium p-nitrophenolate, sodium o-nitrophenolate, sodium chloride and low-boiling-point substances, then pumping the material into a washing kettle from the workshop storage tank for washing, the pumping amount of the material is two thirds of the volume of the washing kettle, then performing washing twice, wherein the adding amount of washing water is one fourth of the pumping amount of the material, stirring for 0.5h, the rotating speed is 60r/min, standing for 2h, and the temperature of washing twice is 65-70 ℃; sending the waste water after washing into a waste water tank, and sending the material after washing into a dry front tank;
(3) and (3) drying: starting a vacuum pump, opening a vacuum valve of a water receiving tank and a water valve of a condenser, opening a material pumping valve, pumping the water-washed material from a pre-drying tank into a dehydration kettle, wherein the pumped material amount is two thirds of the volume of the dehydration kettle, adjusting the pressure of the dehydration kettle to be-0.1-0 Mpa, the temperature of the dehydration kettle is higher than 85 ℃, then stirring, slightly opening steam for dehydration, finishing dehydration when the sight glass of the condenser is basically anhydrous, then closing the vacuum valve and an air outlet valve, and opening air pressure to press the dried material into a post-drying tank;
(4) and (3) rectification: three-stage vacuum distillation is adopted to separate m-chloronitrobenzene and remove a small amount of chlorobenzene, and the specific process is as follows:
column # 1: introducing the dried material obtained in the step (3) into the 1# tower, simultaneously heating, starting a vacuum pump when the temperature of a tower kettle rises to 100 ℃, completely vacuumizing the 1# tower, the 2# tower and the 3# tower to-0.096 Mpa, simultaneously opening a circulating water pump, adjusting the water inlet and outlet of a tower top condenser, performing total reflux for 2-3h to ensure that the interior of the tower is balanced and then starting to extract when the temperature of the tower top is 50-60 ℃, adjusting the temperature of the 1# tower kettle to 145-155 ℃, controlling the pressure to-0.1 Mpa, collecting low-boiling-point substances from the tower top, wherein the low-boiling-point substances are nitrobenzene, water and chlorobenzene with the content of less than 1%, and continuously pumping the material in the tower kettle into the 2# tower;
2# tower: continuously pumping the material in the tower kettle No. 1 into a feed inlet of a tower No. 2, adjusting the temperature of the tower kettle No. 2 to be 170-180 ℃, and the pressure to be-0.1 Mpa, separating m-chloronitrobenzene from the tower top, wherein the content of the m-chloronitrobenzene is more than or equal to 90 percent, and then feeding the m-chloronitrobenzene into a crystallization kettle; continuously pumping the material in the tower kettle 2 into the tower kettle 3, and keeping the balance of the feeding amount and the extracted amount in the process so that the volume of the material in the tower kettle is always one third of the volume of the tower kettle;
3# tower: continuously pumping the material in the tower kettle 2 into the tower 3, adjusting the temperature of the tower kettle 3 to be 170-180 ℃, and the pressure to be-0.1 Mpa, separating the nitrobenzyl ether from the tower kettle, putting the nitrobenzyl ether into a No. 1 intermediate storage tank, and carrying out subsequent treatment; the material at the top of the tower is circularly and continuously pumped into a feed inlet of a No. 2 tower;
(5) and (3) crystallization: pumping m-chloronitrobenzene separated from the No. 2 tower into a crystallization kettle by a pump, stopping the pump after reflux exists in a reflux sight glass, starting a circulating pump, quickly cooling the crystallization kettle, adjusting a water valve of the circulating pump to slowly cool after the temperature is reduced to 45 ℃, completing crystallization when the temperature is lower than 27 ℃, and then detecting the content of the m-chloronitrobenzene; when the content of m-chloronitrobenzene is more than or equal to 99.5 percent, pumping the m-chloronitrobenzene into a No. 2 intermediate storage tank for subsequent preparation of m-chloroaniline or direct packaging for sale; the m-chloronitrobenzene content is between 93 percent and 99.5 percent and is crystallized for use again; when the content of m-chloronitrobenzene is less than 93 percent, uniformly collecting the m-chloronitrobenzene, pumping the m-chloronitrobenzene into a feed inlet of a No. 2 tower for further rectification and purification;
(6) reduction: adding 350g/L sodium hydrosulfide aqueous solution into a reduction kettle, gradually raising the temperature of the reduction kettle to 110 ℃, then adding m-chloronitrobenzene of a No. 2 intermediate storage tank into the reaction kettle through a metering tank, then adjusting the temperature in the kettle to be 135-145 ℃, and the pressure to be 0.25Mpa, carrying out reduction reaction with the sodium hydrosulfide, standing and layering after the reaction is finished, wherein the lower layer is a mixture of water, sodium thiosulfate, sodium hydrosulfide and sodium hydroxide, and conveying the mixture to a sodium bicarbonate preparation process through a pipeline, and the crude product reduction material on the upper layer is conveyed into an amino tank for the next process; the intermediate chloronitrobenzene: the mass ratio of the sodium hydrosulfide is 3: 5.5;
(7) and (3) distillation: introducing the crude product reduced material in the amino tank into a distillation kettle, raising the temperature of the kettle to 170 ℃, removing water and trace impurities in the crude product reduced material through vacuum distillation to obtain a finished product of m-chloroaniline, and leading out the material at the bottom of the kettle for solid waste treatment.
In the invention, the nitroanisole in the No. 1 intermediate storage tank can be introduced into a reduction kettle through a metering tank, 350g/L of sodium hydrosulfide solution is added into the reduction kettle, and the added nitroanisole: the mass ratio of sodium hydrosulfide is 3:5.5, the temperature of a reduction kettle is adjusted to 140 ℃, the pressure is 0.25Mpa, the nitroanisole is reacted with the sodium hydrosulfide solution, after the reaction is finished, the reaction kettle is kept still for layering, the upper layer material is sent into a distillation kettle at 170 ℃, water and trace impurities are removed through vacuum distillation, the anisidine is obtained, and the anisidine is rectified, so that byproducts of anthranylether and p-anisidine are obtained.
The method takes waste meta-oil and industrial waste liquid sodium hydrosulfide as raw materials, prepares m-chloroaniline by methoxylation, crystallization and reduction, and generates byproducts of o-anisidine and p-anisidine, thereby realizing low cost and high yield.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principles of the present invention are intended to be included within the scope of the present invention.
Claims (6)
1. The method for preparing the m-chloroaniline by using the meta-oil is characterized by comprising the following steps of:
(1) burdening reaction: adding meta-position oil into a methoxylation reaction kettle, metering and adding methanol from a methanol metering tank under a closed state, adding a catalyst ammonium chloride, stirring, heating the reaction kettle to 58-63 ℃, adjusting the pressure of the reaction kettle to 0MPa, finally adding sodium hydroxide into the reaction kettle, keeping the temperature unchanged, and sampling and detecting after 5 hours of reaction; wherein, meta-oil: methanol: sodium hydroxide: the mass ratio of ammonium chloride is 1: 0.30: 0.32: 0.045, when the content of the p-nitrochlorobenzene is detected to be less than or equal to 0.1 percent and the content of the o-nitrochlorobenzene is detected to be less than or equal to 2 percent, recovering the methanol, and then transferring to the next washing procedure;
(2) washing with water: conveying the material obtained by the reaction in the step (1) to a workshop storage tank by a pump, pumping the material into a washing kettle from the workshop storage tank for washing, wherein the pumping amount of the material is two thirds of the volume of the washing kettle, then washing twice, wherein the adding amount of washing water is one fourth of the pumping amount of the material, stirring for 0.5h, and standing for 2 h; sending the waste water after washing into a waste water tank, and sending the material after washing into a dry front tank;
(3) and (3) drying: starting a vacuum pump, opening a vacuum valve of a water receiving tank and a water valve of a condenser, opening a material pumping valve, pumping the water-washed materials from a pre-drying tank into a dehydration kettle, wherein the pumped materials are two thirds of the volume of the dehydration kettle, then stirring, slightly opening steam for dehydration, finishing dehydration when the viewing mirror of the condenser is basically anhydrous, then closing the vacuum valve and an air outlet valve, and opening air pressure to press the dried materials into a post-drying tank;
(4) and (3) rectification: three-stage vacuum distillation is adopted to separate m-chloronitrobenzene and remove a small amount of chlorobenzene, and the specific process is as follows:
column # 1: introducing the dried material obtained in the step (3) into the 1# tower, simultaneously heating, starting a vacuum pump when the temperature of a tower kettle rises to 100 ℃, completely vacuumizing the 1# tower, the 2# tower and the 3# tower to-0.096 Mpa, simultaneously opening a circulating water pump, adjusting the water inlet and outlet of a condenser at the top of the tower, performing total reflux for 2-3h to ensure that the interior of the tower is balanced and then begins to be extracted when the temperature of the top of the tower is 50-60 ℃, adjusting the temperature of the 1# tower kettle to 145-155 ℃, and controlling the pressure to-0.1 Mpa, collecting low-boiling-point substances from the top of the tower, and continuously pumping the material in the tower kettle into the 2# tower;
2# tower: continuously pumping the material in the tower kettle No. 1 into a feed inlet of a tower No. 2, adjusting the temperature of the tower kettle No. 2 to be 170-180 ℃, and the pressure to be-0.1 Mpa, separating m-chloronitrobenzene from the tower top, wherein the content of the m-chloronitrobenzene is more than or equal to 90 percent, and then feeding the m-chloronitrobenzene into a crystallization kettle; continuously pumping the material in the tower kettle 2 into the tower kettle 3, and keeping the balance of the feeding amount and the extracted amount in the process so that the volume of the material in the tower kettle is always one third of the volume of the tower kettle;
3# tower: continuously pumping the material in the tower kettle 2 into the tower 3, adjusting the temperature of the tower kettle 3 to be 170-180 ℃, and the pressure to be-0.1 Mpa, separating the nitrobenzyl ether from the tower kettle, putting the nitrobenzyl ether into a No. 1 intermediate storage tank, and carrying out subsequent treatment;
circularly and continuously pumping the tower top material into a feed inlet of a No. 2 tower;
(5) and (3) crystallization: pumping m-chloronitrobenzene separated from the No. 2 tower into a crystallization kettle by a pump, stopping the pump after reflux exists in a reflux sight glass, starting a circulating pump, quickly cooling the crystallization kettle, adjusting a water valve of the circulating pump to slowly cool after the temperature is reduced to 45 ℃, completing crystallization when the temperature is lower than 27 ℃, and then detecting the content of the m-chloronitrobenzene; when the content of m-chloronitrobenzene is more than or equal to 99.5 percent, pumping the m-chloronitrobenzene into a No. 2 intermediate storage tank for subsequent preparation of m-chloroaniline or direct packaging for sale; the m-chloronitrobenzene content is between 93 percent and 99.5 percent and is crystallized for use again; when the content of m-chloronitrobenzene is less than 93 percent, uniformly collecting the m-chloronitrobenzene, pumping the m-chloronitrobenzene into a feed inlet of a No. 2 tower for further rectification and purification;
(6) reduction: adding 350g/L sodium hydrosulfide aqueous solution into a reduction kettle, gradually raising the temperature of the reduction kettle to 110 ℃, then adding m-chloronitrobenzene of a No. 2 intermediate storage tank into the reaction kettle through a metering tank, then adjusting the temperature in the kettle to be 135-145 ℃, and the pressure to be 0.25Mpa, carrying out reduction reaction with the sodium hydrosulfide, standing and layering after the reaction is finished, wherein the lower layer is a mixture of water, sodium thiosulfate, sodium hydrosulfide and sodium hydroxide, and conveying the mixture to a sodium bicarbonate preparation process through a pipeline, and the crude reducing material on the upper layer is conveyed into an amino tank for the next process; the intermediate chloronitrobenzene: the mass ratio of the sodium hydrosulfide is 3: 5.5;
(7) and (3) distillation: introducing the crude product reduced material in the amino tank into a distillation kettle, raising the temperature of the kettle to 170 ℃, removing water and trace impurities in the crude product reduced material through vacuum distillation to obtain a finished product of m-chloroaniline, and leading out the material at the bottom of the kettle for solid waste treatment;
(8) preparation of by-products: introducing the nitrobenzyl ether in the No. 1 intermediate storage tank into a reduction kettle through a metering tank, adding 350g/L of sodium hydrosulfide solution into the reduction kettle, and adding the nitrobenzyl ether: the mass ratio of sodium hydrosulfide is 3:5.5, the temperature of a reduction kettle is adjusted to 140 ℃, the pressure is 0.25Mpa, the nitroanisole is reacted with the sodium hydrosulfide solution, after the reaction is finished, the reaction kettle is kept still for layering, the upper layer material is sent into a distillation kettle at 170 ℃, water and trace impurities are removed through vacuum distillation, the anisidine is obtained, and the anisidine is rectified, so that byproducts of anthranylether and p-anisidine are obtained.
2. The method for preparing the m-chloroaniline by using the meta-oil as claimed in claim 1, wherein the temperature of the two water washes in the step (2) is 65-70 ℃.
3. The method for preparing m-chloroaniline by using meta-oil as claimed in claim 1, wherein the stirring speed in step (1) and step (2) is 60 r/min.
4. The method for preparing m-chloroaniline by using meta-oil as claimed in claim 1, wherein the material obtained by the reaction in step (1) comprises p-nitroanisole, o-nitroanisole, m-chloronitrobenzene, water, sodium p-nitrophenolate, sodium o-nitrophenolate, sodium chloride and low-boiling-point substances.
5. The method for preparing the m-chloroaniline by using the meta-oil as claimed in claim 1, wherein the pressure of the dehydration kettle is-0.1-0 Mpa, and the temperature is higher than 85 ℃.
6. The method for preparing m-chloroaniline by using meta-oil as claimed in claim 1, wherein the low boiling substance is nitrobenzene, water and chlorobenzene with content less than 1%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611246576.1A CN106883129B (en) | 2016-12-29 | 2016-12-29 | Method for preparing m-chloroaniline by using meta-oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611246576.1A CN106883129B (en) | 2016-12-29 | 2016-12-29 | Method for preparing m-chloroaniline by using meta-oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106883129A CN106883129A (en) | 2017-06-23 |
| CN106883129B true CN106883129B (en) | 2021-05-14 |
Family
ID=59176582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611246576.1A Active CN106883129B (en) | 2016-12-29 | 2016-12-29 | Method for preparing m-chloroaniline by using meta-oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106883129B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109369409A (en) * | 2018-11-09 | 2019-02-22 | 宁夏华御化工有限公司 | Nitro-chlorobenzene produces interposition oil separation reutilization system and meta position oil separating method |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1861562A (en) * | 2006-06-19 | 2006-11-15 | 常州市佳森化工有限公司 | Process of producing nitrobenzether aminobenzether amidobenzether from chlorobenzene |
| CN1861563A (en) * | 2006-06-19 | 2006-11-15 | 常州市佳森化工有限公司 | Tech. of producing ortho nitro methyl-phenoxide para nitro methyl-phenoxide and meta nitro chlorobenzene from chlorobenzene |
| CN101607919A (en) * | 2009-06-22 | 2009-12-23 | 扬州铭睿达化工科技有限公司 | A kind of nitro-chlorobenzene that mixes reacts the method for producing anisidine in water solvent |
| CN101935281A (en) * | 2009-06-30 | 2011-01-05 | 邵阳市申强化工有限责任公司 | Method for preparing m-nitrochlorobenzene, o-nitrochlorobenzene and p-nitrochlorobenzene by using nitrochlorobenzene meta-position oil |
| CN102134198A (en) * | 2010-12-29 | 2011-07-27 | 安徽八一化工股份有限公司 | Method for separating nitrochlorobenzene meta-position oil |
| CN103073431A (en) * | 2011-10-26 | 2013-05-01 | 常州市佳森化工有限公司 | Method for preparing o-nitroanisole and p-nitroanisole from mixed nitrochlorobenzene |
| CN103508901A (en) * | 2012-06-29 | 2014-01-15 | 中国石油化工股份有限公司 | Method for synthetizing 3,5-dichloroaniline |
| CN104557557A (en) * | 2013-10-09 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing nitroanisole from m-nitrochlorobenzene oil |
| CN105566121A (en) * | 2014-10-11 | 2016-05-11 | 中国石油化工股份有限公司 | Method for reducing generation of nitrophenol in preparation process of nitroanisole |
-
2016
- 2016-12-29 CN CN201611246576.1A patent/CN106883129B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1861562A (en) * | 2006-06-19 | 2006-11-15 | 常州市佳森化工有限公司 | Process of producing nitrobenzether aminobenzether amidobenzether from chlorobenzene |
| CN1861563A (en) * | 2006-06-19 | 2006-11-15 | 常州市佳森化工有限公司 | Tech. of producing ortho nitro methyl-phenoxide para nitro methyl-phenoxide and meta nitro chlorobenzene from chlorobenzene |
| CN101607919A (en) * | 2009-06-22 | 2009-12-23 | 扬州铭睿达化工科技有限公司 | A kind of nitro-chlorobenzene that mixes reacts the method for producing anisidine in water solvent |
| CN101935281A (en) * | 2009-06-30 | 2011-01-05 | 邵阳市申强化工有限责任公司 | Method for preparing m-nitrochlorobenzene, o-nitrochlorobenzene and p-nitrochlorobenzene by using nitrochlorobenzene meta-position oil |
| CN102134198A (en) * | 2010-12-29 | 2011-07-27 | 安徽八一化工股份有限公司 | Method for separating nitrochlorobenzene meta-position oil |
| CN103073431A (en) * | 2011-10-26 | 2013-05-01 | 常州市佳森化工有限公司 | Method for preparing o-nitroanisole and p-nitroanisole from mixed nitrochlorobenzene |
| CN103508901A (en) * | 2012-06-29 | 2014-01-15 | 中国石油化工股份有限公司 | Method for synthetizing 3,5-dichloroaniline |
| CN104557557A (en) * | 2013-10-09 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing nitroanisole from m-nitrochlorobenzene oil |
| CN105566121A (en) * | 2014-10-11 | 2016-05-11 | 中国石油化工股份有限公司 | Method for reducing generation of nitrophenol in preparation process of nitroanisole |
Non-Patent Citations (1)
| Title |
|---|
| 间氯苯胺的合成研究;万国林等;《广东化工》;20111231;第2.3节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106883129A (en) | 2017-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102241606B (en) | Clean production method of N-cyanoethylaniline | |
| CN104098474B (en) | Nitrotoluene Continuous Liquid Phase catalytic hydrogenating reduction produces the device and method of monomethylaniline | |
| CN102633653A (en) | Method for preparing o-phenylenediamine by catalytic hydrogenation of o-nitrophenylamine | |
| CN103664656A (en) | Synthesis and application of quaternary ammonium salt ionic liquid based on heteropolyacid | |
| CN104725251A (en) | Method for preparing solvent blue 78 | |
| CN103086895B (en) | Method for preparing aromatic amine from mixed nitrochlorobenzene | |
| CN101693649B (en) | Process for preparing 1.3.5-trimethoxybenzene | |
| CN106883129B (en) | Method for preparing m-chloroaniline by using meta-oil | |
| CN103274913A (en) | Method and device for producing methyl isobutyl ketone | |
| CN102910775B (en) | Carbendazim production wastewater pretreatment method | |
| CN102134198B (en) | Method for separating nitrochlorobenzene meta-position oil | |
| CN107082740B (en) | Method for improving yield of prenol prepared by chlorination process | |
| CN103193660B (en) | Synthetic method of 4-alkoxy phenylamine compound | |
| CN105924328A (en) | High-selectivity green hydrolysis technology for preparing benzyl alcohol | |
| CN102659572B (en) | Preparation method of dehydroabietic acid | |
| CN106187787A (en) | A kind of preparation method of 2 amino 4 chlorodiphenyl ethers | |
| CN102627551B (en) | Method for isomerizing rosin resin acid promoted by solid super acid | |
| CN1990456A (en) | Method for production of N, N dimethyl cyclohexylamine | |
| CN105801376B (en) | Silica gel supported imidazole ion liquid is catalyzed the production method of benzene direct oxidation phenol | |
| CN104276928A (en) | Preparation method of 4,6-bi[1-(4-hydroxypheny)-1-methyl ethyl]-1,3-hydroquinone | |
| CN202705267U (en) | Glycol dimethyl ether component recovery device in synthetic product waste salt | |
| CN203440262U (en) | Device for producing trans-1, 2-dichloroethylene with acetylene by adopting catalytic chlorination method | |
| CN105348285A (en) | Low-cost and high-yield adenine preparation method | |
| CN103992230A (en) | Method for preparing diaminobenzene and aniline from nitrobenzene mixture containing dinitrobenzene | |
| CN207276532U (en) | The production system of antioxidant 565 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 233300 No.36 Kaiyuan Avenue, mohekou Industrial Park, Huaishang District, Bengbu City, Anhui Province Applicant after: Anhui Haihua Technology Co., Ltd. Address before: 233000 Anhui province Bengbu Kaiyuan Avenue estuary Industrial Park Huaishang District No. 36 Mo Applicant before: Anhui Haihua Chemical Technology Co., Ltd. |
|
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 233000 No.36, Kaiyuan Avenue, mohekou Industrial Park, Huaishang District, Bengbu City, Anhui Province Applicant after: Anhui Haihua Technology Group Co.,Ltd. Address before: 233300 No.36, Kaiyuan Avenue, mohekou Industrial Park, Huaishang District, Bengbu City, Anhui Province Applicant before: Anhui Haihua Technology Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |