CN110551000A - Industrial production method of m-dichlorobenzene - Google Patents
Industrial production method of m-dichlorobenzene Download PDFInfo
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- CN110551000A CN110551000A CN201810542318.0A CN201810542318A CN110551000A CN 110551000 A CN110551000 A CN 110551000A CN 201810542318 A CN201810542318 A CN 201810542318A CN 110551000 A CN110551000 A CN 110551000A
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- dichlorobenzene
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- dinitrobenzene
- nitrobenzene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
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- 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
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of organic synthesis, in particular to an industrial production method of m-dichlorobenzene, aiming at improving the yield and purity of products. The key points of the technical scheme comprise that benzene and concentrated nitric acid are mixed, and catalytic reaction is carried out by taking manganese dioxide as a catalyst to obtain nitrobenzene; mixing nitrobenzene and concentrated nitric acid, and carrying out secondary catalytic reaction to obtain a mixed nitrobenzene solution; mixing and stirring the mixed nitrobenzene, sodium bisulfite and sodium hydroxide to obtain m-dinitrobenzene; introducing chlorine into m-dinitrobenzene to obtain a crude m-dichlorobenzene solution; removing impurities from the m-dichlorobenzene solution by using a hydrophobic silicon zeolite molecular sieve; then crystallizing, rectifying to remove impurities, and secondarily chlorinating to obtain pure m-dichlorobenzene; and finally, carrying out condensation treatment to obtain a finished product and collecting the finished product.
Description
Technical Field
the invention relates to the technical field of organic synthesis, in particular to an industrial production method of m-dichlorobenzene.
Background
The m-dichlorobenzene is colorless liquid, has pungent smell, is insoluble in water, and is soluble in alcohol and ether. Can carry out chlorination, nitration, sulfonation and hydrolysis reactions, and the reaction is violent when meeting aluminum. At present, the commonly used method for producing m-dichlorobenzene mainly comprises the steps of directly carrying out chlorination process by taking benzene as a raw material, and then carrying out treatment of procedures such as crystallization, rectification and the like to produce the m-dichlorobenzene.
Disclosure of Invention
The invention aims to provide an industrial production method of m-dichlorobenzene, aiming at improving the yield and purity of products.
The technical purpose of the invention is realized by the following technical scheme:
An industrial production method of m-dichlorobenzene comprises the following steps:
S1: mixing benzene and concentrated nitric acid, and carrying out catalytic reaction by using manganese dioxide as a catalyst to obtain nitrobenzene;
S2: adding concentrated nitric acid into the nitrobenzene obtained in the step S1 for mixing, and then adding manganese dioxide for secondary catalytic reaction to obtain a mixed nitrobenzene solution containing o-dinitrobenzene, p-dinitrobenzene and m-dinitrobenzene;
S3: mixing and stirring the mixed nitrobenzene obtained in the step S2 with a mixed solution of sodium bisulfite and sodium hydroxide, and then washing and centrifugally separating to obtain m-dinitrobenzene;
S4: introducing chlorine into m-dinitrobenzene in S3 to perform chlorination reaction of the m-dinitrobenzene in a chlorination kettle to obtain a crude m-dichlorobenzene solution;
S5: adsorbing and removing impurities from the m-dichlorobenzene solution in the S4 by using a hydrophobic silicon zeolite molecular sieve;
s6: feeding the solution subjected to impurity removal in the S5 into a crystallization kettle for crystallization treatment;
s7: feeding the m-dichlorobenzene crystallized in the S6 into a rectifying tower for rectification and impurity removal;
s8: condensing the m-dichlorobenzene subjected to impurity removal in S7, introducing chlorine, and carrying out secondary chlorination reaction to obtain pure m-dichlorobenzene;
S9: and (4) feeding m-dichlorobenzene obtained in the S8 into a condenser for condensation treatment to obtain a finished product, and collecting the finished product.
Further, the mass ratio of benzene to concentrated nitric acid in S1 is 1 (1-1.2).
Further, the mass ratio of nitrobenzene to concentrated nitric acid in S2 is 1 (1-1.2).
further, the mass ratio of sodium bisulfite to sodium hydroxide added in S3 is 1 (1-1.5).
further, the washing and centrifugation process in S3 is: firstly, the mixed solution is washed and centrifugally separated for many times by using dilute ammonia water, then, the mixed solution is washed for the second time by using distilled water, and then, centrifugal separation is carried out.
Further, the reaction temperature of the chlorination kettle in S4 is controlled at 230-250 ℃ during the chlorination reaction.
further, the temperature in the crystallization tank in S6 was 115 ℃.
Further, the reaction temperature of the secondary chlorination reaction in S8 was 230 ℃.
The method for producing m-dichlorobenzene provided by the invention adopts benzene as a raw material, and finally produces the m-dichlorobenzene product with higher purity through twice nitration reaction and repeated chlorination reaction.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
The invention discloses an industrial production method of m-dichlorobenzene, which specifically comprises the following steps.
example 1
S1: mixing benzene and concentrated nitric acid, wherein the mass ratio of the benzene to the concentrated nitric acid is 1:1, and carrying out catalytic reaction by using manganese dioxide as a catalyst to obtain nitrobenzene.
S2: adding concentrated nitric acid into the nitrobenzene obtained in the step S1 for mixing, wherein the mass ratio of the nitrobenzene to the concentrated nitric acid is 1:1, and adding manganese dioxide for secondary catalytic reaction to obtain a mixed nitrobenzene solution containing o-dinitrobenzene, p-dinitrobenzene and m-dinitrobenzene.
S3: and (2) mixing and stirring the mixed nitrobenzene obtained in the step (S2) with a mixed solution of sodium bisulfite and sodium hydroxide, wherein the mass ratio of the sodium bisulfite to the sodium hydroxide is 1:1, washing and centrifugally separating to obtain the m-dinitrobenzene, wherein the specific washing process comprises the steps of washing the mixed solution for multiple times by using dilute ammonia water and centrifugally separating, then washing for the second time by using distilled water, and then centrifugally separating.
S4: chlorine gas is introduced into m-dinitrobenzene in S3, and m-dinitrobenzene is subjected to chlorination reaction in a chlorination kettle at 230 ℃ to obtain a crude m-dichlorobenzene solution.
s5: and (3) adsorbing the m-dichlorobenzene solution in the S4 by using a hydrophobic silicalite molecular sieve to remove impurities.
S6: and (4) feeding the solution subjected to impurity removal in the S5 into a crystallization kettle for crystallization treatment, and controlling the temperature in the crystallization kettle at 115 ℃.
S7: and (3) feeding the m-dichlorobenzene crystallized in the S6 into a rectifying tower for rectification and impurity removal.
S8: and (3) condensing the m-dichlorobenzene subjected to impurity removal in the S7, introducing chlorine, performing secondary chlorination reaction, and controlling the reaction temperature at 230 ℃ to obtain pure m-dichlorobenzene.
S9: and (4) feeding m-dichlorobenzene obtained in the S8 into a condenser for condensation treatment to obtain a finished product, and collecting the finished product.
Example 2
s1: mixing benzene and concentrated nitric acid, wherein the mass ratio of the benzene to the concentrated nitric acid is 1:1.2, and carrying out catalytic reaction by using manganese dioxide as a catalyst to obtain nitrobenzene.
S2: adding concentrated nitric acid into the nitrobenzene obtained in the step S1 for mixing, wherein the mass ratio of the nitrobenzene to the concentrated nitric acid is 1:1.2, and adding manganese dioxide for secondary catalytic reaction to obtain a mixed nitrobenzene solution containing o-dinitrobenzene, p-dinitrobenzene and m-dinitrobenzene.
S3: and (2) mixing and stirring the mixed nitrobenzene obtained in the step (S2) with a mixed solution of sodium bisulfite and sodium hydroxide, wherein the mass ratio of the sodium bisulfite to the sodium hydroxide is 1:1.5, washing and centrifugally separating to obtain the m-dinitrobenzene, wherein the specific washing process comprises the steps of washing the mixed solution for multiple times by using dilute ammonia water and centrifugally separating, washing for the second time by using distilled water, and centrifugally separating.
s4: chlorine is introduced into the m-dinitrobenzene in S3, and the m-dinitrobenzene is subjected to chlorination reaction in a chlorination kettle at the temperature of 250 ℃ to obtain a crude m-dichlorobenzene solution.
s5: and (3) adsorbing the m-dichlorobenzene solution in the S4 by using a hydrophobic silicalite molecular sieve to remove impurities.
s6: and (4) feeding the solution subjected to impurity removal in the S5 into a crystallization kettle for crystallization treatment, and controlling the temperature in the crystallization kettle at 115 ℃.
S7: and (3) feeding the m-dichlorobenzene crystallized in the S6 into a rectifying tower for rectification and impurity removal.
S8: and (3) condensing the m-dichlorobenzene subjected to impurity removal in the S7, introducing chlorine, performing secondary chlorination reaction, and controlling the reaction temperature at 230 ℃ to obtain pure m-dichlorobenzene.
S9: and (4) feeding m-dichlorobenzene obtained in the S8 into a condenser for condensation treatment to obtain a finished product, and collecting the finished product.
Example 3
S1: mixing benzene and concentrated nitric acid, wherein the mass ratio of the benzene to the concentrated nitric acid is 1:1.1, and carrying out catalytic reaction by using manganese dioxide as a catalyst to obtain nitrobenzene.
S2: adding concentrated nitric acid into the nitrobenzene obtained in the step S1 for mixing, wherein the mass ratio of the nitrobenzene to the concentrated nitric acid is 1:1.1, and adding manganese dioxide for secondary catalytic reaction to obtain a mixed nitrobenzene solution containing o-dinitrobenzene, p-dinitrobenzene and m-dinitrobenzene.
s3: and (2) mixing and stirring the mixed nitrobenzene obtained in the step (S2) with a mixed solution of sodium bisulfite and sodium hydroxide, wherein the mass ratio of the sodium bisulfite to the sodium hydroxide is 1:1.3, washing and centrifugally separating to obtain the m-dinitrobenzene, wherein the specific washing process comprises the steps of washing the mixed solution for multiple times by using dilute ammonia water and centrifugally separating, washing for the second time by using distilled water, and centrifugally separating.
S4: chlorine gas is introduced into m-dinitrobenzene in S3, and m-dinitrobenzene is subjected to chlorination reaction in a chlorination kettle, wherein the temperature is controlled at 240 ℃, so that a crude m-dichlorobenzene solution is obtained.
S5: and (3) adsorbing the m-dichlorobenzene solution in the S4 by using a hydrophobic silicalite molecular sieve to remove impurities.
S6: and (4) feeding the solution subjected to impurity removal in the S5 into a crystallization kettle for crystallization treatment, and controlling the temperature in the crystallization kettle at 115 ℃.
S7: and (3) feeding the m-dichlorobenzene crystallized in the S6 into a rectifying tower for rectification and impurity removal.
S8: and (3) condensing the m-dichlorobenzene subjected to impurity removal in the S7, introducing chlorine, performing secondary chlorination reaction, and controlling the reaction temperature at 230 ℃ to obtain pure m-dichlorobenzene.
s9: and (4) feeding m-dichlorobenzene obtained in the S8 into a condenser for condensation treatment to obtain a finished product, and collecting the finished product.
Claims (8)
1. An industrial production method of m-dichlorobenzene is characterized in that: the method comprises the following steps:
S1: mixing benzene and concentrated nitric acid, and carrying out catalytic reaction by using manganese dioxide as a catalyst to obtain nitrobenzene;
S2: adding concentrated nitric acid into the nitrobenzene obtained in the step S1 for mixing, and then adding manganese dioxide for secondary catalytic reaction to obtain a mixed nitrobenzene solution containing o-dinitrobenzene, p-dinitrobenzene and m-dinitrobenzene;
S3: mixing and stirring the mixed nitrobenzene obtained in the step S2 with a mixed solution of sodium bisulfite and sodium hydroxide, and then washing and centrifugally separating to obtain m-dinitrobenzene;
s4: introducing chlorine into m-dinitrobenzene in S3 to perform chlorination reaction of the m-dinitrobenzene in a chlorination kettle to obtain a crude m-dichlorobenzene solution;
S5: adsorbing and removing impurities from the m-dichlorobenzene solution in the S4 by using a hydrophobic silicon zeolite molecular sieve;
S6: feeding the solution subjected to impurity removal in the S5 into a crystallization kettle for crystallization treatment;
S7: feeding the m-dichlorobenzene crystallized in the S6 into a rectifying tower for rectification and impurity removal;
S8: condensing the m-dichlorobenzene subjected to impurity removal in S7, introducing chlorine, and carrying out secondary chlorination reaction to obtain pure m-dichlorobenzene;
S9: and (4) feeding m-dichlorobenzene obtained in the S8 into a condenser for condensation treatment to obtain a finished product, and collecting the finished product.
2. The method for industrially producing m-dichlorobenzene according to claim 1, wherein the reaction is carried out by the following steps: the mass ratio of benzene to concentrated nitric acid in S1 is 1 (1-1.2).
3. The method for industrially producing m-dichlorobenzene according to claim 1, wherein the reaction is carried out by the following steps: the mass ratio of nitrobenzene to concentrated nitric acid in S2 is 1 (1-1.2).
4. The method for industrially producing m-dichlorobenzene according to claim 1, wherein the reaction is carried out by the following steps: the mass ratio of the sodium bisulfite to the sodium hydroxide added in S3 is 1 (1-1.5).
5. the method for industrially producing m-dichlorobenzene according to claim 1, wherein the reaction is carried out by the following steps: the washing and centrifugation process in S3 was: firstly, the mixed solution is washed and centrifugally separated for many times by using dilute ammonia water, then, the mixed solution is washed for the second time by using distilled water, and then, centrifugal separation is carried out.
6. The method for industrially producing m-dichlorobenzene according to claim 1, wherein the reaction is carried out by the following steps: the reaction temperature of the chlorination kettle in the S4 is controlled at 230 ℃ and 250 ℃ during the chlorination reaction.
7. The method for industrially producing m-dichlorobenzene according to claim 1, wherein the reaction is carried out by the following steps: the temperature in the crystallization kettle in S6 was 115 ℃.
8. the method for industrially producing m-dichlorobenzene according to claim 1, wherein the reaction is carried out by the following steps: the reaction temperature of the secondary chlorination reaction in S8 was 230 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201810542318.0A CN110551000A (en) | 2018-05-30 | 2018-05-30 | Industrial production method of m-dichlorobenzene |
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| CN201810542318.0A CN110551000A (en) | 2018-05-30 | 2018-05-30 | Industrial production method of m-dichlorobenzene |
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| CN201810542318.0A Pending CN110551000A (en) | 2018-05-30 | 2018-05-30 | Industrial production method of m-dichlorobenzene |
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Application publication date: 20191210 |