CN113429279B - Resource utilization method of 2, 4-dichloroacetophenone wastewater - Google Patents
Resource utilization method of 2, 4-dichloroacetophenone wastewater Download PDFInfo
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Abstract
The invention provides a resource utilization method of 2, 4-dichloroacetophenone waste water, which creatively puts aluminum salt in the 2, 4-dichloroacetophenone waste water into a reaction system after activated carbon decoloration and negative pressure dehydration, directly obtains fresh anhydrous aluminum trichloride through hydrogen chloride bubbling and toluene carrying water, avoids directly using a large amount of anhydrous aluminum trichloride, adds acetyl chloride into the system, reacts the acetyl chloride and m-dichlorobenzene, after the reaction is finished, puts water and toluene carrying water which are dehydrated under negative pressure into the system again, leads oil and water to be layered through hydrolysis, leads the product to be layered through oil and water in an oil layer, and then obtains the product through rectification, the water layer is continuously recycled and reused through the method, the whole process does not use alkali solution for neutralization, the hydrogen chloride gas consumption is small, catalyst components in the waste water are effectively recycled, no waste water is produced, the discharge of three wastes is effectively reduced, the internal circulation of aluminum salt and water is formed, and the cost is greatly saved.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, relates to a wastewater treatment technology of a pesticide intermediate, and particularly relates to a resource utilization method of 2, 4-dichloroacetophenone wastewater.
Background
2, 4-dichloroacetophenone is an important fine chemical intermediate, and has wide application in the fields of medicines, pesticides and the like, such as: the 2, 4-dichloroacetophenone can be used for synthesizing deep fungal infection resisting medicines of fluconazole and itraconazole, and can also be used for synthesizing low-toxicity, broad-spectrum and systemic bactericides of azaconazole, methylcyclozole, etaconazole and propiconazole.
Most of the traditional synthesis methods of 2, 4-dichloroacetophenone are to take m-dichlorobenzene as a raw material, acetyl chloride or acetic anhydride as an acylation reagent and add AlCl as a Lewis acid3The acetylation reaction is carried out under the catalysis of the (2, 4-dichloroacetophenone). AlCl as catalyst at the end of the acylation reaction3Further complexing with the generated 2, 4-dichloroacetophenone, adding a large amount of water for hydrolysis, and hydrolyzing the generated complex to release 2, 4-dichloroacetophenone product and simultaneously form AlCl-containing3And HCl waste water.
Chinese patent CN109721480A uses AlCl3As a catalyst, acetic anhydride is used as an acylation reagent, electrophilic substitution reaction is carried out on the acetic anhydride and m-dichlorobenzene to prepare 2, 4-dichloroacetophenone, toluene and 10% hydrochloric acid are added for layering after the reaction is finished, and the product 2, 4-dichloroacetophenone is recovered from an oil layer with the yield of 95%, but how to treat a water layer is not mentioned.
Chinese patent CN110922322A uses AlCl3As a catalyst, acetic anhydride is used as an acylation reagent to perform acylation reaction with m-dichlorobenzene recovered from chlorinated aromatic hydrocarbon waste. After the reaction is finished, 2, 4-dichloroacetophenone products are obtained by hydrolysis, delamination, washing of oil layer and distillation, and the patent does not mention how to treat the acidic wastewater containing aluminum trichloride.
The method comprises the steps of neutralizing the waste water with an alkali solution, filtering out aluminum hydroxide, and treating the waste water by methods such as oxidation, biochemistry and the like, wherein the aluminum content in the waste water of the 2, 4-dichloroacetophenone is about 1.5-4%, the chlorine content is 8-25%, the acidity is about 3-10% calculated by hydrochloric acid, the waste water is yellowish, and the COD is about 6000-10000.
Disclosure of Invention
In order to solve the above problems, the present invention provides the following technical solutions:
a resource utilization method of 2, 4-dichloroacetophenone wastewater comprises the following steps:
s1: putting 2, 4-dichloroacetophenone wastewater into a four-mouth bottle, adding activated carbon, refluxing, adsorbing, decoloring, cooling, performing suction filtration, and dehydrating the filtrate under negative pressure until the kettle liquid contains 5-6% of aluminum;
s2: adding m-dichlorobenzene, the kettle liquid obtained in S1 and toluene into a four-mouth bottle, stirring the mixture, bubbling and introducing hydrogen chloride, heating the reactant, carrying out toluene reflux with a water separator to carry out water carrying, separating acidic water from the water separator, and removing the toluene under negative pressure after the water carrying is finished;
s3: cooling the material to a reaction temperature, slowly dropwise adding acetyl chloride into the material through a constant-pressure dropping funnel, keeping the temperature for reacting for 0.5h after the acetyl chloride is dropwise added, slowly heating the material to 105 ℃, and keeping the temperature for reacting for 3 h;
s4: after the reaction is finished, cooling to 70-80 ℃, slowly dripping water into the material with negative pressure, keeping the temperature for reaction for 1 hour after the dripping is finished, cooling, and transferring the material into a separating funnel for standing and layering;
s5: and (3) after removing water from the separated oil layer, rectifying to obtain a finished product of the 2, 4-dichloroacetophenone, and recycling the separated water layer to be applied to the next batch of reaction.
Further, all or part of the water dripped in S4 comes from the water removed under negative pressure in S1 and the acidic water separated by the water separator in S3.
Further, the molar ratio of S2 m-dichlorobenzene to aluminum in the charged kettle liquid is 1: 1.05-1.15.
Furthermore, the molar ratio of S3 m-dichlorobenzene to acetyl chloride is 1: 1.02-1.05.
Further, the reaction temperature in S3 is 40-60 ℃.
Further, in the process of recycling the water layer in S5, the aluminum inventory is insufficient due to the loss of aluminum, and one or more of aluminum trichloride, aluminum hydroxide and basic aluminum carbonate are added to supplement the aluminum recovered from the kettle liquid.
The invention has the following beneficial effects: according to the invention, aluminum salt in the 2, 4-dichloroacetophenone wastewater is creatively decolorized by activated carbon and dehydrated under negative pressure and then is put into a reaction system, so that on one hand, the enrichment of impurities such as tar in the wastewater can be prevented, the subsequent reaction activity is influenced, on the other hand, the dehydration is divided into two steps, a large amount of water is removed firstly, the pressure of subsequent toluene with water is reduced, an anhydrous catalyst is directly obtained by bubbling hydrogen chloride and the toluene with water, and the direct use of a large amount of anhydrous aluminum trichloride for catalytic reaction is avoided; on one hand, anhydrous aluminum trichloride is very easy to absorb water and deliquesce and difficult to store, a large amount of acid gas is generated in the feeding process, equipment is corroded, and the environment is polluted, on the other hand, the aluminum salt solution recovered from waste water is used in the invention, under the acidic condition, water in a reaction system is taken out through toluene, so that fresh anhydrous aluminum trichloride is generated, acetyl chloride is added into the system, under the action of newly generated anhydrous aluminum trichloride, acetyl chloride reacts with m-dichlorobenzene, after the reaction is finished, water and toluene which are extracted under negative pressure are taken out and put into the system again, oil and water are layered through hydrolysis, the product is layered in an oil layer, oil and water are further rectified to obtain the product, the water layer is continuously recycled and reused through the method, the whole process is not neutralized by using an alkali solution, the inevitable increase of the waste water treatment amount after adding the alkali solution is avoided, and the main component of the recovered aluminum salt is aluminum trichloride, the water in the system can be taken out by toluene only by providing an acid environment, the consumption of hydrogen chloride gas is small, the acidic aluminum-containing wastewater is treated, the catalyst components in the acidic aluminum-containing wastewater are effectively recycled, no wastewater is generated, the discharge of three wastes is effectively reduced, the internal circulation of aluminum salt and water is formed, and the cost is greatly saved.
Detailed Description
In order to make the technical means, features and functions of the present invention easier to understand, the technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the specific embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments.
All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A resource utilization method of 2, 4-dichloroacetophenone wastewater comprises the following steps:
s1: adding 800g of 2, 4-dichloroacetophenone wastewater into a four-mouth bottle, adding 8g of activated carbon, refluxing, adsorbing, decoloring, cooling, performing suction filtration, dehydrating 789.8g of filtrate under negative pressure until the residue is 270g, and determining that the aluminum is 5.5 percent;
s2: adding 74.6g (98.5 percent and 0.5mol) of m-dichlorobenzene, the kettle liquid obtained in S1 and 200g of toluene into a four-mouth bottle, stirring the mixture, bubbling and introducing hydrogen chloride, heating the reactant, carrying out toluene reflux and water carrying by using a water separator, separating acidic water from the water separator, and removing the toluene under the negative pressure of-0.085 MPa after the water carrying is finished;
s3: cooling the material to 40 ℃, slowly dripping 40.5g (99 percent, 0.515mol) of acetyl chloride into the material through a constant-pressure dropping funnel, wherein the dripping time is 3 hours, controlling the reaction temperature to be 40 ℃, keeping the temperature of 40 ℃ for 0.5 hour after the dripping of the acetyl chloride is finished, slowly heating the material to 105 ℃, keeping the temperature for 3 hours, and reacting for 3 hours at 105 ℃;
s4: after the reaction is finished, cooling to 75 ℃, wherein the reaction system has negative pressure of 10mmHg, slowly dripping 620g of water into the materials, wherein the dripping water is water removed from S1 under negative pressure and acidic water separated from a water separator in S3, the dripping time is 4 hours, after the dripping is finished, keeping the temperature for reaction for 1 hour, cooling, and transferring the materials into a separating funnel for standing and layering;
s5: after the water in the separated oil layer is removed, the oil layer is rectified to obtain 90.85g (97.8 percent and 0.47mol) of 2, 4-dichloroacetophenone finished product, the yield is 94 percent, and 732g of the separated water layer is recycled and reused in the next batch of reaction.
Description of the drawings: the m-dichlorobenzene used in the embodiment 1 is an industrial product and has the mass percentage of 98.5 percent; the acetyl chloride is an industrial product, and the mass percentage content is 99 percent; the hydrogen chloride gas is industrial product; the materials in the following examples are all from the same sources as those in example 1;
the 2, 4-dichloroacetophenone wastewater used in example 1 contains 1.88% of aluminum, 11.50% of chlorine, and has an acidity of 4.20% calculated by hydrochloric acid; the 2, 4-dichloroacetophenone waste water produced in example 1 contained 2.01% of aluminum, 12.75% of chlorine, and 4.96% of acidity calculated as hydrochloric acid.
Example 2
A resource utilization method of 2, 4-dichloroacetophenone wastewater comprises the following steps:
s1: adding 732g of the 2, 4-dichloroacetophenone wastewater produced in example 1 into a four-mouth bottle, adding 7.3g of activated carbon, refluxing, adsorbing, decoloring, cooling, performing suction filtration, dehydrating 714g of filtrate under negative pressure until 261g of residue is obtained, and determining that the aluminum is 5.5 percent;
s2: adding 74.6g (98.5 percent and 0.5mol) of m-dichlorobenzene, 200g of kettle liquid obtained in S1 and toluene into a four-mouth bottle, supplementing 2.5g (99 percent and 0.018mol) of anhydrous aluminum trichloride, stirring the mixture, bubbling and introducing hydrogen chloride, heating reactants, carrying out toluene reflux and water carrying by using a water separator, separating acidic water from the water separator, and removing the toluene under the negative pressure of-0.085 MPa after the water carrying is finished;
s3: cooling the material to 40 ℃, slowly dripping 40.5g (99 percent, 0.515mol) of acetyl chloride into the material through a constant-pressure dropping funnel, wherein the dripping time is 3 hours, controlling the reaction temperature to be 40 ℃, keeping the temperature of 40 ℃ for 0.5 hour after the dripping of the acetyl chloride is finished, slowly heating the material to 105 ℃, keeping the temperature for 3 hours, and reacting for 3 hours at 105 ℃;
s4: after the reaction is finished, cooling to 75 ℃, wherein the reaction system has negative pressure of 10mmHg, slowly dripping 546g of water into the materials, wherein the dripping water is water removed from the S1 under the negative pressure and acidic water separated from a water separator in S3, the dripping time is 4 hours, after the dripping is finished, keeping the temperature for reaction for 1 hour, cooling, and transferring the materials into a separating funnel for standing and layering;
s5: after the water in the separated oil layer is removed, the oil layer is rectified to obtain 90.1g (97.3 percent, 0.464mol) of the finished 2, 4-dichloroacetophenone, the yield is 92.8 percent, and 655g of the separated water layer is recycled to be used in the next batch of reaction.
The anhydrous aluminum trichloride used in the embodiment 2 is an industrial product, and the mass percentage content is 99%; the 2, 4-dichloroacetophenone waste water produced in example 2 contained 2.27% of aluminum, 14.42% of chlorine, and the acidity was 5.62% calculated as hydrochloric acid.
Example 3
A resource utilization method of 2, 4-dichloroacetophenone wastewater comprises the following steps:
s1: putting 655g of the 2, 4-dichloroacetophenone wastewater produced in the example 1 into a four-mouth bottle, adding 6.6g of activated carbon, refluxing, adsorbing, decoloring, cooling, performing suction filtration, dehydrating 632g of filtrate under negative pressure until 261g of residual kettle liquid is obtained, and determining that the aluminum is 5.5 percent;
s2: adding 74.6g (98.5 percent and 0.5mol) of m-dichlorobenzene, the kettle liquid obtained in S1 and 200g of toluene into a four-mouth bottle, supplementing 1.4g (99 percent and 0.018mol) of aluminum hydroxide, stirring the mixture, bubbling and introducing hydrogen chloride, heating the reactant, carrying out toluene reflux and water carrying by using a water separator, separating acidic water from the water separator, and removing the toluene under the negative pressure of-0.085 MPa after the water carrying is finished;
s3: cooling the material to 40 ℃, slowly dripping 40.5g (99 percent, 0.515mol) of acetyl chloride into the material through a constant-pressure dropping funnel, wherein the dripping time is 3 hours, controlling the reaction temperature to be 40 ℃, keeping the temperature of 40 ℃ for 0.5 hour after the dripping of the acetyl chloride is finished, slowly heating the material to 105 ℃, keeping the temperature for 3 hours, and reacting for 3 hours at 105 ℃;
s4: after the reaction is finished, cooling to 75 ℃, wherein the reaction system has negative pressure of 10mmHg, slowly dripping 473g of water into the material, wherein the dripping time is 4h, the water is obtained from the water removed under the negative pressure in S1 and the acidic water separated from the water separator in S3, keeping the temperature for reaction for 1h, cooling, and transferring the material to a separating funnel for standing and layering;
s5: and (3) after removing water from the separated oil layer, rectifying to obtain 90.5g (97.6 percent, 0.467mol) of the finished 2, 4-dichloroacetophenone product, wherein the yield is 93.5 percent, and 582g of the separated water layer is recycled and reused in the next batch of reaction.
The anhydrous aluminum hydroxide used in the embodiment 3 is an industrial product, and the mass percentage content is 99%; the 2, 4-dichloroacetophenone waste water produced in example 3 contained 2.75% of aluminum, 17.69% of chlorine, and the acidity was 7.06% calculated as hydrochloric acid.
Example 4
A resource utilization method of 2, 4-dichloroacetophenone wastewater comprises the following steps:
s1: adding 582g of the 2, 4-dichloroacetophenone wastewater produced in example 1 into a four-mouth bottle, adding 5.8g of activated carbon, refluxing, adsorbing, decoloring, cooling, performing suction filtration, dehydrating 566g of filtrate under negative pressure until 262.4g of residue is obtained, and determining that the aluminum is 5.5 percent;
s2: adding 74.6g (98.5 percent and 0.5mol) of m-dichlorobenzene, the kettle liquid obtained in S1 and 200g of toluene into a four-mouth bottle, supplementing 1.6g (99 percent and 0.015mol) of basic aluminum carbonate, stirring the mixture, bubbling and introducing hydrogen chloride, heating the reactant, carrying out toluene reflux with water by using a water separator, separating acidic water from the water separator, and removing the toluene under the negative pressure of-0.085 MPa after the water is carried out;
s3: cooling the material to 40 ℃, slowly dripping 40.5g (99 percent, 0.515mol) of acetyl chloride into the material through a constant-pressure dropping funnel, wherein the dripping time is 3 hours, controlling the reaction temperature to be 40 ℃, keeping the temperature of 40 ℃ for 0.5 hour after the dripping of the acetyl chloride is finished, slowly heating the material to 105 ℃, keeping the temperature for 3 hours, and reacting for 3 hours at 105 ℃;
s4: after the reaction is finished, cooling to 75 ℃, wherein the reaction system has negative pressure of 10mmHg, slowly dripping 410g of water into the materials, wherein the dripping water is water removed from S1 under negative pressure and acidic water separated from a water separator in S3, the dripping time is 4 hours, after the dripping is finished, keeping the temperature for reaction for 1 hour, cooling, and transferring the materials into a separating funnel for standing and layering;
s5: after the water in the separated oil layer is removed, the oil layer is rectified to obtain 91.1g (96.9 percent, 0.463mol) of the finished 2, 4-dichloroacetophenone product, the yield is 92.6 percent, and 582g of the separated water layer is recycled and reused in the next batch of reaction.
The basic aluminum carbonate used in example 4 is an industrial product, and the mass percentage content is 99%; the 2, 4-dichloroacetophenone waste water produced in example 3 contained 2.97% of aluminum, 19.27% of chlorine, and the acidity was 7.76% calculated as hydrochloric acid.
The examples 1 to 4 show that a small amount of aluminum loss caused by activated carbon adsorption can be realized by adding any one of aluminum trichloride, aluminum hydroxide and basic aluminum carbonate to complement the amount of aluminum, so that the quality and yield of the product are not adversely affected, and the combination of the aluminum trichloride, the aluminum hydroxide and the basic aluminum carbonate can also realize the same effect.
S5～S9
Water is not supplemented, only water removed under negative pressure in S1 and acidic water separated by a water separator in S3 are used as dropwise added water in S4, and the influence of continuous application of the 2, 4-dichloroacetophenone wastewater on the reaction is examined;
the table shows that water is not supplemented, only water dehydrated under negative pressure in S1 and acidic water separated by a water segregator in S3 are used as dropwise added water in S4, water is continuously reduced due to negative pressure dehydration, reflux loss and water brought out by activated carbon, so that the aluminum content, chlorine content and acidity of the 2, 4-dichloroacetophenone wastewater are continuously increased by calculating the content of hydrochloric acid, when the amount of the dropwise added water in S4 is low to a certain degree, water is supplemented into the system to ensure sufficient hydrolysis of reactants in S4, a small amount of water is supplemented for hydrolysis in each batch of reaction to keep the stability of the reaction, so that the composition stability of the wastewater can be ensured, and the quality and yield stability of products can be ensured;
the examples 1-9 show that the resource utilization method of 2, 4-dichloroacetophenone wastewater has wide composition adaptability to wastewater, can treat both low-concentration wastewater and high-concentration wastewater, has a good application effect, has relatively stable product quality and yield, does not generate wastewater, and can be applied industrially.
Examples 10 to 11
Examining the influence of the molar ratio of m-dichlorobenzene to aluminum in the added kettle liquid on the reaction, adjusting the molar ratio of m-dichlorobenzene to aluminum in the added kettle liquid to be 1: 1.05-1.15, and keeping the rest conditions the same as in example 1;
| examples | M-dichlorobenzene: aluminum (molar ratio) in the kettle solution | 2, 4-Dichloroacetophenone content (%) | Yield (%) |
| 10 | 1：1.05 | 97.2 | 92.65 |
| 1 | 1：1.1 | 97.8 | 94.00 |
| 11 | 1：1.15 | 97.3 | 93.64 |
The table shows that when the molar ratio of m-dichlorobenzene to anhydrous aluminum hydroxide is 1: 1.05-1.15, the content of the 2, 4-dichloroacetophenone product is high, the yield is stable, and the optimal reaction condition is that the molar ratio of dichlorobenzene to anhydrous aluminum hydroxide is 1: 1.1.
Examples 12 to 14
Examining the influence of the molar ratio of m-dichlorobenzene to acetyl chloride on the reaction, adjusting the molar ratio of m-dichlorobenzene to acetyl chloride to be 1: 1.02-1.05, and keeping the rest conditions the same as in example 1;
| examples | M-dichlorobenzene: acetyl chloride (molar ratio) | 2, 4-Dichloroacetophenone content (%) | Yield (%) |
| 12 | 1：1.02 | 97.6 | 92.43 |
| 1 | 1：1.03 | 97.8 | 94.00 |
| 13 | 1：1.04 | 97.3 | 93.39 |
| 14 | 1：1.05 | 96.8 | 93.36 |
The table shows that when the molar ratio of m-dichlorobenzene to acetyl chloride is 1: 1.02-1.05, the content of the 2, 4-dichloroacetophenone product is high, the yield is stable, and the optimal reaction condition is that the molar ratio of dichlorobenzene to acetyl chloride is 1: 1.03.
Examples 15 to 16
Examining the influence of the reaction temperature in S2 on the reaction, adjusting the reaction temperature to be 40-60 ℃, and keeping the conditions the same as those in the example 1;
| examples | Reaction temperature | 2, 4-Dichloroacetophenone content (%) | Yield (%) |
| 15 | 40 | 96.3 | 90.66 |
| 1 | 50 | 97.8 | 94.00 |
| 16 | 60 | 97.2 | 91.63 |
The table shows that the reaction temperature in S2 is 40-60 ℃, the content of 2, 4-dichloroacetophenone is high, the yield is stable, and the reaction temperature of 50 ℃ is the optimal reaction condition.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification or equivalent substitution made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A resource utilization method of 2, 4-dichloroacetophenone wastewater is characterized by comprising the following steps:
s1: putting 2, 4-dichloroacetophenone wastewater into a four-mouth bottle, adding activated carbon, refluxing, adsorbing, decoloring, cooling, performing suction filtration, and dehydrating the filtrate under negative pressure until the kettle liquid contains 5-6% of aluminum;
s2: adding m-dichlorobenzene, the kettle liquid obtained in S1 and toluene into a four-mouth bottle, stirring the mixture, bubbling and introducing hydrogen chloride, heating the reactant, carrying out toluene reflux with a water separator to carry out water carrying, separating acidic water from the water separator, and removing the toluene under negative pressure after the water carrying is finished;
s3: cooling the material to a reaction temperature, slowly dropwise adding acetyl chloride into the material through a constant-pressure dropping funnel, keeping the temperature for reacting for 0.5h after the acetyl chloride is dropwise added, slowly heating the material to 105 ℃, and keeping the temperature for reacting for 3 h;
s4: after the reaction is finished, cooling to 70-80 ℃, slowly dripping water into the material with negative pressure, keeping the temperature for reaction for 1 hour after the dripping is finished, cooling, and transferring the material into a separating funnel for standing and layering;
s5: and (3) after removing water from the separated oil layer, rectifying to obtain a finished product of the 2, 4-dichloroacetophenone, and recycling the separated water layer to be applied to the next batch of reaction.
2. The method for recycling 2, 4-dichloroacetophenone waste water as claimed in claim 1, wherein the water added dropwise in S4 is derived wholly or partially from the water removed under negative pressure in S1 and the acidic water removed from the water separator in S3.
3. The method for recycling 2, 4-dichloroacetophenone waste water as claimed in claim 1, wherein the molar ratio of S2 intermediate dichlorobenzene to aluminum in the kettle liquid is 1: 1.05-1.15.
4. The resource utilization method of the 2, 4-dichloroacetophenone wastewater as claimed in claim 1, wherein the molar ratio of S3 m-dichlorobenzene to acetyl chloride is 1: 1.02-1.05.
5. The resource utilization method of 2, 4-dichloroacetophenone waste water as claimed in claim 1, characterized in that the reaction temperature in S3 is 40-60 ℃.
6. The method for recycling 2, 4-dichloroacetophenone waste water as claimed in claim 1, wherein in S5, during the recycling of the water layer, the aluminum inventory due to the loss of aluminum is insufficient, and the aluminum recovered from the kettle is replenished by adding one or more of aluminum trichloride, aluminum hydroxide and basic aluminum carbonate.
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