CN114291883A - Pretreatment method of 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater - Google Patents
Pretreatment method of 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater Download PDFInfo
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Abstract
The invention discloses a pretreatment method of 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater, which comprises the following steps: mixing the composite catalyst with the 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater, heating and refluxing, performing catalytic oxidation treatment and aeration to finish the treatment of the wastewater, wherein the adopted composite catalyst is prepared by soaking and calcining a mixture consisting of bentonite, activated carbon and manganese dioxide in a manganese sulfate solution. In the invention, after the treatment of the composite catalyst, the COD removal rate of the wastewater is more than 80 percent, the TN removal rate is more than 90 percent, the biodegradability index B/C value of the wastewater is improved to more than 0.4 from 0.05, the pretreated wastewater can reach the standard after the subsequent biochemical treatment and can be discharged, and no malodorous gas is generated in the catalytic oxidation treatment process, no solid waste is increased, and no secondary pollution is caused. The pretreatment method has the advantages of simple process, convenient operation, easy control, low treatment cost and the like, and has high use value and good application prospect.
Description
Technical Field
The invention relates to a pretreatment method of 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater.
Technical Field
The pyraclostrobin is an important intermediate for synthesizing pyraclostrobin, has the advantages of high efficiency, low toxicity, environmental friendliness and the like, is widely used for disease control of crops such as cucumber powdery mildew, downy mildew, banana scab and the like, and has wide market prospect.
At present, the synthetic route of the production process of 1- (4-chlorphenyl) -3-pyrazole alcohol mainly adopts para-chloroaniline to carry out diazotization reaction with sodium nitrite in a hydrochloric acid system, after reduction acidification treatment with sodium sulfite, toluene is used for extracting para-chlorophenylhydrazine to a concentration kettle, and the para-chlorophenylhydrazine is distilled and dehydrated and is used for toluene rectification. Dissolving the concentrate with methanol, adding sodium methoxide as a catalyst, adding methyl acrylate for reflux cyclization, neutralizing a reaction system to acidity after cyclization, precipitating and recovering methanol for reuse after standing, adding water into the concentrated solution, stirring uniformly, adding hydrogen peroxide for oxidation, adding acid for crystallization to obtain a product with the content of more than or equal to 80 percent, wherein the production wastewater mainly comprises a synthesis process of p-chlorophenylhydrazine hydrochloride (PY-1), a synthesis process of 1- (4-chlorophenyl) -3-pyrazolol (PY-3), a water washing and pressure filtration and solvent recovery process, wherein about 20 tons of wastewater is generated when 1 ton of 1- (4-chlorophenyl) -3-pyrazolol product with the content of 80 percent is synthesized, and the wastewater mainly comprises organic compounds such as toluene, p-chlorophenylhydrazine, p-chloroaniline, p-chlorophenylhydrazine hydrochloride, methyl acrylate, 1- (4-chlorophenyl) -3-pyrazolol and the like, the COD is more than 40000mg/L, has the characteristics of complex components, high toxicity, high COD, high salt content and the like, and belongs to high-concentration refractory organic chemical wastewater. However, the pretreatment method of the wastewater from the production of 1- (4-chlorophenyl) -3-pyrazolol is less studied, and at present, the methods mainly include distillation concentration incineration, fenton oxidation, solvent extraction, etc., but the above pretreatment methods have complicated equipment and poor treatment effect, and are liable to generate dioxin and other highly toxic substances during incineration, and on the other hand, fenton oxidation generates a large amount of solid residues to deepen the chromaticity of the wastewater, thereby causing secondary pollution, and thus the problem of wastewater treatment is not fundamentally solved, and thus the method is difficult to be industrially popularized.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the pretreatment method of the 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater, which has the advantages of simple process, convenient operation, easy control, low treatment cost, high removal rate of refractory organic pollutants, high biodegradability of the wastewater, no newly added solid waste and no secondary pollution.
In order to solve the technical problems, the invention adopts the technical scheme that:
a pretreatment method of 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater comprises the following steps: mixing the composite catalyst with the 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater, heating and refluxing, performing catalytic oxidation treatment, and performing aeration treatment on the 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater in the catalytic oxidation process to complete the treatment on the 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater; the composite catalyst is prepared by soaking and calcining a mixture consisting of bentonite, activated carbon and manganese dioxide in a manganese sulfate solution.
In the pretreatment method of the 1- (4-chlorophenyl) -3-pyrazole alcohol production wastewater, the preparation method of the composite catalyst is further improved, and comprises the following steps:
s1, mixing bentonite, activated carbon and manganese dioxide to prepare a carrier;
s2, soaking the carrier obtained in the step S1 in a manganese sulfate solution, and washing with water until no metal ions are detected;
s3, calcining the product obtained in the step S2 to obtain the composite catalyst.
In the method for pretreating 1- (4-chlorophenyl) -3-pyrazolol production wastewater, in step S1, the mass ratio of bentonite, activated carbon, and manganese dioxide is 5-7.5: 3-5.5: 0.2-0.5; the shape of the carrier is granular or short rod-shaped.
In the step S2, the concentration of the manganese sulfate solution is 0.4mol/L to 0.6 mol/L; the soaking time is 20 min-30 min.
In the above method for pretreating wastewater from the production of 1- (4-chlorophenyl) -3-pyrazolol, the calcination is performed at 500-600 ℃ in step S3; the calcining time is 3-4 h.
In the pretreatment method of the 1- (4-chlorophenyl) -3-pyrazole alcohol production wastewater, the mass ratio of the composite catalyst to the 1- (4-chlorophenyl) -3-pyrazole alcohol production wastewater is further improved to 8.2-14: 500.
The pretreatment method of the 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater is further improved, and the 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater is aerated by adopting air; the aeration rate of the air is 0.25m3/h～0.5m3/h。
In the pretreatment method of the 1- (4-chlorophenyl) -3-pyrazole alcohol production wastewater, the time of the catalytic oxidation treatment is further improved to be 3-4 h.
The pretreatment method of the 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater is further improved by carrying out catalytic oxidation treatment on the 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater by using a reaction kettle.
In the pretreatment method of the 1- (4-chlorophenyl) -3-pyrazole alcohol production wastewater, the heating reflux is carried out at 102-107 ℃.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a pretreatment method of 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater, which comprises the steps of mixing a composite catalyst with the 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater, carrying out catalytic oxidation treatment and aeration treatment, and finishing the treatment of the 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater, wherein the composite catalyst is prepared by soaking and calcining a mixture consisting of bentonite, activated carbon and manganese dioxide in a manganese sulfate solution. According to the invention, the mixture of bentonite, activated carbon and manganese dioxide is soaked in manganese sulfate to increase the attachment of manganese ions, so that the catalytic activity of the catalyst is favorably improved, the soaked mixture is calcined, the crystalline phase of metal is changed in the calcining process, the catalytic oxidation state of the catalyst is favorably realized, and the high-efficiency removal of organic pollutants in wastewater is favorably realized, meanwhile, under the synergistic effect of the bentonite and the activated carbon, the manganese dioxide can be effectively fixed, and the specific surface area and active sites of the catalyst are further improved, so that the composite catalyst has more excellent catalytic activity and stability, and the problem of secondary pollution is avoided The TN removal rate is more than 90%, the biodegradability index B/C value of the wastewater is improved to more than 0.4 from 0.05, the pretreated wastewater can reach the standard after subsequent biochemical treatment and can be discharged, and no malodorous gas is generated in the catalytic oxidation treatment process, no solid waste is increased, and no secondary pollution is caused. Meanwhile, the pretreatment method has the advantages of simple process, convenient operation, easy control, low treatment cost and the like, and has high use value and good application prospect.
(2) According to the invention, by optimizing the mass ratio of bentonite to active carbon to manganese dioxide to be 5-7.5: 3-5.5: 0.2-0.5, the advantages brought by the method are as follows: the better catalytic performance is obtained, and the wastewater pretreatment efficiency is obviously improved; the catalyst with more stable performance can be obtained, and the catalyst can be repeatedly used after being activated; the application requirements are met, and simultaneously, the raw material consumption can be saved and the preparation cost can be reduced.
Detailed Description
The invention is further described below with reference to specific preferred embodiments, without thereby limiting the scope of protection of the invention.
The raw materials and instruments used in the following examples are all commercially available; the equipment and the preparation process are conventional equipment and conventional process unless otherwise specified.
The water quality of the wastewater from 1- (4-chlorophenyl) -3-pyrazolol production which is the pretreatment object in the following examples was: the pH value is 7-8, the COD is 40000mg/L, the TN is 850, and the biodegradability index B/C of the wastewater is 0.05.
Example 1:
a pretreatment method of 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater comprises the following steps:
preparing a composite catalyst: 5g of bentonite, 3g of active carbon and 0.2g of manganese dioxide are weighed to prepare a granular carrier, the granular carrier is soaked in a manganese sulfate solution with the concentration of 0.4mol/L for 20min and then dried, and then washed by water until no metal ion is detected, and the granular carrier is calcined for 3h at the high temperature of 600 ℃ to prepare 8.2g of the composite catalyst.
Pouring 500g of 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater into a 1L reaction kettle, adding 8.2g of composite catalyst, heating and refluxing at 102-107 ℃, performing catalytic oxidation treatment, continuously aerating with air, and controlling the aeration amount to be 0.25-0.5 m3And h, the reaction time is 3h, and the treatment of the 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater is completed.
Through detection, COD of the 1- (4-chlorphenyl) -3-pyrazole alcohol effluent after oxidation-aeration pretreatment of the composite catalyst is reduced to 7834mg/L, the removal rate is 80.5%, the total nitrogen removal rate reaches 91%, B/C is 0.43, and the wastewater after pretreatment can reach the discharge standard after biochemical treatment.
Example 2:
a pretreatment method of 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater comprises the following steps:
preparing a composite catalyst: weighing 6g of bentonite, 4.5g of activated carbon and 0.5g of manganese dioxide to prepare a granular carrier, soaking the granular carrier in a manganese sulfate solution with the concentration of 0.4mol/L for 20min, drying, then washing with water until no metal ions are detected, and calcining at the high temperature of 600 ℃ for 3h to prepare 11g of the composite catalyst.
Pouring 500g of 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater into a 1L reaction kettle, adding 11g of composite catalyst, heating and refluxing at 102-107 ℃, performing catalytic oxidation treatment, introducing air for continuous aeration, and controllingThe aeration rate is 0.25-0.5 m3And h, the reaction time is 3h, and the treatment of the 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater is completed.
Through detection, COD of the 1- (4-chlorphenyl) -3-pyrazole alcohol effluent after oxidation-aeration pretreatment of the composite catalyst is reduced to 7552mg/L, the removal rate is 81.2%, the total nitrogen removal rate reaches 90.5%, B/C is 0.44, and the wastewater after pretreatment can reach the discharge standard after biochemical treatment.
Example 3:
a pretreatment method of 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater comprises the following steps:
preparing a composite catalyst: weighing 7.5g of bentonite, 5.0g of active carbon and 0.5g of manganese dioxide to prepare a granular carrier, soaking the granular carrier in a manganese sulfate solution with the concentration of 0.4mol/L for 20min, drying, then washing with water until no metal ions are detected, and calcining at the high temperature of 600 ℃ for 3h to prepare 13g of the composite catalyst.
Pouring 500g of 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater into a 1L reaction kettle, adding 13g of composite catalyst, heating and refluxing at 102-107 ℃, performing catalytic oxidation treatment, introducing continuous aeration, and controlling the aeration rate to be 0.25-0.5 m3And h, the reaction time is 3h, and the treatment of the 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater is completed.
Through detection, COD of the 1- (4-chlorphenyl) -3-pyrazole alcohol effluent after oxidation-aeration pretreatment of the composite catalyst is reduced to 6670mg/L, the removal rate is 83.4%, the total nitrogen removal rate reaches 82.9%, B/C is 0.46, and the wastewater after pretreatment can reach the discharge standard after biochemical treatment.
Example 4:
a pretreatment method of 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater comprises the following steps:
preparing a composite catalyst: weighing 6g of bentonite, 4.5g of activated carbon and 0.3g of manganese dioxide to prepare a granular carrier, soaking the granular carrier in a manganese sulfate solution with the concentration of 0.4mol/L for 20min, drying, then washing with water until no metal ions are detected, and calcining at the high temperature of 600 ℃ for 3h to prepare 10.8g of the composite catalyst.
500g of 1- (4-chlorophenyl) -3-pyrazinePouring the wastewater from the production of the oxazole into a 1L reaction kettle, adding 10.8g of the composite catalyst, heating and refluxing at 102-107 ℃, performing catalytic oxidation treatment, introducing air for continuous aeration, and controlling the aeration rate to be 0.25-0.5 m3And h, the reaction time is 3h, and the treatment of the 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater is completed.
Through detection, COD of the 1- (4-chlorphenyl) -3-pyrazole alcohol effluent after oxidation-aeration pretreatment of the composite catalyst is reduced to 7719mg/L, the removal rate is 82.1%, the total nitrogen removal rate reaches 85.5%, B/C is 0.44, and the wastewater after pretreatment can reach the discharge standard after biochemical treatment.
From the results of the above examples 1-4, it can be seen that, in the pretreatment method of the present invention, after the treatment with the composite catalyst, the wastewater from the production of 1- (4-chlorophenyl) -3-pyrazolol has a COD removal rate of greater than 80% and a TN removal rate of greater than 90%, the biodegradability index B/C of the wastewater is increased from 0.05 to 0.4, the wastewater after the pretreatment can reach the standard for discharge after the subsequent biochemical treatment, and no malodorous gas is generated during the catalytic oxidation treatment, no solid waste is increased, and no secondary pollution is caused. Meanwhile, the pretreatment method has the advantages of simple process, convenient operation, easy control, low treatment cost and the like, and has high use value and good application prospect.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (10)
1. A pretreatment method of 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater is characterized by comprising the following steps: mixing the composite catalyst with the 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater, heating and refluxing, performing catalytic oxidation treatment, and performing aeration treatment on the 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater in the catalytic oxidation process to complete the treatment on the 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater; the composite catalyst is prepared by soaking and calcining a mixture consisting of bentonite, activated carbon and manganese dioxide in a manganese sulfate solution.
2. The pretreatment method of wastewater from the production of 1- (4-chlorophenyl) -3-pyrazolol according to claim 1, wherein said preparation method of said composite catalyst comprises the steps of:
s1, mixing bentonite, activated carbon and manganese dioxide to prepare a carrier;
s2, soaking the carrier obtained in the step S1 in a manganese sulfate solution, and washing with water until no metal ions are detected;
s3, calcining the product obtained in the step S2 to obtain the composite catalyst.
3. The pretreatment method for 1- (4-chlorophenyl) -3-pyrazolol industrial wastewater according to claim 2, wherein in step S1, the mass ratio of bentonite, activated carbon, and manganese dioxide is 5 to 7.5: 3 to 5.5: 0.2 to 0.5; the shape of the carrier is granular or short rod-shaped.
4. The method for pretreating waste water from the production of 1- (4-chlorophenyl) -3-pyrazolol according to claim 3, wherein in step S2, the concentration of the manganese sulfate solution is 0.4-0.6 mol/L; the soaking time is 20 min-30 min.
5. The method for pretreating waste water from the production of 1- (4-chlorophenyl) -3-pyrazolol according to claim 4, wherein said calcining is carried out at a temperature of 500 to 600 ℃ in step S3; the calcining time is 3-4 h.
6. The pretreatment method for wastewater from production of 1- (4-chlorophenyl) -3-pyrazolol according to any one of claims 1 to 5, characterized in that the mass ratio of the composite catalyst to the wastewater from production of 1- (4-chlorophenyl) -3-pyrazolol is 8.2 to 14: 500.
7. According to claim 6The pretreatment method of the 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater is characterized in that air is adopted to carry out aeration treatment on the 1- (4-chlorphenyl) -3-pyrazole alcohol production wastewater; the aeration rate of the air is 0.25m3/h～0.5m3/h。
8. The method for pretreating waste water from the production of 1- (4-chlorophenyl) -3-pyrazolol according to claim 6, wherein the time for the catalytic oxidation treatment is 3 to 4 hours.
9. The method for pretreating waste water from the production of 1- (4-chlorophenyl) -3-pyrazolol according to claim 6, wherein the waste water from the production of 1- (4-chlorophenyl) -3-pyrazolol is subjected to catalytic oxidation treatment using a reaction vessel.
10. The method for pretreating waste water from the production of 1- (4-chlorophenyl) -3-pyrazolol according to any one of claims 1 to 5, wherein the refluxing with heat is performed at 102 ℃ to 107 ℃.
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