CN117886662A - Efficient production method of 2, 6-dichlorofluorobenzene combined with wastewater treatment - Google Patents
Efficient production method of 2, 6-dichlorofluorobenzene combined with wastewater treatment Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
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- CMVQZRLQEOAYSW-UHFFFAOYSA-N 1,2-dichloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1Cl CMVQZRLQEOAYSW-UHFFFAOYSA-N 0.000 claims abstract description 11
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000011698 potassium fluoride Substances 0.000 claims abstract description 8
- 235000003270 potassium fluoride Nutrition 0.000 claims abstract description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000460 chlorine Substances 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 238000009833 condensation Methods 0.000 claims abstract description 6
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- 239000002699 waste material Substances 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 23
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- 239000002105 nanoparticle Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- PCRSJGWFEMHHEW-UHFFFAOYSA-N 2,3,5,6-tetrafluorobenzene-1,4-dicarbonitrile Chemical compound FC1=C(F)C(C#N)=C(F)C(F)=C1C#N PCRSJGWFEMHHEW-UHFFFAOYSA-N 0.000 claims description 10
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 10
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 238000001179 sorption measurement Methods 0.000 claims description 9
- 239000013067 intermediate product Substances 0.000 claims description 8
- 229920001690 polydopamine Polymers 0.000 claims description 8
- 239000007983 Tris buffer Substances 0.000 claims description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims description 7
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000005711 Benzoic acid Substances 0.000 claims description 5
- UVAJHKGWZQPAEZ-UHFFFAOYSA-N C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.NC2=CC=CC=C2 Chemical compound C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.NC2=CC=CC=C2 UVAJHKGWZQPAEZ-UHFFFAOYSA-N 0.000 claims description 5
- 235000010233 benzoic acid Nutrition 0.000 claims description 5
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
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- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 abstract description 5
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- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a high-efficiency production method of 2, 6-dichlorobenzene by combined wastewater treatment, which comprises the following steps: 2, 3-dichloronitrobenzene is put into a reaction kettle filled with potassium fluoride and tetramethyl ammonium chloride, and the temperature is raised for reaction to prepare 3-chloro-2-fluoronitrobenzene; waste liquid obtained by water washing in the production process enters a waste water treatment tank filled with PCN 224/beta-cyclodextrin composite material for treatment; adding 3-chloro-2-fluoronitrobenzene into a reaction kettle, introducing chlorine, heating for reaction, condensing gas escaping from the top in the reaction process, distilling the condensed liquid again, collecting fractions at 170-175 ℃ to obtain a target product, adsorbing the gas which is not condensed in the condensation process by alkali liquor, and introducing the gas and distilled residual liquid into a wastewater treatment tank filled with PCN 224/beta-cyclodextrin composite material for treatment. The method takes 2, 3-dichloronitrobenzene as a raw material to prepare a target product with high purity and high yield through fluorination and chlorination reaction in sequence, and effectively treats the wastewater in the production process, thereby saving energy and protecting environment.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a high-efficiency production method of 2, 6-dichlorofluorobenzene combined with wastewater treatment.
Background
2, 6-dichlorofluorobenzene is an important organic compound and has wide application in many fields. However, during the last decades, there have been challenges and limitations with respect to the production technology and applications of 2, 6-dichlorofluorobenzene. In the early days, 2, 6-dichlorofluorobenzene was mainly produced by the chlorination reaction of phenol. However, this method requires the use of a large amount of chlorinating agent and high temperature conditions, and is not only costly but also environmentally unfriendly. In addition, the 2, 6-dichlorobenzene obtained by the method has lower purity and requires an additional purification step.
With the development of technology, people begin to explore more environment-friendly and efficient production methods. For example, o-dichlorobenzene is used as a raw material and is prepared through a series of reactions. In addition, the application field of 2, 6-dichloro fluorobenzene is also expanding continuously. In the medical field, it can be used for synthesizing some antitumor drugs and antibiotics. In the field of pesticides, it can be used to synthesize some herbicides and pesticides. 2, 6-dichlorobenzene can also be used to synthesize some polymeric materials and functional materials. However, due to the special chemical properties, the production technology and application of 2, 6-dichlorobenzene still need to be studied intensively. Certain wastewater can be generated in the process of synthesizing 2, 6-dichloro fluorobenzene, and the environment can be polluted if the wastewater is not treated in time. Therefore, it is important to provide a method for producing 2, 6-dichlorobenzene by combining wastewater treatment.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the defects existing in the prior art, the method for efficiently producing the 2, 6-dichlorofluorobenzene by combining wastewater treatment is provided, the method takes the 2, 3-dichloronitrobenzene as a raw material to sequentially carry out fluorination and chlorination reactions, the target product with high purity and high yield is prepared, and the wastewater in the production process is effectively treated, so that the method is energy-saving and environment-friendly.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the high-efficiency production method of the 2, 6-dichloro fluorobenzene combined with the wastewater treatment comprises the following steps:
(1) Adding 2, 3-dichloronitrobenzene into a reaction kettle filled with potassium fluoride and tetramethyl ammonium chloride, stirring and mixing, then carrying out heating reaction, filtering the reaction liquid after the reaction is finished, washing a filter cake with water, and then drying to obtain 3-chloro-2-fluoronitrobenzene; waste liquid obtained by water washing in the production process enters a waste water treatment tank filled with PCN 224/beta-cyclodextrin composite material for treatment;
(2) Adding 3-chloro-2-fluoronitrobenzene into a reaction kettle, introducing chlorine from the bottom of the reaction kettle, then carrying out heating reaction, condensing gas escaping from the top in the reaction process, distilling the condensed liquid again, collecting fractions at 170-175 ℃ to obtain a target product, adsorbing the gas which is not condensed during condensation by alkali liquor, and introducing the gas and the residual liquid during distillation into a wastewater treatment tank filled with PCN 224/beta-cyclodextrin composite material for treatment.
As an improved technical scheme, in the step (1), the molar ratio of the 2, 3-dichloronitrobenzene to the potassium fluoride to the tetramethylammonium chloride is 1: (1.05-1.2): (0.01-0.04).
As an improved technical scheme, in the step (1), the temperature of the heating reaction is 170-190 ℃ and the time is 5-10h.
As an improved technical scheme, in the step (2), the temperature of the heating reaction is 180-200 ℃ and the reaction time is 8-12h.
As an improved technical scheme, the PCN 224/beta-cyclodextrin composite material is adopted to treat the wastewater in the production process, the adding amount is 5-10g/L, and the adsorption time is 1-3h.
In order to better solve the technical problems, the invention also discloses a preparation method of the PCN 224/beta-cyclodextrin composite material, which specifically comprises the following steps:
1. dissolving benzoic acid, zirconium oxychloride octahydrate and 5,10,15, 20-tetra (4-aminobenzene) -21H, 23H-porphyrin in N, N-dimethylformamide, heating for reaction, cooling the reaction liquid to room temperature after the reaction is finished, filtering, drying the solid to prepare PCN224 nano particles,
2. and placing the prepared PCN224 nano-particles into a Tris buffer solution for stirring treatment, then adding dopamine, continuously stirring, filtering, washing the precipitate, and drying to prepare the polydopamine modified PCN224 nano-particles.
3. Mixing polydopamine modified PCN224 nano particles, 2,3,5, 6-tetrafluoro-terephthalonitrile and anhydrous potassium carbonate, vacuumizing, adding DMF, reacting under nitrogen atmosphere, filtering after the reaction is finished, adding a dilute hydrochloric acid solution into a precipitate obtained by filtering until no bubbles are generated, washing and drying to obtain an intermediate product;
4. adding the intermediate product, 2,3,5, 6-tetrafluoro-terephthalonitrile and anhydrous potassium carbonate into a reaction vessel, vacuumizing, adding DMF (dimethyl formamide) for reaction under nitrogen atmosphere, filtering after the reaction is finished, dispersing the obtained solid into deionized water, dripping hydrochloric acid solution until no bubbles are generated, collecting the solid, washing and drying to obtain the PCN 224/beta-cyclodextrin composite material.
As an improved technical scheme, in the first step, the mass ratio of the benzoic acid to the zirconium oxychloride octahydrate to the 5,10,15, 20-tetra (4-aminobenzene) -21H, 23H-porphyrin is (100-200): (10-80): (5-20);
and/or the temperature of the reaction is 120 ℃, and the time of the reaction is 20-30h.
As an improved technical scheme, in the second step, the concentration of the Tris buffer solution is 50mmol/L, and the pH is 8.5; and/or the dosage ratio of the PCN224 nano-particles to Tris buffer solution and dopamine is (0.1-0.5) g:300ml: (0.1-0.5) g; and/or the stirring treatment time is 20-50min, and the stirring continuing time is 20-30h.
As an improved technical scheme, in the third step, the mass ratio of the polydopamine modified PCN224 nano-particles, the 2,3,5, 6-tetrafluoro-terephthalonitrile and the anhydrous potassium carbonate is (0.1-0.5): (0.2-0.5): 1, a step of; and/or the reaction temperature is 80-90 ℃ and the reaction time is 10-15h under the nitrogen atmosphere; and/or the concentration of the dilute hydrochloric acid solution is 1mol/L.
As an improved technical scheme, in the fourth step, the mass ratio of the intermediate product, the 2,3,5, 6-tetrafluoro-terephthalonitrile and the anhydrous potassium carbonate is 0.5: (0.2-0.3): (0.5-1); the reaction temperature is 80-90 ℃ and the reaction time is 40-50h under the nitrogen atmosphere.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
the invention uses 2, 3-dichloronitrobenzene as raw material, and prepares the target product through fluorination and chlorination in turn, the preparation process is simple, the reaction steps are short, and the prepared product has high yield. The invention also effectively treats the waste water and the waste gas generated in the reaction process, and PCN 224/beta-cyclodextrin composite material is adopted as an adsorbent in the treatment, the PCN 224/beta-cyclodextrin has larger specific surface area and pore volume, and can effectively adsorb organic pollutants in the waste water, and the unique cyclodextrin structure can realize the effective trapping of the organic pollutants through the interaction of hydrophobic effect, hydrogen bond, van der Waals force and the like; the PCN 224/beta-cyclodextrin has good adsorption effect on different types of organic pollutants, including waste water in the fields of dye, pesticide, petrochemical industry and the like, and can be used in different environments of acid, alkali, salt and the like, so that the PCN 224/beta-cyclodextrin has wide adaptability.
Detailed Description
The invention is further illustrated below with reference to examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention.
The preparation method of the PCN 224/beta-cyclodextrin composite material in the following embodiment specifically comprises the following steps:
1. 140g of benzoic acid, 15g of zirconium oxychloride octahydrate and 6g of 5,10,15, 20-tetra (4-aminobenzene) -21H, 23H-porphyrin are dissolved in 500ml of N, N-dimethylformamide, the mixture is heated to 120 ℃ for reaction for 24 hours, after the reaction is finished, the reaction solution is cooled to room temperature, filtered and the solid is dried, so as to prepare PCN224 nano-particles;
2. placing 0.25g of the PCN224 nano-particles prepared by the method in 300ml of Tris buffer solution with pH of 8.5 and concentration of 50mmol/L, stirring for 30min, adding 0.3g of dopamine, continuously stirring for 28h, filtering, washing the precipitate, and drying to prepare the polydopamine modified PCN224 nano-particles;
3. mixing 0.5g of polydopamine modified PCN224 nano particles, 0.35g of 2,3,5, 6-tetrafluoro-terephthalonitrile and 1g of anhydrous potassium carbonate, vacuumizing for 20min, then adding 30ml of DMF, reacting for 12h under a nitrogen atmosphere at 85 ℃, filtering after the reaction is finished, adding a dilute hydrochloric acid solution with the concentration of 1mol/L into a precipitate obtained by filtering until no bubbles are generated, and finally washing and drying to obtain an intermediate product;
4. adding 0.5g of the intermediate product, 0.25g of 2,3,5, 6-tetrafluoro-terephthalonitrile and 0.8g of anhydrous potassium carbonate into a reaction vessel, vacuumizing for 30min, adding 30ml of DMF, reacting at 85 ℃ for 48h in a nitrogen atmosphere, filtering after the reaction is finished, dispersing the obtained solid into deionized water, dripping a hydrochloric acid solution until no bubbles are generated, collecting the solid, washing and drying to obtain the PCN 224/beta-cyclodextrin composite material.
In the following examples, the yield of the target product was calculated as follows:
yield (%) = (actual yield/theoretical yield) ×100%.
Example 1
The high-efficiency production method of the 2, 6-dichloro fluorobenzene combined with the wastewater treatment comprises the following steps:
(1) 1mol of 2, 3-dichloronitrobenzene is added into a reaction kettle filled with 1.2mol of potassium fluoride and 0.02mol of tetramethyl ammonium chloride, stirred and mixed, then heated to 180 ℃ for reaction for 7 hours, the reaction liquid is filtered after the reaction is finished, and a filter cake is washed by water and then dried to prepare 3-chloro-2-fluoronitrobenzene; waste liquid obtained by water washing in the production process enters a waste water treatment tank filled with PCN 224/beta-cyclodextrin composite material for treatment;
(2) Adding 1mol of 3-chloro-2-fluoronitrobenzene into a reaction kettle, introducing chlorine from the bottom of the reaction kettle, then heating to 190 ℃ for reaction for 9 hours, condensing gas escaping from the top in the reaction process at 10 ℃, distilling the condensed liquid again, and collecting fractions at 170-175 ℃ to obtain a target product, wherein the product yield is 89.5%, and the purity is more than 99%;
the gas which is not condensed during condensation is absorbed by 10 weight percent sodium hydroxide solution and then enters a waste water treatment tank filled with PCN 224/beta-cyclodextrin composite material together with the residual liquid during distillation for treatment;
when the wastewater is treated in the wastewater treatment tank, the addition amount of the PCN 224/beta-cyclodextrin composite material is 5g/L, the adsorption time is 1h, the filtering is carried out after the adsorption, the filtered wastewater is detected, and the removal rate of COD in the wastewater is 98.9%.
Example 2
The high-efficiency production method of the 2, 6-dichloro fluorobenzene combined with the wastewater treatment comprises the following steps:
(1) 1mol of 2, 3-dichloronitrobenzene is added into a reaction kettle filled with 1.2mol of potassium fluoride and 0.03mol of tetramethyl ammonium chloride, stirred and mixed, then heated to 180 ℃ for reaction for 8 hours, the reaction liquid is filtered after the reaction is finished, and a filter cake is washed by water and then dried to prepare 3-chloro-2-fluoronitrobenzene; waste liquid obtained by water washing in the production process enters a waste water treatment tank filled with PCN 224/beta-cyclodextrin composite material for treatment;
(2) Adding 1mol of 3-chloro-2-fluoronitrobenzene into a reaction kettle, introducing chlorine from the bottom of the reaction kettle, then heating to 190 ℃ for reaction for 9 hours, condensing gas escaping from the top in the reaction process at 10 ℃, distilling the condensed liquid again, and collecting fractions at 170-175 ℃ to obtain a target product, wherein the product yield is 90.3%, and the purity is more than 99%;
the gas which is not condensed during condensation is absorbed by 10 weight percent sodium hydroxide solution and then enters a waste water treatment tank filled with PCN 224/beta-cyclodextrin composite material together with the residual liquid during distillation for treatment;
when the wastewater is treated in the wastewater treatment tank, the addition amount of the PCN 224/beta-cyclodextrin composite material is 7g/L, the adsorption time is 3h, the filtering is carried out after the adsorption, the filtered wastewater is detected, and the removal rate of COD in the wastewater is 99.2%.
Example 3
The high-efficiency production method of the 2, 6-dichloro fluorobenzene combined with the wastewater treatment comprises the following steps:
(1) 1mol of 2, 3-dichloronitrobenzene is added into a reaction kettle filled with 1.2mol of potassium fluoride and 0.04mol of tetramethylammonium chloride, stirred and mixed, then heated to 180 ℃ for reaction for 9 hours, the reaction liquid is filtered after the reaction is finished, and a filter cake is washed by water and then dried to prepare 3-chloro-2-fluoronitrobenzene; waste liquid obtained by water washing in the production process enters a waste water treatment tank filled with PCN 224/beta-cyclodextrin composite material for treatment;
(2) Adding 1mol of 3-chloro-2-fluoronitrobenzene into a reaction kettle, introducing chlorine from the bottom of the reaction kettle, then heating to 190 ℃ for reaction for 10 hours, condensing gas escaping from the top in the reaction process at 10 ℃, distilling the condensed liquid again, and collecting fractions at 170-175 ℃ to obtain a target product, wherein the product yield is 89.2%, and the purity is more than 99%;
the gas which is not condensed during condensation is absorbed by 10 weight percent sodium hydroxide solution and then enters a waste water treatment tank filled with PCN 224/beta-cyclodextrin composite material together with the residual liquid during distillation for treatment;
when the wastewater is treated in the wastewater treatment tank, the addition amount of the PCN 224/beta-cyclodextrin composite material is 8g/L, the adsorption time is 3h, the filtering is carried out after the adsorption, the filtered wastewater is detected, and the removal rate of COD in the wastewater is 99.5%.
Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
Claims (10)
1. The high-efficiency production method of the 2, 6-dichloro fluorobenzene combined with wastewater treatment is characterized by comprising the following steps of:
(1) Adding 2, 3-dichloronitrobenzene into a reaction kettle filled with potassium fluoride and tetramethyl ammonium chloride, stirring and mixing, then carrying out heating reaction, filtering the reaction liquid after the reaction is finished, washing a filter cake with water, and then drying to obtain 3-chloro-2-fluoronitrobenzene; waste liquid obtained by water washing in the production process enters a waste water treatment tank filled with PCN 224/beta-cyclodextrin composite material for treatment;
(2) Adding 3-chloro-2-fluoronitrobenzene into a reaction kettle, introducing chlorine from the bottom of the reaction kettle, then carrying out heating reaction, condensing gas escaping from the top in the reaction process, distilling the condensed liquid again, collecting fractions at 170-175 ℃ to obtain a target product, adsorbing the gas which is not condensed during condensation by alkali liquor, and introducing the gas and the residual liquid during distillation into a wastewater treatment tank filled with PCN 224/beta-cyclodextrin composite material for treatment.
2. The method for efficiently producing 2, 6-dichlorofluorobenzene by combining wastewater treatment according to claim 1, which is characterized in that: in the step (1), the molar ratio of the 2, 3-dichloronitrobenzene, the potassium fluoride and the tetramethyl ammonium chloride is 1: (1.05-1.2): (0.01-0.04).
3. The method for efficiently producing 2, 6-dichlorofluorobenzene by combining wastewater treatment according to claim 1, which is characterized in that: in the step (1), the temperature of the heating reaction is 170-190 ℃ and the time is 5-10h.
4. The method for efficiently producing 2, 6-dichlorofluorobenzene by combining wastewater treatment according to claim 1, which is characterized in that: in the step (2), the temperature of the heating reaction is 180-200 ℃ and the reaction time is 8-12h.
5. The method for efficiently producing 2, 6-dichlorofluorobenzene by combining wastewater treatment according to claim 1, which is characterized in that: the addition amount of the PCN 224/beta-cyclodextrin composite material for treating the wastewater in the production process is 5-10g/L, and the adsorption time is 1-3h.
6. The method for efficiently producing 2, 6-dichlorofluorobenzene by combining wastewater treatment according to claim 1, which is characterized in that: the preparation method of the PCN 224/beta-cyclodextrin composite material specifically comprises the following steps:
1. dissolving benzoic acid, zirconium oxychloride octahydrate and 5,10,15, 20-tetra (4-aminobenzene) -21H, 23H-porphyrin in N, N-dimethylformamide, heating for reaction, cooling the reaction liquid to room temperature after the reaction is finished, filtering, drying the solid to prepare PCN224 nano particles,
2. and placing the prepared PCN224 nano-particles into a Tris buffer solution for stirring treatment, then adding dopamine, continuously stirring, filtering, washing the precipitate, and drying to prepare the polydopamine modified PCN224 nano-particles.
3. Mixing polydopamine modified PCN224 nano particles, 2,3,5, 6-tetrafluoro-terephthalonitrile and anhydrous potassium carbonate, vacuumizing, adding DMF, reacting under nitrogen atmosphere, filtering after the reaction is finished, adding a dilute hydrochloric acid solution into a precipitate obtained by filtering until no bubbles are generated, washing and drying to obtain an intermediate product;
4. adding the intermediate product, 2,3,5, 6-tetrafluoro-terephthalonitrile and anhydrous potassium carbonate into a reaction vessel, vacuumizing, adding DMF (dimethyl formamide) for reaction under nitrogen atmosphere, filtering after the reaction is finished, dispersing the obtained solid into deionized water, dripping hydrochloric acid solution until no bubbles are generated, collecting the solid, washing and drying to obtain the PCN 224/beta-cyclodextrin composite material.
7. The method for efficiently producing 2, 6-dichlorofluorobenzene by combining wastewater treatment according to claim 1, which is characterized in that: in the first step, the mass ratio of the benzoic acid to the zirconium oxychloride octahydrate to the 5,10,15, 20-tetra (4-aminobenzene) -21H, 23H-porphyrin is (100-200): (10-80): (5-20);
and/or the temperature of the reaction is 120 ℃, and the time of the reaction is 20-30h.
8. The method for efficiently producing 2, 6-dichlorofluorobenzene by combining wastewater treatment according to claim 1, which is characterized in that: in the second step, the concentration of the Tris buffer solution is 50mmol/L, and the pH value is 8.5;
and/or the dosage ratio of the PCN224 nano-particles to Tris buffer solution and dopamine is (0.1-0.5) g:300ml: (0.1-0.5) g;
and/or the stirring treatment time is 20-50min, and the stirring continuing time is 20-30h.
9. The method for efficiently producing 2, 6-dichlorofluorobenzene by combining wastewater treatment according to claim 1, which is characterized in that: in the third step, the mass ratio of the polydopamine modified PCN224 nano-particles, the 2,3,5, 6-tetrafluoro terephthalonitrile and the anhydrous potassium carbonate is (0.1-0.5): (0.2-0.5): 1, a step of;
and/or the reaction temperature is 80-90 ℃ and the reaction time is 10-15h under the nitrogen atmosphere;
and/or the concentration of the dilute hydrochloric acid solution is 1mol/L.
10. The method for efficiently producing 2, 6-dichlorofluorobenzene by combining wastewater treatment according to claim 1, which is characterized in that: in the fourth step, the mass ratio of the intermediate product, the 2,3,5, 6-tetrafluoro-terephthalonitrile and the anhydrous potassium carbonate is 0.5: (0.2-0.3): (0.5-1);
and/or the reaction temperature is 80-90 ℃ and the reaction time is 40-50h under the nitrogen atmosphere.
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