CN117509999A - Advanced treatment method for organic wastewater - Google Patents
Advanced treatment method for organic wastewater Download PDFInfo
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- CN117509999A CN117509999A CN202410020371.XA CN202410020371A CN117509999A CN 117509999 A CN117509999 A CN 117509999A CN 202410020371 A CN202410020371 A CN 202410020371A CN 117509999 A CN117509999 A CN 117509999A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 58
- 239000003463 adsorbent Substances 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000012528 membrane Substances 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 12
- -1 fluorine-chlorine hydrocarbon Chemical class 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 9
- 238000001728 nano-filtration Methods 0.000 claims abstract description 9
- 239000004519 grease Substances 0.000 claims abstract description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 239000011737 fluorine Substances 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims description 23
- 238000001179 sorption measurement Methods 0.000 claims description 23
- 244000005700 microbiome Species 0.000 claims description 20
- 238000000354 decomposition reaction Methods 0.000 claims description 18
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000011159 matrix material Substances 0.000 claims description 15
- 230000000813 microbial effect Effects 0.000 claims description 11
- 239000010802 sludge Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 7
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 241000589517 Pseudomonas aeruginosa Species 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 235000001727 glucose Nutrition 0.000 claims description 5
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims description 5
- 229960002261 magnesium phosphate Drugs 0.000 claims description 5
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims description 5
- 239000004137 magnesium phosphate Substances 0.000 claims description 5
- 235000010994 magnesium phosphates Nutrition 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000007539 photo-oxidation reaction Methods 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 235000010333 potassium nitrate Nutrition 0.000 claims description 5
- 239000004323 potassium nitrate Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 abstract 2
- 238000004062 sedimentation Methods 0.000 description 18
- 230000001699 photocatalysis Effects 0.000 description 11
- 230000001112 coagulating effect Effects 0.000 description 9
- 230000001954 sterilising effect Effects 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000006303 photolysis reaction Methods 0.000 description 4
- 229920006389 polyphenyl polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- LJEROUHPDCFEGJ-VVTLTYDVSA-N (1r,3r,4s)-4,7,9-trihydroxy-1,3-dimethyl-3,4-dihydro-1h-benzo[g]isochromene-5,10-dione Chemical compound O=C1C2=CC(O)=CC(O)=C2C(=O)C2=C1[C@H](O)[C@@H](C)O[C@@H]2C LJEROUHPDCFEGJ-VVTLTYDVSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 239000003507 refrigerant Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000003421 catalytic decomposition reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Water Treatment By Sorption (AREA)
- Physical Water Treatments (AREA)
Abstract
An advanced treatment method of organic wastewater, which belongs to the technical field of sewage treatment. The method is characterized by comprising the following steps of: (1) Pretreating the wastewater containing the fluorochlorohydrocarbon to remove suspended matters and grease; (2) Adding an adsorbent into the wastewater to adsorb part of the fluorochlorohydrocarbon; (3) Adding photosensitive catalyst particles into the wastewater, and stirring and simultaneously carrying out ultraviolet irradiation to decompose residual fluorochlorohydrocarbon in the wastewater; (4) Filtering out photosensitive catalyst particles and then performing biological treatment; (5) And separating residual trace fluorine-chlorine hydrocarbon from the wastewater by adopting a nanofiltration membrane separation technology. The invention relates to a deep treatment method for wastewater containing fluorine-containing chlorocarbon, which has lower overall treatment cost and more thorough treatment of fluorine-containing chlorocarbon.
Description
Technical Field
An advanced treatment method of organic wastewater, which belongs to the technical field of sewage treatment.
Background
Organic wastewater is very challenging in wastewater treatment because of the characteristics of high toxicity, difficult degradation, difficult removal and the like. Wherein waste water containing fluorochlorohydrocarbons is produced during the refrigerant production process. Fluorochlorohydrocarbons are a class of compounds widely used in refrigerants, foam agents, and solvents. In the refrigerant production process, such as: the separation and purification processes of byproducts, unreacted reactants and impurities, the cleaning, cooling and purifying processes of the reactor, and the absorption process of waste gas containing the fluorochlorohydrocarbon all produce waste water containing the fluorochlorohydrocarbon.
The fluorochlorohydrocarbon compound has the characteristics of high stability, difficult degradation and bioaccumulation. Because of the strong stability of the chemical structure of the fluorochlorohydrocarbon compounds, they are difficult to biodegrade in the natural environment, which means that the conventional biological treatment method has limited effect in treating wastewater containing fluorochlorohydrocarbons.
At present, a method for treating wastewater containing fluorine-containing chlorine hydrocarbon compounds is still lacked, a method for treating wastewater produced by brominated aliphatic hydrocarbon compounds is disclosed in Chinese patent CN102942266A, and the wastewater produced by brominated aliphatic hydrocarbon compounds is treated by adopting technological processes such as chlorination, filtration, reduction and the like. Although the method has a certain reference effect on the wastewater containing the fluorochlorohydrocarbon compounds, the method still lacks pertinency, and the actual treatment effect is not ideal.
Disclosure of Invention
The invention aims to solve the technical problems that: overcomes the defects of the prior art and provides an organic wastewater advanced treatment method with strong pertinence and high treatment efficiency for the fluorine-containing chlorine hydrocarbon compound wastewater.
The technical scheme adopted for solving the technical problems is as follows: the organic wastewater advanced treatment method is characterized by comprising the following steps of:
(1) Pretreating the wastewater containing the fluorochlorohydrocarbon to remove suspended matters and grease;
(2) Adding an adsorbent into the wastewater to adsorb part of the fluorochlorohydrocarbon, wherein the adding amount of the adsorbent is increased by 8 mg-15 mg every 1mg/L of the fluorochlorohydrocarbon concentration;
(3) Adding photosensitive catalyst particles into the wastewater, and stirring and simultaneously carrying out ultraviolet irradiation to decompose residual fluorochlorohydrocarbons in the wastewater: the decomposition temperature is 25-35 ℃, and the reaction time is 60-120 min;
(4) Filtering out photosensitive catalyst particles, and then performing biological treatment, wherein the pH value of wastewater is kept at 6-9, and the temperature is kept at 15-35 ℃;
(5) And separating the residual trace fluorine-chlorine hydrocarbon from the wastewater by adopting a nanofiltration membrane separation technology, wherein the operation pressure is 0.1-0.5 MPa, and the temperature is 20-40 ℃.
The invention provides a deep treatment method for wastewater containing fluorochlorohydrocarbon, which is characterized in that an adsorption method is used for absorbing fluorochlorohydrocarbon organic matters with smaller molecular weight in the wastewater, so that the photocatalytic decomposition process can be more effectively carried out for macromolecules in the wastewater, and the comprehensive adsorption and catalytic decomposition efficiency is higher; the activity of biological decomposition of the fluorocarbon organic matters after photocatalytic decomposition is increased, the fluorocarbon organic matters can be thoroughly decomposed through biological treatment, and finally the advanced treatment of the fluorocarbon wastewater is realized through membrane filtration. The invention has lower overall treatment cost and more thorough treatment of the fluorochlorohydrocarbon.
Preferably, the pretreatment in the step (1) of the treatment method is to sequentially perform grid and precipitation treatment on the wastewater. The traditional grating and precipitation treatment can remove suspended matters and grease more efficiently, and the treatment cost is lower.
Preferably, the adsorbent in step (2) of the above treatment method is a benzoquinone. The molecular structural unit of the poly benzoquinone has higher pi electron density, can form pi-pi stacking interaction with the fluorochlorohydrocarbon molecules, and can adsorb the fluorochlorohydrocarbon. In addition, the surface of the polybenzquinone has a certain polarity, which is helpful for forming non-covalent interactions such as hydrogen bonds with fluorochlorohydrocarbon molecules. The poly benzoquinone has strong adsorption capacity to fluorochlorohydrocarbon organic matters with smaller molecular weight in the wastewater, and can realize high-efficiency and thorough adsorption to the part.
Specifically, the synthetic process of the poly benzoquinone comprises the following steps:
(a) Mixing benzoquinone monomer and potassium chlorate, adding the mixture into N, N-dimethylformamide solvent, and carrying out polymerization reaction under constant temperature stirring, wherein the reaction temperature is controlled to be 65-70 ℃ and the reaction lasts for 10-15 hours;
(b) Filtering, centrifuging, washing with ethanol, and drying to obtain the final product.
The invention provides a synthetic process of poly benzoquinone suitable for being used as a fluorine-chlorine hydrocarbon wastewater adsorbent, potassium chlorate is selected as a catalyst, N-dimethylformamide is used as a solvent, and the surface of the synthesized poly benzoquinone has higher specific surface area and pore structure, which is favorable for fluorine-chlorine hydrocarbon molecules to enter pores and interact with the poly benzoquinone molecules. Thereby realizing effective adsorption of small molecular fluorine-chlorine hydrocarbon in a short time.
Preferably, the photosensitive catalyst particles in step (3) of the above treatment method are TiO 2 ZnO supported catalyst or TiO 2 CdS supported catalyst. The preferred photocatalyst is capable of more efficiently decomposing a part of fluorochlorohydrocarbons having a large molecular weight by ultraviolet rays to break down its stable molecular structure, making it easier to be biologically treated.
Preferably, the biological treatment in the step (4) of the treatment method is microbial co-metabolism, and the microorganism used in the microbial co-metabolism is a complex of pseudomonas-protter and pseudomonas aeruginosa; the growth matrix used in the microorganism co-metabolism is a composite matrix of potassium nitrate, magnesium phosphate and glucose according to the mass ratio of 0.7-0.9:0.1-0.3:10. The fluorochlorohydrocarbon organic matter is difficult to decompose by microorganisms, but after the photocatalytic decomposition according to the invention, the fluorochlorohydrocarbon organic matter can be decomposed in a mode of being co-metabolized by microorganisms.
Specifically, the operation process of the microorganism co-metabolism comprises the following steps: adding a microorganism strain and a growth matrix into a bioreactor, then adding fluorine-containing chlorohydrocarbon wastewater, adjusting the pH to be neutral, and controlling the temperature to be 20-30 ℃; in the treatment process, the microbial addition amount is kept at 3-6 mg/L, the addition amount of the growth substrate is kept at 10-20 g/L, and excessive air is blown in. The preferred microbial co-metabolism process enables more efficient and thorough decomposition.
The organic wastewater advanced treatment method comprises a pretreatment unit, an adsorption unit, a photooxidation unit, a bioreactor, sludge treatment equipment, a membrane separation unit and a post-treatment unit which are sequentially connected.
Compared with the prior art, the organic wastewater advanced treatment method has the following beneficial effects: the invention aims at the problem that the waste water containing the fluorochlorohydrocarbon firstly absorbs fluorochlorohydrocarbon organic matters with smaller molecular weight in the waste water by using an adsorption method, and the selected polyphenyl quinone adsorbent has stronger adsorption force on the fluorochlorohydrocarbon organic matters with smaller molecular weight in the waste water, so that the high-efficiency and thorough adsorption of the part can be realized. The photocatalytic decomposition process can be more effectively carried out on macromolecules in the photocatalytic decomposition process, and the comprehensive adsorption and catalytic decomposition efficiency is higher; the selected photosensitive catalyst can be matched with ultraviolet rays to decompose partial fluorochlorohydrocarbon with large molecular weight more efficiently, the stable molecular structure of the catalyst is destroyed, the catalyst can be decomposed efficiently and thoroughly in a microorganism co-metabolism mode, and finally the advanced treatment of the fluorochlorohydrocarbon wastewater is realized through membrane filtration.
Detailed Description
The present invention will be specifically described below by way of examples. All materials were commercially available and the wastewater treated in each example was wastewater from the same process in the same product, unless otherwise specified.
Synthesis of Polybenzoquinone A
(a) Mixing benzoquinone monomer and potassium chlorate, adding the mixture into N, N-dimethylformamide solvent, and carrying out polymerization reaction under constant temperature stirring, wherein the reaction temperature is controlled at 67 ℃ and the reaction time is controlled at 12 hours;
(b) Filtering, centrifuging, washing with ethanol, and drying to obtain the product.
Synthesis of Polybenzoquinone B
(a) Mixing benzoquinone monomer and potassium chlorate, adding the mixture into N, N-dimethylformamide solvent, and carrying out polymerization reaction under constant temperature stirring, wherein the reaction temperature is controlled to be 65 ℃ and the reaction is carried out for 15 hours;
(b) Filtering, centrifuging, washing with ethanol, and drying to obtain the product.
Synthesis of poly benzoquinone C
(a) Mixing benzoquinone monomer and potassium chlorate, adding the mixture into N, N-dimethylformamide solvent, and carrying out polymerization reaction under constant temperature stirring, wherein the reaction temperature is controlled to be 70 ℃ and the reaction is carried out for 10 hours;
(b) Filtering, centrifuging, washing with ethanol, and drying to obtain the product.
Example 1: pretreatment unit: comprises a grid, a sedimentation tank and an oil-water separator. The wastewater containing fluorine-chlorine hydrocarbon firstly enters a grid to remove large-particle impurities; then flows into a sedimentation tank, and suspended matters are removed through sedimentation; finally separating the grease by an oil-water separator.
Adsorption unit: comprises an adsorption tower and an adsorbent. The pretreated wastewater enters an adsorption tower to be contacted with a polyphenyl quinone A adsorbent, and the adding amount of the adsorbent is increased by 12mg when the concentration of the fluorochlorohydrocarbon is increased by 1 mg/L; adsorbing small molecular fluorochlorohydrocarbon from the waste water.
Photooxidation unit: the absorbed wastewater enters a photocatalytic reactor to carry out photodecomposition reaction; tiO is added into the waste water 2 The ZnO carries catalyst particles, and ultraviolet light irradiation is carried out while stirring so as to decompose residual fluorochlorohydrocarbon in the wastewater: the decomposition temperature is 30 ℃ and the reaction time is 90min; the control system monitors the reaction temperature and time in real time, and ensures high-efficiency oxidation and decomposition of macromolecular fluorochlorohydrocarbon.
Bioreactor and sludge treatment equipment. Adding a microorganism strain and a growth matrix into a bioreactor, allowing the wastewater after photocatalytic decomposition to enter the bioreactor, performing microorganism co-metabolism, adjusting the pH value to be neutral, and controlling the temperature to be 25 ℃; the microorganism strain is the complex strain of Pseudomonas-Proteus and Pseudomonas aeruginosa; the used growth matrix is a composite matrix of potassium nitrate, magnesium phosphate and glucose according to the mass ratio of 0.8:0.2:10; the microbial addition amount is kept at 4.5mg/L and the addition amount of the growth substrate is kept at 15g/L in the treatment process, and excessive air is blown in. The treated sludge is dehydrated and stabilized by a sludge treatment device.
Membrane separation unit: comprises a nanofiltration system, a cleaning system and a control system. The wastewater after biological treatment enters a nanofiltration system, and the chlorofluorocarbon is separated from the wastewater, wherein the operation pressure is 0.3MPa, and the temperature is 30 ℃; the cleaning system regularly cleans the membrane to ensure long-term stable operation of the membrane; the control system monitors operating pressure and temperature in real time.
Post-processing unit: comprises a pH adjusting tank, a sterilizing device and a coagulating sedimentation tank. The wastewater after membrane separation enters a pH regulating tank, and the pH value is regulated by adding acid or alkali; then sterilizing by a sterilizing device; finally, the wastewater enters a coagulating sedimentation tank, residual suspended matters are removed through coagulating sedimentation, and the removal rate of the fluorochlorohydrocarbon after the wastewater containing the fluorochlorohydrocarbon in the example is measured to be 99.98 percent.
Example 2: the treatment procedure and the process conditions were the same as in example 1 except that the adsorbent in the adsorption column was replaced with polyphenylquinone B, and the removal rate of fluorochlorohydrocarbons after the treatment of the wastewater containing fluorochlorohydrocarbons in this example was determined to be 99.93%.
Example 3: the treatment procedure and the process conditions were the same as in example 1 except that the adsorbent in the adsorption column was replaced with a polybenzquinone C, and the removal rate of the fluorochlorohydrocarbon after the treatment of the wastewater containing the fluorochlorohydrocarbon in this example was measured to be 99.91%.
Example 4: pretreatment unit: comprises a grid, a sedimentation tank and an oil-water separator. The wastewater containing fluorine-chlorine hydrocarbon firstly enters a grid to remove large-particle impurities; then flows into a sedimentation tank, and suspended matters are removed through sedimentation; finally separating the grease by an oil-water separator.
Adsorption unit: comprises an adsorption tower and an adsorbent. The pretreated wastewater enters an adsorption tower to be contacted with a polyphenyl quinone A adsorbent, and the adding amount of the adsorbent is increased by 8mg when the concentration of the fluorochlorohydrocarbon is increased by 1 mg/L; adsorbing small molecular fluorochlorohydrocarbon from the waste water.
Photooxidation unit: the absorbed wastewater enters a photocatalytic reactor to carry out photodecomposition reaction; tiO is added into the waste water 2 The ZnO carries catalyst particles, and ultraviolet light irradiation is carried out while stirring so as to decompose residual fluorochlorohydrocarbon in the wastewater: the decomposition temperature is 25 ℃, and the reaction time is 120min; the control system monitors the reaction temperature and time in real time, and ensures high-efficiency oxidation and decomposition of macromolecular fluorochlorohydrocarbon.
Bioreactor and sludge treatment equipment. Adding a microorganism strain and a growth matrix into a bioreactor, allowing the wastewater after photocatalytic decomposition to enter the bioreactor, performing microorganism co-metabolism, adjusting pH to be neutral, and controlling the temperature to be 20 ℃; the microorganism strain is the complex strain of Pseudomonas-Proteus and Pseudomonas aeruginosa; the used growth matrix is a composite matrix of potassium nitrate, magnesium phosphate and glucose according to the mass ratio of 0.7:0.3:10; in the treatment process, the microbial addition amount is kept at 3mg/L, the addition amount of the growth substrate is kept at 10g/L, and excessive air is blown in. The treated sludge is dehydrated and stabilized by a sludge treatment device.
Membrane separation unit: comprises a nanofiltration system, a cleaning system and a control system. The wastewater after biological treatment enters a nanofiltration system, and the chlorofluorocarbon is separated from the wastewater, wherein the operation pressure is 0.1MPa, and the temperature is 40 ℃; the cleaning system regularly cleans the membrane to ensure long-term stable operation of the membrane; the control system monitors operating pressure and temperature in real time.
Post-processing unit: comprises a pH adjusting tank, a sterilizing device and a coagulating sedimentation tank. The wastewater after membrane separation enters a pH regulating tank, and the pH value is regulated by adding acid or alkali; then sterilizing by a sterilizing device; finally, the wastewater enters a coagulating sedimentation tank, residual suspended matters are removed through coagulating sedimentation, and the removal rate of the fluorochlorohydrocarbon after the wastewater containing the fluorochlorohydrocarbon in the example is measured to be 99.11 percent.
Example 5: pretreatment unit: comprises a grid, a sedimentation tank and an oil-water separator. The wastewater containing fluorine-chlorine hydrocarbon firstly enters a grid to remove large-particle impurities; then flows into a sedimentation tank, and suspended matters are removed through sedimentation; finally separating the grease by an oil-water separator.
Adsorption unit: comprises an adsorption tower and an adsorbent. The pretreated wastewater enters an adsorption tower to be contacted with a polyphenyl quinone A adsorbent, and the adding amount of the adsorbent is increased by 15mg when the concentration of the fluorochlorohydrocarbon is increased by 1 mg/L; adsorbing small molecular fluorochlorohydrocarbon from the waste water.
Photooxidation unit: the absorbed wastewater enters a photocatalytic reactor to carry out photodecomposition reaction; tiO is added into the waste water 2 The CdS carries catalyst particles, and ultraviolet light irradiation is carried out while stirring so as to decompose residual fluorochlorohydrocarbon in the wastewater: the decomposition temperature is 35 ℃, and the reaction time is 60min; the control system monitors the reaction temperature and time in real time, and ensures high-efficiency oxidation and decomposition of macromolecular fluorochlorohydrocarbon.
Bioreactor and sludge treatment equipment. Adding a microorganism strain and a growth matrix into a bioreactor, allowing the wastewater after photocatalytic decomposition to enter the bioreactor, performing microorganism co-metabolism, adjusting the pH value to be neutral, and controlling the temperature to be 30 ℃; the microorganism strain is the complex strain of Pseudomonas-Proteus and Pseudomonas aeruginosa; the used growth matrix is a composite matrix of potassium nitrate, magnesium phosphate and glucose according to the mass ratio of 0.9:0.1:10; the microbial addition amount is kept at 6mg/L and the addition amount of the growth substrate is kept at 20g/L in the treatment process, and excessive air is blown in. The treated sludge is dehydrated and stabilized by a sludge treatment device.
Membrane separation unit: comprises a nanofiltration system, a cleaning system and a control system. The wastewater after biological treatment enters a nanofiltration system, and the chlorofluorocarbon is separated from the wastewater, wherein the operation pressure is 0.5MPa, and the temperature is 40 ℃; the cleaning system regularly cleans the membrane to ensure long-term stable operation of the membrane; the control system monitors operating pressure and temperature in real time.
Post-processing unit: comprises a pH adjusting tank, a sterilizing device and a coagulating sedimentation tank. The wastewater after membrane separation enters a pH regulating tank, and the pH value is regulated by adding acid or alkali; then sterilizing by a sterilizing device; finally, the wastewater enters a coagulating sedimentation tank, residual suspended matters are removed through coagulating sedimentation, and the removal rate of the fluorochlorohydrocarbon after the wastewater containing the fluorochlorohydrocarbon in the example is measured to be 98.67%.
Example 6: the treatment steps and process conditions were the same as in example 1 except that the adsorbent of the adsorption tower was replaced with an equal amount of activated carbon, and the removal rate of the fluorochlorohydrocarbon after the treatment of the wastewater containing the fluorochlorohydrocarbon in this example was measured to be 91.34%.
Example 7: the treatment procedure and process conditions were the same as in example 1, except that the catalyst for the photodecomposition reaction was C-doped TiO 2 The removal rate of the fluorochlorohydrocarbon after the treatment of the wastewater containing the fluorochlorohydrocarbon in this example was measured to be 94.36%.
Example 8: the procedure and process conditions were the same as in example 1 except that the microorganism species used was Pseudomonas-Proteus alone, and the removal rate of fluorochlorohydrocarbons after the treatment of the wastewater containing fluorochlorohydrocarbons in this example was determined to be 87.62%.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (8)
1. The advanced treatment method of the organic wastewater is characterized by comprising the following steps of:
(1) Pretreating the wastewater containing the fluorochlorohydrocarbon to remove suspended matters and grease;
(2) Adding an adsorbent into the wastewater to adsorb part of the fluorochlorohydrocarbon, wherein the adding amount of the adsorbent is increased by 8 mg-15 mg every 1mg/L of the fluorochlorohydrocarbon concentration;
(3) Adding photosensitive catalyst particles into the wastewater, and stirring and simultaneously carrying out ultraviolet irradiation to decompose residual fluorochlorohydrocarbons in the wastewater: the decomposition temperature is 25-35 ℃, and the reaction time is 60-120 min;
(4) Filtering out photosensitive catalyst particles, and then performing biological treatment, wherein the pH value of wastewater is kept at 6-9, and the temperature is kept at 15-35 ℃;
(5) And separating the residual trace fluorine-chlorine hydrocarbon from the wastewater by adopting a nanofiltration membrane separation technology, wherein the operation pressure is 0.1-0.5 MPa, and the temperature is 20-40 ℃.
2. The method for deeply treating organic wastewater according to claim 1, which is characterized in that: the pretreatment in the step (1) is to sequentially carry out grating and precipitation treatment on the wastewater.
3. The method for deeply treating organic wastewater according to claim 1, which is characterized in that: the adsorbent in the step (2) is benzoquinone.
4. The method for deeply treating organic wastewater according to claim 3, wherein the synthetic process of the poly benzoquinone is as follows:
(a) Mixing benzoquinone monomer and potassium chlorate, adding the mixture into N, N-dimethylformamide solvent, and carrying out polymerization reaction under constant temperature stirring, wherein the reaction temperature is controlled to be 65-70 ℃ and the reaction lasts for 10-15 hours;
(b) Filtering, centrifuging, washing with ethanol, and drying to obtain the final product.
5. The method for deeply treating organic wastewater according to claim 1, which is characterized in that: the photosensitive catalyst particles in the step (3) are TiO 2 ZnO supported catalyst or TiO 2 CdS supported catalyst.
6. The method for deeply treating organic wastewater according to claim 1, which is characterized in that: the biological treatment in the step (4) is microbial co-metabolism, and the microbial strain used in the microbial co-metabolism is a complex of pseudomonas-pratensis and pseudomonas aeruginosa; the growth matrix used in the microorganism co-metabolism is a composite matrix of potassium nitrate, magnesium phosphate and glucose according to the mass ratio of 0.7-0.9:0.1-0.3:10.
7. The method for deeply treating organic wastewater according to claim 6, wherein the method comprises the following steps: the operation process of the microorganism co-metabolism comprises the following steps: adding a microorganism strain and a growth matrix into a bioreactor, then adding fluorine-containing chlorohydrocarbon wastewater, adjusting the pH to be neutral, and controlling the temperature to be 20-30 ℃; in the treatment process, the microbial addition amount is kept at 3-6 mg/L, the addition amount of the growth substrate is kept at 10-20 g/L, and excessive air is blown in.
8. The method for deeply treating organic wastewater according to claim 1, which is characterized in that: the treatment equipment comprises a pretreatment unit, an adsorption unit, a photooxidation unit, a bioreactor, sludge treatment equipment, a membrane separation unit and a post-treatment unit which are connected in sequence.
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| FR1382071A (en) * | 1963-02-16 | 1964-12-18 | Inst Francais Du Petrole | Olefin isomerization process |
| CN1433972A (en) * | 2003-03-04 | 2003-08-06 | 江苏省环境科学研究院 | Process for degrading organic fluoride from waste water by photocatalysis |
| CN102574705A (en) * | 2009-08-25 | 2012-07-11 | 法斯-施塔格迈尔有限责任公司 | Processes and uses of dissociating molecules |
| CN110903181A (en) * | 2018-09-18 | 2020-03-24 | 中国石油化工股份有限公司 | Method for preparing p-benzoquinone compound by double-catalytic system |
| CN111589425A (en) * | 2020-06-09 | 2020-08-28 | 易少华 | Chitosan-polydopamine-graphene hydrogel adsorption material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1382071A (en) * | 1963-02-16 | 1964-12-18 | Inst Francais Du Petrole | Olefin isomerization process |
| CN1433972A (en) * | 2003-03-04 | 2003-08-06 | 江苏省环境科学研究院 | Process for degrading organic fluoride from waste water by photocatalysis |
| CN102574705A (en) * | 2009-08-25 | 2012-07-11 | 法斯-施塔格迈尔有限责任公司 | Processes and uses of dissociating molecules |
| CN110903181A (en) * | 2018-09-18 | 2020-03-24 | 中国石油化工股份有限公司 | Method for preparing p-benzoquinone compound by double-catalytic system |
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