CN110713292A - Continuous pretreatment system and process for pirimiphos-methyl wastewater - Google Patents
Continuous pretreatment system and process for pirimiphos-methyl wastewater Download PDFInfo
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- CN110713292A CN110713292A CN201911081773.6A CN201911081773A CN110713292A CN 110713292 A CN110713292 A CN 110713292A CN 201911081773 A CN201911081773 A CN 201911081773A CN 110713292 A CN110713292 A CN 110713292A
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- electrocatalytic oxidation
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- 239000002351 wastewater Substances 0.000 title claims abstract description 138
- 239000005924 Pirimiphos-methyl Substances 0.000 title claims abstract description 70
- QHOQHJPRIBSPCY-UHFFFAOYSA-N pirimiphos-methyl Chemical group CCN(CC)C1=NC(C)=CC(OP(=S)(OC)OC)=N1 QHOQHJPRIBSPCY-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 49
- 230000008569 process Effects 0.000 title claims abstract description 37
- 230000003647 oxidation Effects 0.000 claims abstract description 97
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 97
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 17
- 238000003860 storage Methods 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 36
- 239000000945 filler Substances 0.000 claims description 35
- 239000003054 catalyst Substances 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 17
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 17
- 239000000440 bentonite Substances 0.000 claims description 16
- 229910000278 bentonite Inorganic materials 0.000 claims description 16
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 16
- 229940071125 manganese acetate Drugs 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- WGKCEIRLWOKLOE-UHFFFAOYSA-N [P].CC1=NC=CC=N1 Chemical compound [P].CC1=NC=CC=N1 WGKCEIRLWOKLOE-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000008394 flocculating agent Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000002734 clay mineral Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000005189 flocculation Methods 0.000 claims description 5
- 230000016615 flocculation Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000004927 clay Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 6
- 239000011574 phosphorus Substances 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000001477 organic nitrogen group Chemical group 0.000 description 3
- 239000000575 pesticide 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
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- VTSWSQGDJQFXHB-UHFFFAOYSA-N 2,4,6-trichloro-5-methylpyrimidine Chemical compound CC1=C(Cl)N=C(Cl)N=C1Cl VTSWSQGDJQFXHB-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- JKPOPBQENWOUSY-UHFFFAOYSA-N [P].N1=CN=CC=C1 Chemical compound [P].N1=CN=CC=C1 JKPOPBQENWOUSY-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- AYESKMWPTSCYSJ-UHFFFAOYSA-N bis(hydroxymethyl)phosphanylmethanol;hydrochloride Chemical compound [Cl-].OC[PH+](CO)CO AYESKMWPTSCYSJ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000002366 mineral element Substances 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 239000003986 organophosphate insecticide Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- -1 pyrimidyl alcohol Chemical compound 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
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- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
Abstract
The invention discloses a continuous pretreatment system and a continuous pretreatment process for pirimiphos-methyl wastewater, wherein the system comprises a wastewater storage tank, a first water pump, a heater, a three-dimensional electrocatalytic oxidation stripping tower, a first cooler, a neutralization kettle, a second water pump and a settling tank which are sequentially communicated, and the three-dimensional electrocatalytic oxidation stripping tower comprises a stripping tower and a three-dimensional electrocatalytic oxidation device arranged in the stripping tower. The process adopts the system to carry out continuous pretreatment on the p-methylpyrimidine phosphorus wastewater. The system disclosed by the invention can reduce the equipment cost, can realize continuous treatment on the pirimiphos-methyl wastewater, saves energy, reduces the labor intensity, has the characteristics of obvious treatment effect, low investment, low operation cost, convenience for engineering popularization and application and the like, has the advantages of simple treatment process, convenience for operation, low cost, low energy consumption, high treatment efficiency, good treatment effect and the like, and has very important significance for realizing deep treatment of the pirimiphos-methyl wastewater.
Description
Technical Field
The invention belongs to the field of treatment of pirimiphos-methyl wastewater, and relates to a continuous pretreatment system and a continuous pretreatment process for pirimiphos-methyl wastewater.
Background
Pirimiphos-methyl is a broad-spectrum, high-efficiency and low-toxicity organophosphorus insecticide and acaricide, and is widely used for controlling pests such as storage, household hygiene, crops and the like, however, a large amount of sewage is generated in the preparation process of pirimiphos-methyl, which not only seriously hinders the expansion of the capacity of the pirimiphos-methyl, but also is more important, and the treatment of the waste water generated by the preparation process becomes urgent.
The methyl pyrimidine phosphorus wastewater can be divided into eight waste water in three sections of guanidine synthesis, pyrimidyl alcohol synthesis and methyl pyrimidine phosphorus synthesis according to the production process, and the total water amount of the wastewater is as follows: 10 ton ofWaste waterTon ofProduct(s). The methyl pyrimidine phosphorus wastewater contains various toxic and harmful pollutants such as pyrimidines, organic sulfur, organic phosphorus, organic nitrogen and the like, has a B/C ratio of about 0.01, and belongs to high-concentration, high-salt-content and degradation-resistant pesticide wastewater. In the prior art, the absorption method is usually adopted to treat the methyl pyrimidine wastewater, for example, Zhang Yan and the like use bentonite as absorption for the methyl pyrimidine phosphorus wastewater, and for example, Rayleigh forest and the like use lignin/bentonite as a composite absorbent for treating the methyl pyrimidine phosphorus wastewater, but the methyl pyrimidine phosphorus wastewater is treated by the methodThe method for treating the waste water containing the pyrimidine phosphorus has the inherent defects of an adsorption method, only transfers pollutants from the water to an adsorbent, and does not fundamentally solve the problem of harm of pollution sources to the environment. Based on the unsolvable defects in the adsorption method, Li Ming and the like propose a method for removing the pirimiphos-methyl in the wastewater by electrocatalytic oxidation, wherein a lead alloy plate is taken as an anode, a stainless steel plate is taken as a cathode, and the COD of the pirimiphos-methyl wastewater is removed by electrocatalytic oxidation. In addition, no mature and effective industrial treatment method exists at home and abroad for how to effectively treat the pirimiphos-methyl wastewater. Therefore, the method has very important significance in realizing the continuous treatment of the pirimiphos-methyl wastewater with low cost, low energy consumption, low labor intensity, high treatment efficiency and high treatment effect.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a continuous pre-treatment system and a continuous pre-treatment process for the pirimiphos-methyl wastewater, which have the advantages of obvious treatment effect, low investment, low operation cost and convenience for engineering popularization and application.
In order to solve the technical problems, the invention adopts the technical scheme that:
a continuous pretreatment system for pirimiphos-methyl wastewater comprises a wastewater storage tank, a first water pump, a heater, a three-dimensional electrocatalytic oxidation stripping tower, a first cooler, a neutralization kettle, a second water pump and a settling tank which are sequentially communicated; the three-dimensional electrocatalytic oxidation stripping tower comprises a stripping tower, and a three-dimensional electrocatalytic oxidation device is arranged in the stripping tower.
In the above continuous pretreatment system, further improvement is that the three-dimensional electrocatalytic oxidation device is of a cylindrical structure, and the center is provided with IrO2-RuO2the/Ti rod is used as an anode, and a stainless steel plate is used as a cathode around the anode.
In the continuous pretreatment system, the three-dimensional electrocatalytic oxidation device is further improvedAn electrocatalytic oxidation filler is filled between the anode and the cathode; the electrocatalytic oxidation filler is prepared by mixing a catalyst carrier and a metal catalyst solution and then roasting the mixture; the catalyst carrier is a mixture of clay minerals and a curing agent; the metal catalyst solution is Cu2+/Mn2+The mixed solution of (1).
In a further improvement of the above continuous pretreatment system, the method for preparing the electrocatalytic oxidation packing comprises the following steps:
s1, mixing argil, diatomite and bentonite, adding a curing agent to prepare spherical solid, and drying to obtain a catalyst carrier;
s2, adding the catalyst carrier obtained in the step S1 to Cu2+/Mn2+Dipping and drying the mixture solution to obtain a filler precursor;
s3, roasting the filler precursor obtained in the step S2 to obtain the electrocatalytic oxidation filler.
In the above continuous pretreatment system, a further improvement is that in step S1, the mass ratio of the pottery clay, the diatomite and the bentonite is 5-6: 2-3: 3-1; the mass ratio of the curing agent to the total mass of the argil, the diatomite and the bentonite is 0.05 percent; the curing agent is silica gel solution or water glass; the mass concentration of the curing agent is 30 percent; the particle size of the spherical solid is 2-50 mm; the temperature of the drying was 105 ℃.
In the above continuous pretreatment system, further improvement, in the step S2, the Cu2+/Mn2+The mixed solution of (1) is a mixed solution of copper acetate and manganese acetate; cu in the mixed solution of the copper acetate and the manganese acetate2+、Mn2+The molar ratio of (A) to (B) is 1: 1-2; the mass percentage content of copper acetate and manganese acetate in the mixed solution of copper acetate and manganese acetate is 10%; the Cu2+/Mn2+The ratio of the mass of the mixed solution to the total mass of the pottery clay, the diatomite and the bentonite in the step S1 is 20 to 35 percent; the dipping time is 8 h; the temperature of the drying was 105 ℃.
In the above continuous pretreatment system, further modified, in step S3, the roasting is performed at a temperature of 300 ℃; the roasting time is 4 hours.
In the continuous pretreatment system, the top of the three-dimensional electrocatalytic oxidation stripping tower is communicated with an RTO incinerator; a second cooler is communicated between the three-dimensional electrocatalytic oxidation stripping tower and the RTO incinerator; the bottom of the three-dimensional electrocatalytic oxidation stripping tower is communicated with a fan.
As a general technical concept, the invention also provides a continuous pretreatment process of the pirimiphos-methyl wastewater, which adopts the continuous pretreatment system to carry out continuous pretreatment on the pirimiphos-methyl wastewater.
The continuous pretreatment process is further improved and comprises the following steps:
(1) conveying the pirimiphos-methyl wastewater in the wastewater storage tank into a heater through a first water pump, and heating the pirimiphos-methyl wastewater;
(2) feeding the heated pirimiphos-methyl wastewater in the step (1) into a three-dimensional electrocatalytic oxidation stripping tower from the middle upper part of the tower, carrying out electrocatalytic oxidation on the pirimiphos-methyl wastewater in the three-dimensional electrocatalytic oxidation device, and feeding gas into the three-dimensional electrocatalytic oxidation stripping tower from the bottom of the tower through a fan in the electrocatalytic oxidation process to strip the pirimiphos-methyl wastewater to obtain ammonia-removed wastewater;
(3) cooling the ammonia-removing wastewater obtained in the step (2) by a first cooler, then feeding the ammonia-removing wastewater into a neutralization kettle, adding a ferric trichloride solution into the neutralization kettle, stirring, and adding an acid solution to adjust the pH value of the wastewater to 7-8 to obtain mixed wastewater;
(4) and (4) feeding the mixed wastewater obtained in the step (3) into a settling tank through a second water pump, adding a flocculating agent from the upper part of the settling tank for flocculation reaction, and performing solid-liquid separation to finish the pretreatment of the pirimiphos-methyl wastewater.
In the above continuous pretreatment process, a further improvement is that in the step (1), the heating is performed by heating the pirimiphos-methyl wastewater to 50-65 ℃.
In the above continuous pretreatment process, the water inlet flow of the pirimiphos-methyl wastewater in the step (2) is further improved to be 2m3/h～2.5m3H; the current density in the electrocatalytic oxidation process is controlled to be 200A/m2～250A/m2(ii) a The volume ratio of the gas to the pirimiphos-methyl wastewater is 100-150: 1; the gas is air.
In the step (3), the adding mass of the ferric trichloride solution is 1% of the adding mass of the pirimiphos-methyl wastewater; the mass concentration of the ferric trichloride solution is 30%; the acid solution is hydrochloric acid solution; the mass concentration of the acid solution is 30%.
In the above continuous pretreatment process, the addition mass of the flocculant in the step (4) is 1 per mill of the addition mass of the pirimiphos-methyl wastewater; the flocculating agent is a polyacrylamide solution; the mass concentration of the flocculating agent is 5 per mill; the flocculant is mixed with the mixed wastewater in a baffled manner.
In the above continuous pretreatment process, a further improvement is that in the step (2), the gas obtained after the stripping is cooled by a second cooler and then is sent to an RTO incinerator for incineration;
in the above continuous pretreatment process, it is further improved that in the step (4), the filtrate obtained after the solid-liquid separation is sent to a biochemical treatment system for biochemical treatment; and filter pressing the filter residue obtained after the solid-liquid separation, and then sending the filter residue into a solid incinerator for incineration.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a continuous pretreatment system for pirimiphos-methyl wastewater, which comprises a wastewater storage tank, a first water pump, a heater, a three-dimensional electrocatalytic oxidation stripping tower, a first cooler, a neutralization kettle, a second water pump and a settling tank which are sequentially communicated, wherein the three-dimensional electrocatalytic oxidation stripping tower comprises a stripping tower, and a three-dimensional electrocatalytic oxidation device is arranged in the stripping tower. In the continuous pretreatment system, the three-dimensional electrocatalytic oxidation device and the stripping tower are integrated, the three-dimensional electrocatalytic oxidation device is used for decomposing pyrimidine organic matters to reduce COD, organic nitrogen, sulfur and phosphorite can be converted into ammonia nitrogen, inorganic sulfur and inorganic phosphorus, and simultaneously the characteristics of electrocatalytic reaction heat release and small amount of salt electrolysis to increase the pH value of the wastewater are utilized to blow air from the bottom of the tower to remove the ammonia nitrogen, thereby playing the role of the stripping tower, reducing the equipment cost and further utilizing a neutralization kettle and a settling tank to neutralize, flocculate and settle to remove the sulfur and the phosphorus. The continuous pretreatment system can reduce the equipment cost, can realize continuous treatment of the pirimiphos-methyl wastewater, saves energy, reduces labor intensity, has the characteristics of obvious treatment effect, low investment, low operation cost, convenience for engineering popularization and application and the like, can be widely used for treating the pirimiphos-methyl wastewater, and has good use value and good application prospect.
(2) In the continuous pretreatment system, electrocatalytic oxidation filler is filled between an anode and a cathode of a three-dimensional electrocatalytic oxidation device, wherein the electrocatalytic oxidation filler is prepared by mixing a catalyst carrier and a metal catalyst solution and then roasting the mixture, the catalyst carrier is a mixture of clay minerals and a curing agent, and the metal catalyst solution is Cu2+/Mn2+The mixed solution of (1). In the electrocatalytic oxidation filling of the invention, a metal catalyst is roasted to generate a metal oxide, and the metal oxide and mineral elements in clay minerals are polymerized to produce polymers, particularly Cu2+/Mn2+With SiO in the carrier2、Al2O3High temperature reaction to form polymer, Cu2+Improved catalytic activity of the particle electrode, Mn2+The electrocatalytic oxidation filler has good enrichment and activation effects, and the two effects are coordinated, so that the catalytic activity, the conductivity and the stability of the particles are improved, and compared with the existing common fillers (such as argil/copper oxide, argil/copper oxide/zinc oxide, CuO-ZnO porous ceramic and activated carbon particles), the electrocatalytic oxidation filler has the advantages of better conductivity, lower energy consumption, higher stability, stronger catalytic activity, no need of supporting electrolyte and the like. Meanwhile, when the electrocatalytic oxidation filler is used as the filler of a three-dimensional electrocatalytic oxidation device, the defects of low current efficiency,The three-dimensional electrocatalytic oxidation device has the advantages that the mass transfer distance is long, and the like, so that when the three-dimensional electrocatalytic oxidation device is used for treating the methyl pyrimidine phosphorus wastewater, particularly the methyl pyrimidine phosphorus wastewater, a better treatment effect can be obtained, and a very good application prospect is shown in the aspect of effectively treating the methyl pyrimidine phosphorus wastewater.
(3) The preparation method of the electrocatalytic oxidation filler in the continuous pretreatment system comprises the steps of preparing a catalyst carrier from argil, diatomite, bentonite and a curing agent, and then soaking the catalyst carrier in Cu2+/Mn2+Preparing the mixed solution into a filler precursor, and finally roasting the filler precursor to obtain the electrocatalytic oxidation filler. According to the invention, the mixture of the argil, the diatomite and the bentonite is used as a clay mineral, so that the air holes of the filler can be kept in good uniformity, the argil air holes can be rapidly shrunk at high temperature, the diatomite and the bentonite with different expansion coefficients can be added to relieve the shrinkage, and the mass ratio of the argil, the diatomite and the bentonite is optimized to be 5-6: 2-3: 3-1, so that the size of the air holes is controlled to be 0.1-0.4 mu m; the mass ratio of the curing agent to the clay mineral is optimized to be 0.05%, so that the clay mineral can be effectively cured and is not easy to disperse; the mass ratio of the metal catalyst solution to the clay mineral is optimized to be 20-35%, so that the clay mineral can absorb the metal catalyst to the maximum extent, and the preparation of the filler with more excellent performance is facilitated; the mixed solution of copper acetate and manganese acetate has the advantages of cheap and easily obtained raw materials, good water solubility and the like, and Cu in the mixed solution of copper acetate and manganese acetate is optimized2+、Mn2+The molar ratio of (1: 1) - (2) is favorable for fully exerting Cu2+The catalytic activity of (2) and the coordinated exertion of Mn2+The enrichment and activation effects are obtained, so that the synergistic effect of the two is the most efficient. The preparation method of the electrocatalytic oxidation filler has the advantages of simple process, convenience in operation, easiness in control, low raw material cost, low energy consumption, short time consumption, environmental friendliness and the like, is suitable for continuous large-scale batch production, is convenient for industrial utilization, and shows good application prospects.
(4) The invention also provides a continuous pretreatment process of the pirimiphos-methyl wastewaterThe continuous pretreatment system is adopted to pretreat the pirimiphos-methyl wastewater, so that the continuous treatment of the pirimiphos-methyl wastewater can be realized, the wastewater treatment capacity is greatly improved, the energy is saved, and the labor intensity is reduced; can also effectively remove COD, ammonia nitrogen, phosphorus and sulfur in the wastewater, wherein the removal rate of the COD is 70-85 percent, the removal rate of the ammonia nitrogen is about 70-80 percent, the removal rate of the total nitrogen is about 60-70 percent, and the T isPDecrease by 70-85%, TSThe reduction is 80-90%; meanwhile, the biodegradability B/C of the wastewater can be improved to 0.4 from 0.01, so that the biodegradability of the wastewater is improved, and the treated wastewater can be further subjected to advanced treatment by using a biochemical treatment process. The continuous pretreatment process has the advantages of simple process, convenient operation, low cost, low energy consumption, high treatment efficiency, good treatment effect and the like, and has very important significance for realizing the advanced treatment of the pirimiphos-methyl wastewater.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
FIG. 1 is a schematic view of a continuous pretreatment system for pirimiphos-methyl wastewater in example 1 of the present invention.
Illustration of the drawings:
1. a wastewater storage tank; 2. a first water pump; 3. a heater; 4. a three-dimensional electrocatalytic oxidation stripping tower; 5. a first cooler; 6. a neutralization kettle; 7. a second water pump; 8. a settling tank; 9. a second cooler; 10. an RTO incinerator; 11. a fan.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The materials and equipment used in the following examples are commercially available. In the examples of the present invention, unless otherwise specified, the processes used were conventional processes, the equipment used were conventional equipment, and the data obtained were average values of three or more experiments.
Example 1
As shown in figure 1, the continuous pretreatment system for the pirimiphos-methyl wastewater comprises a wastewater storage tank 1, a first water pump 2, a heater 3, a three-dimensional electrocatalytic oxidation stripping tower 4, a first cooler 5, a neutralization kettle 6, a second water pump 7 and a settling tank 8 which are sequentially communicated, wherein the three-dimensional electrocatalytic oxidation stripping tower 4 comprises a stripping tower, and a three-dimensional electrocatalytic oxidation device is arranged in the stripping tower. In this embodiment, the effective height of the stripping tower is 6500mm, and the diameter of the tower is 600 mm.
In this embodiment, the three-dimensional electrocatalytic oxidation apparatus is a cylindrical structure, the center of which uses an IrO-RuO/Ti rod as an anode and the periphery of which uses a stainless steel plate as a cathode, wherein IrO2-RuO2The diameter of the Ti rod is 100 mm; the diameter of the cathode is 400mm, wherein the effective height of the anode and the cathode is 6000 mm.
In this embodiment, an electrocatalytic oxidation filler is filled between an anode and a cathode of the three-dimensional electrocatalytic oxidation device, wherein the electrocatalytic oxidation filler is prepared by mixing a catalyst carrier and a metal catalyst solution and then calcining the mixture, the catalyst carrier is a mixture of clay minerals and a curing agent, and the metal catalyst solution is Cu2+/Mn2+The mixed solution of (1). The electrocatalytic oxidation filler is prepared by the following method, which comprises the following steps:
s1, weighing 10kg of argil, 4kg of diatomite and 6kg of bentonite, mixing, adding 10g of 30% silica gel solution to prepare spherical solid with the particle size of 30mm, and drying at 105 ℃ to obtain the catalyst carrier.
S2, putting the catalyst carrier obtained in the step S1 into a mixed solution of 4.5kg of copper acetate and manganese acetate (the mixed solution is prepared by dissolving 246g of manganese acetate and 200g of copper acetate in water, wherein Cu in the mixed solution is Cu2+、Mn2+1: 1, and the mass percentage content of copper acetate and manganese acetate is 10%), taking out after the impregnation is finished, and drying at 105 ℃ to obtain the filler precursor.
S3, placing the filler precursor obtained in the step S2 in a muffle furnace, roasting for 4 hours at 300 ℃, and decomposing acetate radicals of manganese acetate and copper acetate at high temperature to generate manganese oxide and copper oxide to obtain the electrocatalytic oxidation filler.
In the embodiment, the top of the three-dimensional electrocatalytic oxidation stripping tower 4 is communicated with an RTO incinerator 10, and a second cooler 9 is communicated between the three-dimensional electrocatalytic oxidation stripping tower 4 and the RTO incinerator 10; the bottom of the three-dimensional electrocatalytic oxidation stripping tower 4 is communicated with a fan 11.
Example 2
A continuous pretreatment process of pirimiphos-methyl wastewater, which is implemented by adopting the continuous pretreatment system in example 1, comprises the following steps:
(1) oxidative stripping
(1.1) storing the waste water of the pirimiphos-methyl in a waste water storage tank of a Changde pesticide factory, wherein the discharge amount of the waste water of the pirimiphos-methyl in the pesticide factory is 48 tons/day.
(1.2) the waste water of pirimiphos-methyl (pH 7-8, water quality as shown in Table 1) in the waste water storage tank was fed to a heater by a first water pump and heated to 65 ℃.
(1.3) according to the inflow of 2m3H, feeding the wastewater heated in the step (1.2) into a three-dimensional electrocatalytic oxidation stripping tower from the middle upper part of the tower, and keeping the current density at 200A/m2Carrying out electrocatalytic oxidation on the pirimiphos-methyl wastewater by using a three-dimensional electrocatalytic oxidation device, and simultaneously carrying out electrocatalytic oxidation according to the air flow rate of 200m3And h, sending air into the tower from the bottom of the tower by adopting a fan to blow off the pirimiphos-methyl wastewater to obtain the ammonia-removing wastewater. In the step, after 5 minutes of electrocatalytic oxidation, the pH value of the wastewater is naturally increased to 11 and kept unchanged, and the water temperature is naturally increased to 80 ℃.
(1.4) cooling the ammonia-carrying gas blown off in the step (1.3) by a second cooler, and then sending the cooled ammonia-carrying gas into an RTO incinerator for incineration, wherein the incineration tail gas is directly discharged into the air; in addition, the ammonia-removing wastewater after the oxidation stripping in the step (1.3) is cooled by a first cooler and then enters a neutralization kettle.
(2) Neutralizing flocculation sedimentation
(2.1) adding 30% ferric trichloride solution into the step (1.4) according to the flow of 20kg/h, wherein ammonia is removedIn the neutralization kettle of the waste water, the amount of the waste water is 16m per3150kg of hydrochloric acid solution with the mass concentration of 30% is added into the wastewater, the pH value of the wastewater in the neutralization kettle is adjusted to 7-8, and the obtained mixed wastewater is sent into a settling tank through a second water pump.
(2.2) according to the flow of 2kg/h, a flocculating agent (PAM) with the mass concentration of 5 per mill is put into the settling tank from an inlet at the upper part of the settling tank for flocculation reaction, wherein the flocculating agent (PAM) is mixed with the neutralized mixed wastewater in a baffling manner, and then solid-liquid separation is carried out in the settling tank, so that the pretreatment of the pirimiphos-methyl wastewater is completed. Carrying out filter pressing on solid obtained after solid-liquid separation to obtain 100kg of filter residue produced in the day, and sending the filter residue to a solid waste incinerator for incineration; and (3) allowing the liquid obtained after the solid-liquid separation to enter a biochemical system for further advanced treatment, wherein the water quality condition of the liquid obtained after the solid-liquid separation is shown in Table 1.
TABLE 1 comparison data of water quality before and after treatment of pirimiphos-methyl wastewater from Hende agricultural chemical plant
Example 3
A continuous pretreatment system of pirimiphos-methyl wastewater is different from the continuous pretreatment system of example 1 only in that: the three-dimensional electrocatalytic oxidation device in example 3 differs in the filling material between the anode and the cathode.
In example 3, a method for preparing an electrocatalytic oxidation filler filled between an anode and a cathode of a three-dimensional electrocatalytic oxidation device, comprising the steps of:
s1, weighing 12kg of argil, 6kg of diatomite and 2kg of bentonite, mixing, adding 10g of 30 mass percent water glass, preparing into spherical solid with the particle size of 50mm, and drying at 105 ℃ to obtain the catalyst carrier.
S2, placing the catalyst carrier obtained in the step S1 into a mixed solution of 6.9kg of copper acetate and manganese acetate (the mixed solution is prepared by dissolving 492g of manganese acetate and 200g of copper acetate in water, wherein Cu in the mixed solution is Cu2+、Mn2+1: 2, and the mass percentage content of copper acetate and manganese acetate is 10%) for 8h, taking out after the impregnation is finished, and drying at 105 ℃ to obtain the filler precursor.
S3, placing the filler precursor obtained in the step S2 in a muffle furnace, roasting for 4 hours at 300 ℃, and decomposing acetate radicals of manganese acetate and copper acetate at high temperature to generate manganese oxide and copper oxide to obtain the electrocatalytic oxidation filler.
Example 4
A continuous pretreatment process of pirimiphos-methyl wastewater, which is implemented by adopting the continuous pretreatment system in example 3, comprises the following steps:
(1) oxidative stripping
(1.1) storing the waste water of the pirimiphos-methyl in the pharmaceutical factory in the salt city in a waste water storage tank, wherein the discharge amount of the waste water of the pirimiphos-methyl in the pharmaceutical factory is 60 tons/day.
(1.2) the waste water of pirimiphos-methyl (pH 7-8, water quality as shown in Table 2) in the waste water storage tank was fed to a heater by a first water pump and heated to 50 ℃.
(1.3) according to the inflow of 2.5m3H, feeding the wastewater heated in the step (1.2) into a three-dimensional electrocatalytic oxidation stripping tower from the middle upper part of the tower, and keeping the current density at 250A/m2Carrying out electrocatalytic oxidation on the pirimiphos-methyl wastewater by using a three-dimensional electrocatalytic oxidation device, and simultaneously carrying out electrocatalytic oxidation on the wastewater according to the air flow rate of 375m in the electrocatalytic process3And h, sending air into the tower from the bottom of the tower by adopting a fan to blow off the pirimiphos-methyl wastewater to obtain the ammonia-removing wastewater. In the step, after 5 minutes of electrocatalytic oxidation, the pH value of the wastewater is naturally increased to 12 and kept unchanged, and the water temperature is naturally increased to 70 ℃.
(1.4) cooling the ammonia-carrying gas blown off in the step (1.3) by a second cooler, and then sending the cooled ammonia-carrying gas into an RTO incinerator for incineration, wherein the incineration tail gas is directly discharged into the air; in addition, the ammonia-removing wastewater after the oxidation stripping in the step (1.3) is cooled by a first cooler and then enters a neutralization kettle.
(2) Neutralizing flocculation sedimentation
(2.1) mixing 30% by mass of tris (hydroxymethyl) phosphonium chloride at a flow rate of 25kg/hAdding the ferric chloride solution into the neutralization kettle filled with the ammonia removal wastewater in the step (1.4) according to the proportion of 16m3Adding 180kg of hydrochloric acid solution with the mass concentration of 30% into the wastewater, adjusting the pH value of the wastewater in the neutralization kettle to be 7-8, and feeding the obtained mixed wastewater into a settling tank through a second water pump.
(2.2) according to the flow of 2.5kg/h, a flocculating agent (PAM) with the mass concentration of 5 per mill is introduced into the settling tank from an inlet at the upper part of the settling tank, wherein the flocculating agent (PAM) is mixed with the neutralized mixed wastewater in a baffling manner, and then solid-liquid separation is carried out in the settling tank, so that the pretreatment of the methyl pyrimidine phosphorus wastewater is completed. Carrying out filter pressing on solid obtained after solid-liquid separation to obtain 180kg of filter residue per day, and sending the filter residue to a solid waste incinerator for incineration; and (3) allowing the liquid obtained after the solid-liquid separation to enter a biochemical system for continuous treatment, wherein the water quality condition of the liquid obtained after the solid-liquid separation is shown in Table 2.
TABLE 2 comparison data of water quality before and after treatment of pirimiphos-methyl wastewater from a certain pharmaceutical factory in salt city
Comparative example 1
A continuous pretreatment process of pirimiphos-methyl wastewater is basically the same as the continuous pretreatment process in example 4, and only differs from the continuous pretreatment process in that: in the three-dimensional electrocatalytic oxidation apparatus used in comparative example 1, no material was filled between the anode and the cathode, i.e., the two-dimensional electrocatalytic oxidation apparatus was actually used in comparative example 1.
In comparative example 1, the water quality of the liquid obtained after the solid-liquid separation is shown in Table 3.
TABLE 3 comparison data of water quality before and after treatment of pirimiphos-methyl wastewater from a certain pharmaceutical factory in salt city
As can be seen from tables 1-3, after the treatment by the method, the COD removal rate of the pirimiphos-methyl wastewater is 70-85%, the ammonia nitrogen removal rate is 70-80%, the total nitrogen removal rate is 60-70%, and the T removal rate is TPDecrease by 70-85%, TSThe biodegradability B/C of the wastewater is reduced by 80-90 percent and is improved from 0.01 to 0.4, thereby achieving the purpose of improving the biodegradability of the wastewater. In addition, the three-dimensional electrocatalytic oxidation device and the stripping tower are organically combined into a whole to form the three-dimensional electrocatalytic oxidation stripping tower, so that the cost can be saved, meanwhile, the energy can be saved by adopting a continuous production process, the labor intensity can be reduced, and the method has the characteristics of remarkable treatment effect, low investment, low operation cost and convenience for engineering popularization and application. In addition, as can be seen from tables 2 and 3, under the same energy consumption, the treatment effect of the three-dimensional electrocatalytic oxidation device adopted by the invention is obviously better than that of the two-dimensional electrocatalytic oxidation device, which indicates that the electrocatalytic oxidation catalytic filler adopted by the invention can effectively improve the electrocatalytic oxidation treatment effect of the three-dimensional electrocatalytic oxidation device, can obviously reduce the COD of the pirimiphos-methyl wastewater, can convert organic nitrogen, sulfur and phosphate ore into ammonia nitrogen, inorganic sulfur and inorganic phosphorus, and obtains excellent treatment effect.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. 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 continuous pretreatment system for pirimiphos-methyl wastewater is characterized by comprising a wastewater storage tank (1), a first water pump (2), a heater (3), a three-dimensional electrocatalytic oxidation stripping tower (4), a first cooler (5), a neutralization kettle (6), a second water pump (7) and a settling tank (8) which are sequentially communicated; the three-dimensional electrocatalytic oxidation stripping tower (4) comprises a stripping tower, and a three-dimensional electrocatalytic oxidation device is arranged in the stripping tower.
2. The continuous pretreatment system of claim 1, wherein the three-dimensional electrocatalytic oxidation device is a cylindrical structure centered at IrO2-RuO2the/Ti rod is used as an anode, and a stainless steel plate is used as a cathode around the anode.
3. The continuous pretreatment system according to claim 2, wherein an electrocatalytic oxidation filler is filled between an anode and a cathode of the three-dimensional electrocatalytic oxidation device; the electrocatalytic oxidation filler is prepared by mixing a catalyst carrier and a metal catalyst solution and then roasting the mixture; the catalyst carrier is a mixture of clay minerals and a curing agent; the metal catalyst solution is Cu2+/Mn2+The mixed solution of (1).
4. The continuous pretreatment system of claim 3, wherein the electrocatalytic oxidation packing production method comprises the steps of:
s1, mixing argil, diatomite and bentonite, adding a curing agent to prepare spherical solid, and drying to obtain a catalyst carrier;
s2, adding the catalyst carrier obtained in the step S1 to Cu2+/Mn2+Dipping and drying the mixture solution to obtain a filler precursor;
s3, roasting the filler precursor obtained in the step S2 to obtain the electrocatalytic oxidation filler.
5. The continuous pretreatment system according to claim 4, wherein in step S1, the mass ratio of the pottery clay, the diatomite and the bentonite is 5-6: 2-3: 3-1; the mass ratio of the curing agent to the total mass of the argil, the diatomite and the bentonite is 0.05 percent; the curing agent is silica gel solution or water glass; the mass concentration of the curing agent is 30 percent; the particle size of the spherical solid is 2-50 mm; the temperature of the drying is 105 ℃;
in the step S2, the Cu2+/Mn2+The mixed solution of (1) is a mixed solution of copper acetate and manganese acetate; cu in the mixed solution of the copper acetate and the manganese acetate2+、Mn2+The molar ratio of (A) to (B) is 1: 1-2; of said copper and manganese acetatesThe mass percentage content of copper acetate and manganese acetate in the mixed solution is 10 percent; the Cu2+/Mn2+The ratio of the mass of the mixed solution to the total mass of the pottery clay, the diatomite and the bentonite in the step S1 is 20 to 35 percent; the dipping time is 8 h; the temperature of the drying is 105 ℃;
in the step S3, the roasting is carried out at the temperature of 300 ℃; the roasting time is 4 hours.
6. The continuous pretreatment system according to any one of claims 1 to 5, wherein the top of the three-dimensional electrocatalytic oxidation stripping tower (4) is communicated with an RTO incinerator (10); a second cooler (9) is communicated between the three-dimensional electrocatalytic oxidation stripping tower (4) and the RTO incinerator (10); the bottom of the three-dimensional electrocatalytic oxidation stripping tower (4) is communicated with a fan (11).
7. A continuous pretreatment process of pirimiphos-methyl wastewater, characterized in that the continuous pretreatment process is to carry out continuous pretreatment on pirimiphos-methyl wastewater by using the continuous pretreatment system as claimed in any one of claims 1 to 6.
8. The continuous pretreatment process according to claim 7, comprising the steps of:
(1) feeding the methyl pyrimidine phosphorus wastewater in the wastewater storage tank (1) into a heater (3) through a first water pump (2) to heat the methyl pyrimidine phosphorus wastewater;
(2) feeding the heated pirimiphos-methyl wastewater in the step (1) into a three-dimensional electrocatalytic oxidation stripping tower (4) from the middle upper part of the tower, carrying out electrocatalytic oxidation on the pirimiphos-methyl wastewater in the three-dimensional electrocatalytic oxidation device, and feeding gas into the three-dimensional electrocatalytic oxidation stripping tower (4) from the bottom of the tower through a fan (11) in the electrocatalytic oxidation process to strip the pirimiphos-methyl wastewater to obtain ammonia-removal wastewater;
(3) cooling the ammonia-removing wastewater obtained in the step (2) by using a first cooler (5), then feeding the ammonia-removing wastewater into a neutralization kettle (6), adding a ferric trichloride solution into the neutralization kettle (6), stirring, adding an acid solution to adjust the pH value of the wastewater to 7-8, and thus obtaining mixed wastewater;
(4) and (4) feeding the mixed wastewater obtained in the step (3) into a settling tank (8) through a second water pump (7), adding a flocculating agent from the upper part of the settling tank (8) for flocculation reaction, and performing solid-liquid separation to finish the pretreatment of the pirimiphos-methyl wastewater.
9. The continuous pretreatment process according to claim 8, wherein in the step (1), the heating is carried out by heating the pirimiphos-methyl wastewater to 50-65 ℃;
in the step (2), the water inflow rate of the pirimiphos-methyl wastewater is 2m3/h～2.5m3H; the current density in the electrocatalytic oxidation process is controlled to be 200A/m2～250A/m2(ii) a The volume ratio of the gas to the pirimiphos-methyl wastewater is 100-150: 1; the gas is air;
in the step (3), the adding mass of the ferric trichloride solution is 1% of the adding mass of the pirimiphos-methyl wastewater; the mass concentration of the ferric trichloride solution is 30%; the acid solution is hydrochloric acid solution; the mass concentration of the acid solution is 30%;
in the step (4), the adding mass of the flocculating agent is 1 per mill of the adding mass of the pirimiphos-methyl wastewater; the flocculating agent is a polyacrylamide solution; the mass concentration of the flocculating agent is 5 per mill; the flocculant is mixed with the mixed wastewater in a baffled manner.
10. The continuous pretreatment process according to any one of claims 7 to 9, wherein in the step (2), the gas obtained after the stripping is cooled by a second cooler (9) and then sent to an RTO incinerator (10) for incineration;
in the step (4), the filtrate obtained after the solid-liquid separation is sent into a biochemical treatment system for biochemical treatment; and filter pressing the filter residue obtained after the solid-liquid separation, and then sending the filter residue into a solid incinerator for incineration.
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