CN106830492B - Treatment method of methoxy acrylic ester pesticide product wastewater - Google Patents
Treatment method of methoxy acrylic ester pesticide product wastewater Download PDFInfo
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- CN106830492B CN106830492B CN201710217270.1A CN201710217270A CN106830492B CN 106830492 B CN106830492 B CN 106830492B CN 201710217270 A CN201710217270 A CN 201710217270A CN 106830492 B CN106830492 B CN 106830492B
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- 239000002351 wastewater Substances 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000000575 pesticide Substances 0.000 title claims abstract description 13
- -1 methoxy acrylic ester Chemical class 0.000 title description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 40
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 36
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 35
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000003647 oxidation Effects 0.000 claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- 239000001103 potassium chloride Substances 0.000 claims abstract description 19
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 19
- 238000001704 evaporation Methods 0.000 claims abstract description 17
- 230000008020 evaporation Effects 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 239000012153 distilled water Substances 0.000 claims abstract description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 11
- 229930182692 Strobilurin Natural products 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
- 230000008025 crystallization Effects 0.000 claims abstract description 6
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 4
- 239000007921 spray Substances 0.000 claims description 19
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- 229960004887 ferric hydroxide Drugs 0.000 claims description 9
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000011736 potassium bicarbonate Substances 0.000 claims description 8
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 8
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 8
- 235000011181 potassium carbonates Nutrition 0.000 claims description 8
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 8
- 239000005416 organic matter Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- WBGWGHYJIFOATF-UHFFFAOYSA-M potassium;methyl sulfate Chemical compound [K+].COS([O-])(=O)=O WBGWGHYJIFOATF-UHFFFAOYSA-M 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 239000003814 drug Substances 0.000 claims description 3
- 150000003384 small molecules Chemical class 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 6
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000005119 centrifugation Methods 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 13
- 239000006227 byproduct Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 239000000243 solution Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- MIJGGRRVPKYVNI-UHFFFAOYSA-N S(=O)(=O)(O)O.C[K] Chemical compound S(=O)(=O)(O)O.C[K] MIJGGRRVPKYVNI-UHFFFAOYSA-N 0.000 description 4
- 239000002920 hazardous waste Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000003203 everyday effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 230000001939 inductive effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000005730 Azoxystrobin Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000005800 Kresoxim-methyl Substances 0.000 description 1
- 239000005869 Pyraclostrobin Substances 0.000 description 1
- 239000005857 Trifloxystrobin Substances 0.000 description 1
- WFDXOXNFNRHQEC-GHRIWEEISA-N azoxystrobin Chemical compound CO\C=C(\C(=O)OC)C1=CC=CC=C1OC1=CC(OC=2C(=CC=CC=2)C#N)=NC=N1 WFDXOXNFNRHQEC-GHRIWEEISA-N 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 1
- ZOTBXTZVPHCKPN-HTXNQAPBSA-N kresoxim-methyl Chemical compound CO\N=C(\C(=O)OC)C1=CC=CC=C1COC1=CC=CC=C1C ZOTBXTZVPHCKPN-HTXNQAPBSA-N 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- HZRSNVGNWUDEFX-UHFFFAOYSA-N pyraclostrobin Chemical compound COC(=O)N(OC)C1=CC=CC=C1COC1=NN(C=2C=CC(Cl)=CC=2)C=C1 HZRSNVGNWUDEFX-UHFFFAOYSA-N 0.000 description 1
- ONCZDRURRATYFI-TVJDWZFNSA-N trifloxystrobin Chemical compound CO\N=C(\C(=O)OC)C1=CC=CC=C1CO\N=C(/C)C1=CC=CC(C(F)(F)F)=C1 ONCZDRURRATYFI-TVJDWZFNSA-N 0.000 description 1
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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
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/02—Preparation of sulfates from alkali metal salts and sulfuric acid or bisulfates; Preparation of bisulfates
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
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- 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
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- 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
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- 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
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/10—Inorganic compounds
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- C02F2103/343—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 pharmaceutical industry, e.g. containing antibiotics
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Abstract
The invention relates to a method for treating wastewater of strobilurin pesticide products, which comprises the following steps: collecting and filtering wastewater; adding sulfuric acid, adjusting the pH value, and converting inorganic sylvite into potassium sulfate; UV-photocatalytic oxidation is carried out, so that organic potassium salt is converted into potassium sulfate; adding potassium hydroxide, adjusting the pH value, neutralizing excessive sulfuric acid, and then adding ferric trichloride for precipitation reaction; filtering to remove flocculate; multi-effect evaporation, crystallization, centrifugation and separation to obtain solid potassium sulfate, and the steam condensate and the distilled water are both reused in a workshop. Realizes the resource utilization of the wastewater, realizes zero discharge of the wastewater and has higher economic and environmental benefits.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method for treating wastewater of strobilurin pesticide products.
Background
The method for producing the strobilurin pesticide products such as pyraclostrobin, azoxystrobin, kresoxim-methyl, trifloxystrobin and the like comprises the following steps: raw pesticide, potassium methyl sulfate, potassium carbonate and potassium bicarbonate mixed salt, CODcr 30000-40000 mg/l.
For high-salinity wastewater, the treatment process commonly adopted by the current production enterprises is as follows: the first step is as follows: press filtering and recovering the product; step two, evaporation desalting: the CODcr of the distilled water is 5000 and 10000mg/l, the distilled water is discharged after reaching the standard after being further processed, and the mixed salt is entrusted to be disposed as dangerous waste.
The traditional treatment process has the following problems:
1) because the CODcr concentration of the wastewater is high, the mixed salt obtained by direct evaporation without pretreatment can only be treated as hazardous waste, thereby greatly increasing the treatment cost and wasting useful resources.
2) The distilled water still contains higher organic matters, can be discharged after reaching the standard after being further treated, has higher treatment cost and does not generate economic benefit.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a method for treating wastewater of strobilurin pesticide products, so that the resource utilization of high-concentration high-salt content in the wastewater is realized, the produced potassium sulfate is sold as a byproduct, steam condensate water and distilled water are recycled in a workshop, tail gas is absorbed by alkali and then is discharged up to the standard, no secondary pollution is generated, and good economic and environmental benefits are achieved.
In order to realize the aim, the invention provides a method for treating waste water of strobilurin pesticide products, which comprises the following steps:
1) collecting and filtering wastewater;
2) adding sulfuric acid, adjusting the pH value, and converting inorganic sylvite into potassium sulfate;
3) UV-photocatalytic oxidation is carried out, so that organic potassium salt is converted into potassium sulfate;
4) adding potassium hydroxide, adjusting the pH value, neutralizing excessive sulfuric acid, and then adding ferric trichloride to perform a flocculation precipitation reaction;
5) filtering to remove flocculate;
6) multi-effect evaporation, crystallization, centrifugation and separation to obtain solid potassium sulfate, and the steam condensate and the distilled water are both reused in a workshop.
Further, the filtering step in the step 1) adopts a duplex filter.
Further, the pH value is adjusted to 2.5-3.0 in the step 2).
Further, the inorganic potassium salt in the step 2) is potassium carbonate and potassium bicarbonate, and the reaction formula is as follows:
K2CO3+H2SO4→K2SO4+H2O+CO2↑
2KHCO3+H2SO4→K2SO4+2H2O+2CO2↑。
further, the organic potassium salt in the step 3) is potassium methyl sulfate, and the reaction formula is as follows:
R-H+HO·→R·+H2O
2K(CH3)SO4+3O2→K2SO4+2H2O+2CO2↑+H2SO4。
further, the pH value is adjusted to 6.0-7.0 in the step 4).
Further, the reaction formula in the step 4) is as follows:
H2SO4+2KOH→K2SO4+2H2O
3KOH+FeCl3→Fe(OH)3↓+3KCl。
further, the flocculate in the step 5) comprises ferric hydroxide and a small part of flocculateable small molecular organic matters.
Further, the gas generated by the reaction in the step 2) and the step 3) and the gas generated in the evaporation process in the step 6) are subjected to alkali absorption treatment.
Furthermore, the alkali absorption is carried out by adopting a two-stage spray tower, and the alkali in the alkali absorption is sodium hydroxide aqueous solution or sodium carbonate aqueous solution.
Compared with the prior art, the invention has the following advantages:
1) the duplex filter is adopted to replace the traditional filter pressing in the product recovery process, the operation is simpler and more convenient, and the field environment is greatly improved.
2) The acid adjustment of the wastewater converts the mixed salt of potassium carbonate and potassium bicarbonate into single potassium sulfate, and the UV-photocatalytic oxidation technology is utilized to convert the methyl potassium sulfate into potassium sulfate, so that the conversion from the mixed salt to the single salt in the wastewater is realized, and the mixed salt originally treated as hazardous waste can be recycled.
3) The whole process realizes zero discharge of wastewater and the aim of circular economy: the potassium salt in the wastewater is recovered and sold as a byproduct, the mother liquor is steamed, and the steam condensate and the distilled water are reused in a workshop, so that the water resource is greatly saved.
In conclusion, the invention provides a method for treating wastewater of strobilurin pesticide products, which realizes the resource utilization of high-concentration high-salt content in the wastewater, has good wastewater treatment effect, and effectively solves the defects of high cost, low efficiency and large amount of hazardous wastes in the prior treatment technology. The purpose of recycling the waste water is realized, energy and water resources are saved, and economic and environmental benefits are unified.
Drawings
FIG. 1 is a process flow chart of the wastewater treatment of the strobilurin pesticide product of the present invention.
Detailed Description
In order to better explain the present invention, the following description is given with reference to the accompanying drawings and the specific embodiments.
As shown in figure 1, the wastewater contains 1.3-1.5% of strobilurin pesticide product, 7.2-7.5% of potassium methyl sulfate, 4.8-5.0% of potassium bicarbonate and 1.4-1.6% of potassium carbonate.
Example 1
Step one, waste water is collected and is filtered and retrieve the product: 38 tons of wastewater is produced in a workshop every day, the wastewater enters a wastewater collection tank, the bottom of the tank is conical, a duplex filter is arranged at the outlet of a wastewater pump and used for filtering and recovering products, 0.5 ton of the products can be recovered every day, the duplex filter is provided with pressure interlocking control, when one pressure is high, an alarm is given and the other is switched, the phenomenon that the treatment flow is continuous due to blockage is avoided, 37.5 tons of filtrate is produced every day, and the wastewater enters a second step for treatment.
Step two, adjusting the pH: waste water with a particle size of 3.0m3The volume per hour is pumped into a pH adjusting tank,simultaneously adding 98% of sulfuric acid, controlling the proportion of acid and wastewater according to a mass flow meter, wherein the adding amount of the sulfuric acid is 114kg/h, automatically adjusting the pH value to 2.5, reacting potassium carbonate (45kg/h) and potassium bicarbonate (145kg/h) in the wastewater to generate potassium sulfate (178kg/h), and introducing tail gas into an alkaline washing spray tower through an air inducing system for treatment.
Step three, UV-photocatalytic oxidation: 3.2m for wastewater with pH 2.53The volume per hour is pumped into a UV-photocatalytic oxidation process system to pretreat the wastewater, 27.5 percent hydrogen peroxide and 40 percent ferric trichloride solution are added by an automatic dosing system, the adding amount is respectively 1500ppm and 170ppm, and the organic matter is degraded into CO through the oxidation of hydroxyl free radicals2、H2O, micromolecular acid and methyl potassium sulfate (220kg/h) are oxidized to generate potassium sulfate (128kg/h), and tail gas is introduced into an alkaline washing spray tower through an induced air system for treatment.
Step four, adjusting the pH: the wastewater of the previous step is 3.3m3The amount per hour is pumped into a pH adjusting tank, the waste water is neutralized by 40 percent potassium hydroxide, the proportion of a potassium hydroxide solution to the waste water is controlled according to a mass flow meter, the adding amount of the 40 percent potassium hydroxide is 270kg/h, the pH of the waste water is automatically adjusted to be 6.0, simultaneously, redundant sulfuric acid (72kg/h) reacts to generate potassium sulfate (128kg/h), and the potassium sulfate reacts with trace ferric trichloride (0.025kg/h) added by a UV-photocatalytic oxidation automatic medicine feeding system to generate ferric hydroxide (0.015kg/h) and potassium chloride (0.035 kg/h).
Fifthly, filtering and removing impurities: a small portion of floc (0.025kg/h) formed by the reaction, which includes ferric hydroxide and a small amount of small molecule organic matter that can flocculate, was filtered.
Sixthly, multi-effect evaporation and centrifugal separation: the pH value of the wastewater treated in the first five steps is 6.0 and is 3.3m3The volume per hour is pumped into a multi-effect evaporation system, and the waste water contains 434kg/h K generated by the reaction2SO4With 0.035kg/h KCl, 0.011kg KCl is generated per ton of waste water, and K is contained in per ton of waste water2SO4131.5kg, KCl only accounts for 0.008 percent of the total salt content, so the produced KCl does not influence the byproduct K2SO4The quality of (c). Concentrating in a first, second and third effect evaporator under vacuum state to obtain supersaturated potassium sulfate solution, crystallizing in a crystallization kettle, and centrifuging to obtain sulfuric acidPotassium (490kg/h, content > 85%) is sold as a by-product, steam condensate and distilled water (2.4 m)3/h，CODcr≤500mg/1，NH3N is less than or equal to 30mg/l) is recycled in a workshop, and noncondensable tail gas generated in the evaporation process is introduced into an alkaline washing spray tower through an induced air system for treatment.
The alkali in the alkali washing spray tower treatment involved in the second, third and sixth steps is 2-5% sodium hydroxide aqueous solution.
Example 2
The first step is the same as example 1.
Step two, adjusting the pH: waste water with a particle size of 3.2m3The volume per hour is pumped into a pH adjusting tank, 80% waste sulfuric acid is added at the same time, the proportion of acid and waste water is controlled according to a mass flow meter, the adding volume of the sulfuric acid is 150kg/h, the pH value is automatically adjusted to be 2.8, potassium carbonate (46kg/h) and potassium bicarbonate (150kg/h) in the waste water react to generate potassium sulfate (190kg/h), and tail gas is introduced into an alkaline washing spray tower through an air inducing system for treatment.
Step three, UV-photocatalytic oxidation: 3.3m for wastewater with pH 2.83The volume per hour is pumped into a UV-photocatalytic oxidation process system to pretreat the wastewater, 30 percent hydrogen peroxide and 35 percent ferric trichloride solution are added by an automatic dosing system, the adding amount is 1450ppm and 200ppm respectively, and the organic matter is degraded into CO through the oxidation of hydroxyl free radicals2、H2O, micromolecular acid and methyl potassium sulfate (223kg/h) are oxidized to generate potassium sulfate (130kg/h), and tail gas is introduced into an alkaline washing spray tower through an induced air system for treatment.
Step four, adjusting the pH: the wastewater of the previous step is 3.3m3The volume per hour is pumped into a pH adjusting tank, 38 percent potassium hydroxide is used for neutralizing wastewater, the proportion of a potassium hydroxide solution to the wastewater is controlled according to a mass flow meter, the adding volume of the 38 percent potassium hydroxide is 290kg/h, the pH of the wastewater is automatically adjusted to 6.5, simultaneously, redundant sulfuric acid (94kg/h) reacts to generate potassium sulfate (130kg/h), and the potassium sulfate reacts with trace ferric trichloride (0.026kg/h) added by a UV-photocatalytic oxidation automatic dosing system to generate ferric hydroxide (0.017kg/h) and potassium chloride (0.036 kg/h).
Fifthly, filtering and removing impurities: a small part of flocculate (0.026kg/h) produced by the reaction was filtered, the flocculate consisting of ferric hydroxide and a small amount of small organic flocculants.
Sixthly, multi-effect evaporation and centrifugal separation: the pH value of the wastewater treated in the first five steps is 6.5 and is 3.3m3The volume per hour is pumped into a multi-effect evaporation system, and the waste water contains 450kg/h K generated by reaction2SO4With 0.036kg/h KCl, 0.011kg of KCl is generated in each ton of wastewater, and K is contained in each ton of wastewater2SO4136.4kg, KCl only accounts for 0.008 percent of the total salt content, so the produced KCl does not influence the byproduct K2SO4The quality of (c). Concentrating in a first, second and third effect evaporator under vacuum to obtain supersaturated potassium sulfate solution, crystallizing in a crystallization kettle, centrifuging to obtain potassium sulfate (498kg/h, content greater than or equal to 85%) as byproduct, and steam-condensing water and distilled water (2.5 m)3/h，CODcr≤500mg/l，NH3N is less than or equal to 30mg/l) is recycled in a workshop, and noncondensable tail gas generated in the evaporation process is introduced into an alkaline washing spray tower through an induced air system for treatment.
The alkali in the alkali washing spray tower treatment involved in the second, third and sixth steps is 5-15% sodium carbonate aqueous solution.
Example 3
The first step is the same as example 1.
Step two, adjusting the pH: waste water with a particle size of 3.2m3Pumping the volume/h into a pH adjusting tank, simultaneously adding 98% sulfuric acid, controlling the proportion of acid and wastewater according to a mass flow meter, wherein the adding volume of the sulfuric acid is 125kg/h, automatically adjusting the pH to 3.0, reacting potassium carbonate (48kg/h) and potassium bicarbonate (152kg/h) in the wastewater to generate potassium sulfate (193kg/h), and introducing tail gas into an alkaline washing spray tower through an air inducing system for treatment.
Step three, UV-photocatalytic oxidation: 3.3m for wastewater with pH 3.03The volume per hour is pumped into a UV-photocatalytic oxidation process system to pretreat the wastewater, an automatic dosing system is adopted to add 30 percent hydrogen peroxide and 50 percent ferric trichloride solution, the adding amount is 1400ppm and 150ppm respectively, and the organic matter is degraded into CO through the oxidation of hydroxyl free radicals2、H2O, micromolecular acid and methyl potassium sulfate (225kg/h) are oxidized to generate potassium sulfate (131kg/h), and tail gas is introduced into an alkaline washing spray tower through an induced air system for treatment.
Step four, adjusting the pH: waste of last stepWater at 3.3m3The amount of potassium hydroxide is pumped into a pH adjusting tank, the waste water is neutralized by 40 percent of potassium hydroxide, the proportion of a potassium hydroxide solution to the waste water is controlled according to a mass flow meter, the adding amount of the 40 percent of potassium hydroxide is 280kg/h, the pH of the waste water is automatically adjusted to be 7.0, simultaneously, redundant sulfuric acid (74kg/h) reacts to generate potassium sulfate (131kg/h), and the potassium sulfate reacts with trace ferric trichloride (0.03kg/h) added by a UV-photocatalytic oxidation automatic medicine feeding system to generate ferric hydroxide (0.02kg/h) and potassium chloride (0.04 kg/h).
Fifthly, filtering and removing impurities: a small portion of floc (0.03kg/h) formed by the reaction, which includes ferric hydroxide and a small amount of small molecule organic matter that can flocculate, was filtered.
Sixthly, multi-effect evaporation and centrifugal separation: the pH value of the wastewater treated in the first five steps is 7.0 and is 3.3m3The amount of the waste water is pumped into a multi-effect evaporation system, and 455kg/h K generated in the reaction is contained in the waste water2SO40.04kg/h KCl, 0.012kg of KCl is generated in each ton of wastewater, and each ton of wastewater contains K2SO4142kg, KCl only accounts for 0.008 percent of the total salt content, so the produced KCl does not influence the byproduct K2SO4The quality of (c). Concentrating in a first, second and third effect evaporator under vacuum to obtain supersaturated potassium sulfate solution, crystallizing in a crystallization kettle, centrifuging to obtain potassium sulfate (510kg/h, content is greater than or equal to 85%) as byproduct, and steam condensate and distilled water (2.5 m)3/h，CODcr≤500mg/l，NH3N is less than or equal to 30mg/l) is recycled in a workshop, and noncondensable tail gas generated in the evaporation process is introduced into an alkaline washing spray tower through an induced air system for treatment.
The alkali in the alkali washing spray tower treatment involved in the second, third and sixth steps is 5-10% of sodium hydroxide aqueous solution.
Example 4
Comparing the process of the present invention with the conventional treatment process, the comprehensive benefits of the process of the present invention were analyzed based on the average consumption of examples 1-3, and the results are shown in table 1.
TABLE 1 analysis of the overall benefits (in terms of ton of wastewater)
| Process of treatment | Conventional treatment process | The process of the invention |
| Filtration recovery of products | Filter pressing | Duplex filtration |
| Adjusting the pH | / | 98％H2SO438.4kg, 19 yuan |
| UV-photocatalytic oxidation | / | 100 yuan |
| Adjusting the pH | / | 40% KOH 83.4kg, -83 yuan |
| Filtering to remove impurities | / | / |
| Multiple effect evaporation and centrifugal separation | -180 units | -150 yuan |
| Treatment of distilled water | 100 yuan | Saving water 750kg, 1.7 yuan |
| Hazardous waste treatment/byproduct recovery | 220kg of dangerous waste with the power of-660 yuan | 151.3kg K2SO4By-product, 310 Yuan |
| Combined cost/benefit | -940 element | -40.3 membered |
According to the analysis results obtained in the table 1, the process can save 1079.6 ten thousand yuan compared with the traditional treatment mode according to 1.2 ten thousand tons of annual treated wastewater, and the purposes of recycling the wastewater and saving energy and water resources are realized.
Although a few exemplary embodiments of the present invention have been shown and described, it would be appreciated by those skilled in the art that changes may be made in these exemplary embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the claims and their equivalents.
Claims (2)
1. A method for treating waste water of strobilurin pesticide products comprises the following steps:
1) collecting waste water and filtering by adopting a duplex filter;
2) the wastewater is treated at a rate of 3.0m3Pumping the volume per hour into a pH adjusting tank, simultaneously adding 98% sulfuric acid, controlling the proportion of acid and wastewater according to a mass flow meter, wherein the adding volume of the sulfuric acid is 114kg/h, adjusting the pH to 2.5, reacting 45kg/h potassium carbonate and 145kg/h potassium bicarbonate in the wastewater to generate 178kg/h potassium sulfate, and introducing tail gas into an alkaline washing spray tower through an induced air system for treatment;
3) the wastewater with pH 2.5 generated in step 2) was treated at 3.2m3Pumping the wastewater into a UV-photocatalytic oxidation process system in a volume of/h, and pretreating the wastewater; 27.5 percent of hydrogen peroxide and 40 percent of ferric trichloride solution are added by an automatic medicine adding systemThe addition amounts are 1500ppm and 170ppm respectively; degradation of organic matter to CO by oxidation of hydroxyl radicals2、H2O and a small molecule acid; oxidizing 220kg/h potassium methyl sulfate to generate 128kg/h potassium sulfate, and introducing tail gas into an alkaline washing spray tower through an induced air system for treatment;
4) 3.3m of wastewater generated in the step 3)3Pumping the solution into a pH adjusting tank by a volume/h, neutralizing the wastewater by 40% potassium hydroxide, and controlling the proportion of a potassium hydroxide solution to the wastewater according to a mass flow meter, wherein the adding amount of the 40% potassium hydroxide is 270 kg/h; adjusting the pH value of the wastewater to 6.0, and simultaneously reacting excessive 72kg/h of sulfuric acid to generate 128kg/h of potassium sulfate; 0.025kg/h of ferric trichloride is added into an UV-photocatalytic oxidation automatic dosing system to react to generate 0.015kg/h of ferric hydroxide and 0.035kg/h of potassium chloride;
5) filtering floc of 0.025kg/h generated by the reaction, wherein the floc comprises ferric hydroxide and flocculent micromolecule organic matter;
6) the treated wastewater with pH of 6.0 was treated at 3.3m3The volume per hour is pumped into a multi-effect evaporation system, and the waste water contains 434kg/h K generated by the reaction2SO4And 0.035kg/h KCl; concentrating in a first, second and third effect evaporator under vacuum state to obtain supersaturated potassium sulfate solution, crystallizing in a crystallization kettle, centrifuging to obtain 490kg/h potassium sulfate with content not less than 85%, and 2.4m3/h、CODcr≤500mg/1、NH3The steam condensate water and the distilled water with the N less than or equal to 30mg/l are reused in a workshop; the noncondensable tail gas generated in the evaporation process is introduced into an alkaline washing spray tower through an induced air system for treatment.
2. The method for treating the waste water of the strobilurin pesticide products as claimed in claim 1, wherein the alkali washing spray tower is implemented by adopting a two-stage spray tower, and the alkali in the alkali washing spray tower is an aqueous sodium hydroxide solution or an aqueous sodium carbonate solution.
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