CN106430714A - Method for deep treatment of pesticide wastewater - Google Patents

Method for deep treatment of pesticide wastewater Download PDF

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Publication number
CN106430714A
CN106430714A CN201610947043.XA CN201610947043A CN106430714A CN 106430714 A CN106430714 A CN 106430714A CN 201610947043 A CN201610947043 A CN 201610947043A CN 106430714 A CN106430714 A CN 106430714A
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China
Prior art keywords
waste water
agricultural chemicals
flocculant
adsorption
advanced treating
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Application number
CN201610947043.XA
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Chinese (zh)
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CN106430714B (en
Inventor
何丹农
严良
童琴
代卫国
高小迪
金彩虹
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Shanghai Na Xu Industrial Co Ltd
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Shanghai Na Xu Industrial Co Ltd
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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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/306—Pesticides
    • 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
    • C02F2103/343—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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Water Treatment By Sorption (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

The invention discloses a method for deep treatment of pesticide wastewater. Firstly, Fenton oxidation is adopted for pretreatment, and then the effect of efficiently removing CODCr and ammonia nitrogen is realized in combination with adsorption and flocculation. A Fenton reagent is improved and the oxidative degradation capacity of the reagent is improved; alum in an adsorption flocculant reacts with sodium silicate to produce aluminum hydroxide and silicic acid (silica) flocculent precipitates, the adsorption flocculant is combined with nonionic polyacrylamide and activated carbon, and the adsorption flocculation effect is improved; the sodium silicate replaces weak bases such as ammonia water, carbonate and the like, and rise of the ammonia nitrogen content and CODCr in wastewater is avoided. The method is applied to deep treatment of the pesticide wastewater and has higher oxidative degradation and adsorption and flocculation effects, and the removal rate of CODCr and ammonia nitrogen in the wastewater is high.

Description

A kind of method for agricultural chemicals waste water advanced treating
Technical field
The present invention relates to a kind of method for agricultural chemicals waste water advanced treating, more particularly to a kind of by efficient oxidation- Adsorption-flocculation method advanced treating agricultural chemicals waste water.
Background technology
Agricultural chemicals waste water is the waste water that insecticide factory discharges during pesticide producing, because its waste water quality, the water yield are unstable；Dirty Dye thing concentration is higher, CODCrHigher；Toxicity is big, removes external containing pesticide and centre, also contain phenol, arsenic, hydrargyrum etc. poisonous in waste water Material and many are difficult to biodegradable material；The features such as foul smelling, the respiratory tract to people and mucosa are irritant and become Scientific research difficult point.According to statistics, the wastewater flow rate of national pesticide producing enterprise year discharge nearly 2.0 hundred million tons, wherein processed only account for 7 % of total amount, and process up to standard only account for 1 processed %, and the raising year by year with China's pesticide yield, agricultural chemicals waste water institute The environmental pollution causing, ecosystem deterioration are also increasingly serious.Therefore, the new method that research agricultural chemicals waste water is processed, new technology become For benefiting the scientific research focus of the people's livelihood.
Nowadays, domestic and international agricultural chemicals waste water processing method mainly includes Physical（Absorption method, membrane separation process）, chemical method and Biochemical process（Aerobic biological process and anaerobic bio-treated）And some new methods（Photocatalytic oxidation, magnetic separation method, super Technology of acoustic wave, etc.）.However, the most frequently used adsorbent of absorption method is activated carbon, processing cost is high, and regenerates difficult；Divide according to film Big from technology one-time investment, technical difficulty is big, and membranous system cleaning is difficult, and the water yield that backwash needs is very big, and run and Maintenance cost is high；Bioanalysises operating cost is low, but treatment effect fluctuation is big, and the cycle is long, and agricultural chemicals waste water organic concentration is high, Microorganism is poisoned larger；Fast according to photocatalytic oxidation degradation speed, do not produce secondary pollution, reaction condition is gentle, but It is that general photocatalyst need to be by the use of ultraviolet light as energy, high energy consumption, and also agricultural chemicals waste water turbidity is high, light transmission difference all have impact on Absorptivity, the photocatalyst response rate is low simultaneously, and magnetic separation method and ultrasonic technology are also in laboratory research rank in China Section, this all limits its application in agricultural chemicals waste water process.
Fenton oxidation technology is easy to destroy hardly degraded organic substance chemical constitution in waste water, treatment effeciency height, does not produce two Secondary pollution, simple operation and other advantages, thus the process to high-concentration industrial-water has certain suitability.And traditional chemistry Coagulation process includes cohesion and flocculation, unsatisfactory to dissolubility organic pollution treatment effect, and adhesive flocculant can be Quickly put up a bridge in sewage, form flocks alumen ustum, and rapid precipitation separates removal after its surface adsorption pollutant.
Based on this, combined using Fenton technology pretreatment and adsorption-flocculation technique, overcome the limitation of monotechnics Property, the effect such as comprehensive performance Fenton oxidation, absorption, flocculation sediment is processed to agricultural chemicals waste water, reaches and efficiently reduces The COD of agricultural chemicals waste waterCrPurpose with ammonia nitrogen.
Content of the invention
For overcoming the deficiencies in the prior art, present invention aim at：A kind of side for agricultural chemicals waste water advanced treating is provided Method, the process route being combined using Fenton oxidation pretreatment and adsorption-flocculation carries out advanced treating to agricultural chemicals waste water.
Another object of the present invention is：A kind of adsorption-flocculation of the method for above-mentioned agricultural chemicals waste water advanced treating is provided Agent.
The object of the invention is realized by following proposal：
A kind of method for agricultural chemicals waste water advanced treating, carries out pretreatment initially with Fenton oxidation, then in conjunction with absorption Flocculant reaches efficient removal CODCrEffect with ammonia nitrogen.
The Fenton reagent of the present invention is by the mixture of potassium ferrate or potassium ferrate/ferrous sulfate hydrate and hydrogen peroxide group Become.
Described Fenton oxidation preprocessing process is as follows：By 500mL wastewater flow rate, adjust waste water with 10% dilute sulfuric acid first PH is 2 ~ 3, is then initially charged the potassium ferrate of 100 ~ 125 mg/L, or potassium ferrate and green vitriol（Or 12 water Close ferrous sulfate）Mixture；Stirring 2min, stands 20 min, and the hydrogen peroxide in batches adding 800 ~ 1000 mg/L is aoxidized Degraded 1h, adds alkali liquor to adjust pH7 ~ 8；Then, add 19.5 ~ 26 g adhesive flocculants, stir 2 min, stand 20 min, complete 500mL wastewater flow rate agricultural chemicals waste water advanced treating in pairs.
On the basis of such scheme, described adhesive flocculant is composited by flocculant and adsorbent, wherein, flocculant Combine for Alumen, non-ionic polyacrylamide, sodium silicate, adsorbent is Powdered Activated Carbon.
The concrete preparation method of described adhesive flocculant：50g Alumen is dissolved in 195g water, adds in alum solution 0.1g non-ionic polyacrylamide and 100g Powdered Activated Carbon, the particle diameter of Powdered Activated Carbon be 170 mesh and more than, 40 ~ 60 Stir 30 min with 200 r/min at DEG C, add 45g sodium silicate to stir 60 min, then stand 2 ~ 3h, obtain adhesive flocculant.
Described alkali liquor is 10 % calcium oxide suspensions.
Agricultural chemicals waste water COD can be made using the inventive methodCrRespectively reach 90.0 % and 80.0 more than % with ammonia nitrogen removal frank.
Oxidation-adsorption-flocculation technology that the present invention provides is mainly used in the advanced treating of agricultural chemicals waste water, is also applied for it The process of his industrial waste water.
Compared with prior art, the present invention has the advantage that：
Fenton oxidation and adsorption-flocculation are combined, comprehensive performance oxidative degradation, absorption, flocculation sediment effect；Add high ferro Sour potassium or potassium ferrate/ten sulfate dihydrate ferrous iron mixture replace traditional Fe2+, you can play potassium ferrate oxidation, flocculation sediment Effect, the Fe that its oxidation-reduction process produces2+Also can be to H2O2Play catalytic action, generate the hydroxyl radical free radical of strong oxidizing property； Using 10 % calcium oxide suspensions as the pH of alkali liquor both scalable waste water, also solidifying work can be helped to colloidal particles in waste water With as granular core weighting agent, accelerating the separation of insoluble matter.Alumen and sodium silicate react the aluminium hydroxide producing, silicic acid（Dioxy SiClx）Solidifying flocculent deposit, is combined with non-ionic polyacrylamide and activated carbon, improves absorption, flocculating effect, by silicic acid Sodium replaces the weak base such as traditional ammonia, sodium carbonate, and the ammonia-nitrogen content of waste water both will not be caused to raise, also will not be due to introducing carbonic acid Root is so that CODCrRaise.The oxidation of the present invention-adsorption-flocculation method cannot be only used for the advanced treating of agricultural chemicals waste water, it may also be used for The process of other industrial wastewaters, has certain reference in water treatment field.
Specific embodiment
Below embodiments of the invention are elaborated：The present embodiment is carried out under premised on technical solution of the present invention Implement, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following enforcements Example.
Embodiment 1：
50 g Alumen are dissolved in 195 g water, add 0.1 g non-ionic polyacrylamide and 100 g in alum solution Powdered Activated Carbon（170 mesh), stir 30 min with 200 r/min at 50 DEG C, add 45 g sodium silicate to stir 60 min, more quiet Put 2 h, obtain adhesive flocculant.
Adjusting wastewater pH with 10 % dilute sulfuric acids first is 3, is then initially charged the potassium ferrate of 100 mg/L, stirs 2min, Stand 20 min, the hydrogen peroxide in batches adding 800 mg/L carries out oxidative degradation 1 h, add 10 % calcium oxide suspensions to adjust pH 8, it is subsequently adding 19.5 g adhesive flocculants, stirs 2 min, stand 20 min. CODCrClearance is 92.1%, ammonia nitrogen removal frank For 80.4%.
Embodiment 2：
50 g Alumen are dissolved in 195 g water, add 0.1 g non-ionic polyacrylamide and 100 g in alum solution Powdered Activated Carbon（170 mesh), stir 30 min with 200 r/min at 50 DEG C, add 45 g sodium silicate to stir 60 min, more quiet Put 3 h, obtain adhesive flocculant.
Adjusting wastewater pH with 10 % dilute sulfuric acids first is 2, is then initially charged the potassium ferrate of 80 mg/L, stirs 2min, quiet Put 20 min, then add 20 mg/L ferrous sulfate heptahydrates in batches and the hydrogen peroxide of 800 mg/L carries out oxidative degradation 1 h, plus Enter 10 % calcium oxide suspensions and adjust pH 7, be subsequently adding 26 g adhesive flocculants, stir 2 min, stand 20 min.CODCrGo Except rate is 94.6%, ammonia nitrogen removal frank is 82.5%.
Embodiment 3：
50 g Alumen are dissolved in 195 g water, add 0.1 g non-ionic polyacrylamide and 100 g in alum solution Powdered Activated Carbon（200 mesh), stir 30 min with 200 r/min at 50 DEG C, add 45 g sodium silicate to stir 60 min, more quiet Put 2 h, obtain adhesive flocculant.
Adjusting wastewater pH with 10 % dilute sulfuric acids first is 3, is then initially charged the potassium ferrate of 100 mg/L, stirs 2 min, Stand 20 min, the hydrogen peroxide in batches adding 800 mg/L carries out oxidative degradation 1 h, add 10 % calcium oxide suspensions to adjust pH 8, it is subsequently adding 19.5 g adhesive flocculants, stirs 2 min, stand 20 min.CODCrClearance is 93.4%, ammonia nitrogen removal frank For 81.7%.
Embodiment 4：
50 g Alumen are dissolved in 195 g water, add 0.1 g non-ionic polyacrylamide and 100 g in alum solution Powdered Activated Carbon（200 mesh), stir 30 min with 200 r/min at 50 DEG C, add 45 g sodium silicate to stir 60 min, more quiet Put 3 h, obtain adhesive flocculant.
Adjusting wastewater pH with 10 % dilute sulfuric acids first is 2, is then initially charged the potassium ferrate of 80 mg/L, stirs 2min, quiet Put 20 min, then add 20 mg/L ferrous sulfate heptahydrates in batches and the hydrogen peroxide of 800 mg/L carries out oxidative degradation 1 h, plus Enter 10 % calcium oxide suspensions and adjust pH 7, be subsequently adding 26 g adhesive flocculants, stir 2 min, stand 20 min.CODCrGo Except rate is 96.3%, ammonia nitrogen removal frank is 84.1%.

Claims (6)

1. a kind of method for agricultural chemicals waste water advanced treating is it is characterised in that carry out oxidation in advance initially with Fenton reagent Process, remove COD then in conjunction with adhesive flocculantCrAnd ammonia nitrogen.
2. as claimed in claim 1 a kind of method for agricultural chemicals waste water advanced treating it is characterised in that described Fenton examination Agent is made up of the mixture of potassium ferrate or potassium ferrate/ferrous sulfate hydrate and hydrogen peroxide.
3. as claimed in claim 1 or 2 a kind of method for agricultural chemicals waste water advanced treating it is characterised in that pressing 500mL waste water Amount, adjusting wastewater pH with 10% dilute sulfuric acid first is 2 ~ 3, is then initially charged the potassium ferrate of 100 ~ 125 mg/L, or potassium ferrate Mixture with green vitriol；Stirring 2min, stands 20 min, and the hydrogen peroxide in batches adding 800 ~ 1000mg/L is carried out Oxidative degradation 1h, adds alkali liquor to adjust pH7 ~ 8, is subsequently adding 19.5 ~ 26g adhesive flocculant, stir 2min, stand 20min.
4. as claimed in claim 1 a kind of method for agricultural chemicals waste water advanced treating it is characterised in that described adsorption-flocculation Agent is composited by flocculant and adsorbent, and wherein, described flocculant is Alumen, non-ionic polyacrylamide, sodium silicate Combine, adsorbent is Powdered Activated Carbon.
5. as claimed in claim 4 a kind of method for agricultural chemicals waste water advanced treating it is characterised in that described adsorption-flocculation The concrete preparation method of agent：50 g Alumen are dissolved in 195 g water, add 0.1 g nonionic polypropylene in alum solution Amide and 100 g Powdered Activated Carbons, the particle diameter of Powdered Activated Carbon be 170 mesh and more than, stirred with 200 r/min at 40 ~ 60 DEG C Mix 30 min, add 45 g sodium silicate to stir 60 min, then stand 2 ~ 3 h, obtain adhesive flocculant.
6. as claimed in claim 3 a kind of method for agricultural chemicals waste water advanced treating it is characterised in that described alkali liquor is 10 % calcium oxide suspension.
CN201610947043.XA 2016-10-26 2016-10-26 Method for advanced treatment of pesticide wastewater Expired - Fee Related CN106430714B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107892408A (en) * 2017-10-10 2018-04-10 华北理工大学 A kind of farmland agricultural chemicals waste water purification method
CN108314208A (en) * 2018-02-01 2018-07-24 太原理工大学 A method of utilizing Fe (VI)/Fenton systems oxidizing, flocculating coking wastewater China and Philippines and coal particle object
CN112939167A (en) * 2021-01-29 2021-06-11 安道麦安邦(江苏)有限公司 Composite coagulant for treating organic phosphorus in pesticide wastewater, preparation method and application

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102399032A (en) * 2010-09-07 2012-04-04 中国石油化工股份有限公司 Method for treating organic amine industrial waste water by Fenton-like oxidation-flocculation

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102399032A (en) * 2010-09-07 2012-04-04 中国石油化工股份有限公司 Method for treating organic amine industrial waste water by Fenton-like oxidation-flocculation

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107892408A (en) * 2017-10-10 2018-04-10 华北理工大学 A kind of farmland agricultural chemicals waste water purification method
CN108314208A (en) * 2018-02-01 2018-07-24 太原理工大学 A method of utilizing Fe (VI)/Fenton systems oxidizing, flocculating coking wastewater China and Philippines and coal particle object
CN108314208B (en) * 2018-02-01 2021-10-01 太原理工大学 Method for oxidizing and flocculating phenanthrene and coal particles in coking wastewater by using Fe (VI)/Fenton system
CN112939167A (en) * 2021-01-29 2021-06-11 安道麦安邦(江苏)有限公司 Composite coagulant for treating organic phosphorus in pesticide wastewater, preparation method and application

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