CN102040308B - Method for treating wastewater by combining catalytic oxidation with biological aerated filter - Google Patents

Method for treating wastewater by combining catalytic oxidation with biological aerated filter Download PDF

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Publication number
CN102040308B
CN102040308B CN2009101807731A CN200910180773A CN102040308B CN 102040308 B CN102040308 B CN 102040308B CN 2009101807731 A CN2009101807731 A CN 2009101807731A CN 200910180773 A CN200910180773 A CN 200910180773A CN 102040308 B CN102040308 B CN 102040308B
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waste water
described method
acid
oxidation
oxygenant
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CN102040308A (en
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高峰
桑军强
李本高
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Abstract

The invention relates to a method for treating wastewater by combining catalytic oxidation with a biological aerated filter, which sequentially comprises the following steps of: 1) adding all or part of the wastewater to be treated into a flocculating tank, performing flocculation sedimentation, and adding into an oxidation tank; 2) adding acid into the oxidation tank to regulate the pH value of the wastewater to be 0 to 6, adding an oxidant and a catalyst and performing catalytic oxidation reaction; and 3) adding the oxidized wastewater into a settling tank for settling, discharging supernatant, adding alkali to regulate the pH value to be 6 to 9, adding into the biological aerated filter for treating, and discharging; and making settled acidic sediments flow back to a dissolving tank, adding the acid to regulate the pH value until the sediments are completely dissolved, adding solution into the flocculating tank and performing flocculation sedimentation reaction on the solution and all or part of the wastewater to be treated. Compared with the prior art, the method reduces the consumption of the acid and the alkali and treatment cost.

Description

A kind of catalyzed oxidation associating BAF is handled the method for waste water
Technical field
The present invention relates to a kind of method of wastewater treatment.
Background technology
Along with China's industriallization and process of urbanization, a large amount of industry and domestic pollutant are discharged in the environment, bring more and more serious pollution to water body.The water quality that worsens not only causes numerous regional water quality property lacks of water, increases the cost that entire society obtains water resources, and even more serious is to go back the health of entail dangers to people, thereby need handle the waste water that contains pollutent, makes it can qualified discharge.Along with the continuous development of water technology, most waste water can both obtain handling, but for a long time, the processing of the organic waste water of biodegradability difference is the difficult point in the water technology always in the environment, also is the important difficult problem of puzzlement countries in the world environment circle.
Such waste water is because biodegradability is poor; Be difficult to directly adopt biochemical method to handle; Basically there is not effect through the processing of ordinary methods such as common filtration and flocculation; And charcoal absorption even depth treatment technology cost is too high, and membrane separation technique is because also there is certain difficulty in practical problemss such as investment costliness and film pollution on using.
The research of the biodegradability of catalyzed oxidation technical finesse in recent years difference organic waste water has obtained significant progress.The mechanism of catalyzed oxidation is to combine with oxygenant with catalyzer, in reaction, produces active extremely strong radical (like OH); Through the adduction between radical and the organic cpds, replacement, transfer transport, scission of link etc., make the macromole hardly degraded organic substance oxidative degradation in the water body become to be easy to biodegradable small-molecule substance, even directly be degraded into CO again 2And H 2O is near permineralization.Because it is simple to operate that the catalyzed oxidation technology has, react characteristics such as quick, become the focus that people study.But directly adopt catalyzed oxidation technical finesse waste water cost higher, and adopt the biodegradability of the method raising waste water of catalyzed oxidation, can effectively reduce the processing cost of waste water at method processing waste water, thereby obtain extensive studies through biochemistry.For example:
A.CN1724420A proposes a kind of method of chemical oxidizing-biological biological filtering tank associating water treatment, and this method adopts Fenton reagent-biological aerated filter process to handle chemical plant secondary biochemical water outlet, and the COD of processed waste water can reduce to 30mg/L.
B.CN16366893A proposes a kind of using up and helps Fenton's reaction, flocculation and microbiological deterioration coupling to handle the method for waste water, and its COD clearance can reach 98.9%.
But aforesaid method remains in problems such as the acid and alkali consumption amount are big, and industrial applications is restricted.
Summary of the invention
The objective of the invention is to propose the method that a kind of catalyzed oxidation associating BAF is handled waste water, with the processing cost of further reduction waste water.
The method of the processing waste water among the present invention is on the basis of conventional catalyst method for oxidation, adds alkali after the employing and precipitates the consumption that the mode that refluxes reduces soda acid, improves the treatment effect of catalyzed oxidation.
The method of processing waste water provided by the invention may further comprise the steps in order:
4) make pending waste water all or part of, get into oxidation pond through after flocculation basin carries out flocculation sediment;
5) in oxidation pond, add acid, the pH value 0～8 of regulating waste water adds oxygenant and catalyzer and carries out catalytic oxidation;
6) waste water after the oxidation gets into the settling bowl sedimentation, adds alkali after supernatant is discharged and regulates pH value 5～9, gets into BAF processing back and discharges; The acidic precipitation that settles down is back to and adds acid in the dissolving tank and be adjusted to all dissolvings of deposition, and solution gets into flocculation basin and all or part of pending waste water carries out flocculation precipitation reaction.
The oxygenant that adopts among the present invention can be a kind of in ydrogen peroxide 50, ozone, hypochlorite, perchlorate, the persulphate, preferred ydrogen peroxide 50.
Catalyzer among the present invention can be to go back the ortho states transition metal ion; Can be selected among Fe2+, Mn2+, Ni2+, Co2+, Cd2+, Cu2+, Ag+, Cr3+ and the Zn2+ one or more; Preferred Fe2+; Can derive from ferrous sulfate, iron protochloride, the Iron nitrate one or more, preferably sulfuric acid is ferrous.
The acid that the present invention adds can be a kind of in sulfuric acid, hydrochloric acid, the nitric acid, preferably sulfuric acid.
The alkali that adds among the present invention can be a kind of in sodium hydroxide, Pottasium Hydroxide, sodium hydrogencarbonate, the yellow soda ash, preferred sodium hydroxide.
According to the water quality situation of waste water, in flocculation basin, can also add coagulant aids to strengthen flocculating effect in the present invention, the coagulant aids that is adopted can be one or more in Poly aluminum Chloride (PAC), bodied ferric sulfate, the SEPIGEL 305.
The ratio of the mass concentration of the COD in the oxygenant among the present invention and the waste water be 5: 1～1: 100 preferred 2: 1～1: 20.The mol ratio of oxygenant and catalyzer is 10: 1～1: 3, preferred 5: 1～1: 2.
The pH value of waste water can be 0～8 in the oxidation pond, preferred 2～6.Settling bowl supernatant pH value 6～9, preferred 6-8.The pH value can be less than 2 in the dissolving tank, preferred 0.1～1.
The residence time of waste water in oxidation pond can be 10-120 minute; Preferred 30-60 minute, the residence time in settling tank can be 5～500 minutes, preferred 10～300 minutes; The residence time in BAF can be 0.5～20 hour, preferred 1～10 hour.
Compared with prior art, the present invention has following advantage:
1, reduces the acid and alkali consumption amount, reduced processing cost.
2, before catalytic oxidation, carry out flocculation sediment in advance and handle, improved the treatment effect of waste water.
3, the minimizing of acid and alkali consumption amount can also reduce the salts contg in the waste water, is beneficial to the processing of follow-up reusing sewage.
4, adopt the processing mode of catalyzed oxidation associating BAF, both made the waste water of difficult for biological degradation obtain handling, reduced the cost of independent employing catalyzed oxidation art breading again.
Description of drawings
Fig. 1 is the schematic flow sheet of catalyzed oxidation associating BAF treatment process of the present invention.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed explanation, but the scope that the present invention requires to protect is not limited to the scope that embodiment representes.
Embodiment 1
Handle not standard discharge waste water of certain refinery, adopt H 2O 2Be oxygenant, Fe 2SO 4Be catalyzer, used soda acid is dense H 2SO 4And NaOH.Operational condition is: H 2O 2With the ratio of the mass concentration of organism (COD) in the waste water be 1: 3, H 2O 2/ Fe 2+Mol ratio be 1: 2, oxidation pond pH is 3, settling bowl supernatant pH is 7; The pH of dissolving tank is 0.3, and waste water is 1 hour in the flocculation basin residence time, and the oxidation pond residence time is 60 minutes; The settling bowl residence time is 2 hours, and the residence time of BAF is 4 hours.Result is seen table 1.After can finding out that from the data of table 1 waste water passes through catalytic oxidation treatment, COD and oil-contg significantly reduce, and biodegradability significantly improves, and COD and the oil-contg through the BAF processed waste water further reduces again, satisfies the water quality requirement of qualified discharge.
Table 1 processing refinery is standard discharge waste water not
Project COD/mg/L Oil-contg/mg/L B/C
Former water 130 12 0.04
The catalyzed oxidation water outlet 80 2 0.31
The BAF water outlet 58 0.5
Embodiment 2
H is adopted in the pre-treatment of feed water by reverse osmosis in certain refinery's reusing sewage process 2O 2Be oxygenant, Fe 2SO 4Be catalyzer, used soda acid is dense H 2SO 4And NaOH.Operational condition is confirmed as: H 2O 2With the ratio of the mass concentration of organism (COD) in the waste water be 1: 2, H 2O 2/ Fe 2+Mol ratio is 1: 1, and oxidation pond pH is 5, and settling bowl supernatant pH is 6.5; The pH of dissolving tank is 0.5, and waste water is 1 hour in the flocculation basin residence time, 40 minutes oxidation pond residence time; The settling bowl residence time is 1.5 hours, and the residence time of BAF is 3 hours.After can finding out that from the data of table 1 waste water passes through catalytic oxidation treatment, COD significantly reduces, and biodegradability significantly improves, and the COD through the BAF processed waste water further reduces again, satisfies the into water quality requirement of reverse-osmosis treated.
The pre-treatment of table 2 feed water by reverse osmosis
Project COD/mg/L B/C
Former water 75 0.02
The catalyzed oxidation water outlet 45 0.33
The BAF water outlet 30
Embodiment 3
Handle not standard discharge waste water of certain chemical plant, the employing Youxiaolin is an oxygenant, Fe 2SO 4Be catalyzer, used soda acid is dense H 2SO 4And NaOH.Operational condition is: the ratio of the mass concentration of the organism in Youxiaolin and the waste water (COD) is 1: 3, Youxiaolin/Fe 2+Mol ratio be 1: 1.5, oxidation pond pH is 4, settling bowl supernatant pH is 7.5; The pH of dissolving tank is 0.3, and waste water is 1 hour in the flocculation basin residence time, and the oxidation pond residence time is 60 minutes; The settling bowl residence time is 2 hours, and the residence time of BAF is 4 hours.Result is seen table 3.After can finding out that from the data of table 3 waste water passes through catalytic oxidation treatment, COD and oil-contg significantly reduce, and biodegradability significantly improves, and COD and the oil-contg through the BAF processed waste water further reduces again, satisfies the water quality requirement of qualified discharge.
Table 3 processing chemical plant is standard discharge waste water not
Project COD/mg/L Oil-contg/mg/L B/C
Former water 120 11 0.03
The catalyzed oxidation water outlet 78 2 0.31
The BAF water outlet 57 0.6

Claims (13)

1. a catalyzed oxidation is united the method that BAF is handled waste water, may further comprise the steps in order:
1) makes pending waste water all or part of, get into oxidation pond through after flocculation basin carries out flocculation sediment;
2) in oxidation pond, add acid, the pH value 2～6 of regulating waste water adds oxygenant and catalyzer and carries out catalytic oxidation, and said catalyzer is Fe 2+
3) waste water after the oxidation gets into the settling bowl sedimentation, adds alkali after supernatant is discharged and regulates pH value 6～9, gets into BAF processing back and discharges; The acidic precipitation that settles down is back in the dissolving tank, adds acid and is adjusted to all dissolvings of deposition, and solution gets into flocculation basin and all or part of pending waste water carries out flocculation precipitation reaction.
2. according to the described method of claim 1, it is characterized in that said oxygenant is selected from a kind of in ydrogen peroxide 50, ozone, hypochlorite, perchlorate, the persulphate.
3. according to the described method of claim 1, it is characterized in that said catalyst Fe 2+Derive from ferrous sulfate, iron protochloride, the Iron nitrate one or more.
4. according to the described method of claim 1, it is characterized in that the acid that is added is sulfuric acid, hydrochloric acid or nitric acid.
5. according to the described method of claim 1, it is characterized in that the alkali that is added is sodium hydroxide, Pottasium Hydroxide, sodium hydrogencarbonate or yellow soda ash.
6. according to the described method of claim 1, it is characterized in that in flocculation basin, also add coagulant aids, the coagulant aids that is adopted is one or more in Poly aluminum Chloride (PAC), bodied ferric sulfate, the SEPIGEL 305.
7. according to the described method of claim 1, it is characterized in that the ratio of the mass concentration of the COD in oxygenant and the waste water is 5: 1～1: 100.
8. according to the described method of claim 1, it is characterized in that the ratio of the mass concentration of the COD in oxygenant and the waste water is 2: 1～1: 20.
9. according to the described method of claim 1, it is characterized in that the mol ratio of oxygenant and catalyzer is 10: 1～1: 3.
10. according to the described method of claim 1, it is characterized in that the mol ratio of oxygenant and catalyzer is 5: 1～1: 2.
11., it is characterized in that the pH value of regulating the settling bowl supernatant is 6～8 according to the described method of claim 1.
12., it is characterized in that the pH value is less than 2 in the adjusting dissolving tank according to the described method of claim 1.
13., it is characterized in that the residence time of waste water in oxidation pond is 10-120 minute according to the described method of claim 1, the residence time in settling tank is 5～500 minutes, the residence time in BAF is 0.5～20 hour.
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CN103214044B (en) * 2012-01-18 2014-08-20 中国石油化工股份有限公司 Method for improving biodegradability of waste water produced by caprolactam ammoximation
CN102642995B (en) * 2012-05-07 2014-01-01 重庆大学 Method and system for physicochemical biological combined treatment of drilling wastewater of oil and gas field
CN105271614B (en) * 2015-10-28 2017-12-29 中国海洋大学 A kind of method of Fenton reagent and potassium hydrogen persulfate and microbial association processing bilge-water
CN105417676B (en) * 2016-01-14 2019-03-29 英泰格润环保科技（天津）有限公司 A kind of water body remediation composition and water remediation method
CN106045207A (en) * 2016-07-12 2016-10-26 台州学院 Deep treating method for pharmaceutical wastewater
CN112209561A (en) * 2019-07-12 2021-01-12 新疆天业（集团）有限公司 Wastewater softening treatment device and method
CN110615572A (en) * 2019-09-29 2019-12-27 田雨春 Organic wastewater treatment method
CN111333258B (en) * 2020-03-08 2022-10-04 湖北水清会环保科技有限公司 Method for treating DMF (dimethyl formamide) wastewater by combining catalytic decomposition with biotechnology
CN115477409B (en) * 2021-05-31 2024-02-13 中国石油化工股份有限公司 HPPO wastewater treatment method

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