CN113461222B - Industrial wastewater enhanced oxidation treatment method - Google Patents
Industrial wastewater enhanced oxidation treatment method Download PDFInfo
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- CN113461222B CN113461222B CN202110885836.4A CN202110885836A CN113461222B CN 113461222 B CN113461222 B CN 113461222B CN 202110885836 A CN202110885836 A CN 202110885836A CN 113461222 B CN113461222 B CN 113461222B
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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
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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
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5281—Installations for water purification using chemical agents
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F1/722—Oxidation by peroxides
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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Abstract
An enhanced oxidation treatment method for industrial wastewater comprises the following specific treatment steps: adding a complexing agent into the wastewater, and then adding sulfuric acid; adding ferrous sulfate into the obtained wastewater; adding hydrogen peroxide to the wastewater; after the hydrogen peroxide is decomposed, the wastewater is sent into a complexing agent stripping pool for air stripping; and (4) allowing the blown-out gas to enter an absorption tower, absorbing the treated tail water, and conveying the complexing agent absorbed by the tail water into a Fenton oxidation pond for recycling. The method for treating the wastewater has simple working procedures, separates the complexing agent from the water through air stripping, and continuously recycles the complexing agent after absorption, thereby reducing the dosage of the complexing agent and lowering the treatment cost.
Description
Technical Field
The invention relates to the technical field of industrial wastewater treatment, in particular to an industrial wastewater enhanced oxidation treatment method.
Background
For some industrial organic wastewater which is difficult to be degraded biologically, oxidation process represented by hydroxyl radical, such as Fenton, catalytic ozone, UV/H 2 O 2 The oxidation process becomes the first choice process of the sewage advanced treatment at present, wherein the Fenton process is increasingly emphasized due to low investment and simple operation.
The conventional Fenton process is to add a certain amount of hydrogen peroxide solution and ferrous salt solution into wastewater under a weak acid environment, generate oxidizing species represented by hydroxyl radicals, peroxy anion radicals and the like while catalyzing the decomposition of hydrogen peroxide by ferrous ions to complete the oxidation of organic matters and the reduction of ferric iron, adjust the pH value of the solution to be neutral by adding alkali liquor after the hydrogen peroxide is completely decomposed, and simultaneously add a certain amount of flocculating agent to separate iron sludge from water so as to complete the oxidation reaction process. However, in the actual production, the conventional fenton process has the problems of large ferrous salt addition amount, large sludge generation amount, acid addition amount and alkali addition amount in pH adjustment. In order to solve the above problems, two new processes of complex fenton to reduce pH adjustment and co-catalytic fenton to reduce the amount of added iron salt are more and more regarded. The complex Fenton is that under the condition of pH near-neutral environment, ferrous iron and hydrogen peroxide are added into the waste water, and at the same time, a certain concentration of iron ion complexing agent is added, and the complexing agent can be used under the condition of higher pHWith Fe 2+ /Fe 3+ Forming a complex, making it soluble, thereby passing Fe 2+ /Fe 3+ The reaction with hydrogen peroxide promotes activity. The complex Fenton reaction reduces the dosage of the iron source and the hydrogen peroxide, and achieves more effective and economic treatment effect.
Therefore, the complex fenton method in which the complexing agent is introduced into the conventional fenton becomes a hot spot of the research of the fenton reaction in recent years. However, in the practical application process of the current complex fenton method, because iron ions exist in a stable complex state, the complexing agent and iron salt are difficult to separate from water, so after the hydrogen peroxide is decomposed, the iron ions and the complexing agent are flocculated and precipitated together and then are discharged to subsequent biological treatment or other treatment processes, the loss of the complexing agent is caused, and unnecessary economic loss is brought.
Disclosure of Invention
In order to solve the technical problem in the application process of complexing Fenton in the background technology, the invention provides a method for strengthening and oxidizing industrial wastewater by recycling a complexing agent.
In order to realize the purpose, the invention adopts the following technical scheme:
an enhanced oxidation treatment method for industrial wastewater comprises the following specific treatment steps:
s1, feeding the wastewater into a Fenton oxidation pond, adding a complexing agent into the wastewater under the stirring condition, uniformly mixing, and then adding sulfuric acid until the alkalinity of the wastewater is controlled at 100-200mg/L (calculated by calcium carbonate);
s2, adding ferrous sulfate into the wastewater obtained in the step S1, and reacting for 3-5 min;
s3, adding hydrogen peroxide into the wastewater of S2, and reacting for 4-8 hours;
s4, after the hydrogen peroxide is decomposed, sending the wastewater of the step S3 into a complexing agent stripping pool, and carrying out air stripping at a certain air-water ratio for 15-60 min;
and S5, introducing the gas blown off into an absorption tower, absorbing by using the treated tail water, and sending the complexing agent absorbed by the tail water into the Fenton oxidation pond in the step S1 for recycling.
In step S1, the complexing agent is one of EDTA (ethylene diamine tetraacetic acid), EDDS (ethylenediamine disuccinic acid), citric acid, tartaric acid (2, 3-dihydroxybutanedioic acid), (cis, trans) butenedioic acid, and hexenoic acid.
The molar ratio of the complexing agent added in the step S2 to the ferrous iron ions in the ferrous sulfate is 1: 1-15.
In the stripping process in the step S4, the gas-water ratio is 1500-3000: 1 (m) 3 /m 3 ) The empty tower flow rate is 1.0-3.0 m/s.
In step S5, the liquid-gas ratio of the absorption tower is 0.5-1.0L/m 3 (ii) a The spraying density is 5-10m 3 /m 2 H; the air speed of the empty tower is 0.5-2.0 m/s.
And in the step S5, the wastewater after the air stripping enters a neutralization tank, a flocculation tank and a sedimentation tank in sequence for treatment.
Compared with the prior art, the method for treating the wastewater disclosed by the invention has the advantages that the process is simple, the complexing agent is separated from the water through the air stripping effect and is continuously recycled after being absorbed, the adding amount of the complexing agent is reduced, and the treatment cost is reduced.
Drawings
FIG. 1 is a block diagram of the process flow of the present invention.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
The method for the enhanced oxidation treatment of the industrial wastewater disclosed by the invention separates the complexing agent from water through air stripping, and the complexing agent is continuously recycled after being absorbed, and the specific treatment steps are as follows with reference to the attached figure 1.
S1, feeding the wastewater into a Fenton oxidation pond, adding a complexing agent into the wastewater under the stirring condition, uniformly mixing, then adding sulfuric acid, and controlling the alkalinity of the wastewater to be 100-200mg/L (calculated by calcium carbonate); the complexing agent comprises (cis, trans) butenedioic acid and hexenoic acid besides conventional EDTA (ethylene diamine tetraacetic acid), EDDS (ethylenediamine disuccinic acid), citric acid and tartaric acid (2, 3-dihydroxysuccinic acid).
S2, adding ferrous sulfate into the wastewater obtained in the step S1, and reacting for 3-5 min; the mol ratio of the complexing agent to the ferrous ions is 1: 1-15. As a preferable technical scheme, the mol ratio of the complexing agent to the ferrous ions is 1: 5-10.
S3, adding hydrogen peroxide into the wastewater of S2, and reacting for 4-8 hours; the adding amount of the hydrogen peroxide is 1-5 times (by mass) of the COD of the inlet water, and the molar ratio of the hydrogen peroxide to the ferrous ions is 1-8: 1.
S4, after the hydrogen peroxide is decomposed, sending the wastewater of the step S3 into a complexing agent stripping pool, and carrying out air stripping at a certain air-water ratio for 15-60 min; in the stripping process, the gas-water ratio is 1500-3000: 1 (m) 3 /m 3 ) The empty tower flow rate is 1.0-3.0 m/s.
And S5, introducing the blown-off gas into an absorption tower, and recovering a complexing agent in the gas by using the treated tail water as an absorption liquid. The absorption liquid containing the complexing agent is sent to the fenton oxidation pond in step S1, so as to achieve the purpose of recycling the complexing agent. The liquid-gas ratio of the absorption tower is 0.5-1.0L/m 3 (ii) a The spraying density is 5-10m 3 /m 2 H; the air speed of the empty tower is 0.5-2.0m/s, and the recovery rate of the complexing agent can reach more than 85%.
And in the step S5, the wastewater after being blown off sequentially enters a neutralization tank, a flocculation tank and a sedimentation tank for treatment. Adding alkali liquor into the neutralization tank to adjust the pH value of the wastewater to be neutral; a certain amount of polyacrylamide is added into the flocculation tank to improve the solid-liquid separation efficiency.
In the reaction process, the method for determining the dosage of the medicament comprises the following steps: the adding concentration of the hydrogen peroxide is 1-3 times of the CODcr value of the wastewater, and the adding concentration of the ferrous sulfate is 1/3-1/5 of the adding concentration of the hydrogen peroxide.
Example 1:
taking 5L of wastewater with the CODcr value of 100mg/L, adding citric acid serving as a complexing agent into the wastewater under the stirring condition, wherein the adding amount of the citric acid is 0.2 mmol;
after uniform mixing, adding sulfuric acid into the wastewater until the alkalinity of the wastewater is 100mg/L (using calcium carbonate agent); then adding ferrous sulfate into the wastewater, wherein the adding amount is 1 mmol;
uniformly mixing, adding 5mmol of hydrogen peroxide, and reacting for 4 hours under stirring to completely decompose the hydrogen peroxide;
sending the wastewater into a stripping tank, stripping by using a gas-water ratio of 1500:1, wherein the stripping time is 1h, treated tail water used for the stripped gas is used as an absorption liquid recovery complexing agent, the consumption of the absorption liquid is 4L, the total amount of citric acid in the absorption liquid is measured to be 0.169mmol, and the calculated recovery rate of the citric acid is 84.5%;
and adding a sodium hydroxide solution into the blow-off wastewater to adjust the pH value to be neutral, adding polyacrylamide to react for 15min, settling for 1h, collecting supernatant, and recycling part of the supernatant as absorption liquid.
Example 2:
taking 15L of wastewater with CODcr value of 150mg/L, and adding EDTA (ethylene diamine tetraacetic acid) as a complexing agent into the wastewater under the stirring condition, wherein the addition amount of the EDTA is 0.5 mmol;
after uniform mixing, adding sulfuric acid into the wastewater until the alkalinity of the wastewater is 150mg/L (using calcium carbonate agent); then adding ferrous sulfate into the wastewater, wherein the adding amount is 2 mmol;
uniformly mixing, adding 7mmol of hydrogen peroxide, and reacting for 8 hours under stirring to completely decompose the hydrogen peroxide;
sending the wastewater into a stripping tank, stripping by using a gas-water ratio of 3000:1, wherein the stripping time is 45min, treated tail water used for the stripped gas is used as an absorption liquid recovery complexing agent, the consumption of the absorption liquid is 15L, the total amount of EDTA in the absorption liquid is measured to be 0.43mmol, and the calculated recovery rate of EDTA is 86%;
and adding a sodium hydroxide solution into the blow-off wastewater to adjust the pH value to be neutral, adding polyacrylamide to react for 25min, settling for 2h, collecting supernatant, and recycling part of the supernatant as absorption liquid.
Example 3:
taking 20L of wastewater with CODcr value of 175mg/L, adding tartaric acid as a complexing agent into the wastewater under the condition of stirring, wherein the adding amount of the tartaric acid is 1 mmol;
after uniform mixing, adding sulfuric acid into the wastewater until the alkalinity of the wastewater is 150mg/L (using calcium carbonate agent); then adding ferrous sulfate into the wastewater, wherein the adding amount is 4 mmol;
uniformly mixing, adding 10 mmol of hydrogen peroxide, and reacting for 8 hours under stirring to completely decompose the hydrogen peroxide;
sending the wastewater into a stripping tank, stripping by air-water ratio of 3000:1, wherein the stripping time is 45min, the tail water after treatment of the stripped gas is used as an absorption liquid recovery complexing agent, the consumption of the absorption liquid is 15L, the total amount of EDTA in the absorption liquid is measured to be 3.43mmol, and the calculated recovery rate of EDTA is 85.75%;
and adding a sodium hydroxide solution into the blow-off wastewater to adjust the pH value to be neutral, adding polyacrylamide to react for 25min, settling for 2h, collecting supernatant, and recycling part of the supernatant as absorption liquid.
Claims (2)
1. The method for treating industrial wastewater by intensified oxidation is characterized by comprising the following specific treatment steps:
s1, feeding the wastewater into a Fenton oxidation pond, adding a complexing agent into the wastewater under the stirring condition, uniformly mixing, and then adding sulfuric acid until the alkalinity of the wastewater is controlled at 100-200mg/L (calculated by calcium carbonate); in the step S1, the complexing agent is one of ethylenediamine tetraacetic acid, ethylenediamine disuccinic acid, citric acid, tartaric acid, maleic acid, fumaric acid and caproleic acid;
s2, adding ferrous sulfate into the wastewater obtained in the step S1, and reacting for 3-5 min; the molar ratio of the added complexing agent to ferrous ions in the ferrous sulfate is 1: 1-15;
s3, adding hydrogen peroxide into the wastewater of S2, and reacting for 4-8 hours;
s4, after the hydrogen peroxide is decomposed, sending the wastewater of the step S3 into a complexing agent stripping pool, and carrying out air stripping under a certain air-water ratio of 1500-3000: 1 (m) 3 /m 3 ) The empty tower flow rate is 1.0-3.0 m/s; the air stripping time is 15-60 min;
s5, feeding the gas blown off into an absorption tower, absorbing by using the treated tail water, and feeding the complexing agent absorbed by the tail water into the Fenton oxidation tank in the step S1 for recycling; in step S5, the liquid-gas ratio of the absorption tower is 0.5-1.0L/m 3 (ii) a The spraying density is 5-10m 3 /m 2 H; air velocity of air columnIs 0.5-2.0 m/s.
2. The method for enhanced oxidation treatment of industrial wastewater according to claim 1, wherein the wastewater after the air stripping in step S5 sequentially enters a neutralization tank, a flocculation tank and a sedimentation tank for treatment.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102190575A (en) * | 2010-03-15 | 2011-09-21 | 中国石油化学工业开发股份有限公司 | Method for recovering binary acid from waste alkali liquor in cyclohexane oxidation |
| US20140014586A1 (en) * | 2012-04-19 | 2014-01-16 | Soane Energy, Llc | Treatment of wastewater |
| CN109987750A (en) * | 2019-04-28 | 2019-07-09 | 南京大学 | A method of the promotion Fenton oxidation mediated by calcium and organic acid complex compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102190575A (en) * | 2010-03-15 | 2011-09-21 | 中国石油化学工业开发股份有限公司 | Method for recovering binary acid from waste alkali liquor in cyclohexane oxidation |
| US20140014586A1 (en) * | 2012-04-19 | 2014-01-16 | Soane Energy, Llc | Treatment of wastewater |
| CN109987750A (en) * | 2019-04-28 | 2019-07-09 | 南京大学 | A method of the promotion Fenton oxidation mediated by calcium and organic acid complex compound |
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