CN103212390B - In-situ regeneration method of trichloromethane-adsorbed saturating activated carbon - Google Patents
In-situ regeneration method of trichloromethane-adsorbed saturating activated carbon Download PDFInfo
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- CN103212390B CN103212390B CN201310126689.8A CN201310126689A CN103212390B CN 103212390 B CN103212390 B CN 103212390B CN 201310126689 A CN201310126689 A CN 201310126689A CN 103212390 B CN103212390 B CN 103212390B
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Abstract
The invention belongs to the technical field of environmental protection, and particularly provides an in-situ regeneration method of trichloromethane-adsorbed saturating activated carbon. The method comprises the following steps of: synthesizing iron nanoparticle agents in an artificial way; reacting with hydrogen peroxide to obtain a high-level oxyradical and a high-level hydroxyl radical; and then quickly decomposing trichloromethane which is adsorbed to reach saturation by the activated carbon. The in-situ regeneration method is applicable to the regeneration of the activated carbon in a drinking water plant or an industrial enterprise requiring the activated carbon to treat trichloromethane. Compared with the conventional regeneration method, the in-situ regeneration method provided by the invention is low in cost, less in pollution, simple in technology, and wide in economic benefit and application prospect.
Description
Technical field
The invention belongs to environmental technology field, be specifically related to the method for iron nano-particle catalysis hydrogen peroxide regeneration chloroform absorption saturated activity charcoal.
Background technology
Under the outer water pollution of Now Domestic continues the background of aggravating, active carbon, as a kind of efficient adsorption material, has been widely used in drinking water advanced treatment technical process.Active carbon can remove multiple different organic pollution effectively from water body, but constantly reach Adsorption of Organic saturation state through the active carbon of Long-Time Service, need to change in time or regenerate to ensure that water treatment efficiency regeneration method of active carbon has conducted a research and applied both at home and abroad, be mainly divided three classes: bioanalysis, heating and chemical method.The bio-regeneration of active carbon, at present also lessly see there is successful report, its major defect is that bioanalysis is only applicable to biodegradable polluter, for easily biological-degradable and toxic organics then can not be suitable for, and residual end product is adsorbed on activated carbon surface, regeneration not exclusively; High-temperature heating method of reproduction is huge to active carbon loss, and permissive waste is higher than 10%, and freight is high.Adopt the method to carry out in-situ regeneration chloroform and adsorb saturated active carbon, do not need transfer activity charcoal to special container, active carbon after regeneration is reused, cost is little, pollution-free, activated carbon adsorptive capacity loss is very little, and therefore this research extremely meets the requirement of China's high efficiency, low cost, resource in environmental pollution improvement.
In drinking water treatment technique, active carbon is easy to saturated to chloroform absorption in water.In drinking water treatment, extensive use chlorine carries out pre-oxidation, and due to the existence of organic pollution, oxychloration process inevitably can produce chlorinated secondary product, and chloroform is the material that in various chlorinated secondary product, concentration is the highest.In China's regulation drinking water, Determination of Trichloro Methane must not more than 80 μ g/L, and Environmental Protection Agency (USEPA) regulation chloroform maximum permissible value is 80 μ g/L, and is tending towards stricter.Verified, active carbon has good Adsorption effect most to chloroform, and in nearly all chlorinated secondary product, chloroform is the most easily tightly held by activated carbon saturated, once charcoal absorption is saturated, its result can cause output water chloroform concentration over-standard.Therefore, keep the lasting characterization of adsorption of active carbon to chloroform to be very important, in-situ regeneration chloroform adsorbs saturated activated carbon process affects water factory's normal water supply hardly, is extremely important.
Summary of the invention
The object of the present invention is to provide a kind of efficient, the method that economic, free of contamination in-situ regeneration chloroform adsorbs saturated active carbon.
The present invention synthesizes iron nano-particle reagent by artificial means, advanced oxidation hydroxyl free radical is produced by reacting with hydrogen peroxide, the chloroform that fast decoupled charcoal absorption is saturated, the present invention can be applicable to drinking water plant or needs to carry out regenerating active carbon with the industrial enterprise of charcoal treatment chloroform.
In-situ regeneration chloroform provided by the invention adsorbs the method for saturated active carbon, and concrete steps are:
The first step: prepare iron nano-particle reagent, adopts nanopure water to dissolve six water and iron chloride (FeCl
36H
2o), mix more than 4 days, preparation high concentration iron nano-particle reagent is as stoste, and stoste can be diluted with nanopure water as required, and iron nano-particle diameter need at 40-50nm;
Second step: adsorb saturated activated carbon sample with the iron nano-particle reagent dynamic upward flow drip washing chloroform through being diluted to certain concentration, collects leacheate, repeats drip washing 4-5 time;
3rd step: the 70% hydrogen peroxide upward flow mode that adds in proportion contacts with saturated activity charcoal and regenerates, controlling reactor pH with hydrochloric acid is 2.4-2.7, repeats drip washing 4-5 time;
4th step: stop drip washing, leaves standstill 30--40 minute; Discharge regeneration leacheate, rinse the rear active carbon 2-3 time of regeneration with clear water, regeneration completes.
The present invention is based on the general principle of hydroxyl free radical advanced oxidation:
1. the iron nano-particle reagent of artificial preparation has special diameter scope, can be saturated active carbon and directly be adsorbed to activated carbon capillary inside;
2. the iron nano-particle and the hydrogen peroxide that enter micropore inside react, and generate hydroxyl free radical, from the inner chloroform dividing desorption saturated to external oxidation of active carbon, reach regenerating active carbon object.
Feature of the present invention is: take ferric chloride hexahydrate as iron nano-particle reagent raw material, and through manually preparing iron nano-particle reagent as catalysts, this reagent, owing to having specific diameter range, is easy to be adsorbed saturated charcoal absorption by chloroform; After active carbon fully adsorbs iron nano-particle, reagent reacts in the hydrogen peroxide of follow-up interpolation again, generates hydroxyl free radical material, this material has strong oxidizing property, effectively can decompose the saturated chloroform of absorption activated carbon, regeneration afterproduct is nontoxic, and removes easily through water cleaning.The method adsorbs saturated regenerating active carbon successful to chloroform; compared with existing thermolysis process; cost is little, pollute less, technique is simple; do not need transfer activity charcoal to specific regeneration factory and regenerating unit; in-situ regeneration can be realized; be applicable to the daily regenerating active carbon of drinking water plant to use, meet the requirement of China's high efficiency, low cost, resource in environmental pollution improvement.
The invention has the beneficial effects as follows:
The present invention with the iron nano-particle reagent manually prepared for catalyst, hydroxyl free radical is produced with hydrogen peroxide generation chemical reaction, hydroxyl free radical has the usefulness of fast decoupled chloroform, can be applicable to drinking water plant regenerating active carbon dispose, compared with conventional regeneration mode, cost is little, pollute less, technique is simple, has economic benefit and application prospect widely.
Detailed description of the invention
The invention is further illustrated by the following examples.
Embodiment 1
Certain drinking water plant adopts coal mass active carbon as chloroform adsorption treatment process, ran through 2 years, the removal effect of active carbon to chloroform obviously reduces, when using from the initial stage, the chloroform clearance of 95% is reduced to the chloroform clearance of about 10%, thinks that this active carbon is saturated close to chloroform absorption.The content of organics characterization parameter COD mean value of the former water of activated carbon process run duration is 5.4mg/L, the highest 6.9mg/L, minimum 4.5mg/L, seasonal variations is not obvious, water factory adopts prechlorination mode to carry out pre-oxidation, and the Determination of Trichloro Methane of generation is 100-200 μ g/L.Former water belongs to middle severe organic polluted-water.
Get appropriate absorption saturated activity charcoal to take out, put into preprepared regeneration reactor, reactor diameter is 30cm, the right circular cylinder of height 60m, water inlet and delivery port are set, adopt the regeneration of upward flow, after step regeneration, get activated carbon sample analysis, leading indicator chloroform adsorption efficiency.
Can draw to draw a conclusion by experimental study: after regeneration active carbon to the removal efficiency of chloroform from close to saturation state 10%, return to about 70%, after regeneration after activated carbon filtration, Determination of Trichloro Methane is reduced to 30-60 μ g/L from the 100-200 μ g/L of water inlet.After follow-up sterilization, output water Determination of Trichloro Methane is lower than the drinking water output water standard of national regulation.
Embodiment 2
Certain enterprise manufactures barreled pure water, and adopt oxychloride technique binding activities charcoal to filter, ran through 5 years, Activated Carbon for Adsorption of Organic efficiency obviously reduces, and about 90% is reduced to 35% to the clearance of chloroform from original state.This enterprise take running water as water source, running water is after chlorination again, Determination of Trichloro Methane is 100 μ about g/L, through after charcoal absorption, still can meet the national standard requirement of 80 μ g/L, if but the lower general who has surrendered of charcoal absorption efficiency continuation causes output water defective, therefore carries out regenerating active carbon test.
Reclaim equiment is accessed active carbon filter tank by regenerative process, and bottom intakes, the upward flow mode of top water outlet, and constantly take out activated carbon sample in process of the test and analyze, leading indicator comprises for chloroform removal efficiency.Can draw to draw a conclusion by experimental study: saturated activity charcoal was through the regeneration of 3 hours, chloroform adsorption efficiency returns to about 70% from 35%, according to China " water quality standard for drinking water ", the charcoal treatment water Determination of Trichloro Methane after regeneration is far below national standard.
Reference examples
Certain laboratory adopts carries out test without used active carbon, is soaked and drip washing by active carbon chloroform highly concentrated solution, makes active carbon reach chloroform absorption saturated, adsorbs saturated active carbon and carry out regeneration test.Test is carried out in special container, diameter 30cm, high 60cm, the regeneration of upward flow, and after regeneration, get activated carbon sample analysis, activated carbon sample returns to 84% to the adsorption efficiency of chloroform from 10%.
Claims (1)
1. a method for in-situ regeneration chloroform absorption saturated activity charcoal, is characterized in that comprising the steps:
The first step: prepare iron nano-particle reagent, adopts nanopure water to dissolve ferric chloride hexahydrate, mixes more than 4 days, and preparation high concentration iron nano-particle reagent is as stoste, and stoste is diluted with nanopure water as required, and iron nano-particle diameter is at 40-50nm;
Second step: adsorb saturated activated carbon sample with the iron nano-particle reagent dynamic upward flow drip washing chloroform through being diluted to certain concentration, collects leacheate, repeats drip washing 4-5 time;
3rd step: the 70% hydrogen peroxide upward flow mode that adds in proportion contacts with saturated activity charcoal and regenerates, controlling reactor pH with hydrochloric acid is 2.4-2.7, repeats drip washing 4-5 time;
4th step: stop drip washing, leaves standstill 30--40 minute; Discharge regeneration leacheate, rinse the rear active carbon 2-3 time of regeneration with clear water, regeneration completes.
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| CN201310126689.8A CN103212390B (en) | 2013-04-12 | 2013-04-12 | In-situ regeneration method of trichloromethane-adsorbed saturating activated carbon |
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| CN201310126689.8A CN103212390B (en) | 2013-04-12 | 2013-04-12 | In-situ regeneration method of trichloromethane-adsorbed saturating activated carbon |
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| CN103212390B true CN103212390B (en) | 2015-03-11 |
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| DE102014111393A1 (en) * | 2014-08-11 | 2016-02-11 | Ovivo Luxembourg S.À.R.L. | Process for the in situ regeneration of trihalomethane-loaded activated carbons by alkaline hydrolysis |
| CN115805057A (en) * | 2022-11-29 | 2023-03-17 | 南京誉鼎环境科技有限公司 | Active carbon in-situ adsorption regeneration method applied to high-concentration degradation-resistant wastewater treatment |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5702587A (en) * | 1996-12-20 | 1997-12-30 | Huron Tech Canada, Inc. | Chemical and electrochemical regeneration of active carbon |
| CN101215016A (en) * | 2008-01-11 | 2008-07-09 | 浙江理工大学 | Method for treating organic waste water |
| CN102276082A (en) * | 2011-06-12 | 2011-12-14 | 南昌航空大学 | Treatment method of high-salinity organic wastewater |
| CN102658101A (en) * | 2012-04-19 | 2012-09-12 | 东华大学 | Regeneration method for activated carbon adsorbed and saturated by refractory organics |
| CN102755875A (en) * | 2012-07-04 | 2012-10-31 | 浙江工商大学 | Regenerating method of activated carbon after absorbing organic matters |
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2013
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5702587A (en) * | 1996-12-20 | 1997-12-30 | Huron Tech Canada, Inc. | Chemical and electrochemical regeneration of active carbon |
| CN101215016A (en) * | 2008-01-11 | 2008-07-09 | 浙江理工大学 | Method for treating organic waste water |
| CN102276082A (en) * | 2011-06-12 | 2011-12-14 | 南昌航空大学 | Treatment method of high-salinity organic wastewater |
| CN102658101A (en) * | 2012-04-19 | 2012-09-12 | 东华大学 | Regeneration method for activated carbon adsorbed and saturated by refractory organics |
| CN102755875A (en) * | 2012-07-04 | 2012-10-31 | 浙江工商大学 | Regenerating method of activated carbon after absorbing organic matters |
Non-Patent Citations (3)
| Title |
|---|
| Application of Fenton’s reagent to regenerate activated carbon saturated with organochloro compounds;Luciana Cáassia Toledo等;《Chemosphere》;20031231;第50卷;第1049–1054页 * |
| Fenton法再生废活性炭;陶长元等;《化工进展》;20101231;第29卷;第673-676页 * |
| Sorption and Desorption of Dye Remazol Yellow onto a Mexican Surfactant-modified Clinoptilolite-rich Tuff and a Carbonaceous Material from Pyrolysis of Sewage Sludge;J.Torres-Pérez等;《Water Air Soil Pollut》;20071016;第187卷;第303–313页 * |
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