CN109592821A - A kind of method of EDTA- thallium complex in removal waste water - Google Patents
A kind of method of EDTA- thallium complex in removal waste water Download PDFInfo
- Publication number
- CN109592821A CN109592821A CN201910065537.9A CN201910065537A CN109592821A CN 109592821 A CN109592821 A CN 109592821A CN 201910065537 A CN201910065537 A CN 201910065537A CN 109592821 A CN109592821 A CN 109592821A
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- Prior art keywords
- waste water
- edta
- thallium
- added
- thallium complex
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Classifications
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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
- 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
- C02F1/52—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
- C02F1/72—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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The method of EDTA- thallium complex, the described method comprises the following steps: (1) ferrous salt is added in the waste water of Xiang Hanyou EDTA- thallium complex, stirs evenly in a kind of removal waste water；(2) hydrogen peroxide is added, adjusts waste water system pH to 2.5-3.5, is reacted；(3) after the completion of being stirred to react, alkaline flocculant is added and adjusts the pH value of waste water system to 9-11, and starts flocculation sedimentation, removes solid precipitation.Method of the invention is easy to operate, non-selectivity, reaction efficiency height and nonhazardous；The present invention not only separates complexation heavy metal ion Tl with organic matter EDTA, so that Tl absorption, coagulation, oxidation, precipitating and co-precipitation is got off, while organic pollutant EDTA oxidative degradation is further mineralized into H at small molecule organic compound2O、CO2And inorganic salts, the byproduct of toxic property is not generated；Method of the invention is up to 96.54% or more, TOC removal rate up to 70.42% to Tl removal rate in waste water, is a kind of effective method for purifying EDTA- thallium complex waste water.
Description
Technical field
The present invention relates to technical field of waste water processing, and in particular to a method of EDTA- thallium complex in removal waste water.
Background technique
Water pollution caused by release metal ions and organic pollutant, is always environment protection field difficult point and heat in industry
The problem of point.Thallium (Tl) is a kind of heavy metal of severe toxicity, T1 and its compound be typically found in fiber (optics) glass, pigment and
In dyestuff.It is reported that the toxicity of thallium is much higher than lead (Pb), cadmium (Cd) and mercury (Hg) etc..Waste water containing Tl is discharged to natural environment to ring
Border and human health constitute significant threat.Thallium poisoning will lead to alopecia, muscular atrophy, kidney injury, or even dead.And organic dirt
Object is contaminated, such as ethylenediamine tetra-acetic acid (EDTA) because it is a kind of low cost and widely used chelating agent, is had to metal ion very strong
Complexing power, industry (such as metallurgy, be electroplated and mining industry) in be widely used.Once heavy metal especially T1 and EDTA chela
It closes, forms the high soluble complexes (T1-EDTA) of stability, show bigger toxicity.In addition, EDTA- thallium complex
(T1-EDTA) since its high mobility, extremely stable property and intractable feature can more easily move to other accepting mediums, often
Rule plus alkali neutralization intermediate processing processing complexing heavy metal organic matter effect is poor, such as without reasonably handling, will cause
Serious environmental pollution and threat human health.
Fenton (Fenton) method is a kind of wastewater treatment technology of advanced oxidation, refers to oxydol H2O2In ferrous ion Fe2+'s
The hydroxyl radical free radical OH with strong oxidizing property is generated under catalytic action.OH is a kind of with the strong of 2.8V standard oxidizing potential
Oxidant, OH makes organic matter that chain rupture or open loop occur by attack C=C key, C-N key etc., and then organic pollutant is aoxidized
It is H for small molecule organic material even directly mineralising2O and CO2, to reduce the COD of sewage.The method is high-efficient and nonhazardous, especially
It has outstanding advantage in terms of handling difficult biochemical sewage.Fenton process has been widely used in handling various types of waste water,
Such as alkylbenzene, landfill leachate, phenolic waste water and dyeing waste-water.
Patent publication No. is that the patent of CN103183421A discloses a kind of processing method of waste water containing complex copper, described
Waste water is adjusted to acid after vulcanization acid ferrous iron by method, makes Cu using ferrous reproducibility2+It is reduced into Cu+, to reach Cu
It is acted on EDTA contact break, the rear alkali tune oxidation precipitation that carries out separates metal pollutant.This method, which adds a large amount of ferrous sulfate, to be caused
Water quality is turned to be yellow after processing, and mud amount is big, and sedimentation effect is not good enough, while its method can not effectively oxidative degradation EDTA organic contamination
Object.
Patent publication No. is that the patent of CN101054247A discloses a kind of processing work of complete wiring board production waste water
Skill is directed to the processing of 6 heavy metal species organic wastewaters, by adjusting pH and the reduction displacement of waste water, adds NaOH tune
PH value is eventually adding Ca (OH) to 9 or so2、PAM、PAC、Na2S coagulating sedimentation.This method process flow is longer, is not easy to apply
In industrialized production；Meanwhile technique will lead to Na using vulcanized sodium progress coagulating sedimentation2S acid decomposition generates stink damp
Body causes secondary pollution.
The patent of patent publication No. CN105293775A discloses a kind of combined using pre-oxidation and coagulating sedimentation to handle
Method containing thallium, ammonia nitrogen waste water, the method are added oxidizing agent sodium hypochlorite after the pH to 5-6 by adjusting waste water and carry out pre- oxygen
Change makes Tl+It is oxidized to Tl3+, ferrous sulfate, poly-aluminium waste water formation alumen ustum wadding body are added afterwards, is eventually adding quick lime and adjusts pH value of solution
Achieve the purpose that remove Heavy Metals in Waters ion to alkalinity.This method disadvantage be when adjusting pH value use to it is a large amount of give birth to stones
Ash causes generation mud amount big.It uses sodium hypochlorite as oxidant simultaneously, but sodium hypochlorite has sensitization and releasing
Chlorine is possible to cause to be poisoned, and seriously endangers human health.The method handles the key step of ammonia nitrogen in preoxidation process, processing effect
Fruit is general, does not have superior oxidative degradation ability.
Summary of the invention
EDTA- thallium in a kind of removal waste water is provided it is an object of the invention to overcome in place of the shortcomings of the prior art
The method of complex compound.
To achieve the above object, the technical scheme adopted by the invention is as follows: EDTA- thallium complex (T1- in a kind of removal waste water
EDTA method), the described method comprises the following steps:
(1) ferrous salt and hydrogen peroxide are added in the waste water of Xiang Hanyou EDTA- thallium complex, stirs evenly；
(2) waste water system pH to 2.5-3.5 is adjusted, is reacted；
(3) after completion of the reaction, alkaline flocculant is added and adjusts the pH value of waste water system to 9-11, and starts flocculation sedimentation；
(4) after flocculation sedimentation, waste water system is separated by solid-liquid separation, removes solid precipitation.
Method of the invention utilizes the strong oxidizing property of Fenton reagent (ferrous ion and hydrogen peroxide), and T1-EDTA is complexed
Object is destroyed by Fenton oxidation process, forms T1 (I)/T1 (III) ion and free EDTA of release, then by aoxidizing,
Absorption, condensation, precipitating and co-precipitation, it is final to remove EDTA- thallium complex.
Preferably, the alkaline flocculant is calcium hydroxide.
Preferably, alkaline flocculant is added in step (3) and adjusts the pH value of waste water system to 11.
Preferably, ferrous salt is green vitriol.
Preferably, the molar ratio of the green vitriol and hydrogen peroxide are as follows: 1.0:2-3.
Preferably, the molar ratio of the green vitriol and hydrogen peroxide are as follows: 1.0:2.5.
Preferably, the method reacted in step (2) is to be stirred to react or concussion reaction, the time of reaction are 2-5 hours.
Preferably, the dosage of the ferrous sulfate are as follows: 15-28mmol/L waste water.
Preferably, the dosage of the ferrous sulfate are as follows: 21.6mmol/L waste water.
Preferably, wastewater pH is adjusted to 2.5-3.5 with sulfuric acid or sodium hydroxide solution in step (2).
Preferably, wastewater pH is adjusted to 2.5 with sulfuric acid or sodium hydroxide solution in step (2).
Preferably, the method for separation of solid and liquid described in step (4) is filtering.
The beneficial effects of the present invention are: the present invention provides a kind of methods of EDTA- thallium complex in removal waste water, originally
The method of invention is easy to operate, non-selectivity, reaction efficiency height and nonhazardous；The present invention is not only by complexation heavy metal ion Tl
It is separated with organic matter EDTA, Tl absorption, coagulation, oxidation, precipitating and co-precipitation is expeditiously made to get off, while by organic pollutant
EDTA oxidative degradation is further mineralized into H at small molecule organic compound2O、CO2And inorganic salts, the by-product of toxic property is not generated
Product；Method of the invention is up to 96.54% or more, TOC removal rate up to 70.42% to Tl removal rate in waste water, is a kind of purifying
The effective method of EDTA- thallium complex waste water.
Detailed description of the invention
Fig. 1 is the method flow schematic diagram of the embodiment of the present invention.
Specific embodiment
To better illustrate the object, technical solutions and advantages of the present invention, below in conjunction with specific embodiment to the present invention
It is described further.
Embodiment 1
As the method for EDTA- thallium complex in a kind of removal waste water of the embodiment of the present invention, the method includes following
Step:
(1) 0.24g green vitriol is added in the 40ml waste water of Xiang Hanyou EDTA- thallium complex (Tl-EDTA)
(FeSO4·7H2O), stir evenly；
(2) 0.22ml hydrogen peroxide (30%) is added, adjusts waste water system pH to 3.5, stirring with sulfuric acid or sodium hydroxide
Reaction 2 hours,；
(3) after the completion of being stirred to react, calcium hydroxide powder is added and adjusts the pH value of waste water system to 11, and it is heavy to start flocculation
It forms sediment；
(4) after flocculation sedimentation, waste water system is separated by solid-liquid separation, removes solid precipitation；
Wherein, in the waste water containing EDTA- thallium complex the concentration of thallium be 50 μM, EDTA concentration be 500 μM, the thallium with
The form of ionic forms perhaps EDTA- thallium complex be present in waste water EDTA by it is free or with thallium complexing in the form of exist
In waste water.
Embodiment 2
As the method for EDTA- thallium complex in a kind of removal waste water of the embodiment of the present invention, the present embodiment and embodiment 1
Unique difference are as follows: the time being stirred to react in step (2) be 5 hours.
Embodiment 3
As the method for EDTA- thallium complex in a kind of removal waste water of the embodiment of the present invention, the present embodiment and embodiment 1
Unique difference are as follows: in the waste water containing EDTA- thallium complex the concentration of thallium be 50 μM, EDTA concentration be 50 μM, the thallium with
The form of ionic forms perhaps EDTA- thallium complex be present in waste water EDTA by it is free or with thallium complexing in the form of exist
In waste water.
Embodiment 4
As the method for EDTA- thallium complex in a kind of removal waste water of the embodiment of the present invention, the present embodiment and embodiment 1
Unique difference are as follows: in step (2), adjust waste water system pH to 2.5 with sulfuric acid or sodium hydroxide.
Experimental example 1
To before the processing of the method for embodiment 1-4, the concentration of the thallium of treated waste water and TOC be measured.
Measuring method are as follows: 0.2mL nitric acid (50%, v/v) is added to the water after being separated by solid-liquid separation in step (4) and saves, measurement
The concentration of solution Tl and TOC after after processing.
The results are shown in Table 1.
The removal effect of the method for 1 embodiment 1-4 of table
By the result of embodiment 1-4 it is found that method of the invention has well the EDTA- thallium complex in waste water
Removal effect finds by comparison, comprehensively considers the removal rate of thallium and ethylenediamine tetra-acetic acid, and when pH is 2.5, removal effect is more
It is good.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than protects to the present invention
The limitation of range is protected, although the invention is described in detail with reference to the preferred embodiments, those skilled in the art should
Understand, it can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the essence of technical solution of the present invention
And range.
Claims (9)
1. a kind of method of EDTA- thallium complex in removal waste water, which is characterized in that the described method comprises the following steps:
(1) ferrous salt and hydrogen peroxide are added in the waste water of Xiang Hanyou EDTA- thallium complex, stirs evenly；
(2) waste water system pH to 2.5-3.5 is adjusted, is reacted；
(3) after completion of the reaction, alkaline flocculant is added and adjusts the pH value of waste water system to 9-11, and starts flocculation sedimentation；
(4) after flocculation sedimentation, waste water system is separated by solid-liquid separation, removes solid precipitation.
2. the method according to claim 1, wherein the alkalinity flocculant is calcium hydroxide.
3. the method according to claim 1, wherein ferrous salt is green vitriol.
4. according to the method described in claim 3, it is characterized in that, the molar ratio of the green vitriol and hydrogen peroxide
Are as follows: 1.0:2-3.
5. according to the method described in claim 3, it is characterized in that, the molar ratio of the green vitriol and hydrogen peroxide
Are as follows: 1.0:2.5.
6. the method according to claim 1, wherein the method reacted in step (2) is to be stirred to react or shake
Reaction is swung, the time of reaction is 2-5 hours.
7. according to the method described in claim 4, it is characterized in that, the dosage of the ferrous sulfate are as follows: 15-28mmol/L is useless
Water.
8. the method according to claim 1, wherein being adjusted in step (2) with sulfuric acid or sodium hydroxide solution
Wastewater pH is to 2.5-3.5.
9. the method according to the description of claim 7 is characterized in that being adjusted in step (2) with sulfuric acid or sodium hydroxide solution
Wastewater pH is to 2.5.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110627250A (en) * | 2019-08-15 | 2019-12-31 | 广东工业大学 | Advanced oxidation-alkali regulation precipitation combined method for treating EDTA-Cu wastewater |
| CN112371089A (en) * | 2020-11-16 | 2021-02-19 | 桂林理工大学 | Irregular hexahedron colloidal particle and preparation method and application thereof |
| CN112759171A (en) * | 2021-01-05 | 2021-05-07 | 广州大学 | Method for treating EDTA-Tl wastewater |
| CN112827354A (en) * | 2020-12-28 | 2021-05-25 | 安徽元琛环保科技股份有限公司 | Regeneration method of thallium-poisoned denitration catalyst |
| CN113044945A (en) * | 2021-03-10 | 2021-06-29 | 四川大学 | Method for removing heavy metal-organic matter complex in wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112827354A (en) * | 2020-12-28 | 2021-05-25 | 安徽元琛环保科技股份有限公司 | Regeneration method of thallium-poisoned denitration catalyst |
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| CN113044945A (en) * | 2021-03-10 | 2021-06-29 | 四川大学 | Method for removing heavy metal-organic matter complex in wastewater |
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Application publication date: 20190409 |