CN112759171A - Method for treating EDTA-Tl wastewater - Google Patents

Method for treating EDTA-Tl wastewater Download PDF

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Publication number
CN112759171A
CN112759171A CN202110013745.1A CN202110013745A CN112759171A CN 112759171 A CN112759171 A CN 112759171A CN 202110013745 A CN202110013745 A CN 202110013745A CN 112759171 A CN112759171 A CN 112759171A
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CN
China
Prior art keywords
edta
wastewater
anion exchange
treating
exchange resin
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Pending
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CN202110013745.1A
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Chinese (zh)
Inventor
姚焱
廖文青
张平
刘煜
李伙生
李笛
毛海立
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Guangzhou University
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Guangzhou University
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Priority to CN202110013745.1A priority Critical patent/CN112759171A/en
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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
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • 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
    • C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
    • C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
    • 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
    • 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
    • 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
    • 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
    • C02F2101/303—Complexing agents
    • 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
    • C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical

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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)
  • Removal Of Specific Substances (AREA)

Abstract

The invention discloses a method for treating EDTA-Tl wastewater, which comprises the following steps: 1) removing insoluble substances from EDTA-Tl wastewater, and adding sodium persulfate or/and potassium persulfate; 2) will be loaded with Fe3O4Adding the anion exchange resin into the EDTA-Tl wastewater treated in the step 1), stirring for reaction, standing, discharging supernatant and recovering precipitates. The method has the advantages of high removal rate of more than 99.5 percent of thallium in the EDTA-Tl wastewater, high removal rate of more than 89 percent of EDTA, small chemical reagent dosage and low treatment cost.

Description

Method for treating EDTA-Tl wastewater
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method for treating EDTA-Tl wastewater.
Background
Thallium (Tl) is a toxic heavy metal element, has toxicity exceeding As, Hg, Cd and Pb, and has certain accumulation property. If thallium poisoning occurs, alopecia, muscle atrophy, kidney damage and even death can occur seriously. In view of the toxicity of thallium, strict industrial wastewater thallium pollutant emission standards (in the order of "DB 43T968-2014 industrial thallium pollutant emission standard", "GB 31573-2015 inorganic chemical industry pollutant emission standard" and "DB 44/1989-2017 industrial thallium pollutant emission standard") were established in succession in the south of Hunan, the nation and the Guangdong provinces.
EDTA (ethylene diamine tetraacetic acid) is a chelating agent widely used in the industries of metallurgy, electroplating, mining and the like. The EDTA-Tl wastewater system has complex components, the thallium-containing component comprises free thallium ions and thallium-EDTA complexes, and the EDTA also comprises free EDTA and thallium-EDTA complexes. Trivalent thallium and EDTA can form stable soluble complex, and the complex does not precipitate under strong alkaline condition and has strong migration activity. Monovalent thallium ion (Tl)+) The complex formed with EDTA is unstable, but monovalent thallium ions are similar to potassium ions (K)+) And the precipitate is not generated under the strong alkaline condition. As a result, the treatment difficulty of the EDTA-Tl wastewater is high.
At present, advanced oxidation technologies such as photocatalytic oxidation, electrochemical method, fenton method, etc. have been widely applied to complex breaking treatment, but these methods all have obvious defects, such as: the photocatalytic oxidation method has higher requirements on reaction conditions and has larger limitation in practical application; the electrochemical method is greatly limited by electrode materials, and has poor removal effect on high-concentration complex heavy metals; the Fenton process involves hydrogen peroxide (H)2O2) Low utilization rate, large chemical reagent input amount and the like.
Therefore, development of an EDTA-Tl wastewater treatment method with good treatment effect, small chemical reagent dosage and low cost is urgently needed.
Disclosure of Invention
The invention aims to provide a method for treating EDTA-Tl wastewater.
The technical scheme adopted by the invention is as follows:
a method for treating EDTA-Tl wastewater comprises the following steps:
1) removing insoluble substances from EDTA-Tl wastewater, and adding sodium persulfate or/and potassium persulfate;
2) will be loaded with Fe3O4Adding the anion exchange resin into the EDTA-Tl wastewater treated in the step 1), stirring for reaction, standing, discharging supernatant and recovering precipitates.
Preferably, the method for treating the EDTA-Tl wastewater comprises the following steps:
1) filtering EDTA-Tl wastewater to remove insoluble substances, adjusting the pH value to 2-5, and adding sodium persulfate or/and potassium persulfate;
2) will be loaded with Fe3O4Adding the anion exchange resin into the EDTA-Tl wastewater treated in the step 1), stirring for reaction, adjusting the pH to 8-9, standing, discharging supernatant, and recovering precipitates.
Preferably, the adding amount of the sodium persulfate or/and the potassium persulfate in the step 1) is 5mmol/L to 12 mmol/L. Sodium persulfate is less costly than potassium persulfate, and is preferred.
Preferably, said step 2) of loading with Fe3O4The anion exchange resin is loaded with Fe3O4A strongly basic anion exchange resin.
Further preferably, the load of step 2) is Fe3O4In the anion exchange resin of (3)3O4The load capacity of the catalyst is 8 to 12 percent.
Still more preferably, said step 2) of loading with Fe3O4The anion exchange resin is NDMP-1 magnetic resin (chlorine type, the particle size range is 80-200 mu m, Fe) of the national Innovative Material research center of Jiangsu3O4Loading of 10%).
Preferably, said step 2) of loading with Fe3O4The particle size range of the anion exchange resin is 50-250 μm.
Preferably, said step 2) of loading with Fe3O4The dosage of the anion exchange resin is 2g/L to 4 g/L.
Preferably, the stirring reaction time in the step 2) is 1-2 h.
Preferably, the standing time in the step 2) is 20 min-40 min.
The principle of the invention is as follows: na (Na)2S2O8And K2S2O8Is stable at normal temperature and has weak oxidizing power, but is added with Fe-loaded3O4After anion exchange of the resin, Fe3O4Acting as a catalyst to activate Na2S2O8And K2S2O8Produce strongly oxidizing sulfate radicals (SO)4 -·，E02.6V) and a hydroxyl radical (· OH, E)02.8V), the molecular structure of the thallium-EDTA system is destroyed, EDTA is degraded into small molecules, while monovalent thallium ions are oxidized into trivalent thallium ions, whereas due to tl (oh)3Has a very low solubility product constant (K)sp＝1.68×10-44) After the pH value is adjusted to 8-9, trivalent thallium ions are fully precipitated, and the rest trivalent thallium-EDTA (forming a complex anion) and EDTA (existing in the form of anion) can be further adsorbed and removed by NDMP-1 magnetic resin.
The invention has the beneficial effects that: the method has the advantages of high removal rate of more than 99.5 percent of thallium in the EDTA-Tl wastewater, high removal rate of more than 89 percent of EDTA, small chemical reagent dosage and low treatment cost.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
a method for treating EDTA-Tl wastewater comprises the following steps:
1) 500mL of EDTA-Tl wastewater (total thallium content of 0.51mg/L, total EDTA content of 103mg/L) was filtered to remove insoluble substances, and H was added2SO4Adjusting the pH of the solution to 5 with NaOH solution, and adding sodium persulfate (Na)2S2O8) Until the concentration is 5mmol/L, and mixing uniformly;
2) adding 1g of NDMP-1 magnetic resin into the EDTA-Tl wastewater treated in the step 1), stirring for 2h, adjusting the pH value to 8 by using NaOH solution, standing for 20min after uniform stirring, discharging supernatant and recovering precipitates.
Tests show that the content of thallium in the supernatant is 0.002mg/L, the removal rate of thallium is 99.6%, the content of EDTA in the supernatant is 10.7mg/L, and the removal rate of EDTA is 89.6%.
Example 2:
a method for treating EDTA-Tl wastewater comprises the following steps:
1) 500mL of EDTA-Tl wastewater (total thallium content of 0.75mg/L, total EDTA content of 121mg/L) was filtered to remove insoluble substances, and H was added2SO4The pH of the solution was adjusted to 4.5 with NaOH solution, and sodium persulfate (Na) was added2S2O8) Until the concentration is 6mmol/L, and mixing uniformly;
2) adding 1.2g of NDMP-1 magnetic resin into the EDTA-Tl wastewater treated in the step 1), stirring for 1.5h, adjusting the pH to 9 with NaOH solution, standing for 25min after uniform stirring, discharging supernatant, and recovering precipitates.
Tests show that the content of thallium in the supernatant is 0.002mg/L, the removal rate of thallium is 99.7%, the content of EDTA in the supernatant is 11.1mg/L, and the removal rate of EDTA is 90.8%.
Example 3:
a method for treating EDTA-Tl wastewater comprises the following steps:
1) 500mL of EDTA-Tl wastewater (total thallium content of 1.8mg/L, total EDTA content of 144mg/L) was filtered to remove insoluble substances, and H was added2SO4The pH of the solution was adjusted to 4 with NaOH solution, and sodium persulfate (Na) was added2S2O8) Until the concentration is 8mmol/L, and mixing uniformly;
2) adding 1.5g of NDMP-1 magnetic resin into the EDTA-Tl wastewater treated in the step 1), stirring for 1.5h, adjusting the pH value to 8 by using NaOH solution, standing for 30min after uniform stirring, discharging supernatant and recovering precipitates.
Through tests, the content of thallium in the supernatant is 0.003mg/L, the removal rate of thallium is 99.8%, the content of EDTA in the supernatant is 12.4mg/L, and the removal rate of EDTA is 91.4%.
Example 4:
a method for treating EDTA-Tl wastewater comprises the following steps:
1) 500mL of EDTA-Tl wastewater (total thallium content 5.4mg/L, total EDTA content 167mg/L) was filtered to remove insoluble substances, which were then treated with H2SO4The pH of the solution was adjusted to 3 with NaOH solution, and sodium persulfate (Na) was added2S2O8) Until the concentration is 10mmol/L, and mixing uniformly;
2) adding 1.8g of NDMP-1 magnetic resin into the EDTA-Tl wastewater treated in the step 1), stirring for 1h, adjusting the pH to 9 with NaOH solution, standing for 35min after uniform stirring, discharging supernatant and recovering precipitates.
Through tests, the content of thallium in the supernatant is 0.005mg/L, the removal rate of thallium is 99.9%, the content of EDTA in the supernatant is 11.5mg/L, and the removal rate of EDTA is 93.1%.
Example 5:
a method for treating EDTA-Tl wastewater comprises the following steps:
1) 500mL of EDTA-Tl wastewater (total thallium content 9.8mg/L, total EDTA content 185mg/L) was filtered to remove insoluble substances, which were then treated with H2SO4The pH of the solution was adjusted to 2 with NaOH solution, and sodium persulfate (Na) was added2S2O8) Until the concentration is 12mmol/L, and mixing uniformly;
2) adding 2g of NDMP-1 magnetic resin into the EDTA-Tl wastewater treated in the step 1), stirring for 1h, adjusting the pH value to 9 with NaOH solution, standing for 40min after uniform stirring, discharging supernatant and recovering precipitates.
Through tests, the content of thallium in the supernatant is 0.005mg/L, the removal rate of thallium is 99.9%, the content of EDTA in the supernatant is 14.3mg/L, and the removal rate of EDTA is 92.3%.
Note:
the total thallium content in examples 1 to 5 refers to the total content of thallium ions free from thallium ions in the thallium-EDTA-containing wastewater and thallium ions complexed with EDTA.
The total EDTA content in examples 1 to 5 is the total content of free EDTA and EDTA complexed with thallium ions in the thallium-EDTA-containing wastewater.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A method for treating EDTA-Tl wastewater is characterized by comprising the following steps:
1) removing insoluble substances from EDTA-Tl wastewater, and adding sodium persulfate or/and potassium persulfate;
2) will be loaded with Fe3O4Adding the anion exchange resin into the EDTA-Tl wastewater treated in the step 1), stirring for reaction, standing, discharging supernatant and recovering precipitates.
2. The method for treating EDTA-Tl wastewater according to claim 1, comprising the following steps:
1) filtering EDTA-Tl wastewater to remove insoluble substances, adjusting the pH value to 2-5, and adding sodium persulfate or/and potassium persulfate;
2) will be loaded with Fe3O4Adding the anion exchange resin into the EDTA-Tl wastewater treated in the step 1), stirring for reaction, adjusting the pH to 8-9, standing, discharging supernatant, and recovering precipitates.
3. The method for treating EDTA-Tl wastewater according to claim 1 or 2, wherein: the adding amount of the sodium persulfate or/and the potassium persulfate in the step 1) is 5 mmol/L-12 mmol/L.
4. The method for treating EDTA-Tl wastewater according to claim 1 or 2, wherein: step 2) the load is Fe3O4The anion exchange resin is loaded with Fe3O4A strongly basic anion exchange resin.
5. The method of claim 4, wherein the EDTA-Tl wastewater is treated by: step 2) the load is Fe3O4In the anion exchange resin of (3)3O4The load capacity of the catalyst is 8 to 12 percent.
6. The method of claim 5, wherein the EDTA-Tl wastewater is treated by: step 2) the load is Fe3O4The anion exchange resin is NDMP-1 magnetic resin.
7. The method for treating EDTA-Tl wastewater according to claim 1 or 2, wherein: step 2) the load is Fe3O4The particle size range of the anion exchange resin is 50-250 μm.
8. The method for treating EDTA-Tl wastewater according to claim 1 or 2, wherein: step 2) the load is Fe3O4The dosage of the anion exchange resin is 2g/L to 4 g/L.
9. The method for treating EDTA-Tl wastewater according to claim 1 or 2, wherein: the stirring reaction time of the step 2) is 1-2 h.
10. The method for treating EDTA-Tl wastewater according to claim 1 or 2, wherein: the standing time in the step 2) is 20-40 min.
CN202110013745.1A 2021-01-05 2021-01-05 Method for treating EDTA-Tl wastewater Pending CN112759171A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109592821A (en) * 2019-01-23 2019-04-09 广州大学 A kind of method of EDTA- thallium complex in removal waste water
CN109607595A (en) * 2018-12-18 2019-04-12 广州大学 A method of thallous iodide is prepared by raw material of acid water containing thallium
CN109811129A (en) * 2019-02-18 2019-05-28 广州大学 A method of thallium, mercury and chromium are recycled from acid waste water is smelted
CN109967134A (en) * 2019-03-14 2019-07-05 华南理工大学 A kind of Nano ferric hydroxide modified anion resin composite materials and the preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109607595A (en) * 2018-12-18 2019-04-12 广州大学 A method of thallous iodide is prepared by raw material of acid water containing thallium
CN109592821A (en) * 2019-01-23 2019-04-09 广州大学 A kind of method of EDTA- thallium complex in removal waste water
CN109811129A (en) * 2019-02-18 2019-05-28 广州大学 A method of thallium, mercury and chromium are recycled from acid waste water is smelted
CN109967134A (en) * 2019-03-14 2019-07-05 华南理工大学 A kind of Nano ferric hydroxide modified anion resin composite materials and the preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
何杰: "《工业催化》", 31 July 2014, 中国矿业大学出版社 *
张昊楠: "FexOy@GAC活化过硫酸盐处理络合铜废水的研究", 《中国给水排水》 *

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Application publication date: 20210507