CN114772816A - Method for purifying and treating sewage containing heavy metal thallium - Google Patents
Method for purifying and treating sewage containing heavy metal thallium Download PDFInfo
- Publication number
- CN114772816A CN114772816A CN202210527035.5A CN202210527035A CN114772816A CN 114772816 A CN114772816 A CN 114772816A CN 202210527035 A CN202210527035 A CN 202210527035A CN 114772816 A CN114772816 A CN 114772816A
- Authority
- CN
- China
- Prior art keywords
- thallium
- sewage
- hydroxide
- purification treatment
- treated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010865 sewage Substances 0.000 title claims abstract description 71
- 229910052716 thallium Inorganic materials 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 31
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 13
- -1 thallium ion Chemical class 0.000 claims abstract description 51
- 239000000706 filtrate Substances 0.000 claims abstract description 22
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000746 purification Methods 0.000 claims abstract description 16
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 16
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002244 precipitate Substances 0.000 claims abstract description 14
- 229910021515 thallium hydroxide Inorganic materials 0.000 claims abstract description 13
- QGYXCSSUHCHXHB-UHFFFAOYSA-M thallium(i) hydroxide Chemical compound [OH-].[Tl+] QGYXCSSUHCHXHB-UHFFFAOYSA-M 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- BXJGLLKRUQQYTC-UHFFFAOYSA-N thallium(1+);sulfide Chemical compound [S-2].[Tl+].[Tl+] BXJGLLKRUQQYTC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000001699 photocatalysis Effects 0.000 claims abstract description 8
- 229960004887 ferric hydroxide Drugs 0.000 claims abstract description 7
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims abstract description 7
- 239000002351 wastewater Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 238000000108 ultra-filtration Methods 0.000 claims description 4
- 235000014413 iron hydroxide Nutrition 0.000 claims description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 2
- 238000007146 photocatalysis Methods 0.000 claims 1
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000000047 product Substances 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 229910052742 iron Inorganic materials 0.000 description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 5
- 229910001448 ferrous ion Inorganic materials 0.000 description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910001447 ferric ion Inorganic materials 0.000 description 4
- 239000010881 fly ash Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 4
- 229960001763 zinc sulfate Drugs 0.000 description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 210000001035 gastrointestinal tract Anatomy 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 150000003475 thallium Chemical class 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 241001232253 Xanthisma spinulosum Species 0.000 description 1
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- 229960002594 arsenic trioxide Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010908 plant waste Substances 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 208000026015 thallium poisoning Diseases 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- 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
- C02F1/66—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
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Landscapes
- 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)
Abstract
The invention discloses a sewage purification treatment method containing heavy metal thallium, which comprises the following steps: adjusting the pH value of the sewage to 11-12 by using sodium hydroxide, and then adding a proper amount of sodium sulfide according to the thallium ion content in the sewage to be treated to ensure that monovalent thallium ions in the sewage are precipitated as thallium sulfide. After filtering, ozone is introduced into the filtrate for oxidation to generate ferric hydroxide and thallium hydroxide precipitates. And (4) filtering again, carrying out photocatalytic oxidation on the filtrate to generate water insoluble substance thallium hydroxide precipitate, and finally filtering to obtain qualified clear filtrate. And finally, conveying the clear filtrate to a concentration crystallizer for concentration and crystallization to obtain a high-quality inorganic salt product meeting the national standard.
Description
Technical Field
The invention relates to the field of sewage treatment, in particular to a sewage purification treatment method containing heavy metal thallium.
Background
Heavy metal thallium is a highly toxic chemical, and thallium and cyanide are both in class A in the "extremely toxic substance grade classification and name number" (1993, 10.1). The thallium salt is easy to dissolve in water, so that the thallium content in the foods of vegetables, meat, eggs and the like in the industrial polluted area is 4000 times of that in water and soil. Thallium is absorbed mainly by drinking water and food entering human body from digestive tract, or inhaled by respiratory tract in the form of dust, or absorbed by contact of vapor compound through skin. Thallium can accumulate in the organism for years, causing chronic thallium poisoning. Thallium and its compounds have strong toxicity, much higher than arsenic oxide, and have obvious damage to gastrointestinal tract and kidney.
Thallium ions in thallium-containing sewage are usually monovalent thallium ions, most thallium salts are very soluble in water, and thallium sulfide is hardly soluble in water under alkaline conditions, so the industrial treatment method of thallium-containing sewage is usually to perform flocculation precipitation treatment by using sodium sulfide under alkaline conditions, but the treatment method usually needs to add excessive sodium sulfide, and thallium ions in sewage are difficult to remove cleanly. Practice shows that the thallium-containing sewage is treated by sodium sulfide alone, the treatment effect is unstable, and particularly, the treatment effect is not ideal when the thallium-containing sewage with high salt content, such as thallium-containing sewage with high iron salt content, is treated. Moreover, this treatment method is greatly affected by the pH of the wastewater to be treated because thallium sulfide is soluble under acidic conditions.
Disclosure of Invention
In order to solve the problems that the thallium-containing sewage treatment effect is not ideal and excessive sodium sulfide is needed in the prior art, the invention provides a method for purifying and treating sewage containing heavy metal thallium, which comprises the following steps:
step S1, adjusting the pH value of the sewage to be treated by using sodium hydroxide to 10-12;
step S2, generating thallium sulfide insoluble in water by sodium sulfide for monovalent thallium ions in the sewage treated in the step S1 to precipitate thallium sulfide, wherein the use amount of the sodium sulfide is matched with the content of monovalent thallium ions in the sewage to be treated;
in step S3, the insoluble matter in the wastewater treated in step S2 is filtered off with a plate and frame filter press.
Further, the invention provides a sewage purification treatment method containing heavy metal thallium, which further comprises the following steps:
step S4, ozone is introduced into the sewage treated in the step S3 to generate ferric hydroxide and thallium hydroxide precipitates;
step S5, removing the iron hydroxide and thallium hydroxide precipitates in the sewage treated by step S4 by filtration.
Under alkaline conditions, ozone and hydroxyl in water can generate hydroxyl radicals to oxidize ferrous ions into ferric ions, and meanwhile, most monovalent thallium ions in sewage can be further oxidized into trivalent thallium ions to generate ferric hydroxide and thallium hydroxide precipitates.
Further, the method for purifying and treating the sewage containing the heavy metal thallium, provided by the invention, further comprises the following steps of:
step S6, carrying out photocatalytic oxidation on the filtrate obtained in step S5, oxidizing unoxidized monovalent thallium ions in the filtrate into trivalent thallium ions, and generating water-insoluble thallium hydroxide precipitate;
and step S7, filtering thallium hydroxide in the sewage treated by the step S6 by using an ultrafiltration membrane to obtain qualified clear filtrate.
The method is characterized in that the waste residue and fly ash which have high salt content and contain heavy metal thallium are used as raw materials in industries such as iron and steel plants, smelters and other nonferrous metals to carry out deep processing to produce new materials such as zinc sulfate and zinc oxide, the salt content in the production sewage of the enterprises reaches more than 20%, wherein the heavy metal thallium content reaches more than 45mg/L, and impurities such as iron ions are also contained. After the sewage treated by the sewage purification treatment method containing heavy metal thallium provided by the invention is concentrated, crystallized and dried, the quality of the obtained inorganic salt products such as sodium chloride and potassium chloride respectively reaches the quality requirements of national standards GB/T5461-2016 and GB 25585-2010.
The technical scheme of the invention can produce the following technical effects:
after the treatment of the steps S1-S3 of the method for purifying and treating the sewage containing the heavy metal thallium, the content of thallium ions in the sewage is less than 1mg/L, and other water-insoluble substances are less than 5 mg/L; after the treatment of the step S5, the content of iron ions in the sewage is less than 0.0005mg/L, and most thallium ions in the sewage are removed at the same time, so that the content of thallium ions in the sewage is less than 0.01 mg/L; after the treatment of the step S7, the thallium ion content in the sewage is less than 0.0001mg/L, and the quality of the recovered inorganic salt products such as sodium chloride and potassium chloride respectively reaches the quality requirements of national standard GB/T5461-2016 and GB 25585-2010.
Compared with the prior art, in the thallium-containing sewage purification treatment method, in the thallium-containing sewage purification treatment process, aiming at the characteristic that thallium sulfide is difficult to dissolve in water under an alkaline condition, sodium hydroxide and a proper amount of sodium sulfide are selected for treatment in the first step, most thallium ions can be converted into thallium sulfide for precipitation and filtration through the step, and meanwhile, the problems that sediment is difficult to dehydrate and chemical agents generate secondary pollution due to the fact that excessive sodium sulfide, polyaluminium chloride, polyacrylamide and the like are required to be added in the traditional treatment method are solved. In some waste water for producing zinc sulfate by utilizing waste slag deep processing, iron ions which can affect the quality of inorganic salt byproducts cannot be avoided, and most of the iron ions are ferrous ions which are difficult to remove by adding an inorganic coagulant and a flocculant for treatment, and the ferrous ions need to be converted into ferric ions, the invention utilizes the requirement that thallium sulfide precipitation is required to precipitate under an alkaline condition during sewage treatment, ozone is introduced into the sewage, the ferrous ions are oxidized into the ferric ions by utilizing the characteristic that the ozone generates hydroxyl radicals with strong oxidizing capacity under the alkaline condition, and ferric hydroxide is generated, when the pH value of water is more than 4, the ferric hydroxide can precipitate, so in the one-step treatment process, although the ozone oxidizes and consumes partial hydroxyl in the water, as long as the pH value of the sewage is controlled to be not less than 8, most of the ferric ions precipitate in the form of ferric hydroxide, so that iron ions are removed, meanwhile, hydroxyl free radicals can oxidize monovalent thallium ions in the sewage into trivalent thallium ions, thallium hydroxide precipitate is generated, and thallium hydroxide is insoluble in water, so that most thallium ions in the sewage are also removed; according to the research, a small amount of monovalent thallium ions still exist in the sewage after the treatment of the steps, and in order to ensure the thallium ion content in the sewage, the invention is provided with a step of photocatalytic ozone oxidation, ozone has stronger oxidizing capability under the catalysis of ultraviolet light, and the thallium ion content in the sewage can be reduced to be less than 0.0001mg/L within 1-2 hours, and the iron ion content is also lower than 0.0005 mg/L.
In conclusion, the invention ensures that the thallium-containing sewage purification treatment process with high salt content is more reasonable, thallium ions are treated by times, not only the chemical and ozone consumption is low, but also the treatment cost is low, and 1m of thallium-containing sewage is treated3The sewage, the power consumption only needs 6-8 degrees electricity, the ozone amount only needs 5-8g, the sodium sulfide consumption can be controlled according to thallium ion content in the sewage, do not need to add excessively, do not need to add other inorganic coagulant and polyacrylamide either, therefore has avoided the difficult problem of dehydration of precipitate after polyaddition acrylamide flocculating agent, at present, many enterprises that adopt the sulfuration flocculation method to process, the water content reaches 90% after the filter-pressing of the sediment, this filter residue is hazardous waste, need special treatment, the treatment cost is very high, the water content reaches below 50% after the filter-pressing of the sediment of this technology, and all are inorganic matters, the filter cake quantity is very little, and the filter cake reaches below 40% after air drying, the sodium hydroxide added not only can guarantee the thallium sulfide to subside under the alkaline condition, can also provide the hydroxyl for the ozone of second step of processing. The invention is not limited by raw materials and production scale, and is particularly suitable for industrialized large-scale production devices.
Detailed description of the preferred embodiments
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1:
the fly ash of the steel and iron plant is used as a raw material for producing zinc sulfate, the main components of the fly ash are zinc oxide, potassium chloride and sodium chloride, the fly ash used as the raw material is washed in a countercurrent manner, and the discharged sewage is the sewage to be treated in the embodiment, wherein the contents of the sodium chloride and the potassium chloride in the sewage to be treated reach 22%, the content of thallium ions reaches 100mg/L, and the content of iron ions reaches 230 mg/L. At 30m3Adding the sewage 2 into a stainless steel reaction kettle0m3Firstly, using 10% hydrogen hydroxide to adjust the pH value to 11, starting a reaction kettle to stir, slowly adding 120kg of 25% concentrated sodium sulfide solution under stirring, reacting for 60min at normal temperature and normal pressure, and then performing filter pressing by using a plate-and-frame filter press to obtain filtrate containing 0.9mg/L of thallium ions and 186mg/L of ferrous ions. The filtrate was fed into an oxidation tower by a pump and oxidized with ozone for 5 hours while controlling the amount of total ozone added to 110g, and then the water-insoluble matter was filtered by a precision filter to obtain a filtrate containing iron ions 0.0003mg/L and thallium ions 0.009 mg/L. And (3) conveying the secondary filtrate into a photocatalytic oxidation tank by using a pump, performing catalytic oxidation for 2 hours by using ultraviolet light with the wavelength of 254nm, controlling the total using amount of ozone to be 30mg/L, and finally filtering by using an ultrafiltration membrane filter to obtain filtrate containing 0.00007mg/L of thallium ions and 0.0002mg/L of iron ions.
Example 2:
the method comprises the steps of producing zinc sulfate by using smelting plant waste residues as raw materials, wherein the main components of the waste residues are zinc oxide and sodium chloride, the sewage generated by carrying out countercurrent washing on the raw materials is used as the sewage to be treated in the embodiment, the content of sodium chloride in the sewage to be treated in the embodiment reaches 25%, the content of thallium ions in the sewage to be treated in the embodiment reaches 60mg/L, the content of iron ions in the sewage to be treated in the embodiment reaches 260mg/L, and the concentration of iron ions in the sewage to be treated in the embodiment is 30m3Adding the sewage of 20m into a stainless steel reaction kettle3Firstly, adjusting the pH value to 12 by using 10% of hydrogen hydroxide, starting a reaction kettle for stirring, slowly adding 70kg of 25% concentrated sodium sulfide solution under stirring, reacting for 30min at normal temperature and normal pressure, and then carrying out pressure filtration by using a plate-and-frame filter press to obtain filtrate containing 1.3mg/L of thallium ions and 216mg/L of iron ions. Pumping the filtrate into an oxidation tower by a pump, oxidizing the filtrate by ozone for 4 hours, controlling the total ozone amount added to be 70g, then filtering the water insoluble substance by a precision filter to obtain filtrate containing 0.0004mg/L of iron ions and 0.007mg/L of thallium ions, pumping the secondary filtrate into a photocatalytic oxidation tank by the pump, performing catalytic oxidation for 1.5 hours by ultraviolet light with the wavelength of 254nm, controlling the total ozone amount to be 20mg/L, and finally filtering the filtrate by an ultrafiltration membrane filter to obtain filtrate containing 0.00009mg/L of thallium ions and 0.0004mg/L of iron ions.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A sewage purification treatment method containing heavy metal thallium is characterized by comprising the following steps:
step S1, adjusting the pH value of the sewage to be treated by using sodium hydroxide to 11-12;
step S2, sodium sulfide is used for enabling monovalent thallium ions in the sewage treated by the step S1 to generate thallium sulfide sediment which is insoluble in water, wherein the using amount of the sodium sulfide is matched with the content of the monovalent thallium ions in the sewage to be treated;
in step S3, the water-insoluble matter in the sewage treated in step S2 is filtered off by a plate and frame filter press.
2. The sewage purification treatment method according to claim 1,
further comprising the steps of:
step S4, ozone is introduced into the sewage treated in the step S3 to generate ferric hydroxide and thallium hydroxide precipitates;
step S5, removing the iron hydroxide and thallium hydroxide precipitates in the sewage treated by step S4 by filtration.
3. The sewage purification treatment method according to claim 2, further comprising the steps of:
step S6, carrying out photocatalytic oxidation on the filtrate obtained in step S5, oxidizing unoxidized monovalent thallium ions in the filtrate into trivalent thallium ions, and generating water-insoluble thallium hydroxide precipitate;
and S7, filtering thallium hydroxide in the sewage treated in the S6 by using an ultrafiltration membrane to obtain qualified clear filtrate.
4. The wastewater purification treatment method according to claim 1, wherein the sodium hydroxide concentration in step S1 is 10% by mass.
5. The wastewater purification treatment method according to claim 1, wherein the sodium sulfide concentration in step S2 is 25% by mass.
6. The wastewater purification treatment method according to claim 1, wherein the reaction conditions for generating the thallium sulfide precipitate from sodium sulfide and a monovalent thallium ion in step S2 are as follows: stirring and reacting for 30-60min at normal temperature and normal pressure.
7. The wastewater purification treatment method according to claim 2, wherein in step S4, the ozone introduction amount is 5 to 8g/m3And (4) sewage.
8. The method for wastewater purification treatment according to claim 2, wherein in step S4, the ozone is supplied for 4 to 5 hours at normal temperature and pressure.
9. The wastewater purification treatment method according to claim 3, wherein in step S6, the wavelength of the light used for the photocatalysis is 254 nm.
10. The method for purifying sewage according to claim 3, wherein in step S6, the photocatalytic oxidation time is 1.5 to 2 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210527035.5A CN114772816A (en) | 2022-05-16 | 2022-05-16 | Method for purifying and treating sewage containing heavy metal thallium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210527035.5A CN114772816A (en) | 2022-05-16 | 2022-05-16 | Method for purifying and treating sewage containing heavy metal thallium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114772816A true CN114772816A (en) | 2022-07-22 |
Family
ID=82436110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210527035.5A Pending CN114772816A (en) | 2022-05-16 | 2022-05-16 | Method for purifying and treating sewage containing heavy metal thallium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114772816A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6485696B1 (en) * | 1998-10-30 | 2002-11-26 | The United States Of America As Represented By The Secretary Of The Interior | Recovery/removal of metallic elements from waste water using ozone |
| CN104773863A (en) * | 2015-02-13 | 2015-07-15 | 湖南永清环保研究院有限责任公司 | Deep purification process for thallium-containing waste water |
| CN105540921A (en) * | 2015-12-22 | 2016-05-04 | 湖南森美思环保有限责任公司 | Method for removing thallium in wastewater |
| CN110436674A (en) * | 2019-09-04 | 2019-11-12 | 湖南湘牛环保实业有限公司 | The minimum discharge treatment process of thallium in a kind of low concentration heavy metal water |
| CN216377722U (en) * | 2021-10-19 | 2022-04-26 | 湖南森美思环保有限责任公司 | Thallium-containing wastewater advanced treatment device |
-
2022
- 2022-05-16 CN CN202210527035.5A patent/CN114772816A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6485696B1 (en) * | 1998-10-30 | 2002-11-26 | The United States Of America As Represented By The Secretary Of The Interior | Recovery/removal of metallic elements from waste water using ozone |
| CN104773863A (en) * | 2015-02-13 | 2015-07-15 | 湖南永清环保研究院有限责任公司 | Deep purification process for thallium-containing waste water |
| CN105540921A (en) * | 2015-12-22 | 2016-05-04 | 湖南森美思环保有限责任公司 | Method for removing thallium in wastewater |
| CN110436674A (en) * | 2019-09-04 | 2019-11-12 | 湖南湘牛环保实业有限公司 | The minimum discharge treatment process of thallium in a kind of low concentration heavy metal water |
| CN216377722U (en) * | 2021-10-19 | 2022-04-26 | 湖南森美思环保有限责任公司 | Thallium-containing wastewater advanced treatment device |
Non-Patent Citations (4)
| Title |
|---|
| 付向辉;李立;杨国超;曾娟;: "工业含铊废水处理研究现状与进展", 稀有金属, no. 02 * |
| 方荣茂;: "含砷含铊矿坑水处理工艺及工程应用", 黄金, no. 04 * |
| 田刚;: "氧化-沉淀法处理冶炼废水中铊的研究", 山西冶金, no. 04 * |
| 邱建森;林凡;林国标;方荣茂;吴开兴;: "金铜冶炼企业含铊废水处理工艺研究与运用", 世界有色金属, no. 18, pages 175 - 178 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3842907B2 (en) | Treatment of metal-containing wastewater and method for recovering valuable metals | |
| JP5579414B2 (en) | Treatment method for wastewater containing reducing selenium | |
| CN102923874B (en) | Method for processing wastewater containing heavy metal ions | |
| CN103787537B (en) | A kind for the treatment of process of sewage and application thereof | |
| CN107162276B (en) | Chromium removal method for ferric trichloride etching waste liquid | |
| CN110759532A (en) | High-salt concentrated water treatment process for producing iron phosphate by sodium method | |
| CN111252942A (en) | Imidazole-containing chemical silver plating wastewater treatment system and method | |
| CN111320316A (en) | Landfill leachate membrane concentrated solution treatment method | |
| CN109437277B (en) | Method for green and efficient recovery of copper ions | |
| CN112158932B (en) | Magnetic zero-valent iron polyaluminum chloride composite flocculant and preparation method and application thereof | |
| JP2002192168A (en) | Method for separating and recovering nickel and zinc from nickel and zinc-containing wastewater or sludge | |
| CN112897730A (en) | System and method for treating and recycling high-arsenic high-fluorine waste acid | |
| CN114772816A (en) | Method for purifying and treating sewage containing heavy metal thallium | |
| CN111320302B (en) | Process for standard emission and efficient sedimentation of low-concentration copper-containing wastewater in semiconductor industry | |
| CN211111439U (en) | Treatment device for high-concentration cyanide-containing wastewater | |
| CN114291957A (en) | Method for purifying dechlorination water washing liquid | |
| JP2621090B2 (en) | Advanced wastewater treatment method | |
| CN103172143A (en) | Method for recycling copper from D-threo-beta-Methylsulfonylphenylserine ethyl ester production wastewater | |
| CN104016551B (en) | Based on the high salinity process for treating industrial waste water of biochemistry treatment | |
| CN111453880A (en) | Method for removing waste liquid containing various heavy metals by combined precipitation method | |
| CN113526778A (en) | Treatment process of high-concentration industrial wastewater | |
| CN213060448U (en) | Device for treating waste acid containing thallium and arsenic | |
| CN213060508U (en) | Device for treating thallium-containing waste acid | |
| CN214829693U (en) | High-salt high-ammonia-nitrogen high-hardness wastewater treatment system | |
| CN210528647U (en) | Arsenic-containing acid making wastewater treatment device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |