CN106927550B - Method for recovering fluorine-containing industrial wastewater - Google Patents
Method for recovering fluorine-containing industrial wastewater Download PDFInfo
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- CN106927550B CN106927550B CN201710129856.2A CN201710129856A CN106927550B CN 106927550 B CN106927550 B CN 106927550B CN 201710129856 A CN201710129856 A CN 201710129856A CN 106927550 B CN106927550 B CN 106927550B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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Abstract
Recycling of fluorine-containing industrial wastewaterThe method is implemented. The method is characterized by comprising the following steps: adding quicklime or/and slaked lime into the fluorine-containing industrial wastewater, stirring for reaction, and filtering to obtain wet slag containing calcium fluoride and filtrate containing sulfate radicals; mixing the fluorine-containing industrial wastewater with the wet slag containing calcium fluoride, and filtering to obtain calcium fluoride and a washing liquid; adding quicklime or/and slaked lime into the solution containing sulfate radicals, stirring for reaction, and filtering to obtain wet slag containing calcium sulfate and tail liquid; and adding the sulfuric acid solution into the wet slag containing calcium sulfate, stirring, washing and filtering to obtain gypsum. The method separates fluoride ions and sulfate ions, recovers calcium fluoride and gypsum, improves the comprehensive utilization rate of the wastewater resources, and provides convenient conditions for recycling the wastewater. The process of the invention is applicable to F‑Concentration of more than 1.0g/L, SO4 2‑Concentration of more than 2.0g/L, F‑Concentration of Ca in addition to the first main group2+The total concentration of external metal ions is less than 50: 1.
Description
Technical Field
The invention belongs to the field of metallurgical environmental protection and chemical industry, and particularly relates to a method for recovering industrial wastewater containing fluorine and sulfate radicals.
Technical Field
In recent years, with the rapid increase of economy in China, the total discharge amount of fluorine-containing industrial wastewater is sharply increased at a speed of about 10% per year, so that the problem of fluorine pollution is more serious, and the harm to human is more serious. Therefore, active studies have been made on an effective method for recovering and treating fluorine-containing wastewater.
The fluorine-containing industrial wastewater mainly comprises production wastewater of mining and processing fluorine-containing minerals, synthesizing fluoride, treating metal surface, smelting tantalum and niobium by a wet method and the like, and the wastewater usually dischargedMiddle F-Concentrations varying from tens to thousands of mg/l, some F-Concentrations are even as high as several tens of grams per liter. The wastewater often contains a large amount of sulfate ions in addition to fluorine ions. At present, the method for treating fluorine-containing wastewater at home and abroad mainly comprises the following steps: chemical precipitation, coagulating precipitation, adsorption, biological treatment, etc. The chemical precipitation method is most used and developed, is generally used for pretreatment of high-concentration fluorine-containing wastewater, but is not used properly and is easy to cause secondary pollution.
Taking tantalum-niobium hydrometallurgy wastewater as an example, the wastewater is typical high-concentration fluorine-containing wastewater, and specifically comprises three types, namely ① acid-containing raffinate (HF, H) obtained after acid pickling of tantalum-niobium by extraction2SO4Total acidity of about 8-12N, which accounts for about 5% of the waste water from tantalum-niobium hydrometallurgy, ② fluotantalic acid (H)2TaF7) Fluoroxyniobic acid (H)2NbOF5) Neutralizing and precipitating with liquid ammonia to obtain Nb (OH)5/Ta(OH)5The generated neutralization mother liquor is high-alkali high-fluorine wastewater (pH is more than 10, and contains NH)4 +、F-、SO4 2-More than 100g/L of plasma) accounting for about 15 percent of the tantalum-niobium hydrometallurgy wastewater, ③ the rest 80 percent of the tantalum-niobium hydrometallurgy wastewater is washed Nb (OH)5/Ta(OH)5The generated washing wastewater is ammonia-containing wastewater (pH is about 9, containing NH)4 +、F-、SO4 2-Plasma 2-5g/L or so). Studies on classification experiments on various wastewater treatment methods produced by tantalum-niobium hydrometallurgy, such as Zhang Weining, etc., and on the neutralization of acidic wastewater and washing wastewater with calcium oxide (CaO), fluorine and sulfate ion removal (Zhang Weining, Xuzhong, etc.; Studies on wastewater treatment techniques for tantalum-niobium hydrometallurgy [ M]The fifth academic annual meeting discourse of the nonferrous metal society of China; month 8 in 2003: 110-113), but the obtained large amount of neutralized sediment slag needs to be stacked and buried in a large amount of fields, which not only wastes a large amount of fluorine resources, but also generates serious secondary pollution.
Disclosure of Invention
Aiming at the technical problem, the invention provides a method for recovering fluorine-containing industrial wastewater. The method has the advantages of simple process, convenient operation and low investment, and can effectively separate and recover the fluorine ions and the sulfate ions in the fluorine-containing industrial wastewater.
The technical scheme of the invention comprises the following steps:
(1) adjusting the pH of the fluorine-containing industrial wastewater with pH less than 7 to pH more than or equal to 7 by using ammonia gas, ammonia water or sodium hydroxide, filtering to obtain a wastewater filtrate, and piling up waste residues;
(2) adding quick lime or/and hydrated lime according to the molar ratio of calcium to fluorine of 0.53-0.75 according to the content of fluorine in the wastewater, stirring for reaction for 0.2-8.0 hours, and filtering to obtain wet slag containing calcium fluoride and filtrate containing sulfate radicals;
(3) mixing fluorine-containing industrial wastewater with the calcium fluoride-containing wet slag obtained in the step (2) according to a liquid-solid ratio of 3-7: 1, stirring and washing for 1-16 hours, filtering to obtain calcium fluoride and a washed liquid, and merging the washed liquid into the fluorine-containing industrial wastewater;
(4) adding quick lime or/and slaked lime into the filtrate containing sulfate radical obtained in the step (2) according to the calcium-sulfur molar ratio of 1.05-4.0, stirring and reacting for 0.5-8 hours, filtering to obtain wet slag containing calcium sulfate and tail liquid, and recycling the tail liquid;
(5) adding 0.1-0.5 mol/L sulfuric acid solution into the wet slag containing calcium sulfate in the step (4) according to the liquid-solid ratio of 2-5: 1, stirring and washing for 0.2-24 hours, and filtering to obtain gypsum (CaSO)4·2H2O) and dilute sulfuric acid filtrate; and (3) regulating the dilute sulfuric acid filtrate to 0.1-0.5 mol/L by using concentrated sulfuric acid for recycling.
The process of the invention is applicable to F-Concentration of more than 1.0g/L, SO4 2-Concentration of more than 2.0g/L, F-Concentration of Ca in addition to the first main group2+The total concentration of external metal ions is less than 50: 1. Recovered CaF2The content of CaSO exceeds 95 percent4·2H2The O content is over 97 percent, and the product can be directly sold.
The method has the principle and advantages that ① utilizes the difference of solubility products of calcium fluoride and calcium sulfate to precipitate and separate fluorine ions in the wastewater, most sulfate radicals are left in the solution, not only can the fluorine ions and the sulfate radicals be successfully separated, but also the obtained calcium fluoride can be sold as a product after being washed, ② adds quicklime or/and slaked lime to continue precipitating the sulfate ions in the wastewater, and uses dilute sulfuric acid to precipitate excessive lime in the calcium sulfate slag, so that gypsum can be produced, and conditions are provided for recycling the wastewater.
Detailed Description
Example 1: 100L of fluorine-containing industrial wastewater with the pH value of 3.8, introducing ammonia gas to adjust the pH value to 7.8, filtering, and piling up 76.1g of filter residue; filtrate 100L, F-The content of SO was 3.92g/L4 2-The content of the calcium fluoride is 3.15g/L, quicklime is added according to the calcium-fluorine molar ratio of 0.53, the mixture is stirred and reacted for 0.5 hour, the wet slag containing the calcium fluoride is obtained by solid-liquid separation, the weight of the wet slag is 1.68kg, and F-Content 0.03g/L and sulfate group-containing filtrate 98.8L, SO4 2-The content is 3.02 g/L; mixing fluorine-containing industrial wastewater with the obtained wet slag containing calcium fluoride according to the liquid-solid ratio of 3:1, stirring, washing for 1 hour, filtering to obtain calcium fluoride and a washing liquid, drying the calcium fluoride to 898.42g, and adding CaF2Content 95.09%; washing liquid 5.05L, F-Content 1.89g/L, SO4 2-The content is 8.28g/L, and the washed liquid is merged into the fluorine-containing industrial wastewater for the next cycle; adding slaked lime into the filtrate containing sulfate radical according to the calcium-sulfur molar ratio of 1.05, stirring and reacting for 0.5 hour, and carrying out solid-liquid separation to obtain wet slag containing calcium sulfate and tail liquid, wherein the tail liquid can be recycled. 707.76g of wet slag containing calcium sulfate, adding 0.3mol/L sulfuric acid solution according to the liquid-solid ratio of 3:1, stirring and washing for 0.2 h, filtering and drying to obtain 600.89g of gypsum with the content of 97.38 percent and dilute sulfuric acid filtrate; and regulating the dilute sulfuric acid filtrate to 0.3mol/L by using concentrated sulfuric acid.
Example 2: fluorine-containing industrial wastewater 50L, pH 10.8, F-Content 48.38g/L and SO4 2-The content of the calcium fluoride is 72.40g/L, slaked lime is added according to the calcium-fluorine molar ratio of 0.7, the mixture is stirred and reacted for 4 hours, the wet slag containing the calcium fluoride is obtained by solid-liquid separation, the weight of the wet slag is 13.62kg, and F-Content 0.01g/L and sulfate group-containing filtrate 44.9L, SO4 2-The content is 62.48 g/L; mixing, stirring and washing fluorine-containing industrial wastewater and the obtained wet slag containing calcium fluoride for 8 hours according to a liquid-solid ratio of 5:1, filtering to obtain calcium fluoride and a washing liquid, drying the calcium fluoride by 7.38kg, and drying CaF297.25% of washing liquid 68.2L, F-Content of 36.35g/L, SO4 2-The content is 102.79g/L, and the washed liquid is merged into the fluorine-containing industrial wastewater for the next cycle; adding quicklime to the filtrate containing sulfate radical according to the calcium-sulfur molar ratio of 2.5, stirring and reacting for 4 hours, and carrying out solid-liquid separation to obtain wet slag containing calcium sulfate and tail liquid, wherein the tail liquid can be recycled. Adding a 0.1mol/L sulfuric acid solution into wet residues containing calcium sulfate according to the liquid-solid ratio of 5:1, stirring and washing for 0.5 hour, filtering and drying to obtain 12.84kg of gypsum with the content of 97.05 percent and dilute sulfuric acid filtrate; and regulating the dilute sulfuric acid filtrate to 0.1mol/L by using concentrated sulfuric acid.
Example 3: fluorine-containing industrial wastewater 100L, pH 7.8, F-The content of SO was 19.04g/L4 2-26.69g/L, respectively adding quicklime with calcium-fluorine molar ratio of 0.6 and slaked lime with calcium-fluorine molar ratio of 0.6, stirring for reaction for 8 hr, and performing solid-liquid separation to obtain wet residue of calcium fluoride (weight of 8.93kg, F)-Content 0.05g/L and sulfate group-containing filtrate 97.1L, SO4 2-The content is 24.18 g/L; mixing, stirring and washing the fluorine-containing industrial wastewater with the obtained crude calcium fluoride for 16 hours according to the liquid-solid ratio of 7:1, performing solid-liquid separation to obtain calcium fluoride and a washing liquid, drying the calcium fluoride to weight 4.89kg, wherein CaF295.40% of content, 62.5L of washing liquid, wherein F-The content of SO is 15.06g/L4 2-The content is 36.74g/L, and the washed liquid is merged into the fluorine-containing industrial wastewater for the next cycle; adding quicklime with the calcium-sulfur molar ratio of 2 and slaked lime with the calcium-sulfur molar ratio of 2 to the leaching solution containing sulfate radicals, stirring and reacting for 8 hours, and carrying out solid-liquid separation to obtain wet slag containing calcium sulfate and tail liquid, wherein the tail liquid can be recycled. The wet slag containing calcium sulfate weighs 20.23kg, 0.2mol/L sulfuric acid solution is added according to the liquid-solid ratio of 2:1, stirring and washing are carried out for 24 hours, and 17.19kg of gypsum with the content of 97.82 percent and dilute sulfuric acid filtrate are obtained after filtration and drying; and regulating the dilute sulfuric acid filtrate to 0.2mol/L by using concentrated sulfuric acid.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is to be understood that all changes and modifications that come within the spirit of the invention are desired to be protected by the following claims.
Claims (1)
1. Recycling method of fluorine-containing industrial wastewaterMethod of the fluorine-containing industrial wastewater F-Concentration of more than 1.0g/L, SO4 2-Concentration of more than 2.0g/L, F-Concentration of Ca in addition to the first main group2+The total concentration of external metal ions is less than 50:1, and the method is characterized by comprising the following steps:
(1) adjusting the pH of the fluorine-containing industrial wastewater with pH less than 7 to pH more than or equal to 7 by using ammonia gas, ammonia water or sodium hydroxide, filtering to obtain a wastewater filtrate, and piling up waste residues;
(2) adding quick lime or/and hydrated lime according to the molar ratio of calcium to fluorine of 0.53-0.75 according to the content of fluorine in the wastewater, stirring for reaction for 0.2-8.0 hours, and filtering to obtain wet slag containing calcium fluoride and filtrate containing sulfate radicals;
(3) mixing fluorine-containing industrial wastewater with the calcium fluoride-containing wet slag obtained in the step (2) according to a liquid-solid ratio of 3-7: 1, stirring and washing for 1-16 hours, filtering to obtain calcium fluoride and a washed liquid, and merging the washed liquid into the fluorine-containing industrial wastewater;
(4) adding quick lime or/and slaked lime into the filtrate containing sulfate radical obtained in the step (2) according to the calcium-sulfur molar ratio of 1.05-4.0, stirring and reacting for 0.5-8 hours, filtering to obtain wet slag containing calcium sulfate and tail liquid, and recycling the tail liquid;
(5) adding 0.1-0.5 mol/L sulfuric acid solution into the wet slag containing calcium sulfate in the step (4) according to the liquid-solid ratio of 2-5: 1, stirring and washing for 0.2-24 hours, and filtering to obtain gypsum (CaSO)4·2H2O) and dilute sulfuric acid filtrate; adjusting the dilute sulfuric acid filtrate to 0.1-0.5 mol/L with concentrated sulfuric acid for recycling;
recovered CaF2The content of CaSO exceeds 95 percent4·2H2The O content is over 97 percent and all the products are sold.
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| CN108249617B (en) * | 2018-01-14 | 2019-04-12 | 深圳市创飞格环保技术有限公司 | A kind of trade effluent recovery and treatment method |
| CN108373140A (en) * | 2018-02-26 | 2018-08-07 | 中南大学 | A method of removing fluorine from sulfate liquor |
| CN112811555A (en) * | 2021-02-05 | 2021-05-18 | 盛隆资源再生（无锡）有限公司 | Recycling method of fluorine-containing sulfuric acid waste liquid |
| CN115368628B (en) * | 2022-08-18 | 2024-03-19 | 无锡中天固废处置有限公司 | Desalination regeneration method of salt-containing polyethylene glycol waste liquid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0758627A3 (en) * | 1995-08-16 | 1997-04-16 | Sharp Kk | Water treating method and apparatus treating waste water by using ion exchange resin |
| CN101811792A (en) * | 2009-02-24 | 2010-08-25 | 宝山钢铁股份有限公司 | Processing method of stainless steel cold rolling pickling wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0758627A3 (en) * | 1995-08-16 | 1997-04-16 | Sharp Kk | Water treating method and apparatus treating waste water by using ion exchange resin |
| CN101811792A (en) * | 2009-02-24 | 2010-08-25 | 宝山钢铁股份有限公司 | Processing method of stainless steel cold rolling pickling wastewater |
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Address after: 510650 No. 363, Changxin Road, Guangzhou, Guangdong, Tianhe District Patentee after: Institute of resources comprehensive utilization, Guangdong Academy of Sciences Patentee after: Simei resources (Guangdong) Co.,Ltd. Address before: 510650 No. 363, Changxin Road, Guangzhou, Guangdong, Tianhe District Patentee before: GUANGDONG INSTITUTE OF RESOURCES COMPREHENSIVE UTILIZATION Patentee before: GUANGDONG ZHIYUAN NEW MATERIALS Co.,Ltd. |
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Address after: 510651 No. 363, Changxin Road, Guangzhou, Guangdong, Tianhe District Patentee after: Institute of resource utilization and rare earth development, Guangdong Academy of Sciences Patentee after: Simei resources (Guangdong) Co.,Ltd. Address before: No. 363, Changxing Road, Tianhe District, Guangzhou City, Guangdong Province Patentee before: Institute of resources comprehensive utilization, Guangdong Academy of Sciences Patentee before: Simei resources (Guangdong) Co.,Ltd. |
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