CN113860552A - Method for removing fluorine and chlorine in mine smelting wastewater - Google Patents
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C—CHEMISTRY; METALLURGY
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- 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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- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
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- C02F2101/00—Nature of the contaminant
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- C02F2101/14—Fluorine or fluorine-containing compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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Abstract
The invention discloses a method for removing fluorine and chlorine in mine smelting wastewater, which specifically comprises the following steps: precisely filtering the feed liquid; homogenizing and adjusting; separating fluorine and chlorine by membrane mass transfer; and (4) recovering fluorine and chlorine. The method improves the removal rate of fluorine and chlorine, is beneficial to the improvement of clean production process in the smelting industry, is economic, has lower cost, does not introduce other ions, and has the advantages of universality, compact equipment structure, low investment, small occupied area, high fluorine and chlorine removal efficiency and the like.
Description
Technical Field
The invention relates to the technical field of reducing pollution and improving comprehensive utilization of wastewater resources, in particular to a method for removing fluorine and chlorine in mine smelting wastewater.
Background
Fluorine and chlorine are impurity ions frequently generated in the non-ferrous metal smelting process, and the existence of fluorine and chlorine influences the quality of the air environment, corrodes equipment, influences the quality of electrodeposition products and the like.
Zinc hydrometallurgy is the most main zinc hydrometallurgy method at present, oxidation roasting-neutral acidic combined leaching-purification-electrolysis are adopted to prepare metal zinc, and a large amount of high-polluted acid, strong-acidic and difficultly-treated polluted acid can be generated in a roasting flue gas acid preparation and acidic leaching working section. The sulfuric acid content in the waste acid is as high as 50g/L, and the waste acid can be utilized or discharged after further treatment due to the characteristics of large water amount, high acidity, mixed components, large harm and the like.
The main component of the waste acid generated in the copper and zinc smelting process is sulfuric acid, but the waste acid cannot be directly reused in a system or sold due to the fact that the waste acid contains heavy metals, particularly fluorine and chlorine ions. The main methods for treating the waste acid include lime neutralization, direct concentration and distillation concentration. At present, the mainstream method is still a lime neutralization method, namely, a lime reagent is added into the waste acid, the end point pH is controlled, gypsum slag is generated after reaction, and the treated waste acid is obtained through solid-liquid separation. But because the acid content of the waste acid is high, the reagent consumption of the neutralization process is large, the operation cost is high, and a large amount of neutralization slag is generated.
The existing fluorine and chlorine removal methods mainly comprise a precipitation method and a stripping method. The precipitation method adopts copper salt to precipitate copper and adopts calcium salt to precipitate fluorine, the cost of the copper method for precipitating chloride ions is high, and the problem that valuable components in feed liquid are difficult to recover in the calcium salt fluorine precipitation is solved. The blowing-off method for removing fluorine and chlorine has the problems of high energy consumption, high equipment investment, large occupied area and the like.
In summary, due to various problems in the prior art, the treatment of the waste acid is still forced to adopt a lime neutralization method, and how to simply, economically and efficiently realize the recycling of the waste acid is an urgent problem to be solved in the industry.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for removing fluorine and chlorine in mine smelting wastewater, which can effectively remove fluorine and chlorine in feed liquid by strengthening multiphase mass transfer, realize the purification of the feed liquid and solve the bottleneck technical problem of removing fluorine and chlorine from waste acid and electrolyte in the zinc smelting process.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for removing fluorine and chlorine in mine smelting wastewater specifically comprises the following steps:
s1, precise filtering of the feed liquid: precisely filtering the feed liquid to be treated by using precise filtering equipment, and controlling the content of suspended substances in the filtrate to be lower than 1.0 mg/L;
s2, homogenizing and adjusting: charging air into the feed liquid after the precise filtration treatment, adding sulfuric acid if the pH of the feed liquid is more than 0.5, controlling the pH of the feed liquid to be equal to or lower than 0.5, and not adding sulfuric acid if the pH of the feed liquid is equal to or lower than 0.5;
s3, membrane mass transfer separation of fluorine and chlorine: pumping the feed liquid obtained after the homogenization adjustment in the step S2 into a hydrophobic membrane mass transfer device, and keeping the temperature of the feed liquid at 50-70 ℃; in the membrane mass transfer equipment, microporous membranes are arranged on two sides of a feed liquid channel, feed liquid flows through the feed liquid channel, absorption alkali liquor is arranged outside the microporous membranes, fluorine and chlorine in the feed liquid are diffused into the absorption alkali liquor through the microporous membranes under the action of directional mass transfer separation of the microporous membranes on the fluorine and chlorine, and the removal of the fluorine and chlorine in the feed liquid is realized;
s4, fluorine and chlorine recovery: adding calcium hydroxide into the absorption alkali liquor finally obtained in the step S3, filtering and recovering calcium fluoride, then adding solid sodium hydroxide, increasing the alkali concentration, continuing to use as the absorption alkali liquor, circularly accumulating the concentration of sodium chloride, and realizing supersaturated crystallization and precipitation of sodium chloride; the recovered calcium fluoride is sold to the metallurgical industry as fluorite ore, and the sodium chloride is sold as a snow melting agent or as a raw material in the chlor-alkali industry.
Further, in step S1, the precision filtration equipment is ceramic membrane filtration equipment, polyvinylidene fluoride filtration equipment or polytetrafluoroethylene filtration equipment.
Further, in step S2, the flow rate of the air is 1-5m per ton of water3/h。
Further, in step S3, the mass concentration of the absorbed alkali liquor is 5-50%.
Further, in step S3, the contact residence time of the feed liquid in the membrane mass transfer device is 1-10 h.
Further, in step S3, the microporous membrane is prepared by the following process:
adding polyvinylidene fluoride into an N, N-dimethylformamide solution, wherein the mass ratio of the N, N-dimethylformamide solution to the polyvinylidene fluoride is 2-4: 1, controlling the reaction temperature to be 60-70 ℃, after reacting for 1-2h, gradually adding polyethylene glycol, tri-N-octylamine and quaternized chitosan, wherein the adding amount of the polyethylene glycol is 10-30% of the mass of the polyvinylidene fluoride, the adding amount of the tri-N-octylamine is 0.5-5% of the mass of the polyvinylidene fluoride, the adding amount of the quaternized chitosan is 0.1-0.3% of the mass of the polyvinylidene fluoride, reacting for 2h again, standing and curing; the cured product is extruded, molded and expanded under high pressure, and then sintered for 20-60min at the temperature of 350-400 ℃ and molded.
Further, in step S3, the microporous membrane has a pore size ratio of 70 to 90% and a pore size of 0.05 to 0.2 μm.
The invention has the beneficial effects that: the method improves the removal rate of fluorine and chlorine, is beneficial to the improvement of clean production process in the smelting industry, is economic, has lower cost, does not introduce other ions, and has the advantages of universality, compact equipment structure, low investment, small occupied area, high fluorine and chlorine removal efficiency and the like.
Drawings
FIG. 1 is a schematic flow chart of the method of examples 1 to 3 of the present invention;
FIG. 2 is a schematic diagram of the principle of fluorine and chlorine removal of feed liquid in membrane mass transfer equipment in examples 1-3 of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings, and it should be noted that the present embodiment is based on the technical solution, and the detailed implementation and the specific operation process are provided, but the protection scope of the present invention is not limited to the present embodiment.
Example 1
In waste acid generated by a certain zinc smelting plant in Xinjiang, the concentration of sulfuric acid is 35g/L, the concentration of fluorine ions is 1.5g/L, the concentration of chlorine ions is 3.8g/L, and the content of fluorine and chlorine in waste acid is high, so that the waste acid cannot be directly used as a medicament. As shown in figure 1, the feed liquid is subjected to precise filtration by using a ceramic membrane filtration device, the content of suspended matters is controlled to be about 0.5mg/L, then air is introduced into the filtrate, and the aeration amount per ton of water is controlled to be 3-5m3H is used as the reference value. Then pumping the feed liquid into a membrane mass transfer device, controlling the temperature of the feed liquid to be about 65-70 ℃ through a heating pipe, and controlling the initial concentration of the absorbed alkali liquor to be 40-50%. As shown in figure 2, in the membrane mass transfer device, microporous membranes are arranged on two sides of a feed liquid channel, feed liquid flows through the feed liquid channel, and alkali liquor is absorbed outside the microporous membranes. After 8-10h of reaction, the concentration of the fluorinion in the feed liquid is 8mg/L, the concentration of the chloridion is 15mg/L, the concentration of the sulfuric acid is 34g/L, and the feed liquid can be directly used as a leaching agent of zinc ore. After the absorption alkali liquor is circulated for a certain period, adding industrial-grade calcium hydroxide into the alkali liquor, filtering and recovering calcium fluoride, selling the calcium fluoride as a fluxing agent for electrolytic aluminum, recovering sodium chloride through supersaturated crystallization, using the sodium chloride as a chlorine-alkali industrial raw material, and returning the mother liquor alkali liquor for recycling. The preparation process of the microporous membrane comprises the following steps: adding polyvinylidene fluoride into N, N-dimethylformamide solution, wherein the mass ratio of the N, N-dimethylformamide solution to the polyvinylidene fluoride is 4: 1, controlling the reaction temperature to be 65-70 ℃, after reacting for 2 hours, gradually adding polyethylene glycol, tri-N-octylamine and quaternized chitosan, wherein the addition amount of the polyethylene glycol is that of the polyvinylidene fluoride30% of the mass of the olefin, 5% of tri-n-octylamine and 0.3% of the mass of the polyvinylidene fluoride, reacting for 2 hours again, standing and curing; the cured product is extruded, molded and expanded under high pressure, and then sintered for 60min at 400 ℃ and molded.
The prepared microporous membrane has the aperture ratio of 90 percent, the aperture of 0.2 micron, the inner diameter of the hollow membrane of less than 0.45mm, the outer diameter of less than 1.1mm and the membrane wall thickness of 0.3 mm.
Example 2
In waste acid generated by a certain lead-zinc smelting plant in the north, the concentration of sulfuric acid is 120g/L, the concentration of fluorine ions is 0.6g/L, and the concentration of chlorine ions is 1.8 g/L. As shown in figure 1, the feed liquid is precisely filtered by adopting ceramic membrane filtering equipment, and the content of suspended matters is controlled to be lower than 0.5 mg/L. Introducing air into the filtrate, and controlling aeration amount per ton of water at 1.0m3H is used as the reference value. The temperature of the feed liquid pumped into the membrane mass transfer equipment is controlled to be about 60 ℃ by a heating pipe, and the initial concentration of the absorbed alkali liquor is 5%. As shown in figure 2, in the membrane mass transfer device, microporous membranes are arranged on two sides of a feed liquid channel, feed liquid flows through the feed liquid channel, and alkali liquor is absorbed outside the microporous membranes. Through the directional mass transfer separation effect of the microporous membrane on fluorine and chlorine, fluorine and chlorine in the feed liquid are diffused into the carrying handle through the micropores, and the removal of fluorine and chlorine in the feed liquid is realized. After reacting for 1h, the concentration of the fluorinion in the feed liquid is 9mg/L, the concentration of the chlorion is 12mg/L, the concentration of the sulfuric acid is 108g/L, and the feed liquid can be directly used as a leaching agent of zinc ore or a copper extraction back-extraction agent. After the absorption alkali liquor is circulated for a certain period, adding industrial-grade calcium hydroxide into the alkali liquor, filtering and recovering calcium fluoride, selling the calcium fluoride as a fluxing agent of electrolytic aluminum, recovering sodium chloride through supersaturated crystallization, selling the sodium chloride as a snow melting agent, and returning the sodium chloride crystallization mother liquor for recycling after supplementing alkali.
The processing technology of the microporous membrane comprises the following steps: adding polyvinylidene fluoride into an N, N-dimethylformamide solution, wherein the mass ratio of the N, N-dimethylformamide solution to the polyvinylidene fluoride is 2: 1, controlling the reaction temperature to be 60 ℃, gradually adding polyethylene glycol, tri-N-octylamine and quaternized chitosan after reacting for 1h, wherein the addition amount of the polyethylene glycol is 10% of the mass of the polyvinylidene fluoride, the addition amount of the tri-N-octylamine is 0.5% of the mass of the polyvinylidene fluoride, the addition amount of the quaternized chitosan is 0.1% of the mass of the polyvinylidene fluoride, standing and curing after reacting for 2h again; the cured product is extruded, molded and expanded under high pressure, and then sintered for 20min at 350 ℃ and molded. The aperture ratio is 70%, the aperture is 0.05 micron, the inner diameter of the hollow membrane is less than 0.45mm, the outer diameter is less than 1.1mm, and the wall thickness of the tube is 0.2 mm.
Example 3
In zinc electrolysis leachate of certain zinc smelting plant in Guangdong, the concentration of zinc is 130g/L, the concentration of fluorine ions is 0.8g/L, the concentration of chlorine ions is 2.5g/L, and the pH value is 5. The feed liquid is precisely filtered by a PVDF organic membrane, the content of suspended matters is controlled to be lower than 0.8mg/L, then sulfuric acid is added to regulate the pH value to be 0.5, air is introduced into the filtrate, and the aeration amount per ton of water is controlled to be 2.0-4.0m3H is used as the reference value. The temperature of the feed liquid pumped into the membrane mass transfer equipment is controlled to be about 60-65 ℃ by a heating pipe, and the initial concentration of the absorbed alkali liquor is 25-35%. The feed liquid flows through the feed liquid channel, and the outside of the microporous membrane absorbs alkali liquor. Through the directional mass transfer separation effect of the microporous membrane on fluorine and chlorine, fluorine and chlorine in the feed liquid are diffused into the carrying handle through the micropores, and the removal of fluorine and chlorine in the feed liquid is realized. After reacting for 4-6h, the concentration of fluorine ions in the feed liquid is 5mg/L, the concentration of chlorine ions is 10mg/L, and the treated electrolyte can enter a zinc electrolytic cell for electrodeposition and zinc recovery. After the receiving solution is circulated for a certain period, adding industrial-grade calcium hydroxide into the receiving solution, filtering and recovering calcium fluoride, selling the calcium fluoride as a steel smelting material, recovering sodium chloride through supersaturated crystallization, and using the sodium chloride as a chlor-alkali industrial raw material, wherein the mother liquor alkali liquor is returned for recycling. The preparation process of the microporous membrane comprises the following steps: adding polyvinylidene fluoride into an N, N-dimethylformamide solution, wherein the mass ratio of the N, N-dimethylformamide solution to the polyvinylidene fluoride is 2-3: 1, controlling the reaction temperature to be 60-65 ℃, after reacting for 1-2h, gradually adding polyethylene glycol, tri-N-octylamine and quaternized chitosan, wherein the adding amount of the polyethylene glycol is 15-20% of the mass of the polyvinylidene fluoride, the adding amount of the tri-N-octylamine is 1.5-2.5% of the mass of the polyvinylidene fluoride, the adding amount of the quaternized chitosan is 0.2-0.3% of the mass of the polyvinylidene fluoride, reacting for 1.5h again, standing and curing; the cured product is extruded, molded and expanded under high pressure, and then sintered for 40-50min at the temperature of 350-400 ℃ and molded. The obtained microporous membrane has a pore diameter ratio of 75-80%, a pore diameter of 0.05-0.15 μm, an inner diameter of less than 0.45mm, an outer diameter of less than 1.1mm, and a membrane wallThe thickness is 0.2-0.3 mm.
The existing blowing-off treatment process for fluorine-chlorine wastewater has large floor area and high investment, the method of the embodiment 1-3 has the investment of 60 percent of the blowing-off process, the floor area of 40 percent of the blowing-off process and the treatment cost of 70 percent of the blowing-off process, and has positive economic and technical advantages.
Various corresponding changes and modifications can be made by those skilled in the art based on the above technical solutions and concepts, and all such changes and modifications should be included in the protection scope of the present invention.
Claims (7)
1. A method for removing fluorine and chlorine in mine smelting wastewater is characterized by comprising the following steps:
s1, precise filtering of the feed liquid: precisely filtering the feed liquid to be treated by using precise filtering equipment, and controlling the content of suspended substances in the filtrate to be lower than 1.0 mg/L;
s2, homogenizing and adjusting: charging air into the feed liquid after the precise filtration treatment, adding sulfuric acid if the pH of the feed liquid is more than 0.5, controlling the pH of the feed liquid to be equal to or lower than 0.5, and not adding sulfuric acid if the pH of the feed liquid is equal to or lower than 0.5;
s3, membrane mass transfer separation of fluorine and chlorine: pumping the feed liquid obtained after the homogenization adjustment in the step S2 into a hydrophobic membrane mass transfer device, and keeping the temperature of the feed liquid at 50-70 ℃; in the membrane mass transfer equipment, microporous membranes are arranged on two sides of a feed liquid channel, feed liquid flows through the feed liquid channel, absorption alkali liquor is arranged outside the microporous membranes, fluorine and chlorine in the feed liquid are diffused into the absorption alkali liquor through the microporous membranes under the action of directional mass transfer separation of the microporous membranes on the fluorine and chlorine, and the removal of the fluorine and chlorine in the feed liquid is realized;
s4, fluorine and chlorine recovery: adding calcium hydroxide into the absorption alkali liquor finally obtained in the step S3, filtering and recovering calcium fluoride, then adding solid sodium hydroxide, increasing the alkali concentration, continuing to use as the absorption alkali liquor, circularly accumulating the concentration of sodium chloride, and realizing supersaturated crystallization and precipitation of sodium chloride; the recovered calcium fluoride is sold to the metallurgical industry as fluorite ore, and the sodium chloride is sold as a snow melting agent or as a raw material in the chlor-alkali industry.
2. The method according to claim 1, wherein in step S1, the precision filtration equipment is ceramic membrane filtration equipment, polyvinylidene fluoride filtration equipment or polytetrafluoroethylene filtration equipment.
3. The method of claim 1, wherein the flow rate of the charge air is 1-5m per ton of water charge air in step S23/h。
4. The method according to claim 1, wherein in step S3, the mass concentration of the absorption lye is 5-50%.
5. The method of claim 1, wherein in step S3, the contact residence time of the feed liquid in the membrane mass transfer device is 1-10 h.
6. The method of claim 1, wherein in step S3, the microporous membrane is prepared by:
adding polyvinylidene fluoride into an N, N-dimethylformamide solution, wherein the mass ratio of the N, N-dimethylformamide solution to the polyvinylidene fluoride is 2-4: 1, controlling the reaction temperature to be 60-70 ℃, after reacting for 1-2h, gradually adding polyethylene glycol, tri-N-octylamine and quaternized chitosan, wherein the adding amount of the polyethylene glycol is 10-30% of the mass of the polyvinylidene fluoride, the adding amount of the tri-N-octylamine is 0.5-5% of the mass of the polyvinylidene fluoride, the adding amount of the quaternized chitosan is 0.1-0.3% of the mass of the polyvinylidene fluoride, reacting for 2h again, standing and curing; the cured product is extruded, molded and expanded under high pressure, and then sintered for 20-60min at the temperature of 350-400 ℃ and molded.
7. The method of claim 1 or 6, wherein in step S3, the microporous membrane has a pore size ratio of 70-90% and a pore size of 0.05-0.2 μm.
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| CN108975586A (en) * | 2018-07-16 | 2018-12-11 | 肖平 | Fluorine-containing in tantalum and niobium hydrometallurgy, nitrogen-containing wastewater recovery and treatment method |
| CN109650628A (en) * | 2019-01-08 | 2019-04-19 | 南京圣创科技有限公司 | A method of separating the halide ions such as chlorine, fluorine from sulfate |
| WO2019231004A1 (en) * | 2018-05-28 | 2019-12-05 | 주식회사 영풍 | Zero-liquid discharge process |
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2021
- 2021-10-11 CN CN202111182920.6A patent/CN113860552B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03165814A (en) * | 1989-11-24 | 1991-07-17 | Mitsubishi Heavy Ind Ltd | Method for removing impurity from solution after gypsum separation |
| JP2011212570A (en) * | 2010-03-31 | 2011-10-27 | Ube Industries Ltd | Method and apparatus for treating fluorine compound-containing wastewater |
| CN105540973A (en) * | 2015-12-28 | 2016-05-04 | 中南大学 | Method for purifying and recycling high arsenic polluted acid wastewater |
| CN108191118A (en) * | 2018-01-31 | 2018-06-22 | 南京大学 | A kind of method for recycling fluorinion in waste water |
| WO2019231004A1 (en) * | 2018-05-28 | 2019-12-05 | 주식회사 영풍 | Zero-liquid discharge process |
| CN108975586A (en) * | 2018-07-16 | 2018-12-11 | 肖平 | Fluorine-containing in tantalum and niobium hydrometallurgy, nitrogen-containing wastewater recovery and treatment method |
| CN109650628A (en) * | 2019-01-08 | 2019-04-19 | 南京圣创科技有限公司 | A method of separating the halide ions such as chlorine, fluorine from sulfate |
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