CN104445717B - A kind of lead-zinc smelting wastewater reverse osmosis dope is synchronously except fluorine deliming treatment process - Google Patents

A kind of lead-zinc smelting wastewater reverse osmosis dope is synchronously except fluorine deliming treatment process Download PDF

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CN104445717B
CN104445717B CN201410638971.9A CN201410638971A CN104445717B CN 104445717 B CN104445717 B CN 104445717B CN 201410638971 A CN201410638971 A CN 201410638971A CN 104445717 B CN104445717 B CN 104445717B
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reverse osmosis
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CN104445717A (en
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郑金华
曾令成
晏波
王远文
李军群
徐立成
祝云章
刁小东
吴斌秀
肖元法
罗琨
陈涛
肖贤明
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Shaoguan Smelting Factory Of Shenzhen Zhongjin Lingnan Nonfemet Co ltd
Guangzhou Institute of Geochemistry of CAS
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Shaoguan Smelting Factory Of Shenzhen Zhongjin Lingnan Nonfemet Co ltd
Guangzhou Institute of Geochemistry of CAS
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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
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • 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
    • 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

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  • Engineering & Computer Science (AREA)
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  • Separation Using Semi-Permeable Membranes (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

The present invention relates to a kind of lead-zinc smelting wastewater reverse osmosis dope synchronously except fluorine deliming treatment process, its processing step first carries out oxidation precipitation except fluorine, then precipitation deliming is carried out, carry out adsorption-defluorination again, carry out activated alumina regeneration again, carry out regenerative mixed liquid again except fluorine, carry out the deliming of regenerative mixed liquid again, carry out the process of regenerative mixed liquid again, finally carry out precipitation except fluorine, through filter-press dehydration after the unified collection of the precipitating sludge that deliming process produces, press filtration water returns reverse osmosis dope collecting tank circular treatment, the unified process of mud cake.By adopting oxidation, precipitation, reverse osmosis concentrated liquid fluorine, calcium contents, respectively lower than 3mg/L and 50mg/L, solve fouling that in reverse osmosis dope subsequent evaporation concentration process, fluorion, calcium ion cause, blockage problem after adsorption treatment process.

Description

A kind of lead-zinc smelting wastewater reverse osmosis dope is synchronously except fluorine deliming treatment process
Technical field
The invention belongs to industrial waste water treatment, relate to a kind of lead-zinc smelting wastewater reverse osmosis dope synchronously except fluorine deliming treatment process.
Background technology
In recent years, China enters the heavy metal contamination event high-incidence season, and how to occur that children blood lead exceeds standard event, especially the accidental discharge of mine, smelting enterprise is of common occurrence, causes serious ecological environmental pollution.Lead-zinc smelting is the high pollution industry in non-ferrous metal industry, and the discharge of wastewater containing heavy metal contaminants forms to ecological environment security the side of body of seriously endangering.Lead-zinc smelting wastewater water quality is complicated, and its principal pollutant comprise heavy metal ion lead, zinc, cadmium, chromium, cobalt, nickel, copper and arsenic, fluorochemical, muriate etc., general in acid.Day by day exhausted along with improving constantly of requiring of Environmental Protection in China and water resources, advanced treatment and reclamation and the zero release of lead-zinc smelting wastewater more and more come into one's own.
In 2010, golden south of the Five Ridges Shaoguan Smelter determines the zero discharge treatment implementing smelting wastewater, original waste water disposal facility basis adds the reverse osmosis concentration of the dense water of nanofiltration and the evaporative crystallization of reverse osmosis dope, reverse osmosis produced water and evaporation condensed water reach the water quality standard of tap water, fully recovering, in production, achieves the zero release of waste water and full reuse.After Shaoguan Smelter Zero discharging system builds up, waste water treatment process is that chemical precipitation+ultrafiltration+nanofiltration+reverse osmosis+MVR evaporates, owing to containing a certain amount of fluorion and a large amount of calcium ions, sulfate ion in waste water, after film treating processes is concentrated, in reverse osmosis dope, fluorion, calcium ion and sulfate ion content can reach 30-50mg/L, 1000-2000mg/L and 8000-10000mg/L respectively, in system operation, there is serious fouling and clogging in MVR evaporation unit, and matting weak effect, can only use water blast gun physical cleaning, cleaning difficulty is very big.Foulant composition analysis display is containing a large amount of CaF 2and CaSO 4, therefore, in reverse osmosis dope, the removal of fluorion and calcium ion is to the fouling and clogging solving subsequent evaporation equipment, guarantees that its steady running is most important.
Different from regular industrial waste water, for avoiding reverse osmosis membrane because of the fouling and clogging of fluorion, calcium ion, large quantity high performance Scale inhibitors has been added in reverse osmosis equipment operational process, although therefore fluorion in reverse osmosis dope, calcium ion content are higher, but be difficult to natural sedimentation or natural sedimentation process is extremely slow, therefore can not simply adopt traditional precipitation, absorbing process except fluorine, first must destroy the molecular structure of Scale inhibitors in reverse osmosis dope, be beneficial to fluorion and calcium ion and react and generate calcium fluoride precipitate.Research report and practical operating experiences display, fluorinion concentration can be down to 8-10mg/L by conventional calcium precipitation method defluorinating process, and fluorinion concentration can be down to 1-3mg/L by activated alumina adsorption treatment process, therefore, in lead-zinc smelting wastewater reverse osmosis dope, the removal of fluorion must take combination process for water quality characteristic.On the other hand, in reverse osmosis dope, sulfate ion content is high, and current evaporating and concentrating process not yet well solves calcium ion scale problems, in evaporative process, very easily form CaSO 4precipitation causes fouling and clogging, therefore except the synchronous removal of calcium ion in fluorine process is also very important.
Summary of the invention
For overcoming above-mentioned technical disadvantages, the invention provides a kind of lead-zinc smelting wastewater reverse osmosis dope synchronously except fluorine deliming treatment process, it efficiently can remove fluorion in lead-zinc smelting wastewater and calcium ion, for guaranteeing the steady running of follow-up reverse osmosis dope evaporating, concentrating and crystallizing system, the zero release and the full reuse that realize lead-zinc smelting wastewater provide technical support .
The present invention solves the technological method that its technical problem adopts: a kind of lead-zinc smelting wastewater reverse osmosis dope is synchronously except fluorine deliming treatment process, and its processing step is:
Step 1: mass concentration except fluorine, is first the H of 10% by oxidation precipitation 2o 2add in reverse osmosis dope, dosage is 200mg/L, oxidation time 30min, to destroy the scale effect of Scale inhibitors molecule to reverse osmosis concentrated liquid fluorine ion and calcium ion; PH value is adjusted to 8.5-9.0 by the NaOH solution being 10% with mass concentration again, adds PFS and PAM respectively by the concentration of 30mg/L and 5mg/L, and staticly settle 3h after abundant stirring reaction and obtain supernatant liquor, in supernatant liquor, fluorinion concentration is lower than 10mg/L;
Step 2: precipitation deliming, adds the Na that mass concentration is 20% by 1.2 times of calcium ion volumetric molar concentration in reverse osmosis dope in the supernatant liquor of step 1 generation 2cO 3solution, then the PAM adding 5mg/L, staticly settle 3h after abundant stirring reaction and obtain supernatant liquor, in this supernatant liquor, calcium ion concn is lower than 50mg/L;
Step 3: adsorption-defluorination, gets step 2 and obtains supernatant liquor, and through two-stage activated alumina adsorption treatment, sorbent material is particulate state α-Al 2o 3, particle diameter is 2-3mm, and saturated adsorption capacity is 2.0kg/t, and after two-stage adsorption treatment, in reverse osmosis dope, fluorinion concentration, lower than 3mg/L, then enters evaporation concentration system and is for further processing;
Step 4: activated alumina regenerates, after activated alumina absorption described in step 3 is saturated, first carry out back flushing using reverse osmosis produced water as backwashing water, backwashing time 15min, then configures 3% alum liquor as regenerated liquid, pumps into activated alumina filter material layer, regeneration 1.0h, with reverse osmosis produced water wash after regeneration, drip washing time 0.5h, the back flushing waste liquid produced, regeneration waste liquid and ring waste mixed collection are regenerative mixed liquid;
Step 5: regenerative mixed liquid, except fluorine, adds by 2.5 times of fluorion volumetric molar concentration the Ca (OH) that mass concentration is 10% in regenerative mixed liquid 2solution, adds PFS and PAM by the concentration of 30mg/L and 5mg/L simultaneously respectively, to staticly settle after 3h in regenerative mixed liquid fluorinion concentration lower than 10mg/L after abundant stirring reaction;
Step 6: regenerative mixed liquid deliming, adds the Na that mass concentration is 20% by 1.2 times of calcium ion volumetric molar concentration in the regenerative mixed liquid of step 5 acquisition 2cO 3solution, adds PAM by the concentration of 5mg/L simultaneously, to staticly settle after 3h in regenerative mixed liquid calcium ion concn lower than 50mg/L after abundant stirring reaction;
Step 7: regenerative mixed liquid process, the regenerative mixed liquid processed through step 5, step 6 and former lead-zinc smelting wastewater together enter nanofiltration system place;
Step 8: precipitation is except fluorine, and through filter-press dehydration after the unified collection of the precipitating sludge that deliming process produces, press filtration water returns reverse osmosis dope collecting tank circular treatment, the unified process of mud cake.
in described step 4regenerative mixed liquid total amount is 8% of the total treatment capacity of reverse osmosis dope in the regeneration period.
The invention has the beneficial effects as follows: for the disadvantageous effect of Scale inhibitors in reverse osmosis dope to fluorion, calcium ion reaction precipitation, adopt H 2o 2as oxygenant, destroy the scale effect of Scale inhibitors in reverse osmosis dope, guarantee fluorion, calcium ion reaction precipitation effect; By adopting two-stage activated alumina adsorption-defluorination treatment process to precipitation except the reverse osmosis dope after fluorine, deliming, guarantee that in reverse osmosis dope, fluorinion concentration is lower than 3mg/L; Pass through to add Ca (OH) successively by the regenerative mixed liquid produced activated alumina regenerative process 2, the precipitation agent such as PFS, PAM, Na2CO3, guarantee that in regenerative mixed liquid, fluorion, calcium ion concn are respectively lower than 3mg/L and 50mg/L, then together enter nanofiltration treatment system with lead-zinc smelting wastewater to be for further processing, do not produce new efflux wastewater, guarantee the zero release realizing waste water; By adopting oxidation, precipitation, reverse osmosis concentrated liquid fluorine, calcium contents, respectively lower than 3mg/L and 50mg/L, solve fouling that in reverse osmosis dope subsequent evaporation concentration process, fluorion, calcium ion cause, blockage problem after adsorption treatment process.
Accompanying drawing explanation
Fig. 1 is frame structure schematic diagram of the present invention;
Fig. 2 is embodiment of the present invention structural representation.
In Fig. 2: 1-reverse osmosis dope tank, 2-oxidation tank, 3-is except fluorine setting tank, 4-deliming setting tank, 5-ceramic filter, 6-sandfiltration pot, 7-sand filtration tank, 8-primary adsorption tank, 9-secondary absorption tank, 13-regenerative mixed liquid pool, 14-regenerative mixed liquid is except fluorine setting tank, 15-regenerative mixed liquid deliming setting tank, 16-sludge thickener.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further described.
See Fig. 1, a kind of lead-zinc smelting wastewater reverse osmosis dope is synchronously except fluorine deliming treatment process, and its processing step is:
Step 1: mass concentration except fluorine, is first the H of 10% by oxidation precipitation 2o 2add in reverse osmosis dope, dosage is 200mg/L, oxidation time 30min, to destroy the scale effect of Scale inhibitors molecule to reverse osmosis concentrated liquid fluorine ion and calcium ion; PH value is adjusted to 8.5-9.0 by the NaOH solution being 10% with mass concentration again, adds PFS and PAM respectively by the concentration of 30mg/L and 5mg/L, and staticly settle 3h after abundant stirring reaction and obtain supernatant liquor, in supernatant liquor, fluorinion concentration is lower than 10mg/L;
Step 2: precipitation deliming, adds the Na that mass concentration is 20% by 1.2 times of calcium ion volumetric molar concentration in reverse osmosis dope in the supernatant liquor of step 1 generation 2cO 3solution, then the PAM adding 5mg/L, staticly settle 3h after abundant stirring reaction and obtain supernatant liquor, in this supernatant liquor, calcium ion concn is lower than 50mg/L;
Step 3: adsorption-defluorination, gets step 2 and obtains supernatant liquor, and through two-stage activated alumina adsorption treatment, sorbent material is particulate state α-Al 2o 3, particle diameter is 2-3mm, and saturated adsorption capacity is 2.0kg/t, and after two-stage adsorption treatment, in reverse osmosis dope, fluorinion concentration, lower than 3mg/L, then enters evaporation concentration system and is for further processing;
Step 4: activated alumina regenerates, after activated alumina absorption described in step 3 is saturated, first carry out back flushing using reverse osmosis produced water as backwashing water, backwashing time 15min, then 3% alum liquor is configured as regenerated liquid, pump into activated alumina filter material layer, regeneration 1.0h, with reverse osmosis produced water wash after regeneration, drip washing time 0.5h, the back flushing waste liquid produced, regeneration waste liquid and ring waste mixed collection are regenerative mixed liquid, and regenerative mixed liquid total amount is 8% of the total treatment capacity of reverse osmosis dope in the regeneration period;
Step 5: regenerative mixed liquid, except fluorine, adds by 2.5 times of fluorion volumetric molar concentration the Ca (OH) that mass concentration is 10% in regenerative mixed liquid 2solution, adds PFS and PAM by the concentration of 30mg/L and 5mg/L simultaneously respectively, to staticly settle after 3h in regenerative mixed liquid fluorinion concentration lower than 10mg/L after abundant stirring reaction;
Step 6: regenerative mixed liquid deliming, adds the Na that mass concentration is 20% by 1.2 times of calcium ion volumetric molar concentration in the regenerative mixed liquid of step 5 acquisition 2cO 3solution, adds PAM by the concentration of 5mg/L simultaneously, to staticly settle after 3h in regenerative mixed liquid calcium ion concn lower than 50mg/L after abundant stirring reaction;
Step 7: regenerative mixed liquid process, the regenerative mixed liquid processed through step 5, step 6 and former lead-zinc smelting wastewater together enter nanofiltration system place;
Step 8: precipitation is except fluorine, and through filter-press dehydration after the unified collection of the precipitating sludge that deliming process produces, press filtration water returns reverse osmosis dope collecting tank circular treatment, the unified process of mud cake.
embodiment: certain smelterythe reverse osmosis dope that lead-zinc smelting wastewater zero discharge treatment process produces is handling object, and process continuously by technical process of the present invention, treatment scale is 5m 3/ h, see Fig. 2, its algorithm is as follows:
Step one: from reverse osmosis dope tank 1 with 5m 3reverse osmosis dope is continuously pumped into oxidation tank 2 by/h flow, adds the H of 10% with 10L/h flow continuously 2o 2to oxidation tank 2, oxidation tank 2 water outlet gravity flow enters except fluorine setting tank 3, except the vertical-flow setting tank of cylinder centered by fluorine setting tank, with the NaOH solution that mass concentration is 10%, pH value is adjusted to 8.5-9.0, adds PFS and PAM respectively by the concentration of 30mg/L and 5mg/L;
Step 2: except fluorine setting tank 3 water outlet gravity flow enters deliming setting tank 4, add by 1.2 times of calcium ion volumetric molar concentration in reverse osmosis dope the Na that mass concentration is 20% 2cO 3solution, separately adds the PAM of 5mg/L, and deliming setting tank 4 water outlet enters ceramic filter 5;
Step 3: with 5m from ceramic filter 5 3reverse osmosis dope is continuously pumped into sandfiltration pot 6 by/h flow, and sandfiltration pot water outlet enters sand filtration tank 7, then pumps into primary adsorption tank 8 and secondary absorption tank 9 with pump, and adsorption treatment water outlet enters outlet sump 10 storage and treats next step evaporation concentration process;
Step 4: in adsorption treatment water outlet, namely content of fluoride ion must carry out manipulation of regeneration to the activated alumina in adsorption tanks 8 and 9 more than after 3mg/L, first back flushing is carried out to filtering layer during regeneration, using reverse osmosis produced water as backwashing water water source, its filtering layer rate of expansion adopts 30% ~ 50%, recoil time 15min, backwash rate is 12L/m 2s, the back flushing waste liquid of generation enters regenerative mixed liquid pool 13; After back flushing completes, 3% alum liquor configured is pumped into adsorption tanks 8 and 9, flow velocity is 3 ~ 5m/h, recovery time 1.0h, and the fluorine-containing regeneration waste liquid of generation enters regenerative mixed liquid pool 13; Drip washing is carried out, using reverse osmosis produced water as washing water water source, with 2.5m to the activated alumina after regenerated liquid process 3/ h flow is to adsorption tanks drip washing 0.5h, and the ring waste of generation enters regenerative mixed liquid pool 13, completes the manipulation of regeneration of activated alumina;
Step 5: the back flushing waste liquid that activated alumina regenerative process produces, regeneration waste liquid and ring waste are stored in regenerative mixed liquid pool 13, main containing a large amount of fluorions and a certain amount of suspended substance, pumped into regenerative mixed liquid except fluorine setting tank 14, added by 2.5 times of fluorion volumetric molar concentration the Ca (OH) that mass concentration is 10% 2solution, adds PFS and PAM by the concentration of 30mg/L and 5mg/L simultaneously respectively, and regenerative mixed liquid enters regenerative mixed liquid deliming setting tank 15 except fluorine setting tank 14 water outlet, adds by 1.2 times of calcium ion volumetric molar concentration the Na that mass concentration is 20% 2cO 3solution, adds PAM reaction precipitation by the concentration of 5mg/L simultaneously, and in the water outlet of regenerative mixed liquid deliming setting tank 15, fluorion, calcium ion concn are respectively lower than 10mg/L and 50mg/L, and the nanofiltration device directly entering raw wastewater treatment system carries out further concentration;
Step 6: reverse osmosis dope and regenerative mixed liquid precipitate regularly enter sludge thickener 16 except the precipitating sludge produced in fluorine, deliming process, concentrate rear filter-press dehydration further, and the unified process of mud cake, press filtration water returns reverse osmosis dope tank 1.
Performance of main equipment parameter in above-mentioned processing step is as shown in table 1, and during system cloud gray model, once, treatment effect is as shown in table 2 for every 12h sampling analysis:
Table 1 reverse osmosis dope is synchronously except fluorine deliming system major equipment and parameter
Table 2 treatment effect
Illustrate that the present invention is directed to Scale inhibitors in reverse osmosis dope, to the disadvantageous effect of fluorion, calcium ion reaction precipitation, adopts H by upper table 2o 2as oxygenant, destroy the scale effect of Scale inhibitors in reverse osmosis dope, guarantee fluorion, calcium ion reaction precipitation effect; By adopting two-stage activated alumina adsorption-defluorination treatment process to precipitation except the reverse osmosis dope after fluorine, deliming, guarantee that in reverse osmosis dope, fluorinion concentration is lower than 3mg/L; Pass through to add Ca (OH) successively by the regenerative mixed liquid produced activated alumina regenerative process 2, the precipitation agent such as PFS, PAM, Na2CO3, guarantee that in regenerative mixed liquid, fluorion, calcium ion concn are respectively lower than 3mg/L and 50mg/L, then together enter nanofiltration treatment system with lead-zinc smelting wastewater to be for further processing, do not produce new efflux wastewater, guarantee the zero release realizing waste water; By adopting oxidation, precipitation, reverse osmosis concentrated liquid fluorine, calcium contents, respectively lower than 3mg/L and 50mg/L, solve fouling that in reverse osmosis dope subsequent evaporation concentration process, fluorion, calcium ion cause, blockage problem after adsorption treatment process.

Claims (2)

1. lead-zinc smelting wastewater reverse osmosis dope is synchronously except a fluorine deliming treatment process, it is characterized in that processing step is:
Step 1: mass concentration except fluorine, is first the H of 10% by oxidation precipitation 2o 2add in reverse osmosis dope, dosage is 200mg/L, oxidation time 30min, to destroy the scale effect of Scale inhibitors molecule to reverse osmosis concentrated liquid fluorine ion and calcium ion; PH value is adjusted to 8.5-9.0 by the NaOH solution being 10% with mass concentration again, adds PFS and PAM respectively by the concentration of 30mg/L and 5mg/L, and staticly settle 3h after abundant stirring reaction and obtain supernatant liquor, in supernatant liquor, fluorinion concentration is lower than 10mg/L;
Step 2: precipitation deliming, adds the Na that mass concentration is 20% by 1.2 times of calcium ion volumetric molar concentration in reverse osmosis dope in the supernatant liquor of step 1 generation 2cO 3solution, then the PAM adding 5mg/L, staticly settle 3h after abundant stirring reaction and obtain supernatant liquor, in this supernatant liquor, calcium ion concn is lower than 50mg/L;
Step 3: adsorption-defluorination, gets step 2 and obtains supernatant liquor, and through two-stage activated alumina adsorption treatment, sorbent material is particulate state α-Al 2o 3, particle diameter is 2-3mm, and saturated adsorption capacity is 2.0kg/t, and after two-stage adsorption treatment, in reverse osmosis dope, fluorinion concentration, lower than 3mg/L, then enters evaporation concentration system and is for further processing;
Step 4: activated alumina regenerates, after activated alumina absorption described in step 3 is saturated, first carry out back flushing using reverse osmosis produced water as backwashing water, backwashing time 15min, then configures 3% alum liquor as regenerated liquid, pumps into activated alumina filter material layer, regeneration 1.0h, with reverse osmosis produced water wash after regeneration, drip washing time 0.5h, the back flushing waste liquid produced, regeneration waste liquid and ring waste mixed collection are regenerative mixed liquid;
Step 5: regenerative mixed liquid, except fluorine, adds by 2.5 times of fluorion volumetric molar concentration the Ca (OH) that mass concentration is 10% in regenerative mixed liquid 2solution, adds PFS and PAM by the concentration of 30mg/L and 5mg/L simultaneously respectively, to staticly settle after 3h in regenerative mixed liquid fluorinion concentration lower than 10mg/L after abundant stirring reaction;
Step 6: regenerative mixed liquid deliming, adds the Na that mass concentration is 20% by 1.2 times of calcium ion volumetric molar concentration in the regenerative mixed liquid of step 5 acquisition 2cO 3solution, adds PAM by the concentration of 5mg/L simultaneously, to staticly settle after 3h in regenerative mixed liquid calcium ion concn lower than 50mg/L after abundant stirring reaction;
Step 7: regenerative mixed liquid process, the regenerative mixed liquid processed through step 5, step 6 and former lead-zinc smelting wastewater together enter nanofiltration system place;
Step 8: precipitation is except fluorine, and through filter-press dehydration after the unified collection of the precipitating sludge that deliming process produces, press filtration water returns reverse osmosis dope collecting tank circular treatment, the unified process of mud cake.
2. as claimed in claim 1lead-zinc smelting wastewater reverse osmosis dope synchronously except fluorine deliming treatment process, is characterized in that in described step 4regenerative mixed liquid total amount is 8% of the total treatment capacity of reverse osmosis dope in the regeneration period.
CN201410638971.9A 2014-11-13 2014-11-13 A kind of lead-zinc smelting wastewater reverse osmosis dope is synchronously except fluorine deliming treatment process Active CN104445717B (en)

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CN109607868B (en) * 2018-12-29 2022-02-08 河南龙宇煤化工有限公司 Advanced treatment system and advanced treatment method for low-concentration fluorine-containing wastewater
CN111661950B (en) * 2020-04-03 2022-09-23 湖南中金岭南康盟环保科技有限公司 Method for treating lead-zinc smelting waste acid
CN112194296A (en) * 2020-07-15 2021-01-08 广州中科建禹环保有限公司 Treatment system and method for flue gas deacidification waste liquid of hazardous waste incineration workshop
CN112607917A (en) * 2020-12-30 2021-04-06 九江天赐高新材料有限公司 Method and system for treating fluorine-containing wastewater
CN113354171B (en) * 2021-05-13 2022-11-08 西北矿冶研究院 Process method for deep dearsenization from copper smelting waste acid
CN113480045A (en) * 2021-07-22 2021-10-08 北京国电富通科技发展有限责任公司 Fluorine and silicon removal method for reverse osmosis concentrated water
CN113666561B (en) * 2021-08-26 2023-06-09 上海化工研究院有限公司 High-salt sulfur-containing fluorine-containing wastewater treatment process
CN114906950A (en) * 2022-04-22 2022-08-16 云南驰宏锌锗股份有限公司 Deep defluorination treatment method for lead-zinc smelting high-salinity wastewater

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101293717A (en) * 2008-06-05 2008-10-29 佛山市三水凤铝铝业有限公司 Method for processing and recycling wastewater containing fluorine, chromium ion
CN103303996A (en) * 2013-04-02 2013-09-18 中国科学院生态环境研究中心 Application of activated aluminum oxide defluorination adsorbing material with different surface features

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7329357B2 (en) * 2005-05-31 2008-02-12 Ming-Hui Liao Method for removing fluorine from a fluorine-containing wastewater

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101293717A (en) * 2008-06-05 2008-10-29 佛山市三水凤铝铝业有限公司 Method for processing and recycling wastewater containing fluorine, chromium ion
CN103303996A (en) * 2013-04-02 2013-09-18 中国科学院生态环境研究中心 Application of activated aluminum oxide defluorination adsorbing material with different surface features

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