CN105036406A - Novel wastewater fluorine-removing technology - Google Patents
Novel wastewater fluorine-removing technology Download PDFInfo
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- CN105036406A CN105036406A CN201510379416.3A CN201510379416A CN105036406A CN 105036406 A CN105036406 A CN 105036406A CN 201510379416 A CN201510379416 A CN 201510379416A CN 105036406 A CN105036406 A CN 105036406A
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- Prior art keywords
- filtrate
- gypsum
- neutralization
- waste water
- controls
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- 239000002351 wastewater Substances 0.000 title claims abstract description 31
- 238000005516 engineering process Methods 0.000 title abstract description 4
- 239000000706 filtrate Substances 0.000 claims abstract description 33
- 239000010440 gypsum Substances 0.000 claims abstract description 25
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 25
- 238000005189 flocculation Methods 0.000 claims abstract description 23
- 230000016615 flocculation Effects 0.000 claims abstract description 23
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 12
- 239000002893 slag Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 32
- 238000006386 neutralization reaction Methods 0.000 claims description 23
- 229940037003 alum Drugs 0.000 claims description 10
- 238000010979 pH adjustment Methods 0.000 claims description 9
- 238000004334 fluoridation Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 238000006115 defluorination reaction Methods 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000005987 sulfurization reaction Methods 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 abstract description 15
- 239000011737 fluorine Substances 0.000 abstract description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 14
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 4
- 238000004073 vulcanization Methods 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract 2
- 231100000719 pollutant Toxicity 0.000 abstract 2
- 239000002699 waste material Substances 0.000 abstract 2
- 239000005997 Calcium carbide Substances 0.000 abstract 1
- 239000008394 flocculating agent Substances 0.000 abstract 1
- -1 fluorine ions Chemical class 0.000 abstract 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000000356 contaminant Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 159000000013 aluminium salts Chemical class 0.000 description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000015598 salt intake Nutrition 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Removal Of Specific Substances (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention relates to a novel wastewater fluorine-removing technology. The original technology and equipment can be maximally utilized, waste acid is subjected to a vulcanization treatment so as to remove most heavy metal pollutants, then the waste acid is pre-neutralized in the gypsum step, and the fluorine content of gypsum filtrate in the outlet can be controlled under 60-100 mg/L. Then calcium carbide slag is used to neutralize gypsum filtrate, a flocculating agent is added to carry out flocculation, finally the filtrate is filtered to remove the heavy metal pollutants in wastewater, and the fluorine concentration of the flocculation filtrate can be controlled under 20 to 40 mg/L. Then an aluminum sulfate solution is added to absorb and complex the fluorine ions, the fluorine concentration of wastewater can be reduced to 5 mg/L or less, and other element concentrations are qualified.
Description
Technical field
The present invention relates to a kind of process metallurgy industry high-concentration fluorine-containing waste water technique, be the FLUORIDE REMOVAL IN WASTEWATER technique adopting step-by-step precipitation method to combine with absorption method, belong to industrial waste water treatment.
Background technology
The industries such as smelting affect by fluorine-containing in raw material, the normal fluorochemical containing higher concentration in the acid waste water produced in production process.For these waste water, current most domestic enterprise there is no perfect in fluorine facility.First waste water generally adopt sulfuration method to carry out pre-treatment, by adding Na
2s solution removal major part heavy metal contaminants, fluorine can not be removed in this link, then by adding milk of lime CaCO
3solution carries out pre-neutralization, about control PH3 ~ 5, utilizes the precipitator method to make fluorion and calcium ion generate throw out CaF
2, remove most fluorine.Remove the heavy metal contaminants such as As, Zn, Cd again, meet the requirement of qualified discharge.The shortcoming existed is: in industrial production, wastewater flow rate is large, and waste water fluoro-containing concentration is high, takes above technique, although can remove most fluorine in waste water, Funing tablet, still higher than 5mg/L, can not reach discharging standards; Absorption method is utilized to remove the technique of fluorine, main employing aluminium salt is except fluorine, the shortcoming existed is: this technique is only applicable to the lower waste water of Funing tablet, if waste water fluorine content is large, aluminium salt consumption will be caused many, cost is high, and aluminium salt all can not remove fluorine and cadmium under any PH condition simultaneously simultaneously, therefore likely causes waste water to contain cadmium and exceeds standard.
Summary of the invention
The object of the invention is to overcome the shortcoming and defect existed in above-mentioned prior art, provide that a kind of technique is simple, easy to operate, Be very effective, cheap smelting wastewater defluorinating process.
The present invention is mainly achieved through the following technical solutions.A kind of Novel waste water fluoridation technique, is characterized in that step is as follows:
Step one, gypsum operation: in the filtrate that wastewater from copper smelter sulfuration pretreatment process produces, add CaCO
3solution carries out pre-neutralization, and after reaction, centrifuging obtains gypsum and gypsum filtrate;
Step 2, Neutralization settlement operation: adopt carbide slag to carry out fractional neutralization to gypsum filtrate; After neutralization, add flocculation agent and neutralizer is flocculated, concentrated, filter, with slag and flocculation filtrate in obtaining;
Step 3, Tai-Ace S 150 adsorption-defluorination operation: flocculation filtrate is proceeded in PH adjustment tank and regulates PH, then add alum liquor, stir, complex reaction is to adsorb remaining fluorion.
Preferably, in gypsum operation, PH controls at 3-5.
Preferably, during fractional neutralization, control PH is 7 ~ 8,9 ~ 10 and 11.
Preferably, in step 3, control PH is that the mass ratio of 6 ~ 9, Al/F controls to be about 2:1 ~ 5:1, and the reaction times controls at about 30min.
In the present invention, maximally utilising original technique, equipment, spent acid, after vulcanization process removes most of heavy metal contaminants, enters into gypsum operation and carries out pre-neutralization, and gypsum filtrate outlet can be controlled in 60 ~ below 100mg/l containing F.Then adopt carbide slag to neutralize gypsum filtrate, add flocculation agent flocculation, filter, to remove the heavy metal contaminants in waste water, Funing tablet in flocculation filtrate can be made to can be controlled in 20 ~ below 40mg/L.Then in PH adjustment tank, alum liquor is added, Tai-Ace S 150 and F ion generation complex reaction: Al
3++ 6F
-=[Al(F
6)]
3-, liquid discharge after thickener clarification after process, F concentration in waste water can be down to below 5mg/L, other elements are up to standard.
The method that the present invention adopts the precipitator method to combine with absorption method, except fluorine, effectively can prevent other heavy metals exceeding standards of waste water, and can control within the scope of discharging standards by pH value, technique is simple, reliable, invest little, easy to operate, existing technique is had no adverse effect.
Embodiment
The present invention is further described according to following embodiment, and those skilled in the art can understand, following embodiment only plays the effect of explanation to the present invention.Without departing from the premise in the spirit of the present invention, any improvement the present invention done and substituting all within the scope of protection of the invention.
embodiment 1:
1, gypsum operation
In the filtrate that wastewater from copper smelter sulfuration pretreatment process produces, add the CaCO that concentration is 200g/l
3solution carries out pre-neutralization, controls addition by self-acting valve, regulates PH to be 3 ~ 4, constantly stirs, reaction 50min, then centrifuging, and filter residue is gypsum, and filtrate is called gypsum filtrate, and gypsum filtrate outlet can be controlled in 90 ~ below 100mg/l containing F.
2, Neutralization settlement operation
Carbide slag is adopted to carry out distribution neutralization to gypsum filtrate, the PH of a neutralizing well controls about 7, the PH of Two-step neutralization groove controls about 9, the PH of three neutralizing wells controls more than 11, after neutralization, proceeds in flocculation tank, add flocculation agent flocculation, then concentrated, filter, product be in and slag and flocculation filtrate, in flocculation filtrate, Funing tablet can be controlled in 30 ~ below 40mg/L.
3, Tai-Ace S 150 adsorption-defluorination operation
Flocculation filtrate is proceeded in PH adjustment tank, PH is regulated to be 6 ~ 8, alum liquor is added in adjustment liquid, control to be about 2:1 with the mass ratio of Al/F, stir after 30 minutes, clarification, bottom is absorption slag, upper strata is supernatant liquor, F content in supernatant liquor can be made can be down to below 5mg/l by 30 ~ 40mg/L, reach emission standard.
embodiment 2:
1, gypsum operation
In the filtrate that wastewater from copper smelter sulfuration pretreatment process produces, add the CaCO that concentration is 200g/l
3solution carries out pre-neutralization, controls addition by self-acting valve, regulates PH to be 4 ~ 5, constantly stirs, and reaction 50min, then centrifuging, filter residue is gypsum, and filtrate is called gypsum filtrate.Gypsum filtrate outlet can be controlled in 60 ~ below 80mg/l containing F.
2, Neutralization settlement operation
Carbide slag is adopted to carry out distribution neutralization to gypsum filtrate, the PH of a neutralizing well controls about 8, the PH of Two-step neutralization groove controls about 10, the PH of three neutralizing wells controls more than 11, after neutralization, proceeds in flocculation tank, add flocculation agent flocculation, then concentrated, filter, product be in and slag and flocculation filtrate, in flocculation filtrate, Funing tablet can be controlled in 20 ~ below 30mg/L.
3, Tai-Ace S 150 adsorption-defluorination operation
Flocculation filtrate is proceeded in PH adjustment tank, regulates PH to be 7 ~ 9, in adjustment liquid, add alum liquor, control to be about 5:1 with the mass ratio of Al/F, stir after 30 minutes, clarification, bottom is absorption slag, and upper strata is supernatant liquor, and in supernatant liquor, F content can be down to below 5mg/l by 20 ~ 30mg/L.
In the present invention, in order to accurately control alum liquor addition, the alum liquor of predetermined concentration is configured at Tai-Ace S 150 dilution trap, liquid-feeding pump is installed in the outlet of Tai-Ace S 150 dilution trap, prepare the pipeline of Tai-Ace S 150 dilution trap to PH adjustment tank, install under meter, by liquid-feeding pump, alum liquor is sent into PH adjustment tank and carry out adsorption-defluorination.
Claims (6)
1. a Novel waste water fluoridation technique, is characterized in that step is as follows:
Step one, gypsum operation: in the filtrate that wastewater from copper smelter sulfuration pretreatment process produces, add CaCO
3solution carries out pre-neutralization, and after reaction, centrifuging obtains gypsum and gypsum filtrate;
Step 2, Neutralization settlement operation: adopt carbide slag to carry out fractional neutralization to gypsum filtrate; After neutralization, add flocculation agent and neutralizer is flocculated, concentrated, filter, with slag and flocculation filtrate in obtaining;
Step 3, Tai-Ace S 150 adsorption-defluorination operation: flocculation filtrate is proceeded in PH adjustment tank and regulates PH, then add alum liquor, stir, complex reaction is to adsorb remaining fluorion.
2. Novel waste water fluoridation technique according to claim 1, is characterized in that: in step one, PH controls at 3-5.
3. Novel waste water fluoridation technique according to claim 1, is characterized in that: during fractional neutralization, and the PH of a neutralizing well controls 7 ~ 8, and the PH of Two-step neutralization groove controls 9 ~ 10, and the PH of three neutralizing wells controls more than 11.
4. Novel waste water fluoridation technique according to claim 1, is characterized in that: in step 3, and control PH is 6 ~ 9.
5. the Novel waste water fluoridation technique according to claim 1 or 4, is characterized in that: in step 3, and the mass ratio of Al/F controls as 2:1 ~ 5:1.
6. the Novel waste water fluoridation technique according to claim 1 or 4, it is characterized in that: the alum liquor configuring predetermined concentration at Tai-Ace S 150 dilution trap, liquid-feeding pump is installed in the outlet of Tai-Ace S 150 dilution trap, prepare the pipeline of Tai-Ace S 150 dilution trap to PH adjustment tank, install under meter, by liquid-feeding pump, alum liquor is sent into PH adjustment tank and carry out adsorption-defluorination.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510379416.3A CN105036406A (en) | 2015-07-02 | 2015-07-02 | Novel wastewater fluorine-removing technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510379416.3A CN105036406A (en) | 2015-07-02 | 2015-07-02 | Novel wastewater fluorine-removing technology |
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| Publication Number | Publication Date |
|---|---|
| CN105036406A true CN105036406A (en) | 2015-11-11 |
Family
ID=54443456
Family Applications (1)
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| CN201510379416.3A Pending CN105036406A (en) | 2015-07-02 | 2015-07-02 | Novel wastewater fluorine-removing technology |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108117195A (en) * | 2017-12-29 | 2018-06-05 | 韶关市雅鲁环保实业有限公司 | The waste water fluoride ion removing agent of polymetallic ore mountain and processing method |
| CN108217775A (en) * | 2018-02-05 | 2018-06-29 | 合肥市联任科技有限公司 | A kind of chlorine-contained wastewater inorganic agent and preparation method thereof |
| CN111115906A (en) * | 2020-01-17 | 2020-05-08 | 连云港神汇硅材料科技有限公司 | Silicon dioxide production sewage treatment system and treatment method |
| CN115367918A (en) * | 2022-08-19 | 2022-11-22 | 江西铜业股份有限公司 | Method for removing fluorine from copper smelting wastewater gypsum filtrate |
| CN118579956A (en) * | 2024-06-27 | 2024-09-03 | 广东芳源新材料集团股份有限公司 | A method for simultaneously and deeply removing F, P and COD from wastewater |
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| CN111115906A (en) * | 2020-01-17 | 2020-05-08 | 连云港神汇硅材料科技有限公司 | Silicon dioxide production sewage treatment system and treatment method |
| CN115367918A (en) * | 2022-08-19 | 2022-11-22 | 江西铜业股份有限公司 | Method for removing fluorine from copper smelting wastewater gypsum filtrate |
| CN118579956A (en) * | 2024-06-27 | 2024-09-03 | 广东芳源新材料集团股份有限公司 | A method for simultaneously and deeply removing F, P and COD from wastewater |
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Application publication date: 20151111 |