CN108862703A - A kind of deep treatment method of fluoride waste - Google Patents
A kind of deep treatment method of fluoride waste Download PDFInfo
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- CN108862703A CN108862703A CN201810646182.8A CN201810646182A CN108862703A CN 108862703 A CN108862703 A CN 108862703A CN 201810646182 A CN201810646182 A CN 201810646182A CN 108862703 A CN108862703 A CN 108862703A
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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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- 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
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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
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- 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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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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
- C02F1/66—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
- C02F2001/007—Processes including a sedimentation step
-
- 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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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a kind of deep treatment methods of fluoride waste.The deep treatment method of the fluoride waste includes the following steps：Adjust pH value：Fluoride waste is collected, natural subsidence is added sodium hydroxide solution or hydrochloric acid solution, adjusts the pH value of fluoride waste；Precipitating：Appropriate calcium chloride solution is added into the fluoride waste for regulate pH value, is staticly settled after mixing；Flocculation：Fluoride waste Jing Guo precipitation process is imported into flocculation basin, appropriate polymeric aluminum chlorides solution is added, is stood after mixing, adds appropriate polyacrylamide solution, stands after mixing, be then separated by solid-liquid separation；Absorption：Appropriate defluorination material is added into the waste water after flocculating and solid-liquid separating, is stood after mixing；Micro-filtration：It is discharged after waste water after adsorption treatment is carried out micro-filtration by microporous filter.The deep treatment method of fluoride waste provided by the invention can reduce pharmaceutical use, have preferable effect of settling, and processing cost is low.
Description
Technical field
The present invention relates to water-treatment technology fields, specifically, being related to a kind of deep treatment method of fluoride waste.
Background technique
Currently, the research carried out for fluoride waste has much both at home and abroad, main methods have：Chemical precipitation method,
Flocculation sedimentation, absorption method, crystal seed addition, ion exchange, reverse osmosis, active carbon fluorine removal, electrodialysis and electrocoagulation etc..Fluorine-containing processing
Method is numerous, but all has that effluent quality is unstable, and pharmaceutical use is excessive mostly, or there are secondary pollution problems, so that
These defluorination methods have certain limitation.For example, ion exchange is high to the standard for entering water water quality requirement；Active carbon fluorine removal
Processing cost is high；Reverse osmosis and electrocoagulation complex process, power consumption are big, and cost is high.
Summary of the invention
In order to solve, above-mentioned fluorine-containing wastewater treatment method effluent quality is unstable, pharmaceutical use is excessive, processing cost is high
The technical issues of, the present invention provides a kind of deep treatment method of fluoride waste, and the deep treatment method of the fluoride waste can
Pharmaceutical use is reduced, there is preferable effect of settling, and processing cost is low.
The present invention provides a kind of deep treatment methods of fluoride waste, include the following steps：
Step 1: adjusting pH value：Fluoride waste is collected, is sent into conditioning tank after natural subsidence, is added into conditioning tank suitable
Sodium hydroxide solution or hydrochloric acid solution are measured, the pH value of fluoride waste is adjusted；
Step 2: precipitating：Appropriate calcium chloride solution is added into the fluoride waste for regulate pH value, it is heavy to stand after mixing
It forms sediment；
Step 3: flocculation：Flocculation basin will be imported by the fluoride waste of step 2 processing, appropriate polyaluminium is added
Aluminum solutions stand 10~15 minutes after mixing；Appropriate polyacrylamide solution is added, stands 10~15 minutes after mixing, so
After be separated by solid-liquid separation；
Step 4: absorption：Appropriate defluorination material is added in waste water after being separated by solid-liquid separation into the step 3, it is quiet after mixing
It sets；
Step 5: micro-filtration：After waste water after the step 4 adsorption treatment is carried out micro-filtration by microporous filter
Discharge.
In a kind of preferred embodiment of the deep treatment method of fluoride waste provided by the invention, in the step 1,
The concentration of sodium hydroxide solution is 0.3mol/L, and concentration of hydrochloric acid solution 0.2mol/L, the pH value of fluoride waste is after adjusting to 4
~6.
In a kind of preferred embodiment of the deep treatment method of fluoride waste provided by the invention, in the step 2,
The mass concentration of the calcium chloride is 20~30%, and additional amount is the 10~15% of fluoride waste volume.
In a kind of preferred embodiment of the deep treatment method of fluoride waste provided by the invention, in the step 3,
The mass concentration of the aluminium polychloride is 5%, and additional amount is the 5~10% of fluoride waste volume；The polyacrylamide is pressed
Mass concentration be 1%, additional amount be fluoride waste volume 3~5%.
In a kind of preferred embodiment of the deep treatment method of fluoride waste provided by the invention, in the step 4,
The defluorination material is added by the amount of every liter of fluoride waste of 3~5g/；The preparation method of the defluorination material is：By natural calcium, magnesium
It is that ore crushes, screening obtains the ore particles of 0.5~2mm；The ore particles are calcined 20~30 points through 400~600 DEG C
Zhong Hou takes out, cooled to room temperature；It is molten that the mineral grain after cooling is first put into the phosphoric acid that mass concentration is 5~7%
2~4h is impregnated in liquid, neutrality is washed with water to after taking-up, is then placed into the sodium hydroxide solution that mass concentration is 3~5%
4~6h is impregnated, neutrality is washed with water to after taking-up, up to defluorination material after drying.
Compared to the prior art, the deep treatment method of fluoride waste provided by the invention has the advantages that：This
Invention uses chemical precipitation method to pre-process fluoride waste first, is adjusted by sodium hydroxide solution or hydrochloric acid solution fluorine-containing
The pH value of waste water；Then it is combined by calcium salt precipitation method, aluminium salt method for removing fluor, flocculating polymer method, high-efficiency adsorbent absorption
Mode removes a large amount of fluorine ions in fluoride waste, carries out advanced treating, removal to fluoride waste finally by MF method
Microscopic precipitate particle in fluoride waste entirely handles work to reach the waste water purpose of continuous treatment fluorine ion containing high concentration
Skill is simple, mature, practical, can reduce pharmaceutical use, has preferable effect of settling, and processing cost is low.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's all other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
The present embodiment provides a kind of deep treatment methods of fluoride waste, include the following steps：
(1) pH value is adjusted：
Fluoride waste is collected, is sent into conditioning tank after natural subsidence, the hydrogen that concentration is 0.3mol/L is added into conditioning tank
Sodium hydroxide solution or concentration are the hydrochloric acid solution of 0.2mol/L, adjust the pH value of fluoride waste to 4；
(2) it precipitates：
The calcium chloride solution that mass concentration is 20% is added into the fluoride waste for regulate pH value, additional amount is fluorine-containing useless
The 15% of water volume staticly settles after mixing；
(3) it flocculates：
Flocculation basin will be imported by the fluoride waste of step 2 processing, the polyaluminium that mass concentration is 5% is added
Aluminum solutions, additional amount are the 5% of fluoride waste volume, stand 15 minutes after mixing；Add the polypropylene that mass concentration is 1%
Amide solution, additional amount are the 3% of fluoride waste volume, stand 15 minutes after mixing, are then separated by solid-liquid separation；
(4) it adsorbs：
Appropriate defluorination material is added in waste water after being separated by solid-liquid separation into the step 3, is stood after mixing；The fluorine removal
Material is added by the amount of every liter of fluoride waste of 3g/；The preparation method of the defluorination material is：Natural calcium, magnesium system ore are crushed,
Screening obtains the ore particles of 0.5~2mm；After twenty minutes through 400 DEG C of calcinings by the ore particles, it takes out, naturally cool to
Room temperature；The mineral grain after cooling is first put into the phosphoric acid solution that mass concentration is 5% and impregnates 4h, is washed with water after taking-up
It washs then to place into neutrality in the sodium hydroxide solution that mass concentration is 3% and impregnates 6h, be washed with water to neutrality after taking-up,
Up to defluorination material after drying；
(5) micro-filtration：
It is discharged after waste water after the step 4 adsorption treatment is carried out micro-filtration by microporous filter.
Embodiment 2
The present embodiment provides a kind of deep treatment methods of fluoride waste, include the following steps：
(1) pH value is adjusted：
Fluoride waste is collected, is sent into conditioning tank after natural subsidence, the hydrogen that concentration is 0.3mol/L is added into conditioning tank
Sodium hydroxide solution or concentration are the hydrochloric acid solution of 0.2mol/L, adjust the pH value of fluoride waste to 5；
(2) it precipitates：
The calcium chloride solution that mass concentration is 25% is added into the fluoride waste for regulate pH value, additional amount is fluorine-containing useless
The 13% of water volume staticly settles after mixing；
(3) it flocculates：
Flocculation basin will be imported by the fluoride waste of step 2 processing, the polyaluminium that mass concentration is 5% is added
Aluminum solutions, additional amount are the 8% of fluoride waste volume, stand 14 minutes after mixing；Add the polypropylene that mass concentration is 1%
Amide solution, additional amount are the 4% of fluoride waste volume, stand 13 minutes after mixing, are then separated by solid-liquid separation；
(4) it adsorbs：
Appropriate defluorination material is added in waste water after being separated by solid-liquid separation into the step 3, is stood after mixing；The fluorine removal
Material is added by the amount of every liter of fluoride waste of 4g/；The preparation method of the defluorination material is：Natural calcium, magnesium system ore are crushed,
Screening obtains the ore particles of 0.5~2mm；By the ore particles after 500 DEG C are calcined 25 minutes, takes out, naturally cools to
Room temperature；The mineral grain after cooling is first put into the phosphoric acid solution that mass concentration is 6% and impregnates 3h, is washed with water after taking-up
It washs then to place into neutrality in the sodium hydroxide solution that mass concentration is 4% and impregnates 5h, be washed with water to neutrality after taking-up,
Up to defluorination material after drying；
(5) micro-filtration：
It is discharged after waste water after the step 4 adsorption treatment is carried out micro-filtration by microporous filter.
Embodiment 3
The present embodiment provides a kind of deep treatment methods of fluoride waste, include the following steps：
(1) pH value is adjusted：
Fluoride waste is collected, is sent into conditioning tank after natural subsidence, the hydrogen that concentration is 0.3mol/L is added into conditioning tank
Sodium hydroxide solution or concentration are the hydrochloric acid solution of 0.2mol/L, adjust the pH value of fluoride waste to 6；
(2) it precipitates：
The calcium chloride solution that mass concentration is 30% is added into the fluoride waste for regulate pH value, additional amount is fluorine-containing useless
The 10% of water volume staticly settles after mixing；
(3) it flocculates：
Flocculation basin will be imported by the fluoride waste of step 2 processing, the polyaluminium that mass concentration is 5% is added
Aluminum solutions, additional amount are the 10% of fluoride waste volume, stand 10 minutes after mixing；Add poly- third that mass concentration is 1%
Acrylamide solution, additional amount are the 5% of fluoride waste volume, stand 10 minutes after mixing, are then separated by solid-liquid separation；
(4) it adsorbs：
Appropriate defluorination material is added in waste water after being separated by solid-liquid separation into the step 3, is stood after mixing；The fluorine removal
Material is added by the amount of every liter of fluoride waste of 5g/；The preparation method of the defluorination material is：Natural calcium, magnesium system ore are crushed,
Screening obtains the ore particles of 0.5~2mm；After twenty minutes through 600 DEG C of calcinings by the ore particles, it takes out, naturally cool to
Room temperature；The mineral grain after cooling is first put into the phosphoric acid solution that mass concentration is 7% and impregnates 2h, is washed with water after taking-up
It washs then to place into neutrality in the sodium hydroxide solution that mass concentration is 5% and impregnates 4h, be washed with water to neutrality after taking-up,
Up to defluorination material after drying；
(5) micro-filtration：
It is discharged after waste water after the step 4 adsorption treatment is carried out micro-filtration by microporous filter.
The deep treatment method of fluoride waste provided by the invention has the advantages that：The present invention uses chemistry first
The precipitation method pre-process fluoride waste, and the pH value of fluoride waste is adjusted by sodium hydroxide solution or hydrochloric acid solution；Then
Fluoride waste is removed in such a way that calcium salt precipitation method, aluminium salt method for removing fluor, flocculating polymer method, high-efficiency adsorbent absorption combine
In a large amount of fluorine ions, finally by MF method to fluoride waste carry out advanced treating, remove fluoride waste in it is small
Particle is precipitated, to reach the waste water purpose of continuous treatment fluorine ion containing high concentration, whole processing technology is simple, mature, practical,
Pharmaceutical use can be reduced, there is preferable effect of settling, and processing cost is low.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright description is applied directly or indirectly in other relevant technology necks
Domain is included within the scope of the present invention.
Claims (5)
1. a kind of deep treatment method of fluoride waste, which is characterized in that include the following steps：
Step 1: adjusting pH value：Fluoride waste is collected, is sent into conditioning tank after natural subsidence, appropriate hydrogen is added into conditioning tank
Sodium hydroxide solution or hydrochloric acid solution adjust the pH value of fluoride waste；
Step 2: precipitating：Appropriate calcium chloride solution is added into the fluoride waste for regulate pH value, is staticly settled after mixing；
Step 3: flocculation：Flocculation basin will be imported by the fluoride waste of step 2 processing, it is molten that appropriate aluminium polychloride is added
Liquid stands 10~15 minutes after mixing；Appropriate polyacrylamide solution is added, stands 10~15 minutes after mixing, it is then solid
Liquid separation；
Step 4: absorption：Appropriate defluorination material is added in waste water after being separated by solid-liquid separation into the step 3, is stood after mixing；
Step 5: micro-filtration：It is discharged after waste water after the step 4 adsorption treatment is carried out micro-filtration by microporous filter.
2. the deep treatment method of fluoride waste according to claim 1, which is characterized in that in the step 1, hydrogen-oxygen
The concentration for changing sodium solution is 0.3mol/L, and concentration of hydrochloric acid solution 0.2mol/L, the pH value of fluoride waste is after adjusting to 4~6.
3. the deep treatment method of fluoride waste according to claim 1, which is characterized in that described in the step 2
The mass concentration of calcium chloride is 20~30%, and additional amount is the 10~15% of fluoride waste volume.
4. the deep treatment method of fluoride waste according to claim 1, which is characterized in that described in the step 3
The mass concentration of aluminium polychloride is 5%, and additional amount is the 5~10% of fluoride waste volume；The matter that the polyacrylamide is pressed
Measuring concentration is 1%, and additional amount is the 3~5% of fluoride waste volume.
5. the deep treatment method of fluoride waste according to claim 1, which is characterized in that described in the step 4
Defluorination material is added by the amount of every liter of fluoride waste of 3~5g/；The preparation method of the defluorination material is：By natural calcium, magnesium system mine
Stone crushes, and screening obtains the ore particles of 0.5~2mm；By the ore particles after 400~600 DEG C are calcined 20~30 minutes,
It takes out, cooled to room temperature；The mineral grain after cooling is first put into the phosphoric acid solution that mass concentration is 5~7%
2~4h is impregnated, neutrality is washed with water to after taking-up, then places into the sodium hydroxide solution that mass concentration is 3~5% and impregnates
4~6h is washed with water to neutrality, up to defluorination material after drying after taking-up.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810646182.8A CN108862703A (en) | 2018-06-21 | 2018-06-21 | A kind of deep treatment method of fluoride waste |
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| CN201810646182.8A CN108862703A (en) | 2018-06-21 | 2018-06-21 | A kind of deep treatment method of fluoride waste |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109553218A (en) * | 2018-12-27 | 2019-04-02 | 中核四0四有限公司 | A kind of processing method for uranium conversion fluoride waste |
| CN110066047A (en) * | 2019-04-26 | 2019-07-30 | 广东益诺欧环保股份有限公司 | A kind of method and system handling high fluoride waste water |
| CN110697928A (en) * | 2019-09-11 | 2020-01-17 | 山西晋城无烟煤矿业集团有限责任公司 | Fluorine removal system and method for high-fluorine wastewater |
| CN112174382A (en) * | 2020-10-14 | 2021-01-05 | 上海三邦水处理技术有限公司 | Semiconductor industrial wastewater treatment technology and recycling process |
| CN113292177A (en) * | 2021-05-24 | 2021-08-24 | 安徽诚志显示玻璃有限公司 | Treatment method for high-concentration waste acid glass powder |
| CN113526639A (en) * | 2021-08-24 | 2021-10-22 | 北京盖雅环境科技有限公司 | Compound fluorine removal agent and fluorine removal method for fluorine-containing wastewater |
| CN113603252A (en) * | 2021-04-06 | 2021-11-05 | 河北科技大学 | Coal gasification high-concentration fluorine-containing wastewater treatment process |
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| CN102489241A (en) * | 2011-12-09 | 2012-06-13 | 朱迟 | Preparation and regeneration method of water treatment defluoridation material |
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| CN107162253A (en) * | 2017-05-04 | 2017-09-15 | 常熟三爱富中昊化工新材料有限公司 | A kind of processing method of fluoride waste |
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| EP2160438A1 (en) * | 2007-06-13 | 2010-03-10 | Joseph A. Megy | Phospohorous pentoxide producing methods |
| CN102489241A (en) * | 2011-12-09 | 2012-06-13 | 朱迟 | Preparation and regeneration method of water treatment defluoridation material |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109553218A (en) * | 2018-12-27 | 2019-04-02 | 中核四0四有限公司 | A kind of processing method for uranium conversion fluoride waste |
| CN110066047A (en) * | 2019-04-26 | 2019-07-30 | 广东益诺欧环保股份有限公司 | A kind of method and system handling high fluoride waste water |
| CN110697928A (en) * | 2019-09-11 | 2020-01-17 | 山西晋城无烟煤矿业集团有限责任公司 | Fluorine removal system and method for high-fluorine wastewater |
| CN112174382A (en) * | 2020-10-14 | 2021-01-05 | 上海三邦水处理技术有限公司 | Semiconductor industrial wastewater treatment technology and recycling process |
| CN113603252A (en) * | 2021-04-06 | 2021-11-05 | 河北科技大学 | Coal gasification high-concentration fluorine-containing wastewater treatment process |
| CN113292177A (en) * | 2021-05-24 | 2021-08-24 | 安徽诚志显示玻璃有限公司 | Treatment method for high-concentration waste acid glass powder |
| CN113526639A (en) * | 2021-08-24 | 2021-10-22 | 北京盖雅环境科技有限公司 | Compound fluorine removal agent and fluorine removal method for fluorine-containing wastewater |
| CN113526639B (en) * | 2021-08-24 | 2023-01-10 | 北京盖雅环境科技有限公司 | Compound fluorine removal agent and fluorine removal method for fluorine-containing wastewater |
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