CN100486916C - Method for removing fluorinion in waste water - Google Patents
Method for removing fluorinion in waste water Download PDFInfo
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- CN100486916C CN100486916C CNB2006100604736A CN200610060473A CN100486916C CN 100486916 C CN100486916 C CN 100486916C CN B2006100604736 A CNB2006100604736 A CN B2006100604736A CN 200610060473 A CN200610060473 A CN 200610060473A CN 100486916 C CN100486916 C CN 100486916C
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Abstract
The invention discloses a method to remove fluorinion in waste water, which comprises the following steps: a, adding calcium hydrate solution into industrial waste water with fluorinion; stirring; adjusting the pH value of the waste water at 8. 5-9. 5; setting the reacting time at 15-20 min; b, adding aluminum sulfate solution into the waste water of the step a; stirring; adjusting the pH value of the waste water at 6. 0-6. 5; setting the reacting time at 20-25 min; c, adding polymeric flocculant into the waste water from the step b, stirring; injecting the waste water into desilter; proceeding flocculate deposition; discharging supernatant fluid; getting sediment; proceeding solid-liquid separation; outer-transporting or imbedding the solid sludge. This craft possesses simple procedure and convenient operation, which is fir for the plant with higher waste water output volume.
Description
Technical field
The present invention relates to a kind of method of removing fluorion in the trade effluent.
Background technology
In liquid-crystal display, production process of semiconductor, use the hydrofluoric acid clean substrate glass through regular meeting; to improve the substrate glass surface cleanliness; the trade effluent that is produced in these technologies is owing to contain the fluorion of higher concentration; strict regulation are generally all made to its discharging in various places; in the national standard of China; the content of fluorion does not allow to surpass 10mg/L in the trade effluent of just stipulating to be discharged; this is rigid, a minimum standard; obviously; content of fluoride ion is lower in the waste water; will more meet the industry policy of country, more favourable to the protection of environment.
Publication number is: CN1326900A, open day be: December 19 calendar year 2001, application number is: 01122878.4 Chinese invention patent ublic specification of application has proposed a kind of method that contains fluorion waste water of comparatively effectively handling, and its main technique steps in sequence is: 1. the solution of lime carbonate and hydrochloric acid reaction is joined in the waste water that contains the higher concentration fluorion and go; 2. basic solution such as sodium hydroxide are added in the waste water, more than the pH value to 8.0 of regulating waste water; 3. with Sodium polymetaphosphate and active aluminum, join in the waste water of step 2 as mixture or its aqueous solution of Tai-Ace S 150, the pH value in waste water is 6.0-7.0; 4. in the waste water of step 3, add flocculation agent in due form, behind flocculation sediment, carry out solid-liquid and separate reuse of gained body refuse or landfill.Through after the aforementioned technology, the content of fluoride ion in the waste water can be reduced to below the 10mg/L.
The major defect of aforementioned processing technology is: need according to wastewater flow rate and wherein the content of fluorion decide, control the addition of materials such as lime carbonate, hydrochloric acid, sodium hydroxide, Sodium polymetaphosphate and active aluminum, the chemical agent kind that causes wastewater treatment to be used is many, step is complicated, complicated operation.
Summary of the invention
For overcoming the defective of above-mentioned prior art, it is a kind of simple to operate that technical problem to be solved by this invention is intended to provide, but still the method for fluorion in the removal waste water of fluoride treatment effect is preferably arranged.
For solving the problems of the technologies described above, the present invention proposes a kind of method of removing fluorion in the waste water, comprises the following steps: successively
A. adding aqua calcis in the trade effluent that contains fluorion and stir, is 8.5-9.5 up to the pH of waste water value, and the reaction times is 15-20 minute;
B. adding alum liquor in the step a gained waste water and stir, is 6.0-6.5 up to the pH of waste water value, and the reaction times is 20-25 minute;
C. in the waste water of step b, add polymeric flocculant and stir;
D. after step c gained waste water injection settling tank being carried out flocculation sediment, the supernatant liquor discharging, throw out carries out solid-liquid to be separated, outward transport of gained body refuse or landfill.
Adopt above-mentioned technology, the trade effluent that contains fluorion is after adding aqua calcis, stir, add an amount of alum liquor again, generate comparatively stable, easy sedimentary fluorine-containing colloid, impel by polymeric flocculant again and form oarse-grained flocs unit, be convenient to precipitation, thereby reach the purpose of removing fluorion contained in the waste water.When concrete operations technical process of the present invention, as long as in carry out purpose and the effect that timing monitoring can realize effectively remove in waste water contained fluorion of common PH to the pharmaceutical quantities of being added, employed main medicament kind also has only two kinds of aqua calcis and alum liquors, very simple, especially more practical for the higher factory of the wastewater displacement of fluoride ion.
Description of drawings
Fig. 1 is to use the process flow sheet of the method for fluorion in the removal waste water of the present invention;
Fig. 2 shows the structure diagram of the Waste Water Treatment that uses technology of the present invention.
Embodiment
With reference to accompanying drawing 1 and Fig. 2, in one embodiment of the invention, pending waste water is the trade effluent that contains the high density fluorion that semiconductor production factory is discharged, and its pH value is about 2.5, and fluorinion concentration is that wastewater flow is at 25-30m about 300mg/L
3It is 180m that/h, waste water enter volume
3Behind the equalizing tank 1, squeezing into volume by lift pump 2 is 10m
3In first reaction tank 31, inject aqua calcis by PH meter 4 control dosing pumps to first reaction tank 31, make the pH value of waste water reach 8.5,9.0,9.5 respectively, use stirring pump 5 to stir, stirring reaction intensity is 600s-～700s-, and retention time of sewage is 15-20 minute;
It is 15m that gained waste water injects volume
3Second reaction tank 32 injects alum liquor by PH meter control dosing pump to second reaction tank 32, makes the pH value of waste water reach 6.0-6.5 respectively, and stirring reaction intensity is 500s-～600s-, and retention time of sewage is 20-25 minute;
It is 15m that gained waste water is injected volume
3The 3rd reaction tank 33 injects polymeric flocculant by dosing pump to the 3rd reaction tank, and adding dose is 5mg/L～10mg/L; Stirring reaction intensity is 150s
-～250s
-, retention time of sewage is 20-25 minute;
It is 480m that gained waste water is injected volume by lift pump
3Settling tank 6, retention time of sewage was controlled at about 8-10 hour, gained supernatant liquor output discharging, extracting the relief liquor sample detects, the gained result 1-table 4 that sees the following form respectively, the fluorine-containing flocs unit precipitation of gained is again by sludge dewatering equipment 7 dehydrations, and filtrate is returned aforementioned equalizing tank and is handled again, body refuse is transported outward landfill or is sent brickmaking factory, blending brickmaking reuse.
In following each table, after the PH1 value is meant and has added aqua calcis, the waste water pH value in first reaction tank; After the PH2 value is meant and has added alum liquor, waste water pH value in second reaction tank, T1 is meant the residence time of waste water in first reaction tank, T2 is meant the residence time of waste water in second reaction tank, and F-concentration (mg/L) is meant the fluorion detectable level of the supernatant samples that post precipitation discharged from settling tank.
Table 1:
| The PH1 value | T1 (minute) | The PH2 value | T2 (minute) | F-concentration (mg/L) |
| 8.0 | 20 | 6.0 | 25 | 9.3 |
| 8.5 | 20 | 6.0 | 25 | 8.7 |
| 9.0 | 20 | 6.0 | 25 | 7.2 |
| 9.5 | 20 | 6.0 | 25 | 6.7 |
Table 2:
| The PH1 value | T1 (minute) | The PH2 value | T2 (minute) | F-concentration (mg/L) |
| 8.0 | 20 | 6.5 | 25 | 10.2 |
| 8.5 | 20 | 6.5 | 25 | 9.1 |
| 9.0 | 20 | 6.5 | 25 | 8.2 |
| 9.5 | 20 | 6.5 | 25 | 7.6 |
Table 3:
| The PH1 value | T1 (minute) | The PH2 value | T2 (minute) | F-concentration (mg/L) |
| 8.0 | 20 | 7.0 | 25 | 11.0 |
| 8.5 | 20 | 7.0 | 25 | 10.3 |
| 9.0 | 20 | 7.0 | 25 | 9.2 |
| 9.5 | 20 | 7.0 | 25 | 8.8 |
Table 4:
| The PH1 value | T1 (minute) | The PH2 value | T2 (minute) | F-concentration (mg/L) |
| 8.0 | 20 | 7.5 | 25 | 12.1 |
| 8.5 | 20 | 7.5 | 25 | 11.3 |
| 9.0 | 20 | 7.5 | 25 | 10.7 |
| 9.5 | 20 | 7.5 | 25 | 9.2 |
Data as can be seen from last tabulation: in first reaction tank, by adding pH value that aqua calcis regulates waste water between 8.5-9.5, preferred pH value is 9.5; The pH value that adds alum liquor adjusting waste water in addition in second reaction tank is between 6.0-6.5, and preferred pH value is 6.0, and is better to the fluoride ion removing effect of waste water.
The method of fluorion in the removal waste water of the present invention, operation is simplified, and used medicament kind is less, is convenient to operation, the effect of removing fluorion is also relatively good. and these advantages make the popularization of technology of the present invention, application become more easy for fairly large semiconductor production factory.
Claims (3)
1. a method of removing fluorion in the waste water comprises the following steps: successively
A. adding aqua calcis in the trade effluent that contains fluorion and stir, is 8.5-9.5 up to the pH of waste water value, and the reaction times is 15-20 minute;
B. adding alum liquor in the step a gained waste water and stir, is 6.0-6.5 up to the pH of waste water value, and the reaction times is 20-25 minute;
C. in the waste water of step b, add polymeric flocculant and stir;
D. after step c gained waste water injection settling tank being carried out flocculation sediment, the supernatant liquor discharging, throw out carries out solid-liquid to be separated, outward transport of gained body refuse or landfill.
2. a kind of method of removing fluorion in the waste water as claimed in claim 1 is characterized in that: in described step a, adding aqua calcis is 9.5 up to the pH of waste water value.
3. as claimed in claim 1 or 2 any removed the method for fluorion in the waste water, it is characterized in that: in described step b, adding alum liquor is 6.0. up to the pH of waste water value
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100604736A CN100486916C (en) | 2006-04-30 | 2006-04-30 | Method for removing fluorinion in waste water |
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| CNB2006100604736A CN100486916C (en) | 2006-04-30 | 2006-04-30 | Method for removing fluorinion in waste water |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050531B (en) * | 2009-10-30 | 2012-08-08 | 中芯国际集成电路制造(上海)有限公司 | Fluorine-containing wastewater treatment method |
| CN101973656B (en) * | 2010-10-25 | 2012-11-07 | 中国市政工程中南设计研究总院 | Defluorinating process and device of domestic drinking water of villages and towns |
| KR101340161B1 (en) * | 2011-12-15 | 2013-12-10 | 노바테크 (주) | High Concentration Hydrofluoric Acid Waste Liquor treatment Method |
| CN103833116B (en) * | 2014-03-03 | 2016-06-15 | 江苏永葆环保科技股份有限公司 | A kind of production method and application that utilizes waste hydrochloric acid, aluminium-containing sludge to prepare defluorinating agent |
| CN105271561A (en) * | 2014-06-21 | 2016-01-27 | 广东石油化工学院 | Chemical experiment waste liquid processing system |
| CN104496063A (en) * | 2014-11-17 | 2015-04-08 | 中国石油集团东北炼化工程有限公司吉林设计院 | Method for removing fluorine in wastewater |
| CN104787935B (en) * | 2015-05-07 | 2017-08-11 | 东北电力大学 | A kind of processing method of fluoride waste |
| CN105967294B (en) * | 2016-06-29 | 2019-05-28 | 江苏奥尼斯环保科技有限公司 | A kind of fluorine removal flocculation reaction method of fluoride waste |
| CN109354256B (en) * | 2018-12-05 | 2021-11-19 | 齐鲁工业大学 | Method for removing low-concentration fluorine ions in wastewater |
| CN110803829B (en) * | 2019-10-28 | 2022-07-01 | 佛山市三水凤铝铝业有限公司 | Treatment method for treating fluorine-containing wastewater on surface of aluminum profile |
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