CN101041496B - Treatment method for drainge containing fluorin ion and drainge treating agent - Google Patents
Treatment method for drainge containing fluorin ion and drainge treating agent Download PDFInfo
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- CN101041496B CN101041496B CN200710085726XA CN200710085726A CN101041496B CN 101041496 B CN101041496 B CN 101041496B CN 200710085726X A CN200710085726X A CN 200710085726XA CN 200710085726 A CN200710085726 A CN 200710085726A CN 101041496 B CN101041496 B CN 101041496B
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Abstract
The present invention relates to a method for reducing the fluoride ion amount in the wastewater containing fluoride ion at PH of below 4.0. The composite complexing oxide Mx<2+>My<3+>O(x+3y/2-nz/2)(A<n->)z is added into the wastewater containing fluoride ion at PH of below 4.0, and the formed composite complexing hydroxide particle is separated from the treated wastewater. The present invention provides a method of effective adsorbing and removing the fluoride ion.
Description
Technical field
The present invention relates to reduce the method for content of fluoride ion contained in the following draining of pH4.0 that semiconductor manufacturing factory discharges.Relate in more detail in this draining, contained content of fluoride ion is reduced to below the standard of drainage, even the substandard method of soil.
Technical background
At semiconductor manufacturing factory, hydrofluoric acid is used in a large number as the etching reagent of silicon wafer.Because water waits to clean this hydrofluoric acid, so the pH of draining is low to moderate below 4.0, and contains the fluorine of high density.
Yet according to the standard of drainage of Environmental Agency's issue, the fluorinion concentration that regulation detects in the liquid is below the 8mg/L, and according to the soil standard, is defined as below the 0.8mg/L.
As the method for removing the fluorine in the fluorine-containing draining, proposed in fluorine-containing water, to add calcium salt, make it generate the method (opening flat 10-57969 communique) of insoluble Calcium Fluoride (Fluorspan) with reference to the spy.
In addition, also proposed in fluorine-containing water, to add the method (opening clear 57-197082 communique) of removing fluorine as the adsorbents adsorb of principal constituent with magnesium oxide (this magnesium oxide is can generate the calcining under 400～700 ℃ of magnesian magnesium compound to form) with reference to the spy.
Yet the spy opens the calcium salt that adds described in the flat 10-57969 communique and generates in the method for Calcium Fluoride (Fluorspan) in fluorine-containing draining, and the solubleness of Calcium Fluoride (Fluorspan) to 0.0016g/100g (18 ℃), does not meet the soil standard greatly.In addition, the spy opens the magnesium oxide described in the clear 57-197082 communique to be that the fluorine of sorbent material is removed ability not enough.
Summary of the invention
The present invention is intended to solve above-mentioned prior art problems, and it is the treatment process of the fluorion in the draining below 4.0 that the pH that removes, reduces the fluoride ion that semiconductor manufacturing factory discharges is provided effectively.
The present inventor has furtherd investigate the method for the fluorion in the draining of the low pH (below 4.0) that effectively removes fluoride ion.Found that specific compound complex oxide (Complex He Wrong body acidulants) have a big fluorine adsorptive power.
In addition, also find to reduce to below the standard of drainage 8mg/L, even reduce to below the soil standard 0.8mg/L by in the draining that contains the high density fluorion, adding described specific compound complex oxide, can make the fluorinion concentration of handling in the liquid of back.In addition, further find that the compound complexing hydroxide particle that has adsorbed fluorion is not stripping fluorion in dissolution test again, thereby has finished the present invention.
That is, the pH that the invention provides the fluoride ion that the reduction semiconductor manufacturing factory that the following describes discharges is the method and the treatment agent of the fluorinion concentration in the draining below 4.0.
(1) method of the content of fluoride ion in the above-mentioned draining of reduction, it is characterized in that, toward the compound complex oxide that adds following formula (1) expression during the pH of fluoride ion is draining below 4.0, formed fluorine-containing compound complexing hydroxide particle is separated from the draining of handling.
M
2+ xM
3+ yO
(x+3y/2-nz/2)(A
n-)
z (1)
[in the formula, M
2+Expression is selected from Mg
2+, Zn
2+, Ni
2+, Fe
2+, Ca
2+And Cu
2+In at least a, M
3+Expression is selected from Al
3+And Fe
3+In at least a, A
N-Be the negatively charged ion of n valency, expression is selected from Cl
-, NO
3 -And SO
4 2-In at least a, x, y, z meet the following conditions respectively: 1/8＞y/x＞0,4/8 〉=z/ (x+y) 〉=0.]
(2) method of above-mentioned (1) described reduction fluorion, wherein, the M in the formula (1)
2+Be Mg
2+
(3) method of above-mentioned (1) described reduction fluorion, wherein, the M in the formula (1)
3+Be Al
3+
(4) method of above-mentioned (1) described reduction fluorion, wherein, the BET surface-area of this compound complex oxide is 100～400m
2/ g.
(5) method of above-mentioned (1) described reduction fluorion, wherein, the pH of fluoride ion is that the draining below 4.0 is the draining that semiconductor manufacturing factory is discharged.
(6) method of above-mentioned (1) described reduction fluorion, wherein, the fluorinion concentration in the draining is 1～300mg/L.
(7) method of above-mentioned (1) described reduction fluorion, wherein, treatment temp is 10～25 ℃.
(8) method of above-mentioned (1) described reduction fluorion, wherein, be 5 minutes～3 hours the duration of contact of adding in this draining behind this compound complex oxide.
(9) method of above-mentioned (1) described reduction fluorion wherein, with respect to this draining of 100 weight parts, is used this compound complex oxide 0.05～10 weight part, preferred 0.1～5 weight part.
(10) method of above-mentioned (1) described reduction fluorion wherein, is added agglutinant in the draining of the processing that contains established compound complexing hydroxide particle, and compound complexing hydroxide particle is separated with the draining of handling.
(11) method of above-mentioned (10) described reduction fluorion wherein, with respect to this compound complex oxide 1 weight part, is added this agglutinant of 0.01～0.5 weight part.
(12) method of above-mentioned (1) described reduction fluorion, wherein, the compound complexing hydroxide particle of isolated fluoride ion is not stripping fluorion in No. 46 tests of Environmental Agency's bulletin.
(13) method of above-mentioned (1) described reduction fluorion, wherein, the fluorinion concentration of handling in the draining of back is below the 8mg/L.
(14) method of above-mentioned (1) described reduction fluorion, wherein, the fluorinion concentration of handling in the draining of back is below the 0.8mg/L.
(15) contain the drainge treating agent that is used to remove fluorion of the compound complex oxide of following formula (1) expression.
Embodiment
It is that the embodiment of the method for fluorinion concentration in the draining below 4.0 is characterised in that the present invention reduces fluorine-containing pH that semiconductor manufacturing factory discharges, in this draining, add compound complex oxide, stir, place, after forming fluorine-containing compound complexing hydroxide particle thus, separate this compound complexing hydroxide particle.
The compound complex oxide of the following formula that uses among the present invention (1) expression be compound complexing oxyhydroxide with following formula (2) expression 500～1,000 ℃, the compound that preferably obtains at 750～850 ℃ temperature lower calcination.The compound complexing oxyhydroxide and the manufacture method thereof of this formula (2) expression are on the books in the public clear 48-29479 communique of spy.
M
2+ xM
3+ y(OH)
2x+3y-nz(A
n-)
z·aH
2O (2)
[in the formula, M
2+Expression is selected from Mg
2+, Zn
2+, Ni
2+, Fe
2+, Ca
2+And Cu
2+In at least a, M
3+Expression is selected from least a among Al and the Fe, A
N-Be the negatively charged ion of n valency, expression is selected from least a in the inorganic anion of 1～4 valency or the organic coordination negatively charged ion, and described organic coordination negatively charged ion has 1～4 and is selected from-COOH ,-OH ,-SH ,-SO
3The functional group more than a kind or 2 kinds among the H, a represents integer, x, y, z meet the following conditions respectively: 1/8＞y/x＞0,4/8 〉=z/ (x+y) 〉=0].
The calcining temperature of the oxyhydroxide in the formula (2) is 500～1, and 000 ℃ wide temperature range can obtain having the oxide compound of high BET surface-area, but is preferably 750～850 ℃.
In the compound complex oxide of the formula of Shi Yonging (1) expression in the present invention, as M
2+As mentioned above, can enumerate Mg
2+, Zn
2+, Ni
2+, Fe
2+, Ca
2+Or Cu
2+Preferred Mg
2+, Ca
2+, more preferably Mg
2+
M
3+As mentioned above, can enumerate Al
3+Or Fe
3+Preferred Al
3+
In the present invention, the BET surface-area of the compound complex oxide of formula (1) is preferably 100～400m
2/ g, more preferably 150～400m
2/ g.If the BET surface-area is less than 100m
2/ g, then active low, therefore being transformed into oxyhydroxide in water just needs the long time, and simultaneously, the fluorion loading capacity is little, is disadvantageous.The upper limit is not had special stipulation, but be difficult to obtain to surpass 400m
2The compound complex oxide of/g.
The draining that semiconductor manufacturing factory is discharged is owing to the fluorinion concentration height, and in most cases pH is below 4.0.In addition, pH is low more, this compound complex oxide is fast more to the transformation of compound complexing oxyhydroxide, under the pH situation more than the neutrality, slack-off to the speed that compound complexing oxyhydroxide changes, and this compound complex oxide can not all be transformed into compound complexing oxyhydroxide, and the result can not make fluorion be reduced to expectation concentration.
In the present invention, the fluorinion concentration in this draining is generally 1～300mg/L.The upper limit is not had particular determination, can make the fluorine concentration in the draining be reduced to expectation concentration by the addition of regulating compound complex oxide.In addition, the fluorinion concentration in the draining that semiconductor manufacturing factory is discharged minimum usually is 20mg/L, is 300mg/L to the maximum.
Liquid temperature when in the present invention, this draining contacts with this compound complex oxide is preferably 10～25 ℃.The liquid temperature of draining whole year that this temperature has considered that semiconductor factory discharges, the upper limit is high more good more, but in the winter time, because the liquid temperature is low, makes it reach 25 ℃ of heat energy that needs are a large amount of, considers it is disadvantageous from economic angle.
Among the present invention, be preferably 5 minutes the duration of contact of this draining and this compound complex oxide～3 hours, more preferably 15 minutes～1 hour.If making duration of contact is below 5 minutes, then this compound complex oxide is little to the transformation amount of compound complexing oxyhydroxide, and the fluorine loading capacity is little, is disadvantageous therefore.The upper limit is not had particular determination, if but be more than 3 hours, then the treatment time long, be disadvantageous.
In the present invention, with respect to these draining 100 weight parts, the addition of this compound complex oxide is preferably 0.05～10 weight part, more preferably 0.1～5 weight part.The upper limit there is not particular determination, if but addition surpasses 10 weight parts, precipitate and separate then, and the amount of this compound complexing oxyhydroxide of depleted increases, and is uneconomical.
In the present invention, for the compound complexing hydroxide particle that makes the fluoride ion after processing precipitate and separate from draining easily, preferably add agglutinant.
As this agglutinant, commercially available mineral-type agglutinant and commercially available polymer coagulant all are effective.With respect to this compound complex oxide 1 weight part, addition is preferably 0.01～0.5 weight part, and more preferably 0.2～0.5 weight part is favourable.
In addition, in the present invention, the pH of draining that has isolated the compound complexing hydroxide particle of fluoride ion is preferably 9.5～11.0, but by add mineral acid such as sulfuric acid in this draining, can easily make pH reach the pH5.6-8.6 of standard of drainage.
The compound complexing hydroxide particle of isolated fluoride ion meets the fluorion stripping standard in No. 46 tests of Environmental Agency's bulletin in the present invention.
According to preferred implementation of the present invention, the fluorinion concentration in the draining of fluoride ion is reached below the standard of drainage value 8ppm, even reach below the edatope standard value 0.8ppm.
As mentioned above, according to the present invention, pH by the fluoride ion of discharging at semiconductor manufacturing factory in the draining 4.0 below, adds the compound complex oxide that following formula (1) is represented, can make fluorinion concentration in the draining after the processing reach environmental standard even soil is below the mark.
In addition, even there are a large amount of various negatively charged ion (SO in this draining
4 2-, Cl
-, NO
3 -Deng), also can optionally adsorb and remove fluorion.
Embodiment
By the following examples the present invention is specifically described, but the invention is not restricted to following examples.
In addition, the magnesium in the compound complex compound, aluminium adopt chelating method, carbanion to adopt JIS K9101, chlorion and nitrate ion to adopt ion chromatography, sulfate ion to adopt colorimetry to measure.
Synthesizing of compound complexing oxyhydroxide and oxide compound thereof
Synthesis example 1
At capacity is to add 1.0L magnesium chloride 6 water salt brine solutions (the 6 Shui salt aqueous solution) (Mg in the beaker of 2L
2+=1.3mol/L) and 0.217L aluminum chloride 6 water salt brine solution (Al
3+=0.6mol/L), the liquid temperature is adjusted into 30 ℃.Under agitation with the flow velocity adding 3.4mol/L aqueous sodium hydroxide solution of pump of constant delivery type with 5ml/ minute, pH becomes 11.6 until reaction solution, stopped reaction then.Afterwards, washing and filtering reacting liquid, are pulverized with the laboratory scale impactor after 15 hours 80 ℃ of dryings in baking oven, obtain compound complex compound powder thus.The composition formula of the compound complex compound powder of gained is Mg
10.1Al (OH)
22.35(Cl)
0.853.3H
2O.
Adopt the indirect rotary kiln of laboratory scale 750 ℃ temperature,, obtain compound complex oxide the compound complex compound powder calcining of gained 1 hour.The BET surface-area of the compound complex oxide that obtains is 170m
2/ g, composition formula are Mg
20.2Al
2O
22.35(Cl)
1.7
Synthesis example 2
At capacity is to add 1.0L magnesium nitrate 6 water salt brine solution (Mg in the beaker of 2L
2+=1.25mol/L) and 0.231L aluminum nitrate 6 water salt brine solution (Al
3+=0.45mol/L), the liquid temperature is adjusted into 30 ℃.Under agitation with the flow velocity adding 3.4mol/L aqueous sodium hydroxide solution of pump of constant delivery type, become 11.0 until pH, stopped reaction then with 5mL/ minute.Afterwards, washing and filtering reacting liquid, are pulverized with the laboratory scale impactor after 15 hours 80 ℃ of dryings in baking oven, obtain compound complex compound powder thus.The composition formula of the compound complex compound powder of gained is Mg
12.2Al (OH)
26.0(NO
3)
1.43.2H
2O.
Same with synthesis example 1, the compound complex compound powder of gained to be calcined, the BET surface-area of the compound complex oxide that is obtained is 185m
2/ g, its composition formula are Mg
24.3Al
2O
26.6(NO
3)
0.7
Synthesis example 3
At capacity is to add 1.0L sal epsom 6 water salt brine solution (Mg in the beaker of 2L
2+=1.5mol/L) and 0.3L Tai-Ace S 150 6 water salt brine solution (Al
3+=0.5mol/L), the liquid temperature is adjusted into 30 ℃.Under agitation with the flow velocity adding 3.4mol/L aqueous sodium hydroxide solution of pump of constant delivery type, become 10.8 until pH, stopped reaction then with 5mL/ minute.Afterwards, washing and filtering reacting liquid, are pulverized with the laboratory scale impactor after 15 hours 80 ℃ of dryings in baking oven, obtain compound complex compound powder thus.The composition formula of the compound complex compound powder of gained is Mg
14.1Al (OH)
29.74(SO
4)
0.734.3H
2O.
Same with synthesis example 1, the compound complex compound powder that obtains to be calcined, the BET surface-area of the compound complex oxide that is obtained is 165m
2/ g, its composition formula are Mg
28.2Al
2O
30.47(SO
4)
0.73
Embodiment 1
In containing the 200mL draining of ionic shown in the table 1, add the compound complex oxide 0.3g (0.15 weight part) that synthesis example 1 obtains, with magnetic stirrer 30 minutes (fluid temperature is 22.5 ℃ during stirring) by the semiconductor manufacturing factory discharge.Afterwards, the fluorinion concentration of the supernatant liquor that solid-liquid separation obtains is 1.7mg/L, meets standard of drainage.In addition, the pH of liquid is 10.43.
In addition, the fluorion loading capacity of this compound complex oxide is 3.2mmol/g under this condition.
Various ionic concns (mg/L) and pH in the draining of table 1 semiconductor factory
| F - | Cl - | NO 3 - | SO 4 2- | Na + | Ca 2+ | Mg 2+ | Al 3+ | pH |
| 93.9 | 530 | 100 | 325 | 163 | 76.1 | 10.1 | 1.6 | 2.10 |
F
-：JIS?K?0120?34.1
Cl
-, NO
3 -: chromatography of ions
Other: ICP
Embodiment 2
Except the addition with this compound complex oxide among the embodiment 1 changed 0.75g (0.35 weight part) into, other processing was the same with embodiment 1.As a result, fluorinion concentration is 0.41mg/L, meets the soil standard, and the pH of liquid is 10.50.The fluorion loading capacity of this compound complex oxide is 1.31mmol/g under this condition.
Embodiment 3
Except this compound complex oxide among the embodiment 2 being changed into the compound complex oxide that synthesis example 2 obtained, other processing is the same with embodiment 2.As a result, fluorinion concentration is 0.17mg/L, meets the soil standard.The pH of liquid is 10.44.
In addition, the fluorion loading capacity of this compound complex oxide is 1.97mmol/g under this condition.
Embodiment 4
Except this compound complex oxide among the embodiment 2 being changed into the compound complex oxide that synthesis example 3 obtained, other processing is the same with embodiment 2.As a result, fluorinion concentration is 0.22mg/L, meets the soil standard.The pH of liquid is 10.51.
In addition, the fluorion loading capacity of this compound complex oxide is 1.97mmol/g under this condition.
Embodiment 5
The liquid temperature of the 200mL draining of being discharged by semiconductor manufacturing factory that contains fluorion shown in the table 1 is adjusted to 9～11 ℃, add the compound complex oxide 1.0g (0.5 weight part) that synthesis example 1 obtains, with magnetic stirrer 2 hours (the liquid temperature transfers to 9～11 ℃ all the time during this period).Afterwards, the F ionic concn in the supernatant liquor that solid-liquid separation obtains is 0.25mg/L, meets the soil standard.The pH of liquid is 10.25.
In addition, the fluorion loading capacity of this compound complex oxide is 0.99mmol/g under this condition.
Embodiment 6
Containing ionic shown in the table 1 by 3 of semiconductor manufacturing factory discharge, in the 000mL draining, adding the compound complex oxide 10.5g (0.35 weight part) that synthesis example 1 obtains, stirring 1 hour with chemi-stirrer (ケ ミ ス タ ラ one).Afterwards, add the agglutinant ス カ イ Network リ one Application S 0.3g (adding 0.033 weight part with respect to this oxide compound 1 weight part) that ミ Network ニ エ コ ジ ス テ system (strain) is made, form the good piece of settleability, stirred 20 seconds, solid-liquid can separate fully.Afterwards, stop to stir, add sulfuric acid in the supernatant liquor that solid-liquid separation obtains, regulate pH to 7.5, the fluorinion concentration in this liquid is 0.14mg/L, meets the soil standard.In addition, the fluorion loading capacity of this compound complex oxide is 1.41mmol/g under this condition.
Embodiment 7
According to No. 46, Environmental Agency's bulletin, the compound complexing hydroxide particle of the fluoride ion that solid-liquid separation among the embodiment 6 is obtained is implemented dissolution test, the result, and the fluorinion concentration of stripping meets the soil standard less than 0.1mg/L.
Comparative example 1
In the pH that fluorinion concentration transfers to 98.2mg/L is sample draining (draining of モ デ Le) (sodium fluoride aqueous solution) 200mL of 8.20, add the compound complex oxide that 1g (0.5 weight part) synthesis example 2 obtains, with magnetic stirrer 30 minutes (the liquid temperature during stirring is 22.2 ℃).Afterwards, the F ionic concn in the supernatant liquor that solid-liquid separation obtains is 25.5mg/L, does not meet standard of drainage.The pH of this liquid is 11.85.
In addition, the fluorion loading capacity of this compound complex oxide under this condition is 0.77mmol/g.
Comparative example 2
Except the churning time with the magnetic stirring apparatus in the comparative example 1 changed into 24 hours, other processing is the same with comparative example 1.As a result, fluorinion concentration is 11.3mg/L, does not meet standard of drainage.
In addition, the fluorion loading capacity of this compound complex oxide under this condition is 0.92mmol/g.
By embodiment 1-7 as can be known, in the pH of the fluoride ion that semiconductor manufacturing factory is discharged is draining 4.0 below, add compound complex compound is calcined the compound complex oxide that forms, can effectively remove the fluorion in the draining.And, fluorinion concentration is reached below the standard of drainage 8mg/L and below the soil standard 0.8mg/L.In addition, the maximum adsorption capacity that makes above-mentioned situation become this possible compound complex oxide is respectively 3mmol/g, 1.4mmol/g.
According to this loading capacity,, can obtain by the addition that calculates this compound complex oxide that adds no matter how many fluorinion concentrations in this draining is.
Further, owing to adsorbed compound complexing oxyhydroxide not stripping fluorion in the dissolution test of Environmental Agency's bulletin of fluorion, so the processing of waste is easy, can implement with low expense.
In addition, by comparative example 1～2 as can be known, this compound complex oxide then can not effectively be removed fluorion if not low pH draining.
Claims (12)
1. reduce the pH that contains fluorion that semiconductor manufacturing factory discharges and be the method for the fluorion in the draining below 4.0, it is characterized in that in the pH of the fluoride ion that semiconductor manufacturing factory is discharged is draining 4.0 below, adding the compound complex oxide that following formula (1) is represented, the compound complexing hydroxide particle of formed fluoride ion is separated from the draining of handling
M
2+ xM
3+ yO
(x+3y/2-nz/2)(A
n-)
z (1)
In the formula, M
2+Expression Mg
2+, M
3+Expression Al
3+, A
N-Be the negatively charged ion of n valency, expression is selected from Cl
-, NO
3 -And SO
4 2-In at least a, x, y, z meet the following conditions respectively: 1/8＞y/x＞0,1/2 〉=z/ (x+y)＞0.
2. the method for the fluorion in the above-mentioned draining of the described reduction of claim 1, wherein, the BET surface-area of this compound complex oxide is 100～400m
2/ g.
3. the method for the fluorion in the above-mentioned draining of the described reduction of claim 1, wherein, the fluorinion concentration in this draining is 1～300mg/L.
4. the method for the fluorion in the above-mentioned draining of the described reduction of claim 1, wherein, treatment temp is 10～25 ℃.
5. the method for the fluorion in the above-mentioned draining of the described reduction of claim 1, wherein, be 5 minutes～3 hours the duration of contact of adding in this draining behind this compound complex oxide.
6. the method for the fluorion in the above-mentioned draining of the described reduction of claim 1 wherein, with respect to these draining 100 weight parts, is used this compound complex oxide 0.05～10 weight part.
7. the method for the fluorion in the above-mentioned draining of the described reduction of claim 1 wherein, is added agglutinant in the draining of the processing of the compound complexing hydroxide particle that contains formation, compound complexing hydroxide particle is separated with the draining of handling.
8. the method for the fluorion in the above-mentioned draining of the described reduction of claim 7 wherein, with respect to this compound complex oxide 1 weight part, is added this agglutinant 0.01～0.5 weight part.
9. the method for the fluorion in the above-mentioned draining of the described reduction of claim 1, wherein, the compound complexing hydroxide particle of isolated fluoride ion is not stripping fluorion in No. 46 tests of Environmental Agency's bulletin.
10. the method for the fluorion in the above-mentioned draining of the described reduction of claim 1, wherein, the fluorinion concentration of handling in the draining of back is below the 8mg/L.
11. the method for the fluorion in the above-mentioned draining of the described reduction of claim 1, wherein, the fluorinion concentration of handling in the draining of back is below the 0.8mg/L.
12. contain the drainge treating agent that is used to remove fluorion of the compound complex oxide of following formula (1) expression,
M
2+ xM
3+ yO
(x+3y/2-nz/2)(A
n-)
z (1)
In the formula, M
2+Expression Mg
2+, M
3+Expression Al
3+, A
N-Be the negatively charged ion of n valency, expression is selected from Cl
-, NO
3 -And SO
4 2-In at least a, x, y, z meet the following conditions respectively: 1/8＞y/x＞0,1/2 〉=z/ (x+y)＞0.
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|---|---|---|---|
| JP2006-063013 | 2006-03-08 | ||
| JP2006063013A JP4809080B2 (en) | 2006-03-08 | 2006-03-08 | Waste water treatment method and waste water treatment agent containing fluorine ions |
| JP2006063013 | 2006-03-08 |
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| Publication Number | Publication Date |
|---|---|
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| CN101041496B true CN101041496B (en) | 2011-12-14 |
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| JP5417927B2 (en) * | 2009-03-24 | 2014-02-19 | 電源開発株式会社 | Coal gasification wastewater treatment method |
| JP5943632B2 (en) * | 2012-02-15 | 2016-07-05 | Ｄｏｗａメタルテック株式会社 | Treatment method for fluorine-containing wastewater |
| CN102659254B (en) * | 2012-05-29 | 2013-12-11 | 北京大学 | Method for removing fluorions in drinking water by strengthened magnesium precipitations |
| CN103253788B (en) * | 2012-12-28 | 2014-07-09 | 中国科学院生态环境研究中心 | Method for removing fluorides in water through aluminum base composite metal oxide-based fluorine removing absorption material complexation-absorption |
| CN105645626B (en) * | 2014-11-28 | 2019-04-19 | 中芯国际集成电路制造(上海)有限公司 | Wastewater treatment method |
| CN108816182A (en) * | 2018-05-28 | 2018-11-16 | 苏州佑君环境科技有限公司 | A kind of preparation method of modified coal ash fluorine ion absorber |
| CN108996642B (en) * | 2018-09-04 | 2021-09-10 | 中国铝业股份有限公司 | Treatment method of chlorine-containing wastewater |
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| JP4521109B2 (en) * | 2000-11-07 | 2010-08-11 | 宇部マテリアルズ株式会社 | Wastewater treatment method |
| JP4006584B2 (en) * | 2002-07-10 | 2007-11-14 | 富田製薬株式会社 | Fluorine adsorbent and method for treating fluorine in water |
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