CN101041529A - Drainge treating agent and method for reducing fluorin ion in drainge - Google Patents
Drainge treating agent and method for reducing fluorin ion in drainge Download PDFInfo
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- CN101041529A CN101041529A CNA2007100857490A CN200710085749A CN101041529A CN 101041529 A CN101041529 A CN 101041529A CN A2007100857490 A CNA2007100857490 A CN A2007100857490A CN 200710085749 A CN200710085749 A CN 200710085749A CN 101041529 A CN101041529 A CN 101041529A
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- metal compound
- complex metal
- draining
- treatment agent
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- 238000000034 method Methods 0.000 title claims abstract description 32
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 75
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 229910019440 Mg(OH) Inorganic materials 0.000 claims abstract description 12
- 239000000347 magnesium hydroxide Substances 0.000 claims description 27
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 27
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 26
- 229960001545 hydrotalcite Drugs 0.000 claims description 6
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 6
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 238000007561 laser diffraction method Methods 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 229960001708 magnesium carbonate Drugs 0.000 claims description 2
- 238000000790 scattering method Methods 0.000 claims description 2
- 229940024545 aluminum hydroxide Drugs 0.000 claims 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- 238000004065 wastewater treatment Methods 0.000 abstract 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 23
- 229910052731 fluorine Inorganic materials 0.000 description 23
- 239000011737 fluorine Substances 0.000 description 23
- 229940126062 Compound A Drugs 0.000 description 19
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000007788 liquid Substances 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 239000003513 alkali Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000006228 supernatant Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- PWZFXELTLAQOKC-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide;tetrahydrate Chemical compound O.O.O.O.[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O PWZFXELTLAQOKC-UHFFFAOYSA-A 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000002689 soil Substances 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 description 3
- 239000003518 caustics Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 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 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- -1 complex metal oxides Chemical class 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 235000012245 magnesium oxide Nutrition 0.000 description 1
- 229960000869 magnesium oxide Drugs 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229940091250 magnesium supplement Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention provides a wastewater treatment agent containing fluorine ion constituted by composite metal compound showed by the following formula (I) and method for reducing fluorine ion in wastewater. [Mg(OH)<SUB>2</SUB>]<SUB>x</SUB>.Al<SUB>2</SUB>(OH)<SUB>6-2y-z</SUB>.(CO<SUB>3</SUB>)<SUB>y</SUB>.(Cl)<SUB>z</SUB>.nH<SUB>2</SUB>O (I)(wherein', x,y,z and n satisfy 1<=x<=12,0<=y<=1,0<=z<=1,0.1<=n<=10, 0.1<=(y+z)<=1.5).
Description
Technical field
The present invention relates to contain the treatment agent of draining of fluorion and the method that the fluorion in the draining is reduced.
Background technology
Often fluorions (being sometimes referred to as fluorine) that contain particularly usually use the etching agent of a large amount of hydrofluoric acid as silicon chip more in the plant drainage when making semi-conductor.Though this hydrofluoric acid can water etc. is washed away, and can contain the fluorine of high density in the draining.Fluorine concentration in the standard of drainage regulation inspection liquid of Environmental Agency's issue is below the 8mg/L; Fluorine concentration in the soil standard code inspection liquid is below the 0.8mg/L.
As the method for removing the fluorine in the fluorine-containing draining, proposed in fluorine-containing draining, to add calcium salt and made it generate the method (with reference to Japanese kokai publication hei 10-57969 communique) of insoluble Calcium Fluoride (Fluorspan).
In addition, also proposed in fluorine-containing draining, to add chemical constitution formula
M
1-x 2+M
x 3+(OH
-)
2+x-y(A
n-)
y/n
[in the formula, M
2+Expression is selected from Mg
2+, Ni
2+, Zn
2+, Fe
2+, Ca
2+And Cu
2+In at least a metal ion, M
3+Expression is selected from Al
3+And Fe
3+In at least a metal ion, A
N-Expression n valency negatively charged ion, 0.1≤x≤0.5,0.1≤y≤0.5, n represents 1 or 2.]
The method of shown complex metal hydroxide, and add chemical constitution formula
M
1-x 2+M
x 3+O
2-x/2 2-
[in the formula, M
2+Expression is selected from Mg
2+, Ni
2+, Zn
2+, Fe
2+, Ca
2+And Cu
2+In at least a metal ion, M
3+Expression is selected from Al
3+And Fe
3+In at least a metal ion, 0.1≤x≤0.5.]
The method of shown complex metal oxides (with reference to TOHKEMY 2004-41899 communique).
But for for adding calcium salt in the fluorine-containing draining makes its method that produces Calcium Fluoride (Fluorspan), the solubleness of Calcium Fluoride (Fluorspan) arrives 0.0016g/100g (18 ℃) greatly, does not meet the soil standard.And the method that adds complex metal hydroxide and complex metal oxides in fluorine-containing draining of TOHKEMY 2004-41899 communique can not meet below the fluorine concentration 0.8mg/L of soil standard.
Summary of the invention
One of purpose of the present invention is to provide the drainge treating agent of the absorption property excellence of fluorion.The present invention also aims to remove the method for fluorion in the draining.
The inventor furthers investigate the material of fluorion absorption property excellence.Found that: specific complex metal oxides has excellent fluorine absorption property, and then finishes the present invention.In addition, also find by in the draining that contains the high density fluorine, adding this complex metal compound, can will handle below the 8mg/L that fluorine concentration in the draining of back reach standard of drainage, below the 0.8mg/L of soil standard, and then finish the present invention.
That is, the present invention is constituted, is contained the treatment agent of the draining of fluorion by complex metal compound shown in the following formula (I).
[Mg(OH)
2]
x·Al
2(OH)
6-2y-z·(CO
3)
y·(Cl)
z·nH
2O (I)
(in the formula, x, y, z and n satisfy 1≤x≤12,0≤y≤1,0≤z≤1,0.1≤n≤10,0.1≤(y+z)≤1.5)
The present invention is the method that the fluorion in the draining is reduced, and it is characterized in that, the complex metal compound shown in the following formula (I) is contacted with the draining that contains fluorion.
[Mg(OH)
2]
x·Al
2(OH)
6-2y-z·(CO
3)
y·(Cl)
z·nH
2O (I)
(in the formula, x, y, z and n satisfy 1≤x≤12,0≤y≤1,0≤z≤1,0.1≤n≤10,0.1≤(y+z)≤1.5)
Description of drawings
Fig. 1 is the X-ray diffractogram of complex metal compound A.
Fig. 2 is the X-ray diffractogram of complex metal compound D.
Embodiment
＜drainge treating agent 〉
The present invention is the treatment agent that contains the draining of fluorion, it is characterized in that, this treatment agent is made of the complex metal compound shown in the following formula (I).
[Mg(OH)
2]
x·Al
2(OH)
6-2y-z·(CO
3)
y·(Cl)
z·nH
2O (I)
(in the formula, x, y, z and n satisfy 1≤x≤12,0≤y≤1,0≤z≤1,0.1≤n≤10,0.1≤(y+z)≤1.5)
In the formula (I), x satisfies 1≤x≤12, preferably satisfies 2≤x≤7.Y satisfies 0≤y≤1, preferably satisfies 0.1≤y≤0.8.Z satisfies 0≤z≤1, preferably satisfies 0.1≤z≤0.5.N satisfies 0.1≤n≤10, preferably satisfies 0.5≤n≤5.Y+z satisfies 0.1≤(y+z)≤1.5, preferably satisfies 0.15≤(y+z)≤1.2.
If x is less than 1, then the fluorion loading capacity reduces to heavens, but its reason is also indeterminate.If x is greater than 12, then the growing amount of the aluminium hydroxide sample material in the formula (I) can extremely reduce, so itself or fluorion loading capacity reduce to heavens.If y+z is less than 0.1, then the fluorion adsorption site can tail off to heavens, so the fluorion loading capacity reduces to heavens.Though the high more then fluorion of y+z loading capacity is high more, the material above 1.5 is can't synthetic.In order to make n less than 0.1, when drying, need a large amount of heat energy, therefore unfavorable economically.In addition, if n surpasses 10, then the solid component content in the compound reduces to heavens, and the fluorion loading capacity reduces.
As complex metal compound, compound shown in the preferred following formula (I-1) and the compound shown in the following formula (I-2).
[Mg(OH)
2]
x·Al
2(OH)
6-2y·(CO
3)
y·nH
2O (I-1)
(in the formula (I-1), x, y, n satisfy 1≤x≤12,0≤y≤1,0.5≤n≤3.0)
[Mg(OH)
2]
x·Al
2(OH)
6-2y-z·(CO
3)
y·(Cl)
z·nH
2O (I-2)
(in the formula (I-2), x, y, z and n satisfy 1≤x≤12,0≤y≤1,0≤z≤1,0.1≤n≤10,0.1≤(y+z)≤1.5)
This compound (I-2) can be by using the CO of hydrochloric acid with compound shown in the following formula (I-1)
3Ion-exchange becomes Cl and makes.Complex metal compound can use separately, perhaps uses together more than 2 kinds.
Complex metal compound measures, confirms as the compound of magnesium hydroxide crystallization pattern by x-ray powder diffraction, as the material that has identical chemical constitution with complex metal compound, well-known is hydrotalcite, complex metal compound and hydrotalcite are diverse materials but by the structural analysis of x-ray powder diffraction as can be known.
That is to say that the complex metal compound shown in the formula of the present invention (I) does not have the crystallization pattern of hydrotalcite according to the mensuration of utilizing x-ray powder diffraction to carry out.In addition, according to the mensuration of utilizing identical diffraction approach to carry out, do not see the crystallization pattern of aluminium hydroxide, magnesiumcarbonate, aluminum chloride and magnesium chloride basically yet.
Be preferably as the complex metal compound of drainge treating agent and be easy to the micropartical that spread in draining, the median size of utilizing the laser diffraction and scattering method to measure is preferably 0.1～50 μ m, more preferably 0.5～20 μ m.
Complex metal compound can be made by making the reaction of (1) magnesium hydroxide slurry, (2) aluminum saline solution and (3) carbonic acid alkali aqueous solution or caustic-alkali aqueous solution.
Can enumerate Tai-Ace S 150, aluminum chloride, aluminum nitrate etc. as (2) aluminium salt.Can enumerate yellow soda ash, salt of wormwood, volatile salt etc. as (3) carbonic acid alkali.Can enumerate sodium hydroxide, potassium hydroxide, ammonium hydroxide etc. as (3) caustic alkali.(1) the magnesium hydroxide slurry is so long as Mg (OH)
2Slurry is then without any restriction.
As the mol ratio of each composition, Mg/Al is preferably 0.5～1.5, more preferably 1.0～4.0; Carbonic acid alkali/Al is preferably 0～1.4, more preferably 0.5～1.2; Caustic alkali/Al is preferably 0～2.8, more preferably 1～2.4.
Being characterized as of this reaction method makes with respect to (3) carbonic acid alkali of (2) aluminum saline solution usage quantity or caustic alkali usage quantity below theoretical equivalent.In addition, insufficient alkali source is obtained by magnesium hydroxide.Inferring thus, is not to be the mixture of simple magnesium hydroxide and simple aluminium hydroxide, but becomes non-crystal but have the form of the mixture of aluminium and interactional oxyhydroxide of magnesium and magnesium hydroxide.
In this manufacture method,, can obtain the complex metal compound shown in the formula (I) by in the magnesium hydroxide slurry of necessary amount, dropping into aluminum saline solution, the carbonic acid alkali aqueous solution of necessary amount simultaneously.The preferred reaction pH that adjusts, the pH when making reaction terminating reaches 6.0～9.0, and temperature of reaction is adjusted to 10～50 ℃.The importing of Cl is as long as can obtain with salt acid treatment gained complex metal compound.
The method of fluorinion concentration in the＜reduction draining 〉
The present invention is the method that the fluorinion concentration in the draining is reduced, and it is characterized in that, above-mentioned complex metal compound is contacted with the draining that contains fluorion.Fluorinion concentration in the draining of discharging from semiconductor fabrication factory is generally 0.85～300mg/L, by adjusting the addition of complex metal compound, and also can be corresponding to the draining of high density.
Draining can be carried out Yi Bian drop into complex metal compound by stirring the degree of draining until the whole liquid mixing on one side with contacting of complex metal compound.By this contact, fluorion is adsorbed on the treatment agent.Duration of contact at 5 minutes with interior promptly enough.
The usage quantity of complex metal compound according to the content of fluoride ion in the draining, handle the content of fluoride ion in the draining of back the setting preset value and difference, with respect to the draining of per 100 weight parts, complex metal compound is preferably 0.1～10 weight part, 1～5 weight part more preferably.If below 10 weight parts, the abandonment charge of the waste after then handling uprises, and is unrealistic.If be lower than 0.1 weight part, it is below the mark that the negative ion concentration after then handling in the draining can not be reduced to soil.
Promptly discarded for the supernatant liquor that drops into complex metal compound in draining, will remove fluorion, dropping into agglutinant, to make complex metal compound promptly be deposited in industrial be favourable.In order to reach this purpose, use agglutinant.As the kind of agglutinant, negatively charged ion is that the polyacrylamide amine compound of agglutinant is effective.With respect to the complex metal compound of per 1 weight part, the usage quantity of agglutinant is preferably 0.01～0.5 weight part, 0.05～0.3 weight part more preferably.At this moment, the interpolation of agglutinant can be carried out after adding complex metal compound, also can side by side carry out with it.That is, preferably, add agglutinant making complex metal compound with the draining while of containing fluorion or after contacting.
Temperature when complex metal compound is contacted with agglutinant is preferably 4～60 ℃, more preferably 10～25 ℃.4 ℃ of liquid temperature that is assumed to be winter be assumed to be under 40 ℃ of summer, it is same degree that fluorine is removed efficient.
If use treatment agent of the present invention, the fluorinion concentration in the draining is reached below the 8mg/L.If use treatment agent of the present invention, the fluorinion concentration in the draining is reached below the 0.8mg/L.In addition, if use treatment agent of the present invention, then can make the following draining of pH3 reach pH5.6～8.6.
As mentioned above, treatment agent of the present invention has the excellent fluoride absorption property.By the inventive method, can reduce the fluorion in the draining.In addition, by the inventive method, it is following and then to be reduced to soil below the mark to make fluorinion concentration in the draining be reduced to standard of drainage.In addition, the pH of the draining that contains the high density fluorion about pH4 is neutralized, reach within the standard of drainage by the inventive method.And then, by the inventive method, even if there are a large amount of various negatively charged ion (SO in the draining
4 2-, Cl
-, NO
3 -Deng), also can optionally adsorb fluorion.
Embodiment
Below, specifically describe the present invention according to embodiment, but the present invention is not subjected to the qualification of following examples.Need to prove that the aluminium in the complex metal compound, magnesium are to use the chelating method to measure; The carbonic acid ion is measured according to JIS K 9101; The Cl ion is to use, and RINP2200V that the VOLHARD method is measured, that X-ray diffraction method is to use electric (strain) of science to produce measures by Cu-κ α.
Subject matter: Cu, spectral filter: Ni, voltage: 40KV, electric current: 20mA, sweep velocity: 1 ° of 2 °/minute, 1 ° of RS 0.3mm of grating → DS SS
At volume is to drop into the magnesium hydroxide (キ ス マ F) that 600mL tap water and 100g consonance chemical industry (strain) are produced in the beaker of 3L, make the magnesium hydroxide slurry (2.86 moles/L), under agitation use pump of constant delivery type side by side to drop into 850mL 0.52 mole/L aluminum sulfate aqueous solution and 1 respectively, 0.75 mole/L of 400mL aqueous sodium carbonate with 30 minutes time.Temperature of reaction is 20 ℃, and the pH after reaction finishes is 7.8.
Reaction solution after filtration, washing, use baking oven 60 ℃ dry 20 minutes down, utilize the hammer mill of laboratory scale (lab-scale) to pulverize, obtain complex metal compound A.The composition of the detailed content of reaction conditions and gained complex metal compound A is shown in Table 1.The X-ray diffraction of gained complex metal compound A is illustrated among Fig. 1.As shown in Figure 1, the X-ray diffraction pattern of complex metal compound A only is a magnesium hydroxide crystalline pattern.
Use magnesium hydroxide similarly to Example 1, at volume is modulation 1L2.0 mole/L magnesium hydroxide slurry in the beaker of 3.5L, under agitation use pump of constant delivery type side by side to drop into 770mL 1 mole/L aluminum chloride aqueous solution and 1 respectively, 0.75 mole/L of 250mL aqueous sodium carbonate with 30 minutes time.Temperature of reaction is 30 ℃, and the pH after reaction finishes is 8.3.
Reaction solution after filtration, washing, use baking oven 60 ℃ dry 20 minutes down, utilize laboratory scale hammer mill to pulverize, obtain complex metal compound B.The composition of the detailed content of reaction conditions and gained complex metal compound B is shown in Table 1.
Use magnesium hydroxide similarly to Example 1, at volume is modulation 1L2.5 mole/L magnesium hydroxide slurry in the beaker of 3.5L, under agitation use pump of constant delivery type side by side to drop into 770mL 1 mole/L aluminum nitrate aqueous solution and 1 respectively, 0.75 mole/L of 200mL aqueous sodium carbonate with 30 minutes time.Temperature of reaction is 40 ℃, and the pH after reaction finishes is 8.7.Reaction solution after filtration, washing, use baking oven 60 ℃ dry 20 minutes down, utilize laboratory scale hammer mill to pulverize, obtain complex metal compound C.The composition of the detailed content of reaction conditions and gained complex metal compound C is shown in Table 1.
In the pure water of 1L, behind the suspendible 100g complex metal compound A, filter.Then feed the hydrochloric acid of 0.5 mole/L of 860mL, feed the tap water of 1.5L afterwards again, use baking oven following dry 20 minutes at 60 ℃.Utilize laboratory scale hammer mill to pulverize afterwards, obtain complex metal compound D.The composition of gained complex metal compound D is shown in Table 1.The X-ray diffraction pattern of gained complex metal compound D is shown among Fig. 2.
Table 1
| Synthesis condition | The characteristic of gained complex metal compound | |||||||
| Mg/Al | The Na/ | Reaction pH | Temperature of reaction | X-ray diffraction | Median size | The composition formula of complex | ||
| Embodiment | ||||||||
| 1 | 1.94 | 1.19 | 7.8 | 20℃ | Magnesium hydroxide | 12.5μm | [Mg(OH)
2]
2.7Al
2(OH)
4.0(CO
3)·2.5H
2 | A |
| Embodiment | ||||||||
| 2 | 2.60 | 1.22 | 8.3 | 30℃ | Magnesium hydroxide | 5.3μm | [Mg(OH)
2]
4.1Al
2(OH)
4.0(CO
3)·3.3H
2 | B |
| Embodiment | ||||||||
| 3 | 3.90 | 1.20 | 8.7 | 40℃ | Magnesium hydroxide | 1.5μm | [Mg(OH) 2] 6.3Al 2(OH) 4.0(CO 3)·1.6H 2O | C |
| Embodiment 4 | - | - | - | - | Magnesium hydroxide | 8.5μm | [Mg(OH) 2] 2.5Al 2(OH) 4.8·(CO 3) 0.5· (Cl) 0.2·1.6H 2O | D |
Note 1: Na/Al represents the mol ratio of yellow soda ash/aluminium.
Table 2
Various ionic concns (mg/L) and pH in semiconductor factory's draining
| F - | Cl - | NO 3 - | SO 4 2- | Na + | Ca 2+ | Mg 2+ | Al 3+ | pH |
| 99.6 | 1400 | 800 | 193 | 554 | 1037 | 31.0 | 19.7 | 2.05 |
F
-：JIS K 0102 34.1
Cl
-: ion chromatography
NO
3-: ion chromatography
Other: ICP
Contain the complex metal compound A that adds 1g from semiconductor fabrication factory in the draining that ionic is discharged shown in the table 2 at 100mL, used magnetic stirrer 5 minutes.Carry out solid-liquid separation afterwards, use pH meter to measure the pH value of supernatant liquor, measure fluorine (F) ionic concn according to JIS K0102 34.1.Measurement result is shown in Table 3.
Except the usage quantity that makes complex metal compound A is 3.5g, operation similarly to Example 5.Measurement result is shown in Table 3.
Embodiment 7
Except using complex metal compound B replacement complex metal compound A, operation similarly to Example 6.Measurement result is shown in Table 3.
Embodiment 8
Except using complex metal compound C replacement complex metal compound A, operation similarly to Example 6.Measurement result is shown in Table 3.
Embodiment 9
Except using complex metal compound D replacement complex metal compound A, operation similarly to Example 6.Measurement result is shown in Table 3.
Embodiment 10
After utilizing the method for embodiment 6 to carry out the fluorion adsorption treatment, add the anionic property polymer coagulant [ス ミ Off ロ Star Network FA-40] that 5ppm Sumitomo ア Le ケ system (strain) is produced, after stirring, in the time of 20 seconds, form good agglomerate, can easily carry out solid-liquid separation.Use pH meter to measure the pH value of supernatant liquor, measure fluorine (F) ionic concn according to JIS K0102 34.1.Measurement result is shown in Table 3.
Embodiment 11
In contain the draining that ionic is discharged shown in the table 2 from semiconductor fabrication factory, add pure water, make the aqueous solution that fluorinion concentration reaches 2mg/L.In this aqueous solution of 100mL, add the complex metal compound A of 0.1g, used magnetic stirrer 5 minutes.Carry out solid-liquid separation afterwards, use pH meter to measure the pH value of supernatant liquor, measure fluorine (F) ionic concn according to JIS K0102 34.1.Measurement result is shown in Table 3.
Embodiment 12
In contain the draining that ionic is discharged shown in the table 2 from semiconductor fabrication factory, add Sodium Fluoride, make the aqueous solution that fluorinion concentration reaches 300mg/L.In this aqueous solution of 100mL, add the complex metal compound A of 11.0g, used magnetic stirrer 5 minutes.Carry out solid-liquid separation afterwards, use pH meter to measure the pH value of supernatant liquor, measure fluorine (F) ionic concn according to JIS K0102 34.1.Measurement result is shown in Table 3.
Comparative example 1
Contain adding 1g white lime in the draining that ionic is discharged shown in the table 2 at 100mL from semiconductor fabrication factory, used magnetic stirrer 5 minutes.Carry out solid-liquid separation afterwards, use pH meter to measure the pH value of supernatant liquor, measure fluorine (F) ionic concn according to JIS K0102 34.1.Measurement result is shown in Table 3.
Comparative example 2
Except the usage quantity that makes white lime is 3.5g, similarly operate with comparative example 1.Measurement result is shown in Table 3.
Comparative example 3
Contain the hydrotalcite-based compound (DHT-4) that adds 3.5g consonance chemical industry (strain) production from semiconductor fabrication factory in the draining that ionic is discharged shown in the table 2 at 100mL, used magnetic stirrer 5 minutes.Carry out solid-liquid separation afterwards, use pH meter to measure the pH value of supernatant liquor, measure fluorine (F) ionic concn according to JIS K0102 34.1.Measurement result is shown in Table 3.
Table 3
| Employed compound | X-ray diffraction | Median size (μ m) | F concentration Note 1 (mg/L) | Draining usage quantity (mL) | Sample addition (g) | Handle back liquid pH | F concentration Note 2 (mg/L) | |
| | Complex metal compound A | Magnesium hydroxide | 12.5 | 99.6 | 100 | 1.0 | 6.60 | 7.5 |
| | Complex metal compound A | Magnesium hydroxide | 12.5 | 99.6 | 100 | 3.5 | 7.10 | 0.7 |
| Embodiment 7 | Complex metal compound B | Magnesium hydroxide | 5.3 | 99.6 | 100 | 3.5 | 7.70 | 0.6 |
| Embodiment 8 | Complex metal compound C | Magnesium hydroxide | 1.5 | 99.6 | 100 | 3.5 | 8.03 | 0.7 |
| Embodiment 9 | Complex metal compound D | Magnesium hydroxide | 8.5 | 99.6 | 100 | 3.5 | 6.35 | 0.5 |
| Embodiment 10 | Complex metal compound A | Magnesium hydroxide | 12.5 | 99.6 | 100 | 3.5 | 6.65 | 0.6 |
| Embodiment 11 | Complex metal compound A | Magnesium hydroxide | 12.5 | 2.0 | 100 | 0.1 | 6.10 | 0.6 |
| Embodiment 12 | Complex metal compound A | Magnesium hydroxide | 12.5 | 300 | 100 | 11.0 | 7.20 | 0.6 |
| Comparative example 1 | Ca(OH) 2 | Calcium hydroxide | 2.5 | 99.6 | 100 | 1.0 | 11.10 | 12.3 |
| Comparative example 2 | Ca(OH) 2 | Calcium hydroxide | 2.5 | 99.6 | 100 | 3.5 | 11.86 | 11.0 |
| Comparative example 3 | Mg 4.3Al 2(OH) 12.6(CO 3)· 3.5H 2O | Hydrotalcite | 1.1 | 99.6 | 100 | 3.5 | 6.80 | 10.0 |
Note 1: the fluorine concentration of the draining before handling
Note 2: the fluorine concentration of the draining after the processing
Claims (16)
1. contain the treatment agent of the draining of fluorion, it is characterized in that, this treatment agent is made of the complex metal compound shown in the following formula (I),
[Mg(OH)
2]
x·Al
2(OH)
6-2y-z·(CO
3)
y·(Cl)
z·nH
2O (I)
In the formula, x, y, z and n satisfy 1≤x≤12,0≤y≤1,0≤z≤1,0.1≤n≤10,0.1≤(y+z)≤1.5.
2. the treatment agent of claim 1, the x in its Chinese style (I) satisfies the scope of 2≤x≤7.
3. the treatment agent of claim 1, (y+z) in its Chinese style (I) satisfies 0.15≤(y+z)≤1.2 scope.
4. the treatment agent of claim 1, the n in its Chinese style (I) satisfies the scope of 0.5≤n≤5.
5. the treatment agent of claim 1, wherein complex metal compound has magnesium hydroxide crystalline pattern according to the mensuration of utilizing x-ray powder diffraction to carry out.
6. the treatment agent of claim 1, wherein complex metal compound does not have the crystallization pattern of hydrotalcite, aluminium hydroxide and magnesiumcarbonate according to the mensuration of utilizing x-ray powder diffraction to carry out.
7. the treatment agent of claim 1, wherein the complex metal compound median size of utilizing the laser diffraction and scattering method to measure is the scope of 0.1～50 μ m.
8. the treatment agent of claim 1, wherein complex metal compound can make the fluorinion concentration in the water reach below the 8mg/L.
9. the treatment agent of claim 1, wherein complex metal compound can make the fluorinion concentration in the water reach below the 0.8mg/L.
10. the method that the fluorion in the draining is reduced is characterized in that, the complex metal compound shown in the following formula (I) is contacted with the draining that contains fluorion,
[Mg(OH)
2]
x·Al
2(OH)
6-2y-z·(CO
3)
y·(Cl)
z·nH
2O (I)
In the formula, x, y, z and n satisfy 1≤x≤12,0≤y≤1,0≤z≤1,0.1≤n≤10,0.1≤(y+z)≤1.5.
11. the method for claim 10, wherein the fluorinion concentration in the draining is 0.85～300mg/L.
12. the method for claim 10, this method make the complex metal compound of 0.1～10 weight part contact with the draining of per 100 weight parts.
13. the method for claim 10, contact are to carry out under the temperature of 4～60 ℃ of scopes.
14. the method for claim 10 when contacting or after contact, is added agglutinant in the draining to.
15. the method for claim 14 is added the agglutinant of 0.01～0.5 weight part with respect to the complex metal compound of per 1 weight part.
16. the method for claim 10, wherein the pH of the draining after the contact is 5.6～8.6.
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| JP2006069273A JP4845188B2 (en) | 2006-03-14 | 2006-03-14 | Waste water treatment agent and method for reducing fluorine ions in waste water |
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| JP2006069273 | 2006-03-14 |
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| CN102992440A (en) * | 2012-11-28 | 2013-03-27 | 常州大学 | Purification method of photovoltaic wastewater |
| CN103180251A (en) * | 2010-10-29 | 2013-06-26 | 三菱综合材料株式会社 | Method for processing toxic matter-containing water and processing device |
| CN103224274A (en) * | 2013-05-07 | 2013-07-31 | 西南石油大学 | Preparation method of multinucleated inorganic coagulant |
| CN104944555A (en) * | 2014-03-31 | 2015-09-30 | 株式会社韩水 | Inorganic coagulant for fluorine removing water treatment and production method of inorganic coagulant |
| CN107337299A (en) * | 2017-08-25 | 2017-11-10 | 辽宁工程技术大学 | A kind of fluorine removal water purification agent and preparation method thereof |
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| JP2009195843A (en) * | 2008-02-22 | 2009-09-03 | Teijin Engineering Ltd | Molding containing fine particle of nitrate ion-selective adsorbent and its manufacturing method |
| CN105148850B (en) * | 2015-09-08 | 2017-10-20 | 华南理工大学 | The method of sulfate ion in a kind of composite Adsorption water of layer structure |
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| JPS523353B2 (en) * | 1971-12-25 | 1977-01-27 | ||
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| JPS6034927A (en) * | 1983-08-05 | 1985-02-22 | Kyowa Chem Ind Co Ltd | Purification of cyclohexanone containing organic acid as by-product |
| JP2005193167A (en) * | 2004-01-08 | 2005-07-21 | Sophia Co Ltd | Drainage purification method and purification method |
| JP4036237B2 (en) * | 2004-03-16 | 2008-01-23 | 学校法人早稲田大学 | Hydrotalcite-like substance, method for producing the same, and method for immobilizing harmful substances |
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| CN103180251A (en) * | 2010-10-29 | 2013-06-26 | 三菱综合材料株式会社 | Method for processing toxic matter-containing water and processing device |
| CN105692759A (en) * | 2010-10-29 | 2016-06-22 | 三菱综合材料株式会社 | Method for processing toxic matter-containing water and processing device |
| CN105692759B (en) * | 2010-10-29 | 2019-06-07 | 三菱综合材料株式会社 | The processing method and processing unit of the water to contain hazardous substance |
| CN102992440A (en) * | 2012-11-28 | 2013-03-27 | 常州大学 | Purification method of photovoltaic wastewater |
| CN103224274A (en) * | 2013-05-07 | 2013-07-31 | 西南石油大学 | Preparation method of multinucleated inorganic coagulant |
| CN104944555A (en) * | 2014-03-31 | 2015-09-30 | 株式会社韩水 | Inorganic coagulant for fluorine removing water treatment and production method of inorganic coagulant |
| CN107337299A (en) * | 2017-08-25 | 2017-11-10 | 辽宁工程技术大学 | A kind of fluorine removal water purification agent and preparation method thereof |
| CN107337299B (en) * | 2017-08-25 | 2020-09-29 | 辽宁工程技术大学 | A kind of fluorine-removing water purifying agent and preparation method thereof |
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