CN102428038B - Treatment agent and manufacture method thereof and treatment process - Google Patents
Treatment agent and manufacture method thereof and treatment process Download PDFInfo
- Publication number
- CN102428038B CN102428038B CN201080021862.2A CN201080021862A CN102428038B CN 102428038 B CN102428038 B CN 102428038B CN 201080021862 A CN201080021862 A CN 201080021862A CN 102428038 B CN102428038 B CN 102428038B
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- Prior art keywords
- fluorine
- particle
- treatment agent
- water
- treatment
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- 238000000034 method Methods 0.000 title claims abstract description 94
- 230000008569 process Effects 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- RBLGLDWTCZMLRW-UHFFFAOYSA-K dicalcium;phosphate;dihydrate Chemical compound O.O.[Ca+2].[Ca+2].[O-]P([O-])([O-])=O RBLGLDWTCZMLRW-UHFFFAOYSA-K 0.000 claims abstract description 106
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 90
- 239000011737 fluorine Substances 0.000 claims abstract description 90
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000002245 particle Substances 0.000 claims abstract description 74
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 65
- 239000002689 soil Substances 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 27
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 9
- 239000004576 sand Substances 0.000 claims description 17
- 230000005484 gravity Effects 0.000 claims description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 81
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 16
- 229910019142 PO4 Inorganic materials 0.000 description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 16
- 239000010452 phosphate Substances 0.000 description 16
- 150000003016 phosphoric acids Chemical class 0.000 description 15
- 238000001914 filtration Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 6
- 229940077441 fluorapatite Drugs 0.000 description 5
- 229910052587 fluorapatite Inorganic materials 0.000 description 5
- 238000012856 packing Methods 0.000 description 5
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000011324 bead Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000005189 flocculation Methods 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009471 action Effects 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
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 3
- 159000000007 calcium salts Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000011491 glass wool Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 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
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 210000003608 fece Anatomy 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010871 livestock manure Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004056 waste incineration Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- 241000345998 Calamus manan Species 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- ARLZGEXVMUDUQZ-UHFFFAOYSA-N O.O.[Ca] Chemical compound O.O.[Ca] ARLZGEXVMUDUQZ-UHFFFAOYSA-N 0.000 description 1
- 241001148470 aerobic bacillus Species 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 239000011440 grout Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 235000012950 rattan cane Nutrition 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/06—Calcium compounds, e.g. lime
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
- C11D7/16—Phosphates including polyphosphates
-
- 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
-
- C11D2111/22—
Abstract
The invention provides a kind of can be easy and effectively remove treatment agent and the treatment process of the fluorine in draining.The feature for the treatment of agent of the present invention is, its particle (B) containing dicalcium phosphate dihydrate (A) and be supported with described dicalcium phosphate dihydrate (A).In addition, the feature of a kind for the treatment of process involved in the present invention is, it comprises makes above-mentioned treatment agent contact with the handling object water containing fluorine, remove the operation of the fluorine in this handling object water; The feature of another kind for the treatment of process is, it comprises above-mentioned treatment agent and the mixing with soil containing fluorine, the operation making fluorine in this soil not dissolving.
Description
Technical field
The present invention relates to treatment agent and manufacture method thereof and treatment process.
Background technology
The draining of discharging in the matting of the electrical component such as pickling process, silicon by the electrorefining operation of aluminium, the manufacturing process, stainless steel etc. of phosphatic manure or waste incineration field are washed in cigarette draining, coal firepower stack desulfurization draining etc. containing fluorine, but standard of drainage is set, removing process can be implemented and make draining reach this standard value.
Nowadays, as the fluorine treatment process of actual use, generally have by adding calcium salt thus the Calcium Fluoride (Fluorspan) (CaF of generation insoluble
2) carry out the method for precipitate and separate; Add aluminium salt and make fluorion and aluminium hydroxide (Al (OH)
3) co-precipitation carries out the method that is separated; Or the method flocculation precipitation method based on calcium salt and the flocculation precipitation method based on aluminium salt combined is (for example, referring to non-patent literature 1.)。
On the other hand, recently, the standard of drainage of fluorine and environmental standard become strict, thus need to process to heavens the draining containing fluorine; But adopt the flocculation precipitation method based on calcium salt to be in the past difficult to make it to reach below 8mg/L as standard of drainage.
In addition, based in the coprecipitation method of aluminium hydroxide, there will be a known and add Tai-Ace S 150 (Al
2(SO
4)
316H
2o) as the technology of flocculation agent (for example, referring to patent documentation 1.)。But, in these conventional arts, need to the Tai-Ace S 150 isodose added more than the mud be made up of coprecipitate carry out separating treatment with process water, and make fluorine the disposal of stripping then imbed inferior to the mud after being separated, need to carry out numerous and diverse treatment process.
In order to solve the problem of these prior aries, as the fluorine treatment agent that can reach standard of drainage, recently disclose use insoluble phosphate to make the fluorine in draining carry out removing as fluorapatite immobilization method (for example, referring to patent documentation 2 and 3.)。
In addition, according to patent documentation 2, the Funing tablet in draining just can be made to be below 0.8mg/L by means of only interpolation phosphoric acid salt and/or phosphate cpd.
But, generally for the treatment process of the fluorine-containing draining using phosphoric acid salt and/or phosphate cpd to carry out, its have phosphoric acid salt and/or phosphate cpd and fluorine according to by the determined ratio of their chemical constitution to form the feature of composite salt, maximum chemical theory amount ization both Theory that can remove measure, stoichiometricamount) fluorine, in fact needs phosphoric acid salt and/or phosphate cpd to be made into fine powder to use for this reason.
As the treatment process for making the phosphoric acid salt of fine powder and/or phosphate cpd contact with the draining containing fluorine, the example of the contact groove using dispersing mode can be enumerated (for example, referring to patent documentation 4 and 5.)。
In addition, as easier treatment process, be generally and the draining containing fluorine flow through closely be filled with the phosphoric acid salt of above-mentioned fine powder and/or the packing layer of phosphate cpd to remove the technique of fluorine.
And, as the technology for suppressing fluorine stripping, disclose process of the powdered granule of dicalcium phosphate dihydrate being carried out in water suspend make its granule surface activity, using obtained treatment agent as the technology of the fluorine made in the fluoride pollution soil not treatment agent of dissolving (for example, referring to patent documentation 6.)。In addition, as the gypsum treatment method of the stripping of the fluorine contained by reduction, disclose following method: under there is the condition of the dicalcium phosphate dihydrate of the amount of the ratio of promising 1 ~ 5 mass parts in the calcium sulfate dihydrate in every this gypsum of 100 mass parts, the maintenance of required period is carried out in water, then carry out reclaiming (for example, referring to patent documentation 7.)。
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2005-324137 publication
Patent documentation 2: Japanese Patent No. 3504248 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2004-358309 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2004-122113 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2006-305555 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2007-216156 publication
Patent documentation 7: Japanese Unexamined Patent Publication 2008-297172 publication
Non-patent literature
Non-patent literature 1: towards field abundant it, favour rattan is good great, " treatment technology (Off Star element と ホ ウ element process Ji Intraoperative) of fluorine and boron ", environmental technology, 2000, vol.29, No.4, p.283-289
Summary of the invention
The problem that invention will solve
But, as as described in patent documentation 4 and 5, make the phosphoric acid salt of fine powder and/or phosphate cpd carry out the method for disperseing in contact groove, it has the feature making phosphoric acid salt and/or phosphate cpd and fluorine react the outflow suppressing them; Relative to phosphoric acid salt and/or phosphate cpd, in order to fluorine being immobilized into chemical theory amount ratio, need to carry out micronization to use to phosphoric acid salt and/or phosphate cpd as far as possible, this micro mist can make processing speed decline sometimes.
In addition, as mentioned above, flow through making the draining containing fluorine and be closely filled with the phosphoric acid salt of fine powder and/or the packing layer of phosphate cpd in the method removing fluorine, have following problems: the phosphoric acid salt of filling and/or phosphate cpd be micro mist shape, then more can reduce the water-permeable of packing layer, moreover, the pressure-losses also can be larger, and therefore packing layer is necessary for withstand voltage specification; And have following problems: owing to being fine powder, the state therefore for suspending in water, thus be difficult to be separated with water.
On the contrary, if the phosphoric acid salt of filling and/or phosphate cpd are granular, improve water-permeable by increasing its granularity packing layer, then phosphoric acid salt and/or phosphate cpd react with fluorine on this particle surface, and the fluorine removal amount of the phosphoric acid salt and/or phosphate cpd that therefore there is per unit weight declines such problem.
The object of the present invention is to provide following treatment agent and treatment process, described treatment agent and treatment process make the problem in above-mentioned existing method like this be solved, and can the easy and fluorine effectively removed in draining.
For the means of dealing with problems
The present invention relates to a kind for the treatment of agent, it is characterized in that, this treatment agent contains dicalcium phosphate dihydrate (A) and particle (B), dicalcium phosphate dihydrate (A) support by particle (B).
In addition, the present invention relates to the manufacture method for the treatment of agent, it is the method manufacturing above-mentioned treatment agent, and wherein, this manufacture method comprises use and to incline the operation that barrel-type gravity stirrer mixes dicalcium phosphate dihydrate (A) and particle (B).
The invention further relates to a kind for the treatment of process, wherein, this treatment process comprises makes above-mentioned treatment agent contact with the handling object water containing fluorine, remove the operation of the fluorine in this handling object water.
The invention still further relates to another kind for the treatment of process, wherein, this treatment process comprises above-mentioned treatment agent and the mixing with soil containing fluorine, the operation making fluorine in soil not dissolving.
Below describe the present invention in detail.
The present invention relates to the treatment agent containing dicalcium phosphate dihydrate (A) and particle (B) (wherein not comprising the particle of dicalcium phosphate dihydrate (A)).By dicalcium phosphate dihydrate (A) is supported to particle (B), handling object water containing fluorine is infiltrated in treatment agent of the present invention, thus pulverous dicalcium phosphate dihydrate (A) can be made for a long time substantially to flow out, water-permeable can be made further excellent for a long time, and the Funing tablet in process water can be made to be below 0.8mg/L for a long time.Herein, the particle (B) that refers to as carrier is supported in the mode undertaken to support dicalcium phosphate dihydrate (A).
Treatment agent of the present invention is by being obtained by mixing pulverous dicalcium phosphate dihydrate (A) and particle (B), dicalcium phosphate dihydrate (A) support by particle (B), thus particle diameter is large, thus not easily form agglomerate (throw out), excellent water permeability.In addition, by supporting to particle (B) by dicalcium phosphate dihydrate (A), the treatment agent that can not easily be dispersed, treatability is excellent.Further, the particle diameter due to dicalcium phosphate dihydrate (A) self remains on less state (micronised state), and therefore fluorine removal amount is also sufficient.
Because treatment agent of the present invention contains dicalcium phosphate dihydrate (A), therefore by making water etc. contact with this treatment agent, can except the fluorine in anhydrating etc.In addition, if with fluoride pollution mixing with soil, then can make fluorine in this fluoride pollution soil with the form of fluorapatite in not dissolving, thus fluorine stripping from soil can be suppressed.Dicalcium phosphate dihydrate (A) has given play to the effect of excellence especially for making the fluorine in fluoride pollution soil with the form of fluorapatite in not dissolving.For such as calcium phosphate (Ca
3(PO
4)
2), although it also has make fluorine in the fluoride pollution soil action effect in not dissolving, its action effect is poor compared with dicalcium phosphate dihydrate (A).
Fluorapatite self is the main component of natural Rock Phosphate (72Min BPL), and does not also use organic substance or heavy metal class etc.; If therefore use treatment agent of the present invention, then can not cause secondary environmental pollution, just can be economical and reliably make the fluorine stripping quantity coming from fluoride pollution soil be reduced to below the 0.8mg/L of Soil-environmental standard by simple operation.
For above-mentioned treatment agent, relative to the particle (B) of 100 mass parts, dicalcium phosphate dihydrate (A) is preferably 1 ~ 100 mass parts.By being set in above-mentioned scope, can effectively make dicalcium phosphate dihydrate (A) support by particle (B), water-permeable, treatment agent that fluorine removability is more excellent can be obtained.More preferably, relative to the particle (B) of 100 mass parts, dicalcium phosphate dihydrate (A) is 5 ~ 50 mass parts, more preferably 7 ~ 15 mass parts.
Above-mentioned dicalcium phosphate dihydrate (A) is preferably powder, and more preferably its median size is 30 ~ 70 μm.By the median size for above-mentioned scope, can effectively secondary calcium phosphate be supported to particle (B), the treatment agent of fluorine removability excellence can be obtained simultaneously.
The median size of above-mentioned dicalcium phosphate dihydrate (A) is that the Microtrac9320HRA using Nikkiso Company Limited to manufacture is measured by laser diffraction and scattering method.
For above-mentioned dicalcium phosphate dihydrate (A), the material that its particle surface has carried out sensitization is also one of preferred mode.If carry out suspension process to the powdered granule of dicalcium phosphate dihydrate (A) to carry out sensitization to its particle surface in water, then can increase the effect to above-mentioned fluorine not dissolving further.
For being undertaken stirring or rocking by being suspended in water by the powdered granule of dicalcium phosphate dihydrate (A) by the particle of suspension recovery, present the structure uniformly separating out a large amount of fine crystallines being of a size of tens of nm degree at it.For this particle, its surface is activated, such as, more effectively can make the fluorine not dissolving in fluoride pollution soil.Therefore, as the dicalcium phosphate dihydrate (A) for treatment agent of the present invention, preferably in water, suspension process carried out to the powdered granule of dicalcium phosphate dihydrate (A) thus make its granule surface activity.
Above-mentioned particle (B) is the particle that can support dicalcium phosphate dihydrate (A).By supporting dicalcium phosphate dihydrate (A) to particle (B), the treatment agent of water-permeable, fluorine removability excellence can be obtained.
As above-mentioned particle (B), the filter sand excessively, filtration sandstone etc. that are such as generally used for water purification can be enumerated, but the present invention is not limited to this.Also preferably sand is used as particle (B).
The particle of above-mentioned particle (B) to be preferably in fact particle diameter be 0.3 ~ 3.0mm; More preferably the particle being in fact only 0.3 ~ 3.0mm by particle diameter is formed.As particle (B), preferably all the particle of more than the 90 quality % of particle (B) has the particle diameter of 0.3 ~ 3.0mm, and preferred ratio is more than 99 quality %, and preferred ratio is more than 99.9 quality % further.Particle (B) is not particularly preferably less than the particle of 0.3mm containing particle diameter and does not contain the particle of particle diameter more than 3.0mm.By making particle diameter be above-mentioned scope, effectively can support dicalcium phosphate dihydrate (A), therefore can obtain the more excellent treatment agent of removability of water-permeable, fluorochemicals.Particle (B) is not most preferably in fact containing the particle of particle diameter more than 2.8mm.
The particle diameter of above-mentioned particle (B) uses standard network cribellum (JISZ8801; Reading size: 0.3 ~ 3.0mm; The size of screening washer: φ 200, degree of depth 45mm) to carry out manual screening test and obtain.When seeking not containing the particle of particle diameter more than 2.8mm, use the screening washer of reading size 2.8mm.
The uniformity ratio of above-mentioned particle (B) is preferably less than 1.5.By making uniformity ratio be above-mentioned scope, effectively can support dicalcium phosphate dihydrate (A), the more excellent and treatment agent that removability that is above-mentioned fluorochemicals is more excellent of water-permeable can be manufactured.
The uniformity ratio of above-mentioned particle (B) measures according to JWWAA103-1:2004.
For treatment agent of the present invention, can in the scope not damaging object of the present invention according to expecting containing composition except dicalcium phosphate dihydrate (A) and particle (B) except, but preferably phosphoric acid hydrogen calcium dihydrate (A) and particle (B) total account for more than 99 quality %.
Treatment agent of the present invention is preferably the treatment agent of fluorinated water, is also preferably the treatment agent of fluorine-containing soil.
The invention still further relates to the manufacture method for the treatment of agent, it is the method manufacturing above-mentioned treatment agent, and this manufacture method comprises use and to incline the operation that barrel-type gravity stirrer mixes dicalcium phosphate dihydrate (A) and particle (B).
The barrel-type gravity stirrer that inclines is in tilting mechanism, be provided with the stirrer for the mixing vessel mixed dicalcium phosphate dihydrate (A) and particle (B), as long as the mechanism for being generally known as the barrel-type gravity stirrer that inclines.Tilting mechanism refers to the mechanism for making above-mentioned mixing vessel tilt.
As the form of the barrel-type gravity stirrer that inclines, can enumerate and such as following mixing vessel is installed on tilting mechanism and by the blades installation that is used for carrying out mixing in the stirrer etc. of the internal perisporium of this mixing vessel, described mixing vessel carried out the container of frusto-conical zoarium, one open-ended while other dead end.Above-mentioned mixing vessel preferably can rotate.
When carrying out the mixing of above-mentioned dicalcium phosphate dihydrate (A) and particle (B), usually make tilting mechanism operate and make cylinder opening portion upward, make mixing vessel carry out rotation at certain orientation and drop into dicalcium phosphate dihydrate (A) and particle (B).Utilize blade to be kicked up by input each material and fall below again, by repeating such action to mix.
Owing to inclining, barrel-type gravity stirrer can promote mixing according to the behavior of input material, therefore can when make dicalcium phosphate dihydrate (A) the state that supports by particle (B) obtain good maintenance mix.Therefore, effect excellent has especially been given play in the manufacture of above-mentioned treatment agent.
As the manufacture method of above-mentioned treatment agent, preferably dicalcium phosphate dihydrate (A) and particle (B) are fed into and incline in the mixing vessel of barrel-type gravity stirrer, add water as required and mix.
The invention still further relates to a kind for the treatment of process, this treatment process comprises makes above-mentioned treatment agent contact with the handling object water containing fluorine, remove the operation of the fluorine in this handling object water (below also referred to as " fluorine removing treatment process ".)。
The contact of above-mentioned handling object water and treatment agent can be the intermittent contacts be added into by treatment agent in handling object water, also can be the continous way contact that handling object water is circulated in the post being filled with treatment agent.And intermittent contacts can be utilized to carry out the process of more than 2 times, continous way contact can be utilized to carry out the process of more than 2 times, also intermittent contacts can be carried out to contact with continous way the process of combination.In addition, the packed column in continous way contact can be any one of mobile laminar, fixing laminar or flowing laminar.
Fluorine of the present invention removing treatment process can comprise the operation reclaimed the Funing tablet process water that is below 0.8mg/L.Due to water-permeable and the reaction efficiency excellence of above-mentioned treatment agent, therefore effectively can remove fluorine contained in handling object water, make the Funing tablet in water be below 0.8mg/L.In addition, for above-mentioned treatment agent, because dicalcium phosphate dihydrate (A) supports in the relatively large particle (B) of particle diameter, handling object water therefore can be suppressed to suspend, easily can carry out treatment agent and process being separated of water.
Oil repellent for handling object water is not particularly limited, and no matter content less or many, all can give play to excellent fluorine removing performance, but preference is as being more than 0.1mg/L.From the view point of having given play to effect of the present invention further, more preferably more than 0.8mg/L.
In the present invention, the fluorinion concentration in fluorinated water can utilize the method based on JISK0102 to measure.
Be not particularly limited as the handling object water contacted with above-mentioned treatment agent, as long as the water containing fluorine, the water etc. in plant drainage, thermal water, rivers and creeks can be enumerated.As plant drainage, can enumerate by silicon wafer manufacturing works, semiconductor fabrication factory etc. discharge fluorine-containing containing draining; The pickling draining of being discharged by metal industry plant; Aluminium surface treatment draining; Fluorine manufactures draining; Production of manure draining; Waste incineration draining etc.
From the view point of the height removing efficiency that can obtain fluorion, the pH of above-mentioned handling object water is preferably more than 3.Therefore, the process water obtained by fluorine removing treatment process of the present invention is (hereafter also referred to as " process water ".) pH be also preferably more than 3.Be more preferably above-mentioned pH and be more than 4.When the pH of above-mentioned handling object water or process water is less than 3 or pH is less than 3 in each operation, can use sodium hydroxide, calcium hydroxide etc. that pH is adjusted to more than 3.
In addition, the pH of above-mentioned handling object water and process water is preferably less than 11.If pH is more than 11, then dicalcium phosphate dihydrate (A) is likely made to be difficult to carry out with the reaction of fluorion.When the pH of above-mentioned fluorinated water or process water is more than 11 or pH is more than 11 in each operation, can use hydrochloric acid etc. that pH is adjusted to less than 11.
Utilize above-mentioned fluorine to remove treatment process, the fluorine removal amount that can make every 1g dicalcium phosphate dihydrate (A) is more than 1mg-F/g, is preferably more than 10mg-F/g.
Fluorine removing treatment process of the present invention can comprise following operation: in handling object water, add calcium ion generate Calcium Fluoride (Fluorspan) (CaF
2) operation; And remove the Calcium Fluoride (Fluorspan) generated, operation that the handling object water be reduced fluorinion concentration reclaims.These operations were preferably carried out before making treatment agent contact with the handling object water containing fluorine, removing the operation of the fluorine in this handling object water.These operations, due to the lower calcium cpd of use cost, therefore particularly can cut down cost when the fluorinion concentration of handling object water is high.For above-mentioned calcium ion, preferably with slaked lime (Ca (OH)
2), calcium carbonate (CaCO
3), calcium chloride (CaCl
2) etc. calcium cpd form add.
The fluorine of above-mentioned process water is removed fully, and Funing tablet reduces (being such as 0.8mg/L), meet environmental standard.
The present invention also relates to treatment process further, and the method is by above-mentioned treatment agent and the mixing with soil containing fluorine, makes the treatment process of fluorine in this soil not dissolving (hereinafter also referred to as " fluorine is dissolving treatment process not ".)。When by above-mentioned treatment agent and the mixing with soil containing fluorine, dicalcium phosphate dihydrate (A) and the soluble fluoride ion be present in soil are reacted, are formed Ca
10(PO
4)
6f
2shown fluorapatite, not dissolving.
When dicalcium phosphate dihydrate (A) is separately with mixing with soil containing fluorine, secondary calcium phosphate becomes agglomerate (throw out), cannot disperse fully.But, for treatment agent of the present invention, due to secondary calcium phosphate support by particle (B), therefore excellent dispersion, can effectively with fluorine-containing mixing with soil.
Above-mentioned fluorine not dissolving treatment process such as preferably includes following operation: dicalcium phosphate dihydrate (A) and particle (B) are carried out the operation mixing, manufacture above-mentioned treatment agent; Above-mentioned treatment agent is added into containing the operation in the soil of fluorine; And make added treatment agent and the soil containing fluorine carry out the operation mixed.
Be not particularly limited for dicalcium phosphate dihydrate (A) and particle (B) are carried out mixing the method manufacturing above-mentioned treatment agent, the method etc. such as using the above-mentioned barrel-type gravity stirrer that inclines can be enumerated.
The fluorine stripping quantity of the above-mentioned soil containing fluorine is not particularly limited, such as, can be more than 0.1mg/L, can be more than 0.8mg/L further.
As above-mentioned soil, such as, be preferably soil or mud.
Be not particularly limited as above-mentioned soil, as long as be generally called soil material just can use without particular limitation, can use such as sand, sandy loam, loam, clay loam, clay etc. any one.Also can enumerate suitably mixing water diagenesis crushed material, pumice powder further to mince and volcanic ash soil etc. and the soil etc. adjusted.In addition, also can be as the soil etc. used with soil in home gardening.
As above-mentioned mud, solid that such as generate in the treating processes of lower Large Water Treatment Field or the waste treatment process of factory etc., that obtained by the end product cohesion of organic matter can be enumerated, also call it as mud.The active sludge etc. as the microorganism agglomerate generated when utilizing the micropopulations such as aerobic bacteria to carry out water treatment can also be enumerated in addition.
Invention effect
Treatment agent of the present invention is formed by above-mentioned formation, thus can be easy and fully eliminated the process water of fluorine economically, and the fluorine stripping quantity coming from the soil processed can be made to be below the 0.8mg/L of Soil-environmental standard.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the filtration unit represented in embodiment 1.
Fig. 2 is the schematic diagram of the filtration unit represented in comparative example 1.
Embodiment
Below enumerate embodiment and in further detail the present invention is described, but the present invention is not limited to following embodiment.
(embodiment 1)
By high-rate fitration, with sand, (Tohkemy manufactures, " Japanese water channel association specification JWWAA103-1:2004 specification product; effective diameter: 0.6mm, uniformity ratio: less than 1.5, below maximum diameter 2.8mm, most more than path 0.3mm ") and the powder of dicalcium phosphate dihydrate (peaceful Chemical Industries manufacture, " median size: 54 μm " is (hereinafter referred to as DCPD.)) according to the total amount high speed filtration sand of every 100 mass parts be 90 mass parts, the powder of dicalcium phosphate dihydrate is that the ratio of 10 mass parts is fed in the barrel-type gravity stirrer that inclines (capacity 110L), carries out mixing in 3 minutes.
Fig. 1 is the schematic diagram of the filtration unit representing embodiment 1.As shown in Figure 1, the mixture 2 by the above-mentioned high-rate fitration sand that is obtained by mixing and DCPD is filled in glass post casing 1 (φ 10cm) with glass wool 3, makes filtration unit 5.
Then, the handling object water containing fluorine is injected from the pipe 6 on the top being connected to filtration unit 5 with flow velocity 50ml/min, obtained processing water by the pipe 7 being connected to device bottom.As shown in fig. 1, process by making the handling object water 4 containing fluorine infiltrate in mixture 2 in post casing 1.In the present embodiment, the water-permeable of mixture 2 utilizes the change of level of the water surface 8 to evaluate.Flow and the Funing tablet of the flow of handling object water, Funing tablet and water level and process water have been shown in table 1.In addition, the handling object water containing fluorine and the Funing tablet processed in water adopt the method based on JISK0102 to measure.
Table 1
Even if through 120 days from infiltration, the Funing tablet of process water still maintains below environmental standard value.In addition, even if after 120 days, water level does not also change.That is, water-permeable does not change.
(embodiment 2)
Using the general sand of the grey concrete grout used as civil construction purposes etc. (effective diameter: 0.1 ~ 5mm, maximum diameter for more than 3.0mm and below 5.0mm) and DCPD according to sand in the total amount of every 100 mass parts be 90 mass parts, DCPD is that the ratio of 10 mass parts is fed in the barrel-type gravity stirrer that inclines (capacity 110L), carries out mixing in 3 minutes.
Similarly to Example 1 the mixture obtained is filled in glass post casing, makes filtration unit, the top of the handling object water containing fluorine from filtration unit is injected, water-permeable is evaluated, carries out the mensuration of Funing tablet.Result is shown in table 2.
Table 2
If the result of embodiment 1 and embodiment 2 contrasted, then, compared with situation about being supported by DCPD in general sand, DCPD is supported the excellent water permeability in high-rate fitration sand.This result demonstrates, as the particle (B) of carrier particle diameter for raising water-permeable be important.Be also noted that, compared with general sand, high-rate fitration sand contains more moisture in addition.But in the experiment that the present inventor carries out, then mix with DCPD if be impregnated in pure water by general sand, then the DCPD that can observe a part flocculates.
(comparative example 1)
Be used alone DCPD to replace the mixture of high-rate fitration sand and DCPD, in addition, adopt the method identical with embodiment 1 to test.As shown in Figure 2, DCPD9 and glass wool 3 are filled in glass post casing 1 (φ 10cm) make filtration unit 5a.DCPD is identical with embodiment 1.
Then, the object water containing fluorine injected from the pipe 6 being connected to device top with flow velocity 50ml/min, the water surface 8 of the handling object water of result after the implantation containing fluorine at once rises and reaches above device, therefore cannot obtain processing water.Table 3 shows flow and the Funing tablet of the flow of handling object water, Funing tablet and water level and process water.In addition, owing to cannot obtain processing water, the Funing tablet therefore processing water cannot measure.
Table 3
(comparative example 2)
The bead (effective diameter: 2 ~ 4mm) being glass and resin using general that use as handicraft decorative use, material and DCPD according to bead in the total amount of every 100 mass parts be 90 mass parts, DCPD is that the ratio of 10 mass parts is fed in the barrel-type gravity stirrer that inclines (capacity 110L), carries out mixing in 3 minutes.
Be filled to by the mixture obtained similarly to Example 1 in glass post casing, make filtration unit, inject the handling object water containing fluorine from the top of filtration unit, result bead starts to swim, and the process water on filtration unit top becomes opaque.Similarly to Example 1 water-permeable is evaluated, and measure Funing tablet.Result is shown in table 4.These results represent, DCPD not fully support by bead.
Table 4
Industrial Availability
Treatment agent of the present invention, owing to having above-mentioned formation, therefore can utilize in the field generating the water had containing fluorine or the soil containing fluorine in Electroplating Operations, semiconductor manufacturing industry, electron tube production, glass industry etc. aptly.
Nomenclature
1: glass post casing
2: the mixture of high-rate fitration sand and DCPD
3: glass wool
4: the handling object water containing fluorine
5,5a: filtration unit
6,7: pipe
8: the water surface
9：DCPD
Claims (6)
1. a treatment agent, it is characterized in that, this treatment agent contains dicalcium phosphate dihydrate (A) and particle (B), dicalcium phosphate dihydrate (A) support by particle (B), described particle (B) was filter sand, filtered sandstone or sand, the particle of particle (B) to be in fact particle diameter be 0.3 ~ 3.0mm, wherein, the median size of dicalcium phosphate dihydrate (A) is 30 ~ 70 μm.
2. treatment agent according to claim 1, wherein, the uniformity ratio of particle (B) is less than 1.5.
3. the manufacture method of a treatment agent, it is the method for the treatment agent described in manufacturing claims 1 or 2, the feature of this manufacture method is, it comprises use and to incline the operation that barrel-type gravity stirrer mixes dicalcium phosphate dihydrate (A) and particle (B).
4. a treatment process, is characterized in that, this treatment process comprises makes the treatment agent described in claim 1 or 2 contact with the handling object water containing fluorine, remove the operation of the fluorine in this handling object water.
5. a treatment process, is characterized in that, this treatment process comprises the treatment agent described in claim 1 or 2 and the mixing with soil containing fluorine, the operation making fluorine in this soil not dissolving.
6. treatment process according to claim 5, wherein, described soil is soil or mud.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009122969 | 2009-05-21 | ||
| JP2009-122969 | 2009-05-21 | ||
| PCT/JP2010/058536 WO2010134573A1 (en) | 2009-05-21 | 2010-05-20 | Treatment agent and process for production thereof, and treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102428038A CN102428038A (en) | 2012-04-25 |
| CN102428038B true CN102428038B (en) | 2015-12-02 |
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| CN201080021862.2A Active CN102428038B (en) | 2009-05-21 | 2010-05-20 | Treatment agent and manufacture method thereof and treatment process |
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|---|---|
| JP (1) | JP5582141B2 (en) |
| KR (1) | KR101294490B1 (en) |
| CN (1) | CN102428038B (en) |
| BR (1) | BRPI1011067A2 (en) |
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| WO (1) | WO2010134573A1 (en) |
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| JP2013188740A (en) * | 2012-02-14 | 2013-09-26 | Daikin Industries Ltd | Reactor, treatment equipment, and treatment method |
| JP5915231B2 (en) * | 2012-02-14 | 2016-05-11 | ダイキン工業株式会社 | Processing method and processing equipment |
| WO2014017500A1 (en) * | 2012-07-24 | 2014-01-30 | ダイキン工業株式会社 | Method for treating aqueous solution containing phosphoric acid ions |
| CN105692575B (en) * | 2016-01-27 | 2018-02-09 | 贵州省冶金化工研究所 | A kind of Application way of rock phosphate in powder |
| CN113262805B (en) * | 2021-04-20 | 2023-09-29 | 煤炭科学技术研究院有限公司 | Defluorination catalyst, preparation method thereof and defluorination method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52777A (en) * | 1975-06-24 | 1977-01-06 | Hokko Chem Ind Co Ltd | Method and means for preparation of arrangement of granules |
| JPS58199091A (en) * | 1982-05-14 | 1983-11-19 | Hitachi Plant Eng & Constr Co Ltd | Production of seed crystal material for crystallization treatment of phosphate in liquid |
| JPS59123591A (en) * | 1982-12-28 | 1984-07-17 | Kurita Water Ind Ltd | Treatment of water containing phosphate |
| JPS59173192A (en) * | 1983-03-18 | 1984-10-01 | Matsushita Electric Ind Co Ltd | Filter medium for water treatment and its production |
| AU579647B2 (en) * | 1985-02-21 | 1988-12-01 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for adsorption treatment of dissolved fluorine |
| US6331256B1 (en) | 1998-04-22 | 2001-12-18 | Fujitsu Limited | Treatment process for fluorine-containing water |
| JP2001232167A (en) * | 2000-02-28 | 2001-08-28 | Shimooka Kogyo:Kk | Agitating and mixing device for powder and granular material |
| JP2004358309A (en) * | 2003-06-03 | 2004-12-24 | Ngk Insulators Ltd | Method for treating fluorine in wastewater |
| CN1291916C (en) * | 2005-06-03 | 2006-12-27 | 天津大学 | Process for preparing fluorine reducing ion sieve of aquatic body |
| JP4434156B2 (en) * | 2006-02-17 | 2010-03-17 | 独立行政法人国立高等専門学校機構 | Treatment method of fluorine-contaminated soil |
| JP4752038B2 (en) * | 2007-06-01 | 2011-08-17 | 独立行政法人国立高等専門学校機構 | Method for treating gypsum to reduce elution of contained fluorine |
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| KR20120022996A (en) | 2012-03-12 |
| BRPI1011067A2 (en) | 2016-03-15 |
| WO2010134573A1 (en) | 2010-11-25 |
| KR101294490B1 (en) | 2013-08-07 |
| JPWO2010134573A1 (en) | 2012-11-12 |
| MX2011011570A (en) | 2011-11-18 |
| JP5582141B2 (en) | 2014-09-03 |
| CN102428038A (en) | 2012-04-25 |
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