CN102428038A - Treatment agent and process for production thereof, and treatment method - Google Patents
Treatment agent and process for production thereof, and treatment method Download PDFInfo
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- CN102428038A CN102428038A CN2010800218622A CN201080021862A CN102428038A CN 102428038 A CN102428038 A CN 102428038A CN 2010800218622 A CN2010800218622 A CN 2010800218622A CN 201080021862 A CN201080021862 A CN 201080021862A CN 102428038 A CN102428038 A CN 102428038A
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- fluorine
- particle
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- treatment agent
- treatment
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- 238000000034 method Methods 0.000 title claims abstract description 97
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 105
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 105
- 239000011737 fluorine Substances 0.000 claims abstract description 105
- 239000002245 particle Substances 0.000 claims abstract description 72
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 67
- 239000002689 soil Substances 0.000 claims abstract description 35
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 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 description 102
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 81
- 230000005484 gravity Effects 0.000 claims description 12
- 239000010808 liquid waste Substances 0.000 abstract description 2
- XAAHAAMILDNBPS-UHFFFAOYSA-L calcium hydrogenphosphate dihydrate Chemical compound O.O.[Ca+2].OP([O-])([O-])=O XAAHAAMILDNBPS-UHFFFAOYSA-L 0.000 abstract 2
- 235000019700 dicalcium phosphate Nutrition 0.000 abstract 2
- 239000007788 liquid Substances 0.000 abstract 2
- 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
- 239000004576 sand Substances 0.000 description 15
- 238000001914 filtration Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000008187 granular material Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000843 powder Substances 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
- 238000006243 chemical reaction Methods 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
- 206010070834 Sensitisation Diseases 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 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
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000011491 glass wool Substances 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 230000008313 sensitization Effects 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
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 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
- 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
- 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
- 239000004927 clay Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 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
- 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
- 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
- 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
- 210000003608 fece Anatomy 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 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
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal 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
- 238000003672 processing method Methods 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
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011435 rock Substances 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
- 238000012360 testing method 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
Images
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- 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
-
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Soil Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Removal Of Specific Substances (AREA)
- Processing Of Solid Wastes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Treatment Of Sludge (AREA)
Abstract
Disclosed are a treatment agent and a treatment method which enable the removal of fluorine contained in a liquid waste in a simple manner and with high efficiency. Specifically disclosed are: a treatment agent which is characterized by comprising calcium hydrogenphosphate dihydrate (A) and particles (B) that carry calcium hydrogenphosphate dihydrate (A); a treatment method which is characterized by comprising a step of bringing a fluorine containing liquid to be treated into contact with the treatment agent to remove fluorine contained in the liquid; and a treatment method which is characterized by comprising a step of mixing a fluorine-containing soil with the treatment agent to insolubilize fluorine in the soil.
Description
Technical field
The present invention relates to treatment agent and method of manufacture thereof and treatment process.
Background technology
Draining of in the matting by electrical components such as the pickling process of the manufacturing process of the electrorefining operation of aluminium, phosphatic manure, stainless steel etc., silicon, being discharged or waste incineration field are washed and are contained fluorine in cigarette draining, the coal firepower stack desulfurization draining etc.; But standard of drainage is set, can be implemented to remove processing and make draining reach this standard value.
Nowadays, as the fluorine treatment process of reality use, thereby generally have through adding the Calcium Fluoride (Fluorspan) (CaF that calcium salt generates insoluble
2) carry out the method for precipitate and separate; Add aluminium salt and make fluorion and white lake (Al (OH)
3) co-precipitation carries out isolating method; The method that perhaps will combine based on the flocculation precipitation method of calcium salt and flocculation precipitation method based on aluminium salt is (for example, with reference to non-patent literature 1.)。
On the other hand, recently, it is strict that the standard of drainage of fluorine and environmental standard become, thereby need handle to heavens the draining that contains fluorine; But adopt flocculation precipitation method in the past to be difficult to make it to reach below the 8mg/L as standard of drainage based on calcium salt.
In addition, in the coprecipitation method based on white lake, known have an interpolation Tai-Ace S 150 (Al
2(SO
4)
316H
2O) as the technology of flocculation agent (for example, with reference to patent documentation 1.)。But; At these in the past in the technology; Need be to carrying out separating treatment with mud and treating water more than the Tai-Ace S 150 isodose that adds by coprecipitate constituted, and to the mud after separating make disposal that fluorine can stripping imbed then inferior, need carry out numerous and diverse treatment process.
In order to solve these prior art problems,, disclose recently and used insoluble phosphate to make the fluorine method that immobilization is removed as fluorapatite in the draining (for example, with reference to patent documentation 2 and 3 as the fluorine treatment agent that can reach standard of drainage.)。
In addition, according to patent documentation 2, only just can make the fluorine concentration in the draining through interpolation phosphoric acid salt and/or phosphate cpd is below the 0.8mg/L.
But; General processing method for the fluorine-containing draining of using phosphoric acid salt and/or phosphate cpd to carry out; It has phosphoric acid salt and/or phosphate cpd and fluorine according to the feature that is formed complex salt by the determined ratio of their chemical composition; Maximum can be removed the chemical theory amount! Hua both stoichiometrics, stoichiometric amount) fluorine, in fact phosphoric acid salt and/or phosphate cpd need be made into fine powder for this reason and use.
Make the phosphoric acid salt of fines shape and/or the treatment process that phosphate cpd contacts with the draining that contains fluorine as being used to, the example that can enumerate the contact groove that uses dispersing mode is (for example, with reference to patent documentation 4 and 5.)。
In addition, as easier treatment process, be generally the technology that the packing layer of the phosphoric acid salt that the draining that contains fluorine flow through closely be filled with above-mentioned fines shape and/or phosphate cpd is removed fluorine.
And; As the technology that is used to suppress the fluorine stripping; Disclose powdered granule with dicalcium phosphate dihydrate in water, carry out suspension treatment make its granule surface activityization, with resulting treatment agent as make in the fluoride pollution soil fluorine not the technology of the treatment agent of dissolving (for example, with reference to patent documentation 6.)。In addition; Gypsum treatment process as the stripping that reduces the fluorine that is contained; Following method is disclosed: exist in the calcium sulfate dihydrate in per this gypsum of 100 mass parts under the condition of dicalcium phosphate dihydrate of amount of ratio of promising 1～5 mass parts; In water, carry out the maintenance during required, reclaim then (for example, with reference to patent documentation 7.)。
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2005-324137 communique
Patent documentation 2: No. 3504248 communique of Japanese Patent
Patent documentation 3: TOHKEMY 2004-358309 communique
Patent documentation 4: TOHKEMY 2004-122113 communique
Patent documentation 5: TOHKEMY 2006-305555 communique
Patent documentation 6: TOHKEMY 2007-216156 communique
Patent documentation 7: TOHKEMY 2008-297172 communique
Non-patent literature
Non-patent literature 1: towards the field abundant it, the favour rattan is very great, " treatment technology of fluorine and boron (the plain treatment technology of the plain と ホ of Off Star ウ) ", Environmental Technology, 2000, vol.29, No.4, p.283-289
Summary of the invention
The problem that invention will solve
Yet; Of patent documentation 4 and 5; For in the contact groove, making the phosphoric acid salt of fines shape and/or phosphate cpd carry out the dispersive method,, it make phosphoric acid salt and/or phosphate cpd and fluorine reaction suppress their effusive characteristic while having; With respect to phosphoric acid salt and/or phosphate cpd, in order fluorine to be immobilized into chemical theory amount ratio, to need that as far as possible phosphoric acid salt and/or phosphate cpd are carried out micronization and use, this sometimes micro mist can make processing speed descend.
In addition; As stated, remove in the method for fluorine at the phosphoric acid salt that the draining that contains fluorine is flow through closely be filled with the fines shape and/or the packing layer of phosphate cpd, have following problems: the phosphoric acid salt of filling and/or phosphate cpd be the micro mist shape; Then can reduce the water-permeable of packing layer more; Moreover, the pressure-losses also can be big more, so packing layer is necessary for withstand voltage specification; And have following problems:, in water, be the state that suspends therefore, thereby be difficult to separate with water owing to be fine powder.
On the contrary; If phosphoric acid salt of being filled and/or phosphate cpd be granular, through increasing the packing layer that its granularity improves water-permeable; Then phosphoric acid salt and/or phosphate cpd react with fluorine on this particle surface, therefore have the such problem of the fluorine amount of removing decline of the phosphoric acid salt and/or the phosphate cpd of per unit weight.
The object of the present invention is to provide following treatment agent and treatment process, said treatment agent and treatment process make the problem in the above-mentioned existing method like this be able to solve, and can remove the fluorine in the draining easy and effectively.
The means that are used to deal with problems
The present invention relates to a kind of treatment agent, it is characterized in that, this treatment agent contains dicalcium phosphate dihydrate (A) and particle (B), and dicalcium phosphate dihydrate (A) is supported by particle (B).
In addition, the present invention relates to the method for manufacture of treatment agent, it is a method of making above-mentioned treatment agent, and wherein, this method of manufacture comprises uses the barrel-type gravity stirrer that inclines that dicalcium phosphate dihydrate (A) and particle (B) are carried out the blended operation.
The invention further relates to a kind of treatment process, wherein, this treatment process comprises the operation that makes above-mentioned treatment agent and the process object water that contains fluorine contact, remove the fluorine in this process object water.
The invention still further relates to another kind of treatment process, wherein, this treatment process comprise with above-mentioned treatment agent with the mixing with soil that contains fluorine, make the fluorine operation of dissolving not in the soil.
Below be described in detail the present invention.
The present invention relates to contain the treatment agent of dicalcium phosphate dihydrate (A) and particle (B) (particle that does not wherein comprise dicalcium phosphate dihydrate (A)).Through dicalcium phosphate dihydrate (A) is supported to particle (B); The process object water that contains fluorine is infiltrated in the treatment agent of the present invention; Thereby pulverous dicalcium phosphate dihydrate (A) can not flowed out substantively; Can make water-permeable excellent for a long time further, and can make fluorine concentration in the treating water for a long time for below the 0.8mg/L.Support the particle (B) that is meant as carrier here, and support dicalcium phosphate dihydrate (A) with the mode of undertaking.
Treatment agent of the present invention obtains through pulverous dicalcium phosphate dihydrate (A) and particle (B) are mixed, and dicalcium phosphate dihydrate (A) is supported by particle (B), thereby particle diameter is big, thereby is difficult for forming agglomerate (throw out), and water-permeable is excellent.In addition, through dicalcium phosphate dihydrate (A) is supported to particle (B), can obtain the treatment agent that is difficult for dispersing, the property handled is excellent.Further, because the particle diameter of dicalcium phosphate dihydrate (A) self remains on less state (micro mist state), so the fluorine amount of removing also is sufficient.
Because treatment agent of the present invention contains dicalcium phosphate dihydrate (A), therefore through water etc. contact with this treatment agent, can be except that the fluorine in anhydrating etc.In addition, if with the fluoride pollution mixing with soil, fluorine in this fluoride pollution soil is with the form of fluorapatite does not dissolve change, thereby can suppress fluorine stripping from soil.Dicalcium phosphate dihydrate (A) has been given play to excellent especially effect for making fluorine in the fluoride pollution soil be not dissolve to change with the form of fluorapatite.For for example calcium phosphate (Ca
3(PO
4)
2), though also having the fluorine that makes in the fluoride pollution soil, it is the action effect that does not dissolve change, to compare its action effect poor with dicalcium phosphate dihydrate (A).
Fluorapatite self is the staple of natural Rock Phosphate (72Min BPL), and does not also use organic substance or heavy metal class etc.; Therefore if use treatment agent of the present invention, then can not cause secondary environmental pollution, just can economy and the fluorine stripping quantity that comes from fluoride pollution soil is reduced to below the 0.8mg/L of edatope standard through simple operation.
For above-mentioned treatment agent, with respect to the particle (B) of 100 mass parts, dicalcium phosphate dihydrate (A) is preferably 1～100 mass parts.Through being set in the above-mentioned scope, dicalcium phosphate dihydrate (A) is supported by particle (B), can obtain the more excellent treatment agent of water-permeable, removing property of fluorine.More preferably be that with respect to the particle (B) of 100 mass parts, dicalcium phosphate dihydrate (A) is 5～50 mass parts, further is preferably 7～15 mass parts.
Above-mentioned dicalcium phosphate dihydrate (A) is preferably powder, and more preferably its median size is 30～70 μ m.Through being the median size of above-mentioned scope, can effectively secondary calcium phosphate be supported to particle (B), can obtain the excellent treatment agent of removing property of fluorine simultaneously.
Microtrac 9320 HRA that the median size of above-mentioned dicalcium phosphate dihydrate (A) is to use Nikkiso Company Limited to make measure through the laser diffraction and scattering method.
For above-mentioned dicalcium phosphate dihydrate (A), the material that its particle surface has carried out sensitization also is one of preferred mode.Come its particle surface is carried out sensitization if in water, the powdered granule of dicalcium phosphate dihydrate (A) is carried out suspension treatment, then can further increase the not effect of dissolving of above-mentioned fluorine.
Stir for suspending in water or rock and, demonstrate the structure of separating out a large amount of fine crystallines that are of a size of tens of nm degree on its surface equably by the particle of recover through powdered granule with dicalcium phosphate dihydrate (A).For this particle, its surface is by sensitization, for example can make the fluorine dissolving not in the fluoride pollution soil more effectively.Therefore, as the dicalcium phosphate dihydrate that is used for treatment agent of the present invention (A), preferably in water to dicalcium phosphate dihydrate (A) thus powdered granule carry out suspension treatment and make its granule surface activityization.
Above-mentioned particle (B) is the particle that can support dicalcium phosphate dihydrate (A).Through dicalcium phosphate dihydrate (A) is supported to particle (B), can obtain the treatment agent of water-permeable, removing property of fluorine excellence.
As above-mentioned particle (B), can enumerate and for example generally be used for crossing filter sand, filtering sandstone etc. of water purification, but the present invention is not limited to this.Also preferably use sand as particle (B).
Above-mentioned particle (B) preferably comes down to the particle that particle diameter is 0.3～3.0mm; Be that the particle of 0.3～3.0mm constitutes in fact only more preferably by particle diameter.As particle (B), the above particle of 90 quality % of preferred all particles (B) has the particle diameter of 0.3～3.0mm, and preferred ratio is more than the 99 quality %, and further preferred ratio is more than the 99.9 quality %.Particle (B) does not especially preferably contain particle diameter less than the particle of 0.3mm and do not contain the particle that particle diameter surpasses 3.0mm.Through making particle diameter is above-mentioned scope, can support dicalcium phosphate dihydrate (A) effectively, therefore can obtain the more excellent treatment agent of removing property of water-permeable, fluorochemicals.In fact particle (B) does not most preferably contain the particle that particle diameter surpasses 2.8mm.
The particle diameter of above-mentioned particle (B) is to use standard network cribellum (JIS Z8801; Reading size: 0.3～3.0mm; The size of screening washer: φ 200, degree of depth 45mm) carry out manual screening and test and obtain.Seeking not contain particle diameter, use the screening washer of reading size 2.8mm above under the particulate situation of 2.8mm.
The uniformity ratio of above-mentioned particle (B) is preferably below 1.5.Through making uniformity ratio is above-mentioned scope, can support dicalcium phosphate dihydrate (A) effectively, can make the more excellent treatment agent of removing property of the more excellent and above-mentioned fluorochemicals of water-permeable.
The uniformity ratio of above-mentioned particle (B) is measured according to JWWA A103-1:2004.
For treatment agent of the present invention; Can in the scope of not damaging the object of the invention, contain except that dicalcium phosphate dihydrate (A) and the composition the particle (B), but preferably phosphoric acid hydrogen calcium dihydrate (A) and particle (B) total account for more than the 99 quality % according to expectation.
Treatment agent of the present invention is preferably the treatment agent that fluorinated water is used, and also is preferably the treatment agent that fluorine-containing soil is used.
The invention still further relates to the method for manufacture of treatment agent, it is for making the method for above-mentioned treatment agent, and this method of manufacture comprises uses the barrel-type gravity stirrer that inclines that dicalcium phosphate dihydrate (A) and particle (B) are carried out the blended operation.
The barrel-type gravity stirrer that inclines is in tilting mechanism, to be equipped with to be used for dicalcium phosphate dihydrate (A) and particle (B) are carried out the stirrer of blended mixing vessel, as long as be the mechanism that is generally known as the barrel-type gravity stirrer that inclines.Tilting mechanism is meant the mechanism that is used to make above-mentioned mixing vessel inclination.
Form as the barrel-type gravity stirrer that inclines; For example can enumerate following mixing vessel is installed on tilting mechanism, and will be used to carry out the stirrer etc. that the blended blade is installed on the internal perisporium of this mixing vessel, said mixing vessel has carried out the zoarium of the container of frusto-conical, other ends of open-ended while are inaccessible.Above-mentioned mixing vessel preferably can be rotated.
When carrying out the mixing of above-mentioned dicalcium phosphate dihydrate (A) and particle (B), make tilting mechanism running usually and the peristome that makes tube towards the top, drop into dicalcium phosphate dihydrate (A) and particle (B) while mixing vessel is rotated at certain orientation.Utilize blade that input each material is kicked up and fall the below again, mix through repeating such action.
The barrel-type gravity stirrer can come according to the behavior of input material mixing is promoted owing to incline, and therefore can under the situation that the state that dicalcium phosphate dihydrate (A) is supported by particle (B) is well kept, mix.Therefore, given play to excellent especially effect in the manufacturing of above-mentioned treatment agent.
As the method for manufacture of above-mentioned treatment agent, preferably dicalcium phosphate dihydrate (A) and particle (B) are fed in the mixing vessel of the barrel-type gravity stirrer that inclines, add water as required and mix.
The invention still further relates to a kind of treatment process, this treatment process comprise the operation that makes above-mentioned treatment agent and the process object water that contains fluorine contact, remove the fluorine in this process object water (below be also referred to as " fluorine is removed treatment process ".)。
Above-mentioned process object water can be that treatment agent is added into the intermittent type contact in the process object water with contacting of treatment agent, also can be the continous way contact that process object water is circulated in being filled with the post of treatment agent.And can utilize intermittent type contact carry out more than 2 times processing, can utilize the continous way contact carry out more than 2 times processing, also can carry out the intermittent type contact contact processing of making up with continous way.In addition, the packed column in the continous way contact can be to move laminar, fixing any one of laminar or mobile laminar.
Fluorine of the present invention is removed treatment process can comprise that to fluorine concentration be the operation that the treating water below the 0.8mg/L reclaims.Because the water-permeable of above-mentioned treatment agent is excellent with reaction efficiency, so can to remove the fluorine that contained in the process object water effectively, make the fluorine concentration in the water be below the 0.8mg/L.In addition, for above-mentioned treatment agent,, therefore can suppress process object water and suspend, can easily carry out separating of treatment agent and treating water because dicalcium phosphate dihydrate (A) supports in the relatively large particle of particle diameter (B).
Do not limit for the fluorine content of process object water is special, no matter content is still many less, all can give play to excellent fluorine and remove performance, but preference is as being more than the 0.1mg/L.From can further having given play to the viewpoint of effect of the present invention, more preferably surpass 0.8mg/L.
In the present invention, the fluorinion concentration in the fluorinated water can utilize based on the method for JIS K0102 and measure.
Do not limit as the process object water that contacts with above-mentioned treatment agent is special, get final product, can enumerate the water in plant drainage, thermal water, rivers and creeks etc. so long as contain the water of fluorine.As plant drainage, can enumerate by discharges such as silicon wafer manufacturing works, semiconductor fabrication factory fluorine-containing and contain draining; Pickling draining by the discharge of metal factory; Aluminium surface treatment draining; Fluorine is made draining; Fertilizer is made draining; Waste incineration draining etc.
Remove the viewpoint of efficient from the height that can obtain fluorion, the pH of above-mentioned process object water is preferably more than 3.Therefore, (hereinafter also abbreviates " treating water " as to remove the treating water that treatment process obtains by fluorine of the present invention.) pH preferably also be more than 3.More preferably above-mentioned pH is more than 4.The pH of above-mentioned process object water or treating water can use sodium hydroxide, calcium hydroxide etc. that pH is adjusted into more than 3 less than pH is less than under 3 the situation under 3 the situation or in each operation.
In addition, the pH of above-mentioned process object water and treating water is preferably below 11.If pH surpasses 11, then might make the dicalcium phosphate dihydrate (A) and the reaction of fluorion be difficult to carry out.The pH of above-mentioned fluorinated water or treating water surpasses under 11 the situation or pH surpasses under 11 the situation in each operation, can use hydrochloric acid etc. that pH is adjusted into below 11.
Utilize above-mentioned fluorine to remove treatment process, the fluorine amount of removing that can make every 1g dicalcium phosphate dihydrate (A) is more than the 1mg-F/g, to be preferably more than the 10mg-F/g.
Fluorine of the present invention is removed treatment process can comprise following operation: in process object water, add calcium ion and generate Calcium Fluoride (Fluorspan) (CaF
2) operation; And remove the operation that the Calcium Fluoride (Fluorspan) that is generated, the process object water that fluorinion concentration is reduced reclaim.These operations are preferably carried out before in the operation that makes treatment agent and the process object water that contains fluorine contact, remove the fluorine in this process object water.These operations therefore particularly can cutting down cost under the high situation of the fluorinion concentration of process object water owing to the lower calcium cpd of use cost.For above-mentioned calcium ion, preferably with slaked lime (Ca (OH)
2), lime carbonate (CaCO
3), calcium chloride (CaCl
2) wait the form of calcium cpd to add.
The fluorine of above-mentioned treating water is removed fully, and fluorine concentration reduces (for example being 0.8mg/L), satisfies environmental standard.
The present invention also further relates to treatment process, this method for above-mentioned treatment agent with contain fluorine mixing with soil, make in this soil fluorine not the treatment process of dissolving (hereinafter is also referred to as " fluorine is the dissolving treatment process not ".)。With under above-mentioned treatment agent and the situation of mixing with soil that contains fluorine, dicalcium phosphate dihydrate (A) be present in soluble fluoride ion reaction in the soil, form Ca
10(PO
4)
6F
2Shown fluorapatite, not dissolving.
Dicalcium phosphate dihydrate (A) separately with the situation of the mixing with soil that contains fluorine under, secondary calcium phosphate becomes agglomerate (throw out), can't disperse fully.But, for treatment agent of the present invention because secondary calcium phosphate supported by particle (B), so excellent dispersion, can be effectively and fluorine-containing mixing with soil.
Above-mentioned fluorine not dissolving treatment process for example preferably includes following operation: the operation of dicalcium phosphate dihydrate (A) and particle (B) being mixed, make above-mentioned treatment agent; Above-mentioned treatment agent is added into the operation in the soil that contains fluorine; And make treatment agent that is added and the soil that contains fluorine carry out the blended operation.
The method of making above-mentioned treatment agent is not special to be limited for dicalcium phosphate dihydrate (A) is mixed with particle (B), can enumerate the method for for example using the above-mentioned barrel-type gravity stirrer that inclines etc.
Do not limit the fluorine stripping quantity of the above-mentioned soil that contains fluorine is special, for example can for more than the 0.1mg/L, further can be for more than the 0.8mg/L.
As above-mentioned soil, for example be preferably soil or mud.
Do not limit as above-mentioned soil is special, so long as generally be called the just not use especially restrictedly of material of soil, for example can use sand, sandy loam, loam, clay loam, clay etc. any one.Can enumerate also further that suitably mixing water diagenesis crushed material, pumice powder mince and volcanic ash soil etc. and the soil etc. that carried out adjustment.In addition, also can be as with native employed soil etc. in home gardening.
As above-mentioned mud, can enumerate the solid that for example in the treating processes of following water treatment field or the liquid waste disposal process of factory etc., generates, obtain by the end product cohesion of organic matter, also it is called mud.Can also enumerate active sludge of the mikrobe agglomerate that is generated when carrying out water treatment etc. in addition as micropopulations such as utilizing aerobic bacteria.
The invention effect
Treatment agent of the present invention is formed by above-mentioned the formation, thereby can fully have been removed the treating water of fluorine easy and economically, and can to make the fluorine stripping quantity that comes from the soil of handling be below the 0.8mg/L of edatope standard.
Description of drawings
Fig. 1 is the synoptic diagram of the filtration unit among the expression embodiment 1.
Fig. 2 is the synoptic diagram of the filtration unit in the expression comparative example 1.
Embodiment
Below enumerate embodiment the present invention is described in further detail, but the present invention is not limited to following embodiment.
(embodiment 1)
(Tohkemy makes with sand with high-rate fitration; " the Japanese water channel specification JWWA A103-1:2004 of association specification article; effective diameter: 0.6mm, uniformity ratio: below 1.5, below the maximum diameter 2.8mm, more than the path 0.3mm ") and the powder of dicalcium phosphate dihydrate (peaceful chemical industry manufacturing, " median size: 54 μ m " (below be called DCPD.)) filter according to the total amount high speed of per 100 mass parts that to use sand be that the powder of 90 mass parts, dicalcium phosphate dihydrate is that the ratio of 10 mass parts is fed in the barrel-type gravity stirrer that inclines (capacity 110L), carry out mixing in 3 minutes.
Fig. 1 is the synoptic diagram of the filtration unit of expression embodiment 1.As shown in Figure 1, the high-rate fitration that will be obtained by above-mentioned mixing is filled in the glass post casing 1 (φ 10cm) with glass wool 3 with the mixture 2 of sand and DCPD, processes filtration unit 5.
Then, the process object water that will contain fluorine injects from the pipe 6 on the top that is connected to filtration unit 5 with flow velocity 50ml/min, obtains treating water by the pipe that is connected to the device bottom 7.As shown in fig. 1, through being infiltrated in the mixture 2, handles in the process object water 4 that contains fluorine.In the present embodiment, the water-permeable of mixture 2 is to utilize the change of level of the water surface 8 to estimate.The flow and the fluorine concentration of flow, fluorine concentration and the water level and the treating water of process object water have been shown in the table 1.In addition, the process object water and the fluorine concentration in the treating water that contain fluorine are to adopt to measure based on the method for JIS K0102.
Table 1
Even begin through 120 days from infiltration, the fluorine concentration of treating water still maintains below the environmental standard value.In addition, even after 120 days, water level does not change yet.That is, water-permeable does not change.
(embodiment 2)
To be that 90 mass parts, DCPD are that the ratio of 10 mass parts is fed in the barrel-type gravity stirrer that inclines (capacity 110L) according to sand in the total amount of per 100 mass parts as the general sand of usefulness such as the employed grey concrete grout of civil construction purposes (effective diameter: 0.1～5mm, maximum diameter are for surpassing below 3.0mm and the 5.0mm) and DCPD, and carry out mixing in 3 minutes.
Likewise the mixture that obtains is filled in the glass post casing with embodiment 1, makes filtration unit, the process object water that will contain fluorine injects from the top of filtration unit, and water-permeable is estimated, and carries out the mensuration of fluorine concentration.The result is shown in table 2.
Table 2
If the result of embodiment 1 and embodiment 2 is compared, then with being supported in the situation of general sand, DCPD compares, DCPD is supported in the water-permeable excellence of high-rate fitration with sand.This result demonstrates, and is important as the particle diameter of the particle (B) of carrier for improving water-permeable.Be also noted that in addition with general sand and compare that high-rate fitration contains more water with sand.But, in the experiment that the inventor carried out,, mixes with DCPD then general sand as if being impregnated in the pure water, and the DCPD that then can observe a part flocculates.
(comparative example 1)
Use DCPD to replace the mixture of high-rate fitration separately, in addition, adopt to experimentize with embodiment 1 identical method with sand and DCPD.As shown in Figure 2, DCPD9 and glass wool 3 be filled in the glass post casing 1 (φ 10cm) process filtration unit 5a.DCPD is identical with embodiment 1.
Then, the object water that will contain fluorine injects from the pipe 6 that is connected to device top with flow velocity 50ml/min, and the result contains the process object water of fluorine after injection the water surface 8 rises at once and reaches above the device, therefore can't obtain treating water.Table 3 shows the flow and the fluorine concentration of flow, fluorine concentration and the water level and the treating water of process object water.In addition, owing to can't obtain treating water, so the fluorine concentration of treating water can't be measured.
Table 3
(comparative example 2)
With general, bead that material be glass and resin employed as the handicraft decorative use (effective diameter: 2～4mm) with DCPD be that 90 mass parts, DCPD are that the ratio of 10 mass parts is fed in the barrel-type gravity stirrer that inclines (capacity 110L) according to bead in the total amount of per 100 mass parts, carry out mixing in 3 minutes.
Likewise the mixture that obtains is filled in the glass post casing with embodiment 1, makes filtration unit, inject the process object water that contains fluorine from the top of filtration unit, bead begins to swim as a result, and the treating water on filtration unit top becomes opaque.Likewise water-permeable is estimated with embodiment 1, and measured fluorine concentration.The result is shown in table 4.These results represent that DCPD is not supported by bead fully.
Table 4
The industry utilizability
Treatment agent of the present invention is owing to have an above-mentioned formation, and therefore can be utilized in generations such as electroplating industry, semiconductor manufacturing industry, valve production, glass industry aptly has the water that contains fluorine or contain in the field of soil of fluorine.
Nomenclature
1: glass post casing
2: high-rate fitration is with the mixture of sand and DCPD
3: glass wool
4: the process object water that contains fluorine
5,5a: filtration unit
6,7: pipe
8: the water surface
9：DCPD
Claims (8)
1. a treatment agent is characterized in that, this treatment agent contains dicalcium phosphate dihydrate (A) and particle (B), and dicalcium phosphate dihydrate (A) is supported by particle (B).
2. the described treatment agent of claim 1, wherein, particle (B) comes down to the particle that particle diameter is 0.3～3.0mm.
3. claim 1 or 2 described treatment agents, wherein, the uniformity ratio of particle (B) is below 1.5.
4. claim 1,2 or 3 described treatment agents, wherein, the median size of dicalcium phosphate dihydrate (A) is 30～70 μ m.
5. the method for manufacture of a treatment agent; It is a method of making claim 1,2,3 or 4 described treatment agents; This method of manufacture is characterised in that, it comprises and uses the barrel-type gravity stirrer that inclines that dicalcium phosphate dihydrate (A) and particle (B) are carried out the blended operation.
6. a treatment process is characterized in that, this treatment process comprises the operation that makes claim 1,2,3 or 4 described treatment agents and the process object water that contains fluorine contact, remove the fluorine in this process object water.
7. a treatment process is characterized in that, this treatment process comprise with claim 1,2,3 or 4 described treatment agents and contain fluorine mixing with soil, make the fluorine operation of dissolving not in this soil.
8. the described treatment process of claim 7, wherein, said 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 |
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|---|---|
| JP (1) | JP5582141B2 (en) |
| KR (1) | KR101294490B1 (en) |
| CN (1) | CN102428038B (en) |
| BR (1) | BRPI1011067A2 (en) |
| MX (1) | MX2011011570A (en) |
| WO (1) | WO2010134573A1 (en) |
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| CN113262805A (en) * | 2021-04-20 | 2021-08-17 | 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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| JP5915231B2 (en) * | 2012-02-14 | 2016-05-11 | ダイキン工業株式会社 | Processing method and processing equipment |
| JP2013188740A (en) * | 2012-02-14 | 2013-09-26 | Daikin Industries Ltd | Reactor, treatment equipment, and treatment method |
| JP2014039924A (en) * | 2012-07-24 | 2014-03-06 | Daikin Ind Ltd | 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2001232167A (en) * | 2000-02-28 | 2001-08-28 | Shimooka Kogyo:Kk | Agitating and mixing device for powder and granular material |
| CN1724362A (en) * | 2005-06-03 | 2006-01-25 | 天津大学 | Process for preparing fluorine reducing ion sieve of aquatic body |
| JP2007216156A (en) * | 2006-02-17 | 2007-08-30 | Institute Of National Colleges Of Technology Japan | Treatment agent and treatment method of fluorine-contaminated soil |
Family Cites Families (7)
| 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 |
| 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 |
| JP2004358309A (en) * | 2003-06-03 | 2004-12-24 | Ngk Insulators Ltd | Method for treating fluorine in wastewater |
| 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 |
-
2010
- 2010-05-20 WO PCT/JP2010/058536 patent/WO2010134573A1/en active Application Filing
- 2010-05-20 MX MX2011011570A patent/MX2011011570A/en active IP Right Grant
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- 2010-05-20 JP JP2011514447A patent/JP5582141B2/en active Active
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2001232167A (en) * | 2000-02-28 | 2001-08-28 | Shimooka Kogyo:Kk | Agitating and mixing device for powder and granular material |
| CN1724362A (en) * | 2005-06-03 | 2006-01-25 | 天津大学 | Process for preparing fluorine reducing ion sieve of aquatic body |
| JP2007216156A (en) * | 2006-02-17 | 2007-08-30 | Institute Of National Colleges Of Technology Japan | Treatment agent and treatment method of fluorine-contaminated soil |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113262805A (en) * | 2021-04-20 | 2021-08-17 | 煤炭科学技术研究院有限公司 | Defluorination catalyst, preparation method thereof and defluorination method |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102428038B (en) | 2015-12-02 |
| KR20120022996A (en) | 2012-03-12 |
| MX2011011570A (en) | 2011-11-18 |
| BRPI1011067A2 (en) | 2016-03-15 |
| JPWO2010134573A1 (en) | 2012-11-12 |
| KR101294490B1 (en) | 2013-08-07 |
| WO2010134573A1 (en) | 2010-11-25 |
| JP5582141B2 (en) | 2014-09-03 |
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