WO2018181659A1 - Heavy metal adsorbent - Google Patents
Heavy metal adsorbent Download PDFInfo
- Publication number
- WO2018181659A1 WO2018181659A1 PCT/JP2018/013109 JP2018013109W WO2018181659A1 WO 2018181659 A1 WO2018181659 A1 WO 2018181659A1 JP 2018013109 W JP2018013109 W JP 2018013109W WO 2018181659 A1 WO2018181659 A1 WO 2018181659A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- heavy metal
- silica
- metal adsorbent
- magnesia
- particles
- Prior art date
Links
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 92
- 239000003463 adsorbent Substances 0.000 title claims abstract description 77
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 195
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 168
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 102
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000011148 porous material Substances 0.000 claims abstract description 44
- 239000011246 composite particle Substances 0.000 claims abstract description 18
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 21
- 238000000746 purification Methods 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 238000002459 porosimetry Methods 0.000 claims description 3
- 238000010998 test method Methods 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 7
- 230000035515 penetration Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 77
- 239000011133 lead Substances 0.000 description 30
- 238000001179 sorption measurement Methods 0.000 description 30
- 239000002131 composite material Substances 0.000 description 28
- 238000010304 firing Methods 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 11
- 229920006395 saturated elastomer Polymers 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005469 granulation Methods 0.000 description 10
- 230000003179 granulation Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 238000001132 ultrasonic dispersion Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000010419 fine particle Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000010354 integration Effects 0.000 description 5
- 229910020175 SiOH Inorganic materials 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 230000004323 axial length Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- PWZFXELTLAQOKC-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide;tetrahydrate Chemical compound O.O.O.O.[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O PWZFXELTLAQOKC-UHFFFAOYSA-A 0.000 description 1
- -1 dosonite Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D35/00—Filtering devices having features not specifically covered by groups B01D24/00 - B01D33/00, or for applications not specifically covered by groups B01D24/00 - B01D33/00; Auxiliary devices for filtration; Filter housing constructions
- B01D35/02—Filters adapted for location in special places, e.g. pipe-lines, pumps, stop-cocks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28076—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being more than 1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F2101/20—Heavy metals or heavy metal compounds
Definitions
- the present invention relates to a heavy metal adsorbent, and more particularly to a heavy metal adsorbent that is excellent in lead adsorptivity and that is suitably used as a water purification material.
- amorphous titanosilicate compounds X-type zeolites, A-type zeolites and the like are known as heavy metal adsorbents that adsorb lead and the like (see Patent Document 1).
- heavy metal adsorbents amorphous titanosilicate compounds have a problem that they are quite expensive.
- zeolite-based materials contain aluminum, so that there is a problem that aluminum is eluted. Therefore, use as a filter of a water purifier is restricted, for example.
- silica magnesia preparations and magnesium surface-treated silica gel particles are excellent in adsorption capacity for heavy metals such as iron (see Patent Documents 2 and 3).
- the prices of these silica magnesia preparations and the like are very inexpensive, do not contain aluminum, and are excellent in the saturated adsorption amount of heavy metals.
- such adsorbents have the disadvantage that their ability to remove heavy metals in running water is extremely low.
- an object of the present invention is to provide a heavy metal adsorbent that is inexpensive, does not contain aluminum, and has high removal performance for heavy metals, particularly lead, in running water.
- Another object of the present invention is to provide a heavy metal adsorbent that has particularly high removal performance and can therefore be suitably used as a filter for a water purifier.
- the removal performance is the breakthrough life.
- the breakthrough refers to a state in which the adsorbent is saturated and the adsorption ability is lost, and the adsorption target passes through the adsorbent without being adsorbed.
- the breakthrough life means a period until breakthrough of a certain ratio or more occurs macroscopically.
- the present inventors examined the heavy metal adsorption ability of an inexpensive silica magnesia-based preparation. As a result, it was found that by calcining this preparation at a temperature of 300 to 830 ° C., not only the saturated adsorption amount to lead is improved, but also its removal performance is remarkably improved, and the present invention has been completed.
- the present invention is composed of silica magnesia composite particles in which silica and magnesium oxide are integrally combined, and the pore volume at a pore diameter of 3.5 to 10.0 nm measured by mercury porosimetry is 0.26 to 0.
- a heavy metal adsorbent having a pore volume in the range of 1.30 to 2.50 mL / g at 50 mL / g, 3.5 to 5000.0 nm, and a compressive strength of 1.5 MPa or more. Is provided.
- a water purification material characterized in that the heavy metal adsorbent is contained in an amount of 1 to 30 parts by mass per 100 parts by mass of activated carbon.
- a water purifier characterized by incorporating a water purification material using the heavy metal adsorbent.
- the water purifier characterized by incorporating the said water purification material is provided.
- the heavy metal adsorbent of the present invention is not only inexpensive, but particularly has high adsorbability for lead.
- the saturated adsorption amount for lead is equal to or higher than that of conventionally known silica magnesia preparations, but particularly about twice or more higher in breakthrough life.
- the heavy metal adsorbent is composed of silica magnesia composite particles in which silica and magnesium oxide are integrally combined and does not contain aluminum, so there is no problem of aluminum elution.
- this heavy metal adsorbent since this heavy metal adsorbent has a high particle strength, it is difficult for the particles to collapse. Therefore, it is difficult to cause performance degradation due to particle collapse (for example, generation of a short path due to partial blockage of the filter by the collapsed particles), and for example, adsorption performance can be exhibited over a long period even in flowing water.
- the heavy metal adsorbent of the present invention is particularly suitable as a water purification material used in waterworks and the like. Furthermore, the water purification material obtained by mixing the heavy metal adsorbent of the present invention with another adsorbent is extremely suitable as a filter for a water purifier.
- the heavy metal adsorbent of the present invention comprises silica magnesia composite particles in which silica and magnesium oxide (magnesia) are integrally combined.
- silica-magnesia composite particle silica and magnesia are in close contact with each other without a chemical bond involving recombination or exchange of atoms. That is, silica and magnesia are not physically separated, and the silica magnesia composite particles of the present invention are completely different from a simple mixture of silica and magnesia.
- silica magnesia composite particles are not a simple mixture of silica and magnesia indicates that the lead adsorption performance of the adsorbent of the present invention is silica (Comparative Example 1) and It is understood that it is far superior to any of magnesia (Comparative Example 2).
- the silica magnesia composite particles constituting the heavy metal adsorbent of the present invention have a pore volume of 0.26 to 0.50 mL / g at a pore diameter of 3.5 to 10.0 nm measured by mercury porosimetry, 3.5
- the pore volume at ⁇ 5000.0 nm is in the range of 1.30 to 2.50 mL / g.
- Silica magnesia composite particles having such a pore volume are obtained by integrally combining silica and magnesia by a heat treatment called firing.
- unsintered silica magnesia disclosed in Patent Documents 2 and 3 is clearly different from the silica magnesia composite particles of the present invention.
- the silica magnesia composite particles may be referred to as silica magnesia composite fired particles.
- the silica magnesia composite fired particles of the present invention have the same pore volume as that of the unfired product when the pore diameter is 3.5 to 5000.0 nm.
- the pore volume at a pore diameter of 3.5 to 10.0 nm is considerably larger than that of an unfired product.
- the silica magnesia composite fired particles have higher removal performance against heavy metals, particularly lead in running water, compared to unfired products. This is presumably because the pores having a diameter of 3.5 to 10.0 nm greatly contribute to lead adsorption. That is, since the pore volume at this pore diameter is large, the saturated adsorption amount for lead is increased. Further, the contact time between the pores having such a size and the liquid containing lead becomes longer, and as a result, the breakthrough life is remarkably improved.
- the breakthrough life can be evaluated, for example, as follows. That is, JIS S-3201 household water purifier test method for a mixture obtained by mixing 3 g of the heavy metal adsorbent with 50 g of activated carbon, using sample water having a lead concentration of 0.05 mg / L, and at a filtration flow rate of 3 L / min.
- the soluble lead filtration ability test is performed according to the above. The amount of filtrate water until the lead concentration of filtrate water that has passed through the mixture exceeds 20% of the sample water is measured. The larger the amount of filtered water, the better the removal performance for heavy metals.
- the amount of filtered water per 1 g of the heavy metal adsorbent of the present invention is 250 L or more.
- the amount of filtered water per 1g of unbaked product is about 170L. That is, the breakthrough life of the heavy metal adsorbent of the present invention is significantly longer than that of an unfired product. Moreover, the saturated adsorption amount with respect to lead of the heavy metal adsorbent of the present invention is 1.7 mmol / g or more in the case of the highest performance, but is about 1.5 mmol / g in the unfired product.
- the silica magnesia composite fired particles in the present invention have a compressive strength of 1.5 MPa or more, preferably 2.0 MPa or more, more preferably 2.5 MPa or more, in relation to being a fired product. That is, particle shrinkage occurs by firing, and as a result, compressive strength is improved. If the compressive strength is 1.5 MPa or less, the particles may collapse. In addition, the filter using the water purification material containing such silica magnesia composite fired particles is partially clogged with the collapsed particles, which may cause differential pressure and uneven adsorption performance, There is a possibility that loss increases and a desired filtration flow rate cannot be obtained.
- the compression strength of conventionally known silica magnesia composite unfired particles according to Patent Document 2 and the like is about 1.3 MPa, which is considerably lower than that of the present invention.
- an excessively high compressive strength means that firing was performed more than necessary.
- the obtained silica magnesia composite fired particles do not exhibit the pore distribution described above, and the adsorption performance such as the saturated adsorption amount and breakthrough life of heavy metals, particularly lead, is lowered. Therefore, in the present invention, it is suitable that this compressive strength is suppressed to 10.0 MPa or less, preferably 5.0 MPa or less, more preferably 4.7 MPa or less.
- the fact that the compression strength of the silica magnesia composite fired particles is improved means that the particles are difficult to disintegrate, and the performance degradation of the heavy metal adsorbent due to the disintegration of the particles can be effectively avoided.
- the volume average particle diameter after ultrasonic dispersion (median measured by laser diffraction scattering method) The diameter is about 68% before ultrasonic dispersion when the compressive strength is 2.5 MPa, and about 80% before ultrasonic dispersion when the compressive strength is 4.7 MPa.
- the silica magnesia composite fired particles of the present invention when the same test is performed on the unsintered particles, the volume average particle size is reduced to about 30% before ultrasonic dispersion. Therefore, in the silica magnesia composite fired particles of the present invention, a decrease in the average particle size is suppressed, that is, particle collapse is effectively suppressed.
- the silica magnesia composite fired particles used as the heavy metal adsorbent are very difficult to disintegrate. Therefore, when the silica magnesia composite fired particles are used by mixing with other adsorbents, it is possible to effectively prevent performance degradation due to particle collapse during the mixing operation. Moreover, even when used in running water, it is possible to effectively avoid performance degradation due to particle collapse, and to stably exhibit heavy metal adsorption performance over a long period of time.
- the silica magnesia composite fired particles do not contain aluminum. Therefore, when this is used as a water purification material, the problem of aluminum elution does not occur.
- the ignition loss 1000 degreeC x 30 minutes, 150 degreeC drying reference
- the ignition loss corresponds to the amount of SiOH groups, and the larger the ignition loss, the more SiOH groups remain in the silica magnesia composite fired particles. As will be described later, since it is presumed that the pore distribution and compressive strength of the particles change with the dehydration condensation of SiOH groups by firing, the ignition loss is an index indicating the degree of firing.
- the mass ratio R described above indicates that the pore distribution of the silica magnesia composite fired particles is in the above-described range and is fired under conditions (for example, a firing temperature and a firing time) with high compressive strength.
- the ignition loss is preferably 4.0 to 8.2% by mass, more preferably 4.5 to 7.6% by mass.
- silica magnesia composite fired particles The silica magnesia composite calcined particles described above are prepared by mixing (A) silica (silicon dioxide) and (B) magnesia (magnesium oxide) or magnesia hydrate homogeneously in the presence of moisture to prepare an aqueous slurry. Next, aging is performed, and further, moisture is removed, followed by firing.
- (A) silica which is one of the raw materials, is finely divided into colloidal particles or fine aggregated particles (primary or secondary particles) by homogeneous mixing in water, for example, in water.
- (B) magnesia which is the other raw material is put into water and stirred or pulverized, it hardly dissolves.
- crystals or newly formed hydrates
- At least a part of the crystal is disintegrated or exfoliated to form fine particles made of magnesia and / or magnesia hydrate and dispersed in water (fine particles).
- silica magnesia composite fired particles of the present invention have an integrated structure so as not to be separated by physical means.
- (A) silica and (B) magnesia or magnesia hydrate are used as raw materials. All of these are approved in Japan as filter aids or adsorbents for food production. Therefore, the use as a food refining is not limited by these uses.
- magnesium hydroxide, magnesium chloride, magnesium sulfate, magnesium nitrate, or the like is used as a raw material instead of (B) magnesia particles, sufficient fine particles cannot be formed. Furthermore, when (A) the silica particles and the magnesium component are contacted in water and / or when calcination is performed, chemical bonds such as (A) exchange of atoms and recombination with the silica particles occur. May occur. In the case of such a chemical bond in the (B) magnesia particles that are the raw material of the present invention, since a pore structure peculiar to the heavy metal adsorbent of the present invention may not be formed, magnesium oxide is used in particular. It is preferable to do.
- silica (A) and magnesia or magnesia hydrate (B) it is preferable to select those that facilitate the above-mentioned fine particle formation.
- silica amorphous water-containing silica is suitable, and it may be produced by either gel method or precipitation method.
- the silica particles preferably have small primary particles, and the specific surface area is preferably 40 m 2 / g or more, particularly 140 m 2 / g or more.
- magnesia or magnesia hydrate those having small crystallites and not progressing carbonation with time are preferable.
- a magnesia powder having a specific surface area of 2 m 2 / g or more, preferably 20 m 2 / g or more, particularly preferably 50 m 2 / g or more is used.
- the amount of (A) silica and (B) magnesia or magnesia hydrate used is set so that the aforementioned mass ratio R falls within a predetermined range.
- the degree of integration is different depending on the mass ratio R of the silica component and the magnesia component in the adsorbent.
- a mass ratio of about 2 and preferably 1.3 to 3.0 is suitable for integrally combining a silica component and a magnesia component. Therefore, as shown in the examples described later, it is possible to obtain silica magnesia composite fired particles having a very high degree of integration and high removal performance against heavy metals, particularly lead, in running water.
- the solid content concentration of an aqueous slurry is low is preferable.
- the solid content concentration is preferably 3 to 15% by mass, particularly 8 to 13% by mass.
- the preparation of the aqueous slurry by the above homogeneous mixing and the subsequent aging are generally carried out with stirring in a stirring vessel equipped with a stirring blade, but are carried out under pulverization or dispersion with a wet ball mill or a colloid mill. Can also be done.
- such homogeneous mixing and aging is preferably performed under heating in order to complete integration of particles in a short time. However, when the heating temperature is high, gelation occurs and the composite particles become inhomogeneous. Cheap. Therefore, this heating temperature is usually 100 ° C. or less, preferably 50 to 97 ° C., particularly preferably 50 to 79 ° C.
- an aqueous solution containing a granular material in which silica particles and magnesia particles are integrally combined by performing homogeneous mixing and aging for 0.5 hours or more, particularly 1 to 24 hours, more preferably about 3 to 10 hours. A slurry is obtained.
- Water removal after aging can be performed by evaporation drying using a spray dryer or a slurry dryer. Moreover, after performing a certain amount of dehydration by means such as filtration or centrifugation, drying may be performed using a box dryer, a band dryer, a fluidized bed dryer or the like. Drying is preferably performed at a temperature in the range of 110 to 200 ° C. At this time, (B) magnesia hydrate is dehydrated, and part or all of the hydrated water is removed.
- silica magnesia composite particles having a water content of 10% by mass or less in which at least a part of silica particles and magnesia particles are intimately integrated by dehydration, for example, are granular, powdery, cake-like or nodules. Obtained in the form. If necessary, these are pulverized, classified, or molded, and then fired in a firing furnace to obtain composite fired particles in which silica particles and magnesia particles are integrally combined.
- the above pulverization can be performed by a known dry pulverization method.
- an impact pulverizer such as an atomizer, a dry ball mill, a roller mill, or a jet mill can be used.
- the classification is performed by gravity classification, centrifugal classification, inertia classification, or the like using an ordinary dry classifier.
- silica magnesia composite particles that are not subjected to heat treatment by firing, for example, in the form of a powder having a fine particle content of less than 5 ⁇ m of 20% by volume or less are obtained.
- molding can be performed by arbitrary methods, such as rolling granulation, fluidized bed granulation, stirring granulation, crushing granulation, compression granulation, extrusion granulation. In general, it is preferable to form the particles so that the particles do not become too hard and do not easily powder.
- a spherical unfired silica having a spherical shape having a diameter of 5 ⁇ m to 5 mm, an elliptical spherical shape having a major axis of 5 ⁇ m to 5 mm, or a cylinder having a diameter of 0.5 mm or more and an axial length of 50 mm or less. Magnesia composite particles are obtained.
- silica magnesia composite particles that have not been subjected to heat treatment by firing are commercially available from Mizusawa Chemical Co., Ltd. under the trade name “Mizuka Life”.
- silica magnesia composite fired particles can be obtained by firing “Mizuka Life” manufactured by Mizusawa Chemical Industry Co., Ltd. as shown in the examples described later.
- the above calcining is performed at 300 to 830 ° C., preferably 400 to 800 ° C., more preferably 400 to 750 ° C., particularly preferably 550 to 550 ° C. It is important to carry out at a temperature of 750 ° C.
- silica magnesia composite fired particles having the above-described pore distribution and compressive strength can be obtained. That is, such firing probably causes partial dehydration condensation of SiOH groups present inside the unfired particles, resulting in fluctuations in pore diameter, resulting in pore diameter contributing to adsorption of heavy metals (particularly lead). It seems that the pore volume of 3.5-10.0 nm increases to the above-mentioned range. Further, as a result of the shrinkage of the particles due to firing, the compressive strength is increased to the above-described range.
- the pore volume at a pore diameter of 3.5 to 10.0 nm is lower than the aforementioned range.
- the fired particles obtained do not exhibit the adsorption performance for lead as in the present invention, have a low compressive strength, and are easily collapsed.
- the unsintered particles that are simply removed by drying When the firing temperature is higher than the above range, the degree of particle shrinkage is large, so that the compressive strength is higher and particle collapse is suppressed.
- the pore volume especially the pore volume with a pore diameter of 3.5-10.0 nm, is reduced, resulting in a decrease in saturated adsorption amount and shortened breakthrough life. Decrease.
- the firing as described above is performed so that the pore volume at a pore diameter of 3.5 to 10.0 nm falls within the above-described range.
- the baking may be performed at the above temperature for 0.5 to 5 hours, preferably 2 to 4 hours.
- the composite calcined particles thus obtained are obtained in the form of granules, powders, cakes or nodules, and are granulated into particles of an appropriate size to adsorb heavy metals. Used as an agent.
- granulation means it can carry out by publicly known means, such as spray granulation and rolling granulation.
- spray granulation When a large load is applied to the particles, the pore distribution may be out of the above-mentioned range, and thus means that do not apply the load as much as possible, for example, spray granulation is particularly suitable.
- the silica magnesia composite calcined particles have a silica component and a magnesia component that are not separated from each other and are closely integrated, so that the pH of the suspension is usually 6.0 to 10.0. It is in the range.
- the BET specific surface area measured by the nitrogen adsorption method is 100 m 2 / g or more, more preferably 400 m 2 / g or more, particularly 500 m 2 in that the silica magnesia composite fired particles can stably adsorb heavy metals. / G or more is preferred.
- the heavy metal adsorbent of the present invention is excellent in adsorption performance for heavy metals such as lead, manganese, chromium, nickel, vanadium, copper and iron, particularly lead. Furthermore, since aluminum is not contained, there is no problem of aluminum elution. Therefore, it is suitably used as a water purification material.
- the heavy metal adsorbent of the present invention when mixed with activated carbon and used as a water purification material, is generally used in an amount of 1 to 30 parts by mass per 100 parts by mass of activated carbon.
- the heavy metal adsorbent of the present invention is inexpensive, it can be used effectively as a water purification material, and the water purification material using the heavy metal adsorbent of the present invention or a combination of such heavy metal adsorbent and activated carbon, It is suitable as a cartridge type filter for a water purifier, particularly a household water purifier.
- adsorbents are not particularly limited, but include, for example, titanosilicate compounds, various silicates such as magnesium silicate; various zeolites such as A-type zeolite and X-type zeolite; sepiolite, attapulgite, dosonite, montmorillonite, Various clays such as hydrotalcite; various ion exchange resins;
- the heavy metal adsorbent of the present invention is composed of silica magnesia composite particles in which silica and magnesia approved as food additives are integrally combined, and can be effectively applied to food refining applications.
- it can be used for the purpose of removing the heavy metal from the oil pump which has deteriorated by repeated use and has increased the content of heavy metals such as copper and iron.
- the browning reaction (Maillard reaction) during heating and concentration is suppressed, and flavor and nutritional value of It is effectively used for various purposes such as the purpose of preventing the decrease.
- It can also be used effectively for the purpose of purification by adsorption and removal of heavy metals as impurities from widely useful liquids other than food.
- the heavy metal adsorbent of the present invention has a high saturated adsorption amount and is excellent in suppressing elution after heavy metal adsorption. For this reason, it is also effective to use the heavy metal adsorbent of the present invention as a heavy metal insolubilizing material for an object to be treated contaminated with heavy metals such as incineration ash, sewage sludge, and soil.
- Pore volume It measured by the mercury intrusion method using AutoPore IV 9500 by Micromeritics. The pore volume when the pore diameter is 3.5 to 10.0 nm is obtained from the indentation amount of 20000 to 60000 psia, and the pore volume when the pore diameter is 3.5 to 5000.0 nm is obtained from the indentation amount of 30 to 60000 psia. It was.
- Breakthrough life 3 g of heavy metal adsorbent and 50 g of activated carbon were mixed to prepare a water purification material and incorporated into a water purifier.
- sample water lead nitrate (II) nitrate aqueous solution
- lead concentration 0.05 mg / L
- the amount of filtered water (L / g) required until the lead concentration of the filtered water exceeded 20% of the sample water was determined, and the breakthrough life was evaluated.
- Loss on ignition Loss on ignition (mass%) is obtained by calcining a heavy metal adsorbent dried at 150 ° C. for 2 hours at 1000 ° C. for 30 minutes and then allowing it to cool. Based on.
- Table 1 shows the physical properties and heavy metal adsorption test results of the heavy metal adsorbents shown in the following Examples and Comparative Examples.
- Example 1 The silica magnesia preparation used in Comparative Example 3 was calcined at 550 ° C. for 4 hours and used as a heavy metal adsorbent.
- Example 2 The silica magnesia preparation used in Comparative Example 3 was calcined at 750 ° C. for 2 hours and used as a heavy metal adsorbent.
- Comparative Example 4 The silica magnesia preparation used in Comparative Example 3 was calcined at 900 ° C. for 2 hours and used as a heavy metal adsorbent.
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Abstract
This heavy metal adsorbent comprises silica-magnesia composite particles in which silica and magnesium oxide are integrally combined, wherein a pore volume with a pore diameter of 3.5 to 10.0 nm, measured using a mercury penetration method, is in the range of 0.26 to 0.50 mL/g, the pore volume with a pore diameter of 3.5 to 5000.0 nm is in the range of 1.30 to 2.50 mL/g, and the compressive strength is at least equal to 1.5 MPa. This heavy metal adsorbent is inexpensive, does not contain aluminum, and has good performance for removing heavy metals, in particular lead, from flowing water.
Description
本発明は、重金属吸着剤に関するものであり、より詳細には、鉛に対する吸着性に優れていると共に、さらには水浄化材として好適に使用される重金属吸着剤に関する。
The present invention relates to a heavy metal adsorbent, and more particularly to a heavy metal adsorbent that is excellent in lead adsorptivity and that is suitably used as a water purification material.
従来、鉛等を吸着する重金属吸着剤として、非晶質チタノシリケート化合物、X型ゼオライト、A型ゼオライトなどが知られている(特許文献1参照)。
このような重金属吸着剤において、非晶質チタノシリケート化合物は、かなり高価であるという問題がある。一方、ゼオライト系のものは、アルミニウムを含んでいるため、アルミニウムが溶出するという問題がある。そのため、例えば浄水器のフィルターとしての使用が制限される。 Conventionally, amorphous titanosilicate compounds, X-type zeolites, A-type zeolites and the like are known as heavy metal adsorbents that adsorb lead and the like (see Patent Document 1).
In such heavy metal adsorbents, amorphous titanosilicate compounds have a problem that they are quite expensive. On the other hand, zeolite-based materials contain aluminum, so that there is a problem that aluminum is eluted. Therefore, use as a filter of a water purifier is restricted, for example.
このような重金属吸着剤において、非晶質チタノシリケート化合物は、かなり高価であるという問題がある。一方、ゼオライト系のものは、アルミニウムを含んでいるため、アルミニウムが溶出するという問題がある。そのため、例えば浄水器のフィルターとしての使用が制限される。 Conventionally, amorphous titanosilicate compounds, X-type zeolites, A-type zeolites and the like are known as heavy metal adsorbents that adsorb lead and the like (see Patent Document 1).
In such heavy metal adsorbents, amorphous titanosilicate compounds have a problem that they are quite expensive. On the other hand, zeolite-based materials contain aluminum, so that there is a problem that aluminum is eluted. Therefore, use as a filter of a water purifier is restricted, for example.
また、シリカマグネシア製剤やマグネシウム表面処理シリカゲル粒子は、鉄等の重金属に対する吸着能に優れることが報告されている(特許文献2,3参照)。これらのシリカマグネシア製剤などの価格は、非常に安価であり、アルミニウムを含んでおらず、また重金属の飽和吸着量にも優れている。しかしながら、係る吸着剤は、流水中での重金属除去性能が極端に低いという欠点がある。
In addition, it has been reported that silica magnesia preparations and magnesium surface-treated silica gel particles are excellent in adsorption capacity for heavy metals such as iron (see Patent Documents 2 and 3). The prices of these silica magnesia preparations and the like are very inexpensive, do not contain aluminum, and are excellent in the saturated adsorption amount of heavy metals. However, such adsorbents have the disadvantage that their ability to remove heavy metals in running water is extremely low.
従って、本発明の目的は、安価であり、アルミニウムを含んでおらず、流水中おける重金属、特に鉛に対する除去性能が高い重金属吸着剤を提供することにある。
本発明の他の目的は、除去性能が特に高く、従って、浄水器のフィルターとしても好適に使用し得る重金属吸着剤を提供することにある。
尚、本明細書においては、特記しない限り、除去性能は破過寿命のことである。破過とは、吸着剤が飽和して吸着能が失われ、吸着対象が吸着されないまま吸着剤を通過する状態をいう。また、破過寿命とは、巨視的に見て一定割合以上の破過が発生するまでの期間をいう。本出願では、ろ過水の重金属濃度が試料水の20%を超えた時点としている。吸着剤が破過寿命を過ぎると、その性能が低下し、重金属を十分に除去できなくなる。即ち、破過寿命が長いということは、吸着剤の除去性能が高いことを意味する。 Accordingly, an object of the present invention is to provide a heavy metal adsorbent that is inexpensive, does not contain aluminum, and has high removal performance for heavy metals, particularly lead, in running water.
Another object of the present invention is to provide a heavy metal adsorbent that has particularly high removal performance and can therefore be suitably used as a filter for a water purifier.
In this specification, unless otherwise specified, the removal performance is the breakthrough life. The breakthrough refers to a state in which the adsorbent is saturated and the adsorption ability is lost, and the adsorption target passes through the adsorbent without being adsorbed. The breakthrough life means a period until breakthrough of a certain ratio or more occurs macroscopically. In this application, it is set as the time of the heavy metal concentration of filtered water exceeding 20% of sample water. When the adsorbent has passed the breakthrough life, its performance deteriorates and heavy metals cannot be sufficiently removed. That is, a long breakthrough life means that the adsorbent removal performance is high.
本発明の他の目的は、除去性能が特に高く、従って、浄水器のフィルターとしても好適に使用し得る重金属吸着剤を提供することにある。
尚、本明細書においては、特記しない限り、除去性能は破過寿命のことである。破過とは、吸着剤が飽和して吸着能が失われ、吸着対象が吸着されないまま吸着剤を通過する状態をいう。また、破過寿命とは、巨視的に見て一定割合以上の破過が発生するまでの期間をいう。本出願では、ろ過水の重金属濃度が試料水の20%を超えた時点としている。吸着剤が破過寿命を過ぎると、その性能が低下し、重金属を十分に除去できなくなる。即ち、破過寿命が長いということは、吸着剤の除去性能が高いことを意味する。 Accordingly, an object of the present invention is to provide a heavy metal adsorbent that is inexpensive, does not contain aluminum, and has high removal performance for heavy metals, particularly lead, in running water.
Another object of the present invention is to provide a heavy metal adsorbent that has particularly high removal performance and can therefore be suitably used as a filter for a water purifier.
In this specification, unless otherwise specified, the removal performance is the breakthrough life. The breakthrough refers to a state in which the adsorbent is saturated and the adsorption ability is lost, and the adsorption target passes through the adsorbent without being adsorbed. The breakthrough life means a period until breakthrough of a certain ratio or more occurs macroscopically. In this application, it is set as the time of the heavy metal concentration of filtered water exceeding 20% of sample water. When the adsorbent has passed the breakthrough life, its performance deteriorates and heavy metals cannot be sufficiently removed. That is, a long breakthrough life means that the adsorbent removal performance is high.
本発明者等は、安価なシリカマグネシア系製剤の重金属吸着能について検討した。その結果、この製剤を300~830℃の温度で焼成することにより、鉛に対する飽和吸着量が向上するばかりか、その除去性能が著しく向上することを見出し、本発明を完成するに至った。
The present inventors examined the heavy metal adsorption ability of an inexpensive silica magnesia-based preparation. As a result, it was found that by calcining this preparation at a temperature of 300 to 830 ° C., not only the saturated adsorption amount to lead is improved, but also its removal performance is remarkably improved, and the present invention has been completed.
本発明によれば、シリカと酸化マグネシウムとが一体複合化したシリカマグネシア複合粒子からなり、水銀圧入法で測定した細孔直径3.5~10.0nmでの細孔容積が0.26~0.50mL/g、3.5~5000.0nmでの細孔容積が1.30~2.50mL/gの範囲にあり、且つ圧縮強度が1.5MPa以上であることを特徴とする重金属吸着剤が提供される。
According to the present invention, it is composed of silica magnesia composite particles in which silica and magnesium oxide are integrally combined, and the pore volume at a pore diameter of 3.5 to 10.0 nm measured by mercury porosimetry is 0.26 to 0. A heavy metal adsorbent having a pore volume in the range of 1.30 to 2.50 mL / g at 50 mL / g, 3.5 to 5000.0 nm, and a compressive strength of 1.5 MPa or more. Is provided.
本発明の重金属吸着剤においては、
(1)シリカ成分とマグネシア成分とを、下記式:
R=Sm[質量%]/Mm[質量%]
式中、
Smは、SiO2換算でのシリカ成分の含有量であり、
Mmは、MgO換算でのマグネシア成分の含有量である、
で表される質量比Rが1.3~3.0となる範囲で含有していること、
(2)前記重金属吸着剤3gと活性炭50gとの混合物について、鉛濃度が0.05mg/Lの試料水を用い、ろ過流量3L/minにおいて、JIS S-3201家庭用浄水器試験方法に準拠して溶解性鉛ろ過能力試験を行った際、ろ過水の鉛濃度が試料水の20%を超えるまでのろ過水量が、前記重金属吸着剤1g当り250L以上であること、
(3)水浄化材に使用されること、
が好ましい。 In the heavy metal adsorbent of the present invention,
(1) A silica component and a magnesia component are represented by the following formula:
R = Sm [mass%] / Mm [mass%]
Where
Sm is the content of the silica component in terms of SiO 2 ,
Mm is the content of the magnesia component in terms of MgO.
Containing the mass ratio R represented by the formula 1.3 to 3.0,
(2) For a mixture of 3 g of the above heavy metal adsorbent and 50 g of activated carbon, sample water with a lead concentration of 0.05 mg / L was used, and at a filtration flow rate of 3 L / min, in accordance with JIS S-3201 household water purifier test method. When the soluble lead filtration ability test is performed, the amount of filtrate water until the lead concentration of filtrate exceeds 20% of the sample water is 250 L or more per gram of the heavy metal adsorbent,
(3) Be used for water purification materials
Is preferred.
(1)シリカ成分とマグネシア成分とを、下記式:
R=Sm[質量%]/Mm[質量%]
式中、
Smは、SiO2換算でのシリカ成分の含有量であり、
Mmは、MgO換算でのマグネシア成分の含有量である、
で表される質量比Rが1.3~3.0となる範囲で含有していること、
(2)前記重金属吸着剤3gと活性炭50gとの混合物について、鉛濃度が0.05mg/Lの試料水を用い、ろ過流量3L/minにおいて、JIS S-3201家庭用浄水器試験方法に準拠して溶解性鉛ろ過能力試験を行った際、ろ過水の鉛濃度が試料水の20%を超えるまでのろ過水量が、前記重金属吸着剤1g当り250L以上であること、
(3)水浄化材に使用されること、
が好ましい。 In the heavy metal adsorbent of the present invention,
(1) A silica component and a magnesia component are represented by the following formula:
R = Sm [mass%] / Mm [mass%]
Where
Sm is the content of the silica component in terms of SiO 2 ,
Mm is the content of the magnesia component in terms of MgO.
Containing the mass ratio R represented by the formula 1.3 to 3.0,
(2) For a mixture of 3 g of the above heavy metal adsorbent and 50 g of activated carbon, sample water with a lead concentration of 0.05 mg / L was used, and at a filtration flow rate of 3 L / min, in accordance with JIS S-3201 household water purifier test method. When the soluble lead filtration ability test is performed, the amount of filtrate water until the lead concentration of filtrate exceeds 20% of the sample water is 250 L or more per gram of the heavy metal adsorbent,
(3) Be used for water purification materials
Is preferred.
本発明によれば、また、活性炭100質量部当り、前記重金属吸着剤を1~30質量部の量で含有することを特徴とする水浄化材が提供される。
According to the present invention, there is also provided a water purification material characterized in that the heavy metal adsorbent is contained in an amount of 1 to 30 parts by mass per 100 parts by mass of activated carbon.
また、本発明によれば、前記重金属吸着剤を使用した水浄化材を組み込んだことを特徴とする浄水器が提供される。
Further, according to the present invention, there is provided a water purifier characterized by incorporating a water purification material using the heavy metal adsorbent.
さらに、本発明によれば、前記水浄化材を組み込んだことを特徴とする浄水器が提供される。
Furthermore, according to this invention, the water purifier characterized by incorporating the said water purification material is provided.
本発明の重金属吸着剤は、安価であるばかりか、特に鉛に対する吸着能が高い。例えば、鉛に対する飽和吸着量は、従来公知のシリカマグネシア製剤と比較しても同等以上であるが、特に破過寿命においては、約2倍以上も高い。
しかも、この重金属吸着剤は、シリカと酸化マグネシウムとが一体複合化したシリカマグネシア複合粒子からなっており、アルミニウムを含有しないため、アルミニウムの溶出の問題もない。
さらに、この重金属吸着剤は、粒子強度が高いため、粒子崩壊し難い。従って、粒子崩壊に起因する性能低下(例えば崩壊した粒子によるフィルターの部分的な閉塞に伴うショートパスの発生など)を起こしにくく、例えば、流水中でも長期間にわたって吸着性能を発揮できる。 The heavy metal adsorbent of the present invention is not only inexpensive, but particularly has high adsorbability for lead. For example, the saturated adsorption amount for lead is equal to or higher than that of conventionally known silica magnesia preparations, but particularly about twice or more higher in breakthrough life.
In addition, the heavy metal adsorbent is composed of silica magnesia composite particles in which silica and magnesium oxide are integrally combined and does not contain aluminum, so there is no problem of aluminum elution.
Furthermore, since this heavy metal adsorbent has a high particle strength, it is difficult for the particles to collapse. Therefore, it is difficult to cause performance degradation due to particle collapse (for example, generation of a short path due to partial blockage of the filter by the collapsed particles), and for example, adsorption performance can be exhibited over a long period even in flowing water.
しかも、この重金属吸着剤は、シリカと酸化マグネシウムとが一体複合化したシリカマグネシア複合粒子からなっており、アルミニウムを含有しないため、アルミニウムの溶出の問題もない。
さらに、この重金属吸着剤は、粒子強度が高いため、粒子崩壊し難い。従って、粒子崩壊に起因する性能低下(例えば崩壊した粒子によるフィルターの部分的な閉塞に伴うショートパスの発生など)を起こしにくく、例えば、流水中でも長期間にわたって吸着性能を発揮できる。 The heavy metal adsorbent of the present invention is not only inexpensive, but particularly has high adsorbability for lead. For example, the saturated adsorption amount for lead is equal to or higher than that of conventionally known silica magnesia preparations, but particularly about twice or more higher in breakthrough life.
In addition, the heavy metal adsorbent is composed of silica magnesia composite particles in which silica and magnesium oxide are integrally combined and does not contain aluminum, so there is no problem of aluminum elution.
Furthermore, since this heavy metal adsorbent has a high particle strength, it is difficult for the particles to collapse. Therefore, it is difficult to cause performance degradation due to particle collapse (for example, generation of a short path due to partial blockage of the filter by the collapsed particles), and for example, adsorption performance can be exhibited over a long period even in flowing water.
従って、本発明の重金属吸着剤は、特に上水道などに使用される水浄化材として好適である。さらに、本発明の重金属吸着剤を他の吸着剤と混合した水浄化材は、浄水器のフィルターとして極めて好適である。
Therefore, the heavy metal adsorbent of the present invention is particularly suitable as a water purification material used in waterworks and the like. Furthermore, the water purification material obtained by mixing the heavy metal adsorbent of the present invention with another adsorbent is extremely suitable as a filter for a water purifier.
<重金属吸着剤>
本発明の重金属吸着剤は、シリカと酸化マグネシウム(マグネシア)とが一体複合化したシリカマグネシア複合粒子からなる。シリカマグネシア複合粒子は、シリカとマグネシアとが、原子の組み換えや交換を伴う化学結合を介することなく、それぞれの微細な粒子が緊密に接触している。即ち、シリカとマグネシアとは物理的に分離せず、本発明のシリカマグネシア複合粒子は、単なるシリカとマグネシアの混合物とは全く異なる。
また、このシリカマグネシア複合粒子が、シリカとマグネシアとの単なる混合物でないことは、後述する実施例に示されているように、本発明の吸着剤の鉛吸着性能が、シリカ(比較例1)及びマグネシア(比較例2)の何れよりも遥かに優れていることから理解される。 <Heavy metal adsorbent>
The heavy metal adsorbent of the present invention comprises silica magnesia composite particles in which silica and magnesium oxide (magnesia) are integrally combined. In the silica-magnesia composite particle, silica and magnesia are in close contact with each other without a chemical bond involving recombination or exchange of atoms. That is, silica and magnesia are not physically separated, and the silica magnesia composite particles of the present invention are completely different from a simple mixture of silica and magnesia.
In addition, the fact that the silica magnesia composite particles are not a simple mixture of silica and magnesia indicates that the lead adsorption performance of the adsorbent of the present invention is silica (Comparative Example 1) and It is understood that it is far superior to any of magnesia (Comparative Example 2).
本発明の重金属吸着剤は、シリカと酸化マグネシウム(マグネシア)とが一体複合化したシリカマグネシア複合粒子からなる。シリカマグネシア複合粒子は、シリカとマグネシアとが、原子の組み換えや交換を伴う化学結合を介することなく、それぞれの微細な粒子が緊密に接触している。即ち、シリカとマグネシアとは物理的に分離せず、本発明のシリカマグネシア複合粒子は、単なるシリカとマグネシアの混合物とは全く異なる。
また、このシリカマグネシア複合粒子が、シリカとマグネシアとの単なる混合物でないことは、後述する実施例に示されているように、本発明の吸着剤の鉛吸着性能が、シリカ(比較例1)及びマグネシア(比較例2)の何れよりも遥かに優れていることから理解される。 <Heavy metal adsorbent>
The heavy metal adsorbent of the present invention comprises silica magnesia composite particles in which silica and magnesium oxide (magnesia) are integrally combined. In the silica-magnesia composite particle, silica and magnesia are in close contact with each other without a chemical bond involving recombination or exchange of atoms. That is, silica and magnesia are not physically separated, and the silica magnesia composite particles of the present invention are completely different from a simple mixture of silica and magnesia.
In addition, the fact that the silica magnesia composite particles are not a simple mixture of silica and magnesia indicates that the lead adsorption performance of the adsorbent of the present invention is silica (Comparative Example 1) and It is understood that it is far superior to any of magnesia (Comparative Example 2).
本発明の重金属吸着剤を構成するシリカマグネシア複合粒子は、水銀圧入法で測定した細孔直径3.5~10.0nmでの細孔容積が0.26~0.50mL/g、3.5~5000.0nmでの細孔容積が1.30~2.50mL/gの範囲にある。このような細孔容積を有するシリカマグネシア複合粒子は、焼成という熱処理によりシリカとマグネシアを一体複合化させることで得られるものである。この点において、例えば特許文献2,3に開示されている未焼成のシリカマグネシアと本発明のシリカマグネシア複合粒子とは明確に異なっている。以下、このシリカマグネシア複合粒子を、シリカマグネシア複合焼成粒子と呼ぶことがある。
例えば、本発明におけるシリカマグネシア複合焼成粒子は、細孔直径3.5~5000.0nmでの細孔容積は、未焼成品と同レベルである。一方、細孔直径3.5~10.0nmでの細孔容積は、未焼成品に比してかなり大きい。 The silica magnesia composite particles constituting the heavy metal adsorbent of the present invention have a pore volume of 0.26 to 0.50 mL / g at a pore diameter of 3.5 to 10.0 nm measured by mercury porosimetry, 3.5 The pore volume at ˜5000.0 nm is in the range of 1.30 to 2.50 mL / g. Silica magnesia composite particles having such a pore volume are obtained by integrally combining silica and magnesia by a heat treatment called firing. In this respect, for example, unsintered silica magnesia disclosed in Patent Documents 2 and 3 is clearly different from the silica magnesia composite particles of the present invention. Hereinafter, the silica magnesia composite particles may be referred to as silica magnesia composite fired particles.
For example, the silica magnesia composite fired particles of the present invention have the same pore volume as that of the unfired product when the pore diameter is 3.5 to 5000.0 nm. On the other hand, the pore volume at a pore diameter of 3.5 to 10.0 nm is considerably larger than that of an unfired product.
例えば、本発明におけるシリカマグネシア複合焼成粒子は、細孔直径3.5~5000.0nmでの細孔容積は、未焼成品と同レベルである。一方、細孔直径3.5~10.0nmでの細孔容積は、未焼成品に比してかなり大きい。 The silica magnesia composite particles constituting the heavy metal adsorbent of the present invention have a pore volume of 0.26 to 0.50 mL / g at a pore diameter of 3.5 to 10.0 nm measured by mercury porosimetry, 3.5 The pore volume at ˜5000.0 nm is in the range of 1.30 to 2.50 mL / g. Silica magnesia composite particles having such a pore volume are obtained by integrally combining silica and magnesia by a heat treatment called firing. In this respect, for example, unsintered silica magnesia disclosed in Patent Documents 2 and 3 is clearly different from the silica magnesia composite particles of the present invention. Hereinafter, the silica magnesia composite particles may be referred to as silica magnesia composite fired particles.
For example, the silica magnesia composite fired particles of the present invention have the same pore volume as that of the unfired product when the pore diameter is 3.5 to 5000.0 nm. On the other hand, the pore volume at a pore diameter of 3.5 to 10.0 nm is considerably larger than that of an unfired product.
前記シリカマグネシア複合焼成粒子は、未焼成品と比較して、流水中における重金属、特に鉛に対する除去性能が高い。これは直径が3.5~10.0nmの大きさの細孔が、鉛の吸着に大きく寄与しているためと考えられる。即ち、この細孔直径での細孔容積が大きいため、鉛に対する飽和吸着量が大きくなる。また、このような大きさの細孔と鉛を含有する液体との接触時間も長くなり、結果として、破過寿命も著しく向上している。
The silica magnesia composite fired particles have higher removal performance against heavy metals, particularly lead in running water, compared to unfired products. This is presumably because the pores having a diameter of 3.5 to 10.0 nm greatly contribute to lead adsorption. That is, since the pore volume at this pore diameter is large, the saturated adsorption amount for lead is increased. Further, the contact time between the pores having such a size and the liquid containing lead becomes longer, and as a result, the breakthrough life is remarkably improved.
破過寿命は、例えば以下のようにして評価することができる。即ち、前記重金属吸着剤3gを活性炭50gと混合して得た混合物について、鉛濃度が0.05mg/Lの試料水を用い、ろ過流量3L/minにおいて、JIS S-3201家庭用浄水器試験方法に準拠して溶解性鉛ろ過能力試験を行う。混合物を通過したろ過水の鉛濃度が試料水の20%を超えるまでのろ過水量を測定する。このろ過水量が多いほど、重金属に対する除去性能が優れている。本発明の重金属吸着剤1gあたりの濾過水量は、250L以上である。一方、未焼成品1gあたりの濾過水量は、約170Lである。即ち、本発明の重金属吸着剤の破過寿命は、未焼成品と比較して大幅に長い。
また、本発明の重金属吸着剤の鉛に対する飽和吸着量は、最も性能が高いものでは、1.7mmol/g以上であるが、未焼成品では、1.5mmol/g程度に止まる。 The breakthrough life can be evaluated, for example, as follows. That is, JIS S-3201 household water purifier test method for a mixture obtained by mixing 3 g of the heavy metal adsorbent with 50 g of activated carbon, using sample water having a lead concentration of 0.05 mg / L, and at a filtration flow rate of 3 L / min. The soluble lead filtration ability test is performed according to the above. The amount of filtrate water until the lead concentration of filtrate water that has passed through the mixture exceeds 20% of the sample water is measured. The larger the amount of filtered water, the better the removal performance for heavy metals. The amount of filtered water per 1 g of the heavy metal adsorbent of the present invention is 250 L or more. On the other hand, the amount of filtered water per 1g of unbaked product is about 170L. That is, the breakthrough life of the heavy metal adsorbent of the present invention is significantly longer than that of an unfired product.
Moreover, the saturated adsorption amount with respect to lead of the heavy metal adsorbent of the present invention is 1.7 mmol / g or more in the case of the highest performance, but is about 1.5 mmol / g in the unfired product.
また、本発明の重金属吸着剤の鉛に対する飽和吸着量は、最も性能が高いものでは、1.7mmol/g以上であるが、未焼成品では、1.5mmol/g程度に止まる。 The breakthrough life can be evaluated, for example, as follows. That is, JIS S-3201 household water purifier test method for a mixture obtained by mixing 3 g of the heavy metal adsorbent with 50 g of activated carbon, using sample water having a lead concentration of 0.05 mg / L, and at a filtration flow rate of 3 L / min. The soluble lead filtration ability test is performed according to the above. The amount of filtrate water until the lead concentration of filtrate water that has passed through the mixture exceeds 20% of the sample water is measured. The larger the amount of filtered water, the better the removal performance for heavy metals. The amount of filtered water per 1 g of the heavy metal adsorbent of the present invention is 250 L or more. On the other hand, the amount of filtered water per 1g of unbaked product is about 170L. That is, the breakthrough life of the heavy metal adsorbent of the present invention is significantly longer than that of an unfired product.
Moreover, the saturated adsorption amount with respect to lead of the heavy metal adsorbent of the present invention is 1.7 mmol / g or more in the case of the highest performance, but is about 1.5 mmol / g in the unfired product.
さらに、本発明におけるシリカマグネシア複合焼成粒子は、焼成品であることに関連して、圧縮強度が1.5MPa以上であり、好ましくは2.0MPa以上、より好ましくは2.5MPa以上である。即ち、焼成により粒子の収縮が生じ、結果として、圧縮強度が向上する。
圧縮強度が1.5MPa以下であると、粒子が崩壊する虞がある。また、このようなシリカマグネシア複合焼成粒子を含有する水浄化材を使用したフィルターは、崩壊した粒子により部分的に閉塞されることにより、差圧が生じて吸着性能にムラを生ずる虞や、圧力損失が高まり所望のろ過流量が得られない虞がある。
因みに、特許文献2等により従来公知のシリカマグネシア複合未焼成粒子の圧縮強度は、1.3MPa程度であり、本発明に比してかなり低い。
一方、圧縮強度が過度に高いことは、必要以上に焼成が行われたことを意味する。この場合、得られるシリカマグネシア複合焼成粒子は、前述した細孔分布を示さず、重金属、特に鉛に対する飽和吸着量や破過寿命等の吸着性能が低下する。従って、本発明においては、この圧縮強度は10.0MPa以下、好ましくは5.0MPa以下、より好ましくは4.7MPa以下に抑えられていることが好適である。 Furthermore, the silica magnesia composite fired particles in the present invention have a compressive strength of 1.5 MPa or more, preferably 2.0 MPa or more, more preferably 2.5 MPa or more, in relation to being a fired product. That is, particle shrinkage occurs by firing, and as a result, compressive strength is improved.
If the compressive strength is 1.5 MPa or less, the particles may collapse. In addition, the filter using the water purification material containing such silica magnesia composite fired particles is partially clogged with the collapsed particles, which may cause differential pressure and uneven adsorption performance, There is a possibility that loss increases and a desired filtration flow rate cannot be obtained.
Incidentally, the compression strength of conventionally known silica magnesia composite unfired particles according to Patent Document 2 and the like is about 1.3 MPa, which is considerably lower than that of the present invention.
On the other hand, an excessively high compressive strength means that firing was performed more than necessary. In this case, the obtained silica magnesia composite fired particles do not exhibit the pore distribution described above, and the adsorption performance such as the saturated adsorption amount and breakthrough life of heavy metals, particularly lead, is lowered. Therefore, in the present invention, it is suitable that this compressive strength is suppressed to 10.0 MPa or less, preferably 5.0 MPa or less, more preferably 4.7 MPa or less.
圧縮強度が1.5MPa以下であると、粒子が崩壊する虞がある。また、このようなシリカマグネシア複合焼成粒子を含有する水浄化材を使用したフィルターは、崩壊した粒子により部分的に閉塞されることにより、差圧が生じて吸着性能にムラを生ずる虞や、圧力損失が高まり所望のろ過流量が得られない虞がある。
因みに、特許文献2等により従来公知のシリカマグネシア複合未焼成粒子の圧縮強度は、1.3MPa程度であり、本発明に比してかなり低い。
一方、圧縮強度が過度に高いことは、必要以上に焼成が行われたことを意味する。この場合、得られるシリカマグネシア複合焼成粒子は、前述した細孔分布を示さず、重金属、特に鉛に対する飽和吸着量や破過寿命等の吸着性能が低下する。従って、本発明においては、この圧縮強度は10.0MPa以下、好ましくは5.0MPa以下、より好ましくは4.7MPa以下に抑えられていることが好適である。 Furthermore, the silica magnesia composite fired particles in the present invention have a compressive strength of 1.5 MPa or more, preferably 2.0 MPa or more, more preferably 2.5 MPa or more, in relation to being a fired product. That is, particle shrinkage occurs by firing, and as a result, compressive strength is improved.
If the compressive strength is 1.5 MPa or less, the particles may collapse. In addition, the filter using the water purification material containing such silica magnesia composite fired particles is partially clogged with the collapsed particles, which may cause differential pressure and uneven adsorption performance, There is a possibility that loss increases and a desired filtration flow rate cannot be obtained.
Incidentally, the compression strength of conventionally known silica magnesia composite unfired particles according to Patent Document 2 and the like is about 1.3 MPa, which is considerably lower than that of the present invention.
On the other hand, an excessively high compressive strength means that firing was performed more than necessary. In this case, the obtained silica magnesia composite fired particles do not exhibit the pore distribution described above, and the adsorption performance such as the saturated adsorption amount and breakthrough life of heavy metals, particularly lead, is lowered. Therefore, in the present invention, it is suitable that this compressive strength is suppressed to 10.0 MPa or less, preferably 5.0 MPa or less, more preferably 4.7 MPa or less.
本発明において、前記シリカマグネシア複合焼成粒子の圧縮強度が向上していることは、粒子が崩壊し難いことを意味し、粒子の崩壊による重金属吸着剤の性能低下を有効に回避できる。
後述する実施例に示されているように、シリカマグネシア複合焼成粒子を一定量の水に投入して超音波分散したとき、超音波分散後の体積平均粒子径(レーザ回折散乱法により測定したメジアン径)は、圧縮強度が2.5MPaの場合には、超音波分散前の約68%であり、圧縮強度が4.7MPaの場合には、超音波分散前の約80%である。これに対して、未焼成粒子について同様の試験を行うと、体積平均粒子径は、超音波分散前の約30%に低下する。従って、本発明のシリカマグネシア複合焼成粒子は、平均粒子径の低下が抑制されており、即ち、粒子崩壊が有効に抑制されている。
このように、本発明において、重金属吸着剤として用いるシリカマグネシア複合焼成粒子は、非常に崩壊し難い。従って、係るシリカマグネシア複合焼成粒子を他の吸着剤と混合して使用する場合、混合操作中の粒子崩壊に起因する性能低下を有効に防止することができる。また、流水中で使用した場合においても、粒子崩壊による性能低下を有効に回避でき、長期にわたって、安定して重金属に対する吸着性能を発揮することができる。 In the present invention, the fact that the compression strength of the silica magnesia composite fired particles is improved means that the particles are difficult to disintegrate, and the performance degradation of the heavy metal adsorbent due to the disintegration of the particles can be effectively avoided.
As shown in the examples described later, when silica magnesia composite calcined particles are put into a certain amount of water and ultrasonically dispersed, the volume average particle diameter after ultrasonic dispersion (median measured by laser diffraction scattering method) The diameter is about 68% before ultrasonic dispersion when the compressive strength is 2.5 MPa, and about 80% before ultrasonic dispersion when the compressive strength is 4.7 MPa. On the other hand, when the same test is performed on the unsintered particles, the volume average particle size is reduced to about 30% before ultrasonic dispersion. Therefore, in the silica magnesia composite fired particles of the present invention, a decrease in the average particle size is suppressed, that is, particle collapse is effectively suppressed.
Thus, in the present invention, the silica magnesia composite fired particles used as the heavy metal adsorbent are very difficult to disintegrate. Therefore, when the silica magnesia composite fired particles are used by mixing with other adsorbents, it is possible to effectively prevent performance degradation due to particle collapse during the mixing operation. Moreover, even when used in running water, it is possible to effectively avoid performance degradation due to particle collapse, and to stably exhibit heavy metal adsorption performance over a long period of time.
後述する実施例に示されているように、シリカマグネシア複合焼成粒子を一定量の水に投入して超音波分散したとき、超音波分散後の体積平均粒子径(レーザ回折散乱法により測定したメジアン径)は、圧縮強度が2.5MPaの場合には、超音波分散前の約68%であり、圧縮強度が4.7MPaの場合には、超音波分散前の約80%である。これに対して、未焼成粒子について同様の試験を行うと、体積平均粒子径は、超音波分散前の約30%に低下する。従って、本発明のシリカマグネシア複合焼成粒子は、平均粒子径の低下が抑制されており、即ち、粒子崩壊が有効に抑制されている。
このように、本発明において、重金属吸着剤として用いるシリカマグネシア複合焼成粒子は、非常に崩壊し難い。従って、係るシリカマグネシア複合焼成粒子を他の吸着剤と混合して使用する場合、混合操作中の粒子崩壊に起因する性能低下を有効に防止することができる。また、流水中で使用した場合においても、粒子崩壊による性能低下を有効に回避でき、長期にわたって、安定して重金属に対する吸着性能を発揮することができる。 In the present invention, the fact that the compression strength of the silica magnesia composite fired particles is improved means that the particles are difficult to disintegrate, and the performance degradation of the heavy metal adsorbent due to the disintegration of the particles can be effectively avoided.
As shown in the examples described later, when silica magnesia composite calcined particles are put into a certain amount of water and ultrasonically dispersed, the volume average particle diameter after ultrasonic dispersion (median measured by laser diffraction scattering method) The diameter is about 68% before ultrasonic dispersion when the compressive strength is 2.5 MPa, and about 80% before ultrasonic dispersion when the compressive strength is 4.7 MPa. On the other hand, when the same test is performed on the unsintered particles, the volume average particle size is reduced to about 30% before ultrasonic dispersion. Therefore, in the silica magnesia composite fired particles of the present invention, a decrease in the average particle size is suppressed, that is, particle collapse is effectively suppressed.
Thus, in the present invention, the silica magnesia composite fired particles used as the heavy metal adsorbent are very difficult to disintegrate. Therefore, when the silica magnesia composite fired particles are used by mixing with other adsorbents, it is possible to effectively prevent performance degradation due to particle collapse during the mixing operation. Moreover, even when used in running water, it is possible to effectively avoid performance degradation due to particle collapse, and to stably exhibit heavy metal adsorption performance over a long period of time.
さらに、重金属吸着剤として使用する前記シリカマグネシア複合焼成粒子は、一般に、シリカ成分とマグネシア成分とを、下記式:
R=Sm[質量%]/Mm[質量%]
式中、
Smは、SiO2換算でのシリカ成分の含有量であり、
Mmは、MgO換算でのマグネシア成分の含有量である、
で表される質量比Rが0.1~50となる範囲で含有しており、1.3~3.0、更には1.5~2.5となる範囲で含有していることが、シリカとマグネシアとの一体複合化の度合いが高く、粒子崩壊が抑制される点で好適である。即ち、シリカとマグネシアとの質量比が上記範囲にあるとき、両成分がバランスよく分布して一体複合化し、重金属に対して、安定して均質な吸着性能を発揮できる。 Furthermore, the silica magnesia composite fired particles used as a heavy metal adsorbent generally have a silica component and a magnesia component represented by the following formula:
R = Sm [mass%] / Mm [mass%]
Where
Sm is the content of the silica component in terms of SiO 2 ,
Mm is the content of the magnesia component in terms of MgO.
Is contained in the range of 0.1 to 50, 1.3 to 3.0, more preferably 1.5 to 2.5, This is preferable in that the degree of integration of silica and magnesia is high and particle collapse is suppressed. That is, when the mass ratio of silica and magnesia is in the above range, both components are distributed in a balanced manner and are combined and integrated, and stable and homogeneous adsorption performance can be exerted on heavy metals.
R=Sm[質量%]/Mm[質量%]
式中、
Smは、SiO2換算でのシリカ成分の含有量であり、
Mmは、MgO換算でのマグネシア成分の含有量である、
で表される質量比Rが0.1~50となる範囲で含有しており、1.3~3.0、更には1.5~2.5となる範囲で含有していることが、シリカとマグネシアとの一体複合化の度合いが高く、粒子崩壊が抑制される点で好適である。即ち、シリカとマグネシアとの質量比が上記範囲にあるとき、両成分がバランスよく分布して一体複合化し、重金属に対して、安定して均質な吸着性能を発揮できる。 Furthermore, the silica magnesia composite fired particles used as a heavy metal adsorbent generally have a silica component and a magnesia component represented by the following formula:
R = Sm [mass%] / Mm [mass%]
Where
Sm is the content of the silica component in terms of SiO 2 ,
Mm is the content of the magnesia component in terms of MgO.
Is contained in the range of 0.1 to 50, 1.3 to 3.0, more preferably 1.5 to 2.5, This is preferable in that the degree of integration of silica and magnesia is high and particle collapse is suppressed. That is, when the mass ratio of silica and magnesia is in the above range, both components are distributed in a balanced manner and are combined and integrated, and stable and homogeneous adsorption performance can be exerted on heavy metals.
係るシリカマグネシア複合焼成粒子は、ゼオライトとは異なり、アルミニウムを含んでいない。従って、これを水浄化材として使用したとき、アルミニウムの溶出という問題は生じない。
また、焼成物であることに関連して、その強熱減量(1000℃×30分、150℃乾燥基準)は10質量%以下である。
強熱減量は、SiOH基量に対応し、この強熱減量が大きいほどシリカマグネシア複合焼成粒子にSiOH基が多く残存している。後述するように、焼成によるSiOH基の脱水縮合に伴い、粒子の細孔分布や圧縮強度が変化すると推測されるため、強熱減量は、焼成の度合いを示す指標となる。従って、シリカマグネシア複合焼成粒子の細孔分布を前述した範囲とし、且つ圧縮強度が高くなるような条件(例えば、焼成温度、焼成時間)で焼成されていることを示す点で、上記質量比R等の条件にもよるが、強熱減量は4.0~8.2質量%が好ましく、4.5~7.6質量%がより好ましい。 Unlike the zeolite, the silica magnesia composite fired particles do not contain aluminum. Therefore, when this is used as a water purification material, the problem of aluminum elution does not occur.
Moreover, the ignition loss (1000 degreeC x 30 minutes, 150 degreeC drying reference | standard) is 10 mass% or less in connection with being a baked product.
The ignition loss corresponds to the amount of SiOH groups, and the larger the ignition loss, the more SiOH groups remain in the silica magnesia composite fired particles. As will be described later, since it is presumed that the pore distribution and compressive strength of the particles change with the dehydration condensation of SiOH groups by firing, the ignition loss is an index indicating the degree of firing. Therefore, the mass ratio R described above indicates that the pore distribution of the silica magnesia composite fired particles is in the above-described range and is fired under conditions (for example, a firing temperature and a firing time) with high compressive strength. Depending on the above conditions, the ignition loss is preferably 4.0 to 8.2% by mass, more preferably 4.5 to 7.6% by mass.
また、焼成物であることに関連して、その強熱減量(1000℃×30分、150℃乾燥基準)は10質量%以下である。
強熱減量は、SiOH基量に対応し、この強熱減量が大きいほどシリカマグネシア複合焼成粒子にSiOH基が多く残存している。後述するように、焼成によるSiOH基の脱水縮合に伴い、粒子の細孔分布や圧縮強度が変化すると推測されるため、強熱減量は、焼成の度合いを示す指標となる。従って、シリカマグネシア複合焼成粒子の細孔分布を前述した範囲とし、且つ圧縮強度が高くなるような条件(例えば、焼成温度、焼成時間)で焼成されていることを示す点で、上記質量比R等の条件にもよるが、強熱減量は4.0~8.2質量%が好ましく、4.5~7.6質量%がより好ましい。 Unlike the zeolite, the silica magnesia composite fired particles do not contain aluminum. Therefore, when this is used as a water purification material, the problem of aluminum elution does not occur.
Moreover, the ignition loss (1000 degreeC x 30 minutes, 150 degreeC drying reference | standard) is 10 mass% or less in connection with being a baked product.
The ignition loss corresponds to the amount of SiOH groups, and the larger the ignition loss, the more SiOH groups remain in the silica magnesia composite fired particles. As will be described later, since it is presumed that the pore distribution and compressive strength of the particles change with the dehydration condensation of SiOH groups by firing, the ignition loss is an index indicating the degree of firing. Therefore, the mass ratio R described above indicates that the pore distribution of the silica magnesia composite fired particles is in the above-described range and is fired under conditions (for example, a firing temperature and a firing time) with high compressive strength. Depending on the above conditions, the ignition loss is preferably 4.0 to 8.2% by mass, more preferably 4.5 to 7.6% by mass.
<重金属吸着剤(シリカマグネシア複合焼成粒子)の製造>
上述したシリカマグネシア複合焼成粒子は、(A)シリカ(二酸化ケイ素)と(B)マグネシア(酸化マグネシウム)又はマグネシア水和物とを、水分の存在下で均質に混合して水性スラリーを調製し、次いで熟成を行い、さらに、水分を除去し、引き続いて焼成することにより、製造される。 <Manufacture of heavy metal adsorbent (silica magnesia composite fired particles)>
The silica magnesia composite calcined particles described above are prepared by mixing (A) silica (silicon dioxide) and (B) magnesia (magnesium oxide) or magnesia hydrate homogeneously in the presence of moisture to prepare an aqueous slurry. Next, aging is performed, and further, moisture is removed, followed by firing.
上述したシリカマグネシア複合焼成粒子は、(A)シリカ(二酸化ケイ素)と(B)マグネシア(酸化マグネシウム)又はマグネシア水和物とを、水分の存在下で均質に混合して水性スラリーを調製し、次いで熟成を行い、さらに、水分を除去し、引き続いて焼成することにより、製造される。 <Manufacture of heavy metal adsorbent (silica magnesia composite fired particles)>
The silica magnesia composite calcined particles described above are prepared by mixing (A) silica (silicon dioxide) and (B) magnesia (magnesium oxide) or magnesia hydrate homogeneously in the presence of moisture to prepare an aqueous slurry. Next, aging is performed, and further, moisture is removed, followed by firing.
即ち、水分の存在下、例えば水中での均質混合により、原料の一方である(A)シリカは、コロイド粒子乃至微細凝集粒子(1次乃至2次粒子)まで微細粒子化する。原料の他方である(B)マグネシアは、水中に投入されて撹拌もしくは粉砕されると、殆ど溶解しないが、マグネシア粒子表面の部分的な水和により、その結晶(もしくは新たに生成した水和物の結晶)の少なくとも一部が崩壊又は剥離して、マグネシア及び/又はマグネシア水和物からなる微細な粒子となって水中に分散される(微細粒子化する)。
That is, (A) silica, which is one of the raw materials, is finely divided into colloidal particles or fine aggregated particles (primary or secondary particles) by homogeneous mixing in water, for example, in water. When (B) magnesia which is the other raw material is put into water and stirred or pulverized, it hardly dissolves. However, due to partial hydration on the surface of the magnesia particles, crystals (or newly formed hydrates) At least a part of the crystal) is disintegrated or exfoliated to form fine particles made of magnesia and / or magnesia hydrate and dispersed in water (fine particles).
熟成工程において、これらの微細粒子が均質に分散した水性スラリーから水分が除去され、固形分濃度が上昇していくと、(A)シリカの粒子と(B)マグネシアの粒子とが徐々に又は急激に接近し、原子の交換や組み換えを伴うような化学結合を伴うことなく、一体複合化した形態に至るのである(一体複合化完了)。即ち、本発明のシリカマグネシア複合焼成粒子は、物理的手段により分離しないように一体化された構造である。
In the aging step, when water is removed from the aqueous slurry in which these fine particles are uniformly dispersed and the solid concentration increases, (A) silica particles and (B) magnesia particles gradually or rapidly. To the integrated form without chemical bonding such as exchange of atoms and recombination (completion of integration). That is, the silica magnesia composite fired particles of the present invention have an integrated structure so as not to be separated by physical means.
上述した本発明の重金属吸着剤を製造するためには、原料として、(A)シリカと(B)マグネシア又はマグネシア水和物とを使用する。これらは、何れも食品製造用のろ過助剤もしくは吸着剤として日本において認可されている。従って、これらの使用により食品精製としての用途が制限されることはない。
In order to produce the heavy metal adsorbent of the present invention described above, (A) silica and (B) magnesia or magnesia hydrate are used as raw materials. All of these are approved in Japan as filter aids or adsorbents for food production. Therefore, the use as a food refining is not limited by these uses.
原料として、(B)マグネシアの粒子に代えて、例えば、水酸化マグネシウム、塩化マグネシウム、硫酸マグネシウム、硝酸マグネシウムなどの粒子を用いる場合、十分な微細粒子化ができない。さらに、(A)シリカの粒子とマグネシウム成分が水中で接触したとき、及び/又は焼成を行ったときに、(A)シリカの粒子との間で原子の交換や組み換えを伴うような化学結合が生じる虞がある。本発明の原料である(B)マグネシアの粒子において、このような化学結合が起きた場合は、本発明の重金属吸着剤に特有の細孔構造が形成されない場合があるため、特に酸化マグネシウムを使用することが好ましい。
When, for example, magnesium hydroxide, magnesium chloride, magnesium sulfate, magnesium nitrate, or the like is used as a raw material instead of (B) magnesia particles, sufficient fine particles cannot be formed. Furthermore, when (A) the silica particles and the magnesium component are contacted in water and / or when calcination is performed, chemical bonds such as (A) exchange of atoms and recombination with the silica particles occur. May occur. In the case of such a chemical bond in the (B) magnesia particles that are the raw material of the present invention, since a pore structure peculiar to the heavy metal adsorbent of the present invention may not be formed, magnesium oxide is used in particular. It is preferable to do.
また、シリカ(A)及びマグネシア又はマグネシア水和物(B)としては、前述した微細粒子化が容易となるものを選択するのがよい。
例えば、シリカとしては、非晶質の含水シリカが好適であり、ゲル法及び沈降法の何れかで製造されたものであってよい。また、係るシリカの粒子は、一次粒子が小さいことが好ましく、比表面積が40m2/g以上、特に140m2/g以上であることが好ましい。
また、マグネシア又はマグネシア水和物としては、結晶子の小さく且つ経時による炭酸化が進んでいないものが好ましい。例えば、比表面積が2m2/g以上、好ましくは20m2/g以上、特に好ましくは50m2/g以上のマグネシア粉末が使用される。 Further, as the silica (A) and magnesia or magnesia hydrate (B), it is preferable to select those that facilitate the above-mentioned fine particle formation.
For example, as the silica, amorphous water-containing silica is suitable, and it may be produced by either gel method or precipitation method. The silica particles preferably have small primary particles, and the specific surface area is preferably 40 m 2 / g or more, particularly 140 m 2 / g or more.
Further, as magnesia or magnesia hydrate, those having small crystallites and not progressing carbonation with time are preferable. For example, a magnesia powder having a specific surface area of 2 m 2 / g or more, preferably 20 m 2 / g or more, particularly preferably 50 m 2 / g or more is used.
例えば、シリカとしては、非晶質の含水シリカが好適であり、ゲル法及び沈降法の何れかで製造されたものであってよい。また、係るシリカの粒子は、一次粒子が小さいことが好ましく、比表面積が40m2/g以上、特に140m2/g以上であることが好ましい。
また、マグネシア又はマグネシア水和物としては、結晶子の小さく且つ経時による炭酸化が進んでいないものが好ましい。例えば、比表面積が2m2/g以上、好ましくは20m2/g以上、特に好ましくは50m2/g以上のマグネシア粉末が使用される。 Further, as the silica (A) and magnesia or magnesia hydrate (B), it is preferable to select those that facilitate the above-mentioned fine particle formation.
For example, as the silica, amorphous water-containing silica is suitable, and it may be produced by either gel method or precipitation method. The silica particles preferably have small primary particles, and the specific surface area is preferably 40 m 2 / g or more, particularly 140 m 2 / g or more.
Further, as magnesia or magnesia hydrate, those having small crystallites and not progressing carbonation with time are preferable. For example, a magnesia powder having a specific surface area of 2 m 2 / g or more, preferably 20 m 2 / g or more, particularly preferably 50 m 2 / g or more is used.
上記の水性スラリーの調製に際して、(A)シリカ及び(B)マグネシア又はマグネシア水和物の使用量は、それぞれ、前述した質量比Rが所定の範囲となるように設定する。
In the preparation of the above aqueous slurry, the amount of (A) silica and (B) magnesia or magnesia hydrate used is set so that the aforementioned mass ratio R falls within a predetermined range.
一体複合化の度合いは、吸着剤中のシリカ成分とマグネシア成分の質量比Rによって異なる。例えば、質量比が2付近、好ましくは1.3~3.0であることが、シリカ成分とマグネシア成分とが一体複合化するのに好適である。従って、後述する実施例に示されているように、一体複合化の度合いが非常に高く、流水中における重金属、特に鉛に対する除去性能が高いシリカマグネシア複合焼成粒子を得ることができる。
The degree of integration is different depending on the mass ratio R of the silica component and the magnesia component in the adsorbent. For example, a mass ratio of about 2 and preferably 1.3 to 3.0 is suitable for integrally combining a silica component and a magnesia component. Therefore, as shown in the examples described later, it is possible to obtain silica magnesia composite fired particles having a very high degree of integration and high removal performance against heavy metals, particularly lead, in running water.
水性スラリーの調製において、各原料(A)、(B)や水の投入順序等に制限はないが、凝集やゲル化現象(増粘)が起こると、前述した微細粒子化や一体複合化の進行が妨げられる虞がある。このため、水性スラリーの固形分濃度は低い方が好ましい。一方で、生産性や経済性の見地からは固形分濃度は高い方がよい。従って、固形分濃度は3~15質量%、特に8~13質量%であることが好ましい。
In the preparation of the aqueous slurry, there is no restriction on the raw materials (A), (B), the order of water, etc., but when the aggregation or gelation phenomenon (thickening) occurs, the above-mentioned fine particle formation or integral composite Progress may be hindered. For this reason, the one where the solid content concentration of an aqueous slurry is low is preferable. On the other hand, it is better that the solid content concentration is high from the viewpoint of productivity and economy. Accordingly, the solid content concentration is preferably 3 to 15% by mass, particularly 8 to 13% by mass.
また、上記の均質混合による水性スラリーの調製および引き続いて行われる熟成は、攪拌翼を備えた攪拌槽中で攪拌下に行うのが一般的であるが、湿式ボールミルやコロイドミルによる粉砕又は分散下で行うこともできる。
また、このような均質混合および熟成は、粒子同士の一体複合化を短時間で終了させるために加熱下で行うことが好ましいが、加熱温度が高いとゲル化が生じ、複合粒子が不均質となりやすい。従って、この加熱温度は、通常、100℃以下で行い、50~97℃で行うことが好ましく、50~79℃で行うことが特に好ましい。また、例えば、0.5時間以上、特に1~24時間、より好ましくは3~10時間程度かけて均質混合および熟成を行うことにより、シリカ粒子とマグネシア粒子が一体複合化した粒状物を含む水性スラリーが得られる。 In addition, the preparation of the aqueous slurry by the above homogeneous mixing and the subsequent aging are generally carried out with stirring in a stirring vessel equipped with a stirring blade, but are carried out under pulverization or dispersion with a wet ball mill or a colloid mill. Can also be done.
In addition, such homogeneous mixing and aging is preferably performed under heating in order to complete integration of particles in a short time. However, when the heating temperature is high, gelation occurs and the composite particles become inhomogeneous. Cheap. Therefore, this heating temperature is usually 100 ° C. or less, preferably 50 to 97 ° C., particularly preferably 50 to 79 ° C. Further, for example, an aqueous solution containing a granular material in which silica particles and magnesia particles are integrally combined by performing homogeneous mixing and aging for 0.5 hours or more, particularly 1 to 24 hours, more preferably about 3 to 10 hours. A slurry is obtained.
また、このような均質混合および熟成は、粒子同士の一体複合化を短時間で終了させるために加熱下で行うことが好ましいが、加熱温度が高いとゲル化が生じ、複合粒子が不均質となりやすい。従って、この加熱温度は、通常、100℃以下で行い、50~97℃で行うことが好ましく、50~79℃で行うことが特に好ましい。また、例えば、0.5時間以上、特に1~24時間、より好ましくは3~10時間程度かけて均質混合および熟成を行うことにより、シリカ粒子とマグネシア粒子が一体複合化した粒状物を含む水性スラリーが得られる。 In addition, the preparation of the aqueous slurry by the above homogeneous mixing and the subsequent aging are generally carried out with stirring in a stirring vessel equipped with a stirring blade, but are carried out under pulverization or dispersion with a wet ball mill or a colloid mill. Can also be done.
In addition, such homogeneous mixing and aging is preferably performed under heating in order to complete integration of particles in a short time. However, when the heating temperature is high, gelation occurs and the composite particles become inhomogeneous. Cheap. Therefore, this heating temperature is usually 100 ° C. or less, preferably 50 to 97 ° C., particularly preferably 50 to 79 ° C. Further, for example, an aqueous solution containing a granular material in which silica particles and magnesia particles are integrally combined by performing homogeneous mixing and aging for 0.5 hours or more, particularly 1 to 24 hours, more preferably about 3 to 10 hours. A slurry is obtained.
熟成後の水分除去は、スプレー乾燥機やスラリー乾燥機等を用いての蒸発乾燥により行うことができる。また、ろ過や遠心分離等の手段によりある程度の脱水を行った後に、箱形乾燥機、バンド乾燥機、流動層乾燥機等を用いて乾燥を行ってもよい。乾燥は、110~200℃の範囲の温度で行うことが好ましい。このとき、(B)マグネシア水和物の脱水が起こり、水和水が一部乃至は全部除去される。
Water removal after aging can be performed by evaporation drying using a spray dryer or a slurry dryer. Moreover, after performing a certain amount of dehydration by means such as filtration or centrifugation, drying may be performed using a box dryer, a band dryer, a fluidized bed dryer or the like. Drying is preferably performed at a temperature in the range of 110 to 200 ° C. At this time, (B) magnesia hydrate is dehydrated, and part or all of the hydrated water is removed.
上記のようにして、例えば脱水により、少なくとも一部のシリカ粒子およびマグネシア粒子が緊密に一体複合化した水分含有率10質量%以下のシリカマグネシア複合粒子が、顆粒状、粉状、ケーキ状又は団塊状で得られる。これらは、必要により、粉砕及び分級、又は成形を行った後に、焼成炉中で焼成を行うことにより、シリカ粒子とマグネシア粒子とが一体複合化した複合焼成粒子が得られる。
As described above, silica magnesia composite particles having a water content of 10% by mass or less, in which at least a part of silica particles and magnesia particles are intimately integrated by dehydration, for example, are granular, powdery, cake-like or nodules. Obtained in the form. If necessary, these are pulverized, classified, or molded, and then fired in a firing furnace to obtain composite fired particles in which silica particles and magnesia particles are integrally combined.
上記の粉砕は、それ自体公知の乾式粉砕法により行うことができる。例えばアトマイザーの如き衝撃式粉砕機や、乾式ボールミル、ローラーミル、ジェットミルなどを用いて行うことができる。
また、上記分級は、通常の乾式分級機を用い、重力分級、遠心分級、慣性分級等によって行われる。
このような粉砕及び分級によって、例えば5μm未満の微細粒子含有率が20体積%以下の粉末の形で、焼成による加熱処理が行われていないシリカマグネシア複合粒子が得られる。 The above pulverization can be performed by a known dry pulverization method. For example, an impact pulverizer such as an atomizer, a dry ball mill, a roller mill, or a jet mill can be used.
The classification is performed by gravity classification, centrifugal classification, inertia classification, or the like using an ordinary dry classifier.
By such pulverization and classification, silica magnesia composite particles that are not subjected to heat treatment by firing, for example, in the form of a powder having a fine particle content of less than 5 μm of 20% by volume or less are obtained.
また、上記分級は、通常の乾式分級機を用い、重力分級、遠心分級、慣性分級等によって行われる。
このような粉砕及び分級によって、例えば5μm未満の微細粒子含有率が20体積%以下の粉末の形で、焼成による加熱処理が行われていないシリカマグネシア複合粒子が得られる。 The above pulverization can be performed by a known dry pulverization method. For example, an impact pulverizer such as an atomizer, a dry ball mill, a roller mill, or a jet mill can be used.
The classification is performed by gravity classification, centrifugal classification, inertia classification, or the like using an ordinary dry classifier.
By such pulverization and classification, silica magnesia composite particles that are not subjected to heat treatment by firing, for example, in the form of a powder having a fine particle content of less than 5 μm of 20% by volume or less are obtained.
また、上記成形は、転動造粒、流動層造粒、攪拌造粒、解砕造粒、圧縮造粒、押出造粒等、任意の方法で行うことができる。一般的には、粒子があまり硬くならず、且つ容易に粉化しない程度の強度を有するように成形することが好ましい。
このような成形により、例えば、直径が5μm~5mmである球状、長径が5μm~5mmである楕円球状、又は径が0.5mm以上で、且つ軸長が50mm以下である円柱形状の未焼成シリカマグネシア複合粒子が得られる。 Moreover, the said shaping | molding can be performed by arbitrary methods, such as rolling granulation, fluidized bed granulation, stirring granulation, crushing granulation, compression granulation, extrusion granulation. In general, it is preferable to form the particles so that the particles do not become too hard and do not easily powder.
By such molding, for example, a spherical unfired silica having a spherical shape having a diameter of 5 μm to 5 mm, an elliptical spherical shape having a major axis of 5 μm to 5 mm, or a cylinder having a diameter of 0.5 mm or more and an axial length of 50 mm or less. Magnesia composite particles are obtained.
このような成形により、例えば、直径が5μm~5mmである球状、長径が5μm~5mmである楕円球状、又は径が0.5mm以上で、且つ軸長が50mm以下である円柱形状の未焼成シリカマグネシア複合粒子が得られる。 Moreover, the said shaping | molding can be performed by arbitrary methods, such as rolling granulation, fluidized bed granulation, stirring granulation, crushing granulation, compression granulation, extrusion granulation. In general, it is preferable to form the particles so that the particles do not become too hard and do not easily powder.
By such molding, for example, a spherical unfired silica having a spherical shape having a diameter of 5 μm to 5 mm, an elliptical spherical shape having a major axis of 5 μm to 5 mm, or a cylinder having a diameter of 0.5 mm or more and an axial length of 50 mm or less. Magnesia composite particles are obtained.
焼成による加熱処理が行われていないシリカマグネシア複合粒子としては、例えば水澤化学工業株式会社より、「ミズカライフ」の商品名で市販されている。本発明においては、例えば、後述する実施例に示されているように、水澤化学工業株式会社製「ミズカライフ」を焼成することにより、シリカマグネシア複合焼成粒子を得ることができる。
Examples of silica magnesia composite particles that have not been subjected to heat treatment by firing are commercially available from Mizusawa Chemical Co., Ltd. under the trade name “Mizuka Life”. In the present invention, for example, silica magnesia composite fired particles can be obtained by firing “Mizuka Life” manufactured by Mizusawa Chemical Industry Co., Ltd. as shown in the examples described later.
本発明においては、シリカマグネシア複合焼成粒子を重金属吸着剤として使用するためには、上記の焼成を300~830℃、好ましくは400~800℃、更に好ましくは400~750℃、特に好ましくは550~750℃の温度で行うことが重要である。このような温度での焼成により、前述した細孔分布と圧縮強度とを有するシリカマグネシア複合焼成粒子が得られる。即ち、係る焼成により、おそらく未焼成粒子の内側に存在するSiOH基の部分的な脱水縮合が生じて細孔径の変動が生じ、この結果として、重金属(特に鉛)の吸着に寄与する細孔直径3.5~10.0nmの細孔容積が前述した範囲に増大するものと思われる。また、焼成により粒子の収縮が生じる結果、圧縮強度が前述した範囲に高められる。
In the present invention, in order to use the silica magnesia composite calcined particles as a heavy metal adsorbent, the above calcining is performed at 300 to 830 ° C., preferably 400 to 800 ° C., more preferably 400 to 750 ° C., particularly preferably 550 to 550 ° C. It is important to carry out at a temperature of 750 ° C. By firing at such a temperature, silica magnesia composite fired particles having the above-described pore distribution and compressive strength can be obtained. That is, such firing probably causes partial dehydration condensation of SiOH groups present inside the unfired particles, resulting in fluctuations in pore diameter, resulting in pore diameter contributing to adsorption of heavy metals (particularly lead). It seems that the pore volume of 3.5-10.0 nm increases to the above-mentioned range. Further, as a result of the shrinkage of the particles due to firing, the compressive strength is increased to the above-described range.
焼成温度が上記範囲より低い焼成粒子では、細孔直径3.5~10.0nmでの細孔容積が前述の範囲よりも低い。その結果、得られる焼成粒子は、本発明のような鉛に対する吸着性能を発現せず、圧縮強度が低く、崩壊し易い。尚、単に乾燥により水分を除去したに過ぎない未焼成粒子についても、同様である。
焼成温度が上記範囲よりも高い場合には、粒子の収縮の程度が大きいため、圧縮強度はより高く、粒子崩壊が抑制される。他方、細孔の圧壊により細孔容積、特に細孔直径3.5~10.0nmでの細孔容積が減少する結果、飽和吸着量が低下したり、破過寿命が短くなるなど、吸着性能の低下が生じる。 For the calcined particles having a calcining temperature lower than the above range, the pore volume at a pore diameter of 3.5 to 10.0 nm is lower than the aforementioned range. As a result, the fired particles obtained do not exhibit the adsorption performance for lead as in the present invention, have a low compressive strength, and are easily collapsed. The same applies to the unsintered particles that are simply removed by drying.
When the firing temperature is higher than the above range, the degree of particle shrinkage is large, so that the compressive strength is higher and particle collapse is suppressed. On the other hand, as a result of crushing the pores, the pore volume, especially the pore volume with a pore diameter of 3.5-10.0 nm, is reduced, resulting in a decrease in saturated adsorption amount and shortened breakthrough life. Decrease.
焼成温度が上記範囲よりも高い場合には、粒子の収縮の程度が大きいため、圧縮強度はより高く、粒子崩壊が抑制される。他方、細孔の圧壊により細孔容積、特に細孔直径3.5~10.0nmでの細孔容積が減少する結果、飽和吸着量が低下したり、破過寿命が短くなるなど、吸着性能の低下が生じる。 For the calcined particles having a calcining temperature lower than the above range, the pore volume at a pore diameter of 3.5 to 10.0 nm is lower than the aforementioned range. As a result, the fired particles obtained do not exhibit the adsorption performance for lead as in the present invention, have a low compressive strength, and are easily collapsed. The same applies to the unsintered particles that are simply removed by drying.
When the firing temperature is higher than the above range, the degree of particle shrinkage is large, so that the compressive strength is higher and particle collapse is suppressed. On the other hand, as a result of crushing the pores, the pore volume, especially the pore volume with a pore diameter of 3.5-10.0 nm, is reduced, resulting in a decrease in saturated adsorption amount and shortened breakthrough life. Decrease.
本発明において、上記のような焼成は、細孔直径3.5~10.0nmでの細孔容積が前述した範囲内となるように行われる。例えば0.5~5時間、好適には2~4時間、上記温度での焼成を行えばよい。
In the present invention, the firing as described above is performed so that the pore volume at a pore diameter of 3.5 to 10.0 nm falls within the above-described range. For example, the baking may be performed at the above temperature for 0.5 to 5 hours, preferably 2 to 4 hours.
このようにして得られる複合焼成粒子(すなわち、本発明の重金属吸着剤)は、顆粒状、粉状、ケーキ状又は団塊状で得られ、適宜の大きさの粒子に造粒して、重金属吸着剤として使用される。
造粒手段としては、スプレー造粒、転動造粒等、公知の手段により行うことができる。粒子に大きな負荷が加わると、細孔分布が前述した範囲外となることがあるため、できるだけ負荷のかからない手段、例えば、スプレー造粒が特に好適である。 The composite calcined particles thus obtained (that is, the heavy metal adsorbent of the present invention) are obtained in the form of granules, powders, cakes or nodules, and are granulated into particles of an appropriate size to adsorb heavy metals. Used as an agent.
As granulation means, it can carry out by publicly known means, such as spray granulation and rolling granulation. When a large load is applied to the particles, the pore distribution may be out of the above-mentioned range, and thus means that do not apply the load as much as possible, for example, spray granulation is particularly suitable.
造粒手段としては、スプレー造粒、転動造粒等、公知の手段により行うことができる。粒子に大きな負荷が加わると、細孔分布が前述した範囲外となることがあるため、できるだけ負荷のかからない手段、例えば、スプレー造粒が特に好適である。 The composite calcined particles thus obtained (that is, the heavy metal adsorbent of the present invention) are obtained in the form of granules, powders, cakes or nodules, and are granulated into particles of an appropriate size to adsorb heavy metals. Used as an agent.
As granulation means, it can carry out by publicly known means, such as spray granulation and rolling granulation. When a large load is applied to the particles, the pore distribution may be out of the above-mentioned range, and thus means that do not apply the load as much as possible, for example, spray granulation is particularly suitable.
本発明においては、シリカマグネシア複合焼成粒子は、シリカ成分とマグネシア成分が互いに遊離しておらず、緊密に一体複合化しているため、通常、その懸濁液のpHは6.0~10.0の範囲にある。
In the present invention, the silica magnesia composite calcined particles have a silica component and a magnesia component that are not separated from each other and are closely integrated, so that the pH of the suspension is usually 6.0 to 10.0. It is in the range.
本発明においては、シリカマグネシア複合焼成粒子は、重金属を安定に吸着し得るという点で、窒素吸着法で測定したBET比表面積は、100m2/g以上、更に400m2/g以上、特に500m2/g以上であることが好適である。
In the present invention, the BET specific surface area measured by the nitrogen adsorption method is 100 m 2 / g or more, more preferably 400 m 2 / g or more, particularly 500 m 2 in that the silica magnesia composite fired particles can stably adsorb heavy metals. / G or more is preferred.
本発明の重金属吸着剤は、鉛、マンガン、クロム、ニッケル、バナジウム、銅、鉄等の重金属、特に鉛に対しての吸着性能に優れている。さらに、アルミニウムを含有しないため、アルミニウム溶出の問題がない。従って、特に水浄化材として好適に使用される。
The heavy metal adsorbent of the present invention is excellent in adsorption performance for heavy metals such as lead, manganese, chromium, nickel, vanadium, copper and iron, particularly lead. Furthermore, since aluminum is not contained, there is no problem of aluminum elution. Therefore, it is suitably used as a water purification material.
また、粒子強度が高く、粒子の崩壊を生じにくいため、活性炭、及び/又は、他の吸着剤と混合して使用する場合にも、粒子崩壊による性能低下を生ぜず、安定して吸着性能が発揮される。従って、水浄化材として流水中に配置して使用する用途に好適である。特に各種の有機物やハロゲン化物に対する吸着性に優れた活性炭、及び/又は、その他の吸着剤と混合して使用することが最も好適である。
In addition, since particle strength is high and particle disintegration is unlikely to occur, even when used in admixture with activated carbon and / or other adsorbents, performance does not deteriorate due to particle disintegration, and adsorption performance is stable. Demonstrated. Therefore, it is suitable for the use which arrange | positions and uses in running water as a water purification material. In particular, it is most preferable to use a mixture with activated carbon and / or other adsorbents having excellent adsorptivity to various organic substances and halides.
このように、活性炭と混合して水浄化材として使用する場合、一般に、活性炭100質量部あたり、1~30質量部の量で、本発明の重金属吸着剤が使用される。特に、本発明の重金属吸着剤は安価であることから水浄化材として有効に使用することができ、本発明の重金属吸着剤又は係る重金属吸着剤と活性炭との組み合わせを使用した水浄化材は、浄水器、特に家庭用の浄水器のカートリッジ形式のフィルターとして好適である。
Thus, when mixed with activated carbon and used as a water purification material, the heavy metal adsorbent of the present invention is generally used in an amount of 1 to 30 parts by mass per 100 parts by mass of activated carbon. In particular, since the heavy metal adsorbent of the present invention is inexpensive, it can be used effectively as a water purification material, and the water purification material using the heavy metal adsorbent of the present invention or a combination of such heavy metal adsorbent and activated carbon, It is suitable as a cartridge type filter for a water purifier, particularly a household water purifier.
その他の吸着剤としては、特に制限はないが、例えば、チタノシリケート化合物、ケイ酸マグネシウムなどの各種ケイ酸塩;A型ゼオライト、X型ゼオライトなどの各種ゼオライト;セピオライト、アタパルジャイト、ドーソナイト、モンモリロナイト、ハイドロタルサイトなどの各種粘土;各種イオン交換樹脂;等が挙げられる。
Other adsorbents are not particularly limited, but include, for example, titanosilicate compounds, various silicates such as magnesium silicate; various zeolites such as A-type zeolite and X-type zeolite; sepiolite, attapulgite, dosonite, montmorillonite, Various clays such as hydrotalcite; various ion exchange resins;
本発明の重金属吸着剤は、既に述べた通り、食品添加物として認可されているシリカ及びマグネシアとが一体複合化したシリカマグネシア複合粒子からなり、食品精製の用途に有効に適用できる。例えば、繰返し使用により劣化し、銅や鉄などの重金属の含有量が増加した揚油から前記重金属を除去する目的で使用することができる。また、同様に重金属を多く含む魚貝類エキスや畜肉エキス等の濃縮調味液の原料や煮汁から重金属を除去することで、加熱濃縮時の褐変反応(メイラード反応)を抑制し、風味や栄養価の低下を防止する目的など、種々の目的で有効に使用される。また、食品以外の広く有用な液状物等から不純物としての重金属を吸着除去することで精製する目的にも有効に使用することができる。
As described above, the heavy metal adsorbent of the present invention is composed of silica magnesia composite particles in which silica and magnesia approved as food additives are integrally combined, and can be effectively applied to food refining applications. For example, it can be used for the purpose of removing the heavy metal from the oil pump which has deteriorated by repeated use and has increased the content of heavy metals such as copper and iron. Similarly, by removing heavy metals from raw materials and boiled juice of concentrated seasonings such as fish shellfish extract and meat extract that contain a lot of heavy metals, the browning reaction (Maillard reaction) during heating and concentration is suppressed, and flavor and nutritional value of It is effectively used for various purposes such as the purpose of preventing the decrease. It can also be used effectively for the purpose of purification by adsorption and removal of heavy metals as impurities from widely useful liquids other than food.
また、本発明の重金属吸着剤は、飽和吸着量が高く、重金属吸着後の溶出抑制に優れている。このため、焼却灰、下水汚泥、土壌などの重金属で汚染された被処理物に対して、重金属不溶化材として本発明の重金属吸着剤を使用することも有効である。
The heavy metal adsorbent of the present invention has a high saturated adsorption amount and is excellent in suppressing elution after heavy metal adsorption. For this reason, it is also effective to use the heavy metal adsorbent of the present invention as a heavy metal insolubilizing material for an object to be treated contaminated with heavy metals such as incineration ash, sewage sludge, and soil.
本発明の優れた効果を、次の実験例により説明する。
The excellent effect of the present invention will be explained by the following experimental example.
(1)細孔容積
Micromeritics社製AutoPore IV 9500を用いて水銀圧入法にて測定を行った。細孔直径が3.5~10.0nmでの細孔容積は20000~60000psiaの圧入量より、細孔直径が3.5~5000.0nmでの細孔容積は30~60000psiaの圧入量より求めた。 (1) Pore volume It measured by the mercury intrusion method using AutoPore IV 9500 by Micromeritics. The pore volume when the pore diameter is 3.5 to 10.0 nm is obtained from the indentation amount of 20000 to 60000 psia, and the pore volume when the pore diameter is 3.5 to 5000.0 nm is obtained from the indentation amount of 30 to 60000 psia. It was.
Micromeritics社製AutoPore IV 9500を用いて水銀圧入法にて測定を行った。細孔直径が3.5~10.0nmでの細孔容積は20000~60000psiaの圧入量より、細孔直径が3.5~5000.0nmでの細孔容積は30~60000psiaの圧入量より求めた。 (1) Pore volume It measured by the mercury intrusion method using AutoPore IV 9500 by Micromeritics. The pore volume when the pore diameter is 3.5 to 10.0 nm is obtained from the indentation amount of 20000 to 60000 psia, and the pore volume when the pore diameter is 3.5 to 5000.0 nm is obtained from the indentation amount of 30 to 60000 psia. It was.
(2)圧縮強度
(株)島津製作所製微小圧縮試験機MCT-510を用いて各重金属吸着剤20点の粒子の圧縮強度を測定し、中央値を重金属吸着剤の圧縮強度とした。 (2) Compressive strength The compressive strength of 20 particles of each heavy metal adsorbent was measured using a micro compression tester MCT-510 manufactured by Shimadzu Corporation, and the median value was defined as the compressive strength of the heavy metal adsorbent.
(株)島津製作所製微小圧縮試験機MCT-510を用いて各重金属吸着剤20点の粒子の圧縮強度を測定し、中央値を重金属吸着剤の圧縮強度とした。 (2) Compressive strength The compressive strength of 20 particles of each heavy metal adsorbent was measured using a micro compression tester MCT-510 manufactured by Shimadzu Corporation, and the median value was defined as the compressive strength of the heavy metal adsorbent.
(3)飽和吸着量
鉛濃度が2000ppmの試料水(硝酸鉛(II)水溶液)を調整した。この試料水1Lに重金属吸着剤2.5gを加え、硝酸溶液にてpHを4~5に調整した。得られた混合液を一晩撹拌し、重金属吸着剤をろ過により除去した。ろ液の鉛濃度を(株)日立ハイテクサイエンス製ZA3000を用いてフレーム原子吸光法により測定した。試験前後の鉛濃度から重金属の吸着量を算出し、飽和吸着量とした。 (3) Saturated adsorption amount Sample water (lead nitrate (II) aqueous solution) having a lead concentration of 2000 ppm was prepared. 2.5 g of a heavy metal adsorbent was added to 1 L of this sample water, and the pH was adjusted to 4-5 with a nitric acid solution. The resulting mixture was stirred overnight and the heavy metal adsorbent was removed by filtration. The lead concentration of the filtrate was measured by flame atomic absorption spectrometry using ZA3000 manufactured by Hitachi High-Tech Science Co., Ltd. The amount of heavy metal adsorption was calculated from the lead concentration before and after the test, and was used as the saturated adsorption amount.
鉛濃度が2000ppmの試料水(硝酸鉛(II)水溶液)を調整した。この試料水1Lに重金属吸着剤2.5gを加え、硝酸溶液にてpHを4~5に調整した。得られた混合液を一晩撹拌し、重金属吸着剤をろ過により除去した。ろ液の鉛濃度を(株)日立ハイテクサイエンス製ZA3000を用いてフレーム原子吸光法により測定した。試験前後の鉛濃度から重金属の吸着量を算出し、飽和吸着量とした。 (3) Saturated adsorption amount Sample water (lead nitrate (II) aqueous solution) having a lead concentration of 2000 ppm was prepared. 2.5 g of a heavy metal adsorbent was added to 1 L of this sample water, and the pH was adjusted to 4-5 with a nitric acid solution. The resulting mixture was stirred overnight and the heavy metal adsorbent was removed by filtration. The lead concentration of the filtrate was measured by flame atomic absorption spectrometry using ZA3000 manufactured by Hitachi High-Tech Science Co., Ltd. The amount of heavy metal adsorption was calculated from the lead concentration before and after the test, and was used as the saturated adsorption amount.
(4)破過寿命
重金属吸着剤3gと活性炭50gとを混合して水浄化材を作成し、浄水器に組み込んだ。JIS S-3201(家庭用浄水器試験方法-溶解性鉛ろ過能力試験)に基づいて、鉛濃度が0.05mg/Lの試料水(硝酸鉛(II)水溶液)を調整し、上記浄水器に通水した。試料水の流量は、3L/min(線速度LV=2.5cm/s)とした。ろ過水の鉛濃度が試料水の20%を超えるまでに要したろ過水量(L/g)を求め、破過寿命を評価した。 (4) Breakthrough life 3 g of heavy metal adsorbent and 50 g of activated carbon were mixed to prepare a water purification material and incorporated into a water purifier. Based on JIS S-3201 (Household water purifier test method-Dissolvable lead filtration ability test), sample water (lead nitrate (II) nitrate aqueous solution) with a lead concentration of 0.05 mg / L was prepared, and the above water purifier was I passed water. The flow rate of the sample water was 3 L / min (linear velocity LV = 2.5 cm / s). The amount of filtered water (L / g) required until the lead concentration of the filtered water exceeded 20% of the sample water was determined, and the breakthrough life was evaluated.
重金属吸着剤3gと活性炭50gとを混合して水浄化材を作成し、浄水器に組み込んだ。JIS S-3201(家庭用浄水器試験方法-溶解性鉛ろ過能力試験)に基づいて、鉛濃度が0.05mg/Lの試料水(硝酸鉛(II)水溶液)を調整し、上記浄水器に通水した。試料水の流量は、3L/min(線速度LV=2.5cm/s)とした。ろ過水の鉛濃度が試料水の20%を超えるまでに要したろ過水量(L/g)を求め、破過寿命を評価した。 (4) Breakthrough life 3 g of heavy metal adsorbent and 50 g of activated carbon were mixed to prepare a water purification material and incorporated into a water purifier. Based on JIS S-3201 (Household water purifier test method-Dissolvable lead filtration ability test), sample water (lead nitrate (II) nitrate aqueous solution) with a lead concentration of 0.05 mg / L was prepared, and the above water purifier was I passed water. The flow rate of the sample water was 3 L / min (linear velocity LV = 2.5 cm / s). The amount of filtered water (L / g) required until the lead concentration of the filtered water exceeded 20% of the sample water was determined, and the breakthrough life was evaluated.
(5)平均粒子径の保持率
Malvern社製の超音波分散機能付きレーザ回折散乱式粒度分布測定機マスターサイザー3000を用いて、超音波分散による水中崩壊性を評価した。測定前の分散(分散時間180秒)において、超音波強度0%(超音波分散無し)として測定したメジアン径Dnと、超音波強度100%として測定したメジアン径Dusから、平均粒子径の保持率(%)を下記式:
ΔD = Dus/Dn × 100
式中、
ΔD:平均粒子径の保持率
Dus:超音波分散後の体積平均粒子径
Dn:超音波分散前の体積平均粒子径
により算出した。 (5) Retention rate of average particle diameter The disintegration property in water by ultrasonic dispersion was evaluated using a laser diffraction scattering type particle size distribution measuring instrument master sizer 3000 with an ultrasonic dispersion function manufactured by Malvern. Retention rate of average particle diameter from the median diameter Dn measured as the ultrasonic intensity 0% (no ultrasonic dispersion) and the median diameter Dus measured as the ultrasonic intensity 100% in the dispersion before dispersion (dispersion time 180 seconds) (%) The following formula:
ΔD = Dus / Dn × 100
Where
ΔD: Retention rate of average particle diameter Dus: Volume average particle diameter after ultrasonic dispersion Dn: Calculated by volume average particle diameter before ultrasonic dispersion.
Malvern社製の超音波分散機能付きレーザ回折散乱式粒度分布測定機マスターサイザー3000を用いて、超音波分散による水中崩壊性を評価した。測定前の分散(分散時間180秒)において、超音波強度0%(超音波分散無し)として測定したメジアン径Dnと、超音波強度100%として測定したメジアン径Dusから、平均粒子径の保持率(%)を下記式:
ΔD = Dus/Dn × 100
式中、
ΔD:平均粒子径の保持率
Dus:超音波分散後の体積平均粒子径
Dn:超音波分散前の体積平均粒子径
により算出した。 (5) Retention rate of average particle diameter The disintegration property in water by ultrasonic dispersion was evaluated using a laser diffraction scattering type particle size distribution measuring instrument master sizer 3000 with an ultrasonic dispersion function manufactured by Malvern. Retention rate of average particle diameter from the median diameter Dn measured as the ultrasonic intensity 0% (no ultrasonic dispersion) and the median diameter Dus measured as the ultrasonic intensity 100% in the dispersion before dispersion (dispersion time 180 seconds) (%) The following formula:
ΔD = Dus / Dn × 100
Where
ΔD: Retention rate of average particle diameter Dus: Volume average particle diameter after ultrasonic dispersion Dn: Calculated by volume average particle diameter before ultrasonic dispersion.
(6)強熱減量
強熱減量(質量%)は、150℃で2時間乾燥した重金属吸着剤を1000℃で30分焼成後、放冷し、焼成前の質量と焼成により減少した質量とに基づいて求めた。 (6) Loss on ignition Loss on ignition (mass%) is obtained by calcining a heavy metal adsorbent dried at 150 ° C. for 2 hours at 1000 ° C. for 30 minutes and then allowing it to cool. Based on.
強熱減量(質量%)は、150℃で2時間乾燥した重金属吸着剤を1000℃で30分焼成後、放冷し、焼成前の質量と焼成により減少した質量とに基づいて求めた。 (6) Loss on ignition Loss on ignition (mass%) is obtained by calcining a heavy metal adsorbent dried at 150 ° C. for 2 hours at 1000 ° C. for 30 minutes and then allowing it to cool. Based on.
下記の実施例および比較例に示す重金属吸着剤について、物性および重金属吸着試験結果を表1に示す。
Table 1 shows the physical properties and heavy metal adsorption test results of the heavy metal adsorbents shown in the following Examples and Comparative Examples.
(比較例1)
水澤化学工業(株)製二酸化ケイ素 ミズカソーブC―1を重金属吸着剤として使用した。 (Comparative Example 1)
Mizusawa Chemical Industry Co., Ltd. silicon dioxide Mizukasorb C-1 was used as a heavy metal adsorbent.
水澤化学工業(株)製二酸化ケイ素 ミズカソーブC―1を重金属吸着剤として使用した。 (Comparative Example 1)
Mizusawa Chemical Industry Co., Ltd. silicon dioxide Mizukasorb C-1 was used as a heavy metal adsorbent.
(比較例2)
神島化学工業(株)製酸化マグネシウム スターマグUを重金属吸着剤として使用した。 (Comparative Example 2)
Magnesium oxide Starmag U manufactured by Kamishima Chemical Industry Co., Ltd. was used as a heavy metal adsorbent.
神島化学工業(株)製酸化マグネシウム スターマグUを重金属吸着剤として使用した。 (Comparative Example 2)
Magnesium oxide Starmag U manufactured by Kamishima Chemical Industry Co., Ltd. was used as a heavy metal adsorbent.
(比較例3)
水澤化学工業(株)製シリカマグネシア製剤 ミズカライフF―1G(R=2.1)を重金属吸着剤として使用した。 (Comparative Example 3)
Mizuka Life F-1G (R = 2.1) was used as a heavy metal adsorbent.
水澤化学工業(株)製シリカマグネシア製剤 ミズカライフF―1G(R=2.1)を重金属吸着剤として使用した。 (Comparative Example 3)
Mizuka Life F-1G (R = 2.1) was used as a heavy metal adsorbent.
(実施例1)
比較例3で使用したシリカマグネシア製剤を550℃で4時間焼成し、重金属吸着剤として使用した。 Example 1
The silica magnesia preparation used in Comparative Example 3 was calcined at 550 ° C. for 4 hours and used as a heavy metal adsorbent.
比較例3で使用したシリカマグネシア製剤を550℃で4時間焼成し、重金属吸着剤として使用した。 Example 1
The silica magnesia preparation used in Comparative Example 3 was calcined at 550 ° C. for 4 hours and used as a heavy metal adsorbent.
(実施例2)
比較例3で使用したシリカマグネシア製剤を750℃で2時間焼成し、重金属吸着剤として使用した。 (Example 2)
The silica magnesia preparation used in Comparative Example 3 was calcined at 750 ° C. for 2 hours and used as a heavy metal adsorbent.
比較例3で使用したシリカマグネシア製剤を750℃で2時間焼成し、重金属吸着剤として使用した。 (Example 2)
The silica magnesia preparation used in Comparative Example 3 was calcined at 750 ° C. for 2 hours and used as a heavy metal adsorbent.
(比較例4)
比較例3で使用したシリカマグネシア製剤を900℃で2時間焼成し、重金属吸着剤として使用した。 (Comparative Example 4)
The silica magnesia preparation used in Comparative Example 3 was calcined at 900 ° C. for 2 hours and used as a heavy metal adsorbent.
比較例3で使用したシリカマグネシア製剤を900℃で2時間焼成し、重金属吸着剤として使用した。 (Comparative Example 4)
The silica magnesia preparation used in Comparative Example 3 was calcined at 900 ° C. for 2 hours and used as a heavy metal adsorbent.
Claims (7)
- シリカと酸化マグネシウムとが一体複合化したシリカマグネシア複合粒子からなり、水銀圧入法で測定した細孔直径3.5~10.0nmでの細孔容積が0.26~0.50mL/g、3.5~5000.0nmでの細孔容積が1.30~2.50mL/gの範囲にあり、且つ圧縮強度が1.5MPa以上であることを特徴とする重金属吸着剤。 It is composed of silica magnesia composite particles in which silica and magnesium oxide are integrally combined, and the pore volume at a pore diameter of 3.5 to 10.0 nm measured by mercury porosimetry is 0.26 to 0.50 mL / g, 3 A heavy metal adsorbent having a pore volume in the range of 1.30 to 2.50 mL / g and a compressive strength of 1.5 MPa or more at 0.5 to 5000.0 nm.
- シリカ成分とマグネシア成分とを、下記式:
R=Sm[質量%]/Mm[質量%]
式中、
Smは、SiO2換算でのシリカ成分の含有量であり、
Mmは、MgO換算でのマグネシア成分の含有量である、
で表される質量比Rが1.3~3.0となる範囲で含有している請求項1に記載の重金属吸着剤。 The silica component and the magnesia component are represented by the following formula:
R = Sm [mass%] / Mm [mass%]
Where
Sm is the content of the silica component in terms of SiO 2 ,
Mm is the content of the magnesia component in terms of MgO.
The heavy metal adsorbent according to claim 1, which is contained in a range where the mass ratio R represented by - 前記重金属吸着剤3gと活性炭50gとの混合物について、鉛濃度が0.05mg/Lの試料水を用い、ろ過流量3L/minにおいて、JIS S-3201家庭用浄水器試験方法に準拠して溶解性鉛ろ過能力試験を行った際、ろ過水の鉛濃度が試料水の20%を超えるまでのろ過水量が、前記重金属吸着剤1g当り250L以上である請求項1に記載の重金属吸着剤。 A mixture of 3 g of the heavy metal adsorbent and 50 g of activated carbon was dissolved in accordance with JIS S-3201 household water purifier test method at a filtration flow rate of 3 L / min using sample water with a lead concentration of 0.05 mg / L. 2. The heavy metal adsorbent according to claim 1, wherein when a lead filtration ability test is performed, the amount of filtrate water until the lead concentration of filtrate exceeds 20% of the sample water is 250 L or more per 1 g of the heavy metal adsorbent.
- 水浄化材に使用される請求項1に記載の重金属吸着剤。 The heavy metal adsorbent according to claim 1, which is used as a water purification material.
- 活性炭100質量部当り、請求項4に記載の重金属吸着剤を1~30質量部の量で含有することを特徴とする水浄化材。 A water purification material comprising the heavy metal adsorbent according to claim 4 in an amount of 1 to 30 parts by mass per 100 parts by mass of activated carbon.
- 請求項4に記載の重金属吸着剤を使用した水浄化材を組み込んだことを特徴とする浄水器。 A water purifier incorporating a water purification material using the heavy metal adsorbent according to claim 4.
- 請求項5に記載の水浄化材を組み込んだことを特徴とする浄水器。 A water purifier incorporating the water purification material according to claim 5.
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US20230191360A1 (en) * | 2019-03-27 | 2023-06-22 | W.R. Grace & Co.-Conn. | Silica adsorbent for removal of chlorophyll derivatives from triacylglycerol-based oils |
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