JP5968220B2 - 透過性多孔質複合材料 - Google Patents
透過性多孔質複合材料 Download PDFInfo
- Publication number
- JP5968220B2 JP5968220B2 JP2012523327A JP2012523327A JP5968220B2 JP 5968220 B2 JP5968220 B2 JP 5968220B2 JP 2012523327 A JP2012523327 A JP 2012523327A JP 2012523327 A JP2012523327 A JP 2012523327A JP 5968220 B2 JP5968220 B2 JP 5968220B2
- Authority
- JP
- Japan
- Prior art keywords
- iron
- composite material
- containing compound
- functional component
- iron particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000002131 composite material Substances 0.000 title claims description 132
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 336
- 239000002245 particle Substances 0.000 claims description 150
- 229910052742 iron Inorganic materials 0.000 claims description 129
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 82
- 150000001875 compounds Chemical class 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 38
- 239000012530 fluid Substances 0.000 claims description 35
- 239000000356 contaminant Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000011148 porous material Substances 0.000 claims description 23
- 239000010439 graphite Substances 0.000 claims description 20
- 229910002804 graphite Inorganic materials 0.000 claims description 20
- 238000007906 compression Methods 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 230000006835 compression Effects 0.000 claims description 17
- 238000011282 treatment Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 238000004513 sizing Methods 0.000 claims description 13
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052785 arsenic Inorganic materials 0.000 claims description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 229910021536 Zeolite Inorganic materials 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000010457 zeolite Substances 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 239000011575 calcium Substances 0.000 claims description 9
- 239000003651 drinking water Substances 0.000 claims description 9
- 235000020188 drinking water Nutrition 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 150000002823 nitrates Chemical class 0.000 claims description 8
- 238000006722 reduction reaction Methods 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000000571 coke Substances 0.000 claims description 7
- 150000002826 nitrites Chemical class 0.000 claims description 7
- 238000004438 BET method Methods 0.000 claims description 5
- -1 aluminum silicates Chemical class 0.000 claims description 5
- 229910052793 cadmium Inorganic materials 0.000 claims description 5
- 229910052753 mercury Inorganic materials 0.000 claims description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 4
- 229960004887 ferric hydroxide Drugs 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- 229910001385 heavy metal Inorganic materials 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 239000004571 lime Substances 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 20
- 239000004615 ingredient Substances 0.000 description 20
- 229910002651 NO3 Inorganic materials 0.000 description 18
- 239000000843 powder Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 239000011651 chromium Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 7
- 239000008187 granular material Substances 0.000 description 7
- 239000003673 groundwater Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- 231100000331 toxic Toxicity 0.000 description 7
- 230000002588 toxic effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 150000002484 inorganic compounds Chemical class 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000004663 powder metallurgy Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 238000005029 sieve analysis Methods 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 239000003657 drainage water Substances 0.000 description 1
- 238000009313 farming Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000003898 horticulture Methods 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000011369 optimal treatment Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000009702 powder compression Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002510 pyrogen Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000010334 sieve classification Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
Classifications
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- 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
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- 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
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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Description
なお、下記[1]から[17]は、いずれも本発明の一形態又は一態様であり得る。
[1]
汚染された流体の処理用の多孔質で透過性の複合材料であって、鉄粒子体並びに該鉄体の細孔及び空洞内に遊離の形態で分布し、固定されている炭素含有化合物、カルシウム含有化合物、ナトリウム含有化合物、鉄含有化合物、チタン含有化合物及びアルミニウム含有化合物からなる群から選択される0.01〜10重量%の少なくとも1つの機能成分を含み、該鉄粒子が10μmから10mmの間の粒径範囲を有することを特徴とする上記複合材料。
[2]
鉄粉末粒子が、20μmから5mmの間、好ましくは45μmから2mmの間、又は1μmから2mm、好ましくは1μmから1mm、好ましくは1μmから0.5mmの粒径範囲を有する、[1]に記載の複合材料。
[3]
前記炭素含有化合物が、黒鉛、活性炭及びコークスから選択され、前記鉄含有化合物が、硫酸第二鉄又は硫酸第一鉄、酸化第二鉄、及び水酸化第二鉄から選択され、前記チタン含有化合物がチタニアであり、前記ナトリウム含有化合物がソーダであり、前記カルシウム含有化合物が石灰であり、前記アルミニウム含有化合物が、アルミナ及びゼオライトなどのケイ酸アルミニウムから選択され、好ましくは黒鉛、活性炭、コークス、活性アルミナ及びゼオライトの群から選択される、[1]又は[2]に記載の複合材料。
[4]
前記少なくとも1つの機能成分が、20μm未満、好ましくは0.01〜20μm、好ましくは0.01〜10μm、0.02〜10μm、好ましくは0.02〜5μmの粒径を有する、[1]から[3]までのいずれか一項に記載の複合材料。
[5]
前記鉄粒子が、90%を超える鉄、好ましくは95%を超えるFeの含量を有し、且つ/又は前記鉄粉末が酸化鉄の化学的還元若しくは溶融鉄の微粉化により製造される、[1]から[4]までのいずれか一項に記載のもの。
[6]
BET法により測定したときに0.2m 2 /gを超える、好ましくは0.5m 2 /gを超える、最も好ましくは1m 2 /gを超える比表面積を有する、[1]から[5]までのいずれか一項に記載の複合材料。
[7]
前記少なくとも1つの機能成分の総量が、0.05〜8重量%の間、好ましくは0.1〜5重量%の間である、[1]から[6]までのいずれか一項に記載の複合材料。
[8]
前記鉄粒子が多孔質である、[1]から[7]までのいずれか一項に記載の複合材料。
[9]
径が45μmから850μmの間の粒径範囲を有し、該鉄粉末の少なくとも90重量%のFe含量を有する多孔質粒子のH2還元鉄粉末体を含み、該機能成分が黒鉛及び/又は活性炭から選択される、[1]から[8]までのいずれか一項に記載の複合材料。
[10]
汚染流体の処理のための多孔質で透過性の複合材料を製造する方法であって、
鉄体に相当する10μmから10mmの間の粒径範囲を有する鉄粒子を、0.01〜10重量%の量で存在する遊離形の炭素含有化合物、カルシウム含有化合物、ナトリウム含有化合物、鉄含有化合物、チタン含有化合物及びアルミニウム含有化合物からなる群から選択される少なくとも1つの機能成分と、該機能成分が機械的力により該鉄体中に分布し、固定されるまで、機械的に混合するステップ;
所望により、該少なくとも1つの機能成分の存在下若しくは不存在下で、不活性又は還元雰囲気中300℃から1200℃の間の温度で該鉄体を熱処理するステップ;
所望により、該少なくとも1つの機能成分の存在下若しくは不存在下で、該鉄体を7.0g/cm 3 以下の圧粉体密度を有する圧縮体に圧縮するステップ;及び/又は
所望により、該少なくとも1つの機能成分の存在下若しくは不存在下で、該鉄体をサイズ分けするステップ
を含み、該各ステップが任意の順序で実施することができる上記方法。
[11]
前記所望による圧縮を1000MPa未満、好ましくは600MPa未満、例えば、10〜1000MPa又は20〜600MPaの圧力で行う、[10]に記載の方法。
[12]
前記所望による熱処理を300〜1200℃、好ましくは400〜1200℃、300〜1000℃、400〜1000℃、300〜800℃、400〜800℃、300〜700℃、400〜700℃、300〜600℃、400〜600℃、300〜500℃又は400〜500℃で行う、[10]又は[11]に記載の方法。
[13]
前記鉄粒子が、粒径が45μmから850μmの間の粒径範囲を有し、少なくとも該鉄粉末の90重量%のFe含量を有するH2還元多孔質鉄粉末粒子であり、黒鉛及び/又は活性炭から選択される機能成分と機械的に混合され、該機能成分が該多孔質鉄粒子の細孔内に固定される、[10]から[12]までのいずれか一項に記載の方法。
[14]
流体中の汚染物質の含量を減少させるための、[1]から[9]に記載の複合材料の使用であって、該流体を該透過性複合材料中を通過させる、上記使用。
[15]
流体中の汚染物質の含量を減少させるための、[1]から[9]に記載の複合材料の使用であって、該流体が、水含有流体、好ましくは地下水、河川水、産業廃水、生活排水及び/又は表流水である、上記使用。
[16]
硝酸塩、亜硝酸塩、As、Pb、Hg、Cd、Se、Cr及び六価Crなどの重金属、他の有毒無機物質並びに有毒有機化合物又はそれらの組合せからなる群;好ましくは硝酸塩及び/又は亜硝酸塩、から選択される汚染物質の含量を減少させるための、[1]から[9]に記載の複合材料の使用。
[17]
前記流体が、飲料水として使用されるものである、[1]から[9]に記載の複合材料の使用。
天然に存在する水の試料として、Martinsberg(PA、USA)の地下水を用いた。化学的分析を表2に示す。試験は、図3に示すように試験材料を有するカラムに水をポンプで送り込むことによって実施した。空の床の接触時間EBCTは、25分であった。特定の時間間隔の後に流出水を汚染物質に関して分析した。0時間における汚染物質の含量は、非処理水(流入液)中の含量と等しい。
本発明による各種の透過性多孔質複合材料を硝酸塩減少能力に関して例1で述べた方法により試験した。用いる水は、同じ供給元から入手した。透過性多孔質複合材料は、各種機能成分を、酸化鉄の水素還元により得られ、10〜850μmの間の粒径、約250μmの平均粒径を有する多孔質鉄粉末と、該機能成分が透過性多孔質鉄の細孔内に十分に分布し、固定されるまで30分間混合することによって調製した。
この例では、地下水中の複数の汚染物質を減少させる本発明による透過性多孔質複合材料の能力を示す。ヒ素As、リン酸塩PO4 3−及び六価クロムCrVIを試験前に水に加え、スパイクしたこと以外は、試験を例1に従って実施した。
この例では、例1における材料3と比較した地下水中の複数の汚染物質を減少させる本発明による透過性多孔質複合材料、例2の複合材料2の能力を示す。
この例では、本発明による透過性多孔質複合材料における固定の程度をどのように測定するかを示す。
透過性多孔質複合材料の調製
この例では、調製の方法によって、各種の鉄粉末を透過性多孔質複合材料の製造にどのようにして用いることができるかを示す。用いた鉄粉末及び製造の方法は、透過性多孔質複合材料が20重量%未満の75μm未満、好ましくは10重量%未満の75μm未満のものを有するように選択するものとする。その理由は、より微細な多孔質鉄粒子が水流により容易に運び去られる可能性があるためである。機能成分として、2%のACを用いた。
(1)鉄粉末をTRS(抗折力)バーに圧縮した後、サイズ分けし、所望のサイズに緩やかに粉砕し、その後、機能成分と混合した−CSM
(2)鉄粉末をTRSバーに圧縮した後、窒素雰囲気中で熱処理し、続いてサイズ分けし、所望のサイズに粉砕し、その後、機能成分と混合した−CHSM
(3)機能成分を鉄粉末と混合し、混合物をTRSバーに圧縮した後、サイズ分けし、所望のサイズに緩やかに粉砕した−MCS
(4)機能成分を鉄粉末と混合し、混合物をTRSバーに圧縮した後、窒素雰囲気中で熱処理し、続いてサイズ分けし、所望のサイズに粉砕した−MCHS
この例では、透過性多孔質複合材料の最低限必要な多孔率をどのようにして測定したかを示す。透過性多孔質複合材料の製造に用いることに適する3種の鉄粉末及び本発明による2種の透過性多孔質複合材料を試験した。試験装置は、図3によるものと同様のものである。
Claims (16)
- 硝酸塩、亜硝酸塩、As、Pb、Hg、Cd、Se、Cr及び六価Crなどの重金属からなる群から選択される汚染物質によって汚染された流体の処理用の多孔質で透過性の複合材料であって、鉄粒子体と、該鉄粒子体の細孔及び空洞内に遊離の形態で分布し、固定されている炭素含有化合物、カルシウム含有化合物、ナトリウム含有化合物、鉄含有化合物、チタン含有化合物及びアルミニウム含有化合物からなる群から選択される0.01〜10重量%の少なくとも1つの機能成分と、を含み、該鉄粒子体を構成する鉄粒子が10μmから10mmの間の粒径範囲を有することを特徴とする上記複合材料。
- 前記鉄粒子が、20μmから5mmの間の粒径範囲を有する、請求項1に記載の複合材料。
- 前記炭素含有化合物が、黒鉛、活性炭及びコークスから選択され、前記鉄含有化合物が、硫酸第二鉄又は硫酸第一鉄、酸化第二鉄、及び水酸化第二鉄から選択され、前記チタン含有化合物がチタニアであり、前記ナトリウム含有化合物がソーダであり、前記カルシウム含有化合物が石灰であり、前記アルミニウム含有化合物が、アルミナ及びゼオライトなどのケイ酸アルミニウムから選択される、請求項1又は2に記載の複合材料。
- 前記少なくとも1つの機能成分が、20μm未満の粒径を有する、請求項1から3までのいずれか一項に記載の複合材料。
- 前記鉄粒子が、90%を超える鉄の含量を有し、且つ/又は前記鉄粒子が酸化鉄の化学的還元若しくは溶融鉄の微粉化により製造される、請求項1から4までのいずれか一項に記載のもの。
- BET法により測定したときに0.2m2/gを超える比表面積を有する、請求項1から5までのいずれか一項に記載の複合材料。
- 前記少なくとも1つの機能成分の総量が、0.05〜8重量%の間である、請求項1から6までのいずれか一項に記載の複合材料。
- 前記鉄粒子が多孔質である、請求項1から7までのいずれか一項に記載の複合材料。
- 径が45μmから850μmの間の粒径範囲を有し、少なくとも90重量%のFe含量を有するH 2 還元多孔質鉄粒子を含む鉄粒子体を含み、該機能成分が黒鉛及び/又は活性炭から選択される、請求項1から8までのいずれか一項に記載の複合材料。
- 硝酸塩、亜硝酸塩、As、Pb、Hg、Cd、Se、Cr及び六価Crなどの重金属からなる群から選択される汚染物質によって汚染された汚染流体の処理のための多孔質で透過性の複合材料を製造する方法であって、
鉄粒子体を構成するための10μmから10mmの間の粒径範囲を有する鉄粒子を、0.01〜10重量%の量で存在する炭素含有化合物、カルシウム含有化合物、ナトリウム含有化合物、鉄含有化合物、チタン含有化合物及びアルミニウム含有化合物からなる群から選択される少なくとも1つの機能成分と、該機能成分が機械的力により該鉄粒子体中に遊離の形態で分布し、固定されるまで、機械的に混合するステップ;
所望により、該少なくとも1つの機能成分の存在下若しくは不存在下で、不活性又は還元雰囲気中300℃から1200℃の間の温度で該鉄粒子体を熱処理するステップ;
所望により、該少なくとも1つの機能成分の存在下若しくは不存在下で、該鉄粒子体を7.0g/cm3以下の圧粉体密度を有する圧縮体に圧縮するステップ;及び/又は
所望により、該少なくとも1つの機能成分の存在下若しくは不存在下で、該鉄粒子体をサイズ分けするステップ
を含み、該各ステップが任意の順序で実施することができる上記方法。 - 前記所望による圧縮を1000MPa未満の圧力で行う、請求項10に記載の方法。
- 前記所望による熱処理を400〜1200℃で行う、請求項10又は11に記載の方法。
- 前記鉄粒子が、粒径が45μmから850μmの間の粒径範囲を有し、少なくとも該鉄粒子の90重量%のFe含量を有するH 2 還元多孔質鉄粒子であり、黒鉛及び/又は活性炭から選択される機能成分と機械的に混合され、該機能成分が該H 2 還元多孔質鉄粒子の細孔内に固定される、請求項10から12までのいずれか一項に記載の方法。
- 流体中の汚染物質の含量を減少させるための、請求項1から9に記載の複合材料の使用であって、該流体を該透過性複合材料中を通過させる、上記使用。
- 流体中の汚染物質の含量を減少させるための、請求項1から9に記載の複合材料の使用であって、該流体が、水含有流体である、上記使用。
- 前記流体が、飲料水として使用されるものである、請求項1から9に記載の複合材料の使用。
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