US20020053547A1 - Contact and adsorbent granules - Google Patents
Contact and adsorbent granules Download PDFInfo
- Publication number
- US20020053547A1 US20020053547A1 US09/962,887 US96288701A US2002053547A1 US 20020053547 A1 US20020053547 A1 US 20020053547A1 US 96288701 A US96288701 A US 96288701A US 2002053547 A1 US2002053547 A1 US 2002053547A1
- Authority
- US
- United States
- Prior art keywords
- iron
- water
- suspension
- adsorbent
- aqueous
- 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.)
- Abandoned
Links
- 239000003463 adsorbent Substances 0.000 title claims abstract description 37
- 239000008187 granular material Substances 0.000 title abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 41
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims abstract description 26
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical class [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 claims abstract description 25
- 235000014413 iron hydroxide Nutrition 0.000 claims abstract description 25
- 235000013980 iron oxide Nutrition 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008188 pellet Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 claims abstract description 10
- 239000012530 fluid Substances 0.000 claims abstract description 6
- 238000007493 shaping process Methods 0.000 claims abstract description 5
- MSNWSDPPULHLDL-UHFFFAOYSA-K ferric hydroxide Chemical compound [OH-].[OH-].[OH-].[Fe+3] MSNWSDPPULHLDL-UHFFFAOYSA-K 0.000 claims abstract description 3
- 239000011159 matrix material Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 55
- 239000000725 suspension Substances 0.000 claims description 23
- 239000000049 pigment Substances 0.000 claims description 20
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 229910001385 heavy metal Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 claims description 5
- 239000011343 solid material Substances 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007900 aqueous suspension Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 239000011669 selenium Substances 0.000 claims description 4
- 229910052714 tellurium Inorganic materials 0.000 claims description 4
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- -1 cyano compound Chemical class 0.000 claims description 3
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical class [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 claims description 3
- 150000001495 arsenic compounds Chemical class 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 claims 1
- 230000002745 absorbent Effects 0.000 claims 1
- 150000003841 chloride salts Chemical class 0.000 claims 1
- 150000004673 fluoride salts Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 238000001179 sorption measurement Methods 0.000 description 27
- 239000000463 material Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- 239000000047 product Substances 0.000 description 17
- 229910002588 FeOOH Inorganic materials 0.000 description 16
- 239000011230 binding agent Substances 0.000 description 16
- 239000002245 particle Substances 0.000 description 16
- 238000005299 abrasion Methods 0.000 description 14
- 239000000126 substance Substances 0.000 description 13
- 229910052785 arsenic Inorganic materials 0.000 description 12
- 239000000356 contaminant Substances 0.000 description 12
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical class [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 11
- 229910006540 α-FeOOH Inorganic materials 0.000 description 11
- 239000002609 medium Substances 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- HAYXDMNJJFVXCI-UHFFFAOYSA-N arsenic(5+) Chemical compound [As+5] HAYXDMNJJFVXCI-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 239000012266 salt solution Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003651 drinking water Substances 0.000 description 7
- 235000020188 drinking water Nutrition 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- 229910003328 NaAsO2 Inorganic materials 0.000 description 6
- 238000007792 addition Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- PTLRDCMBXHILCL-UHFFFAOYSA-M sodium arsenite Chemical compound [Na+].[O-][As]=O PTLRDCMBXHILCL-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000004567 concrete Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000004093 cyano group Chemical class *C#N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 239000001034 iron oxide pigment Substances 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 238000012958 reprocessing Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000005202 decontamination Methods 0.000 description 2
- 230000003588 decontaminative effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000008239 natural water Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000012056 semi-solid material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Chemical class 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241001506556 Grammoptera haematites Species 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FQIOHYRHRMILMJ-UHFFFAOYSA-N [Fe+3].OOO Chemical class [Fe+3].OOO FQIOHYRHRMILMJ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- LULLIKNODDLMDQ-UHFFFAOYSA-N arsenic(3+) Chemical compound [As+3] LULLIKNODDLMDQ-UHFFFAOYSA-N 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical class OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- 229940093920 gynecological arsenic compound Drugs 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 235000010213 iron oxides and hydroxides Nutrition 0.000 description 1
- 239000004407 iron oxides and hydroxides Substances 0.000 description 1
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 239000002362 mulch Substances 0.000 description 1
- 239000010841 municipal wastewater Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000012256 powdered iron Substances 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012070 reactive reagent Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910003145 α-Fe2O3 Inorganic materials 0.000 description 1
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- 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
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- 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
- B01J20/06—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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- 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
- B01J20/28014—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 form
- B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0036—Mixed oxides or hydroxides containing one alkaline earth metal, magnesium or lead
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0045—Mixed oxides or hydroxides containing aluminium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide (Fe2O3)
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/50—Agglomerated particles
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the present invention relates to particles, pellets or granules based on iron oxides and/or iron oxyhydroxides having a large specific surface area (50 to over 200 m 2 /g according to BET), processes for their production and their conversion to pellet form with high mechanical resistance, and their use as a contact and/or adsorbent/catalyst for the catalysis of chemical reactions, for the removal of impurities from liquids and/or for gas purification.
- Adsorbents/catalysts containing iron oxides and hydroxides can advantageously be used e.g. in the area of water purification or gas purification.
- this agent is used in horizontal- or vertical-flow filters or adsorber columns or added to the water to be treated in order to remove dissolved, suspended or emulsified organic or inorganic phosphorus, arsenic, antimony, sulfur, selenium, tellurium, beryllium, cyano and heavy metal compounds from, for example, drinking water, process water, industrial and municipal waste water, mineral, holy and medicinal water as well as river, garden pond and agricultural water. It can also be used in so-called reactive walls to separate the cited contaminants from ground water and seepage water aquifers from contaminated sites (waste disposal sites).
- the agent is used in adsorbers for binding undesirable components such as hydrogen sulfide, mercaptans and hydrogen cyanide, as well as other phosphorus, arsenic, antimony, sulfur, selenium, tellurium, cyano and heavy metal compounds in waste gases.
- Gases such as HF, HCI, H 2 S, SO x , NO x can also be adsorbed.
- DE-A 3 120 891 describes a process in which a filtration is performed using activated alumina with a grain size of 1 to 3 mm for the separation principally of phosphates from surface water.
- DE-A 3 800 873 describes an adsorbent based on porous materials such as e.g. hydrophobed chalk with a fine to medium grain size to remove contaminants from water.
- DE-A 3 703 169 discloses a process for the production of a granulated filter medium to treat natural water.
- the adsorbent is produced by granulating an aqueous suspension of kaolin with addition of powdered dolomite in a fluidised bed. The granules are then baked at 900° to 950° C.
- a process for the production and use of highly reactive reagents for waste gas and waste water purification is known from DE-A 40 34 417. Mixtures consisting of Ca(OH) 2 with additions of clays, stone dust, entrained dust and fly ashes, made porous and having a surface area of approx. 200 m 2 /g, are described here.
- DE-A 4 214 487 describes a process and a reactor for the removal of impurities from water.
- the medium flows horizontally through a funnel-shaped reactor, in which finely divided iron hydroxide in flocculent form is used as a sorption agent for water impurities.
- the disadvantage of this process lies in the use of the iron hydroxide in flocculent form, which means that because there is little difference in density between water and iron hydroxide, a reactor of this type can be operated at only very low flow rates and there is a risk of the sorption agent, which is possibly already loaded with contaminants, being discharged from the reactor along with the water.
- JP-A 55 132 633 describes granulated red mud, a by-product of aluminium production, as an adsorbent for arsenic. This consists of Fe 2 O 3 , Al 2 O 3 and SiO 2 . No mention is made of the stability of the granules or of the granulation process.
- a further disadvantage of this adsorbent is the lack of consistency in the composition of the product, its unreliable availability and the possible contamination of the drinking water with aluminium. Since aluminium is suspected of encouraging the development of Alzheimer's disease, contamination with this substance in particular is to be avoided.
- DE-A 19 826 186 describes a process for the production of an adsorbent containing iron hydroxide.
- An aqueous polymer dispersion is incorporated into iron hydroxide in water-dispersible form. This mixture is then either dried until it reaches a solid state and the solid material then comminuted mechanically to the desired shape and/or size or the mixture is shaped, optionally after a preliminary drying stage, and a final drying stage then performed, during which a solid state is achieved.
- a material is obtained in which the iron hydroxide is firmly embedded in the polymer and which is said to display a high binding capacity for the contaminants conventionally contained in waste waters or waste gases.
- the disadvantage of this process lies in the use of organic binders, which further contaminate the water to be treated due to leaching and/or abrasion of organic substances. Furthermore, the stability of the adsorbent composite is not guaranteed in extended use. Bacteria and other microorganisms can also serve as a nutrient medium for an organic binder, presenting a risk that microorganisms may populate the contact and thereby contaminate the medium.
- DE-A 4 320 003 describes a process for the removal of dissolved arsenic from ground water with the aid of colloidal or granulated iron hydroxide. Where fine, suspended iron(III) hydroxide products are used, it is recommended here that the iron hydroxide suspension be placed in fixed-bed filters filled with granular material or other supports having a high external or internal porosity. This process likewise has the disadvantage that, relative to the adsorbent “substrate+iron hydroxide”, only low specific loading capacities are achievable. Furthermore, there is only a weak bond between substrate and iron hydroxide, which means that there is a risk of iron hydroxide or iron arsenate being discharged during subsequent treatment with arsenic-containing water.
- This publication also cites the use of granulated iron hydroxide as an adsorption material for a fixed-bed reactor.
- the granulated iron hydroxide is produced by freeze conditioning (freeze drying) of iron hydroxide obtained by neutralisation of acid iron(III) salt solutions at temperatures of below minus 5° C.
- This production process is extremely energy-intensive and leads to heavily salt-contaminated waste waters.
- this production process only very small granules with low mechanical resistance are obtained.
- this means that the size spectrum is significantly reduced by mechanical abrasion of the particles during operation, which in turn results in finely dispersed particles of contaminated or uncontaminated adsorption agent being discharged from the reactor.
- a further disadvantage of these granules lies in the fact that the adsorption capacity in respect of arsenic compounds is reduced considerably if the granules lose water, by being stored dry for extended periods for example.
- Adsorbent/binder systems obtained by removing a sufficiently large amount of water from a mixture of (a) a crosslinkable binder consisting of colloidal metal or non-metal oxides, (b) oxidic adsorbents such as metal oxides and (c) an acid such that components (a) and (b) crosslink to form an adsorbent/binder system, are known from U.S. Pat. No. 5,948,726. According to the embodiments, colloidal alumina or aluminium oxide is used as binder.
- compositions lie in the need to use acid in their production (column 9, line 4) and in the fact that they are not pure but heterogeneous substances, which is undesirable both for the production, regeneration, removal and permanent disposal of such adsorbents, e.g. on a waste disposal site.
- scope of disclosure of this publication is also intended to include adsorbents that are suitable for the adsorption of arsenic; specific examples are not provided, however. Aluminium oxide is known to be significantly inferior to iron oxides in regard to force of adsorption for arsenic.
- Continuous adsorbers which are commonly grouped together in parallel for operation, are preferably used for water treatment.
- such adsorbers are filled with activated carbon.
- the available adsorbers are then operated in parallel to prevent the flow rate from rising above the maximum permitted by the particular arrangement.
- individual adsorbers are taken out of operation and can be serviced, for example, whereby the adsorption material is subjected to special loads, as described in greater detail below.
- the abrasion should be below 20% by weight, more preferably below 15% by weight, 10% by weight or most preferably below 5% by weight according to the method described in the examples of the present invention.
- An object underlying the present invention was therefore to provide a particle like a contact or an adsorbent/catalyst based on iron-oxygen compounds in pellet form, exhibiting high mechanical resistance in conjunction with a good binding capacity for contaminants contained in liquids and gases without the need to use organic binders or inorganic foreign binders to achieve adequate mechanical resistance, and plants operated with such media.
- This complex object is achieved by the contacts or adsorbents/catalysts according to the invention, their preparation, their use and units filled therewith.
- the invention relates to a unit suitable for the through-flow of a fluid medium at least partially filled with an adsorbent/catalyst in pellet form consisting essentially of iron oxide and/or iron oxyhydroxide embedded in an iron hydroxide matrix.
- the material in question consists essentially of iron oxide and/or oxyhydroxide firmly embedded in Fe(OH) 3 polymer, which—as experiments have shown—has a high binding capacity for the contaminants conventionally contained in waste water or waste gases and exhibits an already adequate mechanical and hydraulic resistance without addition of organic binders or inorganic foreign substances.
- this material is free from foreign binders, it has the further advantage in comparison to adsorbents from the prior art that, after stripping or removal of the adsorbed contaminants where necessary, it can be disposed of completely or supplied to other applications, for instance after grinding it can be used for colouring concrete and other building materials and for conventional pigment applications in plastics, paints and varnishes or for colouring other substrates such as bark mulch or shredded wood.
- adsorbents of this type an aqueous suspension of iron oxyhydroxide and/or iron oxide and iron hydroxide is first prepared, which is either dried until it is solid and the solid material then optionally comminuted mechanically to the desired shape and/or size, or alternatively the dispersion undergoes mechanical shaping, optionally in the semisolid state after predrying, and is then (further) dried until it reaches a solid state.
- the invention therefore also concerns a process for the production of an iron oxide/iron hydroxide-containing adsorbent/catalyst in pellet form.
- the material according to the invention can be obtained by mixing diverse phases of iron oxides and/or iron oxyhydroxides, including Fe(OH) 2 , in pure form or in any mixture in solid, semisolid or suspended form by the addition of Fe(OH) 3 in suspension or in gelatinous form with variable water content, and then dehydrating this mixture completely or with retention of a certain water content, for example by filtration or evaporation, and then mechanically comminuting the solid or semisolid material to the desired shape and/or size, or subjecting the dispersion to mechanical shaping, optionally in the semisolid state after predrying, followed by (additional) drying until a solid state is achieved.
- the Fe(OH) 3 can also be produced in situ from Fe(III) salt solutions and neutralisation or from iron(II) salt solutions by oxidation and neutralisation.
- the residual alkali from the production process for the suspended pigment is preferably reacted with an equivalent amount of Fe(III) salt for this purpose.
- the iron hydroxide Fe(OH) 3 is preferably aqueous to pasty in its original state, whereby the paste can exhibit almost any water content, generally between 10 and 90 wt. %, preferably between 40 and 70 wt. %.
- Freshly prepared iron hydroxide Fe(OH) 3 obtained by precipitation from iron(III) salt solutions or from iron(II) salt solutions by oxidation and neutralisation, can also be used, however.
- Dehydration by evaporation is preferably used if the suspensions to be dehydrated are largely salt-free and/or if lower demands are made of the mechanical strength of the resultant end products in operation.
- Dehydration can alternatively be performed by filtration.
- the filtration performance of the suspensions can be improved by the use of conventional filtration-improving measures, such as are described for example in Solid-Liquid Filtration and Separation Technology, A. Rushton, A. S. Ward, R. G. Holdich, 2nd edition 2000, Wiley-VCH, Weinheim, and in Handbuch der Industriellen Fest/Flüssig-Filtration, H. Gasper, D. ⁇ chsle, E. Pongratz, 2nd edition 2000, Wiley-VCH Weinheim. Coagulants can thus be added to the suspensions, for example.
- the suspensions to be dehydrated can also contain iron carbonates.
- the products according to the invention can undergo drying in air, and/or in vacuo, and/or in a drying oven and/or on belt dryers or in spray dryers at temperatures in the range from 5° to 300° C.
- the material can also be freeze dried.
- the products according to the invention preferably have a residual water content of less than 20 wt. %.
- the material is preferably comminuted by grinding to grain sizes in the range between 0.5 and 20 mm.
- the semisolid material is preferably shaped mechanically in a granulation or pelletising plant or in an extruder, whereby shaped bodies whose size is in the range from 0.5 to 20 mm in diameter or length can be obtained.
- pellets or granules obtained in this way have a high binding capacity for contaminants contained in water, liquids or gases and they additionally have an adequately high resistance to flowing media in terms of mechanical or hydraulic stressing.
- the iron oxyhydroxides or iron oxides treated with Fe(OH) 3 solidify into very hard agglomerates, which without the addition of binders have a high mechanical abrasion resistance and high hydraulic resistance to contact with flowing water, and which have a high binding capacity for the contaminants and trace constituents contained in the water.
- Iron oxyhydroxide pigments e.g. goethite
- iron oxide pigments e.g. haematite, magnetite
- iron carbonates are suitable for use according to the invention.
- the production of iron oxide pigments is prior art, they are obtained by precipitation and oxidation or Penniman reactions from iron(II) salt solutions and iron hydroxide by precipitation from iron(III) salt solutions.
- Such pigments can contain structures based on ⁇ , ⁇ , ⁇ , ⁇ , ⁇ ′, ⁇ phases and/or Fe(OH) 2 and mixed and intermediate phases thereof.
- Yellow iron oxyhydroxides can be calcined to red iron oxides.
- the product displays BET surface areas of 50 to 500 m 2 /g, preferably 80 to 200 m 2 g.
- the primary particle size was determined by measurement from scanning electron micrographs, e.g. at a magnification of 60000:1 (instrument: XL30 ESEM FEG, Philips). If the primary particles are needle-shaped, as in the ⁇ -FeOOH phase for example, the needle width can be given as a measurement for the particle size. Needle widths of up to 100 nm, but mainly between 4 and 50 nm, are observed in the case of nanoparticle ⁇ -FeOOH particles. ⁇ -FeOOH primary particles conventionally have a length:width ratio of 5:1 to 50:1, typically of 5:1 to 20:1. The length:width ratio of the needle shapes can be varied, however, by doping or by special reaction processes. If the primary particles are isometric, as in the ⁇ -Fe 2 O 3 , ⁇ -Fe 2 O 3 , Fe 3 O 4 phases for example, the particle diameters can quite easily also be below 20 nm.
- Yellow iron oxyhydroxide pigments are generally synthesised by precipitating iron(II) hydroxides or carbonates from corresponding iron(II) salt solutions such as e.g. FeSO 4 , FeCl 2 in pure form or as pickling solutions in the acid or alkaline pH range, followed by oxidation to iron(III) oxyhydroxides (see inter alia G. Buxbaum, Industrial Inorganic Pigments, VCH Weinheim, 2nd edition, 1998, p. 231ff). Oxidation of the divalent to the trivalent iron is preferably performed with air, whereby intensive aeration is advantageous. Oxidation with H 2 O 2 also leads to iron oxyhydroxides.
- iron(II) salt solutions such as e.g. FeSO 4 , FeCl 2 in pure form or as pickling solutions in the acid or alkaline pH range
- Oxidation of the divalent to the trivalent iron is preferably performed with air, whereby intensive aeration is advantageous. Oxidation
- NaOH is preferably used as alkaline precipitant.
- Other precipitants such as KOH, Na 2 CO 3 , K 2 CO 3 , CaO, Ca(OH) 2 , CaCO 3 , NH 3 , NH 4 OH, MgO and/or MgCO 3 , can also be used, however.
- nanoparticle ⁇ , ⁇ , ⁇ , ⁇ phases and mixed phases of iron oxyhydroxides displaying a large specific surface area can be prepared, such that the nanoparticles agglomerate in the dry state and possess a high resistance to mechanical and fluid-mechanical abrasion in comminuted form.
- the precipitations e.g. of yellow ⁇ -FeOOH as described in patents U.S. Pat. No. 2,558,303 and U.S. Pat. No.
- 2,558,304 are performed in the alkaline pH range with alkali carbonates as precipitants, and modifiers such as SiO 2 , zinc, aluminium or magnesium salts, hydroxycarbonic acids, phosphates and metaphosphates are generally added. Products produced in this way are described in U.S. Pat. No. 2,558,302. Such nucleus modifiers do not inhibit the subsequent reprocessing, recycling or any other use of the adsorbents according to the invention. In the case of precipitation processes in an aqueous medium, it is known that precipitations in an alkaline environment lead to less solidly agglomerated powders than those in an acid environment.
- nucleus modifiers One of the advantages of nucleus modifiers, however, is that an adequate fine-particle character can be obtained even at elevated reaction temperatures.
- the products described, the process for their production and their use represent an improvement over the prior art.
- the granules according to the invention can be subjected to considerably higher stresses and therefore display a much greater abrasion resistance to mechanical and hydraulic stressing. They can be used directly as such.
- adsorber plants for water purification for example, there is no need even for comminution or rough grinding of the crude dry substance initially obtained from filter cakes or extruders, since the coarse pellets break down independently on contact with water. This results in a random particle-size distribution, but no particles of such a size that they are discharged from the adsorber to any significant extent by the flowing medium.
- Granulation of a semi-wet paste has proven effective as another method of producing granules.
- pellets or strands are formed from a semi-wet paste, e.g. using a simple perforated metal sheet, a roll press or an extruder, and either dried immediately or additionally shaped into a spherical or granular form by means of a spheroniser.
- the still wet spherules or granules can subsequently be dried to any moisture content whatsoever.
- a residual moisture content of ⁇ 50% is recommended to prevent the granules from agglomerating.
- a spherical shape of this type can be advantageous for use in fixed-bed adsorbers due to the improved packing in the adsorber vessel that is obtained in comparison with rough-ground granules or pellets in strand form.
- the quantities of iron oxyhydroxides or iron oxides on the one hand and iron hydroxide on the other to be used according to the invention are determined by the requirements of the product according to the invention in terms of its mechanical stability and abrasion resistance. Although a higher content of (powdered) pigments will generally reduce the mechanical strength of the products according to the invention, filtration of the suspensions is possibly made easier. The person skilled in the art and practising in the particular field of application will be able to determine the optimum mixing ratio for the intended application by means of a few orienting experiments.
- the granules according to the invention are particularly preferably used in the cleaning of liquids, especially for the removal of heavy metals.
- a preferred application in this industrial field is the decontamination of water, particularly of drinking water. Particular attention has recently been paid to the removal of arsenic from drinking water.
- the granules according to the invention are extremely suitable for this purpose, since levels that not only meet but actually fall below even the lowest limiting values set by the US authority the EPA can be achieved using the granules according to the invention.
- the granules can be used in conventional adsorber units, such as are already used with a charge of activated carbon, for example, to remove other types of contaminants.
- Batchwise operation in cisterns or similar containers for example, optionally fitted with agitators, is also possible.
- use in continuous plants such as continuous-flow adsorbers is preferred.
- untreated water to be processed into drinking water conventionally also contains organic impurities such as algae and similar organisms
- the surface of adsorbents especially the outer surface of granular adsorbents, becomes coated during use with mostly slimy deposits, which impede or even prevent the inflow of water and hence the adsorption of constituents to be removed.
- adsorber units are periodically back-flushed with water, a process which is preferably performed at times of low water consumption (see above) on individual units that have been taken out of service.
- the adsorbent is whirled up and the associated mechanical stress to which the surface is subjected causes the undesirable coating to be removed and discharged against the direction of flow during active operation.
- the wash water is conventionally sent to a sewage treatment plant.
- the adsorbents according to the invention have proven to be particularly effective in this process, since their high strength enables them to be cleaned quickly without suffering any significant losses of adsorption material and without the back-flush water sent for waste treatment being rich in discharged adsorption material, which is possibly already highly contaminated with heavy metals.
- the material is comparatively easy to dispose of after use.
- the adsorbed arsenic can be removed by thermal or chemical means in special units, for example, resulting in an iron oxide pigment as a pure substance which can either be recycled for use in the same application or supplied for conventional pigment applications.
- the content of the adsorber can also be used without prior removal of the heavy metals, for example as a pigment for colouring durable construction materials such as concrete, since the heavy metals removed from the drinking water are permanently immobilised in this way and taken out of the hydrological cycle.
- the invention therefore also provides water treatment plants or waterworks in which units filled with the granules according to the invention are operated, and processes for the decontamination of water by means of such units, as well as such units themselves.
- the sample is baked for 1 h at 140° C. in a stream of dry nitrogen before measurement.
- the As, Sb, Cd, Cr, Hg or Pb contents of the contaminated iron oxyhydroxide or of the solutions are determined using mass spectrometry (ICP-MS) according to DIN 38406-29 (1999) or by optical emission spectroscopy (ICP-OES) according to EN-ISO 11885 (1998), with inductively coupled plasma as excitation agent in each case.
- ICP-MS mass spectrometry
- ICP-OES optical emission spectroscopy
- the mechanical and hydraulic abrasion resistance was assessed using the following method: 150 ml of demineralised water were added to 10 g of the granules to be tested, having particle sizes>0.1 mm, in a 500 ml Erlenmeyer flask, which was rotated on a LabShaker shaking machine (Kühner model from Braun) for a period of 30 minutes at 250 rpm. The >0.1 mm fraction was then isolated from the suspension using a screen, dried and weighed. The weight ratio between the amount weighed out and the amount weighed in determines the abrasion value in %.
- An X-ray diffractogram showed that the product consisted of b 100 % ⁇ -FeOOH.
- the needle widths were measured at between 15 and 35 nm, the needle lengths between 70 and 180 nm.
- the needles were extremely agglomerated.
- the BET specific surface area was 131 m 2 /g.
- the abrasion value after 30 minutes was only 7 wt. %.
- the suspension was filtered through a nutsch filter, rinsed with 1000 ml demineralised H 2 O and then dried for 15 h at 105° C. 47.6 g of the dried product was redispersed in 2300 ml 0.1 M FeCl 3 solution and 690 ml of an aqueous NaOH solution (1 N) were then quickly added.
- the suspension was filtered through a nutsch filter, rinsed with 2000 ml demineralised H 2 O and then dried for 15 h at 105° C.
- the dried product was very hard, it was roughly ground and the screen fraction from 1 to 5 mm isolated.
- the adsorption rate for an aqueous NaAsO 2 solution with an original concentration of 23 ⁇ g/l As 3+ was 17 ⁇ g(As 3+ )/g(FeOOH).h after 30 minutes, corresponding to 84% adsorption.
- the batch was washed on a filter press until the residual filtrate conductivity was ⁇ 1000 ⁇ S/cm and the paste pushed through a perforated metal plate with hole diameters of 7 mm and formed into strands.
- the strands were dried on a belt dryer to a residual moisture of approx. 5%.
- the dry pellets were roughly ground to obtain a particle size of 2 mm.
- the material thus obtained had a BET specific surface area of 142 m 2 /g and consisted of 100% ⁇ -FeOOH.
- the needle widths were measured at between 15 and 50 nm, the needle lengths between 10 and 150 nm.
- the needles were extremely agglomerated.
- Adsorption performance The adsorption rate for NaAsO 2 with an original concentration of 2.7 mg/l (As 3+ ) was 2.1 mg(As 3+ )/g(FeOOH).h, for Na 2 HAsO 4 with an original concentration of 2.8 mg/l (As 5+ ) it was 2.0 mg(As 5+ )/g(FeOOH).h, for CdCl 2 (original concentration 2.7 mg (Cd 2+ )II) the adsorption was 1.1 mg (Cd 2+ )/g(FeOOH).h, for KSb(OH) 6 (original concentration 2.6 mg (Sb 5+ )/l) it was 1.9 mg (Sb 5+ )/g(FeOOH).h, for Sb 2 O 3 (original concentration 2.3 mg (Sb 3+ )/l) it was 2.0 mg (Sb 3+ )/g(FeOOH).h, for Na 2 CrO 4 (original concentration 2.6 mg (C
- the very hard material was then roughly ground to form granules having a particle size of between 0.2 and 2 mm.
- the BET specific surface area was 64 m 2 /g.
- the scanning electron micrograph e.g. at a magnification of 60000:1, shows that the ⁇ -FeOOH type needles are agglomerated or glued together by amorphous layers.
Abstract
The present invention relates to pellets or granules based on iron oxides and/or iron oxyhydroxides and iron(III) hydroxide, a unit suitable for the through-flow of a fluid medium at least partially filled with an adsorbent/catalyst in pellet form consisting essentially of iron oxide and/or iron oxyhydroxide embedded in an iron hydroxide matrix, processes for their production comprising filtering, drying and shaping steps and their processes of their use.
Description
- The present invention relates to particles, pellets or granules based on iron oxides and/or iron oxyhydroxides having a large specific surface area (50 to over 200 m2/g according to BET), processes for their production and their conversion to pellet form with high mechanical resistance, and their use as a contact and/or adsorbent/catalyst for the catalysis of chemical reactions, for the removal of impurities from liquids and/or for gas purification.
- Contact and adsorbent granules, including those based on iron oxides and/or iron oxyhydroxides, have already been described. They are predominantly used in continuous processes, whereby they are conventionally found in tower or column-type units through which the medium to be treated flows, and the chemical or physical reaction or adsorption processes take place at the outer and inner surface of the granules. Powdered materials cannot be used for this purpose because they compact in the direction of flow of the medium, thereby increasing the flow resistance until the unit becomes blocked. If a unit is cleaned by back-flushing (see below), large amounts of the powder are discharged and lost or cause an unacceptable contamination of the waste water.
- The flowing media also exert forces on the granules, however, which can lead to abrasion and/or movement through to violent agitation of the granules. Consequently the granules collide, leading to undesirable abrasion. This results in loss of contact or adsorbent material and contamination of the medium to be treated.
- Adsorbents/catalysts containing iron oxides and hydroxides can advantageously be used e.g. in the area of water purification or gas purification. In water purification this agent is used in horizontal- or vertical-flow filters or adsorber columns or added to the water to be treated in order to remove dissolved, suspended or emulsified organic or inorganic phosphorus, arsenic, antimony, sulfur, selenium, tellurium, beryllium, cyano and heavy metal compounds from, for example, drinking water, process water, industrial and municipal waste water, mineral, holy and medicinal water as well as river, garden pond and agricultural water. It can also be used in so-called reactive walls to separate the cited contaminants from ground water and seepage water aquifers from contaminated sites (waste disposal sites).
- In gas purification the agent is used in adsorbers for binding undesirable components such as hydrogen sulfide, mercaptans and hydrogen cyanide, as well as other phosphorus, arsenic, antimony, sulfur, selenium, tellurium, cyano and heavy metal compounds in waste gases. Gases such as HF, HCI, H2S, SOx, NOx can also be adsorbed.
- The removal of phosphorus, arsenic, antimony, selenium, tellurium, cyano and heavy metal compounds from waste oils and other contaminated organic solvents is also possible.
- Contact and adsorbent granules based on iron oxides and/or iron oxyhydroxides are also used for the catalysis of chemical reactions in the gas phase or in the liquid phase.
- Various methods of removing trace constituents and contaminants from aqueous systems with the aid of adsorbents are also known.
- For example, DE-A 3 120 891 describes a process in which a filtration is performed using activated alumina with a grain size of 1 to 3 mm for the separation principally of phosphates from surface water.
- DE-A 3 800 873 describes an adsorbent based on porous materials such as e.g. hydrophobed chalk with a fine to medium grain size to remove contaminants from water.
- DE-A 3 703 169 discloses a process for the production of a granulated filter medium to treat natural water. The adsorbent is produced by granulating an aqueous suspension of kaolin with addition of powdered dolomite in a fluidised bed. The granules are then baked at 900° to 950° C.
- A process for the production and use of highly reactive reagents for waste gas and waste water purification is known from DE-A 40 34 417. Mixtures consisting of Ca(OH)2 with additions of clays, stone dust, entrained dust and fly ashes, made porous and having a surface area of approx. 200 m2/g, are described here.
- The cited processes and the contacts used therein have the shared disadvantage that the component responsible in each case for the selective adsorption of constituents of the media to be cleaned, in other words the actual adsorbent, must be supplemented with large quantities of additives to enable it to be shaped into granules. This significantly reduces the binding capacity for the water contaminants to be removed. Moreover, subsequent reprocessing or reuse of the material is problematic since the foreign substances used as binders first have to be separated out.
- DE-A 4 214 487 describes a process and a reactor for the removal of impurities from water. The medium flows horizontally through a funnel-shaped reactor, in which finely divided iron hydroxide in flocculent form is used as a sorption agent for water impurities. The disadvantage of this process lies in the use of the iron hydroxide in flocculent form, which means that because there is little difference in density between water and iron hydroxide, a reactor of this type can be operated at only very low flow rates and there is a risk of the sorption agent, which is possibly already loaded with contaminants, being discharged from the reactor along with the water.
- JP-A 55 132 633 describes granulated red mud, a by-product of aluminium production, as an adsorbent for arsenic. This consists of Fe2O3, Al2O3 and SiO2. No mention is made of the stability of the granules or of the granulation process. A further disadvantage of this adsorbent is the lack of consistency in the composition of the product, its unreliable availability and the possible contamination of the drinking water with aluminium. Since aluminium is suspected of encouraging the development of Alzheimer's disease, contamination with this substance in particular is to be avoided.
- DE-A 19 826 186 describes a process for the production of an adsorbent containing iron hydroxide. An aqueous polymer dispersion is incorporated into iron hydroxide in water-dispersible form. This mixture is then either dried until it reaches a solid state and the solid material then comminuted mechanically to the desired shape and/or size or the mixture is shaped, optionally after a preliminary drying stage, and a final drying stage then performed, during which a solid state is achieved. In this way a material is obtained in which the iron hydroxide is firmly embedded in the polymer and which is said to display a high binding capacity for the contaminants conventionally contained in waste waters or waste gases.
- The disadvantage of this process lies in the use of organic binders, which further contaminate the water to be treated due to leaching and/or abrasion of organic substances. Furthermore, the stability of the adsorbent composite is not guaranteed in extended use. Bacteria and other microorganisms can also serve as a nutrient medium for an organic binder, presenting a risk that microorganisms may populate the contact and thereby contaminate the medium.
- The presence of foreign auxiliary substances, which are required for the manufacture of the adsorbents, during reprocessing, recycling or reuse of used adsorbents is disadvantageous in principle because the reuse of pure substances is less problematic than is the case with mixed substances. For example, polymeric binders are disadvantageous when iron oxide-based adsorption materials are reused as pigments for concrete coloration because these binders can inhibit dispersion of the pigment in liquid concrete.
- DE-A 4 320 003 describes a process for the removal of dissolved arsenic from ground water with the aid of colloidal or granulated iron hydroxide. Where fine, suspended iron(III) hydroxide products are used, it is recommended here that the iron hydroxide suspension be placed in fixed-bed filters filled with granular material or other supports having a high external or internal porosity. This process likewise has the disadvantage that, relative to the adsorbent “substrate+iron hydroxide”, only low specific loading capacities are achievable. Furthermore, there is only a weak bond between substrate and iron hydroxide, which means that there is a risk of iron hydroxide or iron arsenate being discharged during subsequent treatment with arsenic-containing water. This publication also cites the use of granulated iron hydroxide as an adsorption material for a fixed-bed reactor. The granulated iron hydroxide is produced by freeze conditioning (freeze drying) of iron hydroxide obtained by neutralisation of acid iron(III) salt solutions at temperatures of below minus 5° C. This production process is extremely energy-intensive and leads to heavily salt-contaminated waste waters. Moreover, as a result of this production process only very small granules with low mechanical resistance are obtained. When used in a fixed-bed reactor, this means that the size spectrum is significantly reduced by mechanical abrasion of the particles during operation, which in turn results in finely dispersed particles of contaminated or uncontaminated adsorption agent being discharged from the reactor. A further disadvantage of these granules lies in the fact that the adsorption capacity in respect of arsenic compounds is reduced considerably if the granules lose water, by being stored dry for extended periods for example.
- Adsorbent/binder systems obtained by removing a sufficiently large amount of water from a mixture of (a) a crosslinkable binder consisting of colloidal metal or non-metal oxides, (b) oxidic adsorbents such as metal oxides and (c) an acid such that components (a) and (b) crosslink to form an adsorbent/binder system, are known from U.S. Pat. No. 5,948,726. According to the embodiments, colloidal alumina or aluminium oxide is used as binder.
- The disadvantage of these compositions lies in the need to use acid in their production (column 9, line 4) and in the fact that they are not pure but heterogeneous substances, which is undesirable both for the production, regeneration, removal and permanent disposal of such adsorbents, e.g. on a waste disposal site. The scope of disclosure of this publication is also intended to include adsorbents that are suitable for the adsorption of arsenic; specific examples are not provided, however. Aluminium oxide is known to be significantly inferior to iron oxides in regard to force of adsorption for arsenic.
- Continuous adsorbers, which are commonly grouped together in parallel for operation, are preferably used for water treatment. To free drinking water from organic impurities, for example, such adsorbers are filled with activated carbon. At peak consumption times, the available adsorbers are then operated in parallel to prevent the flow rate from rising above the maximum permitted by the particular arrangement. At times of lower water consumption, individual adsorbers are taken out of operation and can be serviced, for example, whereby the adsorption material is subjected to special loads, as described in greater detail below.
- The use of granules, which can be produced by compacting e.g. powdered iron oxide using high linear forces, has also already been considered. Such granules have already been described as a means of homogeneously colouring liquid concrete. The use of high linear forces for compacting is extremely expensive and energy-intensive, and the stability of the compacted materials is inadequate for extended use in adsorbers. The use of such materials in adsorbers, for example, particularly continuous models, for water purification is therefore of only limited interest. During maintenance or cleaning of adsorber plants by back-flushing in particular (see below), such granules lose large amounts of substance due to the associated agitation. The abraded material renders the waste water from back-flushing extremely turbid. This is unacceptable for a number of reasons: firstly, adsorption material, which is heavily laden with impurities and therefore toxic after extended use, is lost. Secondly, the stream of waste water is laden with abraded material, which can sediment, damaging piping systems and ultimately subjecting the waste treatment plant to undesirable physical and toxicological stresses, to name but a few reasons. Preferably the abrasion should be below 20% by weight, more preferably below 15% by weight, 10% by weight or most preferably below 5% by weight according to the method described in the examples of the present invention.
- An object underlying the present invention was therefore to provide a particle like a contact or an adsorbent/catalyst based on iron-oxygen compounds in pellet form, exhibiting high mechanical resistance in conjunction with a good binding capacity for contaminants contained in liquids and gases without the need to use organic binders or inorganic foreign binders to achieve adequate mechanical resistance, and plants operated with such media. This complex object is achieved by the contacts or adsorbents/catalysts according to the invention, their preparation, their use and units filled therewith.
- The invention relates to a unit suitable for the through-flow of a fluid medium at least partially filled with an adsorbent/catalyst in pellet form consisting essentially of iron oxide and/or iron oxyhydroxide embedded in an iron hydroxide matrix.
- The material in question consists essentially of iron oxide and/or oxyhydroxide firmly embedded in Fe(OH)3 polymer, which—as experiments have shown—has a high binding capacity for the contaminants conventionally contained in waste water or waste gases and exhibits an already adequate mechanical and hydraulic resistance without addition of organic binders or inorganic foreign substances.
- Since this material is free from foreign binders, it has the further advantage in comparison to adsorbents from the prior art that, after stripping or removal of the adsorbed contaminants where necessary, it can be disposed of completely or supplied to other applications, for instance after grinding it can be used for colouring concrete and other building materials and for conventional pigment applications in plastics, paints and varnishes or for colouring other substrates such as bark mulch or shredded wood.
- To prepare adsorbents of this type, an aqueous suspension of iron oxyhydroxide and/or iron oxide and iron hydroxide is first prepared, which is either dried until it is solid and the solid material then optionally comminuted mechanically to the desired shape and/or size, or alternatively the dispersion undergoes mechanical shaping, optionally in the semisolid state after predrying, and is then (further) dried until it reaches a solid state.
- The products obtainable in this way can then be comminuted further, for example by rough grinding or grinding. However, since the products reduce in size autogenously on first coming into contact with water, for example when a freshly charged adsorber unit is first filled with water, this will generally be unnecessary.
- The invention therefore also concerns a process for the production of an iron oxide/iron hydroxide-containing adsorbent/catalyst in pellet form.
- The material according to the invention can be obtained by mixing diverse phases of iron oxides and/or iron oxyhydroxides, including Fe(OH)2, in pure form or in any mixture in solid, semisolid or suspended form by the addition of Fe(OH)3 in suspension or in gelatinous form with variable water content, and then dehydrating this mixture completely or with retention of a certain water content, for example by filtration or evaporation, and then mechanically comminuting the solid or semisolid material to the desired shape and/or size, or subjecting the dispersion to mechanical shaping, optionally in the semisolid state after predrying, followed by (additional) drying until a solid state is achieved. In this way the iron oxide and/or oxyhydroxide is firmly embedded in the Fe(OH)3 polymer. The Fe(OH)3 can also be produced in situ from Fe(III) salt solutions and neutralisation or from iron(II) salt solutions by oxidation and neutralisation. The residual alkali from the production process for the suspended pigment is preferably reacted with an equivalent amount of Fe(III) salt for this purpose.
- The iron hydroxide Fe(OH)3 is preferably aqueous to pasty in its original state, whereby the paste can exhibit almost any water content, generally between 10 and 90 wt. %, preferably between 40 and 70 wt. %. Freshly prepared iron hydroxide Fe(OH)3, obtained by precipitation from iron(III) salt solutions or from iron(II) salt solutions by oxidation and neutralisation, can also be used, however.
- Dehydration by evaporation is preferably used if the suspensions to be dehydrated are largely salt-free and/or if lower demands are made of the mechanical strength of the resultant end products in operation.
- Dehydration can alternatively be performed by filtration. The filtration performance of the suspensions can be improved by the use of conventional filtration-improving measures, such as are described for example in Solid-Liquid Filtration and Separation Technology, A. Rushton, A. S. Ward, R. G. Holdich, 2nd edition 2000, Wiley-VCH, Weinheim, and in Handbuch der Industriellen Fest/Flüssig-Filtration, H. Gasper, D. Öchsle, E. Pongratz, 2nd edition 2000, Wiley-VCH Weinheim. Coagulants can thus be added to the suspensions, for example.
- The suspensions to be dehydrated can also contain iron carbonates.
- The products according to the invention can undergo drying in air, and/or in vacuo, and/or in a drying oven and/or on belt dryers or in spray dryers at temperatures in the range from 5° to 300° C. The material can also be freeze dried.
- The products according to the invention preferably have a residual water content of less than 20 wt. %.
- The material is preferably comminuted by grinding to grain sizes in the range between 0.5 and 20 mm. The semisolid material is preferably shaped mechanically in a granulation or pelletising plant or in an extruder, whereby shaped bodies whose size is in the range from 0.5 to 20 mm in diameter or length can be obtained.
- It was found that the pellets or granules obtained in this way have a high binding capacity for contaminants contained in water, liquids or gases and they additionally have an adequately high resistance to flowing media in terms of mechanical or hydraulic stressing.
- It is particularly surprising that during drying, the iron oxyhydroxides or iron oxides treated with Fe(OH)3 solidify into very hard agglomerates, which without the addition of binders have a high mechanical abrasion resistance and high hydraulic resistance to contact with flowing water, and which have a high binding capacity for the contaminants and trace constituents contained in the water.
- Iron oxyhydroxide pigments (e.g. goethite) and iron oxide pigments (e.g. haematite, magnetite) and/or iron carbonates are suitable for use according to the invention. The production of iron oxide pigments is prior art, they are obtained by precipitation and oxidation or Penniman reactions from iron(II) salt solutions and iron hydroxide by precipitation from iron(III) salt solutions. Such pigments can contain structures based on α, β, γ, δ, δ′, ε phases and/or Fe(OH)2 and mixed and intermediate phases thereof. Yellow iron oxyhydroxides can be calcined to red iron oxides.
- The product displays BET surface areas of 50 to 500 m2/g, preferably 80 to 200 m2g.
- The primary particle size was determined by measurement from scanning electron micrographs, e.g. at a magnification of 60000:1 (instrument: XL30 ESEM FEG, Philips). If the primary particles are needle-shaped, as in the α-FeOOH phase for example, the needle width can be given as a measurement for the particle size. Needle widths of up to 100 nm, but mainly between 4 and 50 nm, are observed in the case of nanoparticle α-FeOOH particles. α-FeOOH primary particles conventionally have a length:width ratio of 5:1 to 50:1, typically of 5:1 to 20:1. The length:width ratio of the needle shapes can be varied, however, by doping or by special reaction processes. If the primary particles are isometric, as in the α-Fe2O3, γ-Fe2O3, Fe3O4 phases for example, the particle diameters can quite easily also be below 20 nm.
- By mixing Fe(OH)3 with pigments and/or nanoparticle iron oxides or iron (oxy)hydroxides, the presence of the cited pigment or nucleus particles in their known particle morphology, held or glued together by the amorphous Fe(OH)3 polymer, can be detected on the scanning electron micrographs.
- Yellow iron oxyhydroxide pigments are generally synthesised by precipitating iron(II) hydroxides or carbonates from corresponding iron(II) salt solutions such as e.g. FeSO4, FeCl2 in pure form or as pickling solutions in the acid or alkaline pH range, followed by oxidation to iron(III) oxyhydroxides (see inter alia G. Buxbaum, Industrial Inorganic Pigments, VCH Weinheim, 2nd edition, 1998, p. 231ff). Oxidation of the divalent to the trivalent iron is preferably performed with air, whereby intensive aeration is advantageous. Oxidation with H2O2 also leads to iron oxyhydroxides. NaOH is preferably used as alkaline precipitant. Other precipitants, such as KOH, Na2CO3, K2CO3, CaO, Ca(OH)2, CaCO3, NH3, NH4OH, MgO and/or MgCO3, can also be used, however.
- By choosing suitable precipitation and oxidation conditions, nanoparticle α, β, γ, δ phases and mixed phases of iron oxyhydroxides displaying a large specific surface area can be prepared, such that the nanoparticles agglomerate in the dry state and possess a high resistance to mechanical and fluid-mechanical abrasion in comminuted form. To steer the precipitated pigments in the direction of the extremely fine-particle character that is required, the precipitations, e.g. of yellow α-FeOOH as described in patents U.S. Pat. No. 2,558,303 and U.S. Pat. No. 2,558,304, are performed in the alkaline pH range with alkali carbonates as precipitants, and modifiers such as SiO2, zinc, aluminium or magnesium salts, hydroxycarbonic acids, phosphates and metaphosphates are generally added. Products produced in this way are described in U.S. Pat. No. 2,558,302. Such nucleus modifiers do not inhibit the subsequent reprocessing, recycling or any other use of the adsorbents according to the invention. In the case of precipitation processes in an aqueous medium, it is known that precipitations in an alkaline environment lead to less solidly agglomerated powders than those in an acid environment.
- One of the advantages of nucleus modifiers, however, is that an adequate fine-particle character can be obtained even at elevated reaction temperatures.
- The products described, the process for their production and their use represent an improvement over the prior art. In contrast to those of the prior art, the granules according to the invention can be subjected to considerably higher stresses and therefore display a much greater abrasion resistance to mechanical and hydraulic stressing. They can be used directly as such. When used in adsorber plants for water purification, for example, there is no need even for comminution or rough grinding of the crude dry substance initially obtained from filter cakes or extruders, since the coarse pellets break down independently on contact with water. This results in a random particle-size distribution, but no particles of such a size that they are discharged from the adsorber to any significant extent by the flowing medium.
- There is absolutely no need for a separate granulation process, such as would be necessary when using conventional iron oxyhydroxides in the form of (flowable) powders, either with the aid of foreign binders or using extremely high linear forces during compacting.
- Granulation of a semi-wet paste has proven effective as another method of producing granules. Here pellets or strands are formed from a semi-wet paste, e.g. using a simple perforated metal sheet, a roll press or an extruder, and either dried immediately or additionally shaped into a spherical or granular form by means of a spheroniser. The still wet spherules or granules can subsequently be dried to any moisture content whatsoever. A residual moisture content of <50% is recommended to prevent the granules from agglomerating. A spherical shape of this type can be advantageous for use in fixed-bed adsorbers due to the improved packing in the adsorber vessel that is obtained in comparison with rough-ground granules or pellets in strand form.
- The quantities of iron oxyhydroxides or iron oxides on the one hand and iron hydroxide on the other to be used according to the invention are determined by the requirements of the product according to the invention in terms of its mechanical stability and abrasion resistance. Although a higher content of (powdered) pigments will generally reduce the mechanical strength of the products according to the invention, filtration of the suspensions is possibly made easier. The person skilled in the art and practising in the particular field of application will be able to determine the optimum mixing ratio for the intended application by means of a few orienting experiments.
- The granules according to the invention are particularly preferably used in the cleaning of liquids, especially for the removal of heavy metals. A preferred application in this industrial field is the decontamination of water, particularly of drinking water. Particular attention has recently been paid to the removal of arsenic from drinking water. The granules according to the invention are extremely suitable for this purpose, since levels that not only meet but actually fall below even the lowest limiting values set by the US authority the EPA can be achieved using the granules according to the invention.
- To this end the granules can be used in conventional adsorber units, such as are already used with a charge of activated carbon, for example, to remove other types of contaminants. Batchwise operation, in cisterns or similar containers for example, optionally fitted with agitators, is also possible. However, use in continuous plants such as continuous-flow adsorbers is preferred.
- Since untreated water to be processed into drinking water conventionally also contains organic impurities such as algae and similar organisms, the surface of adsorbents, especially the outer surface of granular adsorbents, becomes coated during use with mostly slimy deposits, which impede or even prevent the inflow of water and hence the adsorption of constituents to be removed. For this reason adsorber units are periodically back-flushed with water, a process which is preferably performed at times of low water consumption (see above) on individual units that have been taken out of service. The adsorbent is whirled up and the associated mechanical stress to which the surface is subjected causes the undesirable coating to be removed and discharged against the direction of flow during active operation. The wash water is conventionally sent to a sewage treatment plant. The adsorbents according to the invention have proven to be particularly effective in this process, since their high strength enables them to be cleaned quickly without suffering any significant losses of adsorption material and without the back-flush water sent for waste treatment being rich in discharged adsorption material, which is possibly already highly contaminated with heavy metals.
- Since the granules according to the invention are free from foreign binders, the material is comparatively easy to dispose of after use. For instance, the adsorbed arsenic can be removed by thermal or chemical means in special units, for example, resulting in an iron oxide pigment as a pure substance which can either be recycled for use in the same application or supplied for conventional pigment applications. Depending on the application and legal regulations, the content of the adsorber can also be used without prior removal of the heavy metals, for example as a pigment for colouring durable construction materials such as concrete, since the heavy metals removed from the drinking water are permanently immobilised in this way and taken out of the hydrological cycle.
- The invention therefore also provides water treatment plants or waterworks in which units filled with the granules according to the invention are operated, and processes for the decontamination of water by means of such units, as well as such units themselves.
- The BET specific surface area of the products according to the invention is determined by the carrier gas process (He:N2=90:10) using the single-point method, according to DIN 66131 (1993). The sample is baked for 1 h at 140° C. in a stream of dry nitrogen before measurement.
- In order to measure the adsorption of arsenic(III) and arsenic(V), 3 liters of an aqueous solution of NaAsO2 or Na2HAsO4, each with the specified original concentration of approx. 2-3 mg/l arsenic, are treated with 3 g of the sample to be tested in a 5 liter PE flask for a specific period and the flask moved on rotating rollers. The adsorption rate of As ions on iron hydroxide over this specific period, e.g. one hour, is stated as mg(As3+/5+)/g(FeOOH).h, calculated from the balance of the As3+/5+ ions remaining in solution.
- The adsorption of Sb3+, Sb5+, Hg2+, Pb2+, Cr6+ or Cd2+ ions is measured in the same way, whereby the desired concentrations are established by dissolving appropriate amounts of Sb2O3, KSb(OH)6, PbCl2, NaCrO4 or CdCl2 in H2O and adjusting the pH value to 7-9.
- The As, Sb, Cd, Cr, Hg or Pb contents of the contaminated iron oxyhydroxide or of the solutions are determined using mass spectrometry (ICP-MS) according to DIN 38406-29 (1999) or by optical emission spectroscopy (ICP-OES) according to EN-ISO 11885 (1998), with inductively coupled plasma as excitation agent in each case.
- The mechanical and hydraulic abrasion resistance was assessed using the following method: 150 ml of demineralised water were added to 10 g of the granules to be tested, having particle sizes>0.1 mm, in a 500 ml Erlenmeyer flask, which was rotated on a LabShaker shaking machine (Kühner model from Braun) for a period of 30 minutes at 250 rpm. The >0.1 mm fraction was then isolated from the suspension using a screen, dried and weighed. The weight ratio between the amount weighed out and the amount weighed in determines the abrasion value in %.
- The invention is described in greater detail below by means of examples. The examples are intended to illustrate the process and do not constitute a limitation.
- 124 l of an aqueous NaOH solution (114 g/l) were measured out at 24° C. and 171 l of an aqueous solution of FeSO4 (100 g/l) quickly added with stirring, and oxidation was then performed with 10 l air per hour and per mol Fe. Immediately upon completion of oxidation, 56 l of an aqueous solution of Fe2(SO4)3 (100 g/l) were added and stirred for 30 minutes. The yellowish brown suspension thus obtained was processed in the same way as in example 2.
- An X-ray diffractogram showed that the product consisted of b100% α-FeOOH. Using a scanning electron micrograph e.g. at a magnification of 60000:1, the needle widths were measured at between 15 and 35 nm, the needle lengths between 70 and 180 nm. The needles were extremely agglomerated. The BET specific surface area was 131 m2/g. The abrasion value after 30 minutes was only 7 wt. %.
- The adsorption rate for an aqueous NaAsO2 solution with an original concentration of 2.3 mg/l (As3+) was 1.7 mg(As3+)/g(FeOOH).h, the adsorption for an Na2HAsO4 solution with an original concentration of 2.7 mg/l (As5+) was 1.2 mg(As5+)/g(FeOOH).h.
- 7.4 l of an aqueous solution of Fe2(SO4)3 (100 g/l) were added to 7.5 l of an aqueous solution of FeSO4 (150 g/l) and the mixture quickly treated with 2.9 l of an aqueous NaOH solution (200 g/l) at 34° C. with stirring. The reaction mixture was then pre-oxidised for 10 minutes with 290 l of air per hour and then precipitated further with 2.2 l of an aqueous NaOH solution (200 g/l) with stirring. The reaction mixture was then oxidised for a further 15 minutes with 290 l of air per hour. The yellowish brown suspension was filtered off at a nutsch filter and the deposit washed to obtain a residual filtrate conductivity of 1 mS/cm.
- An X-ray diffractogram showed that the product consisted of 100% α-FeOOH. Small particles as well as needles can be seen in the scanning electron micrograph, e.g. at a magnification of 60000:1. In the case of the small particles the needle widths were measured at between 15 and 35 nm, the needle lengths between 30 and 70 nm. In the case of the larger needles, needle widths of up to 50 nm and needle lengths of up to 350 nm were determined. The needles and particles were extremely agglomerated. The BET specific surface area was 177 m2/g. The abrasion value after 30 minutes was only 3 wt. %.
- The adsorption rate for an aqueous NaAsO2 solution with an original concentration of 2.3 mg/l (As3+) was 1.3 mg(As3+)/g(FeOOH).h, for an Na2HAsO4 solution with an original concentration of 2.7 mg/l (As5+) it was 0.7 mg(As5+)/g(FeOOH).h.
- 470 ml of an FeCl3 solution (0.1 N) were added to 45 g of a needle-shaped α-FeOOH pigment powder (Bayferrox® 930, Bayer AG, Leverkusen, Del.) and mixing performed for 5 minutes at 500 rpm. 141 ml of an aqueous NaOH solution (1 N) were then slowly added dropwise and the suspension stirred for 15 minutes.
- The suspension was filtered through a nutsch filter, rinsed with 1000 ml demineralised H2O and then dried for 15 h at 105° C. 47.6 g of the dried product was redispersed in 2300 ml 0.1 M FeCl3 solution and 690 ml of an aqueous NaOH solution (1 N) were then quickly added. The suspension was filtered through a nutsch filter, rinsed with 2000 ml demineralised H2O and then dried for 15 h at 105° C. The dried product was very hard, it was roughly ground and the screen fraction from 1 to 5 mm isolated.
- An X-ray diffractogram showed that the product consisted of 100% α-FeOOH. The BET specific surface area was 99 m2/g. When shaken with water in a beaker, the granules displayed a high abrasion resistance, indicated by the fact that the water was not coloured with pigment, as happens with untreated α-FeOOH pigment powder (Bayferrox® 930), for example.
- The adsorption rate for an aqueous NaAsO2 solution with an original concentration of 23 μg/l As3+, as can conventionally occur in natural water, for example, was 17 μg(As3+)/g(FeOOH).h after 30 minutes, corresponding to 84% adsorption.
- 4096 kg NaOH (as solution with approx. 300 g/l) were measured out and diluted with water to 40 m3. 4950 kg FeSO4 were dissolved with water to form 48.5 m3 solution, cooled to 15° C. and then pumped into the prepared NaOH over 1 h. The suspension was then oxidised with 1500 m3/h air in approx. 2 h. 14.4 m3 FeClSO4 solution (113.4 g/l) were added to approx. 87 m3 of this suspension with stirring, and stirred for a further 30 min. The batch was washed on a filter press until the residual filtrate conductivity was <1000 μS/cm and the paste pushed through a perforated metal plate with hole diameters of 7 mm and formed into strands. The strands were dried on a belt dryer to a residual moisture of approx. 5%. The dry pellets were roughly ground to obtain a particle size of 2 mm. The material thus obtained had a BET specific surface area of 142 m2/g and consisted of 100% α-FeOOH. Using a scanning electron micrograph e.g. at a magnification of 60000:1, the needle widths were measured at between 15 and 50 nm, the needle lengths between 10 and 150 nm. The needles were extremely agglomerated.
- Adsorption performance: The adsorption rate for NaAsO2 with an original concentration of 2.7 mg/l (As3+) was 2.1 mg(As3+)/g(FeOOH).h, for Na2HAsO4 with an original concentration of 2.8 mg/l (As5+) it was 2.0 mg(As5+)/g(FeOOH).h, for CdCl2 (original concentration 2.7 mg (Cd2+)II) the adsorption was 1.1 mg (Cd2+)/g(FeOOH).h, for KSb(OH)6 (original concentration 2.6 mg (Sb5+)/l) it was 1.9 mg (Sb5+)/g(FeOOH).h, for Sb2O3 (original concentration 2.3 mg (Sb3+)/l) it was 2.0 mg (Sb3+)/g(FeOOH).h, for Na2CrO4 (original concentration 2.6 mg (Cr6+)/l) it was 1.1 mg (Cr6+), for PbCl2 (original concentration 1.6 mg (Pb2+)/l) it was 1.57 mg (Pb2+)/g(FeOOH).h.
- 800 g of an aqueous solution of FeCl3 (100 g/l) were added to 525 g of a suspension of a needle-shaped a-FeOOH pigment powder (50 g/l FeOOH, Bayferrox® 920, Bayer AG, Leverkusen, Del.) and an iron hydroxide precipitated on the pigment by addition of 247 g of an aqueous NaOH solution (24%). The suspension was filtered through a nutsch filter, the filter cake rinsed to obtain a residual filtrate conductivity of <1 mS/cm and the filter cake then dried in a drying oven at 75° C. The very hard material was then roughly ground to form granules having a particle size of between 0.2 and 2 mm. The BET specific surface area was 64 m2/g. The scanning electron micrograph, e.g. at a magnification of 60000:1, shows that the α-FeOOH type needles are agglomerated or glued together by amorphous layers.
- The adsorption rate for an aqueous NaAsO2 solution with an original concentration of 2.9 mg/l (As3+) was 1.8 mg(As3+)/g(FeOOH).h, for an Na2HAsO4 solution with an original concentration of 2.8 mg/l (As5+) it was 1.6 mg(As5+)/g(FeOOH).h.
- Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Claims (16)
1. A unit suitable for the through-flow of a fluid medium at least partially filled with an adsorbent/catalyst in pellet form consisting essentially of iron oxide and/or iron oxyhydroxide embedded in an iron hydroxide matrix.
2. The unit of claim 1 wherein the medium is a gas.
3. The unit of claim 1 wherein the medium is a liquid.
4. The unit of claim 3 wherein the medium comprises water.
5. A water treatment plant comprising the unit of claim 1 .
6. A waterwork comprising the water treatment plant of claim 5 .
7. A process for the production of an adsorbent/catalyst comprising the steps of
(a) mixing an aqueous iron(III) hydroxide suspension into an aqueous suspension of iron oxide and/or iron oxyhydroxide, comprising Fe(OH)2 and then
(b) either
(b1) drying the suspension until it reaches a solid state and then mechanically comminuting the solid material to the desired shape and/or size,
or
(b2) mechanically shaping the suspension, optionally in the semisolid state after predrying, followed by additional drying until a solid state is achieved.
8. The process of claim 7 wherein the iron oxides and/or iron oxyhydroxides comprises structures based on α, β, γ, δ, δ′, ε phases and/or Fe(OH)2, ferric hydrite and mixed and intermediate phases thereof.
9. The process of claim 7 wherein iron carbonates are used in addition to or instead of the iron oxides and/or iron oxyhydroxides.
10. The process of claim 7 wherein commercial pigments are used as iron oxides and/or iron (oxy)hydroxides.
11. The process of claim 7 wherein transparent pigments are used as iron oxides and/or iron oxyhydroxides.
12. The process of claim 7 further comprising the step of precipitating the Fe(OH)3 with Fe3+ salts from the series of carbonates, chlorides, fluorides, nitrates, sulfates and sulfites.
13. A process comprising treating a fluid medium in a unit according to claim 1 by contacting the fluid medium with an absorbent/catalyst obtained by a process for the production of an adsorbent/catalyst comprising the steps of
(b) mixing an aqueous iron(ill) hydroxide suspension into an aqueous suspension of iron oxide and/or iron oxyhydroxide, comprising Fe(OH)2 and then
(b) either
(b1) drying the suspension until it reaches a solid state and then mechanically comminuting the solid material to the desired shape and/or size,
or
(b2) mechanically shaping the suspension, optionally in the semisolid state after predrying, followed by additional drying until a solid state is achieved.
14. The process of claim 13 wherein the fluid medium comprises water.
15. The process of claim 13 comprising removing a heavy metal, phosphorus, antimony, beryllium, selenium, tellurium or cyano compound from water.
16. The process of claim 13 comprising removing an arsenic compound from water.
Priority Applications (1)
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US12/217,641 US7767001B2 (en) | 2000-09-26 | 2008-07-07 | Contact and adsorbent granules |
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DE10047996.0 | 2000-09-26 | ||
DE2000147996 DE10047996A1 (en) | 2000-09-26 | 2000-09-26 | Flow-through apparatus useful for e.g. water treatment comprises lumps of adsorbent/reactant comprising iron oxide and/or oxyhydroxide embedded in iron hydroxide matrix |
DE10115417.8 | 2001-03-29 | ||
DE2001115417 DE10115417A1 (en) | 2001-03-29 | 2001-03-29 | Filtration unit for removing pollutants from fluids, especially water, comprises agglomerates of finely divided iron oxide and oxyhydroxide |
DE2001129306 DE10129306A1 (en) | 2001-06-18 | 2001-06-18 | Filtration unit for removing pollutants from fluids, especially water, comprises agglomerates of finely divided iron oxide and oxyhydroxide |
DE10129306.2 | 2001-06-18 |
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EP (1) | EP1328477B1 (en) |
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JP5015407B2 (en) | 2012-08-29 |
KR100788120B1 (en) | 2007-12-21 |
CA2423010A1 (en) | 2003-03-21 |
CN1466549B (en) | 2012-02-15 |
EP1328477B1 (en) | 2011-03-30 |
JP2004509750A (en) | 2004-04-02 |
ATE503727T1 (en) | 2011-04-15 |
KR20030036830A (en) | 2003-05-09 |
TWI313253B (en) | 2009-08-11 |
WO2002026630A1 (en) | 2002-04-04 |
EP1328477A1 (en) | 2003-07-23 |
BR0114179A (en) | 2003-07-22 |
AU2002218168A1 (en) | 2002-04-08 |
US20080271600A1 (en) | 2008-11-06 |
DE50115835D1 (en) | 2011-05-12 |
CA2423010C (en) | 2013-10-22 |
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CN1466549A (en) | 2004-01-07 |
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