WO2014174328A1 - Nanoiron suspension, process for the preparation thereof its use and device for the preparation of nanoiron suspension - Google Patents
Nanoiron suspension, process for the preparation thereof its use and device for the preparation of nanoiron suspension Download PDFInfo
- Publication number
- WO2014174328A1 WO2014174328A1 PCT/HU2013/000038 HU2013000038W WO2014174328A1 WO 2014174328 A1 WO2014174328 A1 WO 2014174328A1 HU 2013000038 W HU2013000038 W HU 2013000038W WO 2014174328 A1 WO2014174328 A1 WO 2014174328A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- tank
- sodium
- sulphate
- optionally
- iron
- Prior art date
Links
- 239000000725 suspension Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 230000008569 process Effects 0.000 title claims abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 163
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 88
- 229910052742 iron Inorganic materials 0.000 claims abstract description 83
- 239000002245 particle Substances 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 37
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 29
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 27
- 239000000047 product Substances 0.000 claims abstract description 24
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 23
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 23
- 229940083608 sodium hydroxide Drugs 0.000 claims abstract description 20
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 18
- 238000005202 decontamination Methods 0.000 claims abstract description 17
- -1 sodium-borohydride Chemical compound 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 17
- 230000003588 decontaminative effect Effects 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 239000007858 starting material Substances 0.000 claims abstract description 12
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims abstract description 11
- 239000011541 reaction mixture Substances 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 239000002351 wastewater Substances 0.000 claims abstract description 5
- 239000002912 waste gas Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 12
- 238000004090 dissolution Methods 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims description 6
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229950011008 tetrachloroethylene Drugs 0.000 claims description 6
- 229910001385 heavy metal Inorganic materials 0.000 claims description 5
- 150000003071 polychlorinated biphenyls Polymers 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 5
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 239000011368 organic material Substances 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000575 pesticide Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 229920003081 Povidone K 30 Polymers 0.000 claims description 2
- 229920003082 Povidone K 90 Polymers 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 239000002689 soil Substances 0.000 abstract description 6
- 239000002105 nanoparticle Substances 0.000 description 59
- 239000000463 material Substances 0.000 description 38
- 239000012071 phase Substances 0.000 description 31
- 238000002347 injection Methods 0.000 description 28
- 239000007924 injection Substances 0.000 description 28
- 230000015572 biosynthetic process Effects 0.000 description 18
- 230000005291 magnetic effect Effects 0.000 description 18
- 239000000356 contaminant Substances 0.000 description 16
- 125000004429 atom Chemical group 0.000 description 15
- 230000008859 change Effects 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- 230000002776 aggregation Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 230000007613 environmental effect Effects 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 238000004220 aggregation Methods 0.000 description 9
- 230000007423 decrease Effects 0.000 description 9
- 230000009257 reactivity Effects 0.000 description 9
- 238000011109 contamination Methods 0.000 description 8
- 238000009533 lab test Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000012544 monitoring process Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 239000000693 micelle Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 238000005067 remediation Methods 0.000 description 5
- 239000013543 active substance Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 229960002415 trichloroethylene Drugs 0.000 description 3
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 101100497923 Viola odorata Voc1 gene Proteins 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000005294 ferromagnetic effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000005381 magnetic domain Effects 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000000593 microemulsion method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 230000005298 paramagnetic effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004549 pulsed laser deposition Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical group [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000009390 chemical decontamination Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- KFUSEUYYWQURPO-UPHRSURJSA-N cis-1,2-dichloroethene Chemical group Cl\C=C/Cl KFUSEUYYWQURPO-UPHRSURJSA-N 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-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
- 238000013507 mapping Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002707 nanocrystalline material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
- 238000009736 wetting Methods 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/64—Heavy metals or compounds thereof, e.g. mercury
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/68—Halogens or halogen compounds
- B01D53/70—Organic halogen compounds
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0043—Preparation of sols containing elemental metal
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/30—Alkali metal compounds
- B01D2251/304—Alkali metal compounds of sodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/608—Sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C02F2101/006—Radioactive compounds
-
- 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
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/322—Volatile compounds, e.g. benzene
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/327—Polyaromatic Hydrocarbons [PAH's]
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
- C02F2101/363—PCB's; PCP's
Definitions
- NANOIRON SUSPENSION PROCESS FOR THE PREPEARTION THEREOF ITS USE AND DEVICE FOR THE PREPARATION OF NANOIRON SUSPENSION
- the invention relates to an iron suspension, which comprises solid iron particles in the nanometer size range, which is prepared from ferrous-sulphate (FeS0 4 ); copper-sulphate (CuS0 4 ), a reducing agent, and/or sodium-borohydride (NaBH 4 ); sodium-hydroxide (NaOH); and optionally additives.
- FeS0 4 ferrous-sulphate
- CuS0 4 copper-sulphate
- NaBH 4 sodium-borohydride
- NaOH sodium-hydroxide
- a process for the preparation of the iron suspension according to the invention, comprising the steps of forming of an aqueous solution comprising: a) aqueous ferrous-sulphate (FeS0 4 ) or hydrated ferrous-sulphate (FeS0 4 x 7H 2 0); sodium-ditionite (Na 2 S 2 0 4 ); sodium-borohydride (NaBH ⁇ ; sodium-hydroxide (NaOH) and hydrated copper-sulphate (CuS0 4 *5H 0) starting materials; b) reaction of the the reaction mixture according to step a) for 0.1-10 hours; and c) obtaining of the suspended product.
- the invention relates to the use of the iron suspension according to the invention for decontamination, preferably for the decontamination of soil, water, waste water or gas mixtures. Further, the invention relates to a device for the preparation of the iron suspension according to the invention.
- nanotechnology may play important role also in the production and storage of energy, as well es in water management, medical biology, optics and electronics.
- a nanoparticle may also take part in different chemical processes as a reactant. The best example for this is the zero-valent iron (ZVI), which can reduce various contaminants.
- ZVI zero-valent iron
- the features of the metallic iron nanoparticles generally may be linked to the small size of the nanoparticles.
- the magnetic characteristics are particularly important, which may consitute the basis of a number of applications.
- the particles in particular tend to aggregate, which in part is due to the magnetic interactions between them.
- this process has to be controlled to be able to successfully utilize the nZVI in any of technological field.
- the zero valent iron - either the nanoparticle, or iron with larger particle size - represents the most promising basis for those kinds of remediation technologies, which aim the decontamination of chlorinated hydrocarbons, reducible inorganic anions and heavy metals that may be found in the underground water.
- the application of iron nanoparticles (nZVI) carries a number of benefits, because on one hand they possess higher reactivity as compared to the micron sized particles, on the other hand it is much easier to target them to the location of the contamination; this has to date been confirmed by a number of field investigations [Quinn, J., et al., Environ. Sci. Technol, 2005. 39: p. 1309-1318., Elliott, D.W. and W.X.
- the electric, optical, magnetic or even chemical characteristics of the nanoparticles significantly differ from the features discovered and known in case of block phase materials. Another important feature of these materials is that the characteristics listed change with the size, shape and composition of the particles. For example, the reactivity of a small cluster consisted of transition metal atoms significantly exceeds the reactivity of the same metal in block phase, and this reactivity may change by multiple magnitudes with the size of the cluster.
- the atoms of materials which do not show magnetic characteristics in block phase, become magnetic when they form a cluster, and the nanocomposites show high magnetic resistance, increased residual magnetism and other magnetic features. These recently experienced phenomena may point to the fact that it is possible to prepare a material from e.g. clusters of nanoparticles, in which the desired combination of the features may be designed.
- a material with block phase consists of so called magnetic domains, all of them containing thousands of atomic spins. Within the domain these spins have an organized structure, but the summation spins of the individual domains show different direction. In the course of a ferromagnetic transition a long term magnetic structure is formed, and the summation spin of the individal domains is also organized.
- the vector of the magnetic momentum may turn as a result of thermal energy, and the process will be accelerated by the increase of temperature. In case of macroscopic particles this means that the material becomes paramagnetic instead of ferromagnetic. In case of nanoparticles the thermal effect is amplified, and above a given temperature (blocking temperature) the magnetic momentum is randomly fluctuated, and the nanoparticle behaves like a paramagnetic atom with high magnetic momentum. This is called superparamagnetic behaviour [Goldstein, A.N., Handbook of Nanophase Materials. 1997, New York: Marcel Dekker, Inc.].
- the environmental effects which may have effect on the features of the micronic and block phase materials, possess high significance in case of the nanoparticles.
- a solvent may reside in the nanopores, which would have been evaporated from the surface of a block phase material. This residual solvent may later render the study of the nanoparticle difficult.
- the surface contamination may be infinitesimal, however, the same amount of a contaminant will principally influence the features in case of a small sized particle.
- Even the relatively stable nanoparticles change as a result of the environmental effects, since the thermodynamics of the small size systems are highly dependent from their environment [Hill, T.L., Nano Lett., 2001. 1: p. 273-275.].
- the size and structure of the nanoparticles, and even their composition depend on the antecedent of the particle and the processing methods. Beside the environmental effects and the antecedent of the particle, it should also be noted that the nanoparticles are in principle dynamics systems. Their shape and structure may change e.g. as a result of an eventual electron or X-ray radiation.
- the above overview can be considered as the common feature of all of the nanoparticles, however, in case of the iron and other nanoparticles, which in general are also chemically unstable, it should also be noted that they may react with other materials present. This reaction may take place within the particle, such is e.g. the appearance of a surface oxide layer, and the eventual reactions thereof.
- the nZVI particles have a core-shell structure, where the metal with high reactivity is inside the shell, in the core.
- Such a system is a lot more complicated than the particles consisting of only one metal, especially if we consider how the characteristics respond to the change of the environment and elapse of time [Li, X.Q., D.W. Elliott, and W.X.
- the nano-iron prepared by pulverization may be considered stable as compared to the particles produced by another method, however, there is no way here either to prepare particles without any oxide coating, which, by the time elapsed, will increase.
- Iron nanoparticles synthetized in a solution were investigated by a surface sensitive method to discover if the oxide coating changes as a result of the contact with air. The result showed that the amount of the oxidated iron increased as early as few minutes passed.
- a number of opportunities may be chosen, such as the synthesis in fluid phase, gas phase or vacuum.
- the nanoparticles prepared by different techniques will have different shapes, and differences may also be found in the structure of the oxide coating.
- the preparation of the particles may be controlled and the characteristics of the coating may also be influenced.
- the coating of the nanoparticles prepared in vacuum or volatile phase is usually a well defined oxide layer.
- Such particles are the most suitable for us to get to know the basic features of the nanoparticles.
- a solution based synthesis or the hydrogen reduction of the oxide nanoparticles should be chosen. In this case, however, nanoparticles are yielded that do not have uniform shape and size, furthermore, they contain contaminants, which remained from the synthesis.
- the system should immediately be quenched either by the removal of the volatile' s source, or by slowing down the process to hinder the growth of the centres. In most cases this happens within a few milliseconds, and enables the continuous or quasi-continuous operation.
- the chemical volatile phase synthesis resembles the chemical volatile phase disjoint (CVD), where thin solid layers are formed onto different surfaces.
- the volatiles of the precursor are led into a reactor with heated walls, into conditions that are favourable for the formation of particles instead of the formation of a thin layer.
- This process may be used in the formation of a variety of materials, and its flexibility is further increased by the high number of precursors used in the CVD process, which may also be advantageously used in the synthesis of nanoparticles.
- the precursor at room temperature may be solid, liquid or gas, but it always enters the reactor in volatile state (bubbled or sublimated).
- the inert gas condensation is especially suitable for the preparation of metal nanoparticles, since a number of metals is evaporated with an appropriate rate at a temperature, which is still relatively simply achievable.
- the steam produced by the evaporation of a solid material is mixed with the cold gas and this leads to the condensation of the solid particles. If the gas used as cold gas reacts with the evaporated metal, then other types of nanoparticles may also be prepared, e.g. by entering oxygen a metal oxide is produced.
- the pulsed laser deposition the saturated steam is produced by a pulsed laser.
- the pulverizing gas aggregation can be used for the deposition of metal iron nanoclusters, for which the magnetron-pulverizer and the gas aggregation techniques are combined.
- the iron atoms coming from the pressurized magnetron pulverizer are impacted with Ar atoms in a water-cooled gas aggregation chamber, which slack them up.
- the average particle size may be varied between 1 and 100 nm by changing the aggregation distance, the performance of the pulverizer, the pressure of the aggregation tube or the proportion of the flowing rate of the He and Ar gases.
- Micelle techniques include beside the normal "oil-in-water” type microemulsions the inverse, "water-in-oil” systems, as well.
- the internal diameter of such nanoreactors is around 50 nm.
- a surfactant amphiphilic
- the disperse system comprises monodisperse drops, the size of which ranges from nanometres to hundreds of nanometres. The size and shape of the drops are determined by the proportion of the surfactant contained by the system as compared to the dispersed phase.
- the nanoparticles prepared in inverse micelles are usually monodispersed, however, the deposition and collection of the particles may be problematic, since the particles prefer the suspended state in such conditions.
- the methods for the collection of the particles - such as e.g. the destabilization of the micelle - lead on the other hand to the aggregation of the particles.
- the surface of the individual particles produced by any of the micelle techniques is therefore always occupied by a surfactant.
- the hydrothermal synthesis is suitable for the preparation of nanocrystalline materials in gramm amounts. In this case the reaction is performed using an aqueous metal salt solution at an elevated temperature and pressure. In the course of the reaction a metal oxide can be prepared as a result of the hydrolysis of the metal ion.
- iron nanoparticles were prepared, in which the average particle size remained under 10 nm, which is much smaller than the average diameter of the nanoparticles synthetised in a solution.
- the oil phase of the V/O (inverse) system was constituted by n-octane, the surfactant was cetyl-trimethyl-ammonium-bromide, and the co- tenside was 1-butanol.
- 0.1 M aqueous solution of FeCl 3 *6H 2 0 was added to the above mixture.
- the X-ray diffraction measurements showed that both the solution phase and the microemulsion methods resulted in amorphous nanoparticles, as no peak with significant intensity was identified in the diffractograms, which could indicate crystalline phase.
- a practical problem in connection with the nanoparticles is their tendency to aggregate, and - accordingly - difficulties in achieving their stability.
- Such atoms/molecules are affected from the two types of media by different forces, therefore their features (energy, coordination number, the arrangement of the atoms, molecular conformation) will be different from that of the block phase atoms/molecules.
- An important problem to be solved is to find what kind of practically feasible conditions are required to preserve the dispersion of the particles of the suspension containing nanoparticles.
- nZVI elemental iron nanoparticles
- the elemental iron nanoparticles (nZVI) efficiently decontaminate the different chlorinated organic compounds, absorb the heavy metals found in the underground water [Zhang, W.X., J Nanoparticle Res., 2003. 5: p. 323-332., Liu, Y., et al., Environ. Sci. Technol. , 2005. 39: p. 1338-1345., Ponder, S.M., J.G. Darab, and T.E. Mallouk, Environ. Sci. Technol, 2000. 34: p. 2564-2569.].
- the nZVI offers a good opportunity for the in situ remediation of the contaminants, which can be reduced with Fe°.
- its big reactivity in itself does not enable nZVI for the in situ application.
- an aqueous phase dispersion be easy to be prepared from nanoparticles, thus, they reach the contamination through the water-filled porous media.
- the mobility of the nZVI particles is insufficient, as the unstable nZVI particles can migrate only a few centimetres in such a medium. [Schrick, B., et al., Chem. Mater., 2004. 16: p. 2187-2193.].
- nZVI is linked to the material of the water storing layer, or the pores are blocked as a result of the aggregation of the particles and the following gelation.
- the state of the art is not free of challenges. [Miiller, N.C. and B. Nowack, Nano zero valent iron - THE solution for water and soil remediation? Report of the ObservatoryNANO. available at www.observatorynano.eu. (October 18, 2010.). 2010.].
- nZVI The following aspects should be addressed to be able to elaborate valuable remediation technologies based on nZVI: a) the passivation of iron; b) the agglomeration of the particles; c) better insight in the mechanisms, abiotic and biotic decomposition; d) mapping of the movement of the particles; e) the production of hydrogen, which decreases the permeability; f) accumulation of the intermediates, e.g. DCE; g) transferring of the laboratory experiments to the field: a great number of factors should be considered, e.g. hydrological, geological, microbiological aspects; and h) the device needed for the admixing and injection of nZVI. Accordingly, the state of the art failed to provide a solution (material, process and device), which is:
- An object of the invention is the production of a device for the preparation of nano iron, which is optionally mobile and which can produce the material desired for the environmental decontamination at the location of the contamination.
- the nanoparticles easily react with the surrounding materials that tend to be reduced, if prolonged period of time has passed between the preparation and usage, the activity of the suspension continuously decreases. This leads to the fact that storage of the active material and the long distance transportation thereof are not only uneconomical, but also decrease the efficiency of the produced active agent. There is therefore a need for the design of a new production line, which may be suitable for the preparation of the active agent in situ in an amount that is sufficient for the decontamination of even an industrial scale contamination.
- the invention relates to an iron suspension comprising solid iron particles in the nanometer size range that is prepared from ferrous-sulphate (FeS0 4 ); copper-sulphate (CuS0 4 ), a reducing agent, prferably sodium-ditionite(Na 2 S 2 0 4 ), and/or sodium-borohydride (NaBH 4 ); sodium-hydroxide (NaOH); and optionally one or more additive(s) selected from the group consisting of polyvnyl-pirrolidone, preferably PVP-K30 or PVP-K90, and as co- metal PdCl 2 x2H 2 0.
- FeS0 4 ferrous-sulphate
- CuS0 4 copper-sulphate
- CuS0 4 copper-sulphate
- NaBH 4 sodium-borohydride
- NaOH sodium-hydroxide
- additive(s) selected from the group consisting of polyvnyl-pirrolidone, preferably PVP-K30 or PVP-K90, and as co-
- the concentration of the iron suspension according to the invention is 1000, 3000, preferably 5000 or 10000 ppm (mg/dm 3 ).
- the iron suspension according to the invention in one embodiment comprises as additive 1 g polyvinyl-pirrolidone based on 1 ppm concentration.
- Fig. 11-12. show the results of the microscopic measurements of the prepared material, where Fig. 11-12. illustrates the TEM recordings of the produced nano-iron suspension.
- the nano-iron suspension is an aqueous system containing solid iron particles. This makes it possible to utilize the suspension directly, since it is a requirement to possess a dilute, aqueous system, for the reason that it is intended to be used - among others - for the treatment of underground water, and it is to be passed down to different depths. In the course of the preparation the reaction conditions require aqueous media, thus the product will be yielded in water, and there is no need for the separation of the end product, washing, or any other additional treatment prior to the injection.
- the system according to the invention is flexible from the point of view of the specific parameters of the end product.
- concentration of the end product may range in a wide spectrum, where the proportion of the specific starting materials and the reaction conditions can freely be selected.
- the present invention relates to a process for the preparation of the aqueous iron suspension comprising solid iron particles in the nanometer size range, comprising the steps of:
- an aqueous solution comprising as starting materials aqueous ferrous-sulphate (FeS0 4 ) or hydrated ferrous-sulphate (FeS0 4 x7H 2 0); sodium-ditionite (Na 2 S 2 0 ); sodium-borohydride (NaBK ; sodium-hydroxide (NaOH) and hydrated copper-sulphate (CuS0 4 x5H 2 0) is prepared;
- step b) the reaction mixture according to step a) is reacted for 0.1-10, preferably approximately for 1 hour, optionally with stirring; and c) the suspension-like product is obtained, and optionally the process is one or more times repeated.
- step a) is proceeded in such a way that
- step f) the reaction mixture according to step e) is reacted for approximately 1 hour;
- the reaction mixture according to step f) is transferred, preferably by pumping into an optionally stirred product tank, from where the product is preferably in one hour obtained; and h) if desired, the steps according to points a) to f) are one or more times repeated.
- the system is flexible, since it is applicable not only for one specific synthesis, but in case of the development of the technology, it remains suitable for the production without transmogrification. In the present case, among the variable opportunities, the following economical and efficient system is disclosed, however, the invention is not in any way limited thereto.
- the basic starting materials are the following: hydrated ferrous-sulphate (FeS0 4 x7H 2 0); sodium-ditionite (Na 2 S 2 0 4 ); sodium-borohydride (NaBKj); sodium-hydroxide (NaOH) and hydrated copper-sulphate (CuS0 4 > ⁇ 5H 2 0).
- the ferrous-sulphate is a relatively cheap, easily reducible iron-salt. For the reason of environmental concerns it has importance which starting salt is chosen, thus, finally ferrous- sulphate was selected.
- the hydrated form is cheaper than the dehydrated form, furthermore the work is done in aqueous phase, thus it does not disturb the system.
- Sodium-ditionite and sodium-borohydride are reducing agents.
- This material is cheap, and it produces the elemental iron in a slightly slower rate though, the process started by the sodium-borohydride is continued by sodium-ditionite more easily, furthermore, using a small excess as compared to the desired amount (20 percent excess), it stabilizes the system, because remaining in the solution after the injection, it will be able to produce elemental iron.
- Sodium-hydroxide plays an important role from a number of point of views. Reduction with sodium-hydroxide takes place at alkaline pH, thus, the acidic pH of the ferrous-sulphate solution is aligned to an appropriate value, making the reaction possible. On the other hand, the sodium-ditionite is unable to produce elemental iron from by the reduction of ferrous- sulphate, but rather said reaction takes place from ferrous-hydroxide (Fe(OH) 2 ) produced from the reaction of ferrous-sulphate and sodium-hydroxide.
- Fe(OH) 2 ferrous-hydroxide
- the copper-sulphate is a good reducing agent of contaminants, however, cannot be used in such an amount as the iron can be, thus it is given to the system as an additional metal in a proportion of 5 to 10 % (as compared to ⁇ the iron) in order to increase the efficiency.
- the first step is the dissolution of the materials.
- the ferrous-sulphate and sodium-hydroxide may be dissolved simultaneously, with the only difference that the solution of ferrous-sulphate before and during the dissolution is bubbled with N 2 gas.
- the water is deoxygenated, which is necessary, because the elemental iron, which is highly active, almost immediately reacts with the oxygen content of the water, during which some kind of ferrous/ferric oxide is produced, which is useless in the decontamination.
- the sodium-hydroxide solution is added to the above solution, simultaneously with the previously dissolved sodium-borohydride solution, slowly.
- reaction time This requires approximately one hour reaction time, which is not a bottleneck, as the production line has been designed in such a way that this reaction time be equivalent with the yield, thus the injection can be done continuously.
- a slurry-like suspension is obtained, which is a product containing nano-iron. This may directly be led into a device which is suitable for injection, and can be passed under ground.
- the invention relates to the use of the aqueous iron suspension comprising solid iron particles in the nanometer size range according to the invention for decontamination, preferably for the decontamination of water, waste water, or gas mixtures, more preferably for the removal of chlorine containing organic materials, heavy metals, and radionuclides, more preferably for the decontamination of poly-chlorinated biphenyls (PCB), solvents and chemical raw materials, such as perchloro-ethylene (PCE), trichloro-ethylene (TCE), carbon-tetrachloride (CT) and vinyl-chloride (VC), benzene, toluene, pesticides, especially DDT, a nitro-aromatic compounds or perchlorates.
- PCB poly-chlorinated biphenyls
- solvents and chemical raw materials such as perchloro-ethylene (PCE), trichloro-ethylene (TCE), carbon-tetrachloride (CT) and vinyl-chloride (VC), benzen
- B second tank suitable for containing a reducing agent, optionally equipped with a stirrer, inlet opening and a relief valve;
- C third tank suitable for containing sodium-hydroxide, optionally equipped with a stirrer, inlet opening and a relief valve;
- a gas tank suitable for storing wash gas connected at least to D reactor tank by a gas tube.
- the device according to the invention is equipped with an H additive tank connected to D reactor tank by a chemical pipe equipped with an interlocking device.
- the A, B, C, D, E, F and H tanks are equipped with a stirring blade and a stirring engine.
- the stirring engines are connected to an electric generator.
- the device according to the invention is placed on a vehicle.
- the invention is illustrated by way of examples, which, however, are not in any way intended to limit the scope of the invention.
- a scalable embodiment of the system according to the invention is based on the 6 stainless steel tanks, in which mixing of the starting material and the reactions take place.
- all tanks, with the exception of F waste tank are equipped with a stirring blade, the veloctiy of which can be changed by the control panel.
- the agitation of the blades is ensured by a central hydrophor, which propels them with the help of oil circulation.
- the switch on and off of these equipments can also be managed from the control panel.
- all tanks also with the exception of F waste tank are equipped with a computer controlled water inlet, which may be opened or closed manually, but automatic operation may also be configured. This is enabled by the pressure-gauge placed in the tanks, thanks to which we have information about the amount of the solution in the tanks (all of the tanks may be equipped with this pressure-gauge).
- all of the tanks are equipped with an outlet opening with a two way valve (open/close), furthermore, three chemical-proof pumps enable the movement of the solutions between the tanks, as well as the obtaining of the product.
- These devices may also be operated centrally.
- the production line is equipped with a gas tank container, a scaffold, from which the tanks are easily available for the operating personnel, an aggregator, from which, if desired, electricity may be obtained, furthermore, the above-mentioned computer, which displays the date in a touchscreen, and makes the control possible either manually, or in automatic operation.
- the production line may be designed in such a way that it is able to produce the material according to the invention in the highest possible amount, however, it is still suitable to be placed onto a truck trailer or a compartment of a truck. By this the system may be transferred to the centrum of the contaminated area, and the material can be produced on the spot.
- Another precondition is the permanent water supply. This may be done using running water, filtered well-water, or water transferred by a sevice unit. If these resources are at disposal, from the above-mentioned starting materials the end product can be prepared in the desired amount.
- 200 liter water is pumped into the A tank according to Fig 1 using a computer, then deoxygenation starts by letting nitrogen gas in (the control unit of the system can open all inlet and outlet valves, pump the content of the tanks and switch on and off all stirring blades, thus all of these steps may be operated from the control panel).
- the control unit of the system can open all inlet and outlet valves, pump the content of the tanks and switch on and off all stirring blades, thus all of these steps may be operated from the control panel).
- 200-200 liter water is pumped into B and C tanks.
- the pre-determined amounts of ferrous-sulphate and copper-sulphate are added to A tank through the upper inlet opening, at the same time the agitation by the stirring blade placed in the tank is started, which helps the dissolution.
- sodium-hydroxide is added to B tank, also with stirring, then sodium- borohydride is placed into the same tank.
- the content of A tank is pumped into D main reactor, which also possesses a nitrogen inlet. Then the content of B tank is pumped into the main reactor and at the same time stirring is started. While the reagents contact under permanent stirring, in the C tank addition and dissolution of sodium- ditionite takes place, which needs a few minutes. Thereafter this solution may also be pumped into the main reactor, then after adding the water needed to reach the final volume of the reaction mixture (300-400 liters), by increasing the intensity of the stirring, and permanent bubbling with nitrogen the 1 hour reaction starts. In the duration of this period of time amounts of the materials needed for the next production cycle may be determined, and the necessary amounts of water may be let in the stirring tanks (A, B, C).
- the next solutions may be prepared in A and B tanks according to the above.
- the final nano-iron suspension should be pumped from D main reactor to E product tank.
- This tank is also equipped with a stirring blade, thus the collection of the product may be started with permanent stirring, and by connecting to the injection device.
- the time required is approximately the same as the time required for the new cycle.
- the suspension In the emptied D main reactor the suspension may be reconstituted in line with the above, and after the expiry of the reaction time the content of the E product tank may be refilled. This makes the injection continuous.
- the system may include an F waste tank, to which any kind of starting material or end product can be pumped in case of the break-down of the system, and the materials may be stored in it until the successful management of the break-down.
- all of the tanks are equipped with a bottom manual valve, which enables the discharge of the tanks in case of an emergency.
- the water supply of the production line may be ensured by water of any kind of origin, with a simple inlet.
- the system is equipped with a scaffold, which can store three gas tanks, furthermore with a reductor, which is connected to the gas tanks through the gas tubes.
- the gas inlet of the tanks may be opened and closed by a manual valve.
- a suspension with the desired concentration may be prepared.
- the amount of the added materials should be changed, but it is possible to prepare an even more concentrated solution in D main reactor, then by pumping into the product tank the appropriate amount, and diluting it with water, any kind of concentrations can be ensured.
- Table 1 the chemical need of some exemplary concentration is disclosed.
- Table 1 Typical concentration values for the iron suspensions according to the invention
- the effectiveness of the nano-iron suspension according to the invention is illustrated by the following examples.
- the analysis of the effects of nano-iron suspensions with 10000 ppm concentration was made after the injection of 2> ⁇ 3 m 3 active agent.
- a complex experimental plan was followed from the laboratory tests, until the analysis of the effectiveness of the field tests.
- the exact composition of the prepared suspension, the efficiency of the preparation and the reaction conditions were optimised. The results were tested first in a laboratory, then in possession of the acceptable results the designed upscaled suspension was prepared and tested in the predetermined test fields.
- nano-iron suspension was prepared and injected under ground into different depths, in 2 parts (3-3 m 3 ).
- underground water samples were taken from the treated area before the treatment, and one month afterwards.
- the results received were in line with the preliminary laboratory values, the prepared suspension was proven to be effective, which is best shown by the singificant decrease of the overall concentration of the chlorinated hydrocarbons.
- the average residual amount for every tested contaminants was 40.51 % of the starting value.
- the measurement of the baseline conditions consisted of the following investigations: measurements of the level of the underground water, VOC1, BTEX and chlorobenzene analytics, AVK measurements in 3 sample collection points, total Fe content measurement.
- the injection of the field was followed by the monitoring.
- the parameters to be measured included the following: measurements of the level of the underground water, VOC1, BTEX and chlorobenzene analytics, AVK measurements in 3 sample collection points, total Fe content measurement (photometric measurement, in each sample collection point).
- the total Fe analyses were made for the reason of the distance effect measuring, thus, the schedule of the soil sample collection monitoring is different for Fe from the measurement of the contamination.
- the injections had the following plan for the well filtered for different depths: in 24.5-25 m depth, 2x 1 m 3 10 000 ppm nano-iron; in 18-19.5 m depth, 2* 1 m 3 10 000 ppm nano-iron; in 9-9.5 m depth, 2x1 m 3 10000 ppm nano-iron.
- the installation of the injection spear took place on the day of the injection.
- the field test (injection) is as follows: a) admixing of nano-iron; b) injection under pressure, approx.
- the redox potential changes in the surrounding wells should be monitored in the course of the injection of the nano-iron; d) once the nano-iron injection has been completed, at least 3 m 3 water, in the present case underground water, should be injected.
- a device is also needed to push the injection spear under ground (25 m depth).
- the devices necessary for the injection and other field work are as follows, hose-pipes, flow-rate gauge, yield gauge, pumps, Eijkelkamp pump, stirring blade, tap water supply, coveralls, gloves, WTW, redox analyser, sample vials.
- the redox potential should be continuously measured in the monitoring well during the injections as well. One hour after the completion of the injections (after the injection of water, too) the sample collection takes place. The scheduling of the total Fe measurements is the same as the schedule of the monitoring.
- the graphs taken from the measured materials show the differences between the starting values (blue curve), and the second injection (red curve), respectively, as a function of the sample collection depths (4 to 28 metres).
- a summarizing table belongs to each graph containing the starting and the last measured values, furthermore the percent decrease of the original concentration (in some cases the increase of the concentration) during the given period of time.
- the ZVI nanoparticles according to the present invention are useful in a number of fields of the environmental technology, thus may be successivefully used for the decontamination of water, wastewaters or gas mixtures. By passing the nanoparticles directly under ground, chlorinated organic materials can effectively be decomposed.
- the technology is very promising in the field of immobilization of heavy metals (e.g. Cr(VI), Hg 2+ es Ni 2+ ) and radionuclides(U0 2 2+ ), furthermore, may be used for the decontamination of poly-chlorinated byphenyls (PCB), pesticides (e.g. DDT), nitro-aromatic compounds or perchlorates.
- PCB poly-chlorinated byphenyls
- DDT pesticides
- nitro-aromatic compounds or perchlorates nitro-aromatic compounds or perchlorates.
- solvents and chemical raw materials such as perchloro- ethylene (PCE), trichloro-ethylene (TCE), carbon-tetrachloride (CT) and vinyl-chloride (VC) is.
- PCE perchloro- ethylene
- TCE trichloro-ethylene
- CT carbon-tetrachloride
- VC vinyl-chloride
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Abstract
An aqueous iron suspension is disclosed, which comprises solid iron particles in the nanometer size range, which is prepared from ferrous-sulphate (FeSO4); copper-sulphate (CuS4), a reducing agent, and/or sodium-borohydride (NaBH4); sodium-hydroxide (NaOH); and optionally additives. Furthermore, a process is disclosed for the preparation of the iron suspension according to the invention, comprising the steps of forming of an aqueous solution comprising: a) aqueous ferrous-sulphate (FeSO4) or hydrated ferrous-sulphate (FeSO4×7H2O); sodium-ditionite (Na2S2O); sodium-borohydride (NaBH4); sodium-hydroxide (NaOH) and hydrated copper-sulphate (CuSO4×5H2O) starting materials; b) reaction of the reaction mixture according to step a) for 0,1-10 hours; and c) obtaining of the suspended product. Furthermore, the invention relates to the use of the iron suspension according to the invention for decontamination, preferably for the decontamination of soil, water, waste water or gas mixtures. Further, the invention relates to a device for the preparation of the iron suspension according to the invention.˙
Description
NANOIRON SUSPENSION, PROCESS FOR THE PREPEARTION THEREOF ITS USE AND DEVICE FOR THE PREPARATION OF NANOIRON SUSPENSION
Subject matter of the invention
The invention relates to an iron suspension, which comprises solid iron particles in the nanometer size range, which is prepared from ferrous-sulphate (FeS04); copper-sulphate (CuS04), a reducing agent, and/or sodium-borohydride (NaBH4); sodium-hydroxide (NaOH); and optionally additives. Furthermore, a process is disclosed for the preparation of the iron suspension according to the invention, comprising the steps of forming of an aqueous solution comprising: a) aqueous ferrous-sulphate (FeS04) or hydrated ferrous-sulphate (FeS04 x7H20); sodium-ditionite (Na2S204); sodium-borohydride (NaBH^; sodium-hydroxide (NaOH) and hydrated copper-sulphate (CuS04*5H 0) starting materials; b) reaction of the the reaction mixture according to step a) for 0.1-10 hours; and c) obtaining of the suspended product. Furthermore, the invention relates to the use of the iron suspension according to the invention for decontamination, preferably for the decontamination of soil, water, waste water or gas mixtures. Further, the invention relates to a device for the preparation of the iron suspension according to the invention.
The technical field
The reactivity of particles of some ten nanometres size shows considerable differences as compared both to the block-phase materials, and the individual atoms and molecules. With the better and better methods for the preparation, visualization, characterization and modeling of the nanoparticles, new opportunities arise to control the rate and product-distribution of chemical reactions. One of the most important field, where the "finetuning" of the characteristics of materials may be exploited is the remediation of environmental contaminants. Nanotechnology may play important role also in the production and storage of energy, as well es in water management, medical biology, optics and electronics. A nanoparticle may also take part in different chemical processes as a reactant. The best example for this is the zero-valent iron (ZVI), which can reduce various contaminants. The features of the metallic iron nanoparticles generally may be linked to the small size of the nanoparticles. In case of a ZVI being in the nanometric size range (nZVI), the magnetic characteristics are particularly important, which may consitute the basis of a number of applications. In the utilization of the iron nanoparticles it is a problem that the particles in
particular tend to aggregate, which in part is due to the magnetic interactions between them. However, this process has to be controlled to be able to successfully utilize the nZVI in any of technological field. The zero valent iron - either the nanoparticle, or iron with larger particle size - represents the most promising basis for those kinds of remediation technologies, which aim the decontamination of chlorinated hydrocarbons, reducible inorganic anions and heavy metals that may be found in the underground water. The application of iron nanoparticles (nZVI) carries a number of benefits, because on one hand they possess higher reactivity as compared to the micron sized particles, on the other hand it is much easier to target them to the location of the contamination; this has to date been confirmed by a number of field investigations [Quinn, J., et al., Environ. Sci. Technol, 2005. 39: p. 1309-1318., Elliott, D.W. and W.X. Zahng, Environ. Sci. Technol., 2000. 35: p. 4922-4926.]. The electric, optical, magnetic or even chemical characteristics of the nanoparticles, the size of which ranges between 1 and 100 nm, significantly differ from the features discovered and known in case of block phase materials. Another important feature of these materials is that the characteristics listed change with the size, shape and composition of the particles. For example, the reactivity of a small cluster consisted of transition metal atoms significantly exceeds the reactivity of the same metal in block phase, and this reactivity may change by multiple magnitudes with the size of the cluster. The atoms of materials, which do not show magnetic characteristics in block phase, become magnetic when they form a cluster, and the nanocomposites show high magnetic resistance, increased residual magnetism and other magnetic features. These recently experienced phenomena may point to the fact that it is possible to prepare a material from e.g. clusters of nanoparticles, in which the desired combination of the features may be designed.
One of the most important questions is how the geometric arrangement of the atoms and its stability change in view of the decrease of the size. Starting from the block phase and decreasing the size of the particles, the most important change is that the proportion of the surface atoms increases as compared to the overall number of the atoms, therefore, the surface pressure, as well as the distance between the atoms also changes. The decrease of the inter- atom distance, and the increase in the surface area per volume have effects on other
characteristics of the material. The change in the thermodynamic free energy on the surface will change the chemical potential, as well. This in turn has an effect also on the termodynamic features, among which the most conspicuous is the change of the melting point [Montano, P.A., et al., Phys. Rev. Lett, 1986. 56: p. 2076-2079.]. The large specific surface, the unique geometric arrangement and the electron structure have an effect on the catalytic characteristics, too. For example, the reactivity of clusters with a small number of atoms may change by several magnitudes, while the particle size changes by only a few atoms. The decrease of the particle size exerts the strongest effect on the magnetic features. A material with block phase consists of so called magnetic domains, all of them containing thousands of atomic spins. Within the domain these spins have an organized structure, but the summation spins of the individual domains show different direction. In the course of a ferromagnetic transition a long term magnetic structure is formed, and the summation spin of the individal domains is also organized. Though it may be expected that in very small clusters and nanoparticles in lack of domains and long term organized structures the magnetic features will be less explicit, as a matter of fact this is not true. Either the material shows magnetism in block phase or not, the nanoparticles formed from it will show completely new characteristics for the reason of the so called quantum effects. These changes give rise to a number of applications, e.g. non-volatile magnetic storage, different sensors or permanent magnets. As a result of the size decrease not only the magnetic momentum of the material, but also the magnetic behaviour will change. The nanoparticles are generally smaller than the individual magnetic domains, thus the magnetic momentums will not extinguish each other within the particle, but rather the nanoparticle behaves like one atom with high magnetic momentum. The vector of the magnetic momentum may turn as a result of thermal energy, and the process will be accelerated by the increase of temperature. In case of macroscopic particles this means that the material becomes paramagnetic instead of ferromagnetic. In case of nanoparticles the thermal effect is amplified, and above a given temperature (blocking temperature) the magnetic momentum is randomly fluctuated, and the nanoparticle behaves like a paramagnetic atom with high magnetic momentum. This is called superparamagnetic behaviour [Goldstein, A.N., Handbook of Nanophase Materials. 1997, New York: Marcel Dekker, Inc.].
The treatment of the sample, the environmental effects, which may have effect on the features of the micronic and block phase materials, possess high significance in case of the
nanoparticles. For example, a solvent may reside in the nanopores, which would have been evaporated from the surface of a block phase material. This residual solvent may later render the study of the nanoparticle difficult. In case of a block phase the surface contamination may be infinitesimal, however, the same amount of a contaminant will principally influence the features in case of a small sized particle. Even the relatively stable nanoparticles change as a result of the environmental effects, since the thermodynamics of the small size systems are highly dependent from their environment [Hill, T.L., Nano Lett., 2001. 1: p. 273-275.]. The size and structure of the nanoparticles, and even their composition depend on the antecedent of the particle and the processing methods. Beside the environmental effects and the antecedent of the particle, it should also be noted that the nanoparticles are in principle dynamics systems. Their shape and structure may change e.g. as a result of an eventual electron or X-ray radiation.
The investigations made by transmission electron microscopy show that the structure of the nanoparticles is not constant as a function of time, but it changes pernanently. This dynamic behaviour may have importance in case of e.g. nanoparticles used as catalysts, since the structural change in time will amend the catalytic activity as well.
The above overview can be considered as the common feature of all of the nanoparticles, however, in case of the iron and other nanoparticles, which in general are also chemically unstable, it should also be noted that they may react with other materials present. This reaction may take place within the particle, such is e.g. the appearance of a surface oxide layer, and the eventual reactions thereof. As a result of the outside oxide layer formed the nZVI particles have a core-shell structure, where the metal with high reactivity is inside the shell, in the core. Such a system is a lot more complicated than the particles consisting of only one metal, especially if we consider how the characteristics respond to the change of the environment and elapse of time [Li, X.Q., D.W. Elliott, and W.X. Zhang, Critical Reviews in Solid State and Materials Sciences, 2006. 31: p. 1 1 1-122.]. Beside these phenomena, the particle reacts with its environment as well, and the reaction partner may e.g. be water or an other type of component of the solution, as well as the contaminants present. The time elapsed can be another serious factor here. As the metallic iron is thermodynamically unstable in most of the environments, it may be expected that in
the course of a longer term storage oxidation or other types of reactions will take place in the material. Although a small amount of rust does not cause considerable changes in the features of the material in block phase, the same amount of corrosion will significantly change the chemical features of the nanoparticles. While attempts are made to store the iron nanoparticles in an inert environment (closed from oxygen, dry place, vacuum), however, by the progression of time, corrosion can still be experienced.
For example, the nano-iron prepared by pulverization may be considered stable as compared to the particles produced by another method, however, there is no way here either to prepare particles without any oxide coating, which, by the time elapsed, will increase. Iron nanoparticles synthetized in a solution (possessing an oxide shell) were investigated by a surface sensitive method to discover if the oxide coating changes as a result of the contact with air. The result showed that the amount of the oxidated iron increased as early as few minutes passed.
Description of the state of the art
A number of attempts have been made in the state of the art to synthetize zero valent iron nanoparticles. Two kinds of approaches may be used for the preparation of small sized nanoparticles [Fryxell, G.E. and G. Cao, Environmental Applications of Materials: Synthesis, Sorbents and Sensors. 2007, London: Imperial College Press.]. One of them is the so called top-down solution, where smaller particles are made from larger ones, the other one is the bottom-up method, where the larger particles are made from smaller ones. In case of nanoparticles, the latter is more usual, that is these are self-organizing systems, but in specific cases it is possible to prepare metallic iron nanoparticles in a ball mill. Within the self- orgainizing approach, a number of opportunities may be chosen, such as the synthesis in fluid phase, gas phase or vacuum. In general, the nanoparticles prepared by different techniques will have different shapes, and differences may also be found in the structure of the oxide coating. In the course of a synthesis in vacuum, the preparation of the particles may be controlled and the characteristics of the coating may also be influenced. The coating of the nanoparticles prepared in vacuum or volatile phase is usually a well defined oxide layer. Such particles are the most suitable for us to get to know the basic features of the nanoparticles. However, there is no possibility with this method to produce sufficient amounts e.g. for the
removal of environmental contaminations. Therefore, for this purpose a solution based synthesis or the hydrogen reduction of the oxide nanoparticles should be chosen. In this case, however, nanoparticles are yielded that do not have uniform shape and size, furthermore, they contain contaminants, which remained from the synthesis.
In the volatile phase synthesis of the nanoparticles such reaction conditions have to be achieved that the volatile phase mixture be thermodynamically unstable as compared to the solid particles.
In general this requires over-saturated steam. If the over-saturation is sufficiently high, furthermore, the condensation is not hindered by anything from reaction kinetics point of view, nucleation starts. For the reason of the residual over-saturation the volatile phase molecules either condensate or react on the surface, which results in the increase of the nanoparticles.
Therefore, if the purpose is the preparation of a small sized nanoparticle, considerable over- saturation is needed to achieve high nucleation density, then the system should immediately be quenched either by the removal of the volatile' s source, or by slowing down the process to hinder the growth of the centres. In most cases this happens within a few milliseconds, and enables the continuous or quasi-continuous operation.
During the synthesis inside a flame the heat produced by the burning processes taking place inside the flame is used for the preparation of the particles. As the formation of the nanoparticles is connected to the reactions taking place inside the flame, it is a chemically very complicated system, which is very difficult to be controlled. This method is basically useful for the preparation of oxides, as there is a highly oxidative environment within the flame.
The chemical volatile phase synthesis resembles the chemical volatile phase disjoint (CVD), where thin solid layers are formed onto different surfaces. The volatiles of the precursor are led into a reactor with heated walls, into conditions that are favourable for the formation of particles instead of the formation of a thin layer. This process may be used in the formation of a variety of materials, and its flexibility is further increased by the high number of precursors
used in the CVD process, which may also be advantageously used in the synthesis of nanoparticles.
The precursor at room temperature may be solid, liquid or gas, but it always enters the reactor in volatile state (bubbled or sublimated).
Among the physical volatile phase synthesis (or physical volatile deposition) processes the most important are the inert gas condensation, the pulsed laser deposition, the spark discharge preparation and the pulverizer gas aggregation. The inert gas condensation is especially suitable for the preparation of metal nanoparticles, since a number of metals is evaporated with an appropriate rate at a temperature, which is still relatively simply achievable. The steam produced by the evaporation of a solid material is mixed with the cold gas and this leads to the condensation of the solid particles. If the gas used as cold gas reacts with the evaporated metal, then other types of nanoparticles may also be prepared, e.g. by entering oxygen a metal oxide is produced. In case of the pulsed laser deposition the saturated steam is produced by a pulsed laser. Although only much smaller amounts of the nanoparticles can be prepared by this method, those materials can also be evaporated in case of which the conventional heating would be insufficient. By generating a spark discharge, the steam of a metal may be produced if the metal in question is used as an electrode, and in the presence of the inert gas the voltage is increased until the discharge value. The electric arc produced between the two electrodes evaporates some metal. By this method relatively small amount of nanoparticles can be produced, however, it is a relatively better reproducible synthesis.
The pulverizing gas aggregation can be used for the deposition of metal iron nanoclusters, for which the magnetron-pulverizer and the gas aggregation techniques are combined. The iron atoms coming from the pressurized magnetron pulverizer are impacted with Ar atoms in a water-cooled gas aggregation chamber, which slack them up. The average particle size may be varied between 1 and 100 nm by changing the aggregation distance, the performance of the pulverizer, the pressure of the aggregation tube or the proportion of the flowing rate of the He and Ar gases.
All of the above methods require extreme reaction conditions, therefore their upscaling utilization in the environmental technologies is either impossible, or uneconomical.
In the circle of the solution phase synthesis one of the oldest methods for the preparation of nanoparticles - especially in case of catalysts - consisted of wetting of the surface of a solid support with the solution of a compound of the metal in question, then the removal of the solvent, and contacting the metal ions with the reagent needed for the preparation of the desired nanoparticle (metal, metal oxide or metal sulphide). The morphology of the produced particles is affected by a number of factors, such as the salt of the metal, the solvent, the ionic strength of the solution and the temperature. Typically micrometer sized, polydisperse particles can be prepared by this method. Attempts were made to reduce iron ions with sodium-borohydride in a solution phase, to yield zero valent iron, which precipitates from the solution. By one of the methods the starting material was ferric(III)-chloride (chloride method), by two other the starting material was ferrous (Il)sulphate (sulphate method). However, none of the methods discussed above is suitable for the preparation of nano-iron possessing the composition and features according to the present invention.
Micelle techniques include beside the normal "oil-in-water" type microemulsions the inverse, "water-in-oil" systems, as well. The internal diameter of such nanoreactors is around 50 nm. In order to prepare normal or inverse micelles a surfactant (amphiphilic) is solved in the continuous phase, then the liquid to be dispersed is added. Thus a thermodynamically stable, transparent, homogeneous system is prepared. The disperse system comprises monodisperse drops, the size of which ranges from nanometres to hundreds of nanometres. The size and shape of the drops are determined by the proportion of the surfactant contained by the system as compared to the dispersed phase. The nanoparticles prepared in inverse micelles are usually monodispersed, however, the deposition and collection of the particles may be problematic, since the particles prefer the suspended state in such conditions. The methods for the collection of the particles - such as e.g. the destabilization of the micelle - lead on the other hand to the aggregation of the particles. The surface of the individual particles produced by any of the micelle techniques is therefore always occupied by a surfactant. Either in a batch, or in continuous mode, the hydrothermal synthesis is suitable for the preparation of nanocrystalline materials in gramm amounts. In this case the reaction is performed using an aqueous metal salt solution at an elevated temperature and pressure. In the
course of the reaction a metal oxide can be prepared as a result of the hydrolysis of the metal ion.
In all methods discussed above - both in steam, and in solution phase - particles may be produced that can be further processed. In the processing care should be taken to avoid the increase of the particle size. The residual materials remained from the processing and synthesis may significantly influence the shape and surface chemistry of the particles.
Using a microemulsion method, iron nanoparticles were prepared, in which the average particle size remained under 10 nm, which is much smaller than the average diameter of the nanoparticles synthetised in a solution. The oil phase of the V/O (inverse) system was constituted by n-octane, the surfactant was cetyl-trimethyl-ammonium-bromide, and the co- tenside was 1-butanol. To the above mixture 0.1 M aqueous solution of FeCl3*6H20 was added. The X-ray diffraction measurements showed that both the solution phase and the microemulsion methods resulted in amorphous nanoparticles, as no peak with significant intensity was identified in the diffractograms, which could indicate crystalline phase.
The technical problem to be solved by the invention A practical problem in connection with the nanoparticles is their tendency to aggregate, and - accordingly - difficulties in achieving their stability. The colloide particles - as it is expectable from their size - possess much larger specific surface as compared to the block phase materials. Therefore in such particles much higher proportion of the atoms or molecules can be found on the interface of the particle and the environment as compared to the block phase materials. Such atoms/molecules are affected from the two types of media by different forces, therefore their features (energy, coordination number, the arrangement of the atoms, molecular conformation) will be different from that of the block phase atoms/molecules. An important problem to be solved is to find what kind of practically feasible conditions are required to preserve the dispersion of the particles of the suspension containing nanoparticles.
The elemental iron nanoparticles (nZVI) efficiently decontaminate the different chlorinated organic compounds, absorb the heavy metals found in the underground water [Zhang, W.X., J Nanoparticle Res., 2003. 5: p. 323-332., Liu, Y., et al., Environ. Sci. Technol. , 2005. 39: p.
1338-1345., Ponder, S.M., J.G. Darab, and T.E. Mallouk, Environ. Sci. Technol, 2000. 34: p. 2564-2569.].
Thanks to the large specific surface and reactivity the nZVI offers a good opportunity for the in situ remediation of the contaminants, which can be reduced with Fe°. However, its big reactivity in itself does not enable nZVI for the in situ application. It is also important that an aqueous phase dispersion be easy to be prepared from nanoparticles, thus, they reach the contamination through the water-filled porous media. To achieve this, the mobility of the nZVI particles is insufficient, as the unstable nZVI particles can migrate only a few centimetres in such a medium. [Schrick, B., et al., Chem. Mater., 2004. 16: p. 2187-2193.]. This may be explained by two reasons: the nZVI is linked to the material of the water storing layer, or the pores are blocked as a result of the aggregation of the particles and the following gelation. The state of the art is not free of challenges. [Miiller, N.C. and B. Nowack, Nano zero valent iron - THE solution for water and soil remediation? Report of the ObservatoryNANO. available at www.observatorynano.eu. (October 18, 2010.). 2010.]. The following aspects should be addressed to be able to elaborate valuable remediation technologies based on nZVI: a) the passivation of iron; b) the agglomeration of the particles; c) better insight in the mechanisms, abiotic and biotic decomposition; d) mapping of the movement of the particles; e) the production of hydrogen, which decreases the permeability; f) accumulation of the intermediates, e.g. DCE; g) transferring of the laboratory experiments to the field: a great number of factors should be considered, e.g. hydrological, geological, microbiological aspects; and h) the device needed for the admixing and injection of nZVI. Accordingly, the state of the art failed to provide a solution (material, process and device), which is:
a) simple,
b) does not require extreme conditions, can be practiced outside the laboratories, in the fields; c) economical, and
d) scalable;
resulting in a nano iron, which is
e) stable,
f) free of aggregation and
g) free of oxides.
An object of the invention is the production of a device for the preparation of nano iron, which is optionally mobile and which can produce the material desired for the environmental decontamination at the location of the contamination. As the nanoparticles easily react with the surrounding materials that tend to be reduced, if prolonged period of time has passed between the preparation and usage, the activity of the suspension continuously decreases. This leads to the fact that storage of the active material and the long distance transportation thereof are not only uneconomical, but also decrease the efficiency of the produced active agent. There is therefore a need for the design of a new production line, which may be suitable for the preparation of the active agent in situ in an amount that is sufficient for the decontamination of even an industrial scale contamination.
To overcome the above problems and satisfy the above need, we have done systematic experimental work, and as a result of this, completed our invention.
Detailed description of the invention
In its first aspect the invention relates to an iron suspension comprising solid iron particles in the nanometer size range that is prepared from ferrous-sulphate (FeS04); copper-sulphate (CuS04), a reducing agent, prferably sodium-ditionite(Na2S204), and/or sodium-borohydride (NaBH4); sodium-hydroxide (NaOH); and optionally one or more additive(s) selected from the group consisting of polyvnyl-pirrolidone, preferably PVP-K30 or PVP-K90, and as co- metal PdCl2x2H20.
In a preferred embodiment the concentration of the iron suspension according to the invention is 1000, 3000, preferably 5000 or 10000 ppm (mg/dm3).
The iron suspension according to the invention in one embodiment comprises as additive 1 g polyvinyl-pirrolidone based on 1 ppm concentration. In one embodiment of the invention the weight proportion of the components is the following: FeS04:Na2S204:NaBH4:CuS04 = 5:3,95:2,25:0,068:0,26, and the amount of PdCl2x2H20 is 1 ,0-0,01% based on the moles of the metal iron, however, the invention is not limited to this specific composition.
In one embodiment of the invention the molar proportion of the components is the following: FeS04:Na2S204:NaBH4:CuS04 = 17,98:22,68:56,26:1,80: 1,04, however, the invention is not limited to this specific composition.
Fig. 11-12. show the results of the microscopic measurements of the prepared material, where Fig. 11-12. illustrates the TEM recordings of the produced nano-iron suspension.
The nano-iron suspension is an aqueous system containing solid iron particles. This makes it possible to utilize the suspension directly, since it is a requirement to possess a dilute, aqueous system, for the reason that it is intended to be used - among others - for the treatment of underground water, and it is to be passed down to different depths. In the course of the preparation the reaction conditions require aqueous media, thus the product will be yielded in water, and there is no need for the separation of the end product, washing, or any other additional treatment prior to the injection.
The system according to the invention is flexible from the point of view of the specific parameters of the end product. Depending from the level of contamination of the area to be treated, the concentration of the end product may range in a wide spectrum, where the proportion of the specific starting materials and the reaction conditions can freely be selected. By this a very multifunctional system is achieved, which is suitable for the solution of not in particular one specific problem, but rather - depending from the conditions and adopting them - the production of the most appropriate active agent. In its second aspect the present invention relates to a process for the preparation of the aqueous iron suspension comprising solid iron particles in the nanometer size range, comprising the steps of:
a) an aqueous solution comprising as starting materials aqueous ferrous-sulphate (FeS04) or hydrated ferrous-sulphate (FeS04x7H20); sodium-ditionite (Na2S20 ); sodium-borohydride (NaBK ; sodium-hydroxide (NaOH) and hydrated copper-sulphate (CuS04x5H20) is prepared;
b) the reaction mixture according to step a) is reacted for 0.1-10, preferably approximately for 1 hour, optionally with stirring; and
c) the suspension-like product is obtained, and optionally the process is one or more times repeated.
In one embodiment of the process according to the invention step a) is proceeded in such a way that
a) the ferrous-sulphate, previously or optionally during the dissolution bubbled with N2 gas and optionally copper-sulphate is measured into a tank optionally equipped with stirrer and relief valve;
b) the sodium-hydroxide is measured into a tank optionally equipped with stirrer and relief valve, which is separated from the tank mentioned in point a);
c) the sodium-borohydride simultaneously with or separated in time from, preferably prior to the sodium-ditionite, is dissolved in a tank optionally equipped with stirrer and relief valve, optionally simultaneously with the steps according to points a) and b);
d) optionally the additives are added to the reaction mixture at any of steps a) to c);
e) following the dissolution according to points a) to d) the content of the tanks according to points a) to c) is transferred to an optionally stirred main reactor, preferably by pumping, preferably in such a way that first the ferrous-sulphate, and optionally the copper-sulphate, then the sodium-hydroxide, then, preferably a few minutes later, the solution according to point c) is charged into the main reactor;
f) the reaction mixture according to step e) is reacted for approximately 1 hour;
g) the reaction mixture according to step f) is transferred, preferably by pumping into an optionally stirred product tank, from where the product is preferably in one hour obtained; and h) if desired, the steps according to points a) to f) are one or more times repeated. There are a number of ways for the preparation of the nano-iron suspension according to the invention. The system is flexible, since it is applicable not only for one specific synthesis, but in case of the development of the technology, it remains suitable for the production without transmogrification. In the present case, among the variable opportunities, the following economical and efficient system is disclosed, however, the invention is not in any way limited thereto.
The basic starting materials are the following: hydrated ferrous-sulphate (FeS04x7H20); sodium-ditionite (Na2S204); sodium-borohydride (NaBKj); sodium-hydroxide (NaOH) and hydrated copper-sulphate (CuS04><5H20). The ferrous-sulphate is a relatively cheap, easily reducible iron-salt. For the reason of environmental concerns it has importance which starting salt is chosen, thus, finally ferrous- sulphate was selected. The hydrated form is cheaper than the dehydrated form, furthermore the work is done in aqueous phase, thus it does not disturb the system. Sodium-ditionite and sodium-borohydride are reducing agents. Probably this is the most problematic point of the design of the reaction according to the invention, as a weak reducing agent would be unsuitable for the production of elemental iron. The stronger reducing agents may be dangerous, and it is important, what kind of decomposition products are formed after the reaction, furthermore, as always, thrift should also be considered. The borohydride is not cheap, however, it is an excellent reducing agent. By using it in a smaller proportion, producing a strongly reductive condition, a part of the iron takes the elemental form (Fe°). The majority of the overall amount of the reducing agent is, however, consisted of sodium- ditionite. This material is cheap, and it produces the elemental iron in a slightly slower rate though, the process started by the sodium-borohydride is continued by sodium-ditionite more easily, furthermore, using a small excess as compared to the desired amount (20 percent excess), it stabilizes the system, because remaining in the solution after the injection, it will be able to produce elemental iron.
Sodium-hydroxide plays an important role from a number of point of views. Reduction with sodium-hydroxide takes place at alkaline pH, thus, the acidic pH of the ferrous-sulphate solution is aligned to an appropriate value, making the reaction possible. On the other hand, the sodium-ditionite is unable to produce elemental iron from by the reduction of ferrous- sulphate, but rather said reaction takes place from ferrous-hydroxide (Fe(OH)2) produced from the reaction of ferrous-sulphate and sodium-hydroxide.
Similarly to the iron, the copper-sulphate is a good reducing agent of contaminants, however, cannot be used in such an amount as the iron can be, thus it is given to the system as an
additional metal in a proportion of 5 to 10 % (as compared to~the iron) in order to increase the efficiency.
In general, all of the starting materials excellently dissolve in water. As the whole reaction line takes place in an aqueous environment, the first step is the dissolution of the materials. The ferrous-sulphate and sodium-hydroxide may be dissolved simultaneously, with the only difference that the solution of ferrous-sulphate before and during the dissolution is bubbled with N2 gas. By this operation the water is deoxygenated, which is necessary, because the elemental iron, which is highly active, almost immediately reacts with the oxygen content of the water, during which some kind of ferrous/ferric oxide is produced, which is useless in the decontamination. After the complete dissolution, the sodium-hydroxide solution is added to the above solution, simultaneously with the previously dissolved sodium-borohydride solution, slowly. During the reaction black-greenish, precipitate-like system is formed, which indicates on one hand the presence of elemental iron produced by the borohydride, on the other hand the presence of the forming ferrous-hydroxide. During the stirring, the sodium- ditionite may also be dissolved, which also easily and quickly dissolves, however, it starts immediately (slowly) decomposing in water, which is a disadvantage for us, as it cannot take part in the reduction, therefore it seems to be reasonable to add sodium-ditionite in small excess amounts. After the complete dissolution, this solution may also be given to the well stirred ferrous-hydroxide solution with permanent stirring. Thus, the entire iron content will exist in elemental form. This requires approximately one hour reaction time, which is not a bottleneck, as the production line has been designed in such a way that this reaction time be equivalent with the yield, thus the injection can be done continuously. Once the reaction time has passed, a slurry-like suspension is obtained, which is a product containing nano-iron. This may directly be led into a device which is suitable for injection, and can be passed under ground.
In another aspect, the invention relates to the use of the aqueous iron suspension comprising solid iron particles in the nanometer size range according to the invention for decontamination, preferably for the decontamination of water, waste water, or gas mixtures, more preferably for the removal of chlorine containing organic materials, heavy metals, and radionuclides, more preferably for the decontamination of poly-chlorinated biphenyls (PCB),
solvents and chemical raw materials, such as perchloro-ethylene (PCE), trichloro-ethylene (TCE), carbon-tetrachloride (CT) and vinyl-chloride (VC), benzene, toluene, pesticides, especially DDT, a nitro-aromatic compounds or perchlorates. In a further aspect, the invention relates to a device for the preparation of the aqueous iron suspension comprising solid iron particles in the nanometer size range according to the invention, which device comprises:
- an A first tank suitable for containing ferrous-sulphate and/or copper-sulphate, optionally equipped with a stirrer and relief valve;
- a B second tank suitable for containing a reducing agent, optionally equipped with a stirrer, inlet opening and a relief valve;
- a C third tank suitable for containing sodium-hydroxide, optionally equipped with a stirrer, inlet opening and a relief valve;
- a D reactor tank connected to B second tank and C third tank by a chemical pipe equipped with an interlocking device;
- an E product tank connected to D reactor tank by a chemical pipe equipped with interlocking devices;
- an F waste tank connected to A first tank, B second tank, C third tank, D reactor tank and E product tank by a chemical pipe equipped with an interlocking device;
- a G water source connected to A first tank, B second tank, C third tank, D reactor tank and E product tank by a chemical pipe equipped with an interlocking device;
- a gas tank suitable for storing wash gas connected at least to D reactor tank by a gas tube.
In one embodiment the device according to the invention is equipped with an H additive tank connected to D reactor tank by a chemical pipe equipped with an interlocking device.
In one embodiment of the device according to the invention the A, B, C, D, E, F and H tanks are equipped with a stirring blade and a stirring engine. In one embodiment of the device according to the invention the stirring engines are connected to an electric generator.
In one embodiment the device according to the invention is placed on a vehicle.
In the following, the invention is illustrated by way of examples, which, however, are not in any way intended to limit the scope of the invention. It can be seen in Fig. 1 that a scalable embodiment of the system according to the invention is based on the 6 stainless steel tanks, in which mixing of the starting material and the reactions take place. In one embodiment all tanks, with the exception of F waste tank are equipped with a stirring blade, the veloctiy of which can be changed by the control panel. The agitation of the blades is ensured by a central hydrophor, which propels them with the help of oil circulation. The switch on and off of these equipments can also be managed from the control panel. In one embodiment all tanks, also with the exception of F waste tank are equipped with a computer controlled water inlet, which may be opened or closed manually, but automatic operation may also be configured. This is enabled by the pressure-gauge placed in the tanks, thanks to which we have information about the amount of the solution in the tanks (all of the tanks may be equipped with this pressure-gauge).
In one embodiment all of the tanks are equipped with an outlet opening with a two way valve (open/close), furthermore, three chemical-proof pumps enable the movement of the solutions between the tanks, as well as the obtaining of the product. These devices may also be operated centrally.
Furthermore, in one embodiment the production line is equipped with a gas tank container, a scaffold, from which the tanks are easily available for the operating personnel, an aggregator, from which, if desired, electricity may be obtained, furthermore, the above-mentioned computer, which displays the date in a touchscreen, and makes the control possible either manually, or in automatic operation.
The production line may be designed in such a way that it is able to produce the material according to the invention in the highest possible amount, however, it is still suitable to be placed onto a truck trailer or a compartment of a truck. By this the system may be transferred to the centrum of the contaminated area, and the material can be produced on the spot. This needs first of all electricity, which may be provided by an aggregator or may be produced by the transporting vehicle itself, which increases the mobility, and overcomes the problem of
dependence from the sources of the electric network. Another precondition is the permanent water supply. This may be done using running water, filtered well-water, or water transferred by a sevice unit. If these resources are at disposal, from the above-mentioned starting materials the end product can be prepared in the desired amount.
In one embodiment of the invention 200 liter water is pumped into the A tank according to Fig 1 using a computer, then deoxygenation starts by letting nitrogen gas in (the control unit of the system can open all inlet and outlet valves, pump the content of the tanks and switch on and off all stirring blades, thus all of these steps may be operated from the control panel). Similarly, 200-200 liter water is pumped into B and C tanks. The pre-determined amounts of ferrous-sulphate and copper-sulphate are added to A tank through the upper inlet opening, at the same time the agitation by the stirring blade placed in the tank is started, which helps the dissolution. Then sodium-hydroxide is added to B tank, also with stirring, then sodium- borohydride is placed into the same tank. Once the dissolution has finished, the content of A tank is pumped into D main reactor, which also possesses a nitrogen inlet. Then the content of B tank is pumped into the main reactor and at the same time stirring is started. While the reagents contact under permanent stirring, in the C tank addition and dissolution of sodium- ditionite takes place, which needs a few minutes. Thereafter this solution may also be pumped into the main reactor, then after adding the water needed to reach the final volume of the reaction mixture (300-400 liters), by increasing the intensity of the stirring, and permanent bubbling with nitrogen the 1 hour reaction starts. In the duration of this period of time amounts of the materials needed for the next production cycle may be determined, and the necessary amounts of water may be let in the stirring tanks (A, B, C). 10 to 15 minutes before the expiry of the one hour reaction time, the next solutions may be prepared in A and B tanks according to the above. After one hour the final nano-iron suspension should be pumped from D main reactor to E product tank. This tank is also equipped with a stirring blade, thus the collection of the product may be started with permanent stirring, and by connecting to the injection device. The time required is approximately the same as the time required for the new cycle. In the emptied D main reactor the suspension may be reconstituted in line with the above, and after the expiry of the reaction time the content of the E product tank may be refilled. This makes the injection continuous. The system may include an F waste tank, to which any kind of starting material or end product can be pumped in case of the break-down of the system, and the materials may be stored in it until the successful management of the
break-down. Beside this, all of the tanks are equipped with a bottom manual valve, which enables the discharge of the tanks in case of an emergency. The water supply of the production line may be ensured by water of any kind of origin, with a simple inlet. For the nitrogen gas supply the system is equipped with a scaffold, which can store three gas tanks, furthermore with a reductor, which is connected to the gas tanks through the gas tubes. The gas inlet of the tanks may be opened and closed by a manual valve.
Using the production line according to the invention, in line with the above description, a suspension with the desired concentration may be prepared. To achieve this, only the amount of the added materials should be changed, but it is possible to prepare an even more concentrated solution in D main reactor, then by pumping into the product tank the appropriate amount, and diluting it with water, any kind of concentrations can be ensured. In the following Table 1 the chemical need of some exemplary concentration is disclosed. Table 1 : Typical concentration values for the iron suspensions according to the invention
The effectiveness of the nano-iron suspension according to the invention is illustrated by the following examples. In the examples the analysis of the effects of nano-iron suspensions with 10000 ppm concentration was made after the injection of 2><3 m3 active agent. In the course
of the experiments a complex experimental plan was followed from the laboratory tests, until the analysis of the effectiveness of the field tests. During the preliminary laboratory tests, after the determination of the appropriate composition, the exact composition of the prepared suspension, the efficiency of the preparation and the reaction conditions were optimised. The results were tested first in a laboratory, then in possession of the acceptable results the designed upscaled suspension was prepared and tested in the predetermined test fields. In the experiments a sample was chosen that was more contaminated than the average, then in the field 6 m3 nano-iron suspension was prepared and injected under ground into different depths, in 2 parts (3-3 m3). To follow the results, underground water samples were taken from the treated area before the treatment, and one month afterwards. The results received were in line with the preliminary laboratory values, the prepared suspension was proven to be effective, which is best shown by the singificant decrease of the overall concentration of the chlorinated hydrocarbons. In summary, the average residual amount for every tested contaminants was 40.51 % of the starting value.
Preliminary laboratory tests
The results of the preliminary laboratory tests are illustrated in the following tables. Prior to the field tests, and after the development work has been finished, products with the selected composition and preparation process were tested by preparing 4 parallel sample lines, treating 4 different underground water samples.
Table 2: The results of the preliminary laboratory tests I.
Table 3: The results of the preliminary laboratory tests II.
B- serie
Efficiency (%)
Contaminant
X5 nZVI excess XI 0 nZVI excess X30 nZVI excess
VOCl 60.51 61.98 75.23
TCE 62.98 66.18 79.30
Table 4: The results of the preliminary laboratory tests III.
As the contaminant contents of the different underground water samples may have differed from each other, we received significantly not different results with a slight deviation. These were tested for the values of TCE (trichloro-ethylene) and VOCl (volume of overall chlorinated hydrocarbons). The excesses mean the excess needs as compared to the theoretical nano-iron requirement (if it is presumed that one iron atom can take part in one dechlorination cycle).
The results show our advanced nano-iron suspension decomposed the majority of the contaminants in one day. It can also be seen that the higher excess of the iron applied does not show a proportionally better result; this may be explained by the time consuming character of the decontamination process, it may last even for several weeks, which cannot be accelerated by the addition of higher amounts (in some cases this may result in unwanted extra costs).
In-situ chemical reduction (ISC ) field test (Torokszentmiklos, Hungary)
Three monitoring points were established in the test field (three channel CMT wells at each point, filtering different depth spaces). With the help of the monitoring points filtering different depths, the concentration change of the contaminant can be monitored. No injection point was needed, as the most efficient injection method for the in situ chemical decontamination is the spear injection, thus injection could be done in one point, but in different depth.
Table 6: Filtering of the CMT wells
The measurement of the baseline conditions consisted of the following investigations: measurements of the level of the underground water, VOC1, BTEX and chlorobenzene analytics, AVK measurements in 3 sample collection points, total Fe content measurement. The injection of the field was followed by the monitoring. The parameters to be measured included the following: measurements of the level of the underground water, VOC1, BTEX and chlorobenzene analytics, AVK measurements in 3 sample collection points, total Fe content measurement (photometric measurement, in each sample collection point). The total Fe analyses were made for the reason of the distance effect measuring, thus, the schedule of the soil sample collection monitoring is different for Fe from the measurement of the contamination. The injections had the following plan for the well filtered for different depths: in 24.5-25 m depth, 2x 1 m3 10 000 ppm nano-iron; in 18-19.5 m depth, 2* 1 m3 10 000 ppm nano-iron; in 9-9.5 m depth, 2x1 m3 10000 ppm nano-iron. The installation of the injection spear took place on the day of the injection. The field test (injection) is as follows: a) admixing of nano-iron; b) injection under pressure, approx. 55 liter/min yield; c) the redox potential changes in the surrounding wells should be monitored in the course of the injection of the nano-iron; d) once the nano-iron injection has been completed, at least 3 m3 water, in
the present case underground water, should be injected. To perform the field test, a device is also needed to push the injection spear under ground (25 m depth). The devices necessary for the injection and other field work are as follows, hose-pipes, flow-rate gauge, yield gauge, pumps, Eijkelkamp pump, stirring blade, tap water supply, coveralls, gloves, WTW, redox analyser, sample vials.
Monitoring of the field test
The redox potential should be continuously measured in the monitoring well during the injections as well. One hour after the completion of the injections (after the injection of water, too) the sample collection takes place. The scheduling of the total Fe measurements is the same as the schedule of the monitoring.
Evaluation of the results The graphs taken from the measured materials show the differences between the starting values (blue curve), and the second injection (red curve), respectively, as a function of the sample collection depths (4 to 28 metres). A summarizing table belongs to each graph containing the starting and the last measured values, furthermore the percent decrease of the original concentration (in some cases the increase of the concentration) during the given period of time.
Table 7: Summarizing data for Fig. 2
Vinyl-chloride g/L)
Well depth
4 6 9 13 15 19 22 25 28 (m)
2011.08.04 858 37700 23800 2550 1330 1760 633 108 1890
2011.09.16 26 15100 5310 487 100 169 118 40 87
Residual % 3.04 40.05 22.31 19.10 7.52 9.60 18.64 37.04 4.60
Table 8: Summarizing data for Fig. 3
Table 9: Summarizing data for Fig. 4
Table 11 : Summarizing data for Fig. 6
cis-dichloro-ethylene (g/L)
Well depth
4 6 9 13 15 19 22 25 28 (m)
2011.08.04 2320 227000 359000 44400 22200 9190 39100 24500 52300
2011.09.16 1710 96200 180000 87 11800 8700 18500 99 19100
Residual % 73.71 42.38 50.14 0.20 53.15 94.67 47.31 0.40 36.52
Table 12: Summarizing data for Fig. 7
Table 13: Summarizing data for Fig. 8
Table 15: Summarizing data for Fig. 10
Toluene
Well depth (m) 9 13 15 19 22 25 28
2011.08.04 424 3920 1390 442 4990 25400 2860
2011.09.07 224 571 71 79 4400 4780 8950
Residual % 52.83 14.57 5.11 17.87 88.18 18.82 312.94
Table 16: The amounts of the residual contaminants
The results obtained show the effectiveness of the injection. In the injection depths (10, 20, 25 metres) the decomposition of the contaminants is expressed, however, it can also be tracked in the spacing depths, which proves the movement of the small sized nanoparticles in the soil, which is otherwise heavy and thick. Beside this, the distribution of the contaminants is caused by the different density data of the contaminants, which results in the accumulation in the different segments of the soil. Industrial applicability
The ZVI nanoparticles according to the present invention are useful in a number of fields of the environmental technology, thus may be succesfully used for the decontamination of water, wastewaters or gas mixtures. By passing the nanoparticles directly under ground, chlorinated organic materials can effectively be decomposed. The technology is very promising in the field of immobilization of heavy metals (e.g. Cr(VI), Hg2+ es Ni2+) and radionuclides(U02 2+), furthermore, may be used for the decontamination of poly-chlorinated byphenyls (PCB), pesticides (e.g. DDT), nitro-aromatic compounds or perchlorates. Among the decontaminated compounds there can be found solvents and chemical raw materials, such as perchloro- ethylene (PCE), trichloro-ethylene (TCE), carbon-tetrachloride (CT) and vinyl-chloride (VC) is. These materials pose a serious threat for the quality of the underground water, especially in the industrialized countries.
Claims
1. An aqueous iron suspension comprising solid iron particles in the nanometer size range, which is prepared from ferrous-sulphate (FeS04); copper-sulphate (CuS04), a reducing agent, preferably sodium-ditionite (Na2S204), and/or sodium-borohydride (NaBFLj); sodium- hydroxide (NaOH); and optionally one or more additive(s) selected from the group consisting of polyvnyl-pirrolidone, preferably PVP-K30 or PVP-K90, and as co-metal PdCl2 x2H20.
2. The iron suspension according to Claim 1, whose concentration is 1000, 3000, preferably 5000 or 10000 ppm (mg/dm3).
3. The iron suspension according to Claim 1 or 2, which comprises as additive 1 g polyvinyl- pirrolidone based on 1 ppm concentration.
4. The iron suspension according to Claims 1 to 3, wherein the weight proportion of the components is the following: FeS04:Na2S20 :NaBH4:CuS04 = 5:3.95:2.25:0.068:0.26, and the amount of PdCl2><2H20 is 1.0-0.01% based on the moles of the metal iron.
6. A process for the preparation of the aqueous iron suspension comprising solid iron particles in the nanometer size range, according to Claims 1 to 5, characterized in that the following steps are taken:
a) an aqueous solution comprising as starting materials aqueous ferrous-sulphate (FeS04) or hydrated ferrous-sulphate (FeS04x7¾0); sodium-ditionite (Na2S204); sodium-borohydride (NaBFLt); sodium-hydroxide (NaOH) and hydrated copper-sulphate (CuS04x5H20) is prepared;
b) the reaction mixture according to step a) is reacted for 0.1-10, preferably approximately for 1 hour, optionally with stirring; and
c) the slurry-like product is obtained, and optionally the process is one or more times repeated.
7. The process according to Claim 6, characterized in that step a) is proceeded in such a way that
a) the ferrous-sulphate, previously or optionally during the dissolution bubbled with N2 gas and optionally copper-sulphate is measured into a tank optionally equipped with stirrer and relief valve;
b) the sodium-hydroxide is measured into a tank optionally equipped with stirrer and relief valve, which is separated from the tank mentioned in point a);
c) the sodium-borohydride simultaneously with or separated in time from, preferably prior to the sodium-ditionite, is dissolved in a tank optionally equipped with stirrer and relief valve, optionally simultaneously with the steps according to points a) and b);
d) optionally the additives are added to the reaction mixture at any of steps a) to c);
e) following the dissolution according to points a) to d) the content of the tanks according to points a) to c) is transferred to an optionally stirred main reactor, preferably by pumping, preferably in such a way that first the ferrous-sulphate, and optionally the copper-sulphate, then the sodium-hydroxide, then, preferably a few minutes later, the solution according to point c) is charged into the main reactor;
f) the reaction mixture according to step e) is reacted for approximately 1 hour;
g) the reaction mixture according to step f) is transferred, preferably by pumping into an optionally stirred product tank, from where the product is preferably in one hour obtained; and h) if desired, the steps according to points a) to f) are one or more times repeated.
8. Use of of the aqueous iron suspension comprising solid iron particles in the nanometer size range according Claims 1 to 5 for decontamination, preferably for the decontamination of water, waste water, or gas mixtures, more preferably for the removal of chlorine containing organic materials, heavy metals, and radionuclides, more preferably for the decontamination of poly-chlorinated biphenyls (PCB), solvents and chemical raw materials, such as perchloro- ethylene (PCE), trichloro-ethylene (TCE), carbon-tetrachloride (CT) and vinyl-chloride (VC), benzene, toluene, pesticides, especially DDT, a nitro-aromatic compounds or perchlorates.
9. A device for the preparation of the aqueous iron suspension comprising solid iron particles in the nanometer size range according to Claims 1 to 5, which device comprises:
- a first tank (A) suitable for containing ferrous-sulphate and/or copper-sulphate, optionally equipped with a stirrer and relief valve;
- a second tank (B) suitable for containing a reducing agent, optionally equipped with a stirrer, inlet opening and and relief valve;
- a third tank (D) suitable for containing sodium-hydoxide, optionally equipped with a stirrer, inlet opening and relief valve;
- a reactor tank (D) connected to second tank (B) and third tank (C) by a chemical pipe equipped with an interlocking device;
- an product tank (E) connected to the reactor tank (D) by a chemical pipe equipped with interlocking devices;
- a waste tank (F) connected to the first tank (A), the second tank (B), the third tank (C), the reactor tank (D) and the product tank (E) by a chemical pipe equipped with an interlocking device;
- a water source (G) connected to the first tank (A), the second tank (B), the third tank (C), the reactor tank (D) and the product tank (E) by a chemical pipe equipped with an interlocking device;
- a gas tank suitable for storing wash gas connected at least to the reactor tank (D) by a gas tube.
10. The device according to Claim 9, characterized in that the device is further equipped with an additive tank (H) connected to the reactor tank (D) by a chemical pipe equipped with an interlocking device.
11. The device according to Claim 10, characterized in that the tanks (A, B, C, D, E, F and H) are equipped with a stirring blade and a stirring engine.
12. The device according to Claim 1 1, characterized in that the stirring engines are connected to an electric generator.
13. The device according to Claim 12, characterized in that the device is placed on a vehicle.
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EP13882945.2A EP2989056B1 (en) | 2013-04-26 | 2013-04-29 | Process for the preparation of a nanoiron suspension |
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HU1300265A HU230721B1 (en) | 2013-04-26 | 2013-04-26 | Process for preparation of nano-iron suspension and installation for it's preparation |
HUP1300265 | 2013-04-26 |
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CN107081433A (en) * | 2017-05-15 | 2017-08-22 | 轻工业环境保护研究所 | A kind of Nanoscale Iron medicament is prepared and injection synchronous integrated equipment in situ |
WO2017197310A1 (en) * | 2016-05-13 | 2017-11-16 | University Of Maryland | Synthesis and functionalization of highly monodispersed iron and iron core/iron oxide shell magnetic particles with broadly tunable diameter |
CN109897954A (en) * | 2019-03-27 | 2019-06-18 | 东北师范大学 | A kind of purification process for cold rolling iron cement |
EP3546055A1 (en) * | 2018-03-28 | 2019-10-02 | ABB Schweiz AG | Method for decomposing a fluoroketone into disposable decomposition products |
WO2022207018A1 (en) * | 2021-03-29 | 2022-10-06 | Univerzita Palackeho V Olomouci | Zerovalent iron nanoparticles stabilized against oxidation and method of preparation thereof |
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WO2017197310A1 (en) * | 2016-05-13 | 2017-11-16 | University Of Maryland | Synthesis and functionalization of highly monodispersed iron and iron core/iron oxide shell magnetic particles with broadly tunable diameter |
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US20220250147A1 (en) * | 2016-05-13 | 2022-08-11 | University Of Maryland, College Park | Synthesis and Functionalization of Highly Monodispersed Iron and Core/Iron Oxide Shell Magnetic Particles With Broadly Tunable Diameter |
CN107081433A (en) * | 2017-05-15 | 2017-08-22 | 轻工业环境保护研究所 | A kind of Nanoscale Iron medicament is prepared and injection synchronous integrated equipment in situ |
EP3546055A1 (en) * | 2018-03-28 | 2019-10-02 | ABB Schweiz AG | Method for decomposing a fluoroketone into disposable decomposition products |
WO2019185727A1 (en) * | 2018-03-28 | 2019-10-03 | Abb Schweiz Ag | Method for decomposing a fluoroketone into disposable decomposition products |
CN109897954A (en) * | 2019-03-27 | 2019-06-18 | 东北师范大学 | A kind of purification process for cold rolling iron cement |
WO2022207018A1 (en) * | 2021-03-29 | 2022-10-06 | Univerzita Palackeho V Olomouci | Zerovalent iron nanoparticles stabilized against oxidation and method of preparation thereof |
Also Published As
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EP2989056A4 (en) | 2017-05-03 |
EP2989056B1 (en) | 2021-02-24 |
EP2989056A1 (en) | 2016-03-02 |
HU230721B1 (en) | 2017-11-28 |
HUP1300265A2 (en) | 2014-10-28 |
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