WO2001028927A1 - Stabilised mixed ferrates and synthesis method thereof - Google Patents

Stabilised mixed ferrates and synthesis method thereof Download PDF

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WO2001028927A1
WO2001028927A1 PCT/FR2000/002850 FR0002850W WO0128927A1 WO 2001028927 A1 WO2001028927 A1 WO 2001028927A1 FR 0002850 W FR0002850 W FR 0002850W WO 0128927 A1 WO0128927 A1 WO 0128927A1
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Prior art keywords
ferrates
ferrous
synthesis
mixed
gas
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PCT/FR2000/002850
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French (fr)
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Cécile JEANNOT
Anne Lechaudel
Omer Evrard
Bernard Dupre
Nathalie Neveux
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Centre International De L'eau - Nan.C.I.E.
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Priority to EP00968029A priority Critical patent/EP1230161A1/en
Priority to AU77999/00A priority patent/AU7799900A/en
Priority to JP2001531722A priority patent/JP2003523912A/en
Publication of WO2001028927A1 publication Critical patent/WO2001028927A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/0018—Mixed oxides or hydroxides
    • C01G49/0081—Mixed oxides or hydroxides containing iron in unusual valence state [IV, V, VI]

Definitions

  • the present invention relates, as new products, to stabilized mixed ferrates
  • a subject of the invention is also a process for the synthesis of said ferrates. Whatever the method of synthesis used, wet or dry, the literature does not cite any crystallized sodium ferrate.
  • Said synthetic route allows the production of a stabilized ferrate corresponding to the general formula M (Fe, X) 0 4 , an example of which is K 2 (Fe, S) 0
  • Such a synthesis process is based on the mixture of three solids _ ⁇ - a ferrous or fer ⁇ que iron salt such as FeS0, 7H 2 0 - an oxidant such as Ca (CIO) 2 a strong base such as KOH
  • the stabilization of Fe0 4 by S0 4 materializes by the formation of a solid solution between K 2 Fe0 4 and K 2 S0 4 which are isomorphic and which have neighboring lattice parameters
  • the present invention relates to ferrates stabilized mixed by the valence of iron, these ferrates include valences (+ V) and (+ VI), mixed by the nature of the cation associated with ferrate substitution of monovalent metals group by other monovalent metal or divalent metal
  • Stabilizing said ferrates is effected by partial substitution of iron oxidation degree by a permanent cation (having the electronic structure of a rare gas) as well as the effect of other stabilizers such as radical OH
  • the invention relates to the general formula ferrates
  • the main objective of the present invention is the use of ferrates in the treatment of drinking water where the tolerated sodium doses are ten times greater than those relating to potassium hence the need to synthesize a ferrate (VI) or (V ) solid sodium
  • KFe0 2 requires a synthesis temperature of 800-900 ° C
  • the present invention further provides a method of synthesizing mixed ferrates by the dry process at room temperature.
  • the method of synthesis of said invention consists of a mixture of a ferrous or fer ⁇ que salt with a solid or gaseous oxidant and a strong base, alkali hydroxide MiOH or alkaline earth M ⁇ (OH) ? or a mixture of the two in proportions different from those given by the reaction stoichiometry (1)
  • the oxidant / iron ratio making it possible to obtain a ferrate (VI) or a mixed salt Fe (VI) -Fe (V)
  • the iron salt is ferrous called ferrous sulfate lo partially dehydrated by wearing at 125 ° C of ferrous sulfate heptahydrate, by-product of the titanium industry (production T ⁇ 0 2) or the steel pickling with acid sulfu ⁇ que
  • the ferrous sulfate used in the synthesis has the formula 15 FeS0 4 , nH 2 0 with 1 ⁇ n ⁇ 7
  • Fe (VI) is stabilized by S (VI) which is part of the composition of the ferrate but unlike a potassium ferrate where K 2 (Fe, S) 0 is stable, Na 2 (Fe, S) 0 4 n ' is not stable and it requires a more basic medium to be able to be preserved This stabilization is ensured by the presence of hydroxyl ions in the sodium ferrate 0
  • S (VI) which is part of the composition of the ferrate but unlike a potassium ferrate where K 2 (Fe, S) 0 is stable, Na 2 (Fe, S) 0 4 n ' is not stable and it requires a more basic medium to be able to be preserved This stabilization is ensured by the presence of hydroxyl ions in the sodium ferrate 0
  • These new basic sodium ferrates correspond to the general formula
  • the products according to the invention find a particularly advantageous application in the treatment of water, in particular but not hmitatively in the following fields disinfection of urban wastewater, decontamination of water containing fungicides, reduction of heavy metals, phenols, oxidation of cyanides, action on COD, TSS and turbidity,

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compounds Of Iron (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention concerns ferrates of formula: M1<+>(3-a)xM2<+>(3-a)1-x[(Fe<6+>y, X<6+>1-y)a,(Fe<5+>z, Y<5+>1-z)1-a]O4 or M1<+>(3-a)bM3<++>(3-a)(1-b)/2[(Fe<6+>y, X<6+>1-y)a, (Fe<5+>z, Y<5+>1-z)1-a]O4-w(OH)2w wherein: 0<a</=1; 0</=x</=1 and 0</=b</=1; 0<y<1 and 0<z<1; 0</=w<2. The invention also concerns a method for synthesizing said ferrates.

Description

Fo r r.i t e s m i x t e s s t a b i l i se s e t n uir t'dc nou r l eu r syn t hèse .For r es t esmix t ess t abili se setn uir t'dc nou rl eu r syn t hèse.
La présente invention a pour objet, à titre de produits nouveaux, des ferrâtes mixtes stabilisésThe present invention relates, as new products, to stabilized mixed ferrates
L'invention a également pour objet un procédé pour la synthèse desdits ferrâtes 5 Quelque soit la méthode de synthèse utilisée, voie humide ou voie sèche, la littérature ne cite aucun ferrate de sodium cristalliséA subject of the invention is also a process for the synthesis of said ferrates. Whatever the method of synthesis used, wet or dry, the literature does not cite any crystallized sodium ferrate.
Les brevets antérieurs font état de la synthèse de K?Fe04 après oxydation en solution aqueuse fortement alcaline d'un sel de fer ferπque par le chlore ou une solution d'hypochloπte de sodium puis K Feθ est précipité à l'aide d'ajout 10 d'hydroxyde de potassiumPrevious patents state the synthesis of K ? Fe0 4 after oxidation in strongly alkaline aqueous solution of an iron salt ferπque by chlorine or a solution of sodium hypochloπte then K Feθ is precipitated using 10 addition of potassium hydroxide
Ce mode de synthèse présente des inconvénients majeurs, à savoir le ferrate (VI) oxyde l'eau quelque soit le pH et une synthèse en solution aqueuse affecte le rendement de reaction , la précipitation de K2Fe0 nécessite des quantités très importantes d'hydroxyde i > de potassium, ce qui entraîne un surcoût important , le ferrate de potassium n'est pas stable dans le temps et requiert des conditions particulières de stockageThis synthesis method has major drawbacks, namely ferrate (VI) oxidizes water whatever the pH and synthesis in aqueous solution affects the reaction yield, the precipitation of K 2 Fe0 requires very large amounts of hydroxide. i> potassium, which leads to a significant additional cost, potassium ferrate is not stable over time and requires special storage conditions
De ce fait, une telle synthèse ne peut être applicable industriellement Pour tenter d'y remédier, le brevet européen EP-A- 0 504 156 propose un 20 mode de synthèse de ferrâtes (VI ) stabilises par voie sèche à température ambianteTherefore, such a synthesis cannot be applied industrially. In an attempt to remedy it, the European patent EP-A-0 504 156 proposes a mode of synthesis of ferrates (VI) stabilized by dry process at room temperature.
Ladite voie de synthèse permet de produire un ferrate stabilisé répondant a la formule générale M(Fe,X)04 dont un exemple est K2(Fe, S)0Said synthetic route allows the production of a stabilized ferrate corresponding to the general formula M (Fe, X) 0 4 , an example of which is K 2 (Fe, S) 0
Un tel procédé de synthèse est base sur le mélange de trois solides _ ^ - un sel de fer ferreux ou ferπque tel FeS0 , 7H20 - un oxydant tel Ca(CIO)2 une base forte telle KOHSuch a synthesis process is based on the mixture of three solids _ ^ - a ferrous or ferπque iron salt such as FeS0, 7H 2 0 - an oxidant such as Ca (CIO) 2 a strong base such as KOH
Le mélange de ces trois réactifs s'opère dans les conditions stoechiométπques données par l'équation ( 1 )The mixture of these three reactants s' operates in the stoechiométπques conditions given by equation (1)
' FeSO, 7H20 + Ca(CIO)2 Ca(OH)2 + 6KOH -> 2 Fβo sSo sJO, +2 KCI + 2Ca(OH)2 + 9H20'FeSO, 7H 2 0 + Ca (CIO) 2 Ca (OH) 2 + 6KOH -> 2 Fβo sSo sJO, +2 KCI + 2Ca (OH) 2 + 9H 2 0
La stabilisation de Fe04 par S04 = se matérialise par la formation d'une solution solide entre K2Fe04 et K2S04 qui sont isomorphes et qui possèdent des paramètres de maille voisinsThe stabilization of Fe0 4 by S0 4 = materializes by the formation of a solid solution between K 2 Fe0 4 and K 2 S0 4 which are isomorphic and which have neighboring lattice parameters
Néanmoins, par simple substitution de la potasse par la soude dans les -. ^ conditions données par l'équation ( 1 ), il est impossible de produire un ferrate (VI) de sodium stable L'invention a pour objet de remédier à cet inconvénient, le besoin se faisant sentir de ferrâtes stabilisés pour des applications industrielles spécifiques La présente invention a pour objet des ferrâtes stabilisés mixtes par la valence du fer ces ferrâtes incluent les valences (+V) et (+VI) , mixtes par la nature du cation associé au groupement ferrate substitution de métaux monovalents par d'autres métaux monovalents ou par des métaux divalentsNevertheless, by simple substitution of potash by soda in the -. ^ conditions given by equation (1), it is impossible to produce a stable sodium ferrate (VI) The object of the invention is to remedy this drawback, the need being felt for ferrates stabilized for specific industrial applications The present invention relates to ferrates stabilized mixed by the valence of iron, these ferrates include valences (+ V) and (+ VI), mixed by the nature of the cation associated with ferrate substitution of monovalent metals group by other monovalent metal or divalent metal
La stabilisation desdits ferrâtes s'opère par substitution partielle du fer a haut degré d'oxydation par un cation stable (possédant la structure électronique d'un gaz rare) ainsi que par l'effet d'autres stabilisants tels que le radical OHStabilizing said ferrates is effected by partial substitution of iron oxidation degree by a permanent cation (having the electronic structure of a rare gas) as well as the effect of other stabilizers such as radical OH
Plus précisément, l'invention a pour objet des ferrâtes de formule généraleMore specifically, the invention relates to the general formula ferrates
M, Va),M/0.a),xl
Figure imgf000003_0001
,.,]04 ouM, V a) , M / 0 . a) , x l
Figure imgf000003_0001
,.,] 0 4 or
1 + (3 a)bM3 ++ (3-aκ , -b)/2[ (Fe6+ y,X6+ I .y)a,(Fe5+ 2,Y5+,z) 1.a]04.w (OH)2. selon la structure du métal substitué, dans lesquelles Mi* est un métal monovalent, Mιv* est un métal divalent, 1 + (3 a) b M 3 ++ (3 - a κ, - b) / 2 [(Fe 6+ y , X 6+ I .y ) a , (Fe 5+ 2 , Y 5+ , z ) 1 . a ] 0 4 . w (OH) 2 . depending on the structure of the substituted metal, in which Mi * is a monovalent metal, Mι v * is a divalent metal,
- C a≤l - O≤x≤l et 0<b≤1- C a≤l - O≤x≤l and 0 <b≤1
- 0<y<l et 0<z<l- 0 <y <l and 0 <z <l
- 0≤w<2- 0≤w <2
Le principal objectif de la présente invention est l'utilisation des ferrâtes dans le traitement des eaux potables où les doses tolérées en sodium sont dix fois plus importantes que celles relatives au potassium d'où la nécessité de synthétiser un ferrate (VI) ou (V) de sodium solideThe main objective of the present invention is the use of ferrates in the treatment of drinking water where the tolerated sodium doses are ten times greater than those relating to potassium hence the need to synthesize a ferrate (VI) or (V ) solid sodium
Si l'on regarde les différents degrés d'oxydation du fer, il apparaît que les composés solides sodés sont preferentiellement à des degrés d'oxydation faibles tandis que le potassium préfère les hauts degrés d'oxydation - Ferrites (III) Na Fe02 synthétisé à température ambiante ,If we look at the different degrees of oxidation of iron, it appears that the solid sodium compounds are preferentially at low degrees of oxidation while potassium prefers the high degrees of oxidation - Ferrites (III) Na Fe0 2 synthesized at room temperature,
KFe02 requiert une température de synthèse de 800-900°CKFe0 2 requires a synthesis temperature of 800-900 ° C
- Ferrâtes (IV) Na4Fe04 synthétisé à 380°C ,- Ferrates (IV) Na 4 Fe0 4 synthesized at 380 ° C,
K4Fe04 jamais observé ,K 4 Fe0 4 never observed,
- Ferrâtes (V) aucun ferrate V de sodium ni de potassium , - Ferrâtes (VI) K2Fe0 connu ,- Ferrates (V) no ferrate V of sodium or potassium, - Ferrates (VI) K 2 Fe0 known,
Na2Fe04 jamais observé La présente invention propose en outre un mode de synthèse de ferrâtes mixtes par voie sèche a température ambianteNa 2 Fe0 4 never observed The present invention further provides a method of synthesizing mixed ferrates by the dry process at room temperature.
Le procédé de synthèse de ladite invention consiste en un mélange d'un sel ferreux ou ferπque avec un oxydant solide ou gazeux et une base forte, hydroxyde 5 d'alcalin MiOH ou d'alcalino-terreux Mι(OH)? ou un mélange des deux dans des proportions différentes de celles données par la stoechiométπe de réaction (1 ) Le rapport oxydant/fer permettant d'aboutir à un ferrate (VI) ou à un sel mixte Fe (VI )-Fe(V)The method of synthesis of said invention consists of a mixture of a ferrous or ferπque salt with a solid or gaseous oxidant and a strong base, alkali hydroxide MiOH or alkaline earth Mι (OH) ? or a mixture of the two in proportions different from those given by the reaction stoichiometry (1) The oxidant / iron ratio making it possible to obtain a ferrate (VI) or a mixed salt Fe (VI) -Fe (V)
Le sel de fer ferreux préconisé est du sulfate ferreux partiellement l o déshydraté en portant à 125° C du sulfate ferreux heptahydraté, sous-produit de l'industrie du titane (production de Tι02) ou du décapage de l'acier à l'acide sulfuπqueThe iron salt is ferrous called ferrous sulfate lo partially dehydrated by wearing at 125 ° C of ferrous sulfate heptahydrate, by-product of the titanium industry (production Tι0 2) or the steel pickling with acid sulfuπque
Apres déshydratation partielle, le sulfate ferreux utilisé dans la synthèse a comme formule 15 FeS04,nH20 avec 1 ≤n<7After partial dehydration, the ferrous sulfate used in the synthesis has the formula 15 FeS0 4 , nH 2 0 with 1 ≤n <7
FeS04,nH20 est alors mélangé à un oxydant solide, l'hypochloπte de calcium et à de la soude dans les proportions minimales données par l'équation (2) ExempleFeS0 4, nH 2 0 is then mixed with a solid oxidant, the hypochloπte calcium and sodium hydroxide in the minimum percentages given by equation (2) Example
Mélange à température ambiante dans un réacteur rotatif de 0 - 100 parties molaires de FeS04,nH20Mixing at room temperature in a rotary reactor of 0 - 100 molar parts of FeS0 4 , nH 2 0
- 200 parties molaires de Ca(CIO)2, Ca(OH)2 - 200 molar parts of Ca (CIO) 2 , Ca (OH) 2
1000 parties molaires de NaOH selon la stoechiométπe de réaction (2)1000 molar parts of NaOH according to the reaction stoichiometry (2)
FeS04,nH20 + 2 Ca(CIO)2,Ca(OH)2 + 10 NaOH -> 2 Na3(Feo 5So 5)04(OH) + 4 NaCI 5 + 2Ca(OH)2 + (n+2)H20FeS0 4 , nH 2 0 + 2 Ca (CIO) 2 , Ca (OH) 2 + 10 NaOH -> 2 Na 3 (Feo 5 So 5 ) 0 4 (OH) + 4 NaCI 5 + 2Ca (OH) 2 + ( n + 2) H 2 0
Fe(VI) est stabilisé par S(VI) qui rentre dans la composition du ferrate mais à la différence d'un ferrate potassique où K2(Fe,S)0 est stable, Na2(Fe,S)04 n'est pas stable et il nécessite un milieu plus basique pour pouvoir être conservé Cette stabilisation est assurée par la présence d'ions hydroxyle dans le ferrate sodé 0 Ces nouveaux ferrâtes basiques de sodium répondent à la formule généraleFe (VI) is stabilized by S (VI) which is part of the composition of the ferrate but unlike a potassium ferrate where K 2 (Fe, S) 0 is stable, Na 2 (Fe, S) 0 4 n ' is not stable and it requires a more basic medium to be able to be preserved This stabilization is ensured by the presence of hydroxyl ions in the sodium ferrate 0 These new basic sodium ferrates correspond to the general formula
Nax+2 (FeyS 1.y)O4(OH)x Avec x≤1 et un rapport molaire Na/Fe>4Na x + 2 (Fe y S 1. Y ) O 4 (OH) x With x≤1 and a Na / Fe molar ratio> 4
Les produits selon l'invention trouvent une application particulièrement 5 intéressante dans le traitement de l'eau, en particulier mais non hmitativement dans les domaines suivants désinfection des eaux residuaires urbaines, décontamination des eaux contenant des fongicides, abattement des métaux lourds, phénols, oxydation des cyanures, action sur la DCO, les MES et la turbidité, The products according to the invention find a particularly advantageous application in the treatment of water, in particular but not hmitatively in the following fields disinfection of urban wastewater, decontamination of water containing fungicides, reduction of heavy metals, phenols, oxidation of cyanides, action on COD, TSS and turbidity,

Claims

REVENDICATIONS
1 Ferrâtes ayant pour formule1 Ferrâtes having formula
M * a),M2 aM-*l (Fe6 X6 ' , y)a,(Fc '„Y5 t , ,), O, ouM * a) , M 2 a M - * l (Fe 6 X 6 ' , y ) a , (Fc ' „Y 5 t,, ), O, or
M (3.a)bM3 ++ (3.a,(..bV2[ ( e6+ y,X6+ ,
Figure imgf000006_0001
Z), .JO,W (OH)2M i o dans lesquellesM (3. A) b M 3 ++ (3. A , ( .. bV2 [(e 6+ y , X 6+ ,
Figure imgf000006_0001
Z ), .JO, W (OH) 2M io in which
M, et M2 sont un cation de métal monovalentM, and M 2 are a monovalent metal cation
M3 est un cation de métal divalentM 3 is a divalent metal cation
X et Y sont des cations stables possédant la structure électronique d'un gaz rare substituant partiellement Fe6+ et Fe5+ 15 - 0<a≤lX and Y are stable cations with the electronic structure of a rare gas partially substituting Fe 6+ and Fe 5+ 15 - 0 <a≤l
- O≤x≤l et O≤b≤l- O≤x≤l and O≤b≤l
- 0<y<l et 0<z<l- 0 <y <l and 0 <z <l
- 0≤w<2- 0≤w <2
2 Ferrâtes selon la revendication 1 , caractérisés en ce que la rapport molaire 0 Mι/Fe>42 Ferrates according to claim 1, characterized in that the molar ratio 0 Mι / Fe> 4
3 Procédé pour la synthèse de ferrâtes selon l'une quelconque des revendications 1 et 2, caractérisé en ce qu'il est conduit par voie sèche à température ambiante, et qu'il consiste à mélanger un sel ferreux ou ferπque avec un oxydant solide ou gazeux et une base forte, hydroxyde d'alcalin MiOH ou 5 d'alcalino-terreux Mi(OH) ou un mélange des deux hydroxydes dans des proportions différentes de celles données par la stoechiométπe de réaction.3 A method for the synthesis of ferrates according to any one of claims 1 and 2, characterized in that it is carried out dry at room temperature, and that it consists in mixing a ferrous or ferπque salt with a solid oxidant or gas and a strong base, alkali hydroxide or MiOH 5 of alkaline earth Mi (OH) or a mixture of the two hydroxides in different proportions from those given by the reaction of stoechiométπe.
4 Procédé selon la revendication 3, caractérisé en ce que le sel de fer ferreux est du sulfate ferreux partiellement déshydraté en portant à 125°C du sulfate ferreux heptahydraté. 0 5 Procédé selon l'une quelconque des revendications 3 et 4, caractérisé en ce que l'oxydant solide est l'hypochloπte de calcium 6 Procédé selon l'une quelconque des revendications 3 et 4, caractérisé en ce que l'oxydant gazeux est du chlore 4 Method according to claim 3, characterized in that the ferrous iron salt is partially dehydrated ferrous sulfate by bringing to 125 ° C ferrous sulfate heptahydrate. 0 5 Process according to any one of Claims 3 and 4, characterized in that the solid oxidizing agent is calcium hypochlorite 6 Process according to any one of Claims 3 and 4, characterized in that the oxidizing gas is chlorine
PCT/FR2000/002850 1999-10-22 2000-10-13 Stabilised mixed ferrates and synthesis method thereof WO2001028927A1 (en)

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EP00968029A EP1230161A1 (en) 1999-10-22 2000-10-13 Stabilised mixed ferrates and synthesis method thereof
AU77999/00A AU7799900A (en) 1999-10-22 2000-10-13 Stabilised mixed ferrates and synthesis method thereof
JP2001531722A JP2003523912A (en) 1999-10-22 2000-10-13 Stable ferrate mixtures and their synthesis

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FR99/13390 1999-10-22
FR9913390A FR2800057B1 (en) 1999-10-22 1999-10-22 STABILIZED MIXED FERRATES AND METHOD FOR THEIR SYNTHESIS

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2908128A1 (en) * 2006-11-08 2008-05-09 Stradia Sa PROCESS FOR THE PREPARATION OF ALKALI METAL FERRATES

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4405573A (en) * 1981-12-17 1983-09-20 Olin Corporation Process for preparing potassium ferrate (K2 FeO4)
EP0354843A1 (en) * 1988-08-09 1990-02-14 Socadour Process for the preparation of alkyl or alkaline earth ferrates by the solid phase
US5284642A (en) * 1989-11-08 1994-02-08 Centre International De L'eau De Nancy (Nan.C.I.E.) Alkali or alkaline earth metal ferrates, their preparation and their industrial applications

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4405573A (en) * 1981-12-17 1983-09-20 Olin Corporation Process for preparing potassium ferrate (K2 FeO4)
EP0354843A1 (en) * 1988-08-09 1990-02-14 Socadour Process for the preparation of alkyl or alkaline earth ferrates by the solid phase
US5284642A (en) * 1989-11-08 1994-02-08 Centre International De L'eau De Nancy (Nan.C.I.E.) Alkali or alkaline earth metal ferrates, their preparation and their industrial applications

Non-Patent Citations (2)

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Title
CHEMICAL ABSTRACTS, vol. 132, no. 16, 17 April 2000, Columbus, Ohio, US; abstract no. 209831, NEVEUX: "synthesis of stabilized potassium ferrate" XP002140593 *
REWAS, vol. 3, 1999, pages 2417 - 2427 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2908128A1 (en) * 2006-11-08 2008-05-09 Stradia Sa PROCESS FOR THE PREPARATION OF ALKALI METAL FERRATES
WO2008065279A2 (en) * 2006-11-08 2008-06-05 Stradia Method for preparing alkali metal ferrates
WO2008065279A3 (en) * 2006-11-08 2008-07-31 Stradia Method for preparing alkali metal ferrates

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