WO1992000808A1 - Method of intercalation of perovskitic particles in the form of pillars into layered clays - Google Patents

Method of intercalation of perovskitic particles in the form of pillars into layered clays Download PDF

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WO1992000808A1
WO1992000808A1 PCT/GR1991/000010 GR9100010W WO9200808A1 WO 1992000808 A1 WO1992000808 A1 WO 1992000808A1 GR 9100010 W GR9100010 W GR 9100010W WO 9200808 A1 WO9200808 A1 WO 9200808A1
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perovskitic
clay
montmorillonite
fsaen
pillars
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PCT/GR1991/000010
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French (fr)
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Philip Pomonis
Stelios Skaribas
Athanasios Ladavos
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Philip Pomonis
Stelios Skaribas
Athanasios Ladavos
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Publication of WO1992000808A1 publication Critical patent/WO1992000808A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/049—Pillared clays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C01B33/40—Clays
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
    • C01G45/1264—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3 containing rare earth, e.g. La1-xCaxMnO3, LaMnO3
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/70—Cobaltates containing rare earth, e.g. LaCoO3
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/70—Nickelates containing rare earth, e.g. LaNiO3
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC

Definitions

  • This invention is referred to a process of intercallation of perovskitic pillars of different composition into swelling clays and the products obtained from such a process.
  • Clays are minerals, abundant in nature, which are used in different applications like for example catalysts and sorbents as well as in different household goods of extensive use like washing machine powders.
  • Of special interest between the clays appear those which possess the ability to swell with adsorption, or absorption, between their aluminosilicate layers of different molecules like water or other chemical compounds.
  • a swelling clay and especially of Na Montmorillonite, is shown.
  • the process of intercalation takes usually place by using different hydroxy-polymers like those of Al, Fe and La, which are mixed with the clay and in a pre-set pH value are inserted into the layers. Then the hydroxy-polymers are dehydrated by heating and leave between the clay layers pillars of the corresponding oxide. In some cases it has been successfully achieved the introduction of two different discrete pillars into the layers of the clay, Le. A10 x and FeO y . Such pillared forms of clays, with one or two discrete oxidic pillars between their layers, are shown in fig.2.
  • SUBSTITUTE SHEET compound forms complexes of the type M(phen)2 + 3 which are inserted between the layer and are decomposed by heating at 350°C. At this point a collapse of layers is observed.
  • the nano-particles which were successfully intercallated in this work between the clay layers were of the form ABO x and they possess the structure of perovskite ABO 3 or its relative structure A2BO 4 (fig.3).
  • the structure A2BO 4 is originated from structure ABO 3 , which characterizes the typical perovskites, if between the layers ABO3 units of AO are inserted .
  • Such materials ABO3 an/or A2BO4 appear tremendous technological applications as burning catalysts.piezocrystals, superconductors etc.
  • thermographs both of ALa(fsaen)N ⁇ 3 .xH 2 ⁇ ,as well as of the pillared ALa(fsaen)N ⁇ 3 .xH 2 ⁇ - Montmorillonite , a thermalbalance TRDA3H of the CHYO BALANCE COORPORATION controlled by a PC was used with simultaneous recording of T, TG, DTG and DTA signals.
  • the amount of samples used was in each case around lOOmgr in platinum cruciblesAs a blank 0--AI 2 O 3 was used.
  • CoLa(fsaen)N ⁇ 3 .H 2 ⁇ shows a complete loss of organic part at 520°C.
  • the total loss observed in the thermobalance is 63.9% as compared to 63.3% which is the theoretical loss according to the reaction :
  • the methods of synthesis of perovskites used up to now are the nitrate and the citrate one.
  • the mixture of nitrate salts of the corresponding metals is heated up to 1100°C for different hours and thus the perovskite phase is formed.
  • citric acid is added in the mixture of nitrate salts for the possible complexation of the corresponding metal ion. Then by heating at 800-900°C perovskites are obtained.
  • Perovskites are also formed by heating of oxides in molten mixtures with NaOH as well as by the method of sol-gel.
  • the present method by the. use of binuclear complexes, results in formation of perovskites at lower temperatures, around 500-600°C.
  • Montmorillonite The pillared clays Montmorillonite-ALa(fsaen) were tested in a thermobalance under conditions similar to those described previously for pure complexes. Two such thermographs for the materials CoLa(fsaen)- Montmorillonite and MnLa(fsaen)-Montmorillonite are shown in fig.10.
  • thermographs indicate that the weight loss occurs in two steps. One up to about 130°C when loss of the adsorbed and/or crystalline water take place endothermically and a second exothermic step around 350-450°C, depending on the sample, when the burning of the organic part of the complex take place exothermically.
  • the total weight loss in pillared Montmorillonites is due to three factors (a) loss of adsorbed water, (b) loss of the crystalline water and (c) loss of the organic part of the complex. Calculation of those three parameters from weight loss experiments resulted
  • SUBSTITUTE SHEET in a value of amount of complexes trapped into Montmorillonite equal to 1.8 mmoles/g, 1.7 mmoles/gr and 1.9 mmoles/g for the materials CoLa(fsaen)- Montmorillonite, NiLa(fsaen)-Montmorilonite and MnLa(fsaen)-
  • LaCoO ⁇ -Mont At 600°C those distances drop to 13.0 A as compared with o the 9.6A of the nonpillared Montmorillonite. Therefore even at the relative high temperatures of 500 and 600oC there exists stable enough pillars between "the aluminosilicate layers and the materials possess a porous structure and high surface and can be used as a sorbents and catalysts in different chemical tranfo ⁇ nations.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

With the proposed method it has been achieved the intercalation of perovskitic micro particles of the general type ABOx, where A is La or other suitable for perovskite structure cation usually a non-reductable while B is a usually reducible metallic cation, into aluminosilicate layered clay, of the type of smectites and especially into Montmorillonite. The method of intercalation proceeds through the synthesis of binuclear complexes of the general formula AB(fsaen) NO3. These complexes are adsorbed into the clay and occupy the space between the aluminosilicate layers. After adsorption the obtained system AB(fsaen)-Montmorillonite is heated and the organic part of the complex cation is burned and removed as volatile products leaving back between the layers of the clay (Montmorillonite) pillars of perovskitic nature ABO3 like for example LaCoO3, LaMnO3, LaNiO3 and LaCuO3. The final products appear high specific surface areas 200-250m2/gr at T=500=600 °C. The interlayer distances between the aluminosilicate sheets are about 16A at 500 °C and 13-14 Å at 600 °C which explains their high surface area. The thermal stability of such materials at high enough temperature of (600-700 °C) makes them potential candidates for use as adsorbents or absorbents as well as heterogeneous catalysts for different industrial applications.

Description

DESCRIPTION
Method of intercalation of perovskitic particles in the form of pillars into layered clays.
FIELD OF INVENTION
This invention is referred to a process of intercallation of perovskitic pillars of different composition into swelling clays and the products obtained from such a process.
BACKGROUND OF INVENTION
Different clays are minerals, abundant in nature, which are used in different applications like for example catalysts and sorbents as well as in different household goods of extensive use like washing machine powders. Of special interest between the clays appear those which possess the ability to swell with adsorption, or absorption, between their aluminosilicate layers of different molecules like water or other chemical compounds. In fig.l the structure of such a swelling clay, and especially of Na Montmorillonite, is shown.
In bibliography it is mentioned for the first time by Barrer and McLeod in 1955 that it is possible to form relative stable porosity in Montmorillonite by substituting the Na ions with alkyl-ammonium. Those ions act as supporting pillars between the aluminosilicate layers of the clay which in this way exhibits its crystal surfaces for adsorption and possible catalytic action. Recently it has been proved that by changing the size and the shape of alkyl- ammonium ion it is possible to create pores of different sizes.
The specific surface area of such swelled clays after the removal of adsorbed or intercallated species can reach the value of 700-800 m2._~-
SUBSTITUTE SHEET Nevertheless in practice such a high surface area can not be achieved since the aluminosilicate layers collapse after the removal of pillars and are bounded each other with Van der Walls forces.
To meet this challenge it has been proposed the pillaring of clays with oxidic pillars. Such an oxidic pillaring results in surface area 100-200 m^g-1 up to 400-600°C. Above this temperature the material looses its surface area and its porosity a fact certainly due to the collapse of pillars and the shrinkage of layers which are then bounded each other without void space between them. Among the different oxidic pillars used up to now with success for intercalating clays are AlOx, FeO, CrOx, BiOx, CuO, ZrOx, NbOx, LaOx> NiOx and a few other cations. Such materials are investigated as catalysts.
The process of intercalation takes usually place by using different hydroxy-polymers like those of Al, Fe and La, which are mixed with the clay and in a pre-set pH value are inserted into the layers. Then the hydroxy-polymers are dehydrated by heating and leave between the clay layers pillars of the corresponding oxide. In some cases it has been successfully achieved the introduction of two different discrete pillars into the layers of the clay, Le. A10x and FeOy. Such pillared forms of clays, with one or two discrete oxidic pillars between their layers, are shown in fig.2.
In some other cases for the introduction of pillars ,some cationic complexes are used which contain in their complex cation a metal ion. Such complexes are exchanged with the sodium of the clay and after heating at 200-300°C the organic part of the complex is burned leaving the oxidic species as supporting pillars. In this way clays pillared with FeOx, NbOx etc., have been prepared. For example in the bibliography has been noticed the pillaring of Montmorillonite with complexes of o-phenanthrolein. This
SUBSTITUTE SHEET compound forms complexes of the type M(phen)2+ 3 which are inserted between the layer and are decomposed by heating at 350°C. At this point a collapse of layers is observed.
The introduction into layered clay of pillars which contain ,within the same pillar, of two kinds of cations appears particular interest and this is exactly the subject covered by the present invention.
The nano-particles which were successfully intercallated in this work between the clay layers were of the form ABOx and they possess the structure of perovskite ABO3 or its relative structure A2BO4 (fig.3). The structure A2BO4 is originated from structure ABO3 , which characterizes the typical perovskites, if between the layers ABO3 units of AO are inserted . Such materials ABO3 an/or A2BO4 appear tremendous technological applications as burning catalysts.piezocrystals, superconductors etc. Therefore a combination of such minute size pillars ABO3 /A2BO4 in a nano-phase with the clay aluminosilicate substrate in a well defined and organized structure is possible to result in materials which can be used as catalysts or sorbents as well as in some other technological applications.
BIBLIOGRAPHY
The non-legally protected bibliography relative to the pillared clays is enormous. The subject is usually covered from the point of view of simple oxidic pillars, we notice the following general and relative recent publications referring to the subject.
1) E.M.Farfan Torres , P.Grange and B.Delmon in "Chemical Physics of Intercalation", Eds. A.P.Legrand and S.Frandois, NATO ASI Series, Plenum Press, (1987)pp.489-495,
2) TJ Pinnavaia , Science , 220 (1983) 365-371
SUBSTITUTE SHEET 3)W.Y.Lee , R.H-Raythatha and BJ. Tatarchuk J.Catalysis ,115(1989) 159-
179
4)J.Sterte ,Clays Clay Miner. ,34(6) (1986) 658-664
5)S.Yamanaka and G.W.Brindley ,Clays Clay Miner. ,26(1)(1978), 21-24 6)S.S.Sing and H.Kodama ,Clays Clay Miner. ,36(5)(1988),397-402
7)K.Suzuki , M.Horio and T.Mori ,Mat.Res.BuU. ,23(1988) ,1711-1718
8)F.Figueras ,Catalysis Review (1988)457-499
From the search of the legally protected bibliography it is asserted that the US Patent IPN W089/00083 by R.Raythatha, B.Tatarchuk and W.L.Lee describes the formation of a pillared clay with two discrete pillars, one of the type AlOx and the other of the form FeOy. The method of preparation is based in the introduction of pillars in the form of hydroxy-polymers and further drying. After reduction the FeOy pillars are transformed to metallic iron. The US Patent 4 176 090 by P.E.W Vanghn et al. describes the introduction of Al-Mg hydroxy-oligo-polymers into clays (smectites) with polymerization in the solid phase. This method is referred to the synthesis using inorganic substrates.
The US Patent 4271043 by P.E.W, Vanghn et al and the US Patent 4248739 referring to similar subjects notice that the pillared colloid inorganic particles are stabilized by the addition of sodium silicate and also notice the addition of two particular cations into the polymeric inorganic species.
METHOD OF PREPARATION
For the introduction of mixed oxidic pillars of perovskitic structure of the type ABO3 or A2BO4 we used organic bi-nuclear complexes of the form shown in fig.4 with ligand the Schiff base which is formed from the reaction
SUBSTITUTE SHEET of 3-formyl salicylic acid with ethylenediamine, and has the chemical name N, N' -bis (3-carboxysalicyIidene) ethylenediamine. In the next this ligand will be referred for convenience as (fsaen) and the corresponding bi-nuclear complex AB(fsaen)NO3 where AB(fsaen) the cationic part of the complex and NO3 the anionic. Such complex compounds have two metal ions similar (A- A) or dissimilar (A-B) which are bridged via oxygen (fig.4). In this way after burning it is achieved the facile formation of the phase ABO3 between the clay layers because of the drastic decrement of the distance the two cations have to travel in order to react i.e., decrement of diffusion limitations. The general method of synthesis of such bi-nuclear complexes is known- from bibliography. α)U.Casellato,P.A.Vigato,D.E.Fenton and M.Vidali, Chem.Soc.Rev.
8,199,(1979) β)H.Okawa ,Y.Nishida .M.Tanaka ,S.Kida .Bull.Chem.SocJpn., 50(1), 127- 131(1977) γ)M.Tanaka ,M.Kitaoka .H.Okawa ,S.Kida .Bull.Chem.SocJpn. , 49(9) 2469- 2473 (1976).
Synthesis of the complex ALaffsaen) NOgcΔ (A-=Ni- Co. Cu, Mn-Δ = H?Q. MeOH). 3-formylsalicylic acid (a moles) were dissolved in solution of sodium carbonate (a2 moles), and a moles of ethylenediamine were added in the solution. In the above warm mixture a 2 moles of the acetic salt of the metal A were added. After reaction at 60°C for 60 min the formed precipitate was separated, washed with warm water and dried under vacuum. The obtained product corresponding to AH2(fsaen).xH2θ was dissolved in r πhanolic solution of lithium hydroxide and in the obtained solution a/2 moles of lanthanum nitrate were added. The precipitate was isolated, washed
SUBSTITUTE SHEET with methanol and dried under vacuum. The final product ALa(fsaen)Nθ3J_H2θ was identified using IR spectra according to the literature (a) (b) (c).
Thermo-gravi_τi£tτ.c studies of the thermal decomposition of complexes AB (fsaen NO3.xH2O.
After synthesis the thermal decomposition of the obtained complexes was studied in a thermobalance. For the study of thermographs both of ALa(fsaen)Nθ3.xH2θ ,as well as of the pillared ALa(fsaen)Nθ3.xH2θ- Montmorillonite ,a thermalbalance TRDA3H of the CHYO BALANCE COORPORATION controlled by a PC was used with simultaneous recording of T, TG, DTG and DTA signals. The amount of samples used was in each case around lOOmgr in platinum cruciblesAs a blank 0--AI2O3 was used. The rate of heating was 5°C/min and the measurements were carried out in a flow of atmospheric air -=10ml/min. A typical thermograph (TG-DTA) shown in fig.5 for the complex
CoLa(fsaen)Nθ3.H2θ shows a complete loss of organic part at 520°C. The total loss observed in the thermobalance is 63.9% as compared to 63.3% which is the theoretical loss according to the reaction :
CoLa(fsaen)Nθ3.H2θ =→- LaCo03+volatile products.
Similar results were obtained for the other complexes of the form NiLa(fsaen) N03.H20 and MnLa(fsaen)N03.H20
X-ray study of the solid products of the thermal decomposition of the complexes AB(fsaen)NQ3.
SUBSTITUTE SHEET After the definition of the temperature neccesaiy for the removal of the organic part of the complexes AB(fsaen)Nθ3, those material were heated in different temperatures and the remaining solids were examined by X-rays in order to define their crystal structure. The X-ray system used was PHILIPS with CoKα radiation. The results are shown in fig. 6,7,8 and 9 for the solid products remaining after heating the complexes NiLa(fsaen) ,CoLa(fsaen) ,CuLa(fsaen) and MnLa(fsaen) at different temperatures. It seems that by this method the formation of the perovskite phase is achieved at temperatures lower than those mentioned in the literature by other methodologies. To be precise the methods of synthesis of perovskites used up to now are the nitrate and the citrate one. In the first the mixture of nitrate salts of the corresponding metals is heated up to 1100°C for different hours and thus the perovskite phase is formed. According to the citrate method, citric acid is added in the mixture of nitrate salts for the possible complexation of the corresponding metal ion. Then by heating at 800-900°C perovskites are obtained.
It has been also noticed in the literature the formation of perovskites by heating the corresponding mixture of oxides in a microwave oven for lOOh. Perovskites are also formed by heating of oxides in molten mixtures with NaOH as well as by the method of sol-gel.
The present method, by the. use of binuclear complexes, results in formation of perovskites at lower temperatures, around 500-600°C.
Method of intercalation of complexes AB(fsaen) into
Montmorillonite
SUBSTITUTE SHEET δ
For intercalation of complexes ALa(fsaen)Nθ3.xΔ(A=Ni, Co, Mn - Δ=H2θ, MeOH) into Montmorillonite and subsequent pillaring the following method was used.
An amount of suspension of Na-Montmorillonite lg/lOOml (Clay Spur, Wyoming USA, particle size <2μ) was mixed with an amount of complex ALa(fsaen)Nθ3.xΔ in ratio Complex /
Figure imgf000010_0001
In the suspension MeOH was added up to 20% v/v. The obtained mixture was stirred for lh at 50°C. The heating stopped when after a temporal increment of its viscosity the suspension was returned to its original situation. The stirring was continued for 10 more days and then the mixture was left for another 5 days stationery. The final product was obtained with centrifugation (6000 rev min) and dried under vacuum.
Study of the thermal decomposition of ALa(fsaenV
Montmorillonite The pillared clays Montmorillonite-ALa(fsaen) were tested in a thermobalance under conditions similar to those described previously for pure complexes. Two such thermographs for the materials CoLa(fsaen)- Montmorillonite and MnLa(fsaen)-Montmorillonite are shown in fig.10.
Those thermographs indicate that the weight loss occurs in two steps. One up to about 130°C when loss of the adsorbed and/or crystalline water take place endothermically and a second exothermic step around 350-450°C, depending on the sample, when the burning of the organic part of the complex take place exothermically. The total weight loss in pillared Montmorillonites is due to three factors (a) loss of adsorbed water, (b) loss of the crystalline water and (c) loss of the organic part of the complex. Calculation of those three parameters from weight loss experiments resulted
SUBSTITUTE SHEET in a value of amount of complexes trapped into Montmorillonite equal to 1.8 mmoles/g, 1.7 mmoles/gr and 1.9 mmoles/g for the materials CoLa(fsaen)- Montmorillonite, NiLa(fsaen)-Montmorilonite and MnLa(fsaen)-
Montmorillonite, correspondingly. Those values agree satisfactorily with the amount of complexes added initially which was set to 2.0 mmol/g.
Surface area measurements of the LaMOx pillared Montmorilonite
In the pillared clays synthesized as above the specific surface areas at different temperatures (150, 300, 500, 600, 700, 800°C) were measured. The system used was a CARLO ERBA Sorpty 1750 model based on the BET method of N2 adsorption at T=77°K. The samples before measurement were heat for 2h at 300°C at P=10-2 Torr, except the measurement at 150°C which was degassed at 100°C. The results are shown in fig.11. We observe that the specific surface areas reach their maximum value 200-250m2/g at T=300°C for LaMnOx, and 500°C for LaNiOx and LaCoOx. Further increment of the temperature result in a drop of surface to about 150m2/g at 600°C and to 100-150m2/g at 700°C while at 800°C the specific surface area tends to zero.
X-ray measurements of the Clays pillared with Perovskite particles. For the measurement a Philips system was used with Fe filtered CoKa radiation. For the exaπiination of the interlayer space in the 001 direction of the pillared Montmorillonite, thin films of them on glass slides were used. The slides after heating at different temperatures (150, 300, 500, 600°C) were measured at 2Θ=2-12°. The results are shown in fig.12, 13, and 14 for the
SUBSTITUTE SHEET systems LaNiOx-Montmorillonite, LaMnOx-Montmorillonite and LaCoOx- Montmorillonite correspondingly.
From the results it can be seen that the obtained products at 500°C o possess an inter-layered distance between the aluminosilicate sheets of 16 A for the LaNiOχ-Mont, 15.1 A for LaMnOx-Mont and 15.3 A for the o
LaCoOχ-Mont. At 600°C those distances drop to 13.0 A as compared with o the 9.6A of the nonpillared Montmorillonite. Therefore even at the relative high temperatures of 500 and 600oC there exists stable enough pillars between "the aluminosilicate layers and the materials possess a porous structure and high surface and can be used as a sorbents and catalysts in different chemical tranfoπnations.
SUBSTITUTE SHEET

Claims

1«.
The process of preparation of pillared clays with pillars of mixed oxidic perovskitic nature and namely ABOx when A is a resistant to reduction metallic cation and B a reducable metallic cation, where the structure ABOx is of perovskite nature, and formed via bi-nuclear complexes which are adsorbed into the swelled clay and thermally decomposed resulting in a intercallated mixed oxidic perovskitic pillar ABOx between the aluminosilicate sheets of- the clay.
2n
The process according to claim 1 during which by the use of binuclear complexes mixed oxidic perovskitic structures are obtained having the form LaCoOχ, LaNiOx, LaMnOx and LaCuOx.
3rd
The products obtained according to the claims 1 and 2 and their use as adsorbents and absorbants.
4th
The products obtained according - to claims 1 and 2 and their use as heterogeneous catalysts in different chemical transformations.
SUBSTITUTE SHEET
PCT/GR1991/000010 1990-07-03 1991-06-27 Method of intercalation of perovskitic particles in the form of pillars into layered clays WO1992000808A1 (en)

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EP1238989A2 (en) * 2001-02-21 2002-09-11 Mitsui Chemicals, Inc. Olefin polymerization catalyst and process for producing olefin polymer with the catalyst
CN115301243A (en) * 2022-07-15 2022-11-08 西北大学 Supported perovskite catalyst, preparation method and application thereof

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WO1988000093A1 (en) * 1986-06-27 1988-01-14 Mobil Oil Corporation Layered metal oxides containing interlayer oxides and their synthesis
WO1989000083A1 (en) * 1987-07-07 1989-01-12 E.C.C. America Inc. Process of preparing mixed pillared clays and reduction products thereof

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GB2182919A (en) * 1985-10-28 1987-05-28 Elf France Bridged layered clays
WO1988000093A1 (en) * 1986-06-27 1988-01-14 Mobil Oil Corporation Layered metal oxides containing interlayer oxides and their synthesis
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Publication number Priority date Publication date Assignee Title
EP1238989A2 (en) * 2001-02-21 2002-09-11 Mitsui Chemicals, Inc. Olefin polymerization catalyst and process for producing olefin polymer with the catalyst
EP1238989A3 (en) * 2001-02-21 2004-01-02 Mitsui Chemicals, Inc. Olefin polymerization catalyst and process for producing olefin polymer with the catalyst
US6897176B2 (en) 2001-02-21 2005-05-24 Mitsui Chemicals, Inc. Olefin polymerization catalyst and process for producing olefin polymer with the catalyst
CN115301243A (en) * 2022-07-15 2022-11-08 西北大学 Supported perovskite catalyst, preparation method and application thereof
CN115301243B (en) * 2022-07-15 2024-01-05 浙江聚泰新能源材料有限公司 Supported perovskite catalyst, preparation method and application thereof

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AU8070691A (en) 1992-02-04

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