WO1992000808A1 - Procede d'intercalation de piliers de particules de perovskite dans les argiles stratifiees - Google Patents

Procede d'intercalation de piliers de particules de perovskite dans les argiles stratifiees Download PDF

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Publication number
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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WO
WIPO (PCT)
Prior art keywords
perovskitic
clay
montmorillonite
fsaen
pillars
Prior art date
Application number
PCT/GR1991/000010
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English (en)
Inventor
Philip Pomonis
Stelios Skaribas
Athanasios Ladavos
Original Assignee
Philip Pomonis
Stelios Skaribas
Athanasios Ladavos
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Philip Pomonis, Stelios Skaribas, Athanasios Ladavos filed Critical Philip Pomonis
Publication of WO1992000808A1 publication Critical patent/WO1992000808A1/fr

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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)
  • Dispersion Chemistry (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Analytical Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

On décrit l'intercalation, dans de l'argile stratifiée à aluminosilicate, par exemple la smectite et notamment la montomorillonite, de microparticules de pérovskite du type général ABOx, où A est La ou un autre cation normalement non réductible et approprié pour les structures de pérovskite, tandis que B est un cation normalement réductible. Le procédé d'intercalation consiste à réaliser une synthèse de complexes binucléaires répondant à la formule générale AB(fsaen) NO3. Ces complexes sont adsorbés par l'argile et occupent le volume compris entre les couches d'aluminosilicate. Ensuite, on chauffe le système AB(fsaen)-montmorillonite obtenu et on brûle la partie organique du cation complexe, laquelle est libérée sous forme de produits volatils, en laissant entre les couches d'argile (montomorillonite) des piliers à caractère pérovskitique constitués par exemple de LaCoO3, de LaMnO3, de LaNiO3 et de LaCuO3. Les produits finals présentent des surfaces spécifiques de 200 à 250 m2/gr à une température comprise entre 500 et 600 °C. Les distances séparant les couches d'aluminosilicate sont d'environ 16A à 500 °C et de 13 à 14 Å à 600 °C, ce qui explique leur grande superficie. La résistance à la chaleur de ce genre de matériaux à des températures allant jusqu'à 600 ou 700 °C rend possible leur utilisation en tant qu'adsorbants ou absorbants, ainsi qu'en tant que catalyseurs hétérogènes destinés à diverses applications industrielles.
PCT/GR1991/000010 1990-07-03 1991-06-27 Procede d'intercalation de piliers de particules de perovskite dans les argiles stratifiees WO1992000808A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GR900100506 1990-07-03
GR90100506 1990-07-03

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WO1992000808A1 true WO1992000808A1 (fr) 1992-01-23

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1238989A2 (fr) * 2001-02-21 2002-09-11 Mitsui Chemicals, Inc. Catalyseur de polymérisation d'oléfine et procédé de préparation d'un polymère oléfinique avec ce catalyseur
CN115301243A (zh) * 2022-07-15 2022-11-08 西北大学 一种负载型钙钛矿催化剂、制备方法及其应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4179409A (en) * 1977-11-09 1979-12-18 Exxon Research & Engineering Co. Hydrocarbon cracking catalyst
GB2182919A (en) * 1985-10-28 1987-05-28 Elf France Bridged layered clays
WO1988000093A1 (fr) * 1986-06-27 1988-01-14 Mobil Oil Corporation Oxydes metalliques en couches contenant des oxydes entre les couches, et leur synthese
WO1989000083A1 (fr) * 1987-07-07 1989-01-12 E.C.C. America Inc. Procede de preparation d'argiles melangees structurees en piliers et leurs produits de reduction

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4179409A (en) * 1977-11-09 1979-12-18 Exxon Research & Engineering Co. Hydrocarbon cracking catalyst
GB2182919A (en) * 1985-10-28 1987-05-28 Elf France Bridged layered clays
WO1988000093A1 (fr) * 1986-06-27 1988-01-14 Mobil Oil Corporation Oxydes metalliques en couches contenant des oxydes entre les couches, et leur synthese
WO1989000083A1 (fr) * 1987-07-07 1989-01-12 E.C.C. America Inc. Procede de preparation d'argiles melangees structurees en piliers et leurs produits de reduction

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1238989A2 (fr) * 2001-02-21 2002-09-11 Mitsui Chemicals, Inc. Catalyseur de polymérisation d'oléfine et procédé de préparation d'un polymère oléfinique avec ce catalyseur
EP1238989A3 (fr) * 2001-02-21 2004-01-02 Mitsui Chemicals, Inc. Catalyseur de polymérisation d'oléfine et procédé de préparation d'un polymère oléfinique avec ce catalyseur
US6897176B2 (en) 2001-02-21 2005-05-24 Mitsui Chemicals, Inc. Olefin polymerization catalyst and process for producing olefin polymer with the catalyst
CN115301243A (zh) * 2022-07-15 2022-11-08 西北大学 一种负载型钙钛矿催化剂、制备方法及其应用
CN115301243B (zh) * 2022-07-15 2024-01-05 浙江聚泰新能源材料有限公司 一种负载型钙钛矿催化剂、制备方法及其应用

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GR1000178B (el) 1992-01-20
AU8070691A (en) 1992-02-04

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