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Cross-Linked Smectites. III. Synthesis and Properties of Hydroxy-Aluminum Hectorites and Fluorhectorites

Published online by Cambridge University Press:  02 April 2024

J. Shabtai ,
Maria Rosell  and
M. Tokarz
J. Shabtai
Affiliation:
Department of Fuels Engineering, University of Utah, Salt Lake City, Utah 84112
Maria Rosell*
Affiliation:
Department of Fuels Engineering, University of Utah, Salt Lake City, Utah 84112
M. Tokarz*
Affiliation:
Department of Fuels Engineering, University of Utah, Salt Lake City, Utah 84112
*
1On leave of absence from EKA AB, Surte, Sweden, 1982.
2On leave of absence from the University of Mining and Metallurgy, Krakow, Poland, 1981–1983.
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Abstract

Interaction of La3+- and Ce3+-exchanged hectorites with oligomeric hydroxy-Al cations results in the formation of cross-linked hectorites possessing moderately high surface areas (~ 220–280 m2/g) and high thermal stability. The basal spacings of these products were generally in the range 17.0–18.0 A, the exact d(001) value depending on the age of the hydroxy-Al oligomeric solution and on the pH of the starting hectorite dispersion. Interaction of Li- or Ce-fluorhectorite with hydroxy-Al oligocations produced the corresponding cross-linked fluorhectorites, which showed markedly higher basal spacings (18.2–20.0 Å for air-dried samples), surface areas (~300–380 m2/g), and thermal stability, as compared with those of the cross-linked hectorites. The cross-linking agent applied in the synthesis of the hydroxy-Al hectorite and fluorhectorite products consisted of a solution of hydroxy-Al oligomers aged for periods of 7 to 27 days. A constant ratio of 2.0 mmole Al/g of smectite was used in all preparations. The high basal spacings and porosity of the newly synthesized products are consistent with a structure similar to that previously proposed for cross-linked hydroxy-Al montmorillonite.

Резюме

Резюме

Результатом взамиодействия гекторитов, обмененных La3+ и Ce3+ с олигомерическими катионами гидрокси-Al, являлось формирование поперечно-связанных гекторитов с умеренно большими площадями поверхности (~220–280 м2/г) и большой термической стабильностью. Промежуточные расстояния этих продуктов находились в общем между 17,0 и 18,0 А; точное значение d(001) зависило от возраста олигомерического раствора гидрокси-Al и от pH начальной дисперсии гекторита. Взаимодействие Li- или Ce-флуоргекторита с олигокатионами гидрокси-Al давало соответствующие поперечно-связанные флуоргекториты, которые имели значительно большие промежуточные расстояния (18,2–20,0 Å для образцов, осушенных в воздухе), площади поверхности (300–380 м2/г), и термические стабильности по сравнению со соответствующими значниями для поперечно-связанных гекторитов. Поперечно-связывающее вещество, использованное для синтеза гидрокси-Al гекторита и флуоргекторита, состояло из раствора олигомеров гидрокси-Al после старения через 7 до 27 дней. Постоянное отношение 2,0 ммоль Al на грамм смектита использовалось во всех подготовках. Большие значения промежуточных расстояний и пороватости ново-синтезированных продуктов находятся в согласии со структурой похожей на ранее предположенную структуру для поперечно-связанного гидрокси-Al монтмориллонита. [E.G.]

Resümee

Resümee

Die Wechselwirkung von La3+- und Ce3+-ausgetauschten Hektoriten mit oligomeren Hydroxy-Al-Kationen führt zur Bildung von kreuzweise verknüpften Hektoriten, die eine maßig große Oberfläche (etwa 220–280 m2/g) und eine hohe thermische Stabilität besitzen. Der Basisabstand dieser Produkte reichte im allgemeinen von 17,0–18,0 Å. Der exakte d(001)-Wert hing vom Alter der oligomeren Hydroxy-Al-Lösung und vom pH der Hektorit-Ausgangssubspension ab. Die Wechselwirkung von Li- oder Ce-Fluorhektorit mit Hydroxy-Al-Oligokationen führte zu entsprechenden kreuzweise verknüpften Fluor-hektoriten, die einen beachtlich größeren Basisabstand (18,2–20,0 Å für Luft-getrocknete Proben), eine größere Oberfläche (etwa 300–380 m2/g) und eine höhere thermische Stabilität im Vergleich zu den kreuzweise verknüpften Hektoriten zeigte. Das Agens, das zur kreuzweisen Verknüpfung bei der Synthese von Hydroxy-Al-Hektorit und Fluor-Hektorit-Produkten verwendet wurde, bestand aus einer Lösung von Hydroxy-Al-Oligomeren, die über einen Zeitraum von 7 bis 27 Tagen gealtert wurden. Ein konstantes Smektit-Verhältnis von 2,0 mMol Al/g wurde in allen Versuchen verwendet. Die großen Basisabstände und die Porosität der neu synthetisierten Produkte stimmen mit einer Struktur überein, die vor kurzem für kreuzweise verknüpften Hydroxy-Al-Montmorillonit vorgeschlagen wurde. [U.W.]

Résumé

Résumé

L'interaction d'hectorites échangées avec La3+ et Ce3+ avec des cations oligomériques hydroxy-Al résulte en la formation d'hectorites à liens croisés possédant des aires de surface modérément élevées (~ 220–280 m2/g) et une haute stabilité thermique. Les espacements de base de ces produits étaient généralement compris entre 17,0–18,0 Å, la valeur exacte de d(001) dépendant de l’âge de la solution oligomérique hydroxy-Al et du pH de la dispersion d'hectorite de départ. L'interaction de fluorhectorite-Li ou -Ce avec des oligocations hydroxy-Al a produit des fluorhectorites à liens croisés correspondantes qui montraient des espacements de base (18,2–20,0 Å pour des échantillons sechés à l'air), des aires de surface (~ 300–380 m2/g) et une stabilité thermique nettement plus élevés, en comparaison avec ceux d'hectorites à liens croisés. L'agent produisant des liens croisés appliqué dans la synthèse des produits hectorite hydroxy-Al et fluorhectorite consistait en une solution d'oligomères hydroxy-Al vieillie pour des périodes de 7 à 27 jours. Une proportion constante de 2,0 mmole Al/g de smectite était employée dans toutes les préparations. Les espacements de base élevés et la porosité des produits nouvellement synthetisés sont fidèles à une structure semblable à celle proposée précédemment pour une montmorillonite hydroxy-Al à liens croisés. [D.J.]

Keywords

Cross-linkingFluorhectoriteHectoriteHydroxyaluminumMolecular sieveSurface areaSynthesisThermal stability

Information

Type
Research Article
Information
Clays and Clay Minerals , Volume 32 , Issue 2 , April 1984 , pp. 99 - 107
Copyright
Copyright © 1984, The Clay Minerals Society

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