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Cross-Linked Smectites. I. Synthesis and Properties of Hydroxy-Aluminum-Montmorillonite

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Clays and Clay Minerals

Abstract

A stable porous system consisting of montmorillonite cross-linked by Al-hydroxide oligomers was synthesized by reacting at room temperature an aqueous solution of such oligomers with a unit-layer dispersion of montmorillonite. The resulting cross-linked montmorillonite (Al-CLM) is a nonswelling material, showing basal spacings of 14.4 to 18.8 Å after air drying and between 14.2 to 18.0 Å after treatment at 110°C. The basal spacing is found to depend on the age and OH/Al ratio of the Al-hydroxide solution, as well as on the relative amounts of the two reactants. A specific surface area of 160 m2/g and a diffraction pattern with a dominant basal spacing of 17.5 Å is obtained by using Al-hydroxide with OH/Al = 1.85, aged for at least 5 days, and by applying an Al/montmorillonite ratio greater than 1.5 in the cross-linking process. The basal spacing of Al-CLM remains essentially unchanged after heating at 220°C, while the specific surface area is not affected by heat treatment up to 480°C.

Two possible configurations of Al-hydroxide oligomers, homogeneously distributed between parallel montmorillonite unit-layers, were considered in order to account for the basal spacing of 17.5–18.8 Å, viz. (a) stacking of two oligomeric ring units in parallel orientation relative to the clay lamellae and (b) perpendicular orientation of individual oligomeric units.

Резюме

Устойчивая пористая система, состоящая из монтмориллонита, поперечно-связанного олигомером гидроокиси Al, была синтезирована в результате реакции, пртекавшей при комнатной температуре, между водным раствором этих олигомеров и диспергированным однородно-слоистым монтмориллонитом. Образованный поперечно-связанный монтмориллонит (Al-ПСМ) представляет собой неразбухающий материал с основными промежутками от 14,4 до 18,8 Å после воздушной просушки и от 14,2 до 18,0 Å после обработки при 110°C. Было обнаружено, что величина основных промежутков зависит от возраста и отношения OH/Al раствора гидроокиси а также от относительных количеств двух реагентов. Специфическая площадь поверхности в 160 м2 / г и дифракционная картина с доминирующим основным промежутком в 17,5 Å были достигнуты с использованием гидроокиси Al c OH/Al=1,85, имеющим возраст не менее 5 дней и использованием отношения А1/монтмориллонит больше 1,5 при процессе поперечного связывания. Основной промежуток Al-ПСМ остается существенно неизменным после прогревания при 2 20°C, в то время как специфическая площадь поверхности не изменяется при тепловой обработке до 480°C.

Были рассмотрены две возможные конфигурации олигомеров гидроокиси Al, гомогенно распределенных между параллельными однородными слоями монтмориллонита, чтобы объяснить основной промежуток в 17,5-18,8 Å, /a/ пакет двух олигомерных колец,параллельно ориентированных по отношению к слоям глины и/б/ перпендикулярно ориентированые отдельные олигомеры.

Kurzreferat

Ein stabiles, poröses System, welches aus mit Al-Hydroxyd oligomeren querverbundenen Montmorillonit besteht, wurde synthetisiert indem bei Zimmertemperatur eine wässrige Lösung dieser Oligomere mit einer Einheitsschichtdispersion von Montmorillonit reagiert wurde.Der resultierende querverbundene Montmorillonit (Al-CLM) ist ein quellfestes Material, das einen Basisabstand von 14,4 bis 18,8 A nach Lufttrocknen und zwischen 14,2 und 18,0 A nach Behandlung bei 110° C besitzt. Es wurde herausgefunden daß der Basisabstand sowohl vom Alter und OH/Al Verhältnis der Al-Hydroxyd-lösung wie auch von den relativen Mengen der beiden reagierenden Substanzen abhängt.Eine spezifische Oberfläche von 160 m2/g und ein Diffraktionsmuster mit einem dominanten Basisabstand von 17,5 A wird erhalten indem Al-Hydroxyd mit OH/AL = 1,85, mindestens 5 Tage lang gealtert, benutzt wird und indem ein Al/Montmorillonit Quotient für die Querverbindung benutzt wird, der größer als 1,5 ist.Der Basisabstand des Al-CLM bleibt im wesentlichen unverändert nach Erhitzen bei 220°C, während die spezifische Oberfläche nicht von Hitzebehandlung bis 480°C beeinflußt ist. Zwei denkbare Konfigurationen der Al-Hydroxydoligomere, homogen verteilt zwischen parallelen Montmorilloniteinzelschichten, wurden erwogen, um den Basisabstand von 17,5–18,8 A zu begründen, nämlich (a) aufstapeln von zwei oligomeren Ringeinheiten in parallelzu den Tonlamellen- Orientierung und (b) senkrechte Orientierung von individuellen oligomeren Einheiten.

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Authors and Affiliations

  1. Department of Soil and Water Science, Faculty of Agriculture, The Hebrew University of Jerusalem, Rehovot, Israel

    N. Lahav & U. Shani

  2. Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, Israel

    J. Shabtai

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  1. N. Lahav
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  2. U. Shani
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Lahav, N., Shani, U. & Shabtai, J. Cross-Linked Smectites. I. Synthesis and Properties of Hydroxy-Aluminum-Montmorillonite. Clays Clay Miner. 26, 107–115 (1978). https://doi.org/10.1346/CCMN.1978.0260205

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