This review of the use of clay minerals and clay mineral nanocomposites as catalysts for reactions begins by considering the structural characteristics responsible for activity, specificity and selectivity. Examples of catalytic activity described include Bronsted and Lewis acidity, redox activity, formation of reactive intermediates and catalysis of cycloaddition reactions. Clay minerals are also useful as supports for acids, ionic liquids, reagents and other catalysts, phase transfer agents and reactions initiated by microwaves, ultrasound or gamma irradiation. The review concludes with examples of the use of clay-based catalysts in the synthesis of ‘complex’ organic molecules and a consideration of the industrial situation of clay mineral usage.

Clay Minerals as Catalysts

Publisher Summary This chapter discusses catalysis by clay minerals, including their use as catalyst supports. In most petrochemical processing, such as cracking, solid catalysts were used for decades. Originally, the catalysts were based on acid-treated clays but for many years now framework silicates (zeolites) proved more effective and selective. Clay minerals have a different and interesting set of properties. They are very effective catalysts for a wide variety of organic reactions, often displaying highly sought product-, regio-, or shape-selectivity. In addition, however, soft dimensional constraints are often displayed. They have significant potential in organic chemical processing. The chapter focuses on smectites and their derivatives, which display by far the highest activity levels and range of reactions catalyzed. The chapter summarizes the performance of clay minerals in different types of reaction. The chapter concludes with a discussion on some recent developments and current utilization of these clays in industrial processes and prospects for the future.

Chapter 10.2 Clay Minerals as Catalysts

The microorganism-containing biocatalysts disclosed have a large population of the microorganisms irreversibly retained in the interior of the biocatalysts. The biocatalysts possess a surprisingly stable population of microorganisms and have an essential absence of debris generation from metabolic activity of the microorganisms. The biocatalysts are composed of highly hydrophilic polymer and have an internal, open, porous structure that promotes community phenotypic changes.

Novel biocatalyst compositions and processes for use

Novel polymer-supported quenching reagents of Formula (I): P-L-Q, wherein P is a polymer of low chemical reactivity which is soluble or insoluble; Q is one or more quenching reagents, or an acid or base addition salts thereof, that are capable of selective covalent reaction with unwanted byproducts, or excess reagents; and L is one or more chemically robust linkers that join P and Q; are described, as well as methods for their preparation and methods for their use in the rapid purification of synthetic intermediates and products in organic synthesis, combinatorial chemistry and automated organic synthesis.

Rapid purification by polymer supported quench

This invention relates to a process for the preparation of bisphenols and bisphenol mixtures by the isomerization of bisphenols on acid or alkaline catalysts in the presence of the corresponding phenols.

Isomerization of bisphenols

A process for preparing p-cumylphenol which comprises reacting phenol and α-methylstyrene in the presence of an inorganic solid acid catalyst having an acid point of an acid strength Ho of up to -3, for example, activated clay and recovering the aimed p-cumylphenol from the reaction mixture thus obtained by distilling the same while introducing an inert gas such as nitrogen and/or steam into the distillation system is disclosed. The p-cumylphenol thus obtained has a high purity and an improved color compared with those obtained by conventional methods.

Process for preparing p-cumylphenol

PURPOSE:To obtain a pyruvic acid ester in high selectivity using an inexpensive and readily handleable catalyst, by oxidizing a lactic acid ester with oxygen in the liquid phase in the presence of the catalyst selected from titanium oxide, zirconium oxide and niobium oxide. CONSTITUTION:A lactic acid ester is oxidized with oxygen in the presence of a catalyst to produce a pyruvic acid ester useful as a raw material for amino acids, e.g. tryptophan, etc., and intermediate for various organic compounds. In the process, one or more compounds selected from titanium oxide, zirconium oxide and niobium oxide, preferably titanium oxide and zirconium oxide are used as the above-mentioned catalyst to carry out the afore-mentioned reaction in the liquid phase and industrially and advantageously afford the aimed compound in high selectivity. The amount of said catalyst used is about 5g based on 1mol lactic acid ester. The reaction temperature is 100-170 deg.C, preferably 120-150 deg.C and the reaction time if <=10hr, particularly preferably <=5hr.

Production of pyruvic acid ester

PURPOSE:To produce the subject compound in high efficiency at a low cost with a simple process by adding a <=4C alcohol in the reaction of an alkali metal salt of an alkylphenol with sodium monochloroacetate in an aliphatic hydrocarbon solvent. CONSTITUTION:An alkylphenoxyacetic acid is produced by adding a <=4C alcohol in the reaction of an alkali metal salt of an alkylphenol with sodium monochloroacetate in an aliphatic hydrocarbon solvent. The process enables the formation of a homogeneous slurry within a short time by adding hot water and heating the mixture even if the amount of the solvent is decreased to cause the solidification of the reaction mixture in the condensation reaction. The <=4C alcohol is e.g. methanol, ethylene glycol or triol and its amount is preferably about 0.10-0.40 pts.wt. per 1 pt.wt. of the alkylphenol.

Production of alkylphenoxyacetic acid

A biocatalyst immobilized by entrapment characterized in that it is a gel of water-insoluble polyuronic acid containing microbial cells or their treated substances, said gel containing a crosslinking agent, said crosslinking agent being bound to a carboxyl group of said polyuronic acid via an amide bond and/or an ester bond thereby to crosslink said polyuronic acid and a process for preparation thereof.

Biocatalysts immobilized by entrapment and process for their preparation

PURPOSE:To purify the titled substance useful as a raw material of 2-phenylethyl alcohol, etc. which are known raw materials of perfumes, economically in an industrial scale, in high yield, by treating a crude reaction liquid containing a styrene oxide compound with a basic aqueous solution, and distilling the treated liquid. CONSTITUTION:A styrene compound is made to react with an organic peroxide (e.g. ethylbenzene hydroperoxide) preferably at a molar ratio of 1-10:1 in the presence of an epoxidization catalyst (preferably molybdenum oxide, etc.) and a cocatalyst (e.g. trimethyl borate) usually at 70-170 deg.C for 0.01-120min. The obtained crude reaction liquid containing a styrene oxide compound is treated with a basic aqueous solution (e.g. aqueous solution of NaOH), and distilled (preferably under vacuum of 10-100mm.Hg at 80-150 deg.C) to effect the purification of the objective compound. The concentration of the basic aqueous solution is preferably 3-30wt%, and the amount of the solution is preferably 10-70vol% based on the above crude liquid.

Imanari Makoto

Papers

Process for preparing p-cumylphenol

Production of pyruvic acid ester

Production of alkylphenoxyacetic acid

Biocatalysts immobilized by entrapment and process for their preparation

Purification of styrene oxide