The method to manufacture acetonitrile industrially from acetylene and ammonia as the raw materials with zinc oxide catalyst has been investigated. At first, fundamental experiments has been carried out to determine the best condition of reaction on a fixed state of catalyst. In intermediate experiments, studies on carriers of the catalyst have been made. Then it was found that the catalyst composed of 50% zinc oxide, 25% kaolin and 25% activated earth was suitable as a catalyst for industrial use in its durability and the yield of product. The experiments were carried out on fluidal state of the catalyst, increasing the diameters of reaction tower step by step in order of 4 cm, 10 cm, 20 cm and 40 cm. As this is remarkable exothermic reaction, to remove the heat of reaction, on the wall of reaction vessel triangular part was set on its bottom. In passing acetylene at the rate of 300 1/min through a reaction tower of diameter 40 cm alternately in 12-hour reaction, 12-hour regeneration, the reaction proceeded smoothly 575 hours, and gave an average yield of 75.1%, with success in industrial application. The low and high boiling parts in the reaction product have been investigated for studies on the refining of acetonitrile and the presence of pyridine base and some nitrites, besides benzene and acetone, was confirmed.
Reduction of butyraldehyde by ethyl alcohol proceeded with fairly high velocity and the decomposition of butyraldehyde was not so much accelerated. Reduction of crotonaldehyde yielded both of crotonalcohol and butyraldehyde, but which route is the main reaction could be determined. Isomerization of crotonalcohol to butyraldehydee is possible but the reaction velocity is not so high. Formation of n-butanol from ethanol seems difficult to proceed only by the reaction route including no reduction of double bond. Formation of butadiene by the dehydration of crotonalcohol is difficult below 350°C. The reaction of ethanol can be explained as a first order reaction including retardation term. Acetaldehyde, formed as a by-product in the reductoin proceeded by ethanol, even occupies about 60% of total acetaldehyde concerned in the condensation reaction of ethanol at the reaction temperature of 450°C.
On the catalytic reduction of nitrobenzene under pressure by use of two kindsof nickel catalyzers, stabilized N-3 and N-103 (Nikki Chemical products), thehydrogen absorption curves were prepared, and the effects of solvents, the amountof catalyzers and the reaction temperatures have been investigated. Though thecomposition and manufacturing process of these two catalyzers were the same, eachof these showed different hydrogen absorption at the reduction temperature of100°c in the presence of water. The reduction of nitrobenzene by N-103 catalyzerwas unable at 100°c when benzene, alcohol or aniline was used as the solvent inplace of water. Under initial pressures of 30-50 kg/cm2 (room temperature) in the presence of water, the absorption time of hydrogen by this catalyzer was not influenced by the pressure. Each of these catalyzers showed rather different behaviors from reduced nickel.