METHOD FOR THE PREPARATION OF 2,4,6-TRIHYDROXYTOLUENE FROM 2,4,6-TRINITROTOLUENE

Статья посвящена усовершенствованию способа получения 2,4,6-тригидрокситолуола, востребованного химического реагента в синтезе азокрасителей и пигментов, а также химико-фармацевтических препаратов и различных полимеров. Основным сырьем для его получения является 2,4,6-тринитротолуол, который подвергают каталитическому гидрированию с последующим гидролизом образовавшегося 2,4,6-триаминотолуола. В данной работе предложены условия многоциклового использования палладиевого катализатора гидрирования 2,4,6-тринитротолуола, позволяющие сохранять активность катализатора и повысить выход 2,4,6-триаминотолуола выше 98 %. Аминопроизводное выделяется в виде дисульфата действием концентрированной серной кислоты. Кроме того, изучено влияние соотношения вода/дисульфат 2,4,6-триаминотолуола на выход 2,4,6-тригидрокситолуола; найдены условия, в которых выход на стадии гидролиза увеличен до 83-84 %. Проведен сравнительный анализ различных способов выделения 2,4,6-тригидрокситолуола из реакционной массы. The paper is concerned with upgrading the synthetic method for 2,4,6-trihydroxytoluene, an in-demand chemical reactant in the synthesis of azo-dyes and pigments, as well as chemical pharmaceuticals and various polymers. The basic feedstock for the synthesis thereof is 2,4,6-trinitrotoluene, which is subjected to catalytic hydrogenation followed by hydrolysis of the resulting 2,4,6-triaminotoluene. Here we suggest conditions for the multicycle use of Pd catalyst employed for the hydrogenation of 2,4,6-trinitrotoluene, which allow the catalyst activity to be retained and the yield of 2,4,6-triaminotoluene to be enhanced above 98%. The amino derivative is liberated as the disulfate by concentrated sulfuric acid. Moreover, we examined how the ratio of water / 2,4,6-triaminotoluene disulfate influences the yield of 2,4,6-trihydroxytoluene. Conditions were found in which the yield from hydrolysis is 83-84 %. Different methods for the isolation of 2,4,6-trihydroxytoluene from the reaction mixture were comparatively analyzed.

A Receiver-Reactor for the Solar Thermal Dissociation of Zinc Oxide

An improved engineering design of a solar chemical reactor for the thermal dissociation of ZnO at above 2000K is presented. It features a rotating cavity receiver lined with ZnO particles that are held by centrifugal force. With this arrangement, ZnO is directly exposed to concentrated solar radiation and serves simultaneously the functions of radiant absorber, chemical reactant, and thermal insulator. The multilayer cylindrical cavity is made of sintered ZnO tiles placed on top of a porous 80%Al2O3–20%SiO2 insulation and reinforced by a 95%Al2O3–5%Y2O3 ceramic matrix composite, providing mechanical, chemical, and thermal stability and a diffusion barrier for product gases. 3D computational fluid dynamics was employed to determine the optimal flow configuration for an aerodynamic protection of the quartz window against condensable Zn(g). Experimentation was carried out at PSI’s high-flux solar simulator with a 10kW reactor prototype subjected to mean radiative heat fluxes over the aperture exceeding 3000suns (peak 5880suns). The reactor was operated in a transient ablation mode with semicontinuous feed cycles of ZnO particles, characterized by a rate of heat transfer—predominantly by radiation—to the layer of ZnO particles undergoing endothermic dissociation that proceeded faster than the rate of heat transfer—predominantly by conduction—through the cavity walls.

A Rotary Receiver-Reactor for the Solar Thermal Dissociation of Zinc Oxide

An improved engineering design of a solar chemical reactor for the thermal dissociation of ZnO at above 2000 K is presented. It features a rotating cavity-receiver lined with ZnO particles that are held by centrifugal force. With this arrangement, ZnO is directly exposed to concentrated solar radiation and serves simultaneously the functions of radiant absorber, chemical reactant, and thermal insulator. The multilayer cavity is made of sintered ZnO tiles placed on top of a porous 80%Al2O3-20%SiO2 insulation and reinforced by a 95%Al2O3-5%Y2O3 ceramic matrix composite, providing mechanical, chemical, and thermal stability and a diffusion barrier for product gases. 3D CFD was employed to determine the optimal flow configuration for an aerodynamic protection of the quartz window against condensable Zn(g). Experimentation was carried out at PSI’s high flux solar simulator with a 10 kW reactor prototype subjected to mean radiative heat fluxes over the aperture exceeding 3000 suns (peak 5880 suns). The reactor was operated in a transient ablation mode with semi-batch feed cycles of ZnO particles, characterized by a rate of heat transfer — predominantly by radiation — to the layer of ZnO particles undergoing endothermic dissociation that proceeded faster than the rate of heat transfer — predominantly by conduction — through the cavity walls.

Application of vermiculite and limestone to desulphurization and to the removal of dust during briquette combustion

Small domestic cooking furnaces are widely used in China. These cooking furnaces release SO2 gas and dust into the atmosphere and cause serious air pollution. Experiments were conducted to investigate the effects of vermiculite, limestone or CaCO3, and combustion temperature and time on desulphurization and dust removal during briquette combustion in small domestic cooking furnaces. Additives used in the coal are vermiculite, CaCO3 and bentonite. Vermiculite is used for its expansion property to improve the contact between CaCO3 and SO2 and to convey O2 into the interior of briquette; CaCO3 is used as a chemical reactant to react with SO2 to form CaSO4; and bentonite is used to develop briquette strength. Expansion of vermiculite develops loose interior structures, such as pores or cracks, inside the briquette, and thus brings enough oxygen for combustion and sulphation reaction. Effective combustion of the original carbon reduces amounts of dust in the fly ash. X-ray diffraction, optical microscopy, and scanning electron microscopy with energy dispersive X-ray analysis show that S exists in the ash only as anhydrite CaSO4, a product of SO2 reacting with CaCO3 and O2. The formation of CaSO4 effectively reduces or eliminates SO2 emission from coal combustion. The major factors controlling S retention are vermiculite, CaCO3 and combustion temperature. The S retention ratio increases with increasing vermiculite amount at 950°C. The S retention ratio also increases with increasing Ca/S molar ratio, and the best Ca/S ratio is 2-3 for most combustion. With 12 g of the original coal, 1 to 2 g of vermiculite, a molar Ca/S ratio of 2.55 by adding CaCO3, and some bentonite, a S retention ratio >65% can be readily achieved. The highest S retention ratio of 97.9% is achieved at 950°C with addition of 2 g of vermiculite, a Ca/S ratio of 2.55 and bentonite.

Radiolysls In the adsorbed state. III. Methyl iodide adsorbed on silica gel

The 60Co γ-radiolysis of methyl iodide adsorbed on silica gel has been studied by examining the hydrocarbon products, which are mainly methane and ethane. These products are formed in large yields, indicating that a large fraction of the energy absorbed in the silica gel is able to cause decomposition of the methyl iodide. The “energy transfer” is thought to occur by electron or excitation transfer to the methyl iodide, leading to the production of methyl radicals.Evidence has been obtained that the silica gel takes part in the system as a chemical reactant as well as being an energy transfer medium, and that changing the nature of the surface changes the course of the reaction. This is most clearly shown in two ways. The ratio of methane to ethane decreases as the surface hydroxyl concentration decreases, and it is concluded that excited methyl radicals form methane by abstraction of hydrogen from surface hydroxyls. Experiments using methyl iodide-d3 adsorbed on protiated silica gel confirm the participation of hydrogen from the silica gel, as the methane is over 85% CD3H, while the ethane is over 95% C2D6.The effect of additives such as N2O and SF6, which are known to be electron scavengers, was also studied. It was shown that methyl iodide is a much better electron scavenger than N2O and is as good an electron scavenger as SF6 in this system.