The catalytic activity of Group VIII transition metals except Os for methanesteam reaction under atmospheric pressure at 350∼600°C was investigated. The following activity sequence was obtained: Ru∼Rh>Ni>Ir>Pd∼Pt>>Co∼Fe.
Ru and Rh were found to possess high and stable activity over a wide range of steam/methane ratio. The rate of reaction on a Rh-silica catalyst was found to be of the zeroth and 0.5th order with respect to methane and steam, respectively.

抄録全体を表示

An alkali catalyst and an alkalized nickel catalyst were prepared form β"-Al₂O₃, one of the alkali polyaluminates. The alkali catalyst was used for catalytic cracking of various petroleum fractions, and the alkalized nickel catalyst was used for steam reforming of n-hexane, and the following results were obtained.
Using the alkali catalyst, a maximum yield of ethylene from naphtha was 47.27% at 800°C when the steam/oil ratio and space velocity were 3.0 and 7.0, respectively. From kerosene and gas oil, ethylene yields were 37.51% and 36.69% at 800°C when the steam/oil ratio and space velocity were 3.0 and 5.0, respectively.
In naphtha cracking, the carbon residue on the catalyst was removed by a steam/oil ratio of 1.5 or higher, and in kerosene and gas oil cracking, the ratio of 3.0 was required.
A high quality fuel gas suitable for high calorie town gas was obtained at 750°C or higher.
Composition of the gas produced with the alkalized nickel catalyst at temperatures in the range of from 500 to 800°C with the steam/carbon ratio of 1.5 and under 1∼20kg/cm²•G pressure was close to that of thermodynamical equilibrium. The steam/carbon mole ratio of 3.0 removed the carbon residue deposited under all operating conditions used in this work. Thus, steam/carbon mole ratios in the range of from 2.0 to 2.5 were considered to be most suitable for effective use of the catalyst.
Characteristic actions of these two types of catalysts were also discussed.

抄録全体を表示

Over-based sulfurized calcium phenates containing from 150 to 800% of the theoretical amount of calcium were prepared from p-octylphenol, calcium oxide, elemental sulfur, ethylene glycol, carbon dioxide, lauryl alcohol and oil, and their IR spectra were studied in connection with their molecular structures.
Their spectra were very similar to one another except for the band intensities. The phenates seem to be constituted of the common structure units. The spectra, moreover, predict that the skelton of the over-based part in their active ingredients is composed of calcium ethylene glyoxide carbonate units, and the -OCH₂CH₂O- group of the unit in the phenates takes the trans configuration with respect to the C-C bond. The spectrum of the intermediate suggests that configuration of the -OCH₂CH₂O- group changes from the gauche form to the trans form with respect to the C-C bond at the CO₂ treatment step.

抄録全体を表示

The effectiveness of molybdenum dialkyldithiocarbamates (I) and di-μ-thio-dithio-bis (dialkyldithiocarbamates) dimolybdenum (II) as antioxidants in the autoxidation of squalane was investigated and compared with zinc dialkyldithiocarbamate. Induction periods of doped squalane were measured using an automatic recording oxygen absorption apparatus.
These compounds show efficient inhibition action and give sharply defined induction periods, there being an abrupt change in O₂ uptake rate. It has been found that the potency as oxidation inhibitor of molybdenum compound (I) and (II) is the same irrespective of their degree of sulfurization. It seems, therefore, that the alkyl group play an important role in the activity of oxidation inhibition.
It has been experimentally found that zinc and molybdenum compounds (I, II) act as peroxide decomposer for tert-butyl hydroperoxide in chroloform solution and squalane hydroperoxide. Seemingly, capacity of molybdenum compounds (I, II) to decompose hydroperoxide is higher than that of zinc dialkyldithiocarbamate. For autoxidation of squalane initiated by azobisisobutyronitrile, the influence of zinc compound on the rate of oxidation is much more pronounced than the molybdenum compounds (I, II).
Therefore, it may be concluded that molybdenum compounds (I, II) suppress the autoxidation of squalane by acting as catalytic peroxide decomposer; on the other hand zinc dialkyldithiocarbamate by terminating the propagation of the oxidative chain reaction.

抄録全体を表示

The vapor-phase oxidation of cis-2-butene, 1, 3-butadiene, acetic acid, and hydrogen were carried out over various MoO₃-Bi₂O₃-P₂O₅ catalysts with different Bi₂O₃ contents. Oxidation activity is compared with dehydration activity for 2-propanol, and the ratios of (dehydrogenation rate)/(dehydration rate) for 2-propanol which were used as measures of acidity and basicity of the catalysts. The acidity of the catalysts increases with an increase in the Bi₂O₃ content and attains a maximum at about Bi/(Mo+Bi)=0.1. The basicity is very low for Bi₂O₃-poor composition, but sharply increases, with an increase in Bi₂O₃ at Bi/(Mo+Bi)>0.5. It has been found that oxidation and isomerization activities for olefins are associated with acidity of the catalyst and that oxidation activity for acidic compounds and activation and adsorption of oxygen are associated with basicity. Selectivity for olefin oxidation is also discussed from the viewpoint of the acid-base nature of the reactant and catalyst.

抄録全体を表示

A catalyst recycling method in the Koch reaction has been investigated using hydrogen fluoride and sulfuric acid as catalyst.
From the experimental results, the following has been proposed as a possible procedure:
Using an anhydrous hydrogen fluoride catalyst, carboxylation was conventionally carried out which was followed by hydrolysis using HF-H₂O in place of H₂O. On subsequent distillation, the hydrogen fluoride catalyst was recovered almost quantitatively as distillate and the RCOOHHF complex was obtained as residue. Treatment of the residue with an equimolar amount of water resulted in the formation of two layers. Carboxylic acid was obtained from the upper layer and the lower layer (HF-H₂O) was recycled to the hydrolysis step.
In the case of the sulfuric acid process, the carboxylic acid produced was effectively extracted with a halogenated hydrocarbon solvent without diluting the sulfuric acid catalyst. The solvent was separated from the carboxylic acid by distillation. The raffinate (H₂SO₄) was reused for carboxylation without reconcentration.

抄録全体を表示

Evaporation losses of hydrocarbons from various sources, such as refinery plants, oil terminals and gas stations, were studied. A correlation involving the volume of discharged gas, temperature and hydrocarbon concentration was derived for crude oil and petroleum products. These gas emission sources were classified according to their mode of evaporation. As a result, hydrocarbon emission factors in terms of annual mean value were obtained for various emission sources, such as cone and floating roof tanks, loading tankers, tank trucks and gas stations; and also the hydrocarbon emission factors far crude oil and such petroleum products as naphtha, gasoline, kerosene, diesel oil and fuel oil. The hydrocarbon emission factors obtained in this study were smaller than those presented by the U. S. EPA.
The calculated hydrocarbon emission factor for loading a tanker which was calculated for the first time, was less than 1/5 of that for loading a tank truck. The hydrocarbon emission factor for loading various kinds of vessels with kerosene and diesel oil was about 1/500 of that for loading the same types of vessels with gasoline.

抄録全体を表示