In the study of hydrodesulfurization of residual oil, determination of the relation between hydrogen consumption and sulfur removal is one of the most important items.
Khafji crude oil (sulfur content 2.78%) was hydrodesulfurized with conventional cobalt-molybdate catalyst using a flow reactor under constant hydrogen pressure at 40kg/cm²G.
1. Hydrogen consumption in hydrcdesulfurization was proportionally increased with increasing of sulfur removal. When sulfur removal was 50%, hydrogen consumption was approximately 40m³ per kiloliter of Khafji crude oil.
2. Vanadium content in oil did not decrease in mild processing, but asphaltene in oil reduced proportionally to the sulfur removal.
3. Reaction order of the removal of sulfur from Khafji crude oil was apparent second order.

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The rate equation of cyclohexane disappearance in cyclohexane reforming reaction under high temperatures and high pressure conditions was determined with a reforming catalyst used in the petroleum naphtha reforming process.
The ranges of reaction conditions were as follows; the reaction temperature 400-470°C, the total pressure 35.0 atm, the liquid hourly space velocity 3-30hr^-1, the mole ratio (m) of hydrogen to cyclohexane feed 5-15, and the initial hydrogen partial pressure (18.0-35.0)m/(1+m) atm. In this work, 0.3-0.7g of the catalyst was packed in a microreactor. Total hydrocarbon products were analyzed into their components, after being injected in their gas phase to the gaschromatograph.
The following conclusions were obtained from the present work:
(I) The rate of cyclohexane disappearance with the stabilized platinum type catalyst under the conditions mentioned above was expressed as to be proportional to cyclohexane partial pressure (p_c), considering the reversive reaction (k'_pp_bp³_h) of benzene to cyclohexane and the rate constant (k) was indicated by the following equation;
k=f₀/V[1+3/(1+m)(1+p³_h/K)]ln1/1-(1+p³_h/K)x-f₀/V3x/(1+m)(1+p³_h/K), where x was the conversion of cyclohexane, t the reaction time, f₀ the standard feed rate of total reactants, V the volume of the catalyst bed, p_h the hydrogen partial pressure, K the equilibrium constant, and k the rate constant.
(II) The apparent activation energy (E) of the cyclohexane reforming reaction was 33.8kcal/mole.
(III) Therefore, the activity of reforming catalysts should be examined with the values of k and E.

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This paper deals with properties of NiO-MgO catalysts, and their activities for n-hexane-steam reaction. Catalysts containing 2∼98% of NiO were prepared by the wet mixing method, and were calcined at 1000°C. The structures of the catalysts were observed by X-ray diffraction method and their reduction with hydrogen was investigated by means of an automatic-recording thermobalance. Their activities were tested in n-hexane-steam reaction under the following conditions: reaction temperature of 550∼850°C, steam/oil ratio of 9, and LHSV of 1.0.
Solid solution of isomorphous substitution was formed by the calcination of a mixture of NiO and MgO, but two types of solid solutions were formed when the mixing of the powders of NiO and MgO was imcomplete. One of these was a solid solution with an excess NiO, and the other with an excess MgO. The former is easily reduced by hydrogen, whereas the latter is reduced with difficulty.
In the n-hexane-steam reaction, the NiO excess solid solution in the catalyst containing 10% by wt. of NiO was reduced at 750°C and became active, but metallic nickel could not be detected by X-ray diffraction. This indicates that the reduced nickel was either very fine in size, or was dispersed into the MgO lattice.

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The vapor phase alkylation of benzene with ethylene over silicaalumina (S. A) catalyst has been studied by a flow method under pressure of 20∼30kg/cm² and within the temperature range of 250∼350°C. By the addition of a small amount of organic halogen compound to the feed, the catalyst showed a remarkably high activity at relatively low temperature and pressure. Among various organic halogen compounds used in the reactions, gem-type halogen compounds, such as carbon tetrachloride, chloroform, trichlorofluoromethane and 1, 1, 1-trichloroethane, served as the accelerators of the reaction, but victype halogen compounds, such as 1, 2-dichloroethane and 1, 2-dichloropropane, decreased the activity of the catalyst.
From an examination of the correlation between the activities and the total acidities of the catalysts, it was found that the activity in the reaction depended upon the acidity of the catalyst. The kinetic study showed that the rate of this reaction was first order with respect to the partial pressure of ethylene and benzene respectively in the initial stage of the reaction, and the apparent activation energy was about 10kcal/mole.

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Competitive experiments in the alkylation of benzene and its homologues with olefins and alcohols were carried out in the presence of boron trifluoride and its complex catalysts.
Considering the results obtained, the substance attacking the benzene ring directly was in the form of a carbonium ion (R⁺), an ion-pair (R⁺…Cat.^-) or a polarized intermediate (R^δ+…Cat.^δ-), according to the type of alkylating reagents and the nature of the catalysts.
Generally speaking, the alkylating reagents producing a stable carbonium ion such as tertiary butyl cation or the complex catalysts making a homogeneous reaction phase had the tendency to give a carbonium ion as the attacking substance. While, in the presence of the alkylating reagents (which produced an unstable carbonium ion and formed a stable ester with acid or the catalysts, giving a heterogeneous reaction phase), the attacking substance seemed to be in the form of an ion-pair or a polarized intermediate.
The form of the attacking substance exerted a great influence on the relative reactivity of benzene homologues.
In the case of the attack by a carbonium ion, the inductive effect of the alkyl groups on the benzene ring was predominant. Hence, toluene and alkylbenzenes were more reactive than benzene in the tertiary butylation or in the propylation, with the catalysts giving a homogeneous reaction phase.
In the case of the attack by an ion-pair, or a polarized intermediate having a less positive charge than a carbonium ion, the inductive effect was surpassed by the stereochemical and probability effects. Hence, benzene showed a higher reactivity than toluene and other alkyl benzenes in the ethylation and the propylation, with the catalysts giving a highly heterogeneous reaction phase. The reactivity of benzene decreased with the decrease of the heterogeneity of the reaction phase.

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Radical telomerization reaction of ethylene and carbon tetrachloride was continuously carried out by flowing both reagents cocurrently through a vertical U-shaped reactor at pressures of 80-200kg/cm², temperatures of 90-104°C and molar flow ratios (C₂H₄/CCl₄) of 1.66-6.86 in the presence of azobisisobutyronitrile as the initiator. Under the said conditions of reaction, conversion of carbon tetrachloride was dependent on the residence time of the reacting mixture in the reactor. The composition of telomer produced, however, was kept constant irrespective of the conversion of carbon tetrachloride and residence time of the reacting mixture under a given temperature, pressure, and flow ratio of ethylene to carbon tetrachloride. With increase of the molar ratio of ethylene to carbon tetrachloride, the composition of the telomer mixture changed similarly as in a batch telomerization process, showing a gradual decrease in the content of the lower telomer homologs. Under a given molar ratio of ethylene to carbon tetrachloride, the pressure of the reaction exerted a considerable influence upon the composition of the telomer mixture, which has not been detected clearly in a batch process.

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The effect of added solvents (aprotic and alicyclic, and hydroxylic fatty solvents) on the radical telomerization reaction of ethylene and carbon tetrachloride was investigated.
Among others, hydroxylic solvents, especially those possessing active hydrogen atoms contiguous to the hydroxyl group exerted a marked influence upon the telomerization initiated by azobisisobutyronitrile (AIBN), giving high yield of tetrachloroalkanes and considerable increase of the content of tetraehloropropane (1:1 adduct). However, the said effect of hydroxylic solvents was largely diminished in a monoethanolamine (MEA)-initiated telomerization reaction. Moreover, this solvent effect was also suppressed by addition of neutralizing agents for evolved hydrogen chloride and by application of high pressure of reaction and high concentration of AIBN (initiator).
Aprotic aromatic solvents showed retarding effect on the telomerization reaction to give low yield of tetrachloroalkanes. The said retarding effect was not observed for aprotic alicyclic solvents.
The composition of tetrachloroalkanes obtained in the presence of aprotic aromatic and alicyclic solvents was the same as in tert-butanol which possesses no active hydrogen atom adjacent to the OH-group.
By way of explanation, a radical reaction between carbon tetrachloride and hydroxylic solvent was assumed to give α-chloroalcohol with large chain-transferring capacity.

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A kinetic study has been made of the synthesis of o- and p-anisaldehyde from anisole-BF₃ complex and CO in hydrogen fluoride solution.
In the preliminary investigation a new white complex was obtained below -60°C, the composition of which was 1 mole anisole-2 moles BF₃-1 mole HF with a m. p. of -60°C. The apparent equilibrium constant for the complex formation has been determined to be 219 at 0°C on the assumption of the existence of o- and p-complex of σ-type.
As to the reaction of anisole with CO, the conditions enabling the liquid phase reaction rate-determining were found to be: a charge ratio of Anisole/HF<30, a stirring speed above 750rpm and an operational temperature below 60°C; the latter being essential to prevent side reactions leading to the formation of tarry matter.
The rate of each o- and p-aldehyde formation is of the first order with respect to the dissolved CO and the complex respectively. The apparent rate constants are 6.67×10^-3 (kg^-1cm²•min^-1) for o- and 4.23×10^-3 for p-aldehyde formation at 40°C and the apparent activation energies 9kcal•mole^-1 for both products.
Compared with the rates of the same reaction with toluene and m-xylene, the rate constant of anisaldehyde formation is much smaller.

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An apparatus for the automatic measurement and monitoring of water content of water-in-oil emulsions is described, consisting of a transformer bridge, a phase detector and a Schmitt trigger circuit.
The water content of such emulsions can be determined up to 5%wt., with an accuracy of 0.05%wt., during flow and at any desired distance. By presetting the measuring capacitor an alarm or monitoring signal will be activated when the water content reaches the corresponding limit.
If a higher degree of accuracy is required, the temperature should be kept constant and zero-balancing be repeated for oils which have deteriorated during prolonged use.

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Percolation is a problem resulting from vapor formation in the fuel system of automobiles as well as vapor lock. Percolation has recently become very serious in Japan. Road tests were carried out using four Japanese cars and one American car to determine the percolation performance of fuels. The percolation performance of fuels was correlative with 30% and 50% evaporated temperature, representing mid-range volatility, however, it was not correlative with Reid vapor pressure and 10% evaporated temperature, representing front end volatility. The influence of cars and test conditions on percolation was also studied.

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The ASTM method has been commonly used, as a standard determination method for the insolubles in used oils. But, a defect of this method is that a part of the coagulant remain in insolubles, and it is difficult to determine insolubles in used oil which contains some type of polymeric detergent. In order to determine insolubles in such used oils, we propose a new method by which insolubles are extracted with a cylindrical filter paper dipped in a mixture of heptane and coagulant prior to use. Some experimental results are described and the best operating conditions examined. Conparison was made between the new and the other methods.

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Wear tests between phosphorous bronze and steel, which are widely used as components of worm gear, were carried out with the Soda four-ball testing machine, consisting of a rotating steel ball and three fixed phosphorous bronze balls. The effect of lubricating oil additives on wear were investigated and the following results were obtained.
(1) In the case of refined straight oil, wear was reduced with the increase of viscosity of the oil.
(2) Organic acids, fatty oils, esters, alcohols and naphthenic soaps were used as additives in these experiments. Most of them exhibited the capacity of reducing wear; above all, a long chain fatty acid such as stearic acid was most effective.
(3) Sulfur compounds such as sulfurized fatty oil or dibenzyl-disulfide and chlorinated paraffin remarkably promoted wear.
(4) Phosphorous compounds such as phosphites and phosphates were highly effective in the presence of sulfur or chlorine compounds. Dialkyl dithiophosphates containing phosphorous in the molecular structure, and generally used as antioxidants, also promoted wear.
(5) Some kinds of commercial EP additives for multipurpose gear oil promoted, while other kinds of them reduced wear.
(6) The wear reducing action of additives such as fatty oil and phosporous compounds is observed also in the rubbing of steel against various copper alloys and in that of soft steel against phosphorous bronze.
(7) It was recognized that there was a close relation between the roughness of rubbing surface and the amount wear. The roughness of rubbed surface was small for the additive of reducing wear, while it was increased for the additive of promoting wear.

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The mechanical and rheological properties of matrix (filler-bitumen mixture) and mastic asphalt were investigated by various tests including the Wheel tracking test and a Simple shear test. There exist considerable differences between so-called no-void bituminous mixtures such as mastic asphalt and conventional bituminous paving mixtures. Generally a stability of the bituminous paving mixtures depends on a interlocking of the aggregate, while the stability of no-void mixtures depends mainly on binder or matrix viscosity. As a factor which controls the rheological properties of matrix and mastic asphalt, the amount of excess matrix and of excess bitumen were considered by the authors.
The relationships between rheological properties and these excess amount of bitumen and of matrix were investigated.

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