Recent progress on the autoxidation of petroleum hydrocarbons and of polycyclic hydrocarbons along with coal was reviewed. Initiation reation by intiators or metal salts is affected by reaction conditions. Propagation reaction depends on the carbon-hydrogen bond dissociation energy but not so much on peroxy radicals. The rate of propagation step is varied with the dielectric constant and water content of the solution, and is increased remarkably by cobalt bromide. Inhibition of autoxidation by phenolic or amine compounds involves the hydrogen abstraction step.The electron releasing substituents on phenols increase the inhibition effect and a synergistic effect may be obtained in the presence of hindered and non-hindered phenols. Polycyclic aromatic hydrocarbon inhibits the autoxidation, but its oxidation proceeds relatively easily in the basic solution. Oxidation of bituminous coal in alkaline aqueous solution under pressure results in the formation of benzene polycarboxylic acids.

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I would like to propose a high temperature-high pressure theory concerning to the origin of petroleum. Organic substances contained in the bodies of plants and animals are said to be related to the origin of petroleum, and this is called organic theory. The existence of some optical active nitrogen compounds in a crude oil are resulted in the proposal of organic theory which relates to the low temperature formation of petroleum by the microbiotic actions.
Recently, petroleum, especially normal paraffins, were found to be easily converted to proptein and amino acid according microbiotic method, so that the presence of optical active nitrogen compounds in crude oil seems to me to be the secondary products from petroleum.
My high temperature-high pressure theory is bassed on the knowledge about high temperature behavior of hot carbon.
The sublimation temperature of carbon is said to be 3, 800-4, 200°C, and when carbon was heated to higher temperature of about 5, 000-6, 000°C, it is completely converted to gaseous state, which is composed of C₁-C₆ in a dicarbene form. These carbon species would be possible to form normal C₁-C₆ paraffins by the reaction of hydrogen atom. I have tried to react carbon dioxide with cyclohexane in a high voltage silent electric discharge tube, and the product obtained were a mixture of Cyclohexanone, cyclohexanol and carbon monoxide. Next, carbon monoxide is subjected to silent electric discharge, and the product was carbon suboxide.
So that carbon dioxide seems to convert to carbon monoxide and oxgen atom, and the final products were hot carbon and oxygen, as shown hereunder;
CO₂→CO+O
2CO→C*+CO₂
C^*+CO→: C^*=C=O
CO→0=C=C*=C=O
If this reaction is carried out in the presence of reducing metallic compounds such as silicium, the product must be hot carbon.
As to the hydrogen source, I would like propose steam. Steam decomposes to hydrogen atoms and hydroxyl radical, and in the presence of reducing metallic compounds, the only product must be hydrogen.
Thus I believe that carbon dioxide and steam would react to form hot carbon and hydrogen atom at high temperature and in the presence of metallic silicium.
The hot carbon and hydrogen atom thus formed seem to convert to petroleum hydrocarbon by the rapid expansion from the high temperature-high pressure conditions to low temperature-low pressure one through a pin hole, being accompanied by the rapid lowering of temperature. The igneous rock would make a high temperature-high pressure petroleum production tank by the mutual approach in the molton state to form a big tank and after the soldification of molton rock, the tank surface would be then covered by water in the form of sea or lake.
The above-mentioned pin hole may be localed at beneath of bottom of sea or lake in some depth.

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In order to obtain the relation between the furnace temperature and the oil temperature, the author has derived the following relations from the experiments, in which fuel oil contained in a cruicible was put into a constant temperature furnace of natural draught.
(1) The oil temperature θ_f at steady state is dependent of furnace temperature θ_g and fuel properties, and independent on initial weight of oil.
(2) The empirical relationship between fuel temperature, furnace temperature and fuel properties is as follows.
θ_f/θ_b=b {θ_g·λ_g/ (α_f·γ_f·γ_f)} ^0.62,
b=4967 (λ_fo/ d_fo) ³-1774 (λ_fo/ d_fo) ²+218 (λ_fo/ d_fo)-8.67
where θ_b=mean boiling temperature of oil (°C)
λ_g=thermal conductivity of air, (kcal/mhr°C)
α_f=temperature conductivity of oil (m²/hr)
γ_f=specific weight of oil (kg/m³)
γ_f=latent heat of evaporation of oil (kcal/kg)
b=constant by the properties of oil
d_fo=specific gravity of oil at 15°C
λ_fo=thermal conductivity of oil at 15°C (kcal/mhr°C)

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(1) The model experiment to make a ball by use of coal powder (as non-caking material) and coldsetting phenolic resin (as caking constituent) in 3 kinds of drums (128mm∅, 190mm∅ and 285mm∅) at the room temperature was carried out.
It was recognized that the ball was increased in size as the amount of blended resin was increased when the diameter of drum was equal, and the ball was increased in size as the diameter of drum was increased when the amount of the blended resin was equal.
(2) In the carbonization of “Miike coal and Tagawa senseki (natural coke) ” and “Yubari coal and Sunagawa low temperature coke” in a rotary retort (200mm∅×180mm) with and without passing air stream, specific volume curves of coke were drawn. By these curves, the course of formation of coke balls was explained, then swelling-and contraction-indexes were obtained. As these indexes indicated caking property, it was revealed that caking property was decreased earlier by carbonization with passing air stream than without passing air stream.
(3) K. B. S. curve and coke button number of samples in the carbonization of said coals in a rotary retort with and without passing air stream were obtained. From these data, the same conclusion as above (2) was obtained.

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The first stage CRG plant in Negishi Works of Tokyo Gas Company was putted on stream in November 1966, and since then it has continued 6, 800 hours of operation without changing CRG catalyst.
During the period, there were several shut-downs of the plant, and we have conducted two overhauls in order to have periodical inspection. The working result of the plant and the catalyst has been very satisfactory which proves that the Gas Council Catalytic Rich Gas Plant is very steady and reliable.

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