The aquathermolysis process is widely considered to be one of the most promising approaches of in-situ upgrading of heavy oil. It is well known that introduction of metal ions speeds up the aquathermolysis reactions. There are several types of catalysts such as dispersed (heterogeneous), water-soluble and oil soluble catalysts, among which oil-soluble catalysts are attracting considerable interest in terms of efficiency and industrial scale implementation. However, the rock minerals of reservoir rocks behave like catalysts; their influence is small in contrast to the introduced metal ions. It is believed that catalytic aquathermolysis process initiates with the destruction of C-S bonds, which are very heat-sensitive and behave like a trigger for the following reactions such as ring opening, hydrogenation, reforming, water–gas shift and desulfurization reactions. Hence, the asphaltenes are hydrocracked and the viscosity of heavy oil is reduced significantly. Application of different hydrogen donors in combination with catalysts (catalytic complexes) provides a synergetic effect on viscosity reduction. The use of catalytic complexes in pilot and field tests showed the heavy oil viscosity reduction, increase in the content of light hydrocarbons and decrease in heavy fractions, as well as sulfur content. Hence, the catalytic aquathermolysis process as a distinct process can be applied as a successful method to enhance oil recovery. The objective of this study is to review all previously published lab scale and pilot experimental data, various reaction schemes and field observations on the in-situ catalytic aquathermolysis process.

In-Situ Heavy Oil Aquathermolysis in the Presence of Nanodispersed Catalysts Based on Transition Metals

Application of confocal laser-scanning microscopy (CLSM) to autofluorescent organic and mineral matter in peat, coals and siliciclastic sedimentary rocks — A qualitative approach

To obtain clean liquid fuel, a study was conducted on upgrading shale oil by hydroconversion. Various W–Ni catalysts were synthesized and characterized using XRD, BET, TG, H2-TPR, and NH3-TPD methods. The effects of tungsten content and calcination temperature on the physicochemical properties and activity of catalysts were systematically investigated. W–Ni/Al2O3 with 15 wt % W-loading and 550 °C calcination temperature was selected as the optimized catalyst. The product distribution of the primary aromatics in shale oil affected by hydrogenation, ring opening, and cracking reactions was discussed. Finally, key reaction parameters such as pressure, liquid hourly space velocity, and H2/oil volume ratio were optimized. Characteristics of gasoline and diesel fractions were also measured.

Upgrading Shale Oil Distillation to Clean Fuel by Coupled Hydrogenation and Ring Opening Reaction of Aromatics on W–Ni/γ-Al2O3 Catalysts

Pyrolysis of Kaa-Khemsky and Mezhegeisky coals was investigated with an increase in temperature to 900 °С with a change in pressure in the reactor by increasing the retention time of volatile substances in the pyrolysis zone at 600 °С and 640 °С. Liquid products of coal pyrolysis were extracted by hexane and benzene. The composition of liquid extracts was studied by chemical analysis, GC-MS and IR-spectroscopy, the solid product of extraction-by elemental analysis and scanning electron microscopy. It was established, that coal nature and pyrolysis conditions affect significantly on the yield of liquid, solid and gaseous products. Also, the retention time of volatile substances in pyrolysis zone influences on the yield of solid product (increases from 60 %wt to 73 % wt) and on composition of hexane and benzene soluble tar fractions. This is also facilitated by an increase in pressure in the reactor as a result of the release of volatile substances from coal in the pyrolysis zone.

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The Influence of Retention of Volatile Substances in Pyrolysis Zone of Kaa-Khemsky and Mezhegeisky Coal Deposits on Component Composition of Coal Tar

The development of mining and processing industries is accompanied by the formation of fine-grained waste materials that must undergo the treatment. Sometimes, grinding materials is a prerequisite for further processing. The issues of coal dust and fine coal granulation conducted to obtain homogeneous and persistent pieces for application in various branches of industry were presented. The article describes the binders and additives were applied in order to change the properties of the granules. The key factors affecting the process of fine-grained coal granulation is discussed. Granulated coal dust is most useful as an alternative fuel for combustion in industrial and household heating systems. However, carbon fuel requires a systematic control of the mechanical strength and resistance to external factors.

http://www.jeeng.net/pdf-89794-24669?filename=The Use of Granulation to.pdf

The Use of Granulation to Reduce Dusting and Manage of Fine Coal

The chemical composition of the distillate fractions with boiling points of to 180, 180–230, and 230–280°C separated from undehydrated coal tar from OAO Altai-Koks was studied by gas chromatography-mass spectrometry. A list of identified aromatic compounds (including N-, O-, and S-containing compounds) and their alkyl derivatives is given. It was found that, upon the complete processing of tar with the recirculation of residual raw materials at the stage of coking and its hydrogenation refining in the presence of suspended Mo- and Ni-containing catalysts and a hydrogen donor (tetralin), the yields of chemical products were the following (wt %): coke, 50–55; absorption oil, 9–12; benzene, naphthalene, tetralin, dimethylnaphthalenes, and other hydrocarbons, 25–30; BTX fraction 4–5; and C1-C4 and CO2, 10–12.

Chemical composition of the distillate fractions of coal tar from OAO Altai-Koks

The relative H-donor capacity of the hydrogenated derivatives of aromatic compounds (benzene, naphthalene, anthracene and phenanthrene) depending on temperature and pressure was studied by the methods of chemical thermodynamics and of quantum chemistry.

Donor capacity of hydroaromatic compounds

The structure parameters of hydrogenation products were analyzed in relation to the composition of oil and coal (intrinsic) paste-forming agents used in the process of coal hydrogenation under a low pressure of hydrogen (6–10 MPa). It was found that the structure characteristics of liquefaction products essentially differed at close values of the structure unsaturation parameter δ; this was likely due to a difference in the material composition of solvents (other than aromatic structures).

Structure of coal hydrogenation products obtained in the presence of oil and coal paste-forming agents

The results of experimental studies on an increase in the reactivity of brown coal from the Erkovetskoe deposit upon hydrogenation under a low pressure of hydrogen (10 MPa) by crushing in a vibrating mill and a universal disintegrator activator (UDA) are reported. The high efficiency of the application of UDA technology to coal preparation at the stage of crushing, catalyst supporting, and coal–oil paste preparation on coal liquefaction by hydrogenation is demonstrated.

Mechanochemical activation of coal from the Erkovetskoe deposit and its reactivity in a liquefaction process

The results of the hydrogenation processing of the semicoking tar (AO Sary Arka Spetskoks, Karaganda, Republic of Kazakhstan) of coal from the Shubarkol deposit in the presence of Mo- and Ni-containing pseudohomogeneous catalytic systems for the production of motor fuel components and chemical substances are reported. It was established that the yield of a gasoline fraction at a temperature of 400°C (5.0 MPa, a 0.015% S additive) was 18.7% with the use of a molybdenum catalyst or 10.6% with a nickel catalyst; therefore, the coal tar can be considered as a potential raw material for obtaining motor fuel components.

A. S. Maloletnev

Papers

Chemical composition of the distillate fractions of coal tar from OAO Altai-Koks

Donor capacity of hydroaromatic compounds

Structure of coal hydrogenation products obtained in the presence of oil and coal paste-forming agents

Mechanochemical activation of coal from the Erkovetskoe deposit and its reactivity in a liquefaction process

Hydrogenation of the semicoking tar of coal from the Shubarkol deposit