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Vol 57, No 7 (2017)

Article

Catalysis in the dispersed phase: Slurry technology in the synthesis of dimethyl ether (Review)

Khadzhiev S.N., Ezhova N.N., Yashina O.V.

Abstract

The world market of dimethyl ether (DME) is rapidly gaining in strength. The review addresses prospects for using the slurry technology in the large-scale world production of DME. The literature and patent data pertaining to the manufacture of dimethyl ether in slurry reactors using finely divided heterogeneous catalysts suspended in inert liquids are generalized. Variants of the slurry technology used in the one-step DME synthesis from syngas and in the two-step DME synthesis (at the stage of dimethyl ether manufacturing via methanol dehydration) are considered. Advantages of the slurry technology over the conventional gas-phase methods of DME production are highlighted.

Petroleum Chemistry. 2017;57(7):553-570
pages 553-570 views

Methanol synthesis in a three-phase slurry reactor with ultrafine catalysts

Ivantsov M.I., Kulikova M.V., Gubanov M.A., Dement’eva O.S., Chudakova M.V., Bondarenko G.N., Khadzhiev S.N.

Abstract

It is shown that the effective synthesis of methanol may be performed in the presence of ultrafine catalyst systems formed by drop thermolysis in situ in a slurry reactor. Using the X-ray powder diffraction and FTIR spectroscopy data on the evolution of Cu–Zn–Al-containing catalyst dispersion during activation and catalysis, possible reasons for ultrafine catalyst deactivation are considered.

Petroleum Chemistry. 2017;57(7):571-575
pages 571-575 views

Dimethyl ether to olefins conversion in a slurry reactor: Effects of the size of particles and the textural and acidic properties of the MFI-type zeolite

Kolesnichenko N.V., Konnov S.V., Pavlov V.S., Yashina O.V., Ezhova N.N., Khadzhiev S.N.

Abstract

Effects of the particle size of a suspended zeolite catalyst based on the commercial MFI-type (high modulus zeolite, HMZ) zeolite on its physicochemical characteristics and catalytic properties in the conversion of dimethyl ether (DME) in a three-phase system with a slurry reactor are studied. In order to gain insight into the relationships between the physicochemical characteristics of MFI-type zeolites and their catalytic properties, the textural, acidic, and catalytic properties of HMZ zeolites and synthesized nanocrystallites of the zeolite with the MFI structure are compared. It was found that, in the conversion of DME in the slurry reactor, the catalytic properties of the MFI zeolite are strongly affected by the size of particles of the suspended catalyst: on passage to nanosized suspensions, the activity of the catalyst grows by several times. Reduction in the size of catalyst particles leads to an increase in the yield of hydrocarbons C5+ and a decrease in the yield of lower olefins. At the same dispersity of suspensions, the catalytic properties of suspended catalysts are considerably affected by the distribution of acid sites over strength in the studied zeolite sample and the fraction of amphoteric sites in them.

Petroleum Chemistry. 2017;57(7):576-583
pages 576-583 views

Oxidative cracking of crude oil by hydrogen peroxide in the presence of iron oxide nanoparticles

Lesin V.I., Lesin S.V., Ivanov E.V.

Abstract

The interaction of hydrogen peroxide aqueous solutions with crude oil and high-boiling refined products, such as fuel oil and vacuum gas oil, in the presence of an oxidative cracking catalyst in the form of iron oxide nanosized particles is studied. This study is aimed at modeling processes occurring in the case of using hydrogen peroxide solutions in the catalytic cracking of crude oil. It is found that, in the presence of iron particles, the reaction of hydrogen peroxide decomposition causes the cracking of petroleum hydrocarbons. This process may be accompanied by reduction in the viscosity and density of crude oil and refined products. The reaction of catalytic cracking performed under these conditions leads to a marked increase in the fraction of light hydrocarbons in the composition of crude oil and high-boiling refined products.

Petroleum Chemistry. 2017;57(7):584-588
pages 584-588 views

Hydrodearomatization catalysts based on molybdenum hexacarbonyl Mo(CO)6 supported on mesoporous aromatic frameworks

Maksimov A.L., Karakhanov E.A., Kulikov L.A., Terenina M.V.

Abstract

A method for synthesizing fine hydrodearomatization catalysts based on the immobilization of molybdenum carbonyl into the pores of mesoporous aromatic frameworks is proposed. It is shown that the amount of the deposited metal and the average size of the resulting particles depend on the support and the deposition method characteristics. The catalytic activity of the synthesized materials in the hydrogenation of bicyclic hydrocarbons at a hydrogen pressure of 5.0 MPa in a temperature range of 330–500°C is studied using the example of naphthalene, methylnaphthalenes, and biphenyl as model substrates.

Petroleum Chemistry. 2017;57(7):589-594
pages 589-594 views

Nickel–molybdenum sulfide naphthalene hydrogenation catalysts synthesized by the in situ decomposition of oil-soluble precursors

Sizova I.A., Maksimov A.L.

Abstract

Nickel–molybdenum sulfide catalysts for the hydrogenation of aromatic hydrocarbons have been prepared by the in situ decomposition of oil-soluble precursors Mo(CO)6 and Ni(С7H15СOO)2 in a hydrocarbon feedstock and characterized by HRTEM and XPS. The resulting Ni–Mo sulfide material exhibits high catalytic activity in the naphthalene hydrogenation reaction. An optimum Mo/Ni ratio of 1/2 has been selected.

Petroleum Chemistry. 2017;57(7):595-599
pages 595-599 views

Formation of an iron-containing catalytic nanoparticle during the three-phase Fischer–Tropsch synthesis: Molecular modeling

Tsvetkov V.B., Kulikova M.V., Khadzhiev S.N.

Abstract

The effect of a polyacrylonitrile additive on the catalytic behavior of an iron-containing suspension under the conditions of Fischer–Tropsch synthesis in a slurry reactor is studied. Modeling of the formation of a catalytic particle using the molecular dynamics method is performed.

Petroleum Chemistry. 2017;57(7):600-607
pages 600-607 views

Ex situ synthesis of sulfided molybdenum-containing ultrafine hydroconversion catalysts

Kadiev K.M., Khadzhiev S.N., Kadieva M.K., Dogova E.S.

Abstract

Nanosized and ultrafine dispersions of sulfided molybdenum catalysts are synthesized from reverse emulsions in the medium of vacuum residue using various molybdenum-containing components and sulfiding agents and temperatures and times of synthesis. Physicochemical methods are applied to investigate the size, dispersion state, composition, and structure of the dispersed phase and their dependence on synthesis conditions. The hydroconversion of West Siberian vacuum residue in the presence of a number of ex situ synthesized sulfided molybdenum-containing catalyst particles is conducted. It is found that they show high activity in suppression of the polycondensation reaction leading to coke formation.

Petroleum Chemistry. 2017;57(7):608-617
pages 608-617 views

A study of the catalytic steam cracking of heavy crude oil in the presence of a dispersed molybdenum-containing catalyst

Mironenko O.O., Sosnin G.A., Eletskii P.M., Gulyaeva Y.K., Bulavchenko O.A., Stonkus O.A., Rodina V.O., Yakovlev V.A.

Abstract

The features of the steam cracking of heavy crude oil in the presence of a dispersed molybdenumcontaining catalyst are studied. The effect of water, the catalyst, and process conditions on the composition and properties of the products of the thermal conversion of heavy crude oil is determined in experiments on thermal cracking, steam cracking, catalytic cracking in the absence of water, and hydrocracking. A complex analysis of the resulting products is conducted; the catalyst-containing solid residue (coke) has been studied by XRD and HRTEM. The effect of the process temperature (425 and 450°C) and time on the yields and properties of the resulting products is studied. The efficiencies of hydrocracking and steam cracking for the production of upgraded low-viscosity semisynthetic oil are compared; the fundamental changes that occur in the catalyst during the studied processes are discussed. Some assumptions about the principle of the catalytic action of the molybdenum-containing catalyst in the steam cracking process are made.

Petroleum Chemistry. 2017;57(7):618-629
pages 618-629 views

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