Уникальные каталитические технологии в области энергоэффективности и энергосбережения

Публикации

2015

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Anton A. Gabrienko, Evgeny V. Morozov, Velu Subramani, Oleg N. Martyanov, and Sergei G. Kazarian.Chemical Visualization of Asphaltenes Aggregation Processes Studied in Situ with ATR-FTIR Spectroscopic Imaging and NMR Imaging//The journal of physical chemistry. 2015, 119, 2646-2660. DOI: 10.1021/jp511891f

ABSTRACT
Crude oil phase behavior and asphaltene precipitation have been studied by two complementary chemical imaging methods for the first time. ATR-FTIR spectroscopic imaging approach has revealed the chemical composition of agglomerated and precipitated asphaltenes upon dilution with a flocculant. Asphaltenes, containing oxygen and nitrogen heteroatomic functional groups, have been detected to be least stable. Aromatic abundant asphaltenes have been observed to have relatively high solubility in crude oil/heptane blends. NMR imaging approach, capable of imaging in the bulk of crude oil samples, has demonstrated that n-heptane causes aggregation which can lead to the stable suspension or to the sedimentation followed by the formation of deposits, depending on flocculant concentration. These processes have been monitored for small and large amounts of heptane added to crude oil. The data obtained by ATR-FTIR spectroscopic imaging and NMR imaging have been correlated to propose a possible link between the chemical structure of asphaltenes and a mechanism of the formation of deposits.

R. G. Kukushkin, O. A. Bulavchenko, V. V. Kaichev, V. A. Yakovlev.Influence of Mo on catalytic activity of Ni-based catalysts inhydrodeoxygenation of esters// Applied Catalysis B: Environmental 163 (2015) 531–538. DOI: 10.1016/j.apcatb.2014.08.001

ABSTRACT
The effect of molybdenum on activity of Ni-based catalysts in the hydrodeoxygenation of fatty acidesters was studied. Catalysts Ni-Cu/Al2O3, Ni-Mo/Al2O3, Cu-Mo/Al2O3, Mo/Al2O3, and Ni-Cu-Mo/Al2O3with different ratios Ni/Mo were prepared and tested in the hydrodeoxygenation of methyl palmitateand ethyl caprate at 300◦C, 1 MPa. It was found that an increase in the Mo content (from 0.0% to 6.9%)in the Ni-Cu-Mo/Al2O3catalysts leads to an increase in the yield of normal alkanes. The catalysts werecharacterized by X-ray photoelectron spectroscopy (XPS), temperature programmed reduction and X-ray diffraction techniques. The XPS data showed that the increase in the conversion of fatty acid esters isrelated to changes in the ratio between different oxidation states of molybdenum (Mo0, Mo4+, and Mo6+)on the surface of the Ni-Cu-Mo/Al2O3catalysts. © 2014 Published by Elsevier B.V.

2014

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Liana F. Nurislamova, Olga P. Stoyanovskaya, Olga A. Stadnichenko, Irek M. Gubaidullin, Valeriy N. Snytnikov and Anastasia V. Novichkova. Few-Step Kinetic Model of Gaseous Autocatalytic Ethane Pyrolysis and Its Evaluation by Means of Uncertainty and Sensitivity Analysis. Chemical Product and Process Modeling. Volume 9, Issue 2, Pages 143-154. ISSN (Online) 1934-2659, ISSN (Print) 2194-6159. DOI: 10.1515/cppm-2014-0008

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В. А. Кириллов, В. А. Собянин, П. В. Снытников.Технология переработки попутных нефтяных газов малоресурсных и малонапорных нефтяных месторождений в метановодородные смеси и товарный природный газ// Нефть. Газ. Новации. – 2014.- №8.- С.44-51.

ABSTRACT
Поднята проблема, связанная со сжиганием в факелах углеводородных газов. Приведена информация об объемах сжигаемого ПНГ по региону ХМАО-Югра. Сделан акцент на одном из путей решения проблемы утилизации ПНГ – применении ПНГ в качестве топлива в двигателях внутреннего сгорания. Рассматриваются проблемы и сложности, связанные с ипользованием ПНГ для целей энергоснабжения. Представлена новая технология, способная решить обозначенные проблемы и направленная на эффективное использование ПНГ в энергогенерирующих системах, – мягкий паровой риформинг (МПР).

Sergey N. Trukhan,Valerii F. Yudanov, Anton A. Gabrienko,Velu Subramani, Sergei G. Kazarian, and Oleg N. Martyanov. In Situ Electron Spin Resonance Study of Molecular Dynamics of Asphaltenes at Elevated Temperature and Pressure// Energy and Fuels. 2014, 28, 6315−6321. DOI: 10.1021/ef5015549

ABSTRACT
A comparison of the behavior of asphaltene molecules extracted from crude oil and dissolved in aromatic solvent as a model system with the behavior of vanadium-containing molecules in real crude oils via electron spin resonance in situ technique showed that the changes of rotational mobility of asphaltene molecules can be related to the changes of the local viscosity and environment of the asphaltenes as well as the characteristic sizes of vanadyl-containing fragments because of aggregation/disaggregation processes in crude oils. The information about the mobility of asphaltene molecules in different local environments at different temperatures and pressures is an important step in understanding both the aggregation of the asphaltenes and crude oil fouling processes in addition to the conditions required for the deposits to be formed.

V. N. Snytnikov, T. I. Mishchenko, Vl. N. Snytnikov, I. G. Chernykh.Autocatalytic dehydrogenation of propane. Research on Chemical Intermediates. (2014) 40:345–356. DOI: 10.1007/s11164-012-0967-1

ABSTRACT
Homogeneous gas-phase pyrolysis of propane was performed by using continuous CO2 laser irradiation for bulk heating of the reaction mixture. Laser energy was absorbed by ethylene, the main product of propane dehydrogenation, and transferred to the reaction medium via collisional relaxation. A mechanism of propane dehydrogenation is suggested to describe the pyrolysis process. The mechanism involves autocatalysis by ethylene and includes propane–ethylene interaction with the formation of ethyl and propyl radicals.

M. M. Zyryanova, P. V. Snytnikov, R. V. Gulyaev, Yu. I. Amosov, A. I. Boronin, V. A. Sobyanin.Performance of Ni/CeO2 catalysts for selective CO methanation in hydrogen-rich gas// Chemical Engineering Journal 238 (2014) 189–197. DOI: 10.1016/j.cej.2013.07.034

ABSTRACT
Selective CO methanation in H2-rich gas mixture containing 10 vol.% H2O and 20 vol.% CO2 was investigated over chlorine doped 1.8–46.1 wt.% Ni/CeO2 catalysts. BET, XRD, TEM, EDX microchemical analysis and XPS techniques were used for catalyst characterization. Among the catalysts studied, the 9.1 wt.% Ni/CeO2 catalyst with the surface Cl/Ce atomic ratio of 0.15 was the most effective. This catalyst provided the reducing of the CO concentration in H2-rich gas to less than 10 ppm over a wide temperature interval (250–320 _C) keeping the selectivity high (>50%). It was shown that ceria-supported small (20–80 A) nickel-containing particles provided good activity, while stable chlorine species maintained high selectivity of the catalyst. 2013 Elsevier B.V. All rights reserved.

M.V. Bykova, D.Yu. Ermakov, S.A. Khromova, A.A. Smirnov,M.Yu. Lebedev, V.A. Yakovlev.Stabilized Ni-based catalysts for bio-oil hydrotreatment:Reactivity studies using guaiacol// Catalysis Today 220– 222 (2014) 21– 31. DOI: 10.1016/j.cattod.2013.10.023

ABSTRACT
The development of catalysts possessing high activity and high stability in the catalytic hydrotreatmentof pyrolysis oils (bio-oil) is of great interest. NiCu bimetallic catalytic systems are very attractive for usein hydrotreatment process due to their low price and high activity in hydrogenation, hydrodeoxygena-tion and hydrocracking reactions. In the present work P-/Mo-containing agents were used to modifybimetallic catalytic system NiCu/SiO2–ZrO2to improve its mechanical strength and stability in acidicmedium. The modified catalysts were tested in hydrodeoxygenation (HDO) of guaiacol—a well-knownmodel compound of bio-oil. HDO process has been carried out in an autoclave at 320◦C, 17 MPa initialhydrogen pressure, reaction time 1 h. It was shown that phosphorus and molybdenum addition to thecatalysts composition results in the decrease of guaiacol conversion and deoxygenation degree. The yieldof undesirable gaseous reaction products (mainly methane) and coking of the catalyst were lower forthe modified catalysts in contrast to the initial NiCu/SiO2–ZrO2system. The catalysts treatment in glacialacetic acid at 118◦C showed that modification by P and Mo gives a significant improvement of catalystsstability in acidic medium (mass loss decreases from 53 wt.% to 1 wt.%). Also a significant improvementof bulk crushing strength has been observed for PMo-modified samples (from 0.5 MPa to 1.2 MPa).© 2013 Elsevier B.V. All rights reserved.

M. M. Zyryanova, P. V. Snytnikov, A. B. Shigarov, V. D. Belyaev, V. A. Kirillov, V. A. Sobyanin.Low temperature catalytic steam reforming of propane–methane mixture into methane-rich gas: Experiment and macrokinetic modeling// Fuel 135 (2014) 76–82. DOI: 10.1016/j.fuel.2014.06.032

ABSTRACT
Steam reforming of propane–methane mixture into methane-rich gas was studied in a fixed-bed continuous-flow reactor in a temperature interval of 150–325 _C under atmospheric pressure over Ni-based catalyst. It was found that the catalyst had good performance under low steam-to-carbon ratio of 0.39–0.58 and provided equilibrium product distribution at GHSV = 670–3100 h_1. Macrokinetic modeling of the experimental data obtained was performed in the framework of isothermal plug-flow reactor model. For the first time the two-step macro-kinetic scheme was suggested, that includes the reactions of irreversible propane steam reforming (first-order on propane): C3H8 + 6H2O?3CO2 + 10H2 with activation energy 112 kJ/mole and reversible CO2 methanation (first-order on hydrogen): CO2 + 4H2 . CH4 + 2H2O with activation energy 50 kJ/mole. It was shown that the proposed scheme describes quantitatively all the experimental results. _ 2014 Elsevier Ltd. All rights reserved.

2013

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M. M. Zyryanova, S. D. Badmaev, V. D. Belyaev, Yu. I. Amosov, P. V. Snytnikov, V. A. Kirillov, and V. A. Sobyanin.Catalytic Reforming of Hydrocarbon Feedstocks into Fuel for Power Generation Units// Catalysis in Industry, 2013, Vol. 5, No. 4, pp. 312–317. DOI: 10.1134/S2070050413040107

ABSTRACT
The feasibility of realization of the multifuel operation principle, specifically, production of a hydrogen_containing gas from various types of hydrocarbon feedstocks using the same catalyst under similar reaction conditions is considered. The steam reforming of two types of hydrocarbon mixtures, namely diesel fuel satisfying GOST (State Standard) R 52368–2005 (EN 590:2004) and a methane–propane mixture imi_tating the composition of associated petroleum gas, has been investigated to clarify this issue. These hydro_carbon feedstocks were chosen for the reason that they are universally used as a fuel for various types of power generation units. Experiments have been carried out in a catalytic flow reactor at 250–480°C (for the meth_ane–propane mixture) and 500–600°C (for diesel fuel) and pressures of 1–15 atm using a nickel_containing catalyst (NIAP_18). This catalyst has been demonstrated to ensure conversion of different types of hydrocar_bon feedstocks into synthesis gas and methane–hydrogen mixtures usable as a fuel for power generation units based on high_temperature fuel cells and for spark_ignition, diesel, and gas–diesel engines.

V. A. Kirillov, A. B. Shigarov, N. A. Kuzin, V. V. Kireenkov, Yu. I. Amosov, A. V. Samoilov, and V. A. Burtsev.Thermochemical Conversion of Fuels into Hydrogen-Containing Gas Using Recuperative Heat of Internal Combustion Engines// Theoretical Foundations of Chemical Engineering, 2013, Vol. 47, No. 5, pp. 524–537. DOI: 10.1134/S0040579513050187

ABSTRACT
The problem of the thermochemical recuperation of heat from the exhaust gases of internal com_bustion engines (ICEs) as a method of increasing of the efficiency of fuels has been considered. The thermo_dynamic analysis of thermochemical recuperation conditions was performed, and maximum efficiency con_ditions were determined. Catalysts for the steam conversion of oxygen_containing fuels into syngas were developed, and the Co–Mn/Al2O3 catalyst was shown to be the most promising. The model of a thermo_chemical heat recuperation system was developed and manufactured, and its bench tests in the conversion of alcohols were performed using the simulated exhaust gases from a heating device. Mathematical models for calculating units of the heat recuperation system were developed. A recuperation system was manufactured and tested in the ICE_free and ICE_integrated variants. Based on the test results, the equivalent fuel con_sumption characteristics of a recuperative ICE was revealed to decrease by 11–22% depending on its load with a decrease in the concentration of hazardous emissions by 8–12 times for CO, 2–3.5 times for CH, and 18–25 times for NOx.

M.M. Zyryanova, P.V. Snytnikov, Yu.I. Amosov, V.D. Belyaev, V.V. Kireenkov, N.A. Kuzin, M.V. Vernikovskaya, V.A. Kirillov, V.A. Sobyanin. Upgrading of associated petroleum gas into methane-rich gas for power plant feeding applications. Technological and economic benefits// Fuel 108 (2013) 282–291. DOI: 10.1016/j.fuel.2013.02.0470

ABSTRACT
Laboratory studies of the reaction of steam reforming of light hydrocarbons into methane–hydrogen mixture were performed. Ni- and Ru-containing systems were studied as the catalysts. The design, scale-out, and operation of an APG catalytic reformer integrated with evaporator-heat-exchanger, water condenser and flame burner were reported. Conversion of heavier hydrocarbon components into methane–hydrogen gas mixture exceeded 95–99% during testing the catalytic reformer at 270–360 _C. Increasing reaction temperature led to increasing H2 and CO contents in the reaction mixture and complete conversion of LPG and ethane fractions. Both initial and reformed APG were used for fueling a power generation unit on the base of gas internal combustion engine MTES-30. In case of initial APG fueling, the power derating was 22%, exhaust gas contained black smoke. When the power generation unit was fueled by methane–hydrogen mixture produced by APG catalytic reforming, the engine power attained the nominal value; the engine showed excellent dynamic and temperature characteristics, stably supported crank rotation frequency. According to economic analysis concerning different types of power plants with electric power of _1000 kW, the plants equipped with a catalytic reformer of APG into methane–hydrogen mixture show faster payback of capital investments, as compared to the plants fed by APG directly, due to longer service life, longer overhaul intervals, and low rated power losses. Catalytic reforming of APG into methane–hydrogen mixture is a promising approach for solving APG utilization problem. _ 2013 Elsevier Ltd. All rights reserved.

2012

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P. V. Snytnikov, S. D. Badmaev, G. G. Volkova, D. I. Potemkin, M. M. Zyryanova, V. D. Belyaev, V. A. Sobyanin.Catalysts for hydrogen production in a multifuel processor by methanol, dimethyl ether and bioethanol steam reforming for fuel cell applications// International Journal of Hydrogen Energy. 37 (2012) 16388 -16396. DOI:10.1016/j.ijhydene.2012.02.116

ABSTRACT
Methanol, dimethyl ether and bioethanol steam reforming to hydrogen-rich gas were studied over CuO/CeO2 and CuOeCeO2/g-Al2O3 catalysts. Both catalysts were found to provide complete conversion of methanol to hydrogen-rich gas at 300e350 _C. Complete conversion of dimethyl ether to hydrogen-rich gas occurred over CuOeCeO2/g-Al2O3 at 350e370 _C. Complete conversion of ethanol to hydrogen-rich gas occurred over CuO/CeO2 at 350 _C. In both cases, the CO content in the obtained gas mixture was low (<2 vol.%). This hydrogen-rich gas can be used directly for fuelling high-temperature PEM FC. For fuelling low-temperature PEM FC, it is needed only to clean up the hydrogen-rich gas from CO to the level of 10 ppm. CuO/CeO2 catalyst can be used for this purpose as well. Since no individual WGS stage, that is necessary in most other hydrogen production processes, is involved here, the miniaturization of the multifuel processor for hydrogen production by methanol, ethanol or DME SR is quite feasible. Copyright . 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved

G. L. Semin, A. R. Dubrovskii, P. V. Snytnikov, S. A. Kuznetsov, and V. A. Sobyanin.Using Catalysts Based on Molybdenum and Tungsten Carbides in the Water–Gas Shift Reaction// Catalysis in Industry, 2012, Vol. 4, No. 1, pp. 59–66. DOI: 10.1134/S2070050412010102

ABSTRACT

М.В. Верниковская, П.В. Снытников, В.А. Кириллов, В.А. Собянин.Экономические преимущества оснащения энергоустановок каталитическим реформером попутных нефтяных газов// Нефть, Газ и бизнес. 2012. № 6, С.68-71

ABSTRACT
В статье обоснована перспективность использования на средних и малых месторождениях нефти технологии предварительной конвертации попутных нефтяных газов в метаново-водородную газовую смесь для использования в качестве топлива в энергетических установках. Определена экономическая эффективность и целесообразность коммерческого применения предлагаемой технологии. The paper proves promising the technology of associated petroleum gas reforming to methane-hydrogen gas mixture for fuelling power generation units at small- and medium-size oil deposits. Economic efficiency and commercial feasibility of the proposed technology is analyzed.

М.В.Верниковская, П.В.Снытников, В.А. Кириллов, В.А. Собянин.Технологические и экологические преимущества переработки попутных нефтяных газов в метано-водородную газовую смесь для питания энергоустановок// Нефтепереработка и нефтехимия. 2012. №11. С. 7-12.

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2011

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D.I. Potemki, P.V. Snytnikov, V.D. Belyaev, V.A. Sobyanin.referential CO oxidation over Cu/CeO2−x catalyst: Internal mass transport limitation// Chemical Engineering Journal 176– 177 (2011) 165– 171. DOI:10.1016/j.cej.2011.08.081

ABSTRACT
The effect of internal mass transport limitation on the preferential CO oxidation in hydrogen-rich mixture over copper-cerium oxide catalyst in a form of pellets and washcoat in microchannel reactor is estimated. Internal effectiveness factor _CO >0.8 in the optimum interval of reaction temperature (170–230 ◦C) is reached if the pellet diameter and washcoat thickness do not exceed 100 and 20 _m, respectively. Compared to conventional packed-bed reactor with catalyst pellets, microchannel catalytic washcoated reactor is more appropriate for practical use. © 2011 Elsevier B.V. All rights reserved.
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