Both freshly prepared and steamed MFI zeolite catalysts have been tested for service life. It has been shown that the zeolite cycle length is increased from 7 to 60 days by steaming. In contrast, comparative testing under mild conditions at 300°С has demonstrated low on-stream stability of the catalyst after steaming. Thermogravimetric analysis data indicate different mechanisms of coke formation on samples at 300°С: polyaromatic coke is produced on the fresh sample and predominantly polyaliphatic coke forms on the steamed sample. It has been found that correct comparison of oligomerization catalysts differing in acidity requires a temperature no less than 380°С, which ensures the formation of polyaromatic coke on both catalysts. As a result of the study, a rapid procedure for accelerated deactivation testing has been developed that makes it possible to obtain data comparable with those of long-term service life tests.

A new method has been suggested for the preparation of high-octane components from the butane–butylene fraction (BBF) in two stages. At the first stage, the BBF olefins are oxidized with N2O into carbonyl compounds with high selectivity without forming the products of deep oxidation and water. The process occurs in the gas phase in a flow reactor without using a catalyst at a temperature of 400°C and a pressure of 2 MPa with high conversion of both olefins and nitrous oxide. The blending octane number of the oxidation product is 118–133 (RON) and 99–104 (MON). At the second stage, the mixture of carbonyl compounds is hydrogenated with hydrogen in the presence of the Ni/Al2O3 catalyst. The hydrogenation occurs at 150–160°C in a flow reactor in the gas phase. The aldehydes are completely transformed into alcohols, while the ketones can remain in the product under certain conditions. The blending octane number of the hydrogenation product is 111–112 (RON) and 95–96 (MON), which is smaller than for the BBF oxidation product, but larger than for the alkylate obtained in the course of conventional butene alkylation with isobutane (RON is 95–97 and MON is 93–95). Synthesis of high-octane components by this procedure can be useful in practice, especially in productions with huge release of nitrous oxide.

A new technology for alkylation on solid AlkiRAN-GPN catalyst with process performance characteristics and an attained material balance competitive with existing sulfuric and hydrofluoric acid alkylation technologies is presented. Data on the effect such parameters as temperature, pressure, iso-butane: olefin ratio, and feedstock hourly space velocity (FHSV)) have on the process’s performance characteristics are given, and their optimum values are recommended. It is shown that using a sectioned reactor at a constant inlet iso-butane: olefin ratio ensures a higher internal ratio of these components and an increase in the total concentration of alkylate in the reaction products at a specified internal iso-butane: olefin ratio. This also lengthens the period of catalyst interregeneration with no losses in the process’s productivity and selectivity. The use of a zeolite based on faujasite in the rare-earth element–calcium form (REECaHY) and ultrastable zeolites as catalysts is substantiated. Higher values of olefin conversion and the alkyl gasoline yield are observed when these zeolites are used. To test the new technology, a demonstration plant of iso-butane alkylation with olefins on heterogeneous catalysts with an alkylate production capacity of 1 t/day is constructed. The results from studies are to be used in developing the basic design of an industrial plant. The construction of the first industrial plant of alkylation on a heterogeneous catalyst with an alkyl gasoline production capacity of 100000 t/year is planned at AO Gazprom Neft Moscow Oil Refinery.

A new CoMo catalyst for selective hydrotreating of FCC gasoline has been developed; the catalyst is intended for the production of hydrotreated gasoline with up to 10 ppm of sulfur and with a research octane number decreased by less than 1.0. The new catalyst allows hydrotreating of FCC gasoline without its preliminary separation into the light and heavy fractions. The hydrotreating conditions were as follows: hourly space velocity 2.2 h–1, temperature 270°C, pressure 2.5 MPa, H2/feed = 150 m3/m3. The high degree of hydrodesulfurization at minimum decrease in the octane number is achieved due to the high activity of the developed catalyst in hydrodesulfurization of the sulfur-containing components of the feedstock and conversion of reactive high-octane olefins of FCC gasoline into less reactive derivatives with high octane numbers. The catalyst is a CoMoS phase deposited on a support containing amorphous aluminosilicate and γ-Al2O3. The method for the preparation of the catalyst is adapted to the equipment of Russian plants and feedstocks. The parameters of hydrotreating using this catalyst ensure the hydrotreating of FCC gasoline to a residual sulfur content of less than 10 ppm with minimum redesign of the equipment currently available at Russian refineries.

Prospects for conversion of refinery gas to high-octane components of motor fuel were discussed. The feedstock of the Russian petrochemical complex can be expanded by introducing light hydrocarbons— nonmarketable refinery waste products—in the production of ecologically safe high-octane components of gasoline based on tert -butanol and isopropanol. A series of articles in the field of related applied research and experimental developments were announced.

It is proposed that the sulfide NiMo system supported on alumina-SAPO-31 composite (NiMo/Al2O3-SAP catalyst) be used to obtain high-quality diesel fuel from a mixture of straight run diesel (SRGO) and light cycle oil (LCO) produced by fluid catalytic cracking (FCC). It is shown that the use of this catalyst ensures the synthesis of diesel fuel of higher quality upon hydroprocessing a feedstock with 30 wt % LCO, compared to the traditional sulfide NiMo/Al2O3 or CoMo/Al2O3 catalysts. It is found that the content of aliphatic hydrocarbons is raised in the products of hydrotreatment, compared to the initial feedstock. This confirms the ability of NiMo/Al2O3-SAP catalyst to facilitate the reaction of ring opening. Using the proposed catalyst should improve the quality of diesel fuels obtained via the hydroprocessing of LCO-containing feedstock.

A NiMo sulfide system with an alumina support containing aluminosilica phosphate SAPO-31 (catalyst NiMo/Al 2 O 3 -SAP) was suggested for synthesis of high-quality diesel fuel from a mixture of straight-run diesel fraction and light catcracking gasoil (LCCG). Against the traditional NiMo/Al 2 O 3 or CoMo/Al 2 O 3 sulfide catalysts, this catalyst was demonstrated to provide production of higher quality diesel fuel through hydroupgrading of the feedstock containing 30 wt.% LCCG. The fact that the proportion of aliphatic hydrocarbons is higher in the products than in the feedstock indicates the activity of the NiMo/Al 2 O 3 -SAP catalyst to ring opening. Application of the suggested catalyst will allow the quality of diesel fuels to be improved during hydroupgrading of the LCCG-containing feedstock.

A new CoMo catalyst was developed for selective hydrotreatment of FCC gasoline to provide no more than 10 ppm of sulfur in the hydrotreated gasoline and no more than 1,0 point RON decrease against the initial RON. The new catalyst allows the FCC gasoline not to be prefractionated into light and heavy fractions before its hydrotreatment. The hydrotreatment conditions are as follows: feed flow rate 2,2 h–1, 270 °C, 2,5 MPa, H 2 /feed = 150 m 3 /m 3 . The high degree of hydrodesulfurization at a minimal decrease in RON is achieved owing to the high catalyst activity to hydrodesulfurization of the sulfur-containing components and to conversion of reactive high-octane olefins of the FCC gasoline to their less reactive derivatives with the high octane numbers. The catalyst is a CoMoS phase on the support containing amorphous aluminosilicate and γ-Al 2 O 3 . The method for the catalyst preparation is adapted to the Russian industrial facilities and to the feedstock available in Russia. Application of the hydrotreatment process based on this catalyst does not need considerable reconstruction of the facilities available at Russian refineries but provide residual sulfur content less than 10 ppm in the hydrotreated FCC gasoline.

A new technology for alkylation over the AlkyRAN-GPN catalyst was developed. The performance and the mass balance achieved using the developed technology is competitive to the parameters of currently employed processes for alkylation with sulfuric acid and hydrogen fluoride. The data on the influence of temperature, pressure, isobutane : olefin ratio, feed flow rate on the process parameters are reported and the optimal conditions recommended. The use of a sectional reactor is shown to allow the isobutane : olefin ratio and the total alkylate concentration in the reaction products to be increased at the constant inlet isobutane : olefin ratio. The service cycle of the catalyst also increases while the process productivity and selectivity does not decrease. The use of faujasite-based zeolites in their calcium-rare-earth and ultrastable forms is rationalized: they provide the highest conversions of olefin and the best yield of alkylgasoline. The construction of a demonstration setup (1 t of alkylate per day) for testing the new technology of isobutane alkylation with olefins over heterogeneous catalysts is in progress. The results obtained will be used for preparation of the engineering bases of the large-scale unit. The first industrial unit for alkylation over a heterogeneous catalyst (100,000 t of alkylgasoline/y) is to be erected at JSC Gazpromneft-Moscow Refinery.

The suggested new method for synthesis of high-octane components from the butane-butylene fraction (BBF) includes two stages. At the first stage, BBF olefins are oxidized at a high selectivity with N2O to carbonyl compounds without formation of deep oxidation products and water. This is a non-catalytic gas phase process achieved in a flow reactor at 400 °C and 2 MPa, conversions of both olefins and nitrogen suboxide being high. The octane number of mixed oxidation products is 118-133 (RON) and 99-104 (MON). The second stage is gas-phase hydrogenation of the mixed carbonyl compounds with hydrogen in the presence of the Ni/Al 2 O 3 catalyst at 150–160 °C in a flow reactor. The aldehydes are transformed to alcohols, while ketones may remain among the products under certain conditions. The octane number of mixed hydrogenation products is 111-112 (RON) and 95-96 (MON) that is inferior to that of the BBF oxidation product but superior to that of the alkylate produced by the traditional processes of butane alkylation with isobutane (95-97 RON, 93-95 MON). The application of the suggested process for synthesis of high-octane components may be of practical importance when concentrated waste of nitrogen suboxide is available.

A NiMo sulfide system with an alumina support containing aluminosilica phosphate SAPO-31 (catalyst NiMo/Al 2 O 3 -SAP) was suggested for synthesis of high-quality diesel fuel from a mixture of straight-run diesel fraction and light catcracking gasoil (LCCG). Against the traditional NiMo/Al 2 O 3 or CoMo/Al 2 O 3 sulfide catalysts, this catalyst was demonstrated to provide production of higher quality diesel fuel through hydroupgrading of the feedstock containing 30 wt.% LCCG. The fact that the proportion of aliphatic hydrocarbons is higher in the products than in the feedstock indicates the activity of the NiMo/Al 2 O 3 -SAP catalyst to ring opening. Application of the suggested catalyst will allow the quality of diesel fuels to be improved during hydroupgrading of the LCCG-containing feedstock.

The effect of localization of acid sites and the nature of the modifier metal on the activity, selectivity, and operation stability of a ZSM-5 zeolite-based catalyst in the oligomerization of the butane–butylene fraction (BBF) has been examined. It has been shown that the selective poisoning of acid sites on the external surface of zeolite crystals reduces coking and increases the yield of the desired gasoline fraction. Introduction of a promoter metal insignificantly affects the catalytic properties of the zeolite. Among Zn, Ga, and La, gallium appears to be the best modifier, which provides an increase in the yield of the desired gasoline fraction by 0.9%. As a result of the study, a BBF oligomerization catalyst has been developed that ensures a threefold increase in the catalyst on-stream time and a 7% increase in the yield of the gasoline fraction as compared with its commercial counterpart.