Изучено гидрирование раствора 2-метилнафталина в н-гептане в присутствии дибензотиофена (400 ppm в пересчете на серу) на Pt–Pd-катализаторах, содержащих мезопористые алюмосиликаты Al-SBA-15. Носители для катализаторов содержали 35 мас. % Al-SBA-15 и 65 мас. % . Содержание Pt и Pd в катализаторах составляло, соответственно, 0.25 и 1.0 мас. %. Эксперименты с модельным сырьем проводили в автоклаве при 240–260°C, начальном давлении водорода 30 атм, массовом соотношении субстрат/металл, равным 30. Установлено, что наибольшей активностью в условиях отравления 400 ppm серы обладает катализатор на основе Al-SBA-15 с Si/Al = 5. Так, конверсия 2-метилнафталина через 3 ч при 260°C составляет 85% при селективности по метилтетралинам 97%. Деароматизация гидроочищенной дизельной фракции, с 45 ppm серы, позволила при 260°C, давлении 30 атм. и скорости подачи 2.4 ч-1 более чем в 4 раза снизить общее содержание ароматических соединений, в том числе уменьшить содержание полициклических ароматических соединений до уровня менее 1 мас. %.

Исследовано окислительное обессеривание пероксидом водорода смесей, моделирующих дизельное топливо, в присутствии азакраун-эфиров и их комплексов с пентахлоридом ниобия при 40–80°C. Установлено, что комплексы азакраун-эфиров с NbCl5 позволяют снизить содержание общей серы в модельных смесях до 13% от исходного количества. Строение применяемого азакраун-эфира незначительно влияет на степень обессеривания модельной смеси.

The hydrogenation of a 2-methylnaphthalene solution in n-heptane in the presence of dibenzothiophene (400 ppm in terms of sulfur) over Pt-Pd catalysts containing Al-SBA-15 mesoporous aluminosilicates has been studied. Supports for the catalysts contained 35 wt % Al-SBA-15 and 65 wt % γ-Al2O3. The Pt and Pd contents of the catalysts was 0.25 and 1.0 wt %, respectively. Experiments with the model feedstock were conducted in an autoclave at 240–260°C, an initial hydrogen pressure of 30 atm, and a substrate/metal weight ratio of 30. It has been found that a catalyst based on Al-SBA-15 with Si/Al = 5 exhibits the highest activity under poisoning with 400 ppm sulfur. Thus, the conversion of 2-methylnaphthalene at 260°C after 3 h was 85% with the selectivity for methyltetralins of 97%. The dearomatization of a hydrotreated diesel fraction with 45 ppm sulfur at 260°C at a pressure of 30 atm and a space velocity of 2.4 h−1 has made it possible to decrease the total aromatic content, in particular reduce the concentration of polycyclic aromatic compounds to a level of less than 1 wt %.

Hydrogen peroxide oxidative desulfurization of model diesel fuel mixtures in the presence of azacrown ethers and their complexes with niobium pentachloride at 40–80°C has been studied. It has been found that the use of complexes of azacrown ethers with NbCl5 leads to a decrease in the total sulfur content in the model mixtures to 13% of the initial amount. The structure of the azacrown ether used has little effect on the extent of desulfurization of the model mixture.

The hydrogenation of a mixture of naphthalene, tetralin, and toluene (a solution in n -heptane) in the presence of dibenzothiophene (150 and 400 ppm on a sulfur basis) over Pt-Pd catalysts containing Al-HMS mesoporous aluminosilicates has been studied. The catalyst supports contained 35 wt % Al-HMS and 65 wt % γ-Al 2 O 3 . The Pt and Pd loadings in the catalysts were 0.2 and 0.8 wt %, respectively. The process was carried out at 200–240°C, a pressure of 30 atm, and a weight hourly space velocity of 1.7 h −1 . It has been found that the catalyst based on Al-HMS with Si/Al = 10 exhibits the highest activity. Thus, in the hydrogenation of a model mixture containing 150 and 400 ppm of sulfur, the conversion of toluene at 240°C was 22.2 and 10.9 wt %, respectively. In the presence of this catalyst, the concentration of aromatic hydrocarbons in the hydrotreated diesel fraction decreased from 28.4 to 6.8 wt %, and the sulfur content decreased from 45 to 5 ppm.

Изучено гидрирование смеси нафталина, тетралина и толуола (раствор в н-гептане) в присутствии дибензотиофена (150 и 400 ppm в пересчете на серу) на Pt,Pd-катализаторах, содержащих мезопористые алюмосиликаты Al-HMS. Носители для катализаторов содержали 35 мас. % Al-HMS и 65 мас. % . Содержание Pt и Pd в катализаторах составляло, соответственно, 0.2 и 0.8 мас. %. Процесс проводили при 200 240о, давлении 30 атм. при массовой скорости подачи сырья 1.7 ч-1. Установлено, что наибольшей активностью обладает катализатор на основе Al-HMS с Si/Al = 10. Так, при гидрировании модельной смеси, содержащей 150 и 400 ppm серы, конверсия толуола при 240о составила, соответственно, 22.2 и 10.9 мас. %. В присутствии указанного катализатора содержание ароматических углеводородов в гидроочищенной дизельной фракции снизилось с 28.4 до 6.8 мас. %, а содержание серы – с 45 до 5 ppm.

The hydroisomerization of n-dodecane on bifunctional catalysts with mesostructured aluminosilicates as an active component has been studied. Aluminosilicates with an Si/Al atomic ratio of 5 to 48 have been prepared using hexadecylamine as a template. Catalyst supports contained 35 wt % mesoporous material and 65 wt % γ-Al2O3. The platinum loading of the catalysts was 0.5% of the support mass. It has been found that the catalysts based on mesoporous aluminosilicates with an Si/Al ratio of 10 and 22 exhibit the highest selectivity. In their presence, the conversion reaches 43–46 wt % with the selectivity for iso-C12H26 of more than 90%.

Изучена гидроизомеризация н-додекана на бифункциональных катализаторах, активными компонентами которых являются структурированные мезопористые алюмосиликаты. Алюмосиликаты с атомным соотношением Si/Al от 5 до 48 получены с использованием гексадециламина в качестве темплата. Носители для катализаторов содержали 35 мас. % мезопористого материала и 65 мас. % -Al2O3. Содержание платины в катализаторах составляло 0.5 мас. % от массы носителя. Установлено, что наибольшей селективностью обладают катализаторы на основе мезопористых алюмосиликатов с соотношением Si/Al равным 10 и 22. В их присутствии конверсия достигает 43–46 мас. % при селективности по изо-С12Н26 более 90%.

Mesoporous aluminosilicates with a Si/Al ratio of 5 to 20, a pore diameter of 30 to 84 Å, and a specific surface area up to 1030 cm3/g have been prepared using hexadecylamine and Pluronic P123 as templates. These materials exhibit high activity in the cracking of hydrotreated vacuum gas oil. Bifunctional catalysts derived on their basis have high selectivity in the hydroisomerization of hexadecane.

The production of the modern premium diesel fuels and base oils with low freezing point requires the inclusion of the various hydrogenation processes, such as isodeparaffinization and aromatic saturation, into the technological schemes. The base reaction of the isodeparaffinization is the transformation of long-chain n-alkanes in the presence of bifunctional catalysts into the branched alkanes, which leads to a significant decrease of the freezing point of the hydrocarbon mixture. In the first part of this work the hydroisomerization of n-dodecane and n-hexadecane on bifunctional catalysts based on mesoporous aluminosilicates was studied. The structured mesoporous aluminosilicates (Si/Al ratio 5-30) were prepared in the form of extrudates by using boehmite as a binder with the platinum content of 0,5% by mass. The highest selectivity in isomerization of n-alkanes was shown by catalysts, based on mesoporous aluminosilicates with Si/Al =5, and in the isomerization of n-C16H34 with Si/Al =20. In the second part, the activity of mesoporous catalysts aromatic and polyaromatic hydrocarbons in the hydrodearomatization (HDA) on the same was investigated. The HDA experiment on a model feed of 10% (wt.) naphthalene in benzene in a flow reactor was carried out. It was established that depending on the module aluminosilicate (in the range of Si/Al was from 5:1 to 20:1), the conversion of naphthalene to decalin and tetralin may proceed quantitatively with no conversion of benzene to cyclohexane. Selectivity was in the range from 55 to 90% by decalin, and from 10 to 45% by tetralin. We found the conditions under which the only product of hydrogenation of naphthalene is tetralin, but the conversion of naphthalene was up to 65%. Also, activity of such catalysts for hydroisomerization and hydrodearomatization processes on hydrotreated straight-run diesel fraction was investigated. Corresponding author: Name: Vilesov First name: Alexander Title: Research associate, PhD Company: A.V.Topchiev Institute of Petrochemical Synthesis of the Russian Academy of Sciences Address: 29 Leninsky prospect, Moscow, 119991 Russia Phone: +7-910-445-86-56 Email: vilesov@gmail.com, vilesov@ips.ac.ru

Mesoporous aluminosilicates with specific surface area up to 1030 m 2 /g and pore diameters from 33 to 43 Å were obtained using hexadecylamine and block copolymers of polyethylene and polypropylene oxides as structural directing agents. The synthesized materials were tested in catalytic cracking of hydrotreated vacuum gas oil at 500°C.