Catalysis in Industry最新文献

英文中文

Porous Alumina-Supported Tungstated Zirconia Catalysts for Heptane Isomerization 用于庚烷异构化的多孔氧化铝支撑钨酸氧化锆催化剂

IF 0.7 Q4 Chemical Engineering

Catalysis in Industry

Pub Date : 2024-05-27 DOI: 10.1134/s207005042470003x

M. D. Smolikov, V. A. Shkurenok, S. S. Yablokova, K. V. Kazantsev, T. I. Gulyaeva, I. V. Muromtsev, A. V. Lavrenov

Abstract

Novel WO₃–ZrO₂ (WZ) catalysts with palladium as an active metal on porous alumina supports of various phase compositions have been synthesized. Aluminas from Sasol molded in the form of extrudates (E) and spherical aluminas (S), in which the phase composition is presented by θ-Al₂O₃, δ-Al₂O₃, and α-Al₂O₃ alumina, have been used as supports. It has been shown that the phase composition of the support has a significant effect on the activity of supported Pd/WZ catalysts based on it. Upon transition from a set of θ- and δ-Al₂O₃ phases to the θ- and α-Al₂O₃ phase composition has led to an increase in the activity of the catalysts, as evidenced by a shift of 10–30°C in the temperature dependences of the heptane conversion to lower temperatures. The appearance of the α-Al₂O₃ phase is accompanied by a decrease in the specific surface area of the catalysts, which leads to an increase in the density of acid sites and, as a consequence, a change in activity. The Pd/WZ catalysts supported on S aluminas are characterized by a higher acidity (3.7–6.3 μmol/m²) as compared to the samples supported on E aluminas (2.8–3.6 µmol/m²). The high acidity of the Pd/WZ/S catalysts intensifies the heptane cracking side reactions to form gaseous C₁–C₄ hydrocarbons. In turn, the moderate acidity of the Pd/WZ/E catalysts contributes to a higher selectivity to heptane isomers (89.2–89.3% at a heptane conversion of 81.5–83.2%) as compared to the catalysts supported on S supports (isomerization selectivity of 84.9–85.6% at a heptane conversion of 80.4–81.4%).

摘要在不同相组成的多孔氧化铝载体上合成了以钯为活性金属的新型 WO3-ZrO2 (WZ) 催化剂。以萨索尔公司生产的挤压成型氧化铝（E）和球形氧化铝（S）为载体，其中氧化铝的相组成为θ-Al2O3、δ-Al2O3 和 α-Al2O3。研究表明，载体的相组成对基于载体的 Pd/WZ 催化剂的活性有显著影响。从一组 θ- 和 δ-Al2O3 相过渡到 θ- 和 α-Al2O3 相组成后，催化剂的活性提高了，这表现在庚烷转化的温度依赖性向低温转变了 10-30°C 。随着 α-Al2O3 相的出现，催化剂的比表面积也随之减小，这导致了酸性位点密度的增加，从而改变了催化剂的活性。与支撑在 E 型铝上的样品（2.8-3.6 µmol/m2）相比，支撑在 S 型铝上的钯/WZ 催化剂具有更高的酸度（3.7-6.3 μmol/m2）。Pd/WZ/S 催化剂的高酸度加强了庚烷裂解副反应，形成气态 C1-C4 碳氢化合物。反过来，Pd/WZ/E 催化剂的中等酸度也有助于提高庚烷异构体的选择性（在庚烷转化率为 81.5-83.2% 时为 89.2-89.3%），而以 S 为载体的催化剂（在庚烷转化率为 80.4-81.4% 时为 84.9-85.6% 的异构化选择性）则无法达到这一水平。

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引用次数: 0

Physicochemical and Catalytic Properties of Bifunctional Catalysts with Different Contents of Zeolite ZSM-22 in the Hydrodeoxygenation of Sunflower Oil 不同含量沸石 ZSM-22 双功能催化剂在葵花籽油氢脱氧反应中的理化和催化特性

IF 0.7 Q4 Chemical Engineering

Catalysis in Industry

Pub Date : 2024-05-27 DOI: 10.1134/s2070050424700065

A. A. Nepomnyashchii, E. R. Saibulina, E. A. Buluchevskiy, T. I. Gulyaeva, R. M. Mironenko, O. V. Potapenko, A. V. Lavrenov

Abstract

The authors study the effect of the content of zeolite ZSM-22 (15–70 wt %) in a support on the physicochemical properties of Pt/ZSM-22–Al₂O₃ catalysts. The dependence of the yield and composition of sunflower oil hydrodeoxygenation products on these catalysts on the temperature (310–340°C), pressure (3‒5 MPa), and weight hourly space velocity (WHSV) (0.8–3 h⁻¹) is determined. The possibility is shown of the full hydrodeoxygenation of sunflower oil with the formation of C₅₊ hydrocarbons containing up to 72% of iso-paraffins with yields of 75–79 wt %.

摘要作者研究了载体中沸石 ZSM-22 的含量（15-70 wt %）对 Pt/ZSM-22-Al2O3 催化剂理化性质的影响。测定了这些催化剂上葵花籽油加氢脱氧产物的产量和组成与温度（310-340°C）、压力（3-5 兆帕）和重量时空速度（WHSV）（0.8-3 h-1）的关系。结果表明，葵花籽油可以完全加氢脱氧，形成 C5+ 碳氢化合物，其中异链烷烃含量高达 72%，产率为 75-79 wt%。

引用次数: 0

Effect of the Composition and Synthesis Method on the Sorption Properties of NaNO3/MgO Sorbents with Respect to Carbon Dioxide 成分和合成方法对 NaNO3/MgO 吸附剂对二氧化碳吸附特性的影响

IF 0.7 Q4 Chemical Engineering

Catalysis in Industry

Pub Date : 2024-05-27 DOI: 10.1134/s2070050424700016

I. E. Nikulina, V. S. Derevshchikov, V. P. Pakharukova, P. V. Snytnikov, D. I. Potemkin

Abstract

In this work, sorbents based on magnesium oxide MgO modified with NaNO₃ taken in a concentration of 5–50 mol % have been synthesized and studied by various methods. It has been shown that the optimum synthesis method is impregnation of the MgO precursor. The optimum concentration of NaNO₃ as a modifier is 10 mol %; this concentration provides a sorption capacity of 6.5 mmol CO₂/g_sorb within 1 h of sorption at 320°C and a CO₂ content of 50 vol %. The sorption capacity achieved in 10 consecutive sorption–desorption cycles for 10 mol % NaNO₃ is 4.5–5.5 mmol CO₂/g_sorb within 30 min of sorption at 50 vol % CO₂ and temperatures of 300 and 350°C for the sorption and desorption stages, respectively. It has been found that an increase in the total sorption pressure to 10 atm makes it possible to decrease the sorption temperature to 220–260°C, and the achieved sorption capacity is 4.0 mmol CO₂/g_sorb at 25 vol % CO₂, which is almost 2 times higher than the sorption capacity value at 1 atm. It has been shown that treatment with steam and hydrogen does not lead to a significant change in the sorption properties and phase composition of MgO modified with NaNO₃.

摘要在这项工作中，采用各种方法合成并研究了用 NaNO3 改性的氧化镁 MgO（浓度为 5-50 mol %）吸附剂。结果表明，最佳的合成方法是浸渍氧化镁前驱体。作为改性剂的 NaNO3 的最佳浓度为 10 摩尔 %；在 320°C 和二氧化碳含量为 50 vol % 的条件下，吸附 1 小时后的二氧化碳吸附量为 6.5 mmol CO2/gsorb。在二氧化碳含量为 50 Vol %、吸附和解吸阶段温度分别为 300°C 和 350°C 的条件下，10 mol % NaNO3 在连续 10 次吸附-解吸循环中的吸附容量为 4.5-5.5 mmol CO2/gsorb，吸附时间为 30 分钟。研究发现，将总吸附压力提高到 10 个大气压可将吸附温度降低到 220-260°C ，在 25 Vol % CO2 的条件下，吸附能力达到 4.0 mmol CO2/gsorb，比 1 个大气压下的吸附能力值高出近 2 倍。研究表明，用蒸汽和氢气处理不会导致用 NaNO3 改性的氧化镁的吸附特性和相组成发生显著变化。

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引用次数: 0

Use of Microwave Irradiation to Synthesize Solketal from Glycerol and Acetone 利用微波辐照从甘油和丙酮合成 Solketal

IF 0.7 Q4 Chemical Engineering

Catalysis in Industry

Pub Date : 2024-05-27 DOI: 10.1134/s2070050424700053

V. A. Bolotov, A. E. Kibilyuk, V. N. Parmon, V. N. Panchenko, M. N. Timofeeva

Abstract

It has been shown that solketal can be synthesized from glycerol and acetone irradiation in the presence of montmorillonite (MM) modified with an aqueous solution of 0.25 mol/L of HCl (0.25M HCl/MM). The reaction has been studied in a methanol solution at an acetone/glycerol molar ratio of 2.45–7.53, a catalyst concentration of 1.2–2.8 wt % (based on glycerol weight), and 30–56°C. It has been shown that solketal is the major product with a selectivity of 96.1–99.2%. The maximum solketal yield of 91.3% with a 98.6% selectivity is obtained within 15 min of reaction at an acetone/glycerol molar ratio of 7.53, a catalyst loading of 2.3 wt % (based on glycerol weight), and 56°C. The catalytic properties of 0.25M HCl/MM in the reaction under microwave and thermal heating conditions have been compared. It has been shown that the solketal yield in the reaction under MW irradiation is 2 times higher than that in the process with thermal heating.

摘要研究表明，在用 0.25 摩尔/升盐酸水溶液（0.25M HCl/MM）修饰过的蒙脱石（MM）存在下，可以用甘油和丙酮辐照合成索酮醛。在丙酮/甘油摩尔比为 2.45-7.53、催化剂浓度为 1.2-2.8 wt %（基于甘油重量）、温度为 30-56°C 的甲醇溶液中对该反应进行了研究。结果表明，溶酮醛是主要产物，选择性为 96.1-99.2%。在丙酮/甘油摩尔比为 7.53、催化剂负载量为 2.3 wt %（以甘油重量为基准）、温度为 56°C 的条件下，反应 15 分钟内可获得 91.3% 的最高溶酮醛产率和 98.6% 的选择性。比较了 0.25M HCl/MM 在微波和热加热条件下反应的催化特性。结果表明，在微波辐照下反应的溶酮产量是热加热工艺的 2 倍。

引用次数: 0

Diesel Fraction Isodewaxing in the Presence of Granular Platinum-Containing SAPO-11 and SAPO-41 Molecular Sieves 粒状含铂 SAPO-11 和 SAPO-41 分子筛存在下的柴油馏分异脱蜡过程

IF 0.7 Q4 Chemical Engineering

Catalysis in Industry

Pub Date : 2024-05-27 DOI: 10.1134/s2070050424700089

R. E. Yakovenko, M. R. Agliullin, I. N. Zubkov, O. D. Denisov, D. V. Serebrennikov, B. I. Kutepov, A. L. Maksimov

Abstract

In this paper, the physicochemical and catalytic properties of SAPO-11 and SAPO-41 molecular sieves granulated with a binder material and promoted with 0.5 wt % Pt have been studied in the isodewaxing of a hydrotreated diesel fraction. It has been shown that the introduction of ~30 wt % of boehmite, which transforms into alumina under calcination, into the granules leads to a decrease in the micropore volume by 50–70% and an increase in the external specific surface area of the material by 6–12% as compared to the highly dispersed samples of the above molecular sieves. It has been found that, at 340°C, 3 MPa, 2.0 h⁻¹, and H₂/feedstock = 800 m³/m³, both samples of bifunctional catalysts provide the production of diesel fuel with a pour point of –42°C and a yield of ~91–92 wt %.

摘要本文研究了用粘合剂材料造粒并用 0.5 wt % Pt 促进的 SAPO-11 和 SAPO-41 分子筛在加氢处理柴油馏分的异脱蜡过程中的物理化学和催化特性。研究表明，与高度分散的上述分子筛样品相比，在颗粒中引入约 30 wt % 的沸石（在煅烧过程中会转化为氧化铝）可使微孔体积减少 50-70%，材料的外比表面积增加 6-12%。研究发现，在 340°C、3 兆帕、2.0 小时-1 和 H2/ 原料 = 800 立方米/立方米条件下，这两种双功能催化剂样品均可生产倾点为 -42°C 的柴油，收率约为 91-92 wt %。

引用次数: 0

Combined Deoxygenation and Isomerization of Sunflower Oil Fatty Acid Triglycerides on Pt/Al2O3-Zeolite Catalysts 铂/Al2O3-沸石催化剂上葵花籽油脂肪酸甘油三酯的联合脱氧和异构化反应

IF 0.7 Q4 Chemical Engineering

Catalysis in Industry

Pub Date : 2024-05-27 DOI: 10.1134/s2070050424700077

A. A. Nepomnyashchii, E. R. Saibulina, E. A. Buluchevskiy, T. I. Gulyaeva, V. L. Yurpalov, R. M. Mironenko, O. V. Potapenko, A. V. Lavrenov

Abstract

The authors study the effect of the type of zeolite (SAPO-11, ZSM-22, ZSM-23, and ZSM-12) in a support (ratio zeolite : Al₂О₃ = 30 : 70) on the physicochemical properties of Pt/Al₂O₃-zeolite catalysts and the composition of products from the hydrodeoxygenation of sunflower oil on them. The possibility of the complete hydrodeoxygenation of sunflower oil at temperatures of 320–350°C, a pressure of 4 MPa, and a weight hourly space velocity (WHSV) of 1 h⁻¹ is shown with 75–82% yields of liquid products. The fraction of iso-alkanes and the yield of direct hydrodeoxygenation products grow along with the concentration of Brønsted acid sites in a catalyst in the order 1%Pt/Al₂O₃-ZSM-22 < 1%Pt/Al₂O₃-ZSM-12 < 1%Pt/Al₂O₃-ZSM-23 < 1%Pt/Al₂O₃-SAPO-11.

摘要作者研究了载体中沸石类型（SAPO-11、ZSM-22、ZSM-23 和 ZSM-12）（沸石与 Al2О3 的比例为 30:70）对铂/Al2O3-沸石催化剂的理化性质及其上葵花籽油加氢脱氧产物组成的影响。结果表明，在温度为 320-350°C、压力为 4 兆帕、重量小时空间速度（WHSV）为 1 小时-1 的条件下，葵花籽油可以完全加氢脱氧，液体产物的产率为 75%-82%。异构烷烃的馏分和直接加氢脱氧产物的产率随着催化剂中布氏酸位点浓度的增加而增加，其顺序为 1%Pt/Al2O3-ZSM-22；1%Pt/Al2O3-ZSM-12；1%Pt/Al2O3-ZSM-23；1%Pt/Al2O3-SAPO-11。

引用次数: 0

Hydrodeoxygenation of Sunflower Oil on Pt/WOx-Al2O3 Catalyst 葵花籽油在 Pt/WOx-Al2O3 催化剂上的加氢脱氧反应

IF 0.7 Q4 Chemical Engineering

Catalysis in Industry

Pub Date : 2024-05-27 DOI: 10.1134/s2070050424700090

A. A. Nepomnyashchii, V. L. Yurpalov, E. A. Buluchevskiy, V. A. Drozdov, T. I. Gulyaeva, R. M. Mironenko, A. V. Lavrenov

Abstract

The authors study the effect of the tungsten oxide in the supports of 0.5% Pt/WO_x-Al₂O₃ catalysts on their acidity, deposited platinum dispersity, and catalytic properties in the hydrodeoxygenation of sunflower oil. It is shown that the of Brønsted acid sites on its surface grows, and the dispersity of deposited platinum in the ready catalyst is reduced when the content of the modifier is increased. The studied samples ensure complete sunflower oil conversion in a hydrogen atmosphere at a liquid weight hourly space velocity (WHSV) of 1 h⁻¹, a temperature of 380°C, and a total pressure of 4 MPa the composition of the support. A nearly stoichiometric yield of C₅₊ products at a level of 82–86 wt % is attained. The acidic properties of the 0.5% Pt/WO_x-Al₂O₃ system determine the possibility for synthesizing the components of diesels with high contents of iso-alkanes as a result of sunflower oil hydrodeoxygenation. Using a catalyst with a nominal tungsten content of 15 wt % WO₃ brings the content of iso-paraffins up to 74% with complete conversion of the initial feedstock for no less than 24 h.

摘要作者研究了 0.5% Pt/WOx-Al2O3 催化剂载体中的氧化钨对其酸度、沉积铂分散度以及葵花籽油加氢脱氧催化性能的影响。结果表明，当改性剂的含量增加时，其表面的布氏酸位点增加，沉积在成品催化剂中的铂的分散度降低。所研究的样品可确保在氢气环境中，在液体重量时空速度（WHSV）为 1 h-1、温度为 380°C、总压强为 4 MPa 的条件下实现葵花籽油的完全转化。C5+ 产物的产量几乎达到了 82-86 wt %。0.5% Pt/WOx-Al2O3 系统的酸性特性决定了合成葵花籽油加氢脱氧过程中异构烷烃含量较高的柴油组分的可能性。使用标称钨含量为 15 wt % WO3 的催化剂，可使异链烷烃的含量达到 74%，初始原料的完全转化时间不低于 24 小时。

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引用次数: 0

“Sowing in Science Brings a Rich Harvest for the People.” Life and Work of S. A. Fokin "科学播种，人民丰收"。斯-阿-福金的生活和工作

IF 0.7 Q4 Chemical Engineering

Catalysis in Industry

Pub Date : 2024-05-27 DOI: 10.1134/s2070050424700107

R. M. Mironenko, A. V. Lavrenov

Abstract

An essay on the scientific activities of the Russian organic chemist and chemical engineer Sergei Alekseevich Fokin (1865–1917) is presented. The name of the scientist is not widely known although he has made the main contribution to the development of oleochemistry and creation of the industrial process of fat hydrogenation in Russia, and his merits have been appreciated by domestic and foreign researchers.

摘要本文介绍了俄罗斯有机化学家和化学工程师谢尔盖-阿列克谢耶维奇-福金（1865-1917 年）的科学活动。这位科学家的名字并不广为人知，尽管他为俄罗斯油脂化学的发展和脂肪氢化工业工艺的创造做出了主要贡献，他的功绩得到了国内外研究人员的赞赏。

引用次数: 0

High-Loaded Copper-Containing Catalysts for Furfural Hydroconversion 用于糠醛加氢转化的高负载含铜催化剂

IF 0.7 Q4 Chemical Engineering

Catalysis in Industry

Pub Date : 2024-05-27 DOI: 10.1134/s2070050424700028

S. A. Selishcheva, A. A. Sumina, O. A. Bulavchenko, V. A. Yakovlev

Abstract

In this paper, high-loaded copper-containing catalysts synthesized by the different methods (sol–gel, fusion, coprecipitation) have been studied in furfural hydroconversion in a batch reactor at a hydrogen pressure of 5.0 MPa and a temperature of 100°C. The reduction temperatures and phase composition of the catalysts have been determined by physicochemical methods. It has been shown that the highest activity in the studied process is exhibited by a coprecipitated copper–alumina catalyst, which provides the production of furfuryl alcohol with a selectivity of 100% at 100–130°C; in addition, in the presence of this catalyst, 2-methylfuran can be synthesized with a yield of 65% at 200°C. The phase composition of the catalyst reduced at a selected temperature and the catalyst after reaction has been determined.

摘要本文研究了采用不同方法（溶胶-凝胶法、熔融法、共沉淀法）合成的高负载含铜催化剂在氢气压力为 5.0 兆帕、温度为 100°C 的间歇反应器中进行糠醛加氢转化的情况。通过物理化学方法确定了催化剂的还原温度和相组成。结果表明，在所研究的工艺中，共沉淀铜氧化铝催化剂的活性最高，在 100-130°C 的温度下，其生产糠醇的选择性为 100%；此外，在该催化剂存在的情况下，在 200°C 的温度下，可合成 2-甲基呋喃，产率为 65%。已测定了在选定温度下还原的催化剂和反应后催化剂的相组成。

引用次数: 0

Formation of Epoxycyclooctane during the Co-Oxidation of Cyclooctene and Alkylbenzenes 环辛烯和烷基苯的共氧化作用生成环氧环辛烷

IF 0.7 Q4 Chemical Engineering

Catalysis in Industry

Pub Date : 2024-05-27 DOI: 10.1134/s2070050424700041

N. I. Kuznetsova, V. N. Zudin

Abstract

Cyclooctene and alkylbenzenes are subjected to co-oxidation in oxygen and a system of two catalysts. Radical catalyst Fe(acac)₃/NHPI mediates the formation of alkylbenzene hydroperoxides, which are consumed in situ during the MoO₃/SiO₂-catalyzed epoxidation of cyclooctene. The chain oxidation rate is limited in cyclooctene and MoO₃/SiO₂, but radical catalyst Fe(acac)₃/NHPI retains fairly high activity in the oxidation of alkylbenzene in hydroperoxide. It is found that isopropylbenzene is a better co-reducing agent than ethylbenzene because it ensures more vigorous and selective formation of epoxycyclooctane. At optimized amounts of components and a temperature of 80°C, selectivity toward epoxycyclooctane reaches 92 and 96% in ethylbenzene or isopropylbenzene, respectively, with more than 70% conversion of cyclooctene.

摘要环辛烯和烷基苯在氧气和两种催化剂体系中发生共氧化反应。自由基催化剂 Fe(acac)3/NHPI 介导了烷基苯氢过氧化物的形成，这些氢过氧化物在 MoO3/SiO2 催化环辛烯环氧化过程中被就地消耗。环辛烯和 MoO3/SiO2 的链氧化速率有限，但自由基催化剂 Fe(acac)3/NHPI 在过氧化氢烷基苯氧化过程中保持了相当高的活性。研究发现，异丙苯是比乙苯更好的共还原剂，因为它能确保环氧环辛烷的形成更有活力和选择性。在各组分的最佳用量和 80°C 的温度下，乙苯或异丙苯对环氧环辛烷的选择性分别达到 92% 和 96%，环辛烯的转化率超过 70%。

引用次数: 0

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