Discontinuous alkylation of diphenylamine with nonene for maximum catalyst utilization

This study examines the alkylation of diphenylamine (DPA) with nonene (NON) in a liquid phase catalyzed by acid-treated clay-based catalysts from commercial suppliers (Fulcat 22B, Nobelin MM, and Jeltar 300). Alkylations were conducted to achieve the highest possible selectivity of diisononyldiphenylamine (DNDPA), low selectivity of monoisononyldiphenylamine, and a maximum triisononyldiphenylamine yield of 4%. This study also examines the reaction conditions to selectively form dialkylated diphenylamine from DPA and NON in a batch reactor. Repeated use of the catalyst during the alkylation of DPA with NON was also investigated. Catalyst deactivation takes place during the alkylation of each batch and intensifies with repeated catalyst use, resulting in low DNDPA selectivity. The regenerated catalyst was sufficiently active only until the regeneration of the first and second batches. After the third batch, the catalyst’s selectivity for DNDPA was very low, and its reuse in the alkylation of DPA with NON was not efficient. Therefore, to achieve the maximum length of catalyst activity, the fresh catalyst was gradually added to the used catalyst from a previous batch, thus maintaining a high activity of eight batches. The reduction in catalyst activity was probably caused by the irreversible adsorption of substances on the surface, a loss of microporous structure, and a loss of surface acidity. DPA or alkylated products are adsorbed on the surface oxygen of the catalyst through nitrogen and form nitro formations. The fresh and regenerated catalysts were characterized by their surface area, surface acidity, pore size distribution, and pore volume.     

Kinetics of thiophene hydrodesulfurization over a supported Mo–Co–Ni catalyst

In this study, the kinetics of thiophene (TH) hydrodesulfurization (HDS) over the Mo–Co–Ni-supported catalyst was investigated. Trimetallic catalyst was synthesized by pore volume impregnation and the metal loadings were 11.5 wt % Mo, 2 wt % Co, and 2 wt % Ni. A large surface area of 243 m²/g and a relatively large pore volume of 0.34 cm³/g for the fresh Mo–Co–Ni-supported catalyst indicate a good accessibility to the catalytic centers for the HDS reaction. The acid strength distribution of the fresh and spent catalysts, as well as for the support, was determined by thermal desorption of diethylamine (DEA) with increase in temperature from 20 to 600 °C. The weak acid centers are obtained within a temperature range between 160 and 300 °C, followed by medium acid sites up to 440 °C. The strong acid centers are revealed above 440 °C. We found a higher content of weak acid centers for fresh and spent catalysts as well as alumina as compared to medium and strong acid sites. The catalyst stability in terms of conversion as a function of time on stream in a fixed bed flow reactor was examined and almost no loss in the catalyst activity was observed. Consequently, this fact demonstrated superior activity of the Mo–Co–Ni-based catalyst for TH HDS. The activity tests by varying the temperature from 200 to 275 °C and pressure from 30 to 60 bar with various space velocities of 1–4 h^?1 were investigated. A Langmuir–Hinshelwood model was used to analyze the kinetic data and to derive activation energy and adsorption parameters for TH HDS. The effect of temperature, pressure, and liquid hourly space velocity on the TH HDS activity was studied.     

Directed C−H Halogenation Reactions Catalysed by PdII Supported on Polymers under Batch and Continuous Flow Conditions

A new generation of N-heterocyclic carbene palladium(II) complexes containing vinyl groups in different positions in the backbone of the N-heterocycle have been developed. The fully characterised monomers were copolymerised with divinylbenzene to fabricate robust polymer supported NHC-Pd^II complexes and these polymers were applied as heterogeneous catalysts in directed C−H halogenation of arenes with a pyridine-type directing group. The catalysts demonstrated medium-high catalytic activity with up to 90 % conversion and 100 % selectivity in chlorination. They are heterogeneous and recyclable (at least six times) with no significant leaching of palladium in batch mode catalysis. The best catalyst was also applied under continuous flow conditions where it disclosed an exceptional activity (90 % conversion) and 100 % selectivity for the mono-halogenated product for at least six days, with no leaching of palladium, no loss of activity and an ability to maintain the original oxidation state of Pd^II.     

Mg-Al-O-t-Bu hydrotalcite as an efficient catalyst for the transesterification of dimethyl carbonate with ethanol

Mg-Al-O-t-Bu hydrotalcite was synthesized and characterized by XRD, FT-IR and TGA-DTA. It was proved to be an active heterogeneous catalyst for the transesterification of dimethyl carbonate (DMC) with ethanol. When the reaction was carried out over Mg-Al-O-t-Bu hydrotalcite at 80°C, 7 h, molar ratio of ethanol to DMC 5:1, 1.0 wt.% of catalyst, the conversion of DMC was 86.4%, the selectivity to diethyl carbonate (DEC) was 61.2%. This heterogeneous catalyst could be used 5 times without loss of its activity.     

Diethylenetriamine-functionalized single-walled carbon nanotubes (SWCNTs) to immobilization palladium as a novel recyclable heterogeneous nanocatalyst for the Suzuki–Miyaura coupling reaction in aqueous media

Pd supported on diethylenetriamine (DETA) modified single-walled carbon nanotubes (SWCNT-DETA/Pd) hybrid materials were fabricated for the first time. The prepared heterogeneous catalyst was characterized by XRD, FTIR, SEM, TGA, and TEM. The catalytic activity of the prepared catalyst was investigated by employing the Suzuki–Miyaura coupling reaction as a model reaction. A series of biphenyl compounds were synthesized through the Suzuki–Miyaura reaction using SWCNT-DETA/Pd²⁺ as a catalyst. The yields of the products were in the range from 80% to 98%. The catalyst can be readily recovered and reused at least for seven consecutive cycles without significant loss of its catalytic activity.     

High-throughput selection for heterogeneous catalysts

A catalyst library of 80 samples with different mass ratios of rare earth elements, cobalt (Co), cerium (Ce), and indium (In), was prepared by impregnation of a fresh HZSM-5 zeolite support. A high-throughput detection setup, based on UV absorption spectroscopy, was developed for heterogeneous catalyst selection. The catalytic properties of the library were tested in the selective catalytic reduction of NO by methane at 673 K. Among the Co/Ce series, the catalyst with Co/Ce = 2:1 and Co/H-ZSM5 = 2.5% has shown remarkable efficiency (up to 78%). In the Ce/In series, the reactivity of the catalyst with the support composition of Ce/In = 1:1 and Ce/H-ZSM5 = 2.0% was < or = 88%. Our initial experiments definitely indicated that this simple and inexpensive multichannel setup can be applied for the selection of other heterogeneous catalysts. According to the variation of the UV light intensity, resulting from the absorption of the reactant or product, it was possible to monitor the relative quantity of reactants or products during a catalytic reaction.     

Heterogeneous Suzuki cross-coupling reactions over palladium/hydrotalcite catalysts

The efficiency of various heterogeneous solids consisting of palladium supported on hydrotalcite as catalysts in the Suzuki cross-coupling reaction between bromobenzene and phenylboronic acid was studied. Based on the catalytic activity results, the reaction develops to an acceptable extent with 100% selectivity at moderate temperatures in the presence of some of the catalysts. The best results were provided by a catalyst consisting of an acetate-pyridine complex of Pd supported on hydrotalcite that gave high conversion values even after three reuses. The reactions conditions were very mild (a temperature of 55 degrees C and atmospheric pressure). In fact, the catalyst provided conversion and selectivity results surpassing those of existing heterogeneous phase catalysts and most homogeneous phase catalysts for the same purpose.     

甲基丙烯醛氧化酯化制甲基丙烯酸甲酯催化剂的制备与应用

甲基丙烯醛氧化酯化制甲基丙烯酸甲酯催化剂的制备与应用;催化剂; 甲基丙烯酸甲酯; 甲基丙烯醛; 氧化-酯化反应     

MIL-100(Fe) Supported Pt−Co Nanoparticles as Active and Selective Heterogeneous Catalysts for Hydrogenation of 1,3-Butadiene

Superior catalytic performance for selective 1,3-butadiene (1,3-BD) hydrogenation can usually be achieved with supported bimetallic catalysts. In this work, Pt−Co nanoparticles and Pt nanoparticles supported on metal–organic framework MIL-100(Fe) catalysts (MIL=Materials of Institut Lavoisier, PtCo/MIL-100(Fe) and Pt/MIL-100(Fe)) were synthesized via a simple impregnation reduction method, and their catalytic performance was investigated for the hydrogenation of 1,3-BD. Pt1Co1/MIL-100(Fe) presented better catalytic performance than Pt/MIL-100(Fe), with significantly enhanced total butene selectivity. Moreover, the secondary hydrogenation of butenes was effectively inhibited after doping with Co. The Pt1Co1/MIL-100(Fe) catalyst displayed good stability in the 1,3-BD hydrogenation reaction. No significant catalyst deactivation was observed during 9 h of hydrogenation, but its catalytic activity gradually reduces for the next 17 h. Carbon deposition on Pt1Co1/MIL-100(Fe) is the reason for its deactivation in 1,3-BD hydrogenation reaction. The spent Pt1Co1/MIL-100(Fe) catalyst could be regenerated at 200 °C, and regenerated catalysts displayed the similar 1,3-BD conversion and butene selectivity with fresh catalysts. Moreover, the rate-determining step of this reaction was hydrogen dissociation. The outstanding activity and total butene selectivity of the Pt1Co1/MIL-100(Fe) catalyst illustrate that Pt−Co bimetallic catalysts are an ideal alternative for replacing mono-noble-metal-based catalysts in selective 1,3-BD hydrogenation reactions.     

聚合物负载季鏻盐催化 CO2 与环氧化物的环加成反应

 制备了聚合物负载的季鏻盐催化剂, 并用于 CO₂ 与环氧氯丙烷环加成反应中. 采用红外光谱、热分析、原子吸收光谱和扫描电子显微镜等手段测定了催化剂的结构、热性能、磷元素含量和表面形貌等. 考察了 CO₂ 压力、温度、催化剂用量和反应时间等对环加成反应性能的影响. 结果表明, 在催化剂用量为 0.09 g, CO₂ 压力为 4.5 MPa, 于 150 ^oC 反应 6 h 时, 3-氯甲基环碳酸酯收率可达 97.7%, 选择性大于 99%. 且催化剂易分离回收, 重复使用 5 次后产物收率和选择性没有明显下降. 同时探讨了该催化剂上 CO₂ 环加成合成环碳酸酯的可能机理.     

The catalytic activity of copper/nickel supported on mesoporous aluminum catalyst towards cyclohexene epoxidation in continuous reactor

The intent of the study is to attain a high selectivity rate and stable interaction between metals in any heterogeneous catalyst. Cyclohexene is extremely valuable in industrial domains such as the synthesis of perfumes and nylons, and the mesoporous alumina was upstretched with a various ratio of bimetal copper (10%) and nickel (5%, 10%, 15%, and 20%) under wet impregnation procedures by the mesoporous aluminum catalyst. This impregnation of a metal and catalyst was used to assess the highest conversion and selectivity of cyclohexene to cyclohexanol. This catalytic nature was validated by analyzing the crystal structure and size using the X-ray diffraction technique. The functional group is identified using FT-IR (Fourier Transform Infrared Spectroscopy), while the surface area is assessed using BET (Brunauer-Emmet-Teller). HR-TEM (transmission electron microscopy) is used to validate the morphology of catalysts and their surface layers; HR-SEM (Scanning Electron Microscopy) is used to highlight and assess microparticles; and NH₃TPD (Temperature-Programmed Desorption) is used to measure the overall acidity of the catalyst. The catalytic performance was proved by the yield achieved by varying parameters such as temperature, pressure, WHSV⁻¹, reaction time, and solvents, which yielded over 98.5% in both cyclohexene conversion and selectivity. In the conversion of the product, H₂O₂ performs as an oxidant, and acetonitrile serves as a solvent at constant mild conditions of 90 °C and 20 bar pressure. Furthermore, even after seven successive runs with the Al₂O₃/Cu (10%)-Ni (15%) mixture, remarkable reusability was attained despite a minor decline in cyclohexanol selectivity. The effective impregnation of copper and nickel into supported mesoporous Al₂O₃ produced a long-lasting, stable hybrid nanostructure with excellent stability and no metal leaching. The current synthesis protocol's advantages and qualities include its efficiency, cost-effectiveness, ecological sustainability, and comfort of synthesis with readily available components.     

Copper supported on phenanthroline-functionalized porous polymer as an active catalyst for the oxidative carbonylation of methanol

Porous organic polymer has recently attracted tremendous interest because of its potential to combine the best features of homogeneous and heterogeneous catalysts. In this study, copper supported on phenanthroline-functionalized porous polymer (Cu@PCP-Phen) was prepared by a co-polymerization method and used as a heterogeneous catalyst for dimethyl carbonate synthesis via the oxidative carbonylation of methanol. The catalyst was characterized by N₂ adsorption, scanning electron microscopy, transmission electron microscopy, ¹³C solid-state nuclear magnetic resonance, and X-ray photoelectron spectroscopy, which suggested that it possessed a big surface area, hierarchical porous structure, and strong electron-donating effect toward copper species. The Cu@PCP-Phen catalyst showed high catalytic activity, which was significantly higher than those achieved with Cu-based catalysts under similar reaction conditions. In addition, the catalyst can be easily separated and reused at least six times with only a slight decrease in activity. The salient features of this protocol are the simplicity in handling of the catalyst, high catalytic activity, excellent selectivity, low copper leaching, and good catalyst recyclability.     

Dehydrocyclization of Diphenylamine to Carbazole over Platinum-Based Bimetallic Catalysts

 Gas phase dehydrocyclization of diphenylamine (DPA) to carbazole over monometallic and bimetallic 0.4 wt% Pt-based catalysts in a fixed bed reactor was studied in the presence of hydrogen at a temperature of 550 ^oC. Alumina and carbon supported Pt catalysts showed very high initial activity (> 95%). The selectivity for carbazole over carbon supported Pt catalysts was slightly lower. Doping of the catalyst with potassium led to an increase in the selectivity for carbazole by 15%. Bimetallic Pt-Sn catalysts prepared by co-impregnation were less selective than catalysts prepared by successive impregnation. The selectivity for carbazole over bimetallic Pt-Sn catalysts prepared by successive impregnation was 75%, but their activity decreased with increased Sn loading. Highly active and reasonably selective catalysts were Ir-doped bimetallic Pt-based catalysts. The conversion of diphenylamine over Pt-Ir catalysts was above 98% and the selectivity for carbazole was nearly 55%, while the lifetime was much longer.     

Ni/Al2O3催化2-甲基呋喃加氢制2-甲基四氢呋喃性能的研究

采用浸渍法制备了不同NiO含量的Ni/Al₂O₃催化剂,并进行了2-甲基呋喃加氢制2-甲基四氢呋喃性能的考察。结果表明,在制备的NiO负载量为10%、20%、25%、30%和40%的Ni/Al₂O₃催化剂中,随着NiO负载量增加,加氢反应的选择性与2-甲基呋喃的转化率均呈现出先增加后减小的趋势。其原因是由于适当增加NiO负载量有利于催化剂表面活性中心的形成,有利于加氢反应的进行;但是过度负载的NiO容易堵塞Al₂O₃载体中的介孔通道,降低反应的转化率与选择性。在釜式反应器中进行反应,对加氢反应条件进行了优化,发现在反应压力为3 MPa、反应温度150℃、机械搅拌速率为1000 r/min时,Ni/Al₂O₃催化2-甲基呋喃加氢制2-甲基四氢呋喃具有较高的选择性。当NiO负载量为25%时,2-甲基四氢呋喃的选择性最高为97.1%,2-甲基呋喃的转化率达到99.4%。     

氮气吹扫和费托合成的脉冲过程以提高α-烯烃的选择性

费托合成可以将煤炭或者生物质气化得到的合成气转化为α-烯烃等重要的化工产品。研究将费托合成和氮气吹扫操作组合成一脉冲过程,在稳定的操作状态下保证费托合成和氮气吹扫交替进行。在传统的费托合成条件下(反应气速为2 000 h^-1,温度为497 K, 压力为 2.0 MPa, 氢碳体积比为2.0)考察了Fe-Co催化剂在脉冲过程中费托合成的活性和选择性。结果表明,N₂吹扫温度和压力分别为517 K和0.2 MPa下的费托合成的C₃烯烷比是未脉冲的相同反应条件下的九倍左右。同时,反应过程中CH₄的选择性和CO的转化率有所下降。在此基础上,通过间歇反应在固定床反应器中进行该脉冲过程,实验结果表明,利用脉冲操作在费托反应中可以获得更高的烯烃选择性。     

Oxidation of benzene to phenol by dioxygen over vanadium oxide nano-plate

Direct oxidation of benzene to phenol with dioxygen is an attractive and challenging subject. V⁴⁺ vanadium species play an important role in the reaction. Nano vanadium oxide which consists mainly of the quadrivalence vanadium species was synthesized via hydrothermal method and used to catalyze the reaction without addition of reducing reagent. Investigations about performances of catalysts show that 3.7% conversion of benzene and nearly 100% selectivity of phenol are given over the fresh catalyst VO-N-A. Morphology observations display that the VO-N-A is made of nano-plate. Thermogravimetric curve illuminates that the catalyst is stable under the reaction temperature.     

Synthesis of Fe—Ni—Ce trimetallic catalyst nanoparticles via impregnation and co-precipitation and their application to dye degradation

In this study, trimetallic catalysts were prepared via the co-precipitation and impregnation methods. In order to investigate the effect of impregnation on the catalytic activity and crystallite size, a trimetallic catalyst, Fe—Ni—Ce, was prepared through the co-precipitation method in one set of experiments, and cerium was impregnated with the Ni—Fe mixture in the final stage of the preparation in another set. Fourier transform infrared spectroscopy was employed to confirm the formation of trimetallic catalysts and the success of the impregnation method. The Brunauer-Emmett-Teller nitrogen adsorption isotherm exhibits a high specific surface area (approximately 39 m² g^?1) for the nanoparticles obtained by the impregnation method. The crystallography and morphology of the trimetallic catalysts thus prepared were characterised by X-ray diffraction and scanning electron microscopy. UV-VIS spectroscopy and methylene blue dye degradation tests were also performed to investigate the catalytic activity of the synthesised catalysts. The crystalline size was found to be smaller for the catalysts prepared by the impregnation method. In addition, the samples synthesised using the cerium impregnation method showed superior activity in the methylene blue dye degradation test. The effect of the catalyst dosage on dye degradation, as well as the effect of the initial dye concentration on the catalyst activity, was also studied for both methods.     

用于甲醇直接气相氧化羰基化的负载铜催化剂

 采用浸渍法制备了负载型铜基催化剂,并用其催化甲醇直接气相氧化羰基化合成碳酸二甲酯(DMC), 考察了浸渍溶剂、载体、助催化剂和铜含量的影响. 结果表明,以CuCl为活性组分原料、浓氨水为浸渍溶剂和活性炭为载体制得的负载铜催化剂显示出很高的催化活性,在特定的反应条件下,该催化剂上甲醇的转化率可达27.7%, DMC选择性可达95%. 分子筛负载的铜催化剂上甲醇的转化率低于1%, 但是生成DMC的选择性高达100%. 催化剂活性随着Cu负载量的增加而增大,但负载量过高可引起甲醇的过度氧化反应,导致DMC选择性下降. 催化剂中添加KOH或钯化合物,有利于提高以CuCl2为活性组分原料制得的铜催化剂的活性,但同时也促进了副反应的发生. 随着反应时间的延长,催化剂的活性组分流失,活性下降,但是生成DMC的选择性维持在95%左右.     

Synthesis new Co–Mn mixed oxide catalyst for the production of light olefins by tuning the catalyst structure

In order to increase the catalyst activity for Fischer–Tropsch synthesis (FTS), the preparation methods of two new catalysts were studied. The chemically identical bimetallic Co–Mn/Al₂O₃ catalysts were synthesized by different synthetic methods: (a) via thermal decomposition of the complex [Co_1.33Mn_0.667(C₇H₃NO₄)₂(H₂O)₅].2H₂O ( 1 ) and (b) by the impregnation technique. The complex was characterized by the single‐crystal analysis, elemental analysis, and Fourier‐transform infrared (FT‐IR) spectroscopy. Both catalysts were characterized by powder X‐ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X‐ray spectrometry (EDS), Brunauer–Emmett–Teller (BET) specific surface area, hydrogen temperature‐programmed reduction (H₂‐TPR), and H₂‐chemisorption. The catalysts' activity was investigated for the Fischer–Tropsch synthesis in a fixed bed microreactor. Higher activity was obtained for the catalyst prepared by thermal decomposition of the inorganic precursor due to its small particle size, superior dispersion, and higher surface area. The results show that the catalyst prepared thermal decomposition has 21% ethylene, 10% propylene, and 50% C₅⁺ selectivity, while methane selectivity of this catalyst is 11% at 250°C. On the other hand, the catalyst obtained by the impregnation method displays 15% ethylene, 8% propylene, 29% C₅⁺_, and 29% methane selectivity at the same temperature.     

Self‐Supported Chiral Titanium Cluster (SCTC) as a Robust Catalyst for the Asymmetric Cyanation of Imines under Batch and Continuous Flow at Room Temperature

A robust heterogeneous self‐supported chiral titanium cluster (SCTC) catalyst and its application in the enantioselective imine‐cyanation/Strecker reaction is described under batch and continuous processes. One of the major hurdles in the asymmetric Strecker reaction is the lack of availability of efficient and reusable heterogeneous catalysts that work at room temperature. We exploited the readily hydrolyzable nature of titanium alkoxide to synthesize a self‐supported chiral titanium cluster (SCTC) catalyst by the controlled hydrolysis of a preformed chiral titanium‐alkoxide complex. The isolated SCTC catalysts were remarkably stable and showed up to 98 % enantioselectivity (ee) with complete conversion of the imine within 2 h for a wide variety of imines at room temperature. The heterogeneous catalysts were recyclable more than 10 times without any loss in activity or selectivity. The robustness, high performance, and recyclability of the catalyst enabled it to be used in a packed‐bed reactor to carry out the cyanation under continuous flow. Up to 97 % ee and quantitative conversion with a throughput of 45 mg h^?1 were achieved under optimized flow conditions at room temperature in the case of benzhydryl imine. Furthermore, a three‐component Strecker reaction was performed under continuous flow by using the corresponding aldehydes and amines instead of the preformed imines. A good product distribution was obtained for the formation of amino nitriles with ee values of up to 98 %. Synthetically useful ee values were also obtained for challenging α‐branched aliphatic aldehyde by using the three‐component continuous Strecker reaction.