光学纯1,2—二苯基乙二醇的不对称催化合成

利用奎宁和奎宁定酯进行不对称催化合成，得到光学纯１，２－二苯基乙二醇产物，对映体过量（ｅ．ｅ．％）高达９６％以上，该反应条件温和，后处理简便。     

催化合成对羟基苯甲酸丁酯的研究

研究了FeCl3·6H2O为催化剂催化合成对羟基苯甲酸丁酯。讨论了催化酯化的各种影响因素,优化的反应条件为:对羟基苯甲酸与丁醇摩尔比为1∶3,催化剂与对羟基苯甲酸的摩尔比为0.04∶1,反应时间2.0h,对羟基苯甲酸丁酯产率为98.9%。     

气相催化合成四氢吡咯的研究进展

综述了气相催化合成四氢吡咯杂环的研究进展,包括四氢呋喃和1,4-丁二醇为原料与氨胺化合成法,ω,ω’-氨基丁醇催化环合法、加氢脱氮法、电化学法等。主要介绍了1,4-丁二醇和四氢呋喃为原料的生产技术路线,揭示了还原胺化和缩合胺化反应合成四氢吡咯中催化剂的特点,以及催化剂载体、助剂组分对胺化反应的影响,指出今后的发展方向是开发具有高效、高选择性催化剂和环境友好合成工艺。     

Controllable synthesis of novel nanoporous manganese oxide catalysts for the direct synthesis of imines from alcohols and amines

A novel template-free oxalate route was applied to synthesize different mesoporous manganese oxides (amorphous manganese oxide (AMO), Mn₅O₈, Mn₃O₄, MnO₂) in the narrow temperature range from 350℃ to 400℃ by controlling the calcination conditions, which were employed as the efficient catalysts for the oxidative coupling of alcohols with amines to imines. The chemical and structural properties of the manganese oxides were characterized by the methods of thermogravimetry analysis and heat flow (TG-DSC), X-ray diffraction (XRD), nitrogen sorption, scanning electron microscope (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), H₂ temperature-programmed reduction (H₂-TPR), and inductively coupled plasma optical emission spectrometry (ICP-OES) techniques. The structures of different manganese oxides were confirmed by characterization. The M-350 (AMO) presented the maximum surface area, amorphous nature, the lowest reduction temperature, the higher (Mn³⁺ + Mn⁴⁺)/Mn²⁺ ratio, and the higher adsorbed oxygen species compared to other samples. Among the catalysts, M-350 showed the best catalytic performance using air as an oxidant, and the conversion of benzyl alcohol (BA) and the selectivity of N-benzylideneaniline (NBA) reached as high as 100% and 97.1% respectively at the lower reaction temperature (80℃) for 1 h. M-350 had also the highest TOF value (0.0100 mmol·mg^-1·h^-1) compared to the other manganese oxide catalysts. The catalyst was reusable and gave 95.8% conversion after 5 reuse tests, the XRD pattern of the reactivated M-350 did not show any obvious change. Lattice oxygen mobility and (Mn³⁺ + Mn⁴⁺)/Mn²⁺ ratio were found to play the important roles in the catalytic activity of aerobic reactions.     

Substitution effects in the heterogeneous catalytic synthesis of flavanones over MgO

Flavanones were synthesized via a series reaction scheme involving the Claisen–Schmidt condensation of 2^′-hydroxyacetophenone and benzaldehydes to form 2^′-hydroxychalcones, and the subsequent isomerization of the 2^′-hydroxychalcones to flavanones. Reactions were carried out at 160 °C heterogeneously using MgO as the catalyst. Substitution effects were investigated by conducting reaction studies involving various para-substituted benzaldehydes (i.e., OH, OCH₃, H, F, Cl, Br and NO₂). Different solvents, including DMSO, nitrobenzene, benzonitrile and tetralin, were used. The results from this work suggest that a negatively charged ketone intermediate, similar to one previously proposed for the homogeneously base-catalyzed reaction, is also involved in the heterogeneous synthesis under these conditions.     

以煤为原料的合成氨工艺选择

对我国合成氨资源分析后 ,认为以煤为原料的氨厂仍有发展前景。提出了煤基合成氨工艺的选择原则 :烟煤型采用水煤浆气化 ,无烟煤或焦炭采用常压气化。重点介绍了常压气化主要工艺的选型 :有廉价氧气源的选择富氧造气 ,一般情况下采用常压间歇造气 ;尽可能采用全低变 ;有蒸汽来源的采用化学吸附脱碳 ,否则应选择物理吸附法 ,慎用变压吸附法 ;合成工段应从压力、塔结构及热回收方式等方面综合考虑。     

氨磺酸催化合成马来酸二丁酯的研究

研究了以氨磺酸为催化剂，马来酸和正丁醇为原料合成马来酸二丁酯，并考察了影响反应的因素。结果表明，醇酸物质的量比为3：1，催化剂用量为0．5g(马来酸为0．05mol的情况下)，带水剂甲苯为5mL，反应时间为1．5h是量适宜的反应条件，醇化率达96．8％。     

Process development for the catalytic conversion of cyclohexene oxide and carbon dioxide into poly(cyclohexene carbonate)

The synthesis of polycarbonates from carbon dioxide is an alternative route to the use of phosgene for the introduction of the carbonate functionality in these polymers. In this work, a preliminary process design has been made for the catalytic conversion of cyclohexene oxide and carbon dioxide into poly(cyclohexene carbonate). For this purpose, the low- and high-pressure phase behaviour, reaction rate and downstream removal of residual cyclohexene oxide from the product stream are described. Based on these findings a design for such a process is suggested and evaluated from a technical and economic perspective. The economic evaluation indicates that the required selling price of PCHC is intermediate to the market price of engineering and specialty polymers.     

丙酸酯在离子液体中的催化合成研究

利用正交实验法获得了在离子液体[Hmim] BF4-中合成丙酸正丁酯的最佳工艺条件,考察了在该离子液体催化下,丙酸和多种醇的酯化反应及催化剂的重复使用性能;实验结果表明,离子液体[Hmim] BF4-催化合成丙酸正丁酯的最佳工艺条件为n离子液体∶n丙酸∶n正丁醇=1∶4∶1,油浴温度140℃,反应时间8 h,此时收率可达77.8%。离子液体[Hmim] BF4-在丙酸酯化反应中具有良好的催化活性,反应条件温和,无腐蚀、无废酸排放,并可以重复使用。     

丙烯酸催化合成新进展

丙烯酸是一种重要的化工中间体和聚合物单体,需求量巨大。我国丰富的煤炭资源和可再生生物质资源为煤基和生物质基丙烯酸合成路线提供坚实的物质保障。本文将综述这两条主要路线,具体包括以煤基化工原料CO、低碳醇（甲醇和乙醇）、甲醛、乙酸、乙烯等为原料的丙烯酸合成路线;以生物质基平台化合物甘油、3-羟基丙酸、乳酸、富马酸、黏糠酸等为原料的丙烯酸合成路线;并对这些路线进行了比较,为路线的选择提供参考。重点关注了这些过程中的催化问题：反应所需的活性位、副反应分析、催化剂的类型与特点以及催化性能与失活机理,为未来实用煤基和生物质基丙烯酸生产用高效稳定廉价催化剂的设计开发提供理论参考。     

甲醇合成塔热套过盈量的工艺控制

通过对８００ｍｍ甲醇合成塔热套过盈量的计算和工艺控制过程分析,给出了最佳的过盈量和可靠的工艺参数。     

Effect of potassium carbonate on catalytic synthesis of calcium carbide at moderate temperature

Calcium carbide was successfully synthesized by carbothermal reduction of lime with coke at 1973 K for 1.5 h. The effect of potassium carbonate as additive on the composition and morphology of the product was investigated using X-ray diffraction and scanning electron microscope. Addition of potassium carbonate increased the yield of calcium carbide. The sample in the presence of potassium carbonate generated acetylene gas of 168.3 L/kg, which was 10% higher than that in the absence of potassium carbonate. This result confirmed the catalytic effect of potassium carbonate on the synthesis of calcium carbide. A possible mechanism of the above effects was that the additive, which was melted at the reduction temperature, dissolved CaO and so promoted the contact between CaO and carbon, which was essential for the solid-solid reaction to form calcium carbide.     

改性粉煤灰催化合成苹果酯的研究

以过硫酸铵改性工业废渣粉煤灰为催化剂,对乙酰乙酸乙酯和乙二醇合成苹果酯的催化工艺进行了系统研究。讨论了反应时间、酯醇比、催化剂用量和带水剂用量对酯化率的影响。最佳反应条件为：n（乙酰乙酸乙酯）：n（乙二醇）：1：1．8,催化剂用量为乙酰乙酸乙酯质量的1．5％,带水剂用量为15mL,反应时间3h。在优化条件下反应,苹果酯产率达到95．9％,选择性98．0％以上。实验表明,改性粉煤灰是合成苹果酯的优良催化剂,与其他酸催化剂相比,它还具有活性高、用量少且可重复使用等优点。     

对甲苯磺酸催化合成乙酸丁酯的研究

研究了以对甲苯磺酸为催化剂 ,乙酸和正丁醇为原料合成乙酸丁酯 ,并考察了影响反应的因素。结果表明 ,醇酸摩尔比为 1 2∶1,催化剂用量为 0 8g(乙酸为 0 2mol的情况下 ) ,带水剂环己烷为 5ml,反应时间为 2 0h是最适宜的反应条件 ,酯化率达 96 9%     

对甲苯磺酸催化合成戊二酸二甲酯的研究

本文研究了对甲苯磺酸催化戊二酸和甲醇合成戊二酸二甲酯的反应,探讨并找到了最佳的反应条件,收率达到94．5％。最佳条件为：以环己烷为带水剂,醇酸摩尔比为10：1,催化剂用量戊二酸的质量百分比为20％,在回流状态下反应3h。     

固体超强酸催化合成己二酸二乙酯的研究

用复合型固体超强酸TiO2-ZrO2／SO4^2-作催化剂，催化合成了己二酸二乙酯。考察了反应时问、原料配比、催化剂用量等对反应的影响，确定了酯化反应最佳反应条件，在此条件下，己二酸二乙酯产率达96．5％。     

Catechol-functionalized microporous organic polymer as supported media for Pd nanoparticles and its high catalytic activity

We report a new hydroxyl functionalized microporous organic polymer (MOPOH) based on the polymerization of catechol with terephthalaldehyde using phenolic resin-inspired chemistry. This catechol-decorated material, with surface area of 874 m² g⁻¹ and micro, mesopores, facilitates the immobilization and dispersion of Pd nanoparticles (NPs) on the polymer matrix. The surface area of the created composite (Pd@MOPOH) decreases to 419 m² g⁻¹ and the pore size distribution is narrowly distributed at 1.54 nm due to the filling of mesopores. The CO₂ capture capacities for MOPOH and Pd@MOPOH at 273 K and 1 bar are 13.4 and 9.2 wt%, respectively. The resultant Pd NPs are crystalline and uniform with a mean diameter of 4.8 nm. The well-dispersed Pd@MOPOH exhibits excellent catalytic activity toward the model reduction of 4-nitrophenol into 4-aminophenol. Significantly, nearly no Pd leaching is detected during the catalytic cycles, showing active and durable nature of the heterogeneous nanocatalyst.     

Machine Learning Based Suggestions of Separation Units for Process Synthesis in Process Simulation

As part of Industry 4.0, workflows in the process industry are becoming increasingly digitalized. In this context, artificial intelligence (AI) methods are also finding their way into the process development. In this communication, machine learning (ML) algorithms are used to suggest suitable separation units based on simulated process streams. Simulations that have been performed earlier are used as training data and the information is learned by machine learning models implemented in Python. The trained models show good, reliable results and are connected to a process simulator using a .NET framework. For further optimization, a concept for the implementation of user feedback will be assigned. The results will provide the fundamental basis for future AI-based recommendation systems.     

Characterization and Activity of Cu/ZSM5 Catalysts for the Oxidation of Phenol with Hydrogen Peroxide

The heterogeneous catalytic wet peroxide oxidation (CWPO), involving total oxidation of organic compounds to CO₂ and H₂O is a possible path for the treatment of toxic and bio‐refractory wastewater streams. The aim of this work was to synthesize and characterize three Cu/ZSM5 catalysts prepared by direct hydrothermal synthesis. The mass ratio of the active metal component in the zeolite ranged from 1.62–3.24 wt %. These materials were tested for CWPO of aqueous phenol in a stainless steel Parr reactor, in batch operation under mild conditions (at atmospheric pressure and a temperature of 353 K). The catalyst weight was 0.1 g dm^–3 and the initial concentration of phenol and hydrogen peroxide were 0.01 mol dm^–3 and 0.1 mol dm^–3, respectively. The catalysts were characterized by powder X‐ray diffraction (XRD), scanning electron microscopy (SEM), AAS and ICP‐MS. Their catalytic performance was monitored in terms of phenol and total organic carbon (TOC) conversion, hydrogen peroxide decomposition, by‐product distribution and the degree of copper leached into the aqueous solution. The experimental results indicated that within 180 min, these catalysts facilitated almost complete elimination of phenol and a significant removal of chemical oxygen demand, without significant leaching of Cu ions from the zeolite. The Cu/ZSM5‐DHS3 catalyst with the highest copper loading was proven to be the best candidate. The useful fraction of hydrogen peroxide that contributed to the removal of the organic compounds quantified in terms of selectivity, S, indicated that the CWPO selectivity was always less than 100 %, which meant that there was some self‐degradation of oxidant. It was also shown that oxidation of phenol took place on the catalyst surface via a heterogeneous mechanism, and that the contribution of any homogeneous reaction mechanism was not significant.     

Highly efficient procedure for the synthesis of biodiesel from soybean oil using chloroaluminate ionic liquid as catalyst

The novel efficient procedure has been developed for the synthesis of biodiesel. The chloroaluminate ionic liquid has been selected for the synthesis of biodiesel. The catalyst was very efficient for the reaction with the yield of 98.5% when the reaction was carried out under the conditions of [Et₃NH]Cl-AlCl₃ (x(AlCl₃) = 0.7), soybean oil 5 g, methanol 2.33 g, 9 h, 70 °C. Operational simplicity, low cost of the catalyst used, high yields, no saponification and reusability are the key features of this methodology.