Tailoring the microenvironment of Ti sites in Ti-containing materials for synergizing with Au sites to boost propylene epoxidation

Au sites supported on Ti-containing materials(Au/Ti-containing catalyst)are currently considered as a promising catalyst for the propylene epoxidation owing to the synergistic effect that hydrogen peroxide species formed on Au sites diffuses to the Ti sites to form the Ti-hydroperoxo intermedi-ates and contributes to the formation of propylene oxide(PO).In principle,thermal treatment will significantly affect the chemical and physical structures of Ti-containing materials.Consequently,the synergy between tailored Ti sites with different surface properties and Au sites is highly expected to enhance the catalytic performance for the reaction.Herein,we systematically studied the intrinsic effects of different microenvironments around Ti sites on the PO adsorption/desorption and conversion,and then effectively improved the catalytic performance by tailoring the number of surface hydroxyl groups.The Ti^(Ⅵ) material with fewer hydroxyls stimulates a remarkable enhancement in PO selectivity and H_(2) efficiency compared to the Ti^(Ⅵ) material that possessed more hydroxyls,offering a 7-fold and 4-fold increase,respectively.As expected,the Ti^(Ⅵ+Ⅳ) and Ti^(Ⅳ) materials also exhibit a similar phenomenon to the Ti^(Ⅵ) materials through the same thermal treatment,which strongly supports that the Ti sites microenvironment is an important factor in suppressing PO con-version and enhancing catalytic performance.These insights could provide guidance for the rational preparation and optimization of Ti-containing materials synergizing with Au catalysts for propylene epoxidation.

Catalytic Reaction Kinetics of Propylene Dimerization to 4-Methyl-1-Pentene Using Cu-K/K_(2)CO_(3) Solid Base Catalyst

The catalysis technology of propylene dimerization to form 4-methyl-1-pentene(4MP1)using a Cu-K/K_(2)CO_(3) solid base catalyst is a well-known heterogeneous catalytic reaction.In this study,the intrinsic kinetics of propylene dimerization were studied in a fixed-bed continuous reactor.Internal and external diffusion during the dimerization reaction experiments were eliminated by adjusting the flow rate of the carrier gas and the particle size of the catalyst support.Then,the concentration changes of each substance at the outlet of the catalyst bed under different residence times were investigated.Moreover,the suitable reaction kinetics equations was derived using the Langmuir Hinshelwood-Hougen-Watson kinetic model.Finally,the activation energy for each reaction involved in the dimerization reaction was calculated.The activation energies of 4MP1,branched by-products,and 1-hexene were 115.0,150.8,and 177.4 kJ/mol,respectively.The effect of process conditions on propylene dimerization with solid base catalysts was studied through kinetic model simulation.By comparing the theoretical values obtained from the simulation with the experimental results,the applicability and accuracy of the kinetic model were verified.

The Oxyalkylation of Hydrophilic Black Alder Bark Extractives with Propylene Carbonate with a Focus on Green Polyols Synthesis

The isolated hydrophilic black alder(Alnus glutinosa)bark extractives were characterized in terms of component and functional composition and converted at 150℃-170℃ into liquid green polyols using solvent-free and lowtoxic base-catalyzed modification with propylene carbonate(PC).FTIR spectroscopy,HP-LC,GC,GPC,and wet chemistry methods were used to characterize the starting constituents,intermediate and final products of the reaction and to monitor the different pathways of PC conversion.The reaction of extractives as well as the model compounds,including catechol,xylose,PEG 400,and benzoic acid,with PC indicated the ability of OH groups of different origins present in the extractives to condense with equivalent amounts of PC.The polyols obtained consist of a copolymer fraction with one oxypropyl unit grafted per OH functionality of extractive components on average and oligo oxypropyl diols with a small number of carbonate linkages in the chain,obtained as a result of remaining PC homopolymerization.The domination of the oxypropylation mechanism vs.transcarbonation for PC ring opening was observed for both copolymerization and homopolymerization processes,making the process of oxypropylation with PC similar to that of conventional oxypropylation.At optimal reaction conditions,including a PC/OH ratio of 3.0 and a 24-h duration at 150°C,uniform polyols with low viscosity of~900 mPa·s^(-1),a biomass content of~27%,and an OHV of~500 mg KOH·g^(-1) were obtained.Increasing the temperature of modification allows shortening the process but drastically increases the polyol viscosity.At fixed temperature values,increasing the PC/OH ratio not only decreases the biomass content but also strongly prolongs the processing.The significantly increased duration of the process using PC as an alternative oxyalkylation agent compared to that of oxyalkylation with propylene oxide is a reasonable trade-off for using a safer and more environmentally friendly technology.

Manipulating Zn^(2+)solvation environment in poly(propylene glycol)-based aqueous Li^(+)/Zn^(2+)electrolytes for high-voltage hybrid ion batteries

Compared with aqueous single-ion batteries,rechargeable aqueous hybrid ion batteries,especially Li^(+)/Zn^(2+)hybrid ion batteries,are receiving extensive interest owing to their low cost,high operating voltage,and energy density.However,their working voltage and lifespan are limited by the decomposition of water and the growth of Zn dendrites.Herein,detrimental side reactions induced by the water reduction and the Zn dendrite growth are successfully suppressed by a poly(propylene glycol)(PPG)-based hybrid ion electrolyte[(1 m Zn(TFSI)2+10 m LiTFSI)in PPG/H2O].The addition of PPG in the electrolyte can not only enhance the bonding strength of hydrogen-bond in water but also tailor the solvation sheath of Zn2+as revealed by synchrotron X-rays.The participated solvation of PPG with Zn^(2+)can weaken Zn-H_(2)O interactions and redistribute Zn^(2+)flux on the surface of the Zn anode,thus inducing favorably even deposition of Zn.In addition,the decomposition of TFSI-contributes a ZnF_(2)-enriched solid electrolyte interface at the Zn anode to further prevent water decomposition and restrain Zn dendrites.The PPG-based electrolyte enables 2.1 V LiMnO_(2)//Zn batteries to deliver high specific capacities(121.7 mAh g^(-1)for a coin cell and 90 mAh g^(-1)for a pouch cell),and maintain 80%of the capacity over 700 cycles at 0.5 C,suggesting a promising pathway for highly reversible aqueous hybrid ion batteries.

Stability and Thermal Property Optimization of Propylene Glycol-Based MWCNT Nanofluids

Propylene glycol-based MWCNT(multi-walled carbon nanotubes)nanofluids were prepared in the framework of a two-step method and by using a suitable PVP(polyvinyl pyrrolidone)dispersant.The BBD(Box-Behnken design)model was exploited to analyze 17 sets of experiments and examine the sensitivity of the absorbance to three parameters,namely the concentration of MWCNT,the SN ratio(mass ratio of carbon nanotubes to sur-factants)and the sonication time.The results have revealed that,while the SN ratio and concentration of MWCNT have a strong effect on the absorbance,the influence of the sonication time is less important.The sta-tistical method of analysis of variance(ANOVA)was further used to determine the F-and p-values of the model.Five experiments were run to validate this approach.Since sample 2 was found to display the greatest absorbance,it was selected for stability monitoring as well as thermal conductivity and viscosity measurements.This sample has been found to be stable;the viscosity decreased with increasing temperature;the addition of MWCNT nano-particles was more effective in improving the thermal conductivity of propylene glycol than other methods in the literature.Moreover,the MWCNT nanofluid based on propylene glycol exhibited higher thermal conductivity at low temperatures.

丙烯环氧化工艺概述及催化剂研究进展

综述了目前已工业化的丙烯环氧化生产环氧丙烷的工艺,包括氯醇法、共氧化法、异丙苯氧化法和过氧化氢氧化法等。以氧气为氧化剂的直接氧化法是最理想的环氧丙烷生产技术,但目前尚未实现工业应用。结合氧气直接氧化法的技术特点,重点讨论了用于该方法的催化剂的研究进展、反应原理及存在的问题,并对其未来的应用和发展方向进行了展望。

CuCe-SAPO-34选择性催化丙烯还原柴油车尾气氮氧化物

采用等体积浸渍法制备Cu Ce-SAPO-44分子筛催化剂,用于选择性催化丙烯还原柴油车尾气氮氧化物(C3H_(6)-SCR)。采用X射线衍射(XRD)、N_(2)吸附-脱附、紫外可见光谱(UV-Vis)、H_(2)程序升温还原(H_(2)-TPR)和NH3程序升温脱附(NH3-TPD)等方法对催化剂的物理化学性质进行表征。研究表明,引入的铈与铜物种之间存在相互作用,有利于生成更多的孤立Cu^(2+)物种,提高了分子筛催化剂的低温氧化还原性能,从而提高了Cu CeSAPO-34的低温脱硝活性。同时,双金属分子筛骨架上具有丰富的Lewis酸性位,有助于C3H_(6)和NO_(x)的吸附和活化。当Cu∶Ce=4∶2时,Cu Ce-SAPO-34催化剂具有最佳的脱硝性能,在含有10%O_(2)和5%H_(2)O的柴油车尾气氛围中,在250℃最高能实现90%以上的脱硝效率。

微纳层叠技术对ACM/PP热塑性弹性体性能的影响

采用微纳层叠共挤出技术制备了ACM/PP热塑性硫化胶(TPV),研究了动态硫化温度、橡塑比、相容剂含量、炭黑与增塑剂含量对TPV力学性能与耐油性能的影响。结果表明,当动态硫化温度为190℃时,TPV具有较好的力学性能,拉伸强度、断裂伸长率、硬度、压缩永久变形分别为12.83 MPa、104.67%、86.50%、50.00%;随着TPV橡塑比的增大,材料的拉伸强度、断裂伸长率、硬度、耐油性能明显降低;当相容剂PP-g-MAH(马来酸酐接枝聚丙烯)的含量为15份时,TPV的综合力学性能与耐油性能最佳;TPV的拉伸强度、压缩永久变形、硬度随炭黑含量的增加而升高,随增塑剂DOTP含量的增加而降低,TPV的耐油性随炭黑含量的增加而提高,随DOTP含量的增加而变差,TPV的断裂伸长率随炭黑与DOTP含量的增加而降低。

烟炱分散型多功能黏指剂的合成与性能

以乙烯丙烯共聚物、马来酸酐、过氧化二叔丁基、防交联剂、乳化剂和胺化物为原料合成了一种多功能分散型黏度指数改进剂.考察了乙丙共聚物接枝马来酸酐过程中接枝率和凝胶率的关系,分别从反应温度、单体马来酸酐和引发剂用量等方面分析了接枝率和凝胶率的变化规律,提出了提高接枝率和降低凝胶率的方法.结果表明,在引入防交联剂的条件下,反应的接枝率和凝胶率达到了较好的平衡,分别为2.8%和3.6%.所得产品具有优异的增稠能力、烟炱分散性能、烟炱磨损性能、抗氧化性能和剪切稳定性能,兼具黏度指数改进剂和无灰分散剂的特点.

高硅ZSM-5沸石孔道和酸性的协同调控及其催化甲醇制丙烯反应性能

通过碱处理结合铬改性策略实现了对高硅ZSM-5沸石孔道和酸性的协同调控,制备出了一种具有适宜酸性的高硅多级孔沸石催化剂。在碱处理的过程中,通过精细调节合成凝胶组成,在沸石晶体中引入的丰富共生界面,诱导了介孔的形成,从而打破了沸石硅铝比对常规碱处理法的限制。在铬改性的过程中,独特的多级孔结构促进了铬在催化剂中的分散,从而实现了对酸性的深度改性。在甲醇制丙烯催化反应中,制备的催化剂表现出了极佳的催化稳定性以及很高的丙烯和总低碳烯烃选择性。

C_(4)烯烃转化制丙烯工艺及催化剂研究

目的开发C_(4)烯烃催化裂解制丙烯工艺和催化剂制备工艺技术,完成小试和工业侧线试验。方法采用固定床评价装置考查了催化剂配方、改性及工业条件对催化剂活性、选择性、稳定性能的影响。结果以ZSM-5分子筛为活性组分的催化剂在C_(4)烯烃转化制丙烯反应中具有较好的活性、选择性、稳定性和再生性,磷的引入未改变催化剂的晶型结构,但降低了催化剂酸性位点数量,并调节了催化剂的n(B酸)/n(L酸),随着磷负载量增加到5%(w),分子筛中磷与铝的相互作用逐渐增强,磷可以和骨架铝和非骨架铝相互作用。结论C_(4)烯烃的转化率达到80%以上,丙烯的选择性达到35%~45%,催化剂的单程寿命达到一个月以上,且经再生后,再生恢复率达95%。

微相分离型聚丙烯热塑性弹性体的力学性能

为了制备相畴尺寸均匀、细小,形态结构易控,力学性能稳定的聚丙烯热塑性弹性体(PTPE),设计出了从聚丙烯(PP)与弹性体的均相体系出发,利用在硫化过程中的能效应使之发生微相分离,能效应和熵效应控制组分相畴的尺寸和形态以制备PTPE的原理和技术,研究了橡/塑比、橡胶配比、PP相对分子质量、引发剂用量、架桥剂用量、反应温度对样品化学结构和力学性能的影响。结果表明,在125℃反应温度下样品配方为:橡塑质量比为70/30、乙丙橡胶与丁苯质量比为80∶20、引发剂用量为2.14份、架桥剂用量为18.2份时,制得试样的综合力学性能最佳,拉伸强度、100%定伸应力、扯断伸长率、撕裂强度、扯断永久变形分别为11.25 MPa、8.78 MPa、384%、58.5 kN/m、78%。

锂系聚烯烃弹性体(TPOE)与聚烯烃树脂的共混行为及性能研究

本文剖析了锂系热塑性聚乙烯-丙烯-丁烯-异丙烯(TPOE)、三元乙丙橡胶(EPDM4770P)、聚烯烃弹性体(POE8480)和聚烯烃(TPO/CA10A)树脂的分子结构,探究了这类聚合物的热学性能和物理机械性能,研究了不同用量的TPOE对PP/PE树脂共混物的热学性能和物理机械性能的影响。结果表明,TPOE/PE=1.6~2.5、TPOE/PP=1.4~2.5的共混物,其热学性能和物理机械性能均可与CA10A及POE8480相媲美。

C_(3)产业链高质量发展研究及建议

分析预测了我国丙烯及其衍生物聚丙烯、丙烯腈、丙烯酸、苯酚/丙酮、环氧丙烷、丁辛醇等的市场供需情况;指出了我国C_(3)产业链产能全面过剩的原因;提出了新形势下进入C_(3)产业链的切入点、高质量发展建议。

Catalytic cracking of light diesel over Au/ZSM-5 catalyst for increasing propylene production

The catalytic cracking of light diesel oil （235–337 ＆#176;C） over gold‐modified ZSM‐5 was investigated in a small confined fluidized bed at 460 ＆#176;C and ambient pressure. Different Au/ZSM‐5 catalysts were prepared by a modified deposition‐precipitation method by changing the preparation procedure and the amount of gold loading and were characterized by X‐ray diffraction, N2 adsorp‐tion‐desorption, temperature‐programmed desorption of NH3, transmission electron microscopy and inductively coupled plasma spectrometer. It was found that a small amount of gold had a posi‐tive effect on the catalytic cracking of light diesel oil and increased propylene production at a rela‐tively low temperature. The maintenance of the ZSM‐5 MFI structure, pore size distribution and the density of weak and strong acid sites of the Au/ZSM‐5 catalysts depended on the preparation pa‐rameters and the Au loading. Simultaneous enhancement of the micro‐activity and propylene pro‐duction relies on a synergy between the pore size distribution and the relative intensity of the weak and strong acid sites. A significant improvement in the micro‐activity index with an increase of 4.5 units and in the propylene selectivity with an increase of 23.2 units was obtained over the Au/ZSM‐5 catalyst with an actual Au loading of 0.17 wt%.

聚丙烯催化剂研究进展

综述了聚丙烯(PP)催化剂的研究进展,包括Ziegler-Natta(Z-N)、茂金属、后过渡金属及复合催化剂,重点分析了载体、助催化剂、给电子体对Z-N催化剂活性、结构及性能的影响,并对比了各类催化剂的优缺点。指出今后需在反应机理、合成工艺、聚合物形貌控制等方面对催化剂进行深入研究和设计,在保证催化剂成本的同时,产出性能指标更加优异的PP产品。

Study on kinetics of propylene polymerizationat different temperatures via Monte Carlo simulation

The elementary reactions of propylene polymerization catalyzed by conventional Ziegler-Natta catalysts was proposed according to the comprehensive view and without considering the effect of any impurity in the material on propylene polymerization. The Monte Carlo simulation technique was employed to investigate the kinetics of propylene polymerization in order to determine the validity of the stationary state assumption and the effects of the polymerization temperature on the polymerization. The simulated total amount of active species, which only increases quickly at the beginning of the polymerization, indicates that the stationary state assumption in the studied system is valid. Moreover, significant effects of polymerization temperature on the polymerization conversion, and the molecular weight and its distribution were also analyzed. The simulated results show that the consumption rate of propylene increases with the increase of polymerization temperature; the maximum values of the number-average degree of polymerization are constant at different polymerization temperatures, however, the peak appears earlier with the higher temperature; as the polymerization temperature increases, the average molecular weight decreases and the molecular weight distribution changes greatly.

中国丙烯及下游产品发展回顾及展望

介绍了2023年中国丙烯及下游产品的供需情况,包括产能、产量、进口量、出口量、消费量及当量消费量,对2023年中国丙烯及下游产品价格及利润情况进行分析,并对2024年中国丙烯及下游产品发展进行展望。

离子液体催化CO_(2)与环氧丙烷合成碳酸丙烯酯反应动力学研究

利用自制烷基功能化催化剂催化环氧丙烷(PO)与CO_(2)环加成生成碳酸丙烯酯(PC),对催化剂用量,反应温度,反应压力及反应时间进行优化,推导了该催化剂催化PC合成的反应机理并建立了动力学方程,讨论了不同温度下PO转化率和PC生成速率随时间变化的规律。实验结果表明,当催化剂用量为0.8%(w)、反应温度140℃、反应压力4.0 MPa、反应时间2.0 h时,PO转化率可达99.61%,PC收率达99.25%。PC合成反应速率与PO的浓度呈线性关系,并遵循一级反应动力学规律。

Effects of Oral Administration of Propylene Glycol and Ca-P-Mg Mixture on Milk Quality and SCC of Dairy Cows after Birth

In order to further study the postpartum care technology of dairy cows,the effects of oral administration of propylene glycol or Ca-P-Mg mixture and compound oral rehydration salts on milk quality and SCC of dairy cows after birth were investigated. The results showed that the milk fat and dry matter contents in the dairy cows administered with Ca-P-Mg mixture and compound oral rehydration salts were higher than those in the dairy cows administered with propylene glycol（P 〈0.05）. However, there were no significant differences in milk sugar and protein contents and SCC between the two administration groups.