Synergistic effect of W and P on ZSM-5 and its catalytic performance in the cracking of heavy oil

In order to develop the conversion of heavy oil with a high yield of propylene in the catalytic cracking process, ZSM-5 zeolite was modified by tungsten and phosphorus, which was proved to be an effective method. Characterization results show that the improvement of catalytic performance could be correlated to the interaction of phosphorus and tungsten species on ZSM-5. P inhibited the aggregation of tungsten species on ZSM-5 and was conductive to convert the tungsten species with octahedral coordination into tetrahedral coordination. And this ultimately led to that more acid sites were reserved after hydrothermal treatment in the tungsten and phosphorus co-modified ZSM-5 catalyst. Phosphorus species played an important role to restrain the dehydrogenation activity of tungsten. In addition, a model reflecting the interaction between tungsten species and ZSM-5 framework was proposed.     

Development of an O-ring from NR/EPDM filled silica/CB hybrid filler for use in a solid oxide fuel cell testing system

This research presents the effects of oxygen pressure and ambient temperatures on the crack behavior of O-rings from a semi-EV of NR/EPDM rubber with silica/CB filler, exposed to the inlet flow and outflow oxygen pressure in a Solid Oxide Fuel Cell (SOFC) environment. Blends of NR/EPDM were prepared with various ratios of silica/CB filler at 00/60, 10/50, 20/40, 30/30, 40/20, 50/10, and 60/00 phr. The fabricated O-ring complied with the standard for O-rings (TIS 2728-2559), with a minimum hardness of 65–75 Shore A, minimum tensile strength of 9 MPa, minimum elongation at break of 200%, and a minimum 100% modulus of 2.7 MPa. The mechanical properties of the compounds were tested, and the appropriate compound was chosen to make the O-rings to test in SOFC. The crack morphology of the fabricated O-rings was investigated and compared with a commercial O-ring after testing in the SOFC. As a result, the compound with silica/CB of 40:20 ratio provided the optimum mechanical properties, and passed the criteria standard of TIS 2728-2559. The mechanical properties of the prepared and commercial O-rings were similar (P-value of commercial with 60/00 = 0.273, 50/10 = 0.273, 40/20 = 0.144, 30/30 = 0.465, 20/40 = 0.465, 10/50 = 1.000 and 00/60 = 0.273; all > 0.05) and and both could still be continued to be used in SOFC despite some inner cracks after 24 h. The price of the prepared O-ring is cheaper than the commercial O-rings due to the low price of NR used in its formulation. Therefore, a prepared O-ring can be used in a SOFC, or other applications due to their mechanical properties and their reasonable price.     

亚乙基桥联多取代茚-芴锆、铪配合物的合成、结构及催化丙烯选择性齐聚研究

合成并表征了一系列新型亚乙基桥联多取代茚-芴锆、铪配合物ansa-C₂H₄-{2-Me-3-Bn-5,6-[1,3-（CH₂）₃]Ind}-（Flu） ZrCl₂（C1）,ansa-C₂H₄-{2-Me-3-Bn-5,6-[1,3-（CH₂）₃]Ind}（2,7-^tBu₂-Flu） ZrCl₂（C2）,ansa-C₂H₄-{2-Me-3-Bn-5,6-[1,3-（CH₂）₃]Ind}（3,6-^tBu₂-Flu） ZrCl₂（C3）,ansa-C₂H₄-{2-Me-3-Bn-5,6-[1,3-（CH₂）₃]Ind}（Flu） HfCl₂（C4）,并对典型配合物进行了X射线单晶衍射分析,确定了其空间结构.研究了该系列配合物在助催化剂作用下催化丙烯齐聚的行为,考察了催化剂结构及反应条件对齐聚反应的影响.配合物C1～C4与改性甲基铝氧烷（MMAO）或三异丁基铝/三苯甲基四（五氟苯基）硼酸盐（TIBA/TrB）组成的催化体系对丙烯齐聚表现出中等到高的催化活性.锆配合物C2和C3在40～100℃条件下普遍具有较高的β-甲基消除（β-Me消除）选择性（最高可达86%）,实现了分子量M_n在400到4500 g·mol^－1范围内的烯丙基封端丙烯齐聚物的高效合成.铪催化剂体系C4/TIBA/TrB的β-Me消除选择性明显高于相应的锆催化剂体系,同时所得齐聚物的分子量更低.     

丙烯直接环氧化Cu基催化剂的研究进展与挑战

作为一种重要的化工原料,环氧丙烷年产量近千万吨,然而目前工业上制备环氧丙烷的方法仍然面临着成本高、副产物多以及污染严重等问题。直接氧气氧化法进行丙烯环氧化因为具有原子经济、环保等优点受到了越来越多的关注。但是,催化过程中丙烯的α-H和环氧丙烷都具有很高的活性,使得在高转化率的条件下提升环氧丙烷选择性成为一个巨大的挑战。研究者们发现相较于其他币族金属,Cu基催化剂表现出更优异的丙烯直接环氧化反应性能。本综述总结梳理了近年来关于Cu基催化剂催化丙烯直接环氧化反应的研究成果,聚焦于Cu基催化剂改性方法,并对Cu基催化剂依然存在的问题和挑战进行深入探讨。     

Poly(propylene carbonate)/poly(3‐hydroxybutyrate)‐based bionanocomposites reinforced with cellulose nanocrystal for potential application as a packaging material

Poly(propylene carbonate) (PPC) is an aliphatic polycarbonate synthesized from carbon dioxide and propylene oxide. Poly(3‐hydroxybutyrate) (PHB) is a type of thermoplastic polyester produced by biological fermentation. The blending of PHB with PPC can effectively enhance the mechanical properties and barrier properties of PPC. Bionanocomposites of PPC/PHB enhanced by cellulose nanocrystal (CNC) are prepared via a two‐step process using polyethylene glycol as a carrier. Results show that the oxygen barrier properties of the composites increased with the increase of the CNC content. When the CNC content is 1 wt%, the oxygen barrier performance increases nearly 18 times. The assumed model can predict the barrier performance of composites with the combined influence of morphology and CNC distribution. This will make PPC/PHB/CNC nanocomposites a very promising degradable material for food packaging application.     

Impact of ionic liquids on silver thermoplastic polyurethane composite membranes for propane/propylene separation

This work describes newly synthesized composite polymeric membranes and their utilization in propane/propylene separation in a gas mixture. The nonporous composite polymers were successfully synthesized by using thermoplastic polyurethane (TPU) and several silver salts/silver salts with ionic liquids (ILs). Our studies showed that silver bis(trifluoromethanesulfonyl)imide (Ag[Tf₂N]) containing membranes outperformed other silver salt containing membranes in terms of selectivity. In addition, to this finding, ILs, as additives for the membranes, enhanced the selectivity by facilitating improved coordination of the olefin with the silver ions in the dense composite polymers.     

Sn/Al2O3催化剂结构与选择性催化还原NO性能

以不同沉淀剂和铝盐与SnCl4共沉淀制备了Sn/Al2O3催化剂.考察了催化剂在富氧条件下催化丙烯选择性还原NO的性能,借助于X射线衍射(XRD)、扫描电镜(SEM)、N2吸附-脱附、吡啶吸附红外光谱(Py-IR)和程序升温还原(TPR)等方法研究了催化剂性能与结构的关系.发现以NH3.H2O和NH4HCO3为沉淀剂、NH4Al(SO4)2为铝盐制备的Sn/Al2O3催化剂催化活性最高,NO转化率达90.9%,最佳催化活性温度为350℃.该催化剂的比表面积为254 m2/g,孔体积为0.878 cm3/g,孔径分布曲线在3~8 nm出现双峰,Sn物种主要以晶态SnO2存在,且表面Lewis酸酸量增加.     

聚丙撑碳酸酯的辐射效应

研究了室温条件下聚丙撑碳酸酯(PPC)在钴-60和电子加速器辐照过程中的响应行为。结果表明,聚丙撑碳酸酯是一种辐射裂解型聚合物,其分子量随着辐射剂量的增加而减小。1mm厚PPC片材在室温和N2气保护条件下,其裂解G值为Gs,γ-ray=10.81;Gs,EB=4.9。不同的裂解G值表明,O2气在聚丙撑碳酸酯的辐射裂解过程中有重要影响。红外光谱研究表明,辐射后聚丙撑碳酸酯在3474cm-1处的峰宽峰高增加,表明其裂解后端—OH基增加。由于裂解作用,辐射后聚丙撑碳酸酯的抗张强度和断裂伸长率均下降。在通常的辐射消毒剂量范围内(25~50kGy),PPC的保留抗张强度大于23MPa,断裂伸长率大于4%,裂解后试样的力学性能依然能够满足实际应用需要,因此PPC可以经受辐射消毒。     

Nd（naph）_3－Al（i－Bu）_3催化马来酸酐和环氧丙烷交替共聚合

研究了马来酸酐和环氧丙烷的交替共聚，发现Ｎｄ（ｎａｐｈ）＿３－Ａｌ（ｉ－Ｂｕ）＿３是马来酸酐（ＭＡｎ）和环氧丙烷（ＰＯ）交替共聚的良好催化剂．用红外光谱、核磁共振研究了共聚物的结构．共聚反应动力学研究表明共聚反应与单体和催化剂浓度均呈一级关系．表观活化能为１１３ｋＪ／ｍｏｌ．     

黏合剂对其ZSM-5分子筛成型物裂解石脑油的影响

为考察成型时,黏合剂性能对ZSM-5分子筛的影响,对同一分子筛用六种不同黏合剂捏合,挤条成型,进行SEM、NH₃-TPD和N₂物理吸附表征。结果表明,六个成型物在形貌和BET比表面积均无明显差异,二次孔数量明显比分子筛原粉增加。所用纯硅溶胶黏合剂的成型物,其NH₃-TPD酸量、微孔体积和微孔比表面积低于其分子筛原粉。所用含铝黏合剂的成型物,其NH₃-TPD酸量、微孔体积和微孔比表面积变化不明显,BJH累积孔体积明显增加。在固定床反应器中于600 ℃裂解石脑油。发现,纯硅溶胶黏合剂成型物的乙烯+丙烯收率明显低于含铝黏合剂。