催化裂化过程中热裂化反应与二次反应的研究

利用连续式小型提升管催化裂化实验装置,研究了重油催化裂化过程中热裂化反应和二次反应的特点;考察了反应温度、剂油比和油气停留时间对热裂化和二次反应（氢转移和异构化反应）的影响;给出了不同反应条件下催化裂化过程中的过裂化点,考察了过裂化点前后热裂化反应在催化裂化过程中所占比例及氢转移和异构化反应的变化。结果表明,降低反应温度,缩短停留时间,增加剂油比可以抑制催化裂化过程中不利的热裂化反应,有利于氢转移和异构化反应的发生;在由反应温度、剂油比和停留时间引起的过裂化点前后,热裂化、氢转移和异构化反应表现出各自的变化特点。     

大庆蜡油催化裂化过程中的质子化裂化反应

在小型固定流化床装置上采用酸性催化剂进行了多系列不同反应深度的催化裂化实验,对大庆VGO催化裂化过程中发生的质子化裂化反应进行了初步的研究。在重质油的催化裂化过程中会出现二次质子化裂化反应。二次质子化裂化反应主要是由于汽油中烷烃重新在酸性催化剂上形成五配位正碳离子随后分解所造成,其产生的原因主要是由于反应后期催化剂对反应中间产物的选择性吸附改变所致。二次质子化裂化反应对温度不敏感。大庆VGO在500℃下反应时二次质子化裂化反应约占整个质子化裂化反应的60%。     

提高USY型FCC催化剂硫转移和催化裂化活性的研究

采用镁、铈、镧和磷对USY型FCC催化剂进行改性,采用FT IR分析方法对改性催化剂的表面酸性进行了表征,研究了硫转移活性组分对催化剂的硫转移和催化裂化活性的影响。结果表明,多次氧化 还原循环后,改性催化剂仍保持较好的硫转移活性,可以达到60%以上。镁的引入会减少基质和分子筛表面强酸的数量,少量镁的引入对催化裂化活性影响不大,铈和镧的引入会使分子筛和基质的表面酸量得到显著增加,提高催化裂化活性,但同时会引起焦炭的增加,磷改性可改善基质和分子筛表面酸性,抑制焦炭的产生,保持催化裂化活性的同时使汽油中的烯烃质量分数下降6%。     

C5烃催化裂解过程中氢转移反应的研究

对C5烃(正戊烷、1-戊烯)的裂解反应产物进行分析,按照理想正碳离子和自由基反应机理,正戊烷和1-戊烯裂解生成低碳烯烃(C2H4+C3H6+C4H8)的摩尔选择性分别达到50％和100％.但是使用MFI-30分子筛,在650℃反应条件下,正戊烷和1-戊烯催化裂解生成低碳烯烃的摩尔选择性分别为23.41％和56.79％,...     

催化裂化烟气硫转移剂的研究进展

催化裂化装置（FCCU）是石油二次加工的重要手段,也是排放硫氧化物（SOx）的主要源头之一.据报道,炼油厂排放的SOx约占其总排放量的6%～7%,而催化裂化（FCC）就占总排放量的5%左右[1].催化裂化（FCC）过程中沉积在焦炭上的硫会转化为SOx（其中SO2占90%以上,其余为SO3）,随再生烟气排出,     

稳定同位素方法研究模型化合物之间的氢转移反应

二十烷,菲作为模型化合物,以四氢萘为供氢剂,在临氮及临氢体系中应用氘代四氢萘考察供氢剂的氢转移反应,发现供氢剂抑制烷烃的裂化,其作用是通过脱氢湮灭自由基来抑制裂化反应。临氮及临氢条件下,与正二十烷与菲的二元体系相比,正二十烷,菲和四氢萘三元体系中四氢萘不仅能生成较多的菲的氢化芳烃产物,而且稳定同位素方法表明氘代四氢萘可以向菲和菲的氢化芳烃产物转移更多的氘,同时发现H12－四氢萘和D12－四氢萘的供氢（氘）率上存在着动力学同位素效应。     

光致噻吨酮与胺类、酚类、醇类的电子转移和氢转移反应

利用激光闪光光解方法研究了一系列胺类、酚类、醇类在脱氧乙腈中猝灭噻吨酮(TX)三重态的反应,得到了相应的瞬态吸收光谱和猝灭速率常数(kq).通过对光谱演变特性的分析,推断出三重态噻吨酮与不含有活泼氢的胺发生了电子转移反应,与含有活泼氢的胺发生了电子-质子转移反应.三重态噻吨酮与酚类、醇类反应中观察到噻吨酮加氢自由基的生成,据此推断出三重态噻吨酮与酚类、醇类发生了氢转移反应.胺类的猝灭速率常数随着反应自由能变(ΔG)的增大而减小,说明电子转移影响了噻吨酮三重态的猝灭.酚类的猝灭速率常数先随ΔG增大而减小,后随酚阳离子的酸性增强逐渐增大,可能是猝灭过程中电子转移影响减弱的同时氢转移影响逐渐增强.醇类的猝灭速率常数随着醇的α-C—H键能的增大而减小,说明α-C—H键能是影响噻吨酮三重态猝灭的关键因素.比较以前研究的胺类、酚类、醇类与三重态呫吨酮(XT)、芴酮(FL)反应的结果可知,由于分子结构差异性的影响,相关的猝灭速率常数按照呫吨酮、噻吨酮、芴酮的顺序逐渐减小.     

咪唑类化合物在乙腈溶液中负氢解离焓的理论研究

在与实验对照的基础上优化出一套计算咪唑类化合物在乙腈溶液中负氢解离焓的理论方法, 即MP2/6-311++G(d,p)//B3LYP/6-31+G(d)结合IEF-PCM溶剂模型及UA0孔穴计算法. 在此基础上, 有目的地设计了14种咪唑类负氢给体, 并计算了其在乙腈溶液中的负氢解离焓, 系统分析了影响其负氢解离焓的各种因素. 结果表明, 取代基的电子效应、体系释放负氢后的芳构化能力、咪唑环2位的苯基对前线分子轨道的贡献程度、体系电荷的分布情况及溶剂化效应等多种因素均能影响咪唑负氢给体在乙腈溶液中的负氢解离焓.     

化学改性对催化裂化催化剂氢转移性能的影响

 研究了用草酸处理裂化催化剂的活性组分USY型分子筛以及在催化剂基质中添加磷改性的氧化铝等方法对裂化催化剂氢转移反应活性的影响. 实验结果表明,酸处理能脱除USY型分子筛孔道中的无定形氧化铝,疏通分子筛孔道,提高分子筛的氢转移反应活性,减少积碳; 对于含稀土的REUSY型分子筛,酸处理首先脱除的是稀土离子,降低了分子筛的裂化反应活性,但提高了氢转移反应活性. 在催化剂基质中添加磷改性的氧化铝能增加基质的弱酸性中心,增加裂化反应的活性中心,提高催化剂的裂化及氢转移反应活性,同时减少催化剂上的积碳.     

煤与废塑料共液化中氢转移的示踪试验研究 Ⅱ．富氢塑料中的氢转移

采用放射性同位素3H标记的聚乙烯塑料进行了先锋褐煤与低密度聚乙烯（LDPE）的共液化示踪试验，并考察了钼灰（FAMo）催化剂和不同溶剂的影响，示踪试验结果表明，在先锋煤与LDPE共液化过程中，富氢塑料LDPE中的含氢基团确实起着供氢作用，而且这种含氢基团向煤液化自由基的氢转移无需经过供氢溶剂进行传递，钼灰催化剂能够加速LDPE塑料的供氢作用，使用非供氢溶剂时，在煤与LDPE共液化反应初期，LDPE中的含氢基团在钼灰催化剂作用下较易向煤热裂解产物转移，并出现供氢竞争现象。     

Reductive Desulfurization of Thioamides to Amines by Catalytic Hydrogen Transfer Reaction

Introduction Reductive desulfurization of thioamides to amines is one of the methods to prepare amines and is generally achieved by a) Zn in acid, b) sodium or aluminum amal- gams, c) lithium alumminium hydride, d) Raney Ni and e) electrolytic reduction. These methods are not very convenient to be operated and some need more complex instrument. Here is reported the reductive desulfurization of thioamides to amines by catalytic hydrogen transfer reaction(CHT).     

Effect of Hydrogen or Syngas Addition on Light Alkene Production by the Catalytic Oxidative Cracking of Hexane 氢气/合成气添加对正己烷催化氧化裂解制低碳烯烃反应的影响

 采用0.1%Pt/MgAl2O4催化剂研究了H2或合成气的添加对高碳烷烃模型化合物正己烷氧化裂解制低碳烯烃反应的影响. 添加H2实验中,随n(H2)/n(O2)从0增加到3,产物中COx的选择性迅速由22.4%降到4.3%,低碳烯烃的选择性则从61.5%增加到73.8%,正己烷的转化率从62.0%增加到72.8%. 添加合成气对低碳烯烃和CO选择性的影响与添加H2的影响相同,只是添加合成气时正己烷的转化率下降了6%左右. 添加合成气的正己烷氧化裂解过程可提供组成可调的产物(含有低碳烯烃、H2和CO),可不经分离直接用作加氢甲酰化生产低碳烯烃衍生物过程的原料.     

Release of Formic Acid from Copper Formate: Hydride,Proton-Coupled Electron and Hydrogen Atom Transfer All Play their Role

Although the mechanism for the transformation of carbon dioxide to formate with copper hydride is well understood, it is not clear how formic acid is ultimately released. Herein, we show how formic acid is formed in the decomposition of the copper formate clusters Cu(II)(HCOO)₃⁻ and Cu(II)₂(HCOO)₅⁻. Infrared irradiation resonant with the antisymmetric C−O stretching mode activates the cluster, resulting in the release of formic acid and carbon dioxide. For the binary cluster, electronic structure calculations indicate that CO₂ is eliminated first, through hydride transfer from formate to copper. Formic acid is released via proton-coupled electron transfer (PCET) to a second formate ligand, evidenced by close to zero partial charge and spin density at the hydrogen atom in the transition state. Concomitantly, the two copper centers are reduced from Cu(II) to Cu(I). Depending on the detailed situation, either PCET or hydrogen atom transfer (HAT) takes place.     

利用色谱-反应联合装置研究渣油及其胶质的反应性能

建立一套色谱－反应联合装置，实现了在微量进样条件下对胜利原油减渣中胶质组分的催化裂化反应性能的考察。结果表明，在特殊设计条件下，色谱－反应联合装置具有快速、简便、再现性能良好的特点，可完成对渣油中胶质组分的催化裂化反应性能考察。     

温度和剂油比对汽油催化裂化脱硫的影响

Increasingly stringent regulations on environmental protection make gasoline desulfurization be a major concern for the present refineries. Accordingly, we proposed an original idea of sulfur reduction by catalytic cracking of FCC gasoline and simultaneously converting most sulfur of sulfides to H 2S. Some progress has been made in exploitation of the catalysts. In this paper, the effect of temperature and catalyst/oil ratio on the FCC gasoline desulfurization over two catalyst samples via catalytic cracking was discussed. The optimum temperature range is 400～420 ℃ for sulfur removal with relatively low cracking loss of gasoline. The highest sulfur removal percentage of 70% can be achieved with a liquid yield of more than 96%. The catalyst samples have higher desulfurization activity and selectivity for the sulfide cracking. In addition, both the gasoline yield and the sulfur content of the desulfurized gasoline decrease with the catalyst/oil ratio.     

Chloride and Hydride Transfer as Keys to Catalytic Upcycling of Polyethylene into Liquid Alkanes

Transforming polyolefin waste into liquid alkanes through tandem cracking-alkylation reactions catalyzed by Lewis-acid chlorides offers an efficient route for single-step plastic upcycling. Lewis acids in dichloromethane establish a polar environment that stabilizes carbenium ion intermediates and catalyzes hydride transfer, enabling breaking of polyethylene C−C bonds and forming C−C bonds in alkylation. Here, we show that efficient and selective deconstruction of low-density polyethylene (LDPE) to liquid alkanes is achieved with anhydrous aluminum chloride (AlCl₃) and gallium chloride (GaCl₃). Already at 60 °C, complete LDPE conversion was achieved, while maintaining the selectivity for gasoline-range liquid alkanes over 70 %. AlCl₃ showed an exceptional conversion rate of 5000 $$ , surpassing other Lewis acid catalysts by two orders of magnitude. Through kinetic and mechanistic studies, we show that the rates of LDPE conversion do not correlate directly with the intrinsic strength of the Lewis acids or steric constraints that may limit the polymer to access the Lewis acid sites. Instead, the rates for the tandem processes of cracking and alkylation are primarily governed by the rates of initiation of carbenium ions and the subsequent intermolecular hydride transfer. Both jointly control the relative rates of cracking and alkylation, thereby determining the overall conversion and selectivity.     

炼油厂催化裂化装置管道气体中氰化物含量的测定

提出了炼油厂催化裂化装置管道气体中氰化物含量的测定方法。优化的采样条件为:在前两个吸收瓶中各装入6mol·L-1氢氧化钠吸收溶液50mL;在第一个吸收瓶中加入碳酸镉;吸收的烟气体积不大于0.1m3;气体流量为2.0~2.5L·min-1。优化的蒸馏条件为:在蒸馏瓶中加入100g·L-1乙二胺四乙酸二钠溶液10mL,在接收瓶内加入40g·L-1氢氧化钠溶液10mL作为吸收液。方法用于吸收后样品的分析,加标回收率在81.7%~92.0%之间。     

The Influence of Elastic Strain on Catalytic Activity in the Hydrogen Evolution Reaction

Understanding the role of elastic strain in modifying catalytic reaction rates is crucial for catalyst design, but experimentally, this effect is often coupled with a ligand effect. To isolate the strain effect, we have investigated the influence of externally applied elastic strain on the catalytic activity of metal films in the hydrogen evolution reaction (HER). We show that elastic strain tunes the catalytic activity in a controlled and predictable way. Both theory and experiment show strain controls reactivity in a controlled manner consistent with the qualitative predictions of the HER volcano plot and the d‐band theory: Ni and Pt's activities were accelerated by compression, while Cu's activity was accelerated by tension. By isolating the elastic strain effect from the ligand effect, this study provides a greater insight into the role of elastic strain in controlling electrocatalytic activity.     

Catalytic Biorefining of Plant Biomass to Non‐Pyrolytic Lignin Bio‐Oil and Carbohydrates through Hydrogen Transfer Reactions

Through catalytic hydrogen transfer reactions, a new biorefining method results in the isolation of depolymerized lignin—a non‐pyrolytic lignin bio‐oil—in addition to pulps that are amenable to enzymatic hydrolysis. Compared with organosolv lignin, the lignin bio‐oil is highly susceptible to further hydrodeoxygenation under low‐severity conditions and therefore establishes a unique platform for lignin valorization by heterogeneous catalysis. Overall, the potential of a catalytic biorefining method designed from the perspective of lignin utilization is reported.     

不同供氢底物用于测定H2O2的酶催化动力学研究

研究了牛血红蛋白(hemoglobin,Hb)作为过氧化物模拟酶,以酸性铬蓝K、罗丹明B、亚甲基蓝不同供氢底物测定H2O2的酶催化反应体系的催化特性和反应条件。探讨了采用不同底物测定时的催化反应机理。用于雨水中H2O2含量的测定,结果满意。