助催化剂对TiCl_4/MgCl_2催化丙烯高温聚合的影响

研究了助催化剂种类(三甲基铝、三异丁基铝、三正己基铝、三乙基铝和甲基铝氧烷)及其含量对无内、外给电子体的TiCl4/MgCl2催化剂催化丙烯高温(100℃)聚合性能的影响,并用结晶分级分析、示差扫描量热和凝胶渗透色谱等方法分析了所得聚丙烯的结晶熔融行为和微观结构。实验结果表明,聚合温度从70℃升至100℃时,TiCl4/MgCl2催化剂的定向能力基本不变;100℃聚合时,以烷基化能力较弱的三异丁基铝为助催化剂时TiCl4/MgCl2催化剂的活性最高,而采用烷基化能力最强的三甲基铝为助催化剂时TiCl4/MgCl2催化剂的活性最低;100℃聚合时,助催化剂的种类对TiCl4/MgCl2催化剂的定向能力影响很小。     

High temperature polymerization of propylene catalyzed by MgCl2‐supported Ziegler–Natta catalyst with various cocatalysts

Four cocatalysts, referred to as ethylaluminoxanes, were synthesized by the reaction between triethylaluminium (AIEt₃) and water under various molar ratios of H₂O/Al at ?78°C. Aluminoxanes were used as cocatalysts for a MgCl₂‐supported Ziegler–Natta catalyst for propylene polymerization at temperatures ranging from 70 to 100°C. When the polymerization was activated by AlEt₃, the activity as well as the molecular weight and isotacticity of the resulting polymer gradually dropped as the temperature varied from 70 to 100°C. When ethylaluminoxane was employed as the cocatalyst, good activity and high molecular weight and isotacticity were obtained at 100°C. Furthermore, when the cocatalyst varied from AlEt₃ to ethylaluminoxane, the atactic fraction and polymer fraction with moderate isotacticity decreased and the high isotactic fraction slightly increased, which indicated that the variation of the cocatalyst significantly affects the isospecificity of active sites. It was suggested that the reactivity of the Al‐Et group and the size of the cocatalyst were correlated to the performance of the Ziegler–Natta catalyst at different temperatures. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1978–1982, 2006     

Nanoconfined Nickel@Carbon Core–Shell Cocatalyst Promoting Highly Efficient Visible‐Light Photocatalytic H2 Production

The realization of large‐scale solar hydrogen (H₂) production relies on the development of high‐performance and low‐cost photocatalysts driven by sunlight. Recently, cocatalysts have demonstrated immense potential in enhancing the activity and stability of photocatalysts. Hence, the rational design of highly active and inexpensive cocatalysts is of great significance. Here, a facile method is reported to synthesize Ni@C core–shell nanoparticles as a highly active cocatalyst. After merging Ni@C cocatalyst with CdS nanorod (NR), a tremendously enhanced visible‐light photocatalytic H₂‐production performance of 76.1 mmol g^?1 h^?1 is achieved, accompanied with an outstanding quantum efficiency of 31.2% at 420 nm. The state‐of‐art characterizations (e.g., synchrotron‐based X‐ray absorption near edge structure) and theoretical calculations strongly support the presence of pronounced nanoconfinement effect in Ni@C core–shell nanoparticles, which leads to controlled Ni core size, intimate interfacial contact and rapid charge transfer, optimized electronic structure, and protection against chemical corrosion. Hence, the combination of nanoconfined Ni@C with CdS nanorod leads to significantly improved photocatalytic activity and stability. This work not only for the first time demonstrates the great potential of using highly active and inexpensive Ni@C core–shell structure to replace expensive Pt in photocatalysis but also opens new avenues for synthesizing cocatalyst/photocatalyst hybridized systems with excellent performance by introducing nanoconfinement effect.     

CoPtx‐loaded Zn0.5Cd0.5S nanocomposites for enhanced visible light photocatalytic H2 production

Zn_0.5Cd_0.5S solid solution, modified with bimetallic CoPt_x nanoparticles, has been prepared using a two‐step organic solution method. The photocatalytic H₂ production rate of CoPt_x–Zn_0.5Cd_0.5S nanocomposites with different composition and percentage of CoPt_x was investigated. The results showed that the 1 wt% CoPt₃–Zn_0.5Cd_0.5S sample had the best activity which was 4.7 times higher than that of pure Zn_0.5Cd_0.5S and 1.2 times higher than that of Pt–Zn_0.5Cd_0.5S for photocatalytic H₂ production. The transient photocurrent response of the Zn_0.5Cd_0.5S showed an obvious increase in the current density after CoPt_x loading. Electrochemical impedance spectra measurements showed that the CoPt_x–Zn_0.5Cd_0.5S nanocomposites with x = 2 and 3 had lower charge transfer resistance R_t than that of Pt–Zn_0.5Cd_0.5S. The enhanced catalytic properties of the CoPt_x–Zn_0.5Cd_0.5S nanocomposites are attributed to their better accumulation ability for photoexcited electrons and higher rate for charge separation and transportation. Copyright © 2016 John Wiley & Sons, Ltd.     

Interface engineering of nanoceramic hematite photoelectrode for solar energy conversion

This work addresses the role of different modifiers on the overall photocurrent response, which allowed a dual material insertion, increasing the charge separation without compromise the surface catalysis. Sn-addition onto nanoceramic hematite photoelectrodes clearly increased flat band potential, promoting a good charge separation, and shifting the onset to a higher potential, attributed to the surface-trapping state created by this modification. Notoriously, Sn-hematite photoelectrodes loaded with NiFeO_x exhibited the highest photocurrent density, suggesting a partially recovered surface-trapping states created during the electrode designing. The well-known cocatalyst acted in the overall photoelectrocatalytic response with no significant effect on the turn-on voltage, in other words, with minor effect related to catalytic efficiency. The dual modification contributes to understand the role of different modifiers allowing to satisfactorily improve charge separation while maintaining the conductivity attributed to IV-group ions.     

甲苯定向氯化合成对氯甲苯

采用天然沸石作为甲苯氯化催化剂再加入助催化剂,进行甲苯氯化反应研究,探讨氯化工艺及各因素的影响,结果表明,甲苯转化率达到99.7%,一氯甲苯产物中55%为对氯甲苯.     

降低催化裂化汽油硫含量的固体助剂

针对金属Ni、V含量较高的催化裂化平衡剂，研制开发了降低催化裂化汽油硫含量的助剂。比较了经复合氧化物改性的不同稀土含量的分子筛及不同化合物改性的硅铝担体对助剂的裂化脱硫性能的影响。对助剂的中型样品进行固定流化床反应器评价结果表明，当高重金属含量的平衡剂中含质量分数为10％的助剂时，裂化产品分布无明显变化，催化裂化汽油的脱硫率可达15％～25％。     

LOSA-1多产丙烯助剂的工业应用

近几年，随着化工市场的兴旺，丙烯的价格一路攀升，国内催化裂化装置在保证原油二次加工负荷的前提下，纷纷通过不同的技术改造、操作调整、改变催化剂等手段来多产液化气和丙烯。为此我公司二催化装置在不做工艺改造的前提下，应用了岳阳三生化工有限公司生产的LOSA-1增产丙烯助剂，取得了液化气产率增加4个百分点以上、丙烯产率增加1.7个百分点以上良好效果。     

新型催化裂化轻质油收率助剂的工业应用

介绍了WD0 1 0 0 2油溶性催化助剂在长岭炼化有限责任公司重油催化裂化装置上的工业应用情况。该助剂通过减缓催化剂在提升管内活性衰减 ,提高催化剂裂化活性、选择性 ,优化提升管内催化裂化反应。该装置使用助剂 36 μg/g ,装置渣油掺炼率由 30 .81%提高到35 .15 %,轻质油收率提高 0 .8个百分点 ,总液体收率提高 0 .6 7个百分点 ,对产品质量无不良影响。加剂调整作用时间短 ,操作灵活、方便。     

第二代降低FCC汽油烯烃助剂的研制

LAP-1助剂可有效降低FCC汽油烯烃含量,但影响FCC产品分布。新开发的LAP-2助剂在LAP-1的基础上对催化剂的活性组分和载体进行了改进,提高了助剂水热稳定性、氢转移活性和异构化能力,协调芳构化与氢转移反应,提高了降烯烃能力,改善了FCC产品分布。