聚合物负载铑催化剂的稳定性研究—三氯化镧的影响

本文研究了聚合物负载铑催化剂引入三氯化镧后在氢甲酰化反应中的催化活性和稳定性,发现在大多数实验条件下,镧的引入对聚合物负载铑催化剂的性能有较大影响。     

聚合物载体负载TiCl4/I-Bu3Al催化烯烃聚合

探讨了聚合物负载烯烃聚合催化剂的合成及用于聚合的研究,研究了聚合物作为载体的催化和赤,并通过ＩＲ,ＤＳＣ,元素分析和粘度法测定分子量等手段对催化剂及聚合物进行了表征,包括合成聚合物负载的Ｔi体系催化剂和用所合成的催化剂进行了乙烯聚合,乙烯、丙烯与丁二烯共聚合的研究。     

聚合物负载贵金属催化剂的合成及其在氢化反应中的应用进展

聚合物负载贵金属催化剂大多具有良好的光学催化活性,并且反应后容易从反应物中分离,重复实用性高,成为近年来人们研究的热点。常见的聚合物载体主要为有机聚合物及多种无机-有机杂化材料。本文主要按聚合物载体种类的不同,综述了聚合物负载Pt、Pd、Rh等贵金属催化剂的制备方法及其在烯烃、二烯烃、炔烃和硝基芳香化合物等物质的催化氢化中的应用情况。同时,对以树形分子为载体的催化剂、负载多元金属催化剂以及负载金型催化剂的研究及应用情况也进行了总结和评述。     

Schiff碱配合物的研究：Ⅷ.聚合物负载Schiff碱的配位作用

高分子量的Schiff碱可应用于离子吸附和催化等领域,已引起人们浓厚的兴趣,本文报道两种二乙烯基苯-苯乙烯聚合物负载的Schiff碱,考察它们对若干金属离子的吸附作用。     

聚合物负载的手性催化剂和手性试剂和合成及应用

近年来,用聚合物负载的手性催化剂和手性试剂完成的不对称合成反应主要集中在潜手性酮的不对称还原反应;烯烃的不对称双羟基化反应;烯烃的不对称环氧化反应;不对称Ｄｉｅｌｓ－Ａｌｄｅｒ反应和饱和碳原子上的不对称取代反应。就近十年来聚合物负载手性催化剂和手性试剂的合成及应用进行了讨论。     

聚合物负载金鸡纳碱类手性相转移催化剂制备手性α-氨基酸研究进展

近年来,基于聚合物载体易分离、可重用等优点,聚合物负载催化剂得到了迅速的发展。本文就聚合物负载金鸡纳碱类催化剂在制备手性α-氨基酸上的应用进行了讨论,并对本领域未来的发展作一展望。     

有机硅聚合物负载硫、膦混合双齿钯配合物的合成与催化性能

负载型钯催化剂;混合双齿高分子配体;羰基化;芳基卤化物;聚合物;有机硅聚合物负载硫、膦混合双齿钯配合物的合成与催化性能     

溶剂化金属原子浸渍法制备聚合物固载Co—Ag催化剂：Ⅰ.组成与？…

为避免有机聚合物因热稳定性差而不能用高温氢气还原金属制备聚合物负载催化剂的弱点,采用溶剂化金属原子浸渍法在温和的条件下直接把零价金属负载在聚合物上,制备了几种不同金属含量的Ｃｏ－Ａｇ催化剂,用Ｘ－射线衍射,Ｘ－射线不电子能谱和磁测定对催化剂进行表征并和普通浸渍法制得的相同金属含量的催化剂进行比较,表明溶剂化金属原子浸地制得催化剂的金属粒度小于普通浸渍法制香的催化剂,面且前者的零价属含量也高于后者。     

聚合物负载的手性催化剂和手性试剂的合成及应用

近年来,用聚合物负载的手性催化剂和手性试剂完成的不对称合成反应主要集中在潜手性酮的不对称还原反应;烯烃的不对称双羟基化反应;烯烃的不对称环氧化反应;不对称Diels-Alder反应和饱和碳原子上的不对称取代反应.就近十年来聚合物负载手性催化剂和手性试剂的合成及应用进行了讨论.     

聚合物负载手性季铵盐的合成与表征

以金鸡纳生物碱中的辛可宁为原料,氯甲基化聚苯乙烯-聚乙二醇、一缩二乙二醇、二缩三乙二醇、乙二醇等为载体合成了几种聚合物负载的手性季铵盐,并对它们的结构用红外光谱、元素分析、扫描电镜和X射线光电子能谱等测试手段进行了表征。     

四氯化锆四元催化体系中乙烯齐聚反应的动力学研究

研究了四氧化锆作主催化剂的四元催化体系中，乙烯压力、催化剂浓度和温度对乙烯齐聚反应的影响．测定了稳定态下乙烯齐聚反应的宏观动力学方程和表观活化能．     

Experimental investigation of fluidized-bed reactor performance for oxidative coupling of methane

Performance of the oxidative coupling of methane in fluidized-bed reactor was experimentally investigated using Mn-Na2WO4/SiO2,La2O3/CaO and La2O3-SrO/CaO catalysts.These catalysts were found to be stable,especially Mn-Na2WO4/SiO2 catalyst.The effect of sodium content of this catalyst was analyzed and the challenge of catalyst agglomeration was addressed using proper catalyst composition of 2%Mn2.2%Na2WO4/SiO2.For other two catalysts,the effect of Lanthanum-Strontium content was analyzed and 10%La2O 3-20%SrO/CaO catalyst was found to provide higher ethylene yield than La2O3/CaO catalyst.Furthermore,the effect of operating parameters such as temperature and methane to oxygen ratio were also reviewed.The highest ethylene and ethane (C2) yield was achieved with the lowest methane to oxygen ratio around 2.40.5% selectivity to ethylene and ethane and 41% methane conversion were achieved over La2O3-SrO/CaO catalyst while over Mn-Na2WO4 /SiO2 catalyst,40% and 48% were recorded,respectively.Moreover,the consecutive effects of nitrogen dilution,ethylene to ethane production ratio and other performance indicators on the down-stream process units were qualitatively discussed and Mn-Na2WO4/SiO2 catalyst showed a better performance in the reactor and process scale analysis.     

乙烯齐聚催化剂研究进展

综述了乙烯齐聚催化剂的研究进展.按照碳链的原子数目,简要介绍了α-烯烃的用途.按照后过渡金属催化剂和前过渡金属催化剂分类介绍了乙烯齐聚催化剂的研究情况,并重点介绍了乙烯三聚催化剂的研究进展,给出了部分聚合机理.文章最后介绍了α-烯烃除用乙烯齐聚催化剂方法外,还有石蜡热裂解、烷烃催化裂解、烷烃脱氢、烯烃二聚和歧化等方法制备.乙烯齐聚法所得产品线性化程度高,聚合度分布窄,分离费用低,产品质量好.在我国,石蜡裂解法为主要生产方法,因此在我国开展乙烯齐聚的研究,开发具有自主知识产权的齐聚催化剂,具有十分重要的意义.     

Dehydration of Ethanol to Ethylene on Ring- and Trilobe-Shaped Catalysts

The indicators of ethanol to ethylene catalytic dehydration process on trilobe- and ring-shaped samples of an alumina catalyst were compared at the fixed parameters: thermal agent temperature and catalyst load. Experiments were performed in a flow-through reactor of a laboratory setup and in a tubular reactor of a pilot installation. The use of the less active ring-shaped catalyst ensures higher values of ethanol conversion, ethylene yield, and catalyst performance and significantly lower hydraulic resistance, compared to the more active trilobe-shaped catalyst. This is caused by lower intensity of the heat absorption on the less active catalyst and, correspondingly, to the higher temperature in the ring bed due to higher bed porosity.     

纳米Cr2O3系列催化剂上CO2氧化乙烷脱氢制乙烯反应

 采用溶胶－凝胶法和共沸蒸馏法耦合技术制备了纳米Cr2O3催化剂，并采用共沉淀法和共沸蒸馏法耦合技术制备了纳米Cr2O3／Al2O3，Cr2O3／ZrO2和Cr2O3／MgO复合催化剂．应用BET，XRD，XPS，TPR和TEM等物理化学方法对催化剂的结构和物化性质进行了表征，并考察了该系列催化剂上CO2氧化乙烷脱氢制乙烯的反应性能．结果表明，纳米Cr2O3催化剂上乙烷和CO2的转化率均明显高于常规Cr2O3催化剂，但乙烯的选择性低于常规Cr2O3催化剂；纳米复合催化剂中的复合成分显著影响催化剂的催化性能．其中，10％Cr2O3／MgO纳米复合催化剂在温度为973K时，乙烷转化率和乙烯选择性分别可达到61．54％和94．79％．纳米催化剂表面Cr的还原性以及Cr6＋／Cr3＋比值是影响乙烷转化率和乙烯选择性的重要因素．     

Effect of acid density of HZSM-5 on the oligomerization of ethylene in FCC dry gas

The oligomerization of ethylene in FCC dry gas over HZSM-5 catalyst with different Si/Al2 ratios was studied. The effect of acid density of catalyst on the oligomerization of ethylene was discussed. By increasing the acid density of catalyst, ethylene conversion showed a linear increase, while the yields of olefins decreased when the acid density of catalyst exceeded 0.14 mmolNH3/g owing to a promotion of hydrogen transfer reaction. Through comparing the average distance between acid sites on catalyst with kinetic diameters of olefins, it was found that the dimerization of ethylene was not restrained by the sparse distribution of acid sites, while the hydrogen transfer reaction of C3 and C4 olefins was limited. On these bases, a conclusion is proposed that the dimerization of ethylene proceeded via Eley-Rideal mechanism, while the hydrogen transfer reaction of C3 and C4 olefins followed the Langmuir-Hinshelwood mechanism.     

Acid and catalytic properties of MnOm?ZrO2 (M=Ca, Ba, Sm, Yb) compositions

The volume stages of ethylene glycol oxidation to glyoxal on silver have been studied by varying the catalyst grain size. Temperature oscillations have been detected in the catalyst layer. The nature of the oscillations and the range of their generation were investigated by varying the oxygen, ethylene glycol and water vapor contents in the reaction mixture. Glyoxal formation was shown to occur on the silver catalyst surface. The generation of oscillations is responsible for the CO to CO₂ oxidation in the volume between the catalyst grains.     

Various activation procedures of Phillips catalyst for ethylene polymerization

Nowadays, the Phillips CrO_x/SiO₂ catalyst is still attracting interest from both industrial and academic fields owing to its unique characteristics for HDPE production. Compared with other industrial catalysts for ethylene polymerization, the Phillips catalyst can be activated by ethylene monomer, CO or Al-alkyl cocatalyst after a simple calcination process (thermal activation). In this work, a brief review of our recent new understanding on various activation procedures, including thermal activation, monomer activation, and CO activation, on industrial Phillips catalyst was presented. A new initiation mechanism, ethylene metathesis mechanism, was proposed according to some experimental evidence during the induction period when ethylene monomer was used to activate the catalyst. Such an ethylene metathesis mechanism was also indirectly confirmed in CO-prereduced Phillips catalyst. The formation of short chain branches in polymer can be rationalized well by this newly proposed unique mechanism during ethylene homo-and copolymerization with hexene-1 using CO-prereduced Phillips catalyst in the presence of triethylaluminum cocatalyst.     

乙二醇二缩水甘油醚的合成及作为阳离子型紫外光固化稀释剂性能研究

以三氟化硼乙醚络合物为催化剂,以氢氧化钠为成环反应的闭环剂,利用乙二醇和环氧氯丙烷为原料合成了乙二醇二缩水甘油醚.研究了催化剂三氟化硼乙醚络合物用量、环氧氯丙烷和乙二醇摩尔比、氢氧化钠和乙二醇摩尔比,以及成环反应温度这些因素对合成反应的影响.结果表明较好的合成反应条件是:三氟化硼乙醚络合物质量分数为0.40%,环氧氯丙烷和乙二醇较佳摩尔比为2.4:1,氢氧化钠和乙二醇较佳摩尔比为2.2:1,较佳的成环反应温度为30℃.同时,把乙二醇二缩水甘油醚作为稀释剂加入到环氧树脂E-51中,利用三芳基锍鎓六氟锑酸盐作为引发剂,制备了阳离子型紫外光固化涂料,其紫外光固化膜的拉伸强度为46.25MPa,杨氏模量为1487.26MPa,断裂伸长率为6.27%.     

酚硝酮为配体的锆催化剂合成与表征及催化乙烯聚合的研究

以水杨醛与苯基羟胺缩合制备的酚硝酮为配体制备了Zr的配合物,采用IR、NMR、元素分析、质谱等表征手段对酚硝酮配体以及催化剂的结构进行了表征.研究了以酚硝酮为配体的Zr的配合物与MAO组成的催化体系催化乙烯聚合的行为.研究结果表明,该催化剂乙烯均聚活性较高且具有较好的耐温性,乙烯均聚的活性大于106g/(molZr·h),催化剂的活性随着温度的升高有较大幅度的提高且在100℃条件下活性仍无明显衰减.另外,采用凝胶渗透色谱以及示差扫描量热法对制备的一系列聚乙烯的分子量、分子量分布以及热性能进行了表征,催化得到的聚乙烯分子量可达到105,熔点在132℃左右.