负载型甲磺酸对合成乙酸异戊酯的催化性能研究

以活性炭、陶瓷球、石英砂、硅胶为载体负载甲磺酸，制得一系列负载型固体酸催化剂，用乙酸和异戊醇的酯化反应作探针反应，研究了这些固体酸的催化性能。结果表明，不同栽体的甲磺酸催化剂的活性与载体表面特性有关，CH3SO3^-／C催化剂对酯化反应显示出极高的催化活性，并可重复使用，在一定条件下，酯收率达97％。     

Ga2(SO4)3-凹凸棒型固体酸催化剂的制备及其对尼泊金庚酯合成的影响

采用凹凸棒负载Ga2(SO4)3制备了Ga2(SO4)3-凹凸棒型固体酸催化剂,对所制催化剂进行红外光谱、X射线衍射等表征,通过尼泊金庚酯的合成考察了催化剂的制备条件、催化活性、重复使用性以及反应动力学.结果表明,催化剂的较优制备条件是凹凸棒经8％硫酸溶液酸化处理,Ga2(SO4)3负载量25％,焙烧温度300℃,焙烧时间2.5h.在较优反应条件下,平均产率为92.1％.催化剂经过5次重复使用,产率仍不低于84.0％.动力学研究表明反应为二级反应,反应表观活化能为93.90 kJ/mol.     

甲乙酮合成仲丁胺凹凸棒土负载的Ni-B合金催化剂的研究

制备了凹凸棒土负载型Ni-B合金催化剂,考察了其对甲乙酮氢化胺化合成仲丁胺的催化活性.利用XPS、TEM等手段考察了不同酸浓度的处理对凹凸棒土载体以及由此得到的负载型催化剂的结构和催化性能的影响.并对性能优越的Ni-B/PAL-3催化剂作了简单的寿命评价实验.     

强酸性阳离子交换树脂负载金属离子催化制备乙酸正丙酯

以冰乙酸和正丙醇为原料,用强酸性阳离子交换树脂负载金属离子作为催化剂催化制备乙酸正丙酯,以乙酸的转化率作为考察指标,考察了树脂种类,负载四种金属离子及负载条件对催化剂性能的影响。用制备的负载催化剂,考察了酸醇摩尔比、反应时间、催化剂用量等对反应的影响,以及催化剂的重复使用性能。实验表明,负载金属锆离子的催化性能最好,负载条件为锆盐浓度为1.0%,负载温度为50℃,负载时间为1 h为最佳。反应最佳条件为反应酸醇摩尔比1∶1,反应时间3 h,催化剂用量为乙酸质量的20%,沸腾状态反应,反应的转化率为68.79%。催化剂经10次重复使用后催化能力没有明显的下降,说明催化剂的使用寿命较长。     

纳米二氧化钛负载凹土催化剂的制备及催化聚酯反应研究

制备了一种以锐钛矿为主的混晶纳米二氧化钛,并将其均匀负载于纳米凹凸棒土（ATP）上,得到了一类纳米复合催化剂,对二氧化钛及复合催化剂分别进行了X-射线衍射和透射电镜表征。利用催化聚酯反应对二氧化钛及多种复合催化剂的性能进行了评价,结果表明：与常规聚酯催化剂Sb2O3相比较,纳米二氧化钛可达到与Sb2O3相近的催化活性,但催化性能不稳定,聚酯产品b值较高;将二氧化钛负载于纳米凹凸棒土表面后,催化活性中心达到了理想的分散,催化性能更加稳定,同时也改善了聚酯的色相,b值从14.05降为8.17。此外,讨论了复合催化剂对聚酯产品物化性能的影响,通过DSC、TGA等测试手段,发现复合催化剂制备的聚酯结晶温度升高,二甘醇含量和热降解性能与常规聚酯相近。     

Ga2(SO4)3/凹凸棒固体酸催化剂的制备及催化合成丁酸己酯

采用凹凸棒负载Ga2(SO4)3制备了Ga2(SO4)3/凹凸棒固体酸催化剂,用红外光谱、X射线衍射等对催化剂结构进行了表征,通过丁酸己酯的酯化反应考察了催化剂的制备条件、催化活性、重复使用性以及反应动力学。催化剂较优制备条件是:凹凸棒经1.1 mol/L硫酸溶液酸化处理,Ga2(SO4)3负载量占催化剂总质量的25%,焙烧温度350℃,焙烧时间2.0 h,在该条件下平均酯化率为98.1%。催化剂经5次重复使用后,酯化率仍不低于85%。反应动力学研究表明:反应级数为2,表观活化能为76.17 kJ/mol。     

Pd／CNFs催化剂在Heck反应中的应用

文章考查了纳米碳纤维（CNFs）作为催化剂戴体负载贵金属钯所制备的催化剂用于Heck反应的催化性能；比较了不同制备方法所制备的Pd／CNFs催化剂的催化性能，Pd／CNFs的热稳定性及其重复使用性能。结果表明，Pd／cNFs催化剂是一类催化性能好、热稳定性高、适用面广且有很好重复使用性能的Heck反应非均相催化剂。     

果胶负载金属催化剂制备苯甲酸的研究

以橘子皮为原料,采用超声提取技术提取了果胶。以金属离子溶液浸没法分别制备到负载锰,铜金属离子的两种果胶催化剂。采用负载金属离子的果胶为催化剂,试验了苯甲醛氧化反应,获得了苯甲醛催化氧化反应的优化实验条件。比较了所得两种催化剂对该反应的催化效果,结果表明锰离子负载果胶的催化剂催化效率更高。在该优化实验条件下,获得了67.2%的苯甲酸收率。对催化剂回收实验表明,催化剂可以再生利用,表明该苯甲醛催化氧化反应符合绿色化学理念。     

固体酸催化淀粉一锅法制备果葡糖浆的研究

研究了几种负载型固体酸催化剂催化淀粉转化为果葡糖浆的催化效果,其中,超稳Y型分子筛（USY）负载硫酸制备得到的SO₄^2-/USY可以作为双功能催化剂,既催化淀粉水解为葡萄糖,又使葡萄糖异构为果糖,实现了淀粉一锅法制备果葡糖浆的工艺途径,具有良好的催化效果。对催化剂的制备条件进行优化,发现较佳的制备条件为1.5 mol/L H₂SO₄和550℃的焙烧温度。以此为催化剂对反应条件进行优化,获得较佳的反应条件是5%淀粉（淀粉/水）、催化剂用量为淀粉质量的30%、反应温度为150℃、反应时间为1 h、转速400 r/min,得到的果葡糖浆得率为86.18%,含58.34%的葡萄糖和27.84%的果糖。对催化剂进行物理吸附表征,发现USY具有较高的比表面积和孔隙度,通过浸渍焙烧过程能有效使硫酸通过键合作用吸附在USY表面上。对催化剂进行NH₃程序升温脱附和元素分析表征发现,催化剂的重复使用活性降低与含碳有机质沉积和催化活性中心的SO₄^2-流失有关。通过简单的焙烧（除去表面积碳）和硫酸中浸渍活化（增加SO₄^2-）的催化剂再生方法,可以有效地恢复SO₄^2-/USY的催化活性。     

活性炭负载磷钨酸催化合成苹果酯

以活性炭负载磷钨酸为催化合成了苹果酯，确定了反应的最优条件，实验结果表明，催化剂的催化活性高，可重复使用。     

凹凸棒负载型催化剂的制备及处理低浓度有机物效能

面向城镇污水的高标准排放技术,为进一步提高臭氧催化氧化处理水中低浓度有机物的性能,制备了凹凸棒负载型催化剂。采用粒径分析、扫描电镜（SEM）、X射线衍射仪（XRD）、傅里叶变换红外吸收光谱仪（FTIR）、X射线光电子能谱（XPS）对催化剂进行了表征。考察了焙烧温度和焙烧时间对催化剂性能的影响,分析了优化后臭氧氧化反应催化剂对废水的处理效能。结果表明,催化剂的优化焙烧温度和焙烧时间分别为500℃和3h,且使用优化的催化剂时,从效能和效益的角度出发,废水处理性能最佳。当进气流速为0.3L/min,催化剂投量为0.4g/L,反应时间为15min时,废水化学需氧量（COD）浓度由72.5mg/L减少为47.5mg/L。铁基氧化物负载到凹凸棒后起到的作用并不是简单的功能叠加,而是实现了功能互促的效应。     

粉煤灰-凹凸棒石为载体锰基催化剂低温脱硝性能研究

介绍以粉煤灰-凹凸棒石为复合载体、载入过渡金属Mn为活性成分制得MnxOy/FA-PG催化剂的过程。考察制备方法、前驱体、煅烧温度、负载量及粒径大小等因素对催化剂脱硝性能的影响,并通过BET、XRD和SEM等对催化剂进行表征试验。结果表明：以沉淀法与等体积浸渍法制备的Mn（x）/FA-PG催化剂在低温下的活性相差不大;以Mn（NO3）2为前驱体通过浸渍法制得的MnxOy/FA-PG催化剂在低温条件下活性明显优于Mn（CH3COO）2;煅烧温度对催化剂活性影响很大,当煅烧温度在400℃,煅烧时间3 h时,在100℃脱硝率即可达到90%以上;当粒径为0.38～0.83 mm时,催化剂的活性最佳。     

Solventless Silane Alcoholysis Catalyzed by Recoverable Dirhodium(II) Perfluorocarboxylates

We have developed a novel reaction protocol for the highly efficient and sustainable catalysis of the silane alcoholysis reaction. The catalysts of choice are dirhodium(II) perfluorocarboxylates bearing long perfluoroalkyl chains, which are easily prepared in one step from commercial precursors. Under optimized reaction conditions, these catalysts exhibit up to about 50 times higher activity and 100 times higher productivity than analogous dirhodium(II) complexes described in the prior art. Furthermore, the reaction can be run in a completely solventless fashion. Finally, heterogenization of these catalysts has been accomplished through a novel strategy based on fluorous chemistry. Indeed, perfluorinated catalysts of this kind are easily adsorbed on silica which has been previously functionalized at its surface with perfluoroalkyl chains. Use of such supported catalysts (bonded fluorous phase catalysts) allows an easy and almost complete catalyst separation and recycling with improved catalytic performance.     

Heteropolyacid salts catalysts supported on silylated attapulgite for cyclohexane oxidation

以硅烷化凹凸棒黏土为载体,满孔浸渍法制备了负载型杂多酸盐催化剂,采用X射线衍射、比表面积测定、傅里叶变换红外光谱等手段对催化剂进行了表征。分别考察了双氧水用量、杂多酸盐负载量及循环使用次数等因素对环己烷氧化反应的影响。结果表明,负载型杂多酸盐CoH₇P₂Mo₁₅V₃O₆₂能显著提高环己烷氧化能力;催化剂回收烘干后可直接重复利用,催化活性没有明显降低。在优化条件下,环己烷转化率达到35.28%,目标产物环己醇和环己酮的总收率达到12.48%。实验表明,负载型杂多酸盐CoH₇P₂Mo₁₅V₃O₆₂是一种具有应用前景的催化剂,便于与产物分离,且对设备和环境污染小。     

Highly dispersed MgO-supported model Pd-Mo catalysts prepared from bimetallic clusters: Chemisorption and selective catalytic reduction of NO

Model supported palladium and palladium-molybdenum catalysts prepared from organometallic precursors and previously characterized by a variety of chemical and physical methods were examined by IR spectroscopy of NO chemisorption and tested for their activities as catalysts in the competitive NO + CO + O₂ reaction. The IR results reveal distinctive behavior of the catalyst made from a bimetallic precursor, and the activity results show that this catalyst is more selective for NO reduction than the other catalysts, but its stability is vulnerable to the reaction conditions. The high selectivity is attributed to Pd-Mo interactions, which are inferred to be stronger in the catalyst prepared from a bimetallic precursor than in catalysts prepared from monometallic precursors.     

Preparation of silica‐supported late transition metal catalyst and ethylene polymerization

A Correction has been published for this article in Polymer International 51(6) 2002, 561 The late transition metal catalyst 2,6‐bis[1‐(2,6‐diisopropylphenylimino)ethyl]pyridine iron(II) chloride was supported on silica. Fourier transform infrared spectroscopy, scanning electronic micrograph and X‐ray photoelectron spectroscopy measurements were utilized to examine the process of supporting catalyst on silica and investigate the possible mechanism of support. Furthermore, ethylene polymerizations with the supported catalysts were carried out in various conditions such as different reaction temperatures and Al/Fe molar ratios. The results showed that MAO first reacted with the hydroxyl of silica forming Si? O? Al bonds and then the catalyst was bridged through MAO on the surface of silica. Compared with homogeneous catalysts, the supported catalysts show some decrease in catalyst activity. However, they can show good activity at a lower Al/Fe molar ratio with MAO as co‐catalyst and give rise to higher molecular weight and melting temperature of the polymer. Better morphology of polyethylene was obtained by a supported catalyst than by its corresponding homogeneous catalyst. The late transition metal catalyst 2,6‐bis[1‐(2,6‐diisopropylphenylimino)ethyl]pyridine iron(II) chloride was supported on silica. Fourier transform infrared spectroscopy, scanning electronic micrograph and X‐ray photoelectron spectroscopy measurements were utilized to examine the process of supporting catalyst on silica and investigate the possible mechanism of support. Furthermore, ethylene polymerizations with the supported catalysts were carried out in various conditions such as different reaction temperatures and Al/Fe molar ratios. The results showed that MAO first reacted with the hydroxyl of silica forming Si? O? Al bonds and then the catalyst was bridged through MAO on the surface of silica. Compared with homogeneous catalysts, the supported catalysts show some decrease in catalyst activity. However, they can show good activity at a lower Al/Fe molar ratio with MAO as co‐catalyst and give rise to higher molecular weight and melting temperature of the polymer. Better morphology of polyethylene was obtained by a supported catalyst than by its corresponding homogeneous catalyst. © 2002 Society of Chemical Industry     

Attapulgite‐supported aluminum oxide hydroxide catalyst for synthesis of poly(ethylene terephthalate)

A novel nanocomposite catalyst was prepared from immobilization of aluminum oxide hydroxide onto the attapulgite. Characterizations with scanning electron microscopy (SEM) and wide angle X‐ray diffraction (XRD) of the as‐prepared catalyst revealed that AlO(OH) nanoparticles were distributed on the attapulgite. Thermogravimetric analysis‐infrared spectrometry (TGA‐IR) of the mixture prepared by mixing of bishydroxy ethylene terephthalate (BHET) and the catalyst indicated that attapulgite‐supported aluminum oxide hydroxide catalyst can catalyze BHET polycondensation under the applied conditions. A kinetic model for determining the activation energy has been applied to evaluate the catalyst activity. The catalyst activity was examined through comparative experiments, and the results showed that the new catalyst exhibited higher activity for BHET polycondensation under identical reaction conditions, and the viscosity‐average molecular weight of poly(ethylene terephthalate) (PET) product obtained was increased about 2000 g/mol. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Zn-Mg复合氧化物催化大豆油甘油解合成单甘酯

采用共沉淀法制备了一系列不同Zn、Mg物质的量比的Zn-Mg复合氧化物,将其用于催化大豆油甘油解合成单甘酯(MG),采用XRD、氮气吸附-脱附仪、SEM、TEM对Zn-Mg复合氧化物结构与性能进行了表征,并测定了催化剂的表面碱强和碱量。优化了合成单甘酯的工艺条件,并考察了Zn-Mg复合氧化物的重复使用性能。结果表明,改变Zn、Mg物质的量比不仅可以调控Zn-Mg复合氧化物的碱强与碱量,还可以调控其比表面积、孔容等结构参数;不同Zn、Mg物质的量比复合氧化物的催化活性变化趋势与其碱强度(H)在15.0H17.2间碱量变化趋势相一致;n(Zn)/n(Mg)=0.1时,复合氧化物(ZM0.1)具有最好的催化甘油解反应活性;使用该催化剂合成单甘酯的适宜条件为:n(甘油)∶n(大豆油)=3∶1,反应温度210℃,反应时间2 h,催化剂用量为大豆油质量的0.6%,该条件下大豆油转化率达95.6%,单甘酯收率为58.5%。ZM0.1催化剂重复使用4次时大豆油转化率仍达80.9%。     

Microgels as new support materials for heterogeneous cocatalysts in ethylene polymerization reactions

Microgels are monodisperse poly(organosiloxane) microparticles that can be functionalized at their surface. These materials were tested as supports for heterogeneous cocatalysts of the methylaluminoxane type and were used for the polymerizations of olefins with transition‐metal catalysts. The cocatalysts were synthesized directly on the surfaces of the microgel particles by the partial hydrolysis of trimethylaluminum and were then used for the activation of homogeneous catalyst precursors. Complexes of various chemical natures were successfully activated and optimized through variations in the Al/H₂O ratio used for the synthesis. Metallocene dichloride complexes and coordination compounds of iron and nickel were tested as catalysts for ethylene polymerization, and the results were compared with the results for the homogeneous systems and heterogeneous systems supported on silica gel (SiO₂). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3021–3029, 2002     

纳米二氧化硅负载磷钨酸催化合成2-十二烷基苯

采用纳米二氧化硅为载体,负载磷钨酸制备催化剂,催化合成制备2-十二烷基苯。实验表明:纳米二氧化硅负载磷钨酸制备的催化剂在烷基化反应中表现出很好的催化性能;优化的工艺条件为m(苯)∶m(1-十二烯)=8∶1,反应时间为2h,反应温度为80℃,催化剂负载量和加入量分别为20%(m/m)和2%(m/m,以反应物总量计);催化剂对苯与1-十二烯合成反应表现出较高活性和选择性。通过对反应产物进行高效液相色谱质谱联用仪分析,结果显示产物直链性较好。