共查询到19条相似文献,搜索用时 218 毫秒
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采用不同负载顺序或制备过程制备了 Pd-SiW12/SiO2 催化剂, 考察了它们在乙烯直接氧化制乙酸反应中的催化性能. 结果表明, Pd 和 SiW12 的负载顺序与 Pd 负载后的处理条件对 Pd-SiW12/SiO2 催化剂上 Pd 的分散度影响较大, 但对催化剂表面 B 酸量影响不大, 而 Pd 分散度较高时, 相应催化剂活性较高. 将 Pd 和 SiW12 同时负载于 SiO2 上时, 催化剂表现出较高的催化乙烯直接氧化制乙酸反应活性. 相似文献
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Re/HZSM-5体系上的甲烷无氧芳构化反应 总被引:1,自引:0,他引:1
与Mo/HZSM-5相比,Re/HZSM-5也是较好的甲烷无氧芳构化催\r\n化剂,其初活性较高,但随着反应的进行,催化剂失活的速率较快.通\r\n过NH3-TPD,H2-TPR和MASNMR等手段,对催化剂的酸性和分子筛骨架\r\n铝的变化以及铼物种的还原性能进行了研究.结果表明,催化剂酸性的\r\n在反应中起着重要的作用,但不同铼担载量的催化剂酸性的变化比较复\r\n杂,不同于Mo/HZSM-5体系.总的来看,并不是酸性越强或酸量越多\r\n,催化剂的催化性能就越好;催化剂的酸性和酸量都有一个最佳值.担\r\n载铼物种后,铼物种可与分子筛的骨架铝发生强烈的相互作用,最终导\r\n致骨架脱铝.Re/HZSM-5催化剂具有较高的低温活性,在较低温度下\r\n可被还原性气氛还原,且还原后的活性物种单一. 相似文献
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Pd-SiW12/SiO2催化剂上乙烯直接氧化制乙酸的反应机理 总被引:5,自引:0,他引:5
利用积分反应器和微分反应器对Pd-SiW12/SiO2催化剂上乙烯直接氧化生成乙酸的反应机理进行了探讨.乙烯在积分反应中氧化的主要产物为乙酸(选择性为77.6%),很少生成乙醛(选择性仅为8.1%);而在微分反应中氧化的主要产物是乙醛(选择性为98.4%).在微分反应中分别以乙醛和乙醇为主反应物时,乙醛氧化完全生成乙酸,选择性为100%,而乙醇氧化生成乙酸的选择性低于0.15%.可以认为,在Pd-SiW12/SiO2催化剂上,水蒸气存在下乙烯主要经由中间物乙醛而生成乙酸.通过对含有不同组分和不同还原条件处理的催化剂活性的比较,认为目的反应主要发生在Pd与SiW12相互接触的部位,催化剂中的Pd0是活性Pd物种的主要形态. 相似文献
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制备条件对Al1P1.30Ti0.30Si0.17体系催化剂性能的影响 总被引:2,自引:0,他引:2
从制备催化剂的原料、沉淀剂种类、铝沉淀物终点的pH值、水量\r\n及原料的加入顺序等方面考察了制备条件对AlP1.30-Ti0.30Si0.1\r\n7体系的结构及催化性能的影响.结果表明,以自制新鲜氢氧化铝为铝\r\n源,以硅溶胶为硅源,以钛酸丁酯为钛源,以氨水为沉淀剂,在pH=6\r\n.2,c(Al3+)=0.64mol/L(V(H2O)=200ml)的条件下,采用\r\n通常的沉淀方法可制备出性能优良的催化剂.催化剂的酸性是影响其催\r\n化性能的主要因素,主产物选择性与酸强度有关,酸强度高的催化剂具\r\n有较低的主产物选择性;催化剂的活性与其孔径及表面酸量有关;催化\r\n剂中的B酸中心是反应可能的活性中心. 相似文献
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不同环大小分子筛对钼基分子筛催化剂上甲烷无氧芳构化反应的影响 总被引:2,自引:0,他引:2
钼基分子筛催化剂,由于不同分子筛的孔道大小及孔道形状不同\r\n,对甲烷芳构化反应表现出不同的催化性能.具有8元环孔道结构的小\r\n孔ERS-7分子筛没有催化活性,说明甲烷的芳构化反应离不开分子筛孔\r\n道的择形作用,较小的孔道中不能生成苯等芳烃.具有10元环孔道结构\r\n的ZSM-5,ZSM-11和ZRP-1三种分子筛具有较好的催化性能,但由于\r\n其孔道大小及孔道形状的差别在催化行为上表现出一定的差异.具有1\r\n0元环和12元环孔道结构的MCM-22分子筛,尤其对苯等轻芳烃而言,催\r\n化性能最佳.具有12元环孔道结构的JQX-1以及中孔分子筛SBA-15,\r\n虽然具有一定的催化性能,但活性较低.研究结果表明,孔道大小与苯\r\n分子动态直径相近或孔道稍大的分子筛是催化甲烷芳构化反应的良好载\r\n体,孔道过大或过小都不利于苯和萘等芳烃的生成. 相似文献
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镍配合物[N,N]NiBr2的合成及其催化乙烯齐聚研究 总被引:2,自引:0,他引:2
吡啶甲醛类化合物与苯胺类化合物缩合形成有机配体[N,N],\r\n它与金属镍的卤化物NiBr2作用可形成稳定的配合物[N,N]NiBr2.这\r\n种配合物在含铝助催化剂存在下显示出较高的催化乙烯齐聚的活性,所\r\n得乙烯齐聚物具有较高的支化度和较低的α-烯烃含量.实验结果表明\r\n,吡啶环与苯环上的取代基对催化反应的活性具有不同的影响,助催化\r\n剂的种类及用量、反应溶剂和乙烯压力等对该体系的催化反应活性及产\r\n物结构具有直接影响.研究结果表明,通过调节催化聚合反应的工艺条\r\n件,有可能实现控制聚合产物的分子量和分子量分布,以及提高产物中\r\nα-烯烃的含量等. 相似文献
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硫化物对Pd/树脂催化剂上异戊二烯选择加氢催化性能的影响 总被引:4,自引:0,他引:4
在流体并流向上的气液固三相固定床反应器中考察了多种硫化物\r\n对负载Pd催化剂上异二戊烯加氢反应活性的影响.结果表明,在低温(\r\n60℃)和液相加氢条件下,硫化氢、二硫化碳、二甲基硫醚、二甲基二\r\n硫醚、硫醇及噻吩都能使强酸性树脂负载的Pd催化剂上异戊二烯加氢反\r\n应活性下降;随着硫化物含量的增加,异戊二烯加氢活性下降的程度增\r\n大.在硫的质量分数相同(8×10-6)的情况下,这些硫化物使催化剂\r\n失活程度的大小顺序为:二硫化碳>硫化氢>二甲基二硫醚≈乙硫醇>\r\n二甲基硫醚>噻吩.其中噻吩基本上不导致催化剂失活. 相似文献
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制备蜂窝状筛网进行NH3选择性催化还原NO的反应 总被引:3,自引:0,他引:3
制备了蜂窝状筛网催化剂,并用于以NH3为还原剂选择性催化还\r\n原NO的反应.蜂窝状筛网催化剂具有热响应迅速、传质系数较高、压力\r\n降适中、机械强度较高、几何可变形性、抗热震性能好、催化剂回收简\r\n便和成本较低等一系列优点.阐述了蜂窝状筛网催化剂的制备工艺,并\r\n采用扫描电镜、比表面积测定、X射线衍射、活性评价等手段考察了筛\r\n网预处理方法对其催化活性的影响.实验结果表明,最佳的预处理方法\r\n是首先经稀酸刻蚀,然后于500℃下焙烧20h. 相似文献
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乙烯直接氧化制乙酸的研究Ⅱ.助剂对Pd-Se/H4SiW12O40/SiO2催化性能的影响 总被引:2,自引:0,他引:2
研究了不同助剂促进的负载型Pd-Se/H4SiW12O40/SiO2催化剂对乙烯直接氧化制乙酸反应的影响.采用固定床微反装置评价了催化剂的性能,并采用C2H4和O2吸附量测定、吸附C2H4的TPD-MS和TPSR-MS等技术对催化剂进行了表征.结果表明,以SiO2为载体,以硅钨酸为助剂,Pd-Se-Na-Ru组成的催化剂体系其催化性能比文献报道的结果明显提高.在原料气配比n(C2H4)∶n(N2)∶n(O2)∶n(H2O)=55∶14∶9∶22,反应物空速GHSV=3844h-1,反应压力p=1.4MPa,反应温度θ=155℃条件下,乙烯的转化率和乙酸的选择性分别为8.0%和87.4%,乙酸的单程时空产率达372.0g/(L·h).吸附量测定表明,吸附在催化剂表面上的C2H4/O2比值高对于提高乙酸的选择性是有利的. 相似文献
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采用浸渍法分别用硫酸锰、醋酸锰、氯化锰和硝酸锰为原料制备了Mn-H4SiW12O40/SiO2 杂多酸催化剂。在常压连续流动固定床反应器中,考察了二甲醚选择氧化制取甲缩醛的反应活性。实验结果表明,催化剂的催化活性顺序为Mn-Cl2H4SiW12O40/SiO2>Mn(NO3)2H4SiW12O40/SiO2>MnSO4H4SiW12O40/SiO2>Mn(AC)2H4SiW12O40/SiO2。并进一步考察了反应温度对不同锰盐前驱体催化剂性能的影响。结果表明,随温度的升高,硫酸锰修饰的H4SiW12O40/SiO2 催化剂催化氧化比较剧烈,在613K时二甲醚转化率高达42.4%,但此时甲缩醛选择性仅为0.9%。采用氯化锰修饰的H4SiW12O40/SiO2催化剂,二甲醚催化氧化反应较缓和,并且甲缩醛的选择性明显高于分别采用硫酸锰、醋酸锰和硝酸锰改性的催化剂,在593K反应1h时,二甲醚转化率为8.6%,甲缩醛选择性达到37.5%。H2-TPR结果显示,硫酸锰改性的催化剂高温氧化性能明显强于另外三种催化剂,氯化锰的修饰使得催化剂的低温氧化性能变强。XRD结果表明,MnCl2 H4SiW12O40/SiO2催化剂的衍射特征峰明显强于其他三种催化剂,并且发现了MnO2衍射特征峰。 相似文献
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Synthesis of Acetic Acid on Pd-H_4SiW_(12)O_(40)-Based Catalysts by Direct Oxidation of Ethylene 下载免费PDF全文
Xinping Wang Kegong Fang Jianlu Zhang Tianxi CaiState Key Laboratory of Fine Chemicals Dalian University of Technology Dalian China Manuscript received April revised May 《天然气化学杂志》2002,(Z1)
Synthesis of acetic acid by direct oxidation of ethylene on Pd-H4SiW12O40-based catalysts was studied in a fixed-bed integral reactor and a pulse differential reactor. From the performance of the catalysts with different compositions and configurations, it is proposed that acetic acid is predominantly produced via an intermediate of acetaldehyde. This can be easily confirmed by comparing the product distributions in the integral and the differential reactors. The active sites for acetic acid formation are considered to exist mainly at the boundaries between the H4SiW12O40 and the Pd particles. The Pd-based catalysts reduced by H2/N2 have higher activities than those reduced by hydrazine, as explained by the degree of Pd dispersion obtained from the characteristics of hydrogen chemical adsorption. It was found that the Pd-Se-SiW12/SiO2 catalyst with selenium tetrachloride as a precursor was more active than that with potassium selenite, and that the acetic acid yield can be greatly increased by adding a s 相似文献
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LUO Li WANG Sen WU Zhiwei QIN Zhangfeng DONG Mei WANG Jianguo FAN Weibin 《高等学校化学研究》2022,38(1):229-236
Although zeolites are characterized by their special acidic properties, there is still no clear consensus on the effect of zeolite support acidity on the catalytic activity of supported Pd catalyst in methane oxidation. Herein, a series of Pd/H-ZSM-5 and Pd/Silicalite-1 catalysts was prepared by the deposition-precipitation method and used in lean methane oxidation. The effect of ZSM-5 support acidity on the catalytic performance of Pd/ZSM-5 was investigated. The results indicate that with the decrease of Si/Al ratio(x), viz., the increase of acid sites in H-ZSM-5(x), the catalytic activity of Pd/H-ZSM-5(x) increases substantially; the activity of various catalysts in the lean methane oxidation decreases in the order of Pd/H-ZSM-5(28)>Pd/H-ZSM-5(48)>Pd/H-ZSM-5(88)>Pd/H-ZSM-5(204)>Pd/Silicalite-1. Furthermore, various characterization measures reveal that the catalytic activity of Pd/H-ZSM-5(x) in lean methane oxidation is mainly related to the Lewis acid sites in the H-ZSM-5 support, whereas less relevant to the Brønsted acid sites. The abundant Lewis acid sites in H-ZSM-5 are capable to enhance the interaction between the Pd species and H-ZSM-5 support, which can inhibit the agglomeration of Pd particles and improve the dispersion of Pd species, and thus boost the catalytic activity of Pd/H-ZSM-5 in methane oxidation. 相似文献
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通过浸渍法分别在Al(OH)_3和Al_2O_3中引入SiO_2,经焙烧后制备具有不同表面酸性质的SiO_2-Al_2O_3载体,以上述SiO_2-Al_2O_3及Al_2O_3为载体,采用等体积浸渍法制备Ni负载量为15%的Ni/SiO_2-Al_2O_3催化剂(分别为Ni/SA-1和Ni/SA-2)与Ni/Al_2O_3.采用N2物理吸附、Py-FTIR、NH3-TPD、XRD、H2-TPR和H2-TPD手段对催化剂进行表征,考察了表面酸性质对催化剂催化1,4-丁炔二醇高压加氢性能的影响.结果表明,SiO_2引入方式会影响Ni/Al_2O_3催化剂表面酸性质及活性组分Ni在载体表面的分散行为.在Al(OH)3中引入SiO_2时,Ni/SA-1催化剂不仅活性组分具有高分散度,而且表面具有丰富的L酸位点,L酸位点与Ni活性中心协同作用有效提高了催化剂的高压加氢性能.而在Al_2O_3中直接引入SiO_2时,SiO_2覆盖了Al_2O_3表面的L酸位点,催化剂活性组分分散度较低,表现出低的加氢活性. 相似文献
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Synthesis of acetic acid by direct oxidation of ethylene on Pd-H4SiW12O40-based catalysts was studied in a fixed-bed integral reactor and a pulse differential reactor,From the performance of the catalysts with different compositions and configurations,it is proposed that acetic acid is predominantly produced via an intermediate of acetaldehyde ,This can be easily confirmed by comparing the product distributions in the integral and the differential reactors,The active sites for acetic acid formation are considered to exist mainly at the boundaries between the H2SiW12O40 and the Pd particles,The Pd-based catalysts reduced by H2/N2 have higher activities than those reduced by hydrazine,as explained by the degree of Pd dispersion obtained from the characteristics of hydrogen chemical adsorption It was found that the Pd-Se-SiW12/SiO2 catalyst with selenium tetrachloride as a precursor was more active than that with potassium selenite ,and that the acetic acid yield can be greatly increased by adding a suitable amount of dichloroethane (C2H4Cl2/C2H4 mole ratio=0.03) to the reactants. 相似文献
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The effect of pure and high silica Hβ zeolites on the catalytic performance of toluene combustion over Pd/H/3 catalyst was evaluated.Pure and high silica β zeolites were prepared by direct synthesis procedures,then 0.1 wt% of palladium was impregnated on different Hβ zeolites via incipient wetness technique using palladium nitrate as the Pd source.The Pd/Hβ catalysts were characterized by XRD,N2 adsorption/desorption,H2O adsorption,NH3-TPD,H2-TPR and XPS techniques.With increasing the SIO2/Al2O3 ratio of β zeolite,the activity of the Pd/Hβ catalysts for toluene combustion increased clearly and the pure silica β zeolite supported Pd catalyst showed the best catalytic activity.The superior catalytic performance of Pd/β catalyst prepared from pure silica β zeolite was attributed to its high hydrophobicity and the preserving ability for PdO active species. 相似文献