发泡镍负载CuO/ZnO/Al2O3对甲醇水蒸汽重整的催化作用

以三维网状多孔发泡镍为载体，制备了负载CuO/ZnO/Al₂O₃的催化剂，研究了催化剂对甲醇水蒸汽重整制氢气的催化作用，考察了催化剂的制备方法、重整反应温度、催化反应器液体空速对催化反应以及催化剂稳定性的影响。结果表明，通过预先在发泡镍上包覆一层Al₂O₃，能够提高催化剂负载的均匀性，所制备的催化剂具有很好的低温初活性和选择性。在反应温度为220 ℃，液体空速为7.2 h^-1的条件下，甲醇初始转化率为98.36%，CO₂选择性为98.4%，产品气中CO摩尔分数为0.41%。通过40 h的连续实验，甲醇转化率始终维持在80%以上，产品气中CO摩尔分数保持在0.5%，CO2的选择性维持在98%。     

Ni-Fe/Al_2O_3催化剂催化乙醇水蒸气重整制氢研究

利用浸渍法制备了不同组成的Ni-Fe/Al2O3催化剂,对催化剂进行了X射线衍射(XRD)表征。以乙醇水蒸气重整(SRE)反应为探针,采用固定床反应器考察了催化剂组成、反应温度对活性和选择性的影响。实验结果表明,Ni-Fe/Al2O3较Ni,Fe单独担载的Ni/Al2O3,Fe/Al2O3选择性高,低温活性好,Ni是主要活性组分,Ni,Fe配比影响活性和选择性,其中Ni10Fe5性能最佳。400℃时,乙醇转化率可达100%,H2,CO和CO2选择性分别55.4%,0.86%和82.18%;450℃时,乙醇转化率为100%,H2,CO和CO2选择性分别67.18%,4.30%和91.01%,且反应温度影响SRE反应系统中各相关反应在系统中的权重。     

活性形貌对CuO/ZnO/Al2O3催化加氢反应的影响

以硝酸铜、硝酸锌等为原料,采用沉淀-沉积法制备了载体是介孔Al_2O_3的CuO/ZnO/Al_2O_3催化剂,通过改变焙烧时间可得到不同活性组分形貌(团簇球状和棒状)的催化剂,并用于CO/CO_2加氢反应。通过XRD、BET、N_2吸附-脱附、TEM、H_2-TPR、CO_2-TPD、NH_3-TPD和FTIR对催化剂进行了表征与测试。结果表明,活性组分(CuO/ZnO)形貌的改变影响了催化剂的Cu O晶粒尺寸、比表面积、孔径及其还原性能,且对催化剂的酸性位点和碱性位点的相对数量影响较大。团簇球状催化剂中活性组分的分散度高、易还原、碱性位多、酸性位少,有利于甲醇的生成;而棒状催化剂中孔道不均匀、碱性位少、酸性位多,更有利于二甲醚(DME)的生成。活性测试结果表明,团簇球状催化剂表现出高甲醇选择性(95.05%)和低DME选择性(4.18%);棒状催化剂的产物选择性与团簇球状相反,表现出高DME选择性(75.41%)和低甲醇选择性(12.81%)。     

Ni-Cu/Al_2O_3·SiO_2催化剂上乙醇水蒸气重整制氢———燃料电池氢源技术

本文研究了Cu的含量对Ni-Cu/Al2O3.SiO2催化剂上乙醇水蒸气重整制氢性能的影响。活性测试表明：Cu含量为5%时,催化剂的性能最好,400℃时的氢气选择性为61.2%,600℃时的氢气选择性达到92.0%。TPR显示：随着Cu含量的增加,载体与NiO之间的相互作用变弱。XRD得出：含5%Cu的催化剂中Cu组分的分散度好,有助于提高催化剂的性能。     

机械研磨燃烧法制备Cu/ZnO/Al2O3甲醇合成催化剂

引言Cu/ZnO/Al2O3催化剂近年来广泛应用于低压甲醇合成、二甲醚合成和水煤气变换等领域[1-2],该催化体系具有活性高、使用寿命长、反应温度及     

CO2对CuO/ZnO/Al2O3催化剂前体老化及催化性能的影响

采用并流共沉淀法制备CuO/ZnO/Al2O3甲醇合成催化剂前体,在通入CO2条件下老化,采用XRD、FT-IR、DTG、H2-TPR、XPS等表征手段对制备的前体及焙烧后的催化剂进行表征,研究不同CO2通入量对前体晶相转变、微观结构及其焙烧后催化性能的影响。研究结果表明,老化阶段通入CO2后,沉淀母液的pH值趋于7,产生CO32?离子,进而影响Zn2+的沉淀,促进Cu2+进入Zn5(CO3)2(OH)6晶格中取代Zn2+形成绿铜锌矿(Zn,Cu)5(CO3)2(OH)6物相,有助于增强焙烧后催化剂的Cu-Zn之间协同作用,增加活性组分Cu分散度。CO2通入量为40 mL/min时,制备的催化剂在浆态床合成甲醇过程中表现出良好的催化活性和稳定性,甲醇时空收率（STY）达到301.78 g/(kg?h),失活率仅为0.15%/d,与未通入CO2辅助老化制备的催化剂相比,时空收率提高了9.72%,平均失活率降低了33.33%。     

Highly selective supported Pd catalysts for steam reforming of methanol

Steam reforming of methanol, CH₃OH + H₂O 3H₂ + CO₂, was carried out over various Pd catalysts (Pd/SiO₂, Pd/Al₂O₃, Pd/La₂O₃, Pd/Nb₂O₅, Pd/Nd₂O₃, Pd/ZrO₂, Pd/ZnO and unsupported Pd). The reaction was greatly affected by the kind of support. The selectivity for the steam reforming was anomalously high over Pd/ZnO catalysts.     

丙三醇水蒸气重整制氢M/Al2O3催化剂

以Al2O3为载体,采用浸渍法制备了Cu、Co、Ni、Pt/Al2O3四种单一组分催化剂(M/Al2O3)。研究了M/Al2O3催化剂对丙三醇水蒸气重整制氢反应的适用性及反应行为;考察了制备条件及还原条件,通过活性、稳定性及抗积炭性进行了催化剂的活性评价,并对催化剂进行了TPR、XRD表征。研究发现M/Al2O3催化剂用于丙三醇水蒸气重整制氢均表现出一定活性;其中Cu/Al2O3催化剂具有一定的抗积炭性;Pt/Al2O3催化剂表现出较好的抗积炭性、高温活性,但稳定性较差;Co/Al2O3催化剂表现出较好的稳定性;Ni/Al2O3催化剂表现出较好的低温活性。     

A highly efficient Cu/ZnO/Al2O3 catalyst via gel-coprecipitation of oxalate precursors for low-temperature steam reforming of methanol

The impact of preparation methods on the structure and catalytic behavior of Cu/ZnO/Al₂O₃ catalysts for H₂ production from steam reforming of methanol (SRM) has been reported. The results show that the nanostructured Cu/ZnO/Al₂O₃ catalyst obtained by a novel gel-coprecipitation of oxalate precursors has a high specific surface area and high component dispersion, exhibiting much higher activity in the SRM reaction as compared to the catalysts prepared by conventional coprecipitation techniques. It is suggested that the superior catalytic performance of the oxalate gel-coprecipitation-derived Cu/ZnO/Al₂O₃ catalyst could be attributed to the generation of “catalytically active” copper material with a much higher metallic copper specific surface as well as a stronger Cu–Zn interaction due to an easier incorporation of zinc species into CuC₂O₄ · x H₂O precursors as a consequence of isomorphous substitution between copper and zinc in the oxalate gel-precursors.     

Catalytic activity of Pt‐Re‐Pb/Al2O3 naphtha reforming catalysts

BACKGROUND: The main purpose of the naphtha reforming process is to obtain high octane naphtha, aromatic compounds and hydrogen. The catalysts are bifunctional in nature, having both acid and metal sites. The metal function is supplied by metal particles (Pt with other promoters like Re, Ge, Sn, etc.) deposited on the support. The influence of the addition of Pb to Pt‐Re/Al₂O₃ naphtha reforming catalysts was studied in this work. The catalysts were prepared by co‐impregnation and they were characterized by means of temperature programmed reduction, thermal programmed desorption of pyridine and several test reactions such as cyclohexane dehydrogenation, cyclopentane hydrogenolysis and n‐heptane reforming. RESULTS: It was found that Pb interacts strongly with the (Pt‐Re) active phase producing decay in the metal function activity. Hydrogenolysis is more affected than dehydrogenation. Part of the Pb is deposited over the support decreasing the acidity and the strength of the most acidic sites. CONCLUSION: The n‐heptane reforming reaction shows that Pb modifies the stability and selectivity of the Pt‐Re catalysts. Small Pb additions increase the stability and greatly improve the selectivity to C₇ isomers and aromatics while they decrease the formation of low value products such as methane and gases. Copyright © 2011 Society of Chemical Industry     

Co/La2O3催化乙醇水蒸汽重整制氢反应的研究

采用浸渍、热分解、氢还原等步骤制备了一系列Co/La2O3,催化剂,并将其应用于乙醇水蒸汽重整制氢反应.采用固定床反应考察了温度和水醇比对催化剂性能的影响.用N2吸附、XRD、TPR等手段对催化剂进行了表征.结果表明:5%Co/La2O3,催化剂对乙醇水蒸汽重整制氢反应表现出最高的活性.在500℃、水醇比为3:1时,乙醇的转化率达可到64.8%,H2的产率和选择性分别为1.0 mol/mol和86.1%.另外,在反应温度低于450℃时,H2的选择性可达90%以上.     

KF/Al2O3催化菜籽油与甲醇合成生物柴油的研究

用等体积浸渍法制备了KF/Al2O3催化剂,并将其用于菜籽油与甲醇酯交换合成生物柴油的研究.考察了反应条件、优化了合成工艺,结果表明制得的KF/Al2O3催化剂在适宜的条件下合成生物柴油的产率达96.7%,同时提出了合成反应的机理.     

CuO含量对Pd/Al2O3催化剂乙醇氧化性能的影响

采用浸渍法制备了一系列具有不同CuO含量的Pd-CuO/Al₂O₃催化剂，并将其用于乙醇氧化反应，其结构与性质通过XRD、H₂-TPR和NH₃-TPD等手段进行分析。结果发现，催化剂的活性并不是随着CuO含量的增加而增强，Pd-1.0%CuO/Al₂O₃催化剂表现出最佳的活性，其点火温度和完全转化温度比Pd/Al₂O₃催化剂至少降低了50℃。与Pd/Al₂O₃催化剂相比，含CuO催化剂增强的衍射峰强度以及氢化钯分解峰的消失，说明Pd-Cu合金结构的形成有利于Pd、Cu物种之间的协同作用。对于Pd-1.0%CuO/Al₂O₃催化剂来说，还原峰向低温的移动以及还原峰面积的增大说明该催化剂上氧化性物质更易被还原且数量在增加，这对于氧化反应是十分有利的，新出现的还原峰表示Pd、Cu的相互作用生成了新物种。NH₃-TPD结果中更高含量的低温酸有利于高活性，而且新出现的脱附峰说明形成了新的酸性位点。     

Ni-Co/Al_2O_3催化乙醇水蒸气重整制氢性能研究

利用浸渍法制备Ni-Co/Al2O3催化剂,考察催化剂组成、反应温度、水醇比、液体空速对乙醇水蒸气重整反应的影响。结果表明,Ni-Co/Al2O3催化剂中Co含量的增加会提高氢气和一氧化碳的选择性,降低甲烷和二氧化碳的选择性,催化剂Ni7.5Co7.5催化性能最佳,450℃时乙醇转化率达到100%,氢气选择性为79.78%,二氧化碳选择性为91.89%。反应温度会影响乙醇水蒸气重整制氢反应中相关反应的权重和产物的分布。加大水醇比降低一氧化碳选择性,提高二氧化碳选择性;提高液体空速,加大一氧化碳选择性。Ni-Co/Al2O3催化剂反应前后发生明显的物相重构,Co3O4被还原成Co,Co与Ni共同起活性作用,Co3O4作为催化剂前体在乙醇水蒸气重整中显示出良好的活性。     

Ethanol steam reforming over Ni/La–Al2O3 catalysts: Influence of lanthanum loading

Hydrogen production from ethanol reforming over nickel catalysts supported on lanthanum loaded Al₂O₃ substrates was studied. Activity results revealed the enhancement in the reforming stability of the Ni catalysts with the increase in the lanthanum loading on Al₂O₃ substrates. Catalytic behavior of Ni/La–Al₂O₃ catalysts in the ethanol steam reforming was found to be the contribution of the activity of the La–Al₂O₃ supports for the ethanol dehydration reaction and the activity of the nickel metallic phase that catalyzes both dehydrogenation and CC bond rupture. Physicochemical characterization of catalysts revealed that acidity, nickel dispersion and nickel-support interaction depend on the La-loading on Al₂O₃. The better reforming stability of catalysts with the increase in La content was explained in terms of the ability of nickel surface and/or La–Ni interactions to prevent the formation of carbon filaments.     

Characterization of Sn doped Ni/Al2O3 steam reforming catalysts by XPS

XPS measurements have shown that tin oxides are more readily reduced to metallic tin by hydrogen in Ni/Al₂O₃ systems than on pure Al₂O₃. During the reductive activation of Sn doped Ni/Al₂O₃ catalysts, surface segregation of the dopant was observed. This finding may explain that tin enhances the selectivity of the steam reforming catalysts only when added in very low concentrations and that it acts as a poison at higher loadings.     

Effect of Constant‐Rate Reduction on the Performance of a Ternary Cu/ZnO/Al2O3 Catalyst in Methanol Synthesis

A multi‐functional flow set‐up was developed for the rate‐ and temperature‐controlled reduction of copper catalysts, their application in high‐pressure methanol synthesis and the determination of the copper surface area by N₂O frontal chromatography. The influence of constant‐rate reduction on the catalytic properties of a ternary Cu/ZnO/Al₂O₃ catalyst was investigated. The temperature during the constant‐rate reduction was found to decrease, indicating autocatalytic kinetics, but no significant catalytic effect of the milder reduction conditions was observed compared with a slow linear heating ramp.     

Hydrogen production by oxidative methanol reforming on Pd/ZnO: Catalyst preparation and supporting materials

Pd and Pd–Zn alloy were supported on various supporting materials using impregnation, co-precipitation and microemulsion methods, and their catalytic performances in oxidative methanol reforming (OMR) were investigated. Pd/ZnO exhibited much higher selectivity than either Pd/Al₂O₃ or Pd/ZrO₂ in the OMR for hydrogen production. This was attributed to the presence of Pd–Zn alloy on the ZnO support. Elemental Pd on Al₂O₃ or ZrO₂ promotes methanol decomposition reaction and increases CO formation. Using a microemulsion method, a highly selective Pd/ZnO can be obtained with much lower Pd loading than that in samples prepared by co-precipitation. Modification of Al₂O₃ with ZnO produced a ZnAl₂O₄ phase, which was found to be a good support for the Pd/ZnO catalyst. Highly active and selective Pd/ZnO/ZnAl₂O₄ catalysts for the OMR reaction, containing much lower Pd loadings have been developed by impregnation of the supports with an aqueous solution of Pd(NO₃)₂ + Zn(NO₃)₂.     

NiO-CeO2/ZnO催化剂制备及其乙醇水蒸气重整制氢性能

通过共沉淀法制备了一系列不同质量分数CeO2的NiO-CeO2/ZnO催化剂,在固定床反应器中检测其制氢性能。运用XRD、BET、SEM等手段对催化剂进行表征发现:CeO2质量分数决定催化剂的制氢性能,其中15%NiO/5%CeO2/ZnO表现出最好的氢气产率和选择性。质量分数为5%CeO2的加入,可以有效地增强NiO与CeO2、ZnO之间的相互作用,减小活性组分NiO的粒径,促进其分散性,增大比表面积,NiO也更易于被还原,从而得到更好的制氢性能。     

氧化铈形貌对甲醇水蒸气重整制氢CuO/CeO2催化剂性能的影响

采用简单的改变焙烧气氛的方法改变水热法合成的CeO2纳米材料的形貌,得到的CeO2纳米材料再通过浸渍法制备CuO/CeO2催化剂,并将其应用于甲醇水蒸汽重整制氢反应。采用SEM、XRD、BET、H2-TPR、N2O滴定和XPS等对催化材料进行了表征,着重探讨了氧化铈形貌对催化剂结构、性质和性能的影响。结果表明,纳米棒状结构的CeO2负载CuO后得到的CuO/CeO2催化剂性能最佳,这主要是因为纳米棒状结构的CeO2与CuO的相互作用较强,表面存在较多的晶格缺陷和氧空穴,进而使得CuO/CeO2催化剂表相Cu含量增加,Cu物种的还原温度较低,催化活性较好。当反应温度为260 °C、水醇物质的量比为1.2、甲醇气体空速为800 h-1时,甲醇转化率可达100%,重整气中CO摩尔含量为0.16%。