TiO_(2)掺杂Cu-ZnO-Al_(2)O_(3)催化合成气制甲醇

通过共沉淀法制备多组添加TiO_(2)助剂改性的Cu-ZnO-Al_(2)O_(3)(CZA)基甲醇合成催化剂(TiO_(2)掺杂CZA,即TiO_(2)/CZA,TiO_(2)/CZA=0/10,0.5/10,1.0/10,2.0/10和3.0/10),采用氮气吸脱附BET、H_(2)-TPR、NH_(3)-TPD和SEM等技术对其进行表征,并考察不同助剂添加量对合成气制甲醇催化性能的影响。结果表明,TiO_(2)助剂可以调变催化剂活性组分铜物种的分散度、比表面积、晶粒大小和形貌结构等。其中TiO_(2)/CZA比低于0.5/10时,催化剂具有粒度小、颗粒分布均匀的特点,能够促进Cu物种分散,使催化剂表面酸性降低,有利于催化剂表面对CO和H_(2)的吸附和活化,促进CO转化和甲醇的生成。当TiO_(2)/CZA比为0.5/10时,催化剂比表面积为102.20 m^(2)·g^(-1),CO转化率为64.2%,催化剂活性最好;而当TiO_(2)/CZA比高于0.5/10时,过量助剂可能占据催化剂孔道和覆盖表面活性位,降低活性组分分散性,造成CuO与H_(2)有效接触减少,催化活性下降。因此,添加适量TiO_(2)助剂可促进CO加氢反应合成甲醇,增强CZA催化剂的耐热稳定性。     

Effects of catalyst composition on methanol synthesis from CO2/H2

Effects of catalyst composition have been studied for Cu/support and Cu/ZnO/supports in methanol synthesis from CO₂/H₂. A strong effect of support has been observed. Different supports brought about different behavior in temperature-programmed reduction of copper, different copper surface areas, and different catalytic activity and selectivity. It seemed possible to find catalyst supports that might perform better than commercial Cu/ZnO/Al₂O₃ catalysts. A correlation was observed between catalytic activity and the copper surface area which was varied by using different supports. However, the sup]>orts appeared to influence other catalytic properties as well, for example, the surface oxygen coverage.     

In situ FTIR studies of methanol adsorption and dehydrogenation over Cu/SiO2 catalyst

In situ FTIR spectroscopy was used to identify the adsorbed species and the intermediates during methanol dehydrogenation over Cu/SiO₂ catalyst, and a schematic reaction network was proposed. Methoxy species on copper, which were derived from adsorbed methanol, dehydrogenated into formaldehyde. Then several competitive pathways took place. The adsorbed formaldehyde could desorb to the gas phase, or react with another adsorbed methoxy group to form methyl formate, and/or undergo further dehydrogenation to CO and H₂. Carbon monoxide formed from the decomposition first adsorbed on high-index planes of copper, and then on low-index planes as the reaction progressed. With the increase of temperature, the concentration of formaldehyde and CO in gas phase increased, and that of methyl formate decreased.     

Effects of space velocity on methanol synthesis from Co2/Co/H2 over Cu/ZnO/Al2O3 catalyst

The space velocity had profound and complicated effects on methanol synthesis from CO₂/CO/H₂ over Cu/ZnO/Al₂O₃ at 523 K and 3.0MPa. At high space velocities, methanol yields as well as the rate of methanol production increased continuously with increasing CO₂ concentration in the feed. Below a certain space velocity, methanol yields and reaction rates showed a maximum at CO₂ concentration of 5–10%. Different coverages of surface reaction intermediates on copper appeared to be responsible for this phenomenon. The space velocity that gave the maximal rate of methanol production also depended on the feed composition. Higher space velocity yielded higher rates for CO₂/ H₂ and the opposite effect was observed for the CO/H₂ feed. For CO₂/CO/H₂ feed, an optimal space velocity existed for obtaining the maximal rate.     

A novel low-temperature methanol synthesis method from CO/H2/CO2 based on the synergistic effect between solid catalyst and homogeneous catalyst

The activity of a binary catalyst in alcoholic solvents for methanol synthesis from CO/H₂/CO₂ at low temperature was investigated in a concurrent synthesis course. Experiment results showed that the combination of homogeneous potassium formate catalyst and solid copper–magnesia catalyst enhanced the conversion of CO₂-containing syngas to methanol at temperature of 423–443 K and pressure of 3–5 MPa. Under a contact time of 100 g h/mol, the maximum conversion of total carbon approached the reaction equilibrium and the selectivity of methanol was 99%. A reaction pathway involving esterification and hydrogenolysis of esters was postulated based on the integrative and separate activity tests, along with the structural characterization of the catalysts. Both potassium formate for the esterification as well as Cu/MgO for the hydrogenolysis were found to be crucial to this homogeneous and heterogeneous synergistically catalytic system. CO and H₂ were involved in the recycling of potassium formate.     

A new method of low-temperature methanol synthesis on Cu/ZnO/Al2O3 catalysts from CO/CO2/H2

A new synthesis method of low-temperature methanol proceeded on Cu/ZnO/Al₂O₃ catalysts from CO/CO₂/H₂ using 2-butanol as promoters. The Cu/ZnO/Al₂O₃ catalysts were prepared by co-impregnation of r-Al₂O₃ with an aqueous solution of copper nitrate and zinc nitrate. The total carbon turnover frequency (TOF), the yield and selectivity of methanol were the highest by using the Cu/ZnO/Al₂O₃ catalyst with copper loading of 5% and the Zn/Cu molar ratio of 1/1, which precursor were not calcined, and reduced at 493 K. The activity of the catalysts increased due to the presence of the CuO/ZnO phase in the oxidized form of impregnation Cu/ZnO/Al₂O₃ catalysts. The active sites of the Cu/ZnO/Al₂O₃ catalyst for methanol synthesis are not only metallic Cu but also special sites such as the Cu–Zn site, i.e. metallic Cu and the Cu–Zn site work cooperatively to catalyze the methanol synthesis reaction.     

二氧化碳加氢合成二甲醚CuO-ZnO-Al2O3/HZSM-5型催化剂的研究

以乙醇为溶剂，草酸作沉淀剂，采用共沉淀浸渍法制备了性能优良的二氧化碳加氢合成二甲醚催化剂(CuO-ZnO-Al₂O₃/HZSM-5)，在245℃、2.0MPa、2400h-1、H₂/CO₂=2.79的条件下，CO2转化率达22.61%，二甲醚选择性为45.90%，甲醇选择性为14.81%，含氧化合物收率为13.73%。对CuO-ZnO-Al₂O₃/HZSM-5催化剂进行了反应条件及活性稳定性的初步考察。     

MnOx/WO3/TiO2低温选择性催化还原NOx机理的原位红外研究

浸渍法制备15% MnO_x/5% WO₃/TiO₂低温脱硝催化剂,利用原位傅里叶变换红外（in situ FT-IR）设计包括多种吸附反应以及不同预处理方式的微观暂态试验与微观稳态试验,研究其NH₃-SCR脱硝反应机理,并推测反应路径。结果表明,催化剂的NH₃-SCR反应主要以Eley-Rideal机理方式进行,仅在一定温度条件下可以看到Langmuir-Hinshclwood反应路径。催化剂表面Lewis酸位的NH₃吸附是还原剂的主要来源,Brønsted酸位吸附的NH₄⁺随温度上升参与反应的比例略有提高。NH₃的吸附活化是整个反应的控制步骤,吸附态NH₃更易与NO₂发生反应,NO与催化剂表面的相互作用明显弱于NO₂。NO会在催化剂表面氧化活性中心形成大量双齿配位型硝酸盐,阻碍NH₃的吸附和活化,O₂存在条件下促进NH₃-SCR反应进行,阻止NO在催化剂表面形成双齿硝酸盐。NO与NH₃在催化剂表面存在吸附竞争,NO的吸附作用强于NH₃,温度达到100℃后吸附的NH₃方可大量活化并与NO_x发生进一步反应。     

FTIR studies on the CO,CO2 and H2 co-adsorption over Ru-RuO x /TiO2 catalyst

FTIR spectra of a Ru-RuO_x/TiO₂ catalyst obtained on co-adsorption of CO, CO₂ and H₂ in the temperature range of 300–500 K were found to be the sum total of corresponding spectra observed during methanation of individual oxides. The two oxides compete for metal sites and at each temperature they reacted simultaneously to form distinct transient Ru(CO)_n type species even though the nature, the stability and the reactivity of these species were different in the two cases. The monocarbonyl species formed during adsorption/reaction of CO alone or of CO + H₂ were bonded more strongly than those formed during CO₂ + H₂ reaction.     

助剂二氧化硅对CO2加氢制备甲醇CuO-ZnO-Al2O3-ZrO2催化剂性能的影响

采用共沉淀法制备了一系列CuO-ZnO-Al₂O₃-ZrO₂(CZAZ)催化剂,用于二氧化碳加氢合成甲醇。通过加入少量的助剂二氧化硅得到了一系列CZAZ/SiO₂改性催化剂。采用XRD、BET、H₂-TPR、NH₃-TPD以及CO₂-TPD等技术进行表征,研究了助剂二氧化硅含量对催化剂的物理化学性质以及组织结构的影响。结果表明,助剂二氧化硅的含量对催化剂的组织结构具有较大的影响。同时评价了该组催化剂参与二氧化碳加氢合成甲醇反应的催化性能。测试结果表明,采用助剂二氧化硅质量分数为4%的改性催化剂,表现出较为优良的催化活性。助剂二氧化硅促进了活性组分氧化铜的分散,并且经过二氧化硅改性的CZAZ催化剂具有更大的比表面积,这些因素都对该催化剂在二氧化碳加氢合成甲醇方面的良好表现起到重要作用。     

添加氧化锆对二氧化碳加氢合成二甲醚催化剂Cu-ZnO-Al2O3/HZSM-5性能的影响

本文采用共沉淀沉积法及化学还原法制备了一系列的非晶态铜基催化剂,在常规固定床高压流动反应装置上对其CO2加氢合成二甲醚催化性能进行了研究。结果表明:添加ZrO2提高CO2转化率;经NH3-TPD表征可知,氧化锆能增强催化剂表面酸性。另外,催化剂中HZSM-5分子筛含量增大,能显著提高二甲醚的选择性。XRD分析表明,催化剂中各个组分分散均匀。     

Effects of zirconia promotion on the activity of Cu/SiO2 for methanol synthesis from CO/H2 and CO2/H2

The effect of zirconia promotion on Cu/SiO₂ for the hydrogenation of CO and CO₂ at 0.65 MPa has been investigated at temperatures between 473 and 573 K. With increasing zirconia loading, the rate of methanol synthesis is greatly enhanced for both CO and CO₂ hydrogenation, but more significantly for CO hydrogenation. For example, at 533 K the methanol synthesis activity of 30.5 wt% zirconia-promoted Cu/SiO₂ is 84 and 25 times that of unpromoted Cu/SiO₂ for CO and CO₂ hydrogenation, respectively. For all catalysts, the rate of methanol synthesis from CO₂/H₂ is higher than that from CO/H₂. The apparent activation energy for methanol synthesis from CO decreases from 22.5 to 17.5 kcal/mol with zirconia addition, suggesting that zirconia alters the reaction pathway. For CO₂ hydrogenation, the apparent activation energies (~12 kcal/mol) for methanol synthesis and the reverse water-gas shift (RWGS) reaction are not significantly affected by zirconia addition. While zirconia addition greatly increases the methanol synthesis rate for CO₂ hydrogenation, the effect on the RWGS reaction activity is comparatively small. The observed effects of zirconia are interpreted in terms of a mechanism which zirconia serves to adsorb either CO or CO₂, whereas Cu serves to adsorb H₂. It is proposed that methanol is formed by the hydrogenation of the species adsorbed on zirconia.     

Influence of titania on zirconia promoted Cu/SiO2 catalysts for methanol synthesis from CO/H2 and CO2/H2

The effects of adding mixtures of titania and zirconia on the methanol synthesis activity and selectivity of Cu/SiO₂ were investigated. The synthesis of methanol from both CO/H₂ and CO₂/H₂ mixtures was examined at 0.65 MPa and temperatures between 448 and 573 K. For CO hydrogenation, the addition of ZrO₂ alone increased the methanol synthesis activity of Cu/SiO₂ by up to three-fold. Substitution of a portion of the ZrO₂ by TiO₂ decreased the methanol synthesis activity of the catalyst relative to that observed when only ZrO₂ is added. ZrO₂ addition also enhanced the methane synthesis activity by as much as seven fold. In the case of CO₂ hydrogenation, the maximum methanol synthesis activity is achieved when a 50/50 wt% mixture of ZrO₂ and TiO₂ is added to Cu/SiO₂. Neither the presence of the oxide additive nor its composition had any effect on the activity of the reverse water–gas-shift reaction, which suggests that this reaction proceeds only on Cu. The observed effects of ZrO₂ and TiO₂ on the catalytic activity of methanol synthesis from CO and CO₂, and methane synthesis from CO, are interpreted in terms of the strength and concentration of acidic and basic groups on the surface of the dispersed oxide.     

Kinetics studies of dimethyl carbonate synthesis from urea and methanol over ZnO catalyst

A kinetic experiment of dimethyl carbonate (DMC) synthesis by urea methanol over ZnO catalyst was carried out in an isothermal fixed-bed reactor. A kinetic model based on the mole fraction was proposed and the kinetic parameters were estimated from the experimental results. The model predictions were compared with the experimental data and fair agreements were found. The effects of the reaction temperature (443–473 K), space time (0–4.7 h mol⁻¹ kg _cat ) and urea mass percent (5–9%) in feed on DMC mole fraction were investigated. It was found that the reactions are mainly influenced by the reaction temperature and space time rather than urea mass percent in feed. The experimental and simulated results indicated that the reaction from MC to DMC was the rate-controlling step in the DMC synthesis process from urea and methanol. It is important to remove the DMC and byproduct ammonia to achieve a high selectivity of DMC. This implies that reactive distillation might be used in the DMC synthesis on an industrial scale to achieve a higher selectivity of DMC.     

二氧化碳加氢合成甲醇反应铜基催化剂研究进展

二氧化碳加氢合成甲醇反应是二氧化碳利用的重要途径,其中催化剂的研究是技术的关键。本文针对反应采用的铜基催化剂,从铜基催化剂的制备方法、活性组分铜的分散度、铜粒径以及铜与载体间界面作用等方面,分别对其影响催化剂的活性、甲醇的选择性以及稳定性作用进行研究综述。通过分析认为:催化剂的制备方法影响催化剂的铜分散度、铜粒径及铜与载体间的作用,从而影响催化剂催化性能。其中在共沉淀法的基础上进行改进是目前催化剂制备方法的研究趋势,且增加铜分散度、减小铜粒径及增大铜与载体间作用对二氧化碳加氢合成甲醇反应铜基催化剂的催化性能有不同程度的影响。该综述为进一步研制高活性、高甲醇选择性和优异稳定性的新型催化剂提供参考。     

Cu/Al2O3催化剂用于H2O2分解生成羟基自由基的效率

非均相Fenton催化反应是降解废水中有机污染物的有效方法。提高H₂O₂分解生成羟基自由基（·OH）的利用率是提升废水处理效率、降低成本的关键。使用溶胶-凝胶法制备了Cu/Al₂O₃催化剂,基于·OH的生成效率,通过单因素实验发现反应温度、反应溶液pH及H₂O₂初始浓度是决定H₂O₂利用率的主要因素。通过响应面法进行实验设计,分析响应面方程,考察了H₂O₂初始浓度、溶液pH及反应温度三个因素之间的交互作用及其对反应过程的影响。以H₂O₂利用率的最大化为目标优化反应条件,当H₂O₂初始浓度、溶液pH及反应温度分别为707 mg·L^-1、5.12及59.4℃时,H₂O₂利用率可高达0.57,与实验结果相对误差仅为3.5%。所得结果对降低废水处理成本、提高降解效率具有重要的指导作用。     

Cu基CO2合成甲醇催化剂载体的研究进展

氧化物载体与Cu之间的相互作用、CO₂的活化位点、表面反应机理、表面反应路径直接影响CO₂催化加氢的产物分布。因此,探明不同金属–载体的相互作用和界面微观结构至关重要。本文综述了CO₂催化加氢合成甲醇Cu基催化剂载体的研究现状,重点综述了ZnO、ZrO₂、CeO₂、TiO₂这4种具有氧空位的载体,并简单总结了SiO₂、Al₂O₃、Zn-Zr、Ce-Zr、钙钛矿等其他氧化物载体。Cu与ZnO之间的强金属相互作用（SMSI）所形成的Cu/ZnO_x是主要的活性位点,对其微观结构与反应机理研究得较为充分;对Cu/ZrO₂的研究主要集中在ZrO₂晶相的影响,不同的研究者所获得的结论尚存在争议;对Cu/CeO₂的机理研究停留在反向CeO₂/Cu(111)模型表面,负载型催化剂上不同晶面的CeO₂与Cu的相互作用强度不同,并影响反应性能;Cu/TiO₂中TiO₂的影响因素较多,如晶型、晶面等,目前对其研究尚不全面。最后,本文分析并展望了CO₂加氢制甲醇催化剂载体的研究方向,未来将采用与实际催化剂一致的正向模型表面进行基础研究,并基于原位表征手段对反应过程中催化剂的结构变化进行探索,最终设计高效、低成本的多元复合物载体的Cu基催化剂。     

Au/Fe2O3催化剂上CO选择氧化反应性能的研究

采用共沉淀法、沉积-沉淀法和浸渍法制备了1.5%Au/Fe2O3催化剂,考察了不同方法制备的Au/Fe2O3催化剂对富氢气体中CO选择氧化反应性能的影响。结果表明,浸渍法制得的催化剂在40℃~60℃时CO的转化率为100%;共沉淀法与沉积-沉淀法制得的催化剂在80℃以下CO的转化率均为100%;沉积-沉淀法制得的催化剂在100℃时CO的转化率依然高于95%。上述三种催化剂CO氧化反应的选择性均高于40%,且在CO完全转化时选择性在50%以上。     

Activity and stability of Cu/ZnO/Al2O3 catalyst promoted with B2O3 for methanol synthesis

The addition of B₂O₃ to a Cu/ZnO/Al₂O₃ catalyst increased the activity of the catalyst for methanol synthesis after an induction period during the reaction. The stability of the B₂O₃-containing Cu/ZnO/Al₂O₃ catalyst was greatly improved by the addition of a small amount of colloidal silica to the catalyst. This revised version was published online in July 2006 with corrections to the Cover Date.