Mechanism of the formation of precursors for the Cu/ZnO methanol synthesis catalysts by a coprecipitation method

Precursors of Cu/ZnO catalysts with various Cu/Zn molar ratios were prepared by a coprecipitation method. It was found that amorphous copper hydroxycarbonate and sodium zinc carbonate were intermediates for the formation of various precursors such as hydrozincite, malachite and aurichalcite. Aurichalcite having a high Cu/Zn ratio was prepared from a mechanical mixture of these intermediates.     

The effect of ZnO in methanol synthesis catalysts on Cu dispersion and the specific activity

The effect of ZnO in Cu/ZnO catalysts prepared by the coprecipitation method has been studied using measurements of the surface area of Cu, the specific activity for the methanol synthesis by hydrogenation of CO₂, and XRD. Although the Cu surface area increases with increasing ZnO content (0–50 wt%) as is generally known, the specific activity of the Cu/ZnO catalysts with various weight ratios of Cu:ZnO is greater than that of a ZnO-free Cu catalyst. These facts clearly indicate that the role of ZnO in Cu/ZnO catalysts can be ascribed to both increases in the Cu dispersion and the specific activity. The XRD results indicate the formation of a Cu–Zn alloy in the Cu particles of the Cu/ZnO catalysts, leading to the increase in specific activity. It is thus considered that the Cu–Zn surface alloy or a Cu–Zn site is the active site for methanol synthesis in addition to metallic copper atoms that catalyze several hydrogenation steps during the methanol synthesis. Furthermore, the advantage of the coprecipitation method through a precursor of aurichalcite is ascribed to both improvements in the Cu surface area and the specific activity. This revised version was published online in July 2006 with corrections to the Cover Date.     

Structural characterization of malachite-like coprecipitated precursors of the binary CuO-ZnO catalysts: bulk and surface properties

Copper and zinc hydroxycarbonates with Cu/Zn atomic ratios of 100/0, 92/8, 85/15, 77/23, 67/33 and 50/50 were prepared by coprecipitation at constant pH. The samples with higher Cu/Zn ratios are monophasic with malachite structure, whereas the richer zinc samples contain, in addition to malachite, the aurichalcite phase, whose concentration is very low in the 77/23 specimen but increases with zinc content. The cell volume of the zincian-malachite phase decreases up to 30% of zinc content. This result is related, as also shown by DTA measurements, to an increasing stability of compounds richer in zinc, to increasing covalent effects and/or to less octahedral site distortion around the metal atoms when zinc substitutes Cu²⁺ ions in the malachite structure. XPS investigations have shown that both in the monophasic and biphasic samples the surface Cu/Zn atomic ratios are nearly equal to those found by chemical analysis, so indicating that an homogeneous dispersion of zinc in the solid solutions and a good interdispersion of the zincian-malachite and aurichalcite phases are both achieved. A comparative study of the photoelectron and X-ray excited Auger transitions of Cu and Zn gives also support for an increasing covalency of the chemical bonds in zincian-malachites with respect to pure malachite. Moreover, the analysis of the initial state effect on the full width half maximum of the Cu(2p_3/2) and of the Zn(2p_3/2) peaks gives evidence that zinc substitutes copper in the less octahedrally distorted (type-II) metal site of the malachite structure.     

Deactivation of CuZn Catalysts Used in Glycerol Hydrogenolysis to Obtain 1,2-Propanediol

Different CuZn catalysts were prepared by coprecipitation method with Cu/Zn atomic ratio of 0.2, 0.4, 1.0, 2.5 and 6.0. Monometallic Zn and Cu catalysts and a bimetallic catalyst (Cu/Zn?=?2.5) prepared by physical mixture of the precursors were also studied. These catalysts were tested in the glycerol hydrogenolysis reaction and the higher yields to 1,2-propanediol were achieved for Cu/Zn atomic ratio?≥?1 samples. The deactivation of a representative catalyst (Cu/Zn?=?1) was evaluated and its yield to 1,2 propanediol decreases until ca 40% after five runs. To explain this behavior, fresh and used catalysts were characterized by different techniques. Chemical analysis of solid catalysts and liquid reaction medium confirmed the leaching of Zn species under our reaction conditions. This process promotes Cu sintering which is proposed as the actual reason of the observed deactivation in the glycerol hydrogenolysis for this catalytic system.     

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%。     

Methanol synthesis over Cu/ZnO catalysts prepared by ball milling

Cu/ZnO catalysts (with a Cu/Zn atomic ratio of 30/70) have been prepared by high intensity mechanical mixing of copper and zinc oxide powder in air and under vacuum. During milling in vacuum gradual amorphisation of the constituents occurs, as evidenced by broadening of the Cu⁰ and ZnO diffraction peaks in XRD, but the two original phases remain. The result of such treatment is a catalyst with low BET area and low Cu metal surface area. Consequently, the activity of the vacuum milled samples in batch methanol production from synthesis gas (CO/CO₂/H₂=20/5/75) at 50 bar and 250°C is low. Milling in air leads to oxidation of the copper metal phase and much higher BET surface area and, after reduction, Cu metal surface area. Prolonged milling times in air result in more than 90% Cu²⁺ formation as evidenced by TPR. Activity in methanol synthesis for the air milled samples is comparable to a conventional Cu/ZnO catalyst prepared by coprecipitation. It is concluded that high intensity ball milling at ambient conditions is a promising method to prepare mixed oxide catalysts or catalyst precursors. This revised version was published online in July 2006 with corrections to the Cover Date.     

三组分铜铬催化剂催化甘油制备羟基丙酮的研究

用共沉淀法制备了Cu-Cr-Zn催化剂,考察了Cu/Cr/Zn比、沉淀温度、沉淀时pH值、煅烧温度等制备条件对甘油制备羟基丙酮的影响,并对催化剂进行了表征。结果表明:共沉淀法制备Cu-Cr-Zn催化剂具有较高的催化活性,而且其稳定性和再生能力较好,适宜催化剂制备条件为:Cu/Cr/Zn比为1∶1∶0.5,沉淀温度为70℃,沉淀时pH值为8.0,煅烧温度为400℃,羟基丙酮的选择性可达到90.2%。     

Cu–ZnO and Cu–ZnO/Al2O3 Catalysts for the Reverse Water-Gas Shift Reaction. The Effect of the Cu/Zn Ratio on Precursor Characteristics and on the Activity of the Derived Catalysts

Comparison is made between Cu–ZnO and alumina-supported Cu–ZnO as catalysts for the reverse water-gas shift (RWGS) reaction. For both types of catalyst the Cu/Zn ratio has been varied between Cu-rich and Zn-rich compositions. By applying X-ray diffractometry, X-ray line broadening, optical reflectance spectroscopy and other techniques the effects on the structural and physical properties of the hydroxycarbonate precursors, the calcined products and the ultimately derived catalysts are determined. The presence of alumina decreases the crystallite size of the CuO and ZnO particles produced on calcination and at high Cu/Zn ratios increases the dispersion of copper in the final catalyst. The activities of the catalysts for the RWGS reaction at 513K are compared and the most active are shown to be those which are Cu rich (Cu/Zn > 3) and contain alumina as support. The activities of all the catalysts can be rationalized by referring the activity to unit surface area of copper metal.     

甲醇水蒸汽重整制氢催化剂制备的研究

针对燃料电池用氢制备用于甲醇水蒸汽重整制氢的Cu/Zn/Al系列催化剂,研究催化剂组成、制备方法对催化剂性能的影响。利用热分析和X射线衍射等分析手段对催化剂前驱体和焙烧后催化剂样品进行分析和表征。结果表明,铜基催化剂对甲醇水蒸汽重整制氢反应有较好的活性和选择性,合适的组成是Cu、Zn和Al的原子质量百分比为45∶45∶10和47.5∶47.5∶5,210 ℃反应转化率达到100%;并流共沉淀法和热分解法制备的催化剂都具有较好的催化性能。     

Cu–Zn–Cr2O3 Catalysts for Dimethyl Ether Synthesis: Structure and Activity Relationship

The CuO dispersed on ZnCr₂O₄ catalysts derived from Cu–Zn–Cr hydrotalcite like layered double hydroxide precursors with varying Zn/Cr ratios have been synthesized, characterized by BET—Surface area, X-ray diffraction (XRD), temperature programmed reduction (TPR), electron spin resonance (ESR), N₂O titrations and the activities were evaluated for single step dimethyl ether (STD) synthesis from syngas. It is observed that the copper species were in highly dispersed state over Cu–ZnO–Cr₂O₃ at high Zn/Cr ratios while the copper cluster were present at low Zn/Cr ratios. The ESR analysis revealed signals due to isolated Cu²⁺ at high Zn/Cr ratios and clustered Cu²⁺ at low Zn/Cr ratio in fresh catalysts and only Cr³⁺ species in used catalysts. The TPR results indicated that the reduction peak shifted to high temperatures with an increase in chromium content due to large copper crystallites, which was supported by XRD analysis. The conversion of syngas to DME was well correlated with the copper metal surface areas, indicating that STD synthesis can be controlled by methanol synthesis rate.     

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.     

用于低温液相合成甲醇的Cu/MgO/ZnO催化剂

采用并流共沉淀法制备了不同Cu:(Mg+Zn)及Mg:Zn摩尔比的铜基催化剂Cu/MgO/ZnO,用于低温液相甲醇的合成,并对比了Cu/ZnO及Cu/MgO催化剂,分析了催化剂中载体MgO的作用. 结果表明,MgO的引入有利于催化剂中Cu+的生成并均匀分散在载体中,可提高催化剂的催化活性. 以合成气CO+H2为原料,在443 K和5.0 MPa条件下,采用液体石蜡作溶剂,考察了催化剂的催化性能. 结果表明,Cu/MgO/ZnO催化剂的活性优于Cu/ZnO和Cu/MgO催化剂,且当Cu:Mg:Zn=2:1:1时催化性能最好,此时合成气中CO的转化率为63.56%,甲醇的选择性为99.09%,时空收率为5.413 mol/(kg×h). 分析了Cu/MgO催化剂在高温反应条件下的失活现象,认为铜烧结是其失活的主要原因.     

A Cu/Zn/Al/Zr Fibrous Catalyst that is an Improved CO<Subscript>2</Subscript> Hydrogenation to Methanol Catalyst

A series of Cu/Zn/Al/Zr CO₂ hydrogenation to methanol catalysts containing different ratios of Al/Zr were prepared using a co-precipitation procedure. SEM, TEM, and XRD characterization showed that all the catalysts comprised crystallites in a fibrous structure and their Cu/Zn crystallite dispersions were better than that of a commercial (COM) catalyst. It is suggested that the high dispersion and stability of the Cu/Zn crystallites due to the fibrous structure enhanced CO₂ hydrogenation, and the added Zr component further improved the catalyst. A 5% Zr addition gave a methanol space time yield 80% higher than that on the COM catalyst.     

基于CuAl-LDH载体制备高分散Cu/ZnO/Al2O3催化剂及其催化性能

通过沉积沉淀法制备了以层状CuAl-LDH为载体负载不同Cu/Zn比例的前体,经热处理得到CuZnAl-LDO复合催化剂,应用于合成气制甲醇反应。采用电感耦合等离子体发射光谱（ICP）、X射线衍射（XRD）、H₂程序升温还原（H₂-TPR）、N₂O化学吸附、N₂吸脱附、透射电镜（TEM）和X射线光电子能谱技术（XPS）等手段对前体及催化剂进行表征,考察了水滑石的限域效应和金属-载体相互作用对催化剂活性及稳定性的影响。结果发现：由于水滑石特殊的层状结构,具有较大比表面积和丰富孔道结构,促进了Cu物种的分散,有利于催化剂表面对CO和H₂的吸附,增加了Cu、Zn之间的相互作用,提高了催化剂的催化活性。在水滑石前体拓扑转变过程中,层板羟基和水脱除后形成的粗糙表面对所负载的Cu活性物种起到限域作用,抑制了Cu的迁移和团聚。其中,Cu_0.6Zn_0.3Al_0.1-LDO催化剂催化合成甲醇的时空收率达到883mg/(g?h),且反应120h后仅下降2.8%,较共沉淀制备催化剂失活速率降低了81%,表现出较好的催化活性及稳定性。     

胶溶剂对完全液相法制备的Cu/Zn/Al催化剂结构和性能的影响

采用完全液相法制备了Cu/Zn/Al浆状催化剂,考察了胶溶剂HNO3用量对催化性能的影响。结果表明,适量的胶溶剂HNO3用量可以减小Cu0晶粒度,提高催化剂的活性;胶溶剂的用量可以改变催化剂各组分之间的相互作用,过多的HNO3会导致催化剂活性的降低。     

Gas phase hydrogenation of maleic anhydride to γ-butyrolactone by Cu–Zn–Ti catalysts

Cu–Zn–Ti catalysts were prepared by coprecipitation method. The calcined and reduced Cu–Zn–Ti catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR), and N₂ adsorption. The calcined Cu–Zn–Ti catalysts were composed of CuO, ZnO, and amorphous TiO₂. There were two kinds of CuO species present in the calcined Cu–Zn–Ti catalyst. At a lower copper content, CuO species interacted with ZnO and TiO₂; at a higher copper content, both the surface-anchored and bulk CuO species were present. After reduction, metallic copper (Cu^o) appeared in all Cu–Zn–Ti catalysts. Cu^o produced by reduction of the surface-anchored CuO favored the deep hydrogenation of maleic anhydride. ZnO and TiO₂ had synergistic effect on the catalytic activity of Cu–Zn–Ti catalysts in hydrogenation of maleic anhydride.     

Preparation of Cu/ZrO2 catalysts for methanol synthesis from CO2/H2

Cu/ZrO₂ catalysts for methanol synthesis from CO₂/H₂ were respectively prepared by deposition coprecipitation (DP) and solid state reaction (SR) methods. There is an intimate interaction between copper and zirconia, which strongly affects the reduction property and catalytic performance of the catalysts. The stronger the interaction, the lower the reduction temperature and the better the performance of the catalysts. Surface area, pore structure and crystal structure of the catalysts are mainly controlled by preparation methods and alkalinity of synthesis system. The conversion of CO₂ and selectivity of methanol are higher for DP catalysts than for SP catalysts.     

Effect of pressure on direct synthesis of DME from syngas over metal-pillared ilerites and metal/metal-pillared ilerites

The effect of pressure on the direct synthesis of dimethyl ether (DME) from syngas over metal (Cu, Zn) pillared ilerites and metal (Cu, Zn) impregnated metal-pillared ilerites was explored. The prepared catalysts were characterized by XRD, BET, ICP-AES, SEM and FT-IR. The direct DME synthesis reaction was carried out in a differential fixed bed reactor with the prepared catalysts at various pressures (10, 20, 30 bar), 250°C and H₂/CO ratio of 2. The Cu/Zn-pillared ilerite catalyst showed the highest catalytic activity among the prepared catalysts at 20 bar, in which CO conversion was about 62% and DME selectivity was about 89%. CO conversion increased with pressure, and DME selectivity increased with pressure in the range of 10–20 bar, and above the pressure slightly decreased with pressure. The optimum pressure for this reaction was 20 bar.     

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.     

Cu-Cr2O3催化剂上二氟乙酸甲酯催化加氢合成二氟乙醇

采用共沉淀法制备了Cu-Cr₂O₃催化剂,考察了铜含量对Cu-Cr₂O₃催化剂的二氟乙酸甲酯加氢合成二氟乙醇性能的影响。运用X射线衍射(XRD)、程序升温还原(TPR)、BET和Raman光谱技术对该催化剂进行了表征。结果表明,还原态Cu-Cr₂O₃催化剂物相主要由Cu和Cr₂O₃组成,然而30Cu-Cr₂O₃和50Cu-Cr₂O₃催化剂存在少量CuCr₂O₄和CuCrO₂复合氧化物。随着铜含量的增加,Cu-Cr₂O₃催化剂的二氟乙酸甲酯单程转化率呈现先上升后下降的趋势,而二氟乙醇选择性保持在70%左右; 30Cu-Cr₂O₃催化剂的二氟乙酸甲酯单程转化率达到最大值97%。Cu-Cr₂O₃催化剂的二氟乙酸甲酯加氢反应比速率随着铜含量的增加呈现增大的趋势,反应比速率的提高可能与催化剂中CuCr₂O₄和CuCrO₂物种的存在有关。