A study on the preparation of supported metal oxide catalysts using JRC-reference catalysts. I. Preparation of a molybdena–alumina catalyst. Part 2. Volume of an impregnation solution

Ten types of 13 wt% MoO₃/Al₂O₃ catalysts were prepared by a conventional impregnation or equilibrium adsorption method using a common extrudate support. These catalysts were subjected to a comprehensive characterization and catalytic reactions to find important preparation parameters in practical preparations. It was demonstrated in the present group study that the formation of crystalline MoO₃ was strongly correlated with the Mo segregation on the outer surface of the extrudate. When the amount of the impregnation solution was large (ca. 10 cm³ g-Al₂O₃⁻¹), a considerably homogeneous distribution and high dispersion of Mo oxide species were attained irrespective of the other preparation parameters. It is suggested that when a pore volume impregnation or incipient wetness technique is employed, drying processes strongly affect the dispersion and distribution of Mo oxide species. Drying at a reduced pressure is suggested to result in a segregation of Mo oxides on the outer surface of the extrudate, and accordingly a formation of crystalline MoO₃.     

A study on the preparation of supported metal oxide catalysts using JRC-reference catalysts. I. Preparation of a molybdena–alumina catalyst. Part 1. Surface area of alumina

This is the first report of a group study on the preparation of a MoO₃/Al₂O₃ catalyst to find predominant preparation parameters for better and reproducible catalyst preparations. Variously prepared MoO₃/Al₂O₃ catalysts possessing 13 wt% MoO₃ were subjected to multiprong characterizations and catalytic tests. It was found that the surface area of the support was the most predominant preparation parameter for the dispersion of Mo oxide species; the dispersion increased as the surface area of the support increased. The formation of crystalline MoO₃ was observed at a surface Mo concentration higher than 3.2 Mo nm⁻². With sulfided MoO₃/Al₂O₃, it was established that the dispersion of Mo sulfide species increased with increasing surface area of the support and was in proportion to that of Mo oxide precursor species. The hydrodesulfurization activity of sulfided MoO₃/Al₂O₃ was proportional to the NO adsorption capacity. It is suggested that a homogeneous distribution of Mo oxide species is attained by an equilibrium adsorption technique. However, it was revealed that the surface area of the catalyst and Mo distribution were considerably modified by preparation parameters, such as drying processes, other than the surface area.     

A study on the preparation of supported metal oxide catalysts using JRC-reference catalysts. I. Preparation of a molybdena–alumina catalyst. Part 3. Drying process

In the present part of the group study on the preparation of 13 wt% MoO₃/Al₂O₃, the effects of drying processes were investigated on the physicochemical and catalytic properties. Two series of catalysts were prepared by a conventional impregnation technique and by an equilibrium adsorption method using a common extrudate support. XPS and EPMA results demonstrated that the distribution of Mo oxide species in extrudates was strongly affected by drying processes. A rapid drying, in particular at a reduced pressure, was found to induce a strong segregation of Mo oxides on the outer surface of the extrudates, forming a sharp egg shell type distribution of Mo. On the other hand, drying under static conditions produced a moderate egg shell type distribution, suggesting that a slow drying rate is favorable for a homogeneous distribution of Mo. The equilibrium adsorption technique was found to provide considerably flat Mo profiles inside the extrudates except for the utmost surfaces where Mo concentrations increased steeply.     

A comparative study of supported MoO3 catalysts prepared by the new “slurry” impregnation method and by the conventional method: their activity in transesterification of dimethyl oxalate and phenol

A new preparation method for supported MoO₃ catalyst, slurry impregnation, has been described and compared with the conventional impregnation method. Slurry MoO₃/water is used instead of the solution ammonium heptamolybdate, AHM [(NH₄)₆Mo₇O₂₄]. The MoO₃/γ-alumina, MoO₃/active carbon, and MoO₃/silica catalysts with different Mo loadings were prepared by slurry and by conventional method. The low solubility of MoO₃ was sufficient to transport molybdenum species from solid MoO₃ to the adsorbed phase. The equilibrium was achieved after several hours at 95 °C based on the loading amount of molybdenum. Only the process of drying was needed; calcination was not necessary and was left out. This is an important advantage for active carbon support because oxidative degradation of active carbon impregnated by molybdena starts at a relatively low temperature of about 250 °C during calcination on air. The activity was tested in the transesterification of dimethyl oxalate (DMO) and phenol at 180 °C. The dependences of catalytic activity on Mo loadings for the slurry prepared catalysts were similar to the dependences for the samples prepared by the conventional impregnation method with AHM. The activities of the slurry impregnation MoO₃/γ-Al₂O₃ catalysts were almost the same as those of catalysts prepared conventionally. Although the performances of slurry impregnation MoO₃/SiO₂ catalysts for transesterification of DMO were slightly better than those of the corresponding catalysts prepared by conventional impregnation, no waste solution and no calcining nitrogenous gases were produced. Therefore, we conclude that the new slurry impregnation method for preparation of supported molybdenum catalysts is an environmentally friendly process and a simple, clean alternative to the conventional preparation using solutions of (NH₄)₆Mo₇O₂₄. The present work will lead to a remarkable improvement in the catalyst preparation for the transesterification reaction.     

MgO-supported Mo, CoMo and NiMo sulfide hydrotreating catalysts

The most common preparation of high surface area MgO (100–500 m² g⁻¹) is calcination of Mg(OH)₂ obtained either by precipitation or MgO hydration or sol–gel method. Preparation of MoO₃/MgO catalyst is complicated by the high reactivity of MgO to H₂O and MoO₃. During conventional aqueous impregnation, MgO is transformed to Mg(OH)₂, and well soluble MgMoO₄ is easily formed. Alternative methods, that do not impair the starting MgO so strongly, are non-aqueous slurry impregnation and thermal spreading of MoO₃. Mo species of MoO₃/MgO catalyst are dissolved as MgMoO₄ during deposition of Co(Ni) by conventional aqueous impregnation. This can be avoided by using non-aqueous impregnation. Co(Ni)Mo/MgO catalysts must be calcined only at low temperature because Co(Ni)O and MgO easily form a solid solution. Literature data on hydrodesulfurization (HDS) activity of MgO-supported catalysts are often contradictory and do not reproduced well. However, some results suggest that very highly active HDS sites can be obtained using this support. Co(Ni)Mo/MgO catalysts prepared by non-aqueous impregnation and calcined at low temperature exhibited strong synergism in HDS activity. Co(Ni)Mo/MgO catalysts are much less deactivated by coking than their Al₂O₃-supported counterparts. Hydrodenitrogenation (HDN) activity of Mo/MgO catalyst is similar to the activity of Mo/Al₂O₃. However, the promotion effect of Co(Ni) in HDN on Co(Ni)Mo/MgO is lower than that on Co(Ni)Mo/Al₂O₃.     

Effects of small MoO3 additions on the properties of nickel catalysts for the steam reforming of hydrocarbons III. Reduction of Ni-Mo/Al2O3 catalysts

Ni/Al₂O₃ catalyst modified by small amounts of Mo show unusual properties in the steam reforming of hydrocarbons. There are no data about the effect of small amounts of molybdenum on reduction of the Ni-Mo supported catalysts. The properties of these very complex systems depend on the conditions of successive preparation stages (calcination, reduction) or the process conditions.

A series of Ni/Al₂O₃ catalysts modified by Mo were prepared in order to investigate the influence of promoter amounts and preparation sequence on their properties. Temperature programmed reduction (TPR) has been employed to study the reducibility of Ni-Mo/Al₂O₃ catalysts. Catalysts were further characterized by BET area, H₂ chemisorption and X-ray diffraction measurements.

The TPR curves of Ni-Mo/Al₂O₃ catalysts are very complex. Mo addition leads to the decrease of catalysts reducibility. However, complete reduction of NiO and MoO₃ can be achieved at 800 °C. The reduction course depends on the sequence of nickel and molybdenum addition into the support. Precise measurements of Ni peaks positions in the XRD pattern of Ni/Al₂O₃ and Ni-Mo/Al₂O₃ samples show the possibility of Ni-Mo solid solution formation.     

High temperature calcined K–MoO3/γ-Al2O3 catalysts for mixed alcohols synthesis from syngas: Effects of Mo loadings

One series of oxidized K–MoO₃/γ-Al₂O₃ samples with different Mo loadings (MoO₃/Al₂O₃ (wt ratio)=0.05–0.45) was prepared by impregnating K and Mo compounds and successive calcination in air at 800°C. The oxidized samples were sulfided and then utilized for mixed alcohols synthesis from syngas. The structural information from laser Raman spectroscopy (LRS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), ammonia saturation, temperature programmed desorption (TPD) and ethanol decomposition were studied to elucidate the reaction properties.

The results indicated that with Mo loading increased from MoO₃/Al₂O₃=0.05 to 0.25, the total yields of mixed alcohols and hydrocarbons decreased, but the selectivity to mixed alcohols was enhanced sharply from 3% to 50%. With Mo loading increased from MoO₃/Al₂O₃=0.25 to 0.45, the CO conversion was enhanced, but the selectivity to mixed alcohols leveled off. On these catalysts, Fischer–Tropsch (FT) synthesis to linear alcohols and the condensation reaction of low alcohols to form branched i-C₄OH occurred at the same time. With increased Mo loading, activity of the alcohols condensation became high.

Structural studies demonstrated that on oxidized samples with increased Mo loading the same K–Mo–O species was formed, but the dispersion of these K–Mo species decreased. The catalyst's acidity decreased remarkably with Mo loading up to MoO₃/Al₂O₃=0.25, and stayed unchanged as Mo loading was further increased to MoO₃/Al₂O₃=0.45. With increased Mo loading, the activity for ethanol dehydration changed parallel to the acidity. Results of the activity experiments for mixed alcohols' synthesis and the structural measurements indicated that the dispersion state of Mo species and the content of unreduced Mo species influenced the total CO conversion, and that the acidity of the catalyst controlled the selectivity to mixed alcohols.     

Supported MoO3 catalysts: preparation by the new “slurry impregnation” method and activity in hydrodesulphurization

A new preparation of supported MoO₃ is described. Slurry MoO₃/water is used instead of the solution (NH₄)₆Mo₇O₂₄. Preparation and HDS activity are illustrated for MoO₃ supported over Al₂O₃, active carbon and ZrO₂. Another application of the new principle is the preparation of high surface area MoO₃/MgO by the reaction of MgO with slurry (NH₄)₆Mo₇O₂₄/methanol. Texture of MgO that is deteriorated in aqueous solution of (NH₄)₆Mo₇O₂₄ is stable in that slurry. “Slurry impregnation” is a special case of equilibrium adsorption impregnation. It is simple and it provides monolayer dispersion of molybdena.     

Effect of the order of potassium introduction on the texture and activity of Mo/Al2O3 catalysts in water gas shift reaction

The effect of deposition and order of potassium introduction on the texture and activity of Mo/γ-Al₂O₃ catalysts in water gas shift (WGS) reaction was investigated. The samples were synthesised by incipient wetness impregnation of the carrier with aqueous solutions of the corresponding salts followed by drying and calcination after each deposition step. The prepared catalyst precursors were sulphided at 400°C for 2 h with 6% H₂S in H₂ before testing in WGS reaction in a glass flow apparatus at 400°C under atmospheric pressure.

The results show that potassium deposition alone on the bare γ-Al₂O₃ (sample K/Al₂O₃) decreases the specific surface after calcination by blocking the constrictions between the pores in the primary porous texture. In the WGS reaction conditions part of the pores are deblocked and a redistribution in the pore volumes occurs.

The deposition of the Mo (sample Mo/Al₂O₃) also results in a decrease in both specific surface and total pore volume with respect to the bare support. However after catalytic activity test no substantial changes in its texture were observed.

The addition of K to the Mo (sample KMo/Al₂O₃) leads to nonuniformity in distribution of molybdenum–oxygen entities due to partial migration of the MoO_x species to the external surface. The specific surface is not changed during the reaction test.

The deposition of Mo on K/Al₂O₃ contributes to the uniform distribution of oxomolybdenum species in the porous texture of the support. This uniformity is preserved to a high extent in the catalytic reaction as well. The activity in the synthesised samples in the WGS reaction decreases in the order MoK/Al₂O₃ > Mo/Al₂O₃ > KMo/Al₂O₃.     

Hydrodesulfurization over supported monometallic, bimetallic and promoted carbide and nitride catalysts

The preparation of alumina-supported β-Mo₂C, MoC_1−x (x≈0.5), γ-Mo₂N, Co–Mo₂C, Ni₂Mo₃N, Co₃Mo₃N and Co₃Mo₃C catalysts is described and their hydrodesulfurization (HDS) catalytic properties are compared to conventional sulfide catalysts having similar metal loadings. Alumina-supported β-Mo₂C and γ-Mo₂N catalysts (Mo₂C/Al₂O₃ and Mo₂N/Al₂O₃, respectively) are significantly more active than sulfided MoO₃/Al₂O₃ catalysts, and X-ray diffraction, pulsed chemisorption and flow reactor studies of the Mo₂C/Al₂O₃ catalysts indicate that they exhibit strong resistance to deep sulfidation. A model is presented for the active surface of Mo₂C/Al₂O₃ and Mo₂N/Al₂O₃ catalysts in which a thin layer of sulfided Mo exposing a high density of sites forms at the surface of the alumina-supported β-Mo₂C and γ-Mo₂N particles under HDS conditions. Cobalt promoted catalysts, Co–Mo₂C/Al₂O₃, have been found to be substantially more active than conventional sulfided Co–MoO₃/Al₂O₃ catalysts, while requiring less Co to achieve optimal HDS activity than is observed for the sulfide catalysts. Alumina-supported bimetallic nitride and carbide catalysts (Ni₂Mo₃N/Al₂O₃, Co₃Mo₃N/Al₂O₃, Co₃Mo₃C/Al₂O₃), while significantly more active for thiophene HDS than unpromoted Mo nitride and carbide catalysts, are less active than conventional sulfided Ni–Mo and Co–Mo catalysts prepared from the same oxidic precursors.     

High-throughput preparation and testing of MoNbSbV mixed oxide catalysts for direct oxidation of propane to acrylic and acetic acids

An automated robotic method using a solution at pH=2 containing four precursor salts dissolved has been developed and validated for high-throughput preparation of Mo, Nb, Sb and V mixed metal oxide solids, which are known to be selective for propane oxidation to acrylic (AA) and acetic (AcA) acids. Spherical shaped silica beads of exceptionally narrow size distribution were synthesised using oil drop technique from a Brace™ instrument. Automated impregnation of the beads by the previous solution has been developed and validated. Catalytic studies were performed using a conventional micro-reactor system with an Ultra-Fast™ GC analysis (<2 min against >30 min). After calcination of the samples under either N₂ or air at 873 K, a mixture of phases was obtained, such as VSbO₄, Mo_xM_1−xO_2.8 (M=V and/or Nb), Sb₄₍₂₎Mo₁₀O₃₁, and other minor phases, such as MoO₃ if activated in air. Mixed oxide samples calcined under N₂ gave better catalytic activity and selectivity to AA/AcA compared to those calcined under air. Measures of catalytic performance of 16 supposedly identical materials fell within a ±5% range of the median values, showing that our experimental set-up is relevant to combinatorial studies. By preparing 15 samples of different chemical composition, optimum catalytic performance was found to correspond to Mo_0.55 Nb_0.09 Sb_0.18V_0.18 mixed oxide calcined at 773 K under N₂, containing a mixture of phases, in particular Mo_xM_1−xO_2.8 and Sb₂Mo₁₀O₃₁, similarly to the M1 and M2 phases observed for MoNbTeV mixed oxide catalysts.     

一种新γ相氧化铝负载的铁铝双金属催化剂用于反向水煤气转化反应(英文)

In reverse water gas shift (RWGS) reaction CO₂ is converted to CO which in turn can be used to produce beneficial chemicals such as methanol. In the present study, Mo/Al₂O₃, Fe/Al₂O₃ and Fe-Mo/Al₂O₃ catalysts were synthesised using impregnation method. The structures of catalysts were studied using X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) method, inductively coupled plasma atomic emission spectrometer (ICP-AES), temperature programmed reduction (H₂-TPR), CO chemisorption, energy dispersive X-ray (EDX) and scanning electron microscopy (SEM) techniques. Kinetic properties of all catalysts were investigated in a batch reactor for RWGS reaction. The results indicated that Mo existence in structure of Fe-Mo/Al₂O₃ catalyst enhances its activity as compared to Fe/Al₂O₃. This enhancement is probably due to better Fe dispersion and smaller particle size of Fe species. Stability test of Fe-Mo/Al₂O₃ catalyst was carried out in a fixed bed reactor and a high CO yield for 60 h of time on stream was demonstrated. Fe₂(MoO₄)₃ phase was found in the structures of fresh and used catalysts. TPR results also indicate that Fe₂(MoO₄)₃ phase has low reducibility, therefore the Fe₂(MoO₄)₃ phase signifificantly inhibits the reduction of the remaining Fe oxides in the catalyst, resulted in high stability of Fe-Mo/Al₂O₃ catalyst. Overall, this study introduces Fe-Mo/Al₂O₃ as a novel catalyst with high CO yield, almost no by-products and fairly stable for RWGS reaction.     

The catalytic reactions of n-pentane and 1-pentene on different molybdenum oxides and metal surfaces

Catalytic reactions of n-pentane and 1-pentene were performed as a function of reaction temperature, on different molybdenum oxides and metal surfaces. These oxides such as Mo₂O₅ and MoO₂ were obtained following the exposure of MoO₃/TiO₂ to hydrogen at different temperatures up to 673 K. Metallic Mo(0) state is obtained at reduction temperatures beyond 723 K. Identification of the Mo chemical species was performed using in situ XPS-UPS surface techniques. The combination of both techniques provides valuable information on the chemical composition of the upper 10 atomic monolayers. X-ray diffraction and HRTEM techniques were also employed. The reduction procedure of MoO₃ does not follow the same pathway when it is deposited on an Al₂O₃ support. A strong electronic interaction between the two species promotes the formation of an Al₂(MoO₄)₃ complex as revealed by XRD measurements. Catalytic active functions present on the different Mo species surfaces are of the acidic type (Lewis and Brönsted) on Mo₂O₅, metal-acid (bifunctional) on MoO₂ and metal function on metallic Mo(0). Consequently, a specific catalytic reaction of n-pentane, such as hydroisomerization to iso-pentane, which is rationalized in terms of a bifunctional mechanism, is expected to occur on MoO₂. Different isomerization reactions of 1-pentene were obtained in the case of MoO₃/TiO₂ and MoO₃/Al₂O₃ at reduction temperatures below 573 K. However, in the case of Mo on the alumina support, the conversion of 1-pentene to iso-pentane is low and irreproducible, contrary to what has been observed for Mo on titania.     

A model catalyst approach to the effects of the support on Co–Mo hydrodesulfurization catalysts

Co–Mo model sulfide catalysts, in which CoMoS phases are selectively formed, were prepared by means of a CVD technique using Co(CO)₃NO as a precursor of Co. It is shown by means of XPS, FTIR and NO adsorption that CoMoS phases form selectively when the Mo content exceeds monolayer loading. A single exposure of MoS₂/Al₂O₃ to a vapor of Co(CO)₃NO at room temperature fills the edge sites of the MoS₂ particles. It is suggested that the maximum potential HDS activity of MoS₂/Al₂O₃ and Co–Mo/Al₂O₃ catalysts can be predicted by means of Co(CO)₃NO as a “probe” molecule. An attempt was made to determine the fate of Co(CO)₃NO adsorbed on MoS₂/Al₂O₃. The effects of the support on Co–Mo sulfide catalysts in HDS and HYD were investigated by use of CVD-Co/MoS₂/support catalysts. XPS and NO adsorption showed that model catalysts can also be prepared for SiO₂-, TiO₂- and ZrO₂-supported catalysts by means of the CVD technique. The thiophene HDS activity of CVD-Co/MoS₂/Al₂O₃, CVD-Co/MoS₂/TiO₂ and CVD-Co/MoS₂/Al₂O₃ is proportional to the amount of Co species interacting with the edge sites of MoS₂ particles or CoMoS phases. It is concluded that the support does not influence the HDS reactivity of CoMoS phases supported on TiO₂, ZrO₂ and Al₂O₃. In contrast, CoMoS phases on SiO₂ show catalytic features characteristic of CoMoS Type II. With the hydrogenation of butadiene, on the other hand, the Co species on MoS₂/TiO₂, ZrO₂ and SiO₂ have the same activity, while the Co species on MoS₂/Al₂O₃ have a higher activity.     

Selective catalytic hydrogenation of naphthalene to tetralin over a NiMo/Al2O3 catalyst

The selective catalytic hydrogenation of naphthalene to high-value tetralin was systematically investigated. A series of Al₂O₃ catalysts containing different active metals (Co, Mo, Ni, W) were prepared by incipient wetness impregnation. The effects of different active metals forms (oxidation, reduction, sulfuration) and reaction conditions on naphthalene hydrogenation were investigated and the catalysts were characterized by XRD, XPS, BET, NH₃- TPD and SEM. Especially, Ni-Mo/Al₂O₃ was first used in this reactive system. The results show that the oxidative 4%NiO-20%MoO₃/Al₂O₃ is the best catalyst for the preparation of tetralin. The conversion of naphthalene and the selectivity of tetralin can reach 95.62% and 99.75% respectively at 200 ℃, 8 h and 6 MPa. Compared with reduced and sulfureted 4%NiO-20%MoO₃/Al₂O₃ catalysts, oxidative 4%NiO-20%MoO₃/Al₂O₃ has a well dispersed and uniform monolayer of the active metals, larger pore volume and size, and larger total acidity. NiO-MoO₃/Al₂O₃ has a synergistic effect between NiO activity and MoO₃ selectivity.     

Interaction of vanadium and nickel porphyrins with catalysts, relevance to catalytic demetallisation

The binding of vanadium and nickel porphyrins to γ-Al₂O₃, SiO₂-Al₂O₃ MoO₃/Al₂O₃, NiO/Al₂O₃, and to Co- and Ni-Mo/Al₂O₃ catalysts in their oxide and sulfide forms, and their subsequent decomposition reactions when heated in nitrogen or exposed to hydrogen and thiophene in catalytic hydrodesulfurisation, have been studied by electron spin resonance. We wished to discover which part of the porphyrin molecule became bound to the catalyst and to which surface sites. Our main conclusions are that the porphyrins are bound to the catalyst by a donor-acceptor interaction,, the delocalised π-system of the porphyrin ring being the electron donor, and the Bronsted and/or Lewis acid function of the catalyst being the acceptor. Depending on the conditions, oxidation or hydrogenation of the porphyrin ring at the meso carbons is the initial stage in the decomposition of the bound porphyrins.     

Characterization and catalytic activity of Pd/V2O5/Al2O3 catalysts on benzene total oxidation

The role of vanadium oxide and palladium on the benzene oxidation reaction over Pd/V₂O₅/Al₂O₃ catalysts was investigated. The Pd/V₂O₅/Al₂O₃ catalysts were more active than V₂O₅/Al₂O₃ and Pd/Al₂O₃ catalysts. The increase of vanadium oxide content decreased the Pd dispersion and increased the benzene conversion. A strong Pd particle size effect on benzene oxidation reaction was observed. Although the catalysts containing high amount of V⁴⁺ species were more active, the Pd particle size effect was responsible for the higher activity.     

Co/Al_2O_3催化剂制备及其合成重质烃的反应性能

以不同孔道结构Al_2O_3作载体,甲醇、乙醇和柠檬酸作分散剂,通过等体积浸渍法制备系列Co/Al_2O_3费托合成催化剂。采用XRD、TG-DSC和H2-TPR等考察制备方法对催化剂结构的影响,并在固定床反应器中对催化剂进行性能评价。结果表明,采用具有适宜孔道结构Al_2O_3作载体才能获得综合性能较好的催化剂,3种分散剂的加入,促进了钴物种在载体上的分散,增强了钴与载体间的相互作用,改善了催化剂费托合成反应活性,显著提高了重质烃时空收率。     

ZrO2添加对MoO3/Al2O3催化剂耐硫甲烷化性能的影响

采用共沉淀法制备了ZrO₂-Al₂O₃复合载体,并进一步制备了MoO₃/ZrO₂-Al₂O₃催化剂,考察了不同ZrO₂质量分数对催化剂结构及其耐硫甲烷化性能的影响。利用N₂物理吸附、X射线衍射、H₂程序升温还原和透射电子显微镜等手段对催化剂的结构进行了表征。结果表明,MoO₃/ZrO₂-Al₂O₃中ZrO₂的添加可以明显削弱MoO₃与载体间的相互作用,促进Mo物种的还原,适量ZrO₂的存在还有助于提高催化剂的比表面积,改善Mo活性相的分散性,使催化剂表现出优异的耐硫甲烷化活性。     

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。