碱/碱土金属修饰Ni基催化剂的CO2吸附与甲烷化性能

采用分步浸渍法制备了碱/碱土金属修饰Ni基催化剂Ni-M/Al₂O₃ (M=K₂CO₃, Na₂CO₃, MgO, CaO)。探究了碱/碱土金属的添加对改性Ni基催化剂CO₂吸附和甲烷化性能的影响。研究发现,碱/碱土金属的添加提高了Ni/Al₂O₃催化剂表面的碱性活性位点密度,强化了其CO₂吸附性能。碱/碱土金属类型影响Ni-M/Al₂O₃催化剂碱性活性位点的分布、NiO物相的转化及Ni的分散度,进而影响其甲烷化性能。MgO添加使NiO物相转化为与载体呈强相互作用的β型和γ型NiO,降低了催化剂表面的强碱性活性位点比例,有利于CO₂吸附活化。Ni-MgO/Al₂O₃的CO₂吸附容量最高为0.68mmolCO₂/g,其CO₂转化率和CH₄选择性分别高达58.4%和95.4%,其在烟气CO₂捕集与原位甲烷化中极具应用前景。     

负载型K2CO3/Al2O3吸收剂吸收CO2反应机理

利用热重分析仪、扫描电镜和氮吸附仪对不同粒径的K₂CO₃颗粒和负载型K₂CO₃/Al₂O₃二氧化碳吸收剂的碳酸化特性进行研究。负载后的吸收剂比表面积和孔隙结构得到较大改善,使得碳酸化反应速率和转化率均提高,吸收剂碳酸化特性得到改善。纯K₂CO₃颗粒吸收剂的反应速率和转化率随着粒径的增加而减小,负载型吸收剂的反应速率和转化率随着粒径的增加略增大。研究了不同粒径和反应时间对K₂CO₃/Al₂O₃颗粒微观结构的影响,结果表明K₂CO₃/Al₂O₃颗粒具有较稳定的微观结构。采用负载型粒子模型对K₂CO₃/Al₂O₃吸收剂吸收CO₂碳酸化过程进行研究,所建立的粒子模型计算结果与试验值吻合较好。利用建立的模型对不同CO₂浓度下K₂CO₃/Al₂O₃吸收剂碳酸化反应特性进行模拟计算,模拟结果具备一定的合理性和准确性,为开展进一步研究提供了基础。     

The storage of nitrogen oxides on alumina-supported barium oxide

The storage and release of NO₂ on alumina-supported barium oxide has been studied with particular attention to the stoichiometry of the two processes. At 400 °C the storage process is characterised by a short period of complete uptake, possibly as nitrito or nitro species, followed by a slower partial uptake in which approximately one NO is released for every three NO₂ lost. The latter reaction appears to supply the oxygen necessary to store NO₂ as nitrate ions. Molecular O₂ has little direct involvement even if in large excess. The second storage reaction also occurs, but to a much lesser extent, with Al₂O₃ alone. During temperature programmed desorption, release of NO_x from Al₂O₃ peaks at 430 °C with evolution of NO₂ and some O₂. Release from BaO/Al₂O₃ exhibits an additional peak near 520 °C corresponding to formation of NO and a higher O₂ concentration. The NO may arise from NO₂ since BaO/Al₂O₃ has activity for NO₂ decomposition by 500 °C. Although CO₂ at low concentration is rapidly taken up by BaO/Al₂O₃ at 400 °C it is displaced by NO₂ and does not interfere with storage. Thermodynamic calculations show that the formation of Ba(NO₃)₂ by the reaction of NO₂ with bulk BaCO₃ under the conditions used here is more favourable above 380 °C if NO is evolved than if O₂ is consumed.     

Quantified NOx adsorption on Pt/K/gamma-Al2O3 and the effects of CO2 and H2O

A multi-component NO_x-trap catalyst consisting of Pt and K supported on γ-Al₂O₃ was studied at 250 °C to determine the roles of the individual catalyst components, to identify the adsorbing species during the lean capture cycle, and to assess the effects of H₂O and CO₂ on NO_x storage. The Al₂O₃ support was shown to have NO_x trapping capability with and without Pt present (at 250 °C Pt/Al₂O₃ adsorbs 2.3 μmols NO_x/m²). NO_x is primarily trapped on Al₂O₃ in the form of nitrates with monodentate, chelating and bridged forms apparent in Diffuse Reflectance mid-Infrared Fourier Transform Spectroscopy (DRIFTS) analysis. The addition of K to the catalyst increases the adsorption capacity to 6.2 μmols NO_x/m², and the primary storage form on K is a free nitrate ion. Quantitative DRIFTS analysis shows that 12% of the nitrates on a Pt/K/Al₂O₃ catalyst are coordinated on the Al₂O₃ support at saturation.

When 5% CO₂ was included in a feed stream with 300 ppm NO and 12% O₂, the amount of K-based nitrate storage decreased by 45% after 1 h on stream due to the competition of adsorbed free nitrates with carboxylates for adsorption sites. When 5% H₂O was included in a feed stream with 300 ppm NO and 12% O₂, the amount of K-based nitrate storage decreased by only 16% after 1 h, but the Al₂O₃-based nitrates decreased by 92%. Interestingly, with both 5% CO₂ and 5% H₂O in the feed, the total storage only decreased by 11%, as the hydroxyl groups generated on Al₂O₃ destabilized the K–CO₂ bond; specifically, H₂O mitigates the NO_x storage capacity losses associated with carboxylate competition.     

Devitrification of a glass obtained from porphyric sands, MgO (15%) and TiO2 (4%)

A glass of composition: SiO₂ = 59·84%; Al₂O₃ = 11·45%; MgO = 15·34%; TiO₂ = 4·23%; K₂O = 3·80%; Na₂O = 2·48%; CaO = 1·08%; Fe₂O₃ = 1·78%; was prepared from porphyric sands by addition of MgO and TiO₂. The quenched glass is demixed on a very fine scale. The non-isothermal devitrification has been studied. Three-dimensional crystal growth has been observed. The experimental data suggest a mechanism controlled by the crystal-glass interface reaction. The crystal growth activation energy E_c = 467 ± 20 kJ/mole has been evaluated. The temperature of most efficient nucleation is approximately T_N = 720°C.     

Na2CO3基吸附剂颗粒制备及其脱碳性能

采用挤压-滚圆法制备Na₂CO₃基CO₂吸附剂微球颗粒,在自行设计的CO₂吸收系统中对制备的样品进行脱碳性能测试。结合相关表征测试,探明不同载体、不同负载量的Na₂CO₃基吸附剂的微观结构、脱碳性能以及机械性能的变化规律和内在原因。研究表明：不同载体的Na₂CO₃基吸附剂颗粒脱碳性能存在明显差异,其中氧化铝负载的吸附剂（Na₂CO₃/Al₂O₃）的脱碳性能最好,可达1.14mmol/g。铝酸钙水泥负载的吸附剂（Na₂CO₃/CA）机械性能较好,但其脱碳性能最差。结合吸附剂脱碳和机械性能的综合考量,Na₂CO₃/Al₂O₃是最为合适的CO₂吸附剂,并进一步研究不同Na₂CO₃负载量的影响。研究发现随着Na₂CO₃负载量的变化,吸附剂的微观结构、脱碳性能以及机械性能都存在明显的差异。虽然60%负载量的Na₂CO₃/Al₂O₃吸附剂颗粒的机械性能和脱碳效果较好,但其成球度较差,影响其实际应用。质量分数40%负载量的Na₂CO₃/Al₂O₃吸附剂颗粒具有良好的脱碳性能、机械性能以及成球度,CO₂脱除量为1.36mmol/g。总体而言,利用挤压-滚圆法制备的Na₂CO₃基吸附剂颗粒具有良好的流动特性、脱碳性能和机械性能,适用于电厂烟气中的CO₂脱除。     

Formation and stability of barium aluminate and cerate in NOx storage-reduction catalysts

The formation and stability of BaAl₂O₄ and BaCeO₃ in Pt-Ba/Al₂O₃ and Pt-Ba/CeO₂ based NO_x storage-reduction (NSR) catalysts has been investigated using kinetic measurements, X-ray diffraction, thermal analysis and X-ray absorption spectroscopy. In as-prepared state, the Ba-component in the NSR catalysts was made up of amorphous BaO and BaCO₃. The formation of BaAl₂O₄ started above 850 °C, whereas the formation of BaCeO₃ was already observed at 800 °C and was faster than that of BaAl₂O₄. The stability of BaAl₂O₄ and BaCeO₃ in various liquid and gaseous atmospheres was different. BaAl₂O₄ was rapidly hydrated at room temperature in the presence of water and transformed to Ba(NO₃)₂ and γ-alumina in the presence of HNO₃, whereas BaCeO₃ was decomposed to much lower extent under these conditions. Interestingly, BaCeO₃ was transformed to Ba(NO₃)₂/CeO₂ in the presence of NO₂/H₂O at 300–500 °C. Also, the presence of CO₂ led to decomposition of barium cerate, which has important consequences for the catalyst ageing under NO_x-storage conditions and can be exploited for regeneration of thermally aged NSR-catalysts.     

Al18B4O33 aluminium borate: A new efficient support for palladium in the high temperature catalytic combustion of methane

Well crystallised aluminium borate Al₁₈B₄O₃₃ has been synthesised from alumina and boric acid with a BET area of 18 m²/g after calcination at 1100 °C. Afterwards, 2 wt.% Pd/Al₁₈B₄O₃₃ was prepared by conventional impregnation of Pd(NO₃)₂ aqueous solution and calcination in air at 500 °C. The catalytic activity of Pd/Al₁₈B₄O₃₃ in the complete oxidation of methane was measured between 300 and 900 °C and compared with that of Pd/Al₂O₃. Pd/Al₁₈B₄O₃₃ exhibited a much lower activity than Pd/Al₂O₃ when treated in hydrogen at 500 °C or aged in O₂/H₂O (90:10) at 800 °C prior to catalytic testing. Surprisingly, a catalytic reaction run up to 900 °C in the reaction mixture induced a steep increase of the catalytic activity of Pd/Al₁₈B₄O₃₃ which became as active as Pd/Al₂O₃. Moreover, the decrease of the catalytic activity observed around 750 °C for Pd/Al₂O₃ and attributed to PdO decomposition into metallic Pd was significantly shifted to higher temperatures (820 °C) in the case of Pd/Al₁₈B₄O₃₃. The existence of two distinct types of PdO species formed on Al₁₈B₄O₃₃ and being, respectively, responsible for the improvement of the activity at low and high temperature was proposed on the basis of diffuse reflectance spectroscopy and temperature-programmed desorption of O₂.     

Catalytic removal of perchloroethylene (PCE) over supported chromium oxide catalysts

The oxidation of perchloroethylene (PCE) was investigated over chromium oxide catalysts supported on SiO₂, SiO₂–Al₂O₃, activated carbon, mordenite type zeolites, MgO, TiO₂ and Al₂O₃. Supported chromium oxide catalysts were more active than any other metal oxide catalysts including noble metal examined in the present study. PCE removal activity of chromium oxide catalysts mainly depended on the type of supports and the content of metal loaded on the catalyst surface. TiO₂ and Al₂O₃ containing high surface areas were effective for the high performance of PCE removal, since the formation of well dispersed Cr(VI) active reaction sites for the present reaction system, was enhanced even for the high Cr loading on the catalyst surface. CrO_x catalysts supported on TiO₂ and Al₂O₃ also exhibited stable PCE removal activity at a low feed concentration of PCE of 30 ppm up to 100 h at 350°C. However, significant catalyst deactivation was observed at high PCE concentration of 10 000 ppm. CrO_x/TiO₂ revealed stronger water tolerance than CrO_x/Al₂O₃ due to the surface hydrophobicity.     

Quantification of the in situ DRIFT spectra of Pt/K/γ-A12O3 NOx adsorber catalysts

A method to quantify DRIFT spectral features associated with the in situ adsorption of gases on a NO_x adsorber catalyst, Pt/K/Al₂O₃, is described. To implement this method, the multicomponent catalyst is analysed with DRIFT and chemisorption to determine that under operating conditions the surface comprised a Pt phase, a pure γ-Al₂O₃ phase with associated hydroxyl groups at the surface, and an alkalized-Al₂O₃ phase where the surface –OH groups are replaced by –OK groups. Both DRIFTS and chemisorption experiments show that 93–97% of the potassium exists in this form. The phases have a fractional surface area of 1.1% for the 1.7 nm-sized Pt, 34% for pure Al₂O₃ and 65% for the alkalized-Al₂O₃. NO₂ and CO₂ chemisorption at 250 °C is implemented to determine the saturation uptake value, which is observed with DRIFTS at 250 °C. Pt/Al₂O₃ adsorbs 0.087 μmol CO₂/m²and 2.0 μmol NO₂/m², and Pt/K/Al₂O₃ adsorbs 2.0 μmol CO₂/m²and 6.4 μmol NO₂/m². This method can be implemented to quantitatively monitor the formation of carboxylates and nitrates on Pt/K/Al₂O₃ during both lean and rich periods of the NO_x adsorber catalyst cycle.     

Tri-reforming of methane: a novel concept for catalytic production of industrially useful synthesis gas with desired H2/CO ratios

A novel process concept called tri-reforming of methane has been proposed in our laboratory using CO₂ in the flue gases from fossil fuel-based power plants without CO₂ separation [C. Song, Chemical Innovation 31 (2001) 21–26]. The proposed tri-reforming process is a synergetic combination of CO₂ reforming, steam reforming, and partial oxidation of methane in a single reactor for effective production of industrially useful synthesis gas (syngas). Both experimental testing and computational analysis show that tri-reforming can not only produce synthesis gas (CO + H₂) with desired H₂/CO ratios (1.5–2.0), but also could eliminate carbon formation which is usually a serious problem in the CO₂ reforming of methane. These two advantages have been demonstrated by tri-reforming of CH₄ in a fixed-bed flow reactor at 850 °C with supported nickel catalysts. Over 95% CH₄ conversion and about 80% CO₂ conversion can be achieved in tri-reforming over Ni catalysts supported on an oxide substrate. The type and nature of catalysts have a significant impact on CO₂ conversion in the presence of H₂O and O₂ in tri-reforming in the temperature range of 700–850 °C. Among all the catalysts tested for tri-reforming, their ability to enhance the conversion of CO₂ follows the order of Ni/MgO > Ni/MgO/CeZrO > Ni/CeO₂ ≈ Ni/ZrO₂ ≈ Ni/Al₂O₃ > Ni/CeZrO. The higher CO₂ conversion over Ni/MgO and Ni/MgO/CeZrO in tri-reforming may be related to the interaction of CO₂ with MgO and more interface between Ni and MgO resulting from the formation of NiO/MgO solid solution. Results of catalytic performance tests over Ni/MgO/CeZrO catalysts at 850 °C and 1 atm with different feed compositions confirm the predicted equilibrium conversions based on the thermodynamic analysis for tri-reforming of methane. Kinetics of tri-reforming were also examined. The reaction orders with respect to partial pressures of CO₂ and H₂O are different over Ni/MgO, Ni/MgO/CeZrO, and Ni/Al₂O₃ catalysts for tri-reforming.     

Processing of hot pressed Al2O3–Cr2O3/Cr-carbide nanocomposite prepared by MOCVD in fluidized bed

Nanosized particles dispersed uniformly on Al₂O₃ particles were prepared from the decomposition of precursor Cr(CO)₆ by metal organic chemical vapor deposition (MOCVD) in a fluidized chamber. These nanosized particles consisted of Cr₂O₃, CrC_1−x, and C. A solid solution of Al₂O₃–Cr₂O₃ and an Al₂O₃–Cr₂O₃/Cr₃C₂ nanocomposite were formed when these fluidized powders were pre-sintered at 1000 and 1150 °C before hot-pressing at 1400 °C, respectively. In addition, an Al₂O₃–Cr₂O₃/Cr-carbide (Cr₃C₂ and Cr₇C₃) nanocomposite was formed when the particles were directly hot pressed at 1400 °C. The interface between Cr₃C₂ and Al₂O₃ is non-coherent, while the interface between Cr₇C₃ and Al₂O₃ is semi-coherent.     

A facile synthesis of 3,5-dimethyl-4-hydroxybenzaldehyde via copper-mediated selective oxidation of 2,4,6-trimethylphenol

2,4,6-Trimethylphenol was selectively oxidized to 3,5-dimethyl-4-hydroxybenzaldehyde in very good yields using catalytic or equivalent amounts of CuCl₂ in the presence of K₂CO₃ and H₂O₂ in i-PrOH at 65 °C. The effect of the molar ratios of CuCl₂, K₂CO₃ and H₂O₂ on the yields and product distribution was examined. The oxidation reaction was found to proceed smoothly without the use of additives or ligands which were reported to be necessary.     

A pilot plant study for catalytic decomposition of PCDDs/PCDFs over supported chromium oxide catalysts

Chromium oxide catalysts supported on TiO₂ and Al₂O₃ were examined in a fixed-bed flow reactor system for the removal of PCE (perchloroethylene), a simulant of 2,3,7,8-TCDD (2,3,7,8-tetrachlorodibenzo-p-dioxin), and in a pilot plant employing actual flue gas from a sintering plant for the removal of PCDDs/PCDFs (poly-chlorinated dibenzo-dioxin/poly-chlorinated dibenzo-furan). The 12.5 wt.% chromium oxides supported on TiO₂ and Al₂O₃ revealed excellent stability and performance of PCE removal in the feed gas stream containing water vapor. In a pilot plant study, the catalysts washcoated on the honeycomb reactor revealed 93–95% of PCDDs/PCDFs removal activity over CrO_x/Al₂O₃-HC20 (CrO_x/Al₂O₃ catalyst washcoated on 20 cell-honeycomb), and more than 99% of the decomposition activity over CrO_x/TiO₂-HC20 (CrO_x/TiO₂ catalyst washcoated on 20 cell-honeycomb) at 325 °C and 5000 h⁻¹ of reactor space velocity without the de novo synthesis of PCDDs/PCDFs. In particular, CrO_x/TiO₂-HC20 showed 94% of PCDDs/PCDFs decomposition activity even at 280 °C reaction temperature. The catalyst also exhibited significant NO removal activity. The chromium oxide seems to be a promising catalyst for the removal of PCDDs/PCDFs and NO_x contained in the flue gas.     

K2CO3/γ-A12O3催化剂在棉籽油制备生物柴油中的应用

利用等体积浸渍法制备K₂CO₃/γ-A1₂O₃负载型固体碱催化剂,应用于棉籽油和甲醇酯交换反应制备生物柴油。对催化剂使用前的保存条件、水分、重复使用性能、游离脂肪酸影响以及失活和再生进行了分析。结果表明,固体催化剂K₂CO₃/γ-Al₂O₃具有较好的抗水性,酸度对催化剂影响明显,重复使用4次未经活化的催化剂,催化活性明显降低,催化剂应密封保存。K₂CO₃/γ-A1₂O₃负载型固体碱催化剂经济实惠且催化效果良好。     

Plasma-Sprayed Aluminum and Titanium Adherends: II. Durability Studies for Wedge Specimens Bonded with Polyimide Adhesive

The durability of plasma-sprayed metals bonded with a polyimide adhesive has been studied. Metal adherend surfaces were prepared for adhesive bonding by plasma-spraying inorganic powders on aluminum and titanium. The plasma-sprayed materials included Al₂O₃, AlPO₄. MgO, and SiO₂ on aluminum, and TiO₂, TiSi₂, MgO, and SiO₂ on titanium. The coatings were sprayed at two different thicknesses. Durability studies of samples prepared in a wedge-type geometry were carried out. Bonded specimens were maintained in an environmental cycle that included exposure to the conditions; low temperature, - 20°C; relative humidity at elevated temperature, 70% RH at 66°C; elevated temperature (160°C) in air, high temperature (160°C) in vacuum (130 torr, 0.2 atm.), and room temperature. Crack growth rate and mode of failure were determined. The results of the durability tests indicate that thin coatings (25 μm) of plasma-sprayed materials perform better than thicker (150 μm) coatings. The crack growth rate for thin coatings (25 μm) of Al₂O₃, AlPO₄, SiO₂, and MgO plasma-sprayed on aluminum was equivalent to that for phosphoric acid anodized aluminum. Similarly, the durability performance for titanium samples prepared with a 25 μm-thick TiO₂, TiSi₂, and SiO₂ plasma-sprayed coatings was equivalent to that for a Turco®-prepared titanium surface. Although the evaluation of durability as a function of surface chemistry was an objective of the study, it was not possible to evaluate the effect, since most failures occurred within the adhesive (cohesive failure) during the environmental tests. That failure occurred in the adhesive indicates that the coating-adherend and the coating-adhesive interactions are sufficiently robust to prevent interfacial failure under the experimental conditions investigated.     

TPR and infrared measurements with cu/zno/al2o3 based catalysts for the synthesis of methanol and higher alcohols from co + h2

The influence of different promoters (CeO₂, MnO_x, K₂CO₃) on various properties of a standard coprecipitated Cu/ZnO/Al₂O₃ catalyst has been examined. The catalysts prepared were characterized by Cu surface area, PTIR and TPR measurements. It was found that addition of K₂CO₃ reduced the Cu surface area by about 30%, whereas the Cu surface area did not decrease with addition of the other promoters. The reduction behaviour was affected by the addition of K₂CO₃ as well as by MnO_x, but not by CeO₂. The cause of these effects is possibly an electronic interaction between the promoter and Cu ions.The effect of the different promoters on the activity and selectivity has also been studied. The K₂CO₃ promoted catalyst has an optimum selectivity to higher alcohols at 280 °C; addition of Mn made the catalyst more selective towards methanol. At 300 °C, the Ce promoted catalyst had a high selectivity to methanol and iso-butanol. The promoting effect of the additives may be caused by stabilization of the surface intermediates leading to alcohols. Infrared measurements of adsorbed CO or adsorbed methanol on materials with and without K did not, however, provide any evidence for a difference in reaction mechanism.     

Effects of additives on sintering of CVD-MgO powders

The effects of a large number of sintering aids for the densification of magnesia were examined. Al₂O₃, BaO, Fe₂O₃, P₂O₅, SiO₂, TiO₂, Y₂O₃ and ZrO₂ are effective for the sintering of CVD-MgO powders at low doping levels. The effects of TiO₂ and ZrO₂ are significant. Heavy doping is harmful for densification. The eight oxides above are also effective for the sintering of seawater MgO, but the degree of effectiveness is smaller than for CVD-MgO. In the doping of BaO, P₂O₅, SiO₂ and TiO₂, which form eutectic liquids with MgO below 1600°C, there is an optimum firing temperature for densification.

Vickers hardness of doped MgO is proportional to the relative density and is unaffected by doping. Corrosion resistance of MgO ceramics for liquid PbO is also unaffected by dopants, except for P₂O₅.     

Reforming of methane with carbon dioxide to synthesis gas over supported Rh catalysts

Reforming of methane with carbon dioxide to synthesis gas (CO/H₂) has been investigated over rhodium supported on SiO₂, TiO₂, γ-Al₂O₃, MgO, CeO₂, and YSZ (ZrO₂ (8 mol% Y₂O₃)) catalysts in the temperature range of 650–750°C at 1 bar total pressure. A strong carrier effect on the initial specific activity, deactivation rate, and carbon accumulation was found to exist. A strong dependence of the specific activity of the methane reforming reaction on rhodium particle size was observed over certain catalysts. Tracing experiments (using ¹³CH₄) coupled with temperature-programmed oxidation (TPO) revealed that the carbon species accumulated on the surface of the Rh/Al₂O₃ catalyst during reforming reaction at 750°C are primarily derived from the CO₂ molecular route. The amount of carbon present on the working catalyst surface which is derived from the CH₄ molecular route is found to be very small.     

Oxidative dehydrogenation of propane over vanadium oxide based catalysts Effect of support and alkali promoter

The oxidative dehydrogenation of propane was investigated using vanadia type catalysts supported on Al₂O₃, TiO₂, ZrO₂ and MgO. The promotion of V₂O₅/Al₂O₃ catalyst with alkali metals (Li, Na, K) was also attempted. Evaluation of temperature programmed reduction patterns showed that the reducibility of V species is affected by the support acid–base character. The catalytic activity is favored by the V reducibility of the catalyst as it was confirmed from runs conducted at 450–550°C. V₂O₅/TiO₂ catalyst exhibits the highest activity in oxydehydrogenation of propane. The support’s nature also affects the selectivity to propene; V₂O₅ supported on Al₂O₃ catalyst exhibits the highest selectivity. Reaction studies showed that addition of alkali metals decreases the catalytic activity in the order non-doped>Li>Na>K. Propene selectivity significantly increases in the presence of doped catalysts.