掺杂方式对纳米（Ce-Zr-Pr）O2/γ-Al2O3陶瓷载体涂层性能的影响

采用在拟薄水铝石溶胶中分别掺杂纳米(Ce-Zr-Pr)O2固溶体粉末和前驱体溶胶的方式,制备(Ce-Zr-Pr)O2/γ-Al2O3蜂窝陶瓷载体涂层。并利用XRD、H2-TPR、BET和氧脉冲等手段研究掺杂方式对涂层的晶相结构、还原性能、比表面积和储氧性能的影响,由SEM照片观察涂层的表面形貌。结果表明,两种掺杂方式制备(Ce-Zr-Pr)O2/γ-Al2O3涂层均具有较好的织构和储氧性能。其中前驱体溶胶掺杂方式制备涂层液的粒径小,分布范围窄,且涂层表面光滑均匀,比表面积和储氧性能较高。(Ce-Zr-Pr)O2/γ-Al2O3蜂窝陶瓷载体涂层负载的单Pd三效催化剂具有低的起燃温度和优异的三效催化转化活性。     

Co-Mo/γ-Al2O3耐硫脱氧催化剂的TPD-TPR研究

采用等体积浸渍法制备了Co-Mo/γ-Al2O3非贵金属耐硫脱氧催化剂,在实验室微反装置上进行了脱氧活性考评,利用程序升温脱附法(TPD)对该脱氧剂H2、O2的脱附行为进行了研究;同时,利用程序升温还原法(TPR)对新鲜样及中试失活样进行了研究.结果表明,在该催化剂上H2存在两个脱附峰,对应有两种吸附活化位:O2有四个脱附峰,对应有四种吸附活化位,水汽吸附会优先占据弱吸附活性位,从而抑制了其对H2和O2的活化吸附量.催化剂有三种耗氢还原峰,峰面积呈肥胖型,且在各个温度下都有还原,活性组份Co-Mo与Al2O3之间协同作用,直接影响着催化剂脱氧活性,新鲜样中的活性物种与载体间的作用要比失活样的强.研究结果对Co-Mo/γ-Al2O3非贵金属耐硫脱氧催化剂的使用、失活和再生有重要的意义.     

车用三效催化剂剖析

对两种国外公司车用三效催化剂进行全面剖析,采用XRF测定催化剂涂层中各组分含量,采用XRD、XPS、H_2-TPR和TEM对催化剂进行物化性能表征。结果表明,A公司的三效催化剂是将Pd和Rh贵金属分别负载到γ-Al_2O_3和Ce_(0.35)Zr_(0.65)O_2固溶体材料上,B公司的三效催化剂是将Pd和Rh贵金属负载到Ce_(0.35)Zr_(0.65)O_2和γ-Al_2O_3混合载体上。     

负载型铜铬催化剂催化甘油氢解制备1,2-丙二醇

采用浸渍法制备了γ-Al2O3负载的铜铬催化剂,并考察了其在甘油氢解制备1,2-丙二醇反应中的性能。研究发现,Cu/Cr原子比对催化剂性能有很大影响,当Cu/Cr=2.35时,1,2-丙二醇收率达到最大。对失活催化剂的差热-热重(TG-DTA)分析显示,催化剂存在较严重的结焦。采用BaO、MgO等碱性氧化物对γ-Al2O3载体进行改性,通过NH3-TPD表征发现,改性载体酸性有所降低。从评价结果看,改性催化剂的活性有所降低,但稳定性未见改善,说明甘油氢解反应需要酸性位的参与,而酸性并不是引起催化剂的失活的主要原因。     

顺酐加氢制γ-丁内酯Cu-CeO_2-Al_2O_3催化剂失活与再生研究

采用共沉淀法制备了Cu-Ce O2-Al2O3(CCA)催化剂,用于顺酐(MA)常压气相加氢制γ-丁内酯(GBL)反应,表现了很好的催化性能,MA的转化率和GBL的选择性均达到100%,然而催化剂容易失活。采用扫描电子显微镜、热失重、N2O分解和X射线粉末衍射表征研究了CCA催化剂的失活原因和中间产物琥珀酸酐(SA)对CCA催化剂失活的影响,并考察了N2-air-H2法对CCA催化剂的再生效果;同时,通过设计试验对CCA催化剂上MA加氢制GBL反应历程进行了分析。结果表明:CCA催化剂的失活主要是由于表面沉积物的生成覆盖了催化剂表面活性位,而表面沉积物的生成与SA的浓度有关;通过N2-air-H2再生法能够完全恢复CCA催化剂的催化性能。此外,给出了CCA催化剂上MA加氢制GBL可能的反应历程。     

复合氧化物催化剂催化氧化甲苯性能

以γ-Al2O3为催化剂载体,铜、锰为活性组分,稀土元素铈为助催化剂,采用浸渍法制备复合氧化物催化剂5%Cu/γ-Al2O3、5%Mn/γ-Al2O3、5%Cu-5%Mn/γ-Al2O3和5%Cu-5%Mn-1.6%Ce/γ-Al2O3,并考察其催化氧化甲苯性能。研究表明,复合氧化物催化剂催化氧化甲苯具有显著的效果,5%Cu-5%Mn/γ-Al2O3催化剂和5%Cu-5%Mn-1.6%Ce/γ-Al2O3催化剂表现出良好的低温活性和催化性能,对甲苯的完全燃烧温度分别为340℃和285℃。采用SEM和BET对催化剂进行表征,结果表明,催化剂的催化活性与活性组分在催化剂表面的分散度和催化剂的孔结构相关。     

氢能载体甲基环己烷在Ni/γ-Al_2O_3上的脱氢反应

采用自制的比表面积为241m2/g的纳米γ-Al2O3为载体,用等体积浸渍法制备了不同Ni含量的Ni/γ-Al2O3催化剂,采用X射线衍射、扫描电镜、比表面积测定等手段对所制备的催化剂进行了表征。利用微型连续管式反应器,考察了Ni/γ-Al2O3催化剂对甲基环己烷(MCH)气相脱氢的催化性能。结果表明:使用负载量为20%的Ni/γ-Al2O3催化剂,在653K、0.5MPa,v(MCH)/v(N2)=7/12,混合进样体积空速212h-1条件下,MCH脱氢转化率达到94.58%,产物甲苯的选择性接近100%。实验结果还表明,使用镍基催化剂替代铂等贵金属催化剂在储氢技术中具有较好的应用前景。     

氧化铝基载体组成对钴基催化剂结构和费-托合成催化性能的影响

以γ-Al2O3为原料制备Ni-γ-Al2O3、Zn-γ-Al2O3和Al2O3载体,并采用等容浸渍法制备了钴基费-托合成用催化剂。结果表明:高温焙烧使氧化铝晶型和孔结构发生较大变化;镍添加后在载体表面形成高分散的氧化镍物种;而锌添加后与载体发生反应生成了铝酸锌;负载型催化剂中,四氧化三钴粒径大小主要取决于载体孔结构。CoPt/γ-Al2O3、CoPt/Zn-γ-Al2O3、CoPt/Ni-γ-Al2O3具有相近的费-托合成催化性能,而CoPt/Al2O3呈现出最高的催化活性和最低的甲烷选择性。表明,钴物种粒径和载体结构是影响催化剂费-托合成催化性能的主要因素。     

催化湿式氧化法处理糖蜜酒精废液的催化剂研制

以非贵金属Cu、Fe、Mn、Ce为主要活性成分和TiO2、γ-Al2O3为载体制备催化剂,在高温高压下进行催化湿式氧化处理糖蜜酒精废液的试验,考察了载体、焙烧温度、成分配比对催化剂催化活性与稳定性的影响。结果表明:催化剂Fe-Mn/γ-Al2O3(摩尔比3:1:1)的催化效果好,金属离子溶出量低,且连续使用效果也较好。     

乙苯CO_2脱氢规整结构催化剂

以堇青石蜂窝陶瓷为第一载体、γ-Al2O3为第二载体,制备了用于乙苯CO2脱氢的Fe系催化剂。研究发现,当Fe2O3负载量为10%时,Fe2O3/γ-Al2O3催化剂对于乙苯CO2脱氢反应活性最佳;添加适量碱金属、碱土金属和稀土元素氧化物为助剂改善Fe2O3/γ-Al2O3催化剂性能,催化剂活性明显提高,稳定性也有所增加。通过与传统颗粒催化剂比较,采用规整结构γ-Al2O3涂层堇青石负载的Fe系催化剂,乙苯转化率和苯乙烯选择性均有明显提高,反应温度为600℃、反应压力为常压、EB∶CO2为1∶10(摩尔比)、乙苯液时体积空速为1.0 h-1时,乙苯转化率可达85%,苯乙烯选择性为98%。     

Structural Characteristics of Natural-Gas-Vehicle-Aged Oxidation Catalyst

Deactivation of the natural-gas-vehicle-aged Pt/Pd oxidation catalyst supported on γ-alumina-based washcoat was studied by electron microscopy, X-ray diffractometry, X-ray photoelectron spectroscopy, and catalytic activity measurements. Significant structural changes were detected in the used catalyst compared to the fresh one. Grain size of the washcoat had grown but its structure had remained the same, γ-alumina, as in the fresh catalyst. Sintering of the noble metal particles had occurred, particle sizes varied from ~5 up to ~100 nm. Decomposition of palladium oxide and platinum oxide to metallic Pd and Pt occurred followed by the formation of the bimetallic Pt/Pd crystals. Also reformation of palladium oxide was detected. In addition, the inlet part of the used catalyst was totally covered by a poisoning layer. Due to these structural changes and poisoning, the activity of the vehicle-aged catalyst had decreased significantly compared to the fresh one. All the changes were stronger in the inlet than in the outlet part of the used catalyst indicating higher operating temperature and more extensive thermal deactivation and poisoning in the inlet than in the outlet part of the converter.     

元素掺杂对γ-Al2O3热稳定性影响的研究进展

γ-Al2O3作为化工领域广泛使用的催化剂载体,具有吸附性好,比表面积大,活性高等显著优点.但是γ-Al2O3属于亚稳态,高温下有向α-Al2O3转化的趋势,这就会影响催化剂的活性,降低γ-Al2O3的效能.经研究发现向γ-AlO3中掺杂一些元素能有效的提高其热稳定性.作者综述了近年来掺杂元素对γ-Al2O3热稳定性研究的进展情况.     

Effects of temperature and feed composition on catalytic dehydration of methanol to dimethyl ether over γ-alumina

Catalytic dehydration of methanol to dimethyl ether (DME) is performed in an adiabatic fixed bed heterogeneous reactor by using acidic γ-alumina. By changing the mean average temperature of the catalyst bed (or operating temperature of the reactor) from 233 up to 303 °C, changes in methanol conversion were monitored. The results showed that the conversion of methanol strongly depended on the reactor operating temperature. Also, conversion of pure methanol and mixture of methanol and water versus time were studied and the effect of water on deactivation of the catalyst was investigated. The results revealed that when pure methanol was used as the process feed, the catalyst deactivation occurred very slowly. But, by adding water to the feed methanol, the deactivation of the γ-alumina was increased very rapidly; so much that, by increasing water content to 20 weight percent by weight, the catalyst lost its activity by about 12.5 folds more than in the process with pure methanol. Finally, a temperature dependent model developed to predict pure methanol conversion to DME correlates reasonably well with experimental data.     

活性氧化铝制备及改性

氧化铝催化剂载体领域中,γ-Al2O3应用最为广泛。文章综述了γ-Al2O3载体的应用、制备工艺,并总结了制备方法的改善,添加助剂和选择合适的前驱体的方法,对活性氧化铝进行改性,开发出大比表面积、适宜孔径分布及热稳定性良好的γ-Al2O3载体的研究成果。     

Supported nickel catalysts with a controlled molecular architecture for the catalytic reformation of methane

In this work a lanthanum and nickel catalyst having perovskite structure, grown on a γ-alumina carrier, is being presented. The structure of the catalyst was confirmed by XRD. The behaviour of this material under the conditions of steam reforming has been studied and the influence of the temperature, the space velocity and the steam/carbon ratio on the conversion of methane and the product distribution in the process was determined. In all cases at higher temperatures conversions of more than 90% and high selectivities were achieved. The experiments to determine the stability of the catalyst demonstrated that no deactivation in experimental runs of more than 17 h occurred. Additionally a study of the catalyst after the reaction showed that only lowly structured carbonaceous species were formed on the catalyst surface, which is not expected to inhibit strongly the initial catalytic activity.     

Heterogeneous catalytic methylation of catechol

It has been shown that, after a partial deactivation, γ-alumina (γ-Al₂O₃) is a good catalyst for selective methylation of 1,2-benzenediol in the temperature range of 260–310°C. The main products are the desired 3-methyl-1,2-benzenediol and 2-methoxyphenol, which may be converted in another step into 3-methyl-1,2-benzenediol, giving an overall selectivity for the desired products of 80 to 90%. The catechol forms a strongly chemisorbed surface species on γ-alumina and its steric adsorption model correlates with the kinetic data.     

Influence of the intermediate layer on the hydrothermal stability of sol-gel derived hybrid silica membranes

The hydrothermal stability of microporous silica hybrid sol-gel derived membranes is often only tested for either the mesoporous intermediate membrane layer or the microporous separation layer. In this work an investigation is done on the interaction between the intermediate γ-alumina layer and the hybrid (BTESE-derived) silica separation layer during hydrothermal treatment. Although bare γ-alumina is degraded during a hydrothermal treatment, a coating of hydrophobic BTESE on γ-alumina retains its gas separation performance, albeit with a lower mechanical adhesion between the hybrid silica separation layer and the γ-alumina intermediate layer. Applying a monoaluminumphosphate (MAP) coating between the α-alumina support and the γ-alumina layer stabilizes the γ-alumina membrane. A BTESE coating on a MAP modified γ-alumina membrane did not show any signs of delamination after hydrothermal testing. Moreover, a significant increase in the H₂^/N₂ (perm)selectivity, factor 3, was observed for these membranes.     

Combined differential and integral kinetic modeling in an infrared cell-recycle reactor

The dehydration of 2-propanol over γ-alumina was studied at 246 °C by combined in situ ir measurements of adsorbed species and steady-state reaction kinetics. The resulting kinetic model accounted for catalyst deactivation, product inhibition, and autoinhibition by 2-propanol. The model also predicted the integral kinetic behavior during transient (batch) operation of the reactor.     

Ru-Pt catalysts supported on Al2O3 and SiO2─Al2O3 for the selective ring opening of naphthenes

Alumina and silica-alumina supported Ru-Pt catalysts were evaluated for the ring opening of naphthenes. Pt, Ru, and Ru-Pt catalysts were prepared by the impregnation of inorganic precursors over γ-alumina and silica-alumina supports. The catalysts were evaluated by temperature programmed reduction (TPR), pyridine temperature programmed desorption (TPD), CO-FTIR, and by test reactions of 33DM1B isomerization, cyclohexane dehydrogenation, cyclopentane hydrogenolysis, and the ring opening of decalin. The strong interaction between the metals (Pt-Ru) was attributed to their reductions occurring simultaneously. The acidity and strength of the acid sites of the monometallic Ru catalyst were higher than those of the monometallic Pt catalyst. The total acidity (Lewis and Brønsted) and the strength of the acid sites were higher for the silica-alumina supported catalysts. The silica-alumina catalysts had 10 times more Brønsted acidity than the γ-alumina ones and an increased activity and selectivity to decalin ring opening products. Supported monometallic Ru had the best performance for the ring opening reaction.     

Total oxidation catalysts based on manganese or copper oxides and platinum or palladium II: Activity, hydrothermal stability and sulphur resistance

Deactivation of catalysts based on either manganese oxides, copper oxides, platinum, palladium or combinations of these metal oxides and noble metals supported on γ-alumina was studied. The activity of the catalysts for the oxidation of carbon monoxide, naphthalene and methane, in a mixture resembling the flue gases from wood combustion, was measured before and after exposure of the catalysts either to a temperature of 900°C in the presence of steam or to sulphur dioxide. Most of the mixed catalysts were more resistant to hydrothermal and sulphur treatments than the catalysts with a single active component. After the hydrothermal treatment the activity of the MnO_x catalyst was enhanced. When Pt is combined with MnO_x or CuO_x, the loss of activity of Pt was decreased during the hydrothermal treatment. Also, the hydrotreated mixed MnO_x–Pd and CuO_x–Pd catalysts were more active than the treated Pd catalyst for the oxidation of methane. After sulphur treatment, the activities of the mixed MnO_x–Pt (Pt: 0.05 mol%), MnO_x–Pd and CuO_x–Pd catalysts were improved for the oxidation of carbon monoxide and naphthalene. Among the catalysts studied, the MnO_x–Pt, CuO_x–Pt and CuO_x–Pd catalysts, with a metal oxide and a noble metal loading of 10 and 0.1 mol%/γ-alumina, respectively, had the best combination of activity, thermal stability and resistance to sulphur treatment.