Pd/Al2O3催化剂的制备及其在对氨基苯酚合成中的应用

用等体积浸渍法制备了Pd/Al2O3催化剂。采用ICP、XRD、HRTEM和XPS等对催化剂的组成和形貌进行表征。结果表明，Pd粒子均匀分布在Al₂O₃的表面，粒径约为5 nm。在对硝基苯酚催化加氢制备对氨基苯酚的反应中，对催化剂的催化性能进行了考察。Pd/Al₂O₃催化剂的催化活性随着Pd负载量的增大而增大；其与市售的骨架镍、纳米镍以及2%Pd/C相比，显现了优异的催化活性；Pd/Al₂O₃具有高的催化选择性；Pd/Al2O3的催化活性稳定性明显优于骨架镍；随着使用次数的增加，Pd/Al₂O₃的催化活性有所降低，这可能是因为Pd粒子的团聚。     

PdAg、PdAu合金纳米晶的制备及其催化性能研究

采用硼氢化钠一步还原法,首先得到PdAg和PdAu双金属合金纳米颗粒.利用XRD、TEM以及紫外可见光光谱技术对其进行了表征分析.结果表明,PdAg和PdAu两种合金都具有纳米颗粒分散均匀且颗粒尺寸小等优点.随后采用胶体沉积法将两种合金均匀地负载到Al2O3上,成功获得PdAg/Al2O3和PdAu/Al2O3两种金属纳米催化剂.在邻氯硝基苯加氢反应中,与Pd/Al2O3纳米催化剂相比,PdAg/Al2O3催化剂显示出95.5％的选择性,而PdAu/AI2O3催化剂的选择性高达98.7％,这可能归因于Pd与Ag或Au金属间的协同效应.     

蒽醌加氢钯催化剂载体改性研究

针对Pd/Al2O3催化剂载体的改性进行研究,将1 000℃焙烧后的氧化铝粉末与未焙烧的活性氧化铝粉末按不同比例混合和焙烧制备载体,采用等体积浸渍法制得负载Pd的Pd/Al2O3催化剂。采用XRD、BET、NH3-TPD和HOT对载体以及催化剂进行表征,并考察催化剂的蒽醌加氢性能。结果表明,提高载体中焙烧后氧化铝粉末的比例,导致载体中γ-Al2O3减少和δ-Al2O3增多,载体酸性降低,Pd分散度变大,从而提高了催化剂氢化效率。当焙烧后氧化铝质量分数为40%时,分散度和活性表面积达到最大,晶粒度最小,氢化效率最高,催化活性最佳。     

Pd-Based Catalyst on Alumina with Perovskite (La0.67Fe0.83Cu0.17O3) to Reduce Ammonia Content in Natural Gas Exhaust

Catalysis Letters - La0.67Fe0.83Cu0.17O3 with perovskite structure was prepared by sol–gel method, and 1.5 wt% Pd/Al2O3 was prepared by initial wet impregnation method. Pd/Al2O3 and...     

Ca助剂对钯负载催化剂在苯酚液相原位加氢反应中的影响

利用等体积浸渍法制备了一系列不同助剂的Pd／Al2O3催化剂,并利用固定床管式反应器考察了以上催化剂在“苯酚＋甲醇＋水”耦合反应体系中的性能。结果表明Ca的促进作用较明显,进一步考察了Ca助剂的含量对催化剂活性的影响,并通过BET和CO吸附表征探讨了Ca助剂对催化剂结构以及Pd分散度的影响。     

负载型铜催化剂的三效催化性能及应用

采用等体积浸渍法制备了以CeO2、Al2O3以及CeO2/Al2O3为载体的负载型CuO催化剂及其老化样品,采用XRD和H2-TPR等技术对老化前后催化剂的结构和氧化还原性能进行了表征。结果显示,对于老化前后的CuO/CeO2/Al2O3催化剂,CuO均能够很好地分散在载体上,即CeO2/Al2O3具有较好的抗烧结能力。考察了不同载体、CeO2和CuO负载质量分数对CuO/CeO2/Al2O3样品三效催化性能的影响,并将制得的CuO/CeO2/Al2O3催化剂与贵金属三效催化剂Pd/CeO2/Al2O3相比较,考察了高温焙烧之后的CuO/CeO2/Al2O3老化样品对CO、C3H6和NO的三效催化性能。结果表明,以10%CeO2/Al2O3为载体,CuO负载质量分数为7%的CuO/CeO2/Al2O3催化剂对汽车尾气脱除催化反应具有较高的催化活性;与Pd/CeO2/Al2O3比较,CuO/CeO2/Al2O3具有更好的低温活性,CO、HC和NOx的起燃温度分别为130℃、250℃和250℃,在350℃三种原料气的转化率均达到90%;老化实验表明,CuO/CeO2/Al2O3具有较好的抗老化性能。     

CH4与CO检测气敏元件中催化剂的制备与反应性能研究

实现CH₄和CO的多参数检测，催化剂及其催化反应性能是基础。研究了纳米载体Al₂O₃的制备方法，对其孔径分布和前驱体的颗粒度进行了BET和TEM的测定，对CH₄和CO在Pd/Al₂O₃催化剂上的催化反应性能进行了评价。结果表明,采用共沉淀-凝胶工艺和控制制备条件可以得到适宜孔径的催化剂载体。CH₄和CO在Pd/Al₂O₃催化剂上的催化反应性能有较大的差异。催化反应可以满足对CH₄和CO的多参数检测的需要。     

废钯催化剂中钯的回收

介绍了分别从废Pd /Al2 O3、Pd/C、Pd/Cu催化剂中回收钯的各种方法 ,并对其优劣性进行了分析。     

工艺条件对钯系催化剂乙炔选择性加氢性能的影响

为了研究工艺条件对钯系催化剂选择性加氢性能的影响,制备Pd/Al_2O_3、Pd-Ag/Al_2O_3和Pd-Ag/Al_2O_3-KOH催化剂,并在微型催化剂评价装置上进行乙炔选择性加氢反应,考察了工艺条件(压力、空速)对催化剂性能的影响。结果表明,随着压力的升高,催化剂活性提高,乙烯选择性会下降;随着空速的提高,催化剂乙炔转化率先升高后降低,MAPD转化率迅速下降,乙烯选择性提高。     

载体及活性组分对甲烷低温燃烧催化性能的影响

以一定浓度的Pd为活性组分,-γA l2O3为载体,用浸渍法制备了甲烷低温燃烧催化剂,运用固定床反应装置着重研究载体对甲烷低温燃烧反应的催化性能的影响。同时采用同一种载体条件下,重点考察不同浓度的单一活性组分Pd或Pt和(Pt-Pd)双活性组分催化剂对甲烷低温燃烧反应的催化性能的影响。结果表明,由不同载体,负载同一浓度活性组份制备出的催化剂活性有较大差异。(Pt-Pd)/A l2O3双组分燃烧催化剂,性能优于单一组分的Pd/A l2O3或Pt/A l2O3催化剂,(Pd-Pt)/A l2O3体系具有较高的甲烷催化燃烧活性,催化燃烧的起燃温度最低。相比当(Pd 0.2%-Pt 0.1%)/A l2O3时催化剂活性最高,CH4转化率50%的温度为345℃,完全转化温度为405℃。通过1 000 h稳定性试验,显示出甲烷完全氧化温度为405℃左右,具有较好的低温活性及热稳定性。     

Highly active methanol decomposition catalyst derived from Pd‐hydrotalcite dispersed on mesoporous silica

Pd‐hydrotalcite (abbreviated as Pd(HT)) was dispersed on HMS (hexagonal mesoporous silica) by synthesizing Pd(HT) in an HMS suspension, and the resultant product (Pd(HT)/HMS) was used as a catalyst precursor for methanol decomposition to synthesis gas. The IR spectra of Pd(HT)/HMS showed all the bands of Pd(HT) and HMS with little shift, which indicated that Pd(HT) was synthesized in the Pd(HT)/HMS. Pd(HT)/HMS did not show the XRD pattern of Pd(HT) when the mass ratio of Pd(HT) to HMS was from 2/1 to 1/2. This indicated that Pd(HT) was formed in very small particles in the Pd(HT)/HMS after dispersion. Two endothermic peaks of Pd(HT) in the DTA curve shifted to lower temperatures in the Pd(HT)/HMS because the small Pd(HT) particles formed in the Pd(HT)/HMS were easily collapsed by heat treatment. Pd(HT)/HMS was thermally decomposed and reduced to form a supported Pd catalyst (abbreviated Pd(Mg(Al)O)/HMS) for methanol decomposition. Pd(Mg(Al)O)/HMS at 3.6 wt% showed a 52.5% conversion which was much higher than those over 3.6 wt% Pd(Mg(Al)O) (34.7%) and 3.6 wt% Pd/HMS (13.7%) for methanol decomposition at 523 K. The conversions of methanol over Pd(Mg(Al)O) and Pd/HMS increased with the increase in Pd loadings from 3.6 to 15 wt% and decreased when the Pd loadings were over 15 wt%. In contrast, the conversion over Pd(Mg(Al)O)/HMS increased with the increase in Pd loading even when the Pd loading was up to 30%. 30 wt% Pd(Mg(Al)O)/HMS showed a 91.7% conversion which was about twice that over 15 wt% Pd(Mg(Al)O) (47.1%) at 523 K. The Pd(Mg(Al)O)/HMS catalyst showed a larger BET surface area and Pd metal surface area than those of Pd(Mg(Al)O). By characterization using XPS analyses, the metal–support interaction between small Pd and small Mg(Al)O became stronger in the Pd(Mg(Al)O)/HMS catalyst. Large surface area, high Pd dispersion and strong metal–support interaction caused the high catalytic activity for methanol decomposition to synthesis gas over the Pd(Mg(Al)O)/HMS catalyst. This revised version was published online in July 2006 with corrections to the Cover Date.     

乙二醇选择性氧化制备乙醇酸催化剂体系的研究

制备了用于选择性氧化乙二醇制备乙醇酸的Pt—Bi／Al2O3、Pd—Bi／Al2O3催化剂；考察了负载金属催化剂的含量、氧气压力及反应温度等条件对目标反应产物催化性能的影响。试验结果表明，Pt—Bi／Al2O3催化剂比Pd—Bi／Al2O3具有更佳的催化性能，于343K及300kPa氧气分压等条件下，在含Pt2．0％的Pt—Bi／Al2O3催化剂体系中，乙醇酸的收率可达到93．60％。确定了最佳的乙二醇氧化制备乙醇酸的绿色氧化工艺条件。     

FeCrAl金属壁载PdZn/Al2O3催化剂上甲醇水蒸汽重整制氢

采用等体积浸渍法制备了不同Pd负载量和不同Pd与Zn物质的量比的PdZn/Al<,2>O<,3>甲醇水蒸汽重整颗粒催化剂,结果表明,Pd负载质量分数9.25%和n(Pd):n(Zn)=0.24的催化剂表现出较佳的催化性能.XRD表征表明,由于生成了较大的Pd-Zn合金粒子,从而有利于甲醇重整反应的进行.制备了金属壁载型...     

Pd／Al2O3催化剂上裂解C5馏分选择性加氢反应研究

研究了负载在Al2O3载体上的贵金属钯（Pd）基催化剂在裂解C5馏分中选择性加氢反应中的性能。结果表明,Pd／Al2O3催化剂上可进行选择性加氢的反应条件区域为压力0．5～1．0MPa、体积空速2—4h^-1、氢油体积比100：1～300：1和反应温度为55—65℃,在此反应条件下,炔烃能被完全加氢去除,同时二烯烃发生部分转化,转化产物主要为单烯烃,其中二烯烃转化的产物主要是热力学相对稳定的单烯烃;在选定的反应条件中,随温度升高、压力增加、氢油比增加,炔烃、二烯烃转化率提高;而随液时空速增加,二烯烃转化率有所下降;在各反应条件中,温度和压力对催化剂加氢性能影响较为显著;制备的Pd／Al2O3催化剂对于炔烃和二烯烃具有好的选择性加氢能力,可能原因一方面是由于反应条件选择较缓和,另一方面是原料中硫的存在。     

异氟尔酮在蛋壳型Pd/Al2O3催化剂上的选择性加氢

采用等体积浸渍法制备出蛋壳型Pd/Al2O3催化剂,采用连续加氢固定床微反装置研究了异佛尔酮(IP)的选择性加氢反应,考察了载体焙烧温度、蛋壳层厚度、Pd负载量及粒子大小、溶剂等反应条件对Pd/Al2O3催化剂上IP选择性加氢的影响.结果表明,蛋壳型Pd/Al2O3是IP选择性加氢制备3,3,5-三甲基环己酮(TMCH)的优异催化剂,反应条件缓和,IP转化率及TMCH选择性均可达到99.5％以上,具有良好的工业应用前景.     

Condensation of aldehydes for environmentally friendly synthesis of 2-methyl-3-phenyl-propanal by heterogeneous catalysis

Eco-friendly synthesis in “one-pot” of 2-methyl-3-phenyl-propanal from benzaldehyde and propanal was studied using a multifunctional catalyst as an alternative to the three-step conventional process involving basic, acidic and hydrogenating catalysts. Mg(Al)O mixed oxides obtained from hydrotalcite precursor achieved the two first steps of condensation and dehydration. Addition of water to the solvent improves the activities and selectivities of Mg(Al)O, thanks to the reconstruction of the lamellar structure with OH⁻ as compensating anions, acting as Brønsted basic sites. Mg(Al)O was then used as support for a multifunctional catalyst impregnated with Pd. Pd/Mg(Al)O led to 45% dihydrocinnamaldehyde selectivity at 43% conversion in benzaldehyde in the “one-pot” process.     

PREPARATION OF ULTRAFINE Al 2 O 3 USING PLASMA JET AND ITS APPLICATION FOR SYNTHESIS OF DIMETHYL CARBONATE

A direct preparation of Al 2 O 3 from aluminum and oxygen under plasma jet conditions has been performed in this work. The XRD characterization of such plasma-prepared alumina shows that a production of δ-Al 2 O 3 has been achieved. The size of the alumina particles ranged from several tens to 200 nm, based on SEM analysis. The effectiveness of plasma-prepared alumina as a catalyst support has been demonstrated by the catalytic synthesis of dimethyl carbonate over Pd/Al 2 O 3 .     

非晶态Pd-B/Al2O3催化剂用于邻氯硝基苯加氢合成邻氯苯胺的研究

用化学还原法制得了Pd-B/Al2O3非晶态催化剂,并用于邻氯硝基苯液相加氢反应的研究.采用XRD、SEM、SAED等技术手段对催化剂进行了表征,表明Pd-B以超细颗粒的形式分散在载体上,并且明确了催化剂的非晶态性质、结构形态等.以邻氯硝基苯液相加氢为目标反应,对所制备催化剂的催化性能进行系统评价.在反应温度90℃、氢气压力1.0MPa的反应条件下,邻氯硝基苯的转化率达99.9%,邻氯苯胺的选择性达98.0%;在不加脱卤抑制剂的情况下,脱卤率小于2%,表明负载Pd系非晶态催化剂具有较好的邻氯硝基苯加氢活性及良好的选择性,优于Pd基晶态催化剂和Ni基晶态催化剂.从催化剂的微观结构、金属-载体相互作用、活性组分在载体表面的几何效应和电子效应等方面对非晶态催化剂响影响邻氯硝基苯加氢性能进行了讨论和解释.     

脱氢芳樟醇选择性加氢合成芳樟醇

研究制备了负载型双金属Pd-Bi/Al2O3催化剂,用于固定床中脱氢芳樟醇选择性加氢生成芳樟醇的反应。考察了催化剂中活性组分Pd的负载量,以及在不同反应温度下Pd与Bi的原子配比对反应活性和选择性的影响。实验结果表明,当催化剂中Pd负载量为0.6‰,Pd/Bi原子比为1,在反应温度90℃和反应压力1.5MPa时,反应转化率为95.7%,生成芳樟醇的选择性达到85.3%。     

Activity and selectivity of a {\text{Pd/}}\gamma {\text{ - Al}}_{\text{2}} {\text{O}}_{\text{3}} catalytic membrane in the partial hydrogenation reactions of acetylene and 1,3-butadiene

A ${\text{Pd/}}\gamma {\text{ - Al}}_{\text{2}} {\text{O}}_{\text{3}}$ membrane supported on a macroporous $\alpha {\text{ - Al}}_{\text{2}} {\text{O}}_{\text{3}}$ tube was prepared by sol–gel processing and used in the partial hydrogenation of acetylene and 1,3-butadiene. The average pore diameter of the ${\text{Pd/}}\gamma {\text{ - Al}}_{\text{2}} {\text{O}}_{\text{3}}$ membrane was 3.6 nm. The gases were separated by Knudsen diffusion. The activity and selectivity of the ${\text{Pd/}}\gamma {\text{ - Al}}_{\text{2}} {\text{O}}_{\text{3}}$ membrane was compared to that of ${\text{Pd/}}\gamma {\text{ - Al}}_{\text{2}} {\text{O}}_{\text{3}}$ catalysts used in a conventional packed bed reactor. The highest selectivity to the partially hydrogenated products occurred when the reactant was premixed with H₂ and was passed through the membrane wall.