共查询到20条相似文献,搜索用时 468 毫秒
1.
用流动反应法和TPSRMS等技术研究了CO在Pd/γAl2O3和含有ZrO2的催化剂上的吸脱附行为、表面反应及催化氧化活性,同时用XRD技术测定了催化剂的物相结构。结果表明,在Pd/γAl2O3催化剂中用浸渍法添加ZrO2或掺杂超细ZrO2后,催化剂的氧化活性均有明显提高;COTPSR的实验结果表明,CO在氧化态Pd催化剂上程序升温脱附过程中主要与表面氧发生氧化反应,而在还原态Pd催化剂上发生歧化反应,并发现CO2的脱附量及脱附峰温次序与对CO的氧化活性有一致的对应关系。 相似文献
2.
对比考察了Mo/CuH-ZSM-5和Mo/H-ZSM-5催化剂的甲烷无氧芳构化性能,并用XRD,XPS,ESR等多种测试手段对反应前后催化剂上的Mo物种及铜助剂的价态变化进行了详细研究,发现Cu(Ⅱ)部分取代H-ZSM-5变换位上的H^+后,抑制了活性组分MoO2的还原,而Cu物种自身被还原,进而将这种价态变化与催化剂的活性进行了关联。 相似文献
3.
4.
利用金属蒸气法制备了三种不同金属重量比的树脂固载及活性炭负载Pd-Cu双金属催化剂。透射电镜(TEM)和X-射线衍射(XRD)测定结果表明催化剂中Pd-Cu已形成合金。合金粒度极小,平均直径小于5mm。树脂固载催化剂金属粒度远小于活性炭负载催化剂的金属粒度。X-射线光电子能谱(XPS)结果表明Pd和Cu均以零价态存在。在4-甲基-3-戊烯-2-酮加氢反应中,树脂固载催化剂的活性和选择性均高于相应的 相似文献
5.
6.
本文通过化学修饰的方法改变了γ-Al_2O_3载体等电点(IEPS),并用具有不同等电点的Al_2O_3作载体,以(NH_4)_2PdCl4为活性组分前身制备了一系列Pd/Al_2O_3催化剂,在固定床微反色谱装置上考察了其对CO氧化的催化活性,用Hi—O_2滴定、紫外漫反射光谱(DRS)、透射电子显微镜(TEM)中的能量色散谱(EDXS)等方法对上述催化剂进行了表征,结果表明:Al_2O_3的等电点(IEPS)对所得催化剂中金属分散度和浓度分布都有明显影响,IEPS越高。活性组分越靠近外表面,在相同担载量下,其分散度也越高。这主要是由于载体IEPS的改变,导致了(NH_4)_2PdCl_4在γ-Al_2O_3上吸附机理的变化,并使所得催化剂对CO氧化的催化活性发生了规律性的变化。 相似文献
7.
铁助剂对Pd/Al2O3催化剂抗硫性能的影响 总被引:2,自引:0,他引:2
借助CO探针分子原位红外(in-situIR)、TEM(EDS)、XPS和XRD对一系列Pd-Fe/Al_2O_3、Pd-Pt/Al_2O_3和Pd(或Pt)/Al_2O_3模型催化剂进行了表征,结果表明,硫在中毒Pd(或Pt)/Al_2O_3时,毒物H_2S优先吸附于催化剂的多位活性中心上,主要以电子效应影响催化剂的活性.铁的引入,提高了活性组分Pd的分散度,多位活性中心的减少不利于H_2S在催化剂上的吸附;Pd-Fe协同作用的结果,增强了催化剂对吸附S~(2-)氧化成毒性较小的S~(6+)或可逸出系统的SO_2的能力,从而明显地提高了催化剂的抗硫中毒能力. 相似文献
8.
本文采用微反-色谱,穆斯堡尔谱及XPS等分析手段,研究了碳氧定向反应生成CO的Fe/C系催化剂中助剂K,Cr的作用。结果表明,助剂能大大提高定向氧化反应活性,并能稳定主活性组分的价态和提高其分散度。复合催化剂Fe-K-Cr/C无论在催化活性,稳定性及抗烧结性能方面都优于单组分催化剂。 相似文献
9.
10.
11.
12.
13.
Wei-Chao Xing Ji-Min An Jing Lv Faisal Irshad Yu-Jun Zhao Sheng-Ping Wang Xin-Bin Ma 《中国化学快报》2021,32(2):796-800
A novel Pd-Fe/α-Al_2O_3 catalyst was synthesized by incipient-wetness impregnation method with bayberry tannin as chelating promoter and commercial hollow column Raschig ring a-Al_2O_3 as support for the synthesis of diethyl oxalate from CO and ethyl nitrite.A variety of characterization techniques including N_2 physical adsorption,optical microscopy,scanning electron microscopy and energy dispersive system(SEM-EDS),inductively coupled plasma optical emission spectroscopy(ICP-OES),X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),transmission electron microscopy(TEM),were employed to explore the relationship between the physicochemical properties and activity of catalysts.It indicated that a large number of phenolic hydroxyl groups in bayberry tannin can efficiently anchor the active component Pd,reduce the particle size and make the active Pd as a multi-ring distribution on the commercial a-Al_2O_3 suppo rt,which we re beneficial to improve the catalytic activity for the production of diethyl oxalate from CO and ethyl nitrite.0.3 wts Pd-Fe/α-Al_2O_3 showed excelle nt catalytic activity and selectivity in a continuous flow,fixed-bed reactor with the loading amount of 10 mL catalysts,Under the mild reaction conditions,the space-time yield of diethyl oxalate was 978 g L ~1 h ~1 and CO conversion was 44% with the selectivity to diethyl oxalate of 95.5%. 相似文献
14.
CO偶联临氢反应Pd-Fe/Al2O3催化剂的XPS研究 总被引:2,自引:0,他引:2
利用XPS及氩离子溅射等技术对CO偶联和临氢反应中所用催化剂\r\n表面活性组分和助剂的含量及其化学状态进行了分析,并通过测定氢在\r\n催化剂表面的化学吸附,以及氢浓度对催化剂活性的影响,探讨了CO偶\r\n联反应中催化剂临氢失活的主要原因.XPS表征结果表明,CO偶联反应\r\n中催化剂活性组分以Pd0和Pd2+形式共存;而临氢反应后仅以Pd0形式\r\n存在,助剂FeO从催化剂的内部向表面迁移且有少量Fe2+转变为Fe3+\r\n.催化剂临氢失活的主要原因是H2在活性组分Pd及助剂Fe(主要是FeO\r\n)表面均可形成解离吸附,形成的金属氢化物可在低活化能条件下发生\r\n迁移.这种迁移有利于副产物乙醇的生成,从而削弱了CO偶联主反应,\r\n催化剂表面活性组分Pd的相对含量减少,并几乎处于钝化状态,导致临\r\n氢反应中CO转化率、草酸二乙酯选择性及空时收率均下降.停止通入H\r\n2后,催化剂的活性可恢复至正常状态. 相似文献
15.
The gaseous phase syntheses of diethyl oxalate and oxalic acid from CO are an important project of chemical technology[1]. Oxygencontent of CO is as high as 57%(wt) and its source is abundant. It is best of all economical and reasonable that oxy-compound is synthesized with carbon monoxide. In particular the reaction of CO coupling reaction can take place under moderate reaction conditions with low consumption of energy to produce oxalic acid and diethyl oxalate, which are feed stocks for ethylene glycol syntheses by the hydrogenation of oxalate, as well as for products such as pesticides, pharmaceuticals, foodstuffs, polymers, and fine chemicals. 相似文献
16.
研究了固定床中CO在双金属负载型催化剂Pd-Fe/Al2O3上气固相催化偶联反应制备草酸二乙酯的催化剂工程问题。其中对催化剂载体、活性组分负载量、不同含量的助剂和载体的焙烧温度进行了详细的研究。对催化剂进行了200倍放大制备,并于放大200倍的工业模式装置上用工业原料气进行了1000小时的连续运转考察。结果表明,CO总转化率接近100%,CO单程转化率大于60%,CO选择性大于 95% ,草酸二乙酯的空时收率大于600 g/(L cat.h)。 相似文献
17.
The chemical state of Pd at the surfaces of two sizes of Pd powders and ceria-supported Pd during low-temperature CO oxidation has been studied using X-ray photoelectron spectroscopy (XPS). During oxidation in O(2), metallic Pd powder is converted into PdO, and the thickness of the PdO layer increases with increasing reaction temperature. A similar Pd oxidation process occurs during the catalytic CO oxidation reaction, but the extent of the Pd oxidation is less due to the presence of CO which is a reducing agent. The reaction rate data indicate that the larger size Pd powder is about three times more active than the smaller size Pd powder on a surface area basis at 160 degrees C. Catalytic CO oxidation data obtained from 10 wt % Pd supported on nanocrystalline ceria powder indicate that there is a strong chemical interaction between the ceria and the supported Pd. The Pd is present as PdO on the fresh catalyst. During reaction, small amounts of Pd metal and PdO(2) are formed at 50 degrees C while less Pd metal and only a small amount of PdO(2) are present after running the reaction at 110 degrees C. At 50 degrees C, the catalytic activity decays rapidly due to accumulation of carbonate or bicarbonate species on the surface. This decay does not occur at 110 degrees C due to decomposition of the bicarbonate species. 相似文献
18.
JingangFang ZhenghuaLi GenhuiXu BaoweiWang TieliXiang 《天然气化学杂志》2003,12(4):243-246
Destructive tests of the catalyst was carried out to study the effect of temperature on the catalytic activity of CO coupling to diethyl oxalate (DEO) over a Pd-Fe/Al2O3 catalyst. It was found that a temperature jump could cause the deactivation of the Pd-Fe/α-Al2O3 catalyst. The catalyst deactivated at different temperatures has different characteristics. After deactivation the crystal structure of α-Al2O3 did not change, but the Pd particle size was enlarged. Most of the Pd^0 were oxidized to Pd^2 . and Fe^2 was oxidized to Fe^3 on the surface of the deactivated catalyst. The catalyst could be regenerated, but its original activity could not be recovered completely. 相似文献
19.
The chemical reactions and kinetics of the catalytic coupling reaction of carbon monoxide to diethyl oxalate were studied in the presence of hydrogen over a supported palladium catalyst in the gaseous phase at the typical coupling reaction conditions. The experiments were performed in a continuous flow fixed-bed reactor. The results indicated that hydrogen only reacts with ethyl nitrite to form ethanol, and kinetic studies revealed that the rate-determining step is the surface reaction of adsorbed hydrogen and the ethoxy radical (EtO-). A kinetic model is proposed and a comparison of the observed and calculated conversions showed that the rate expressions are of rather high confidence. 相似文献
20.
Fandong Meng Genhui Xu Zhenhua Pa DuState Key Laboratory of C Chemical Technology Tianjin University Tianjin China Luoyang Petrochemical Engineering Corporation Luoyang China 《天然气化学杂志》2002,(Z2)
The chemical reactions and kinetics of the catalytic coupling reaction of carbon monoxide to diethyl oxalate were studied in the presence of hydrogen over a supported palladium catalyst in the gaseous phase at the typical coupling reaction conditions. The experiments were performed in a continuous flow fixed-bed reactor. The results indicated that hydrogen only reacts with ethyl nitrite to form ethanol, and kinetic studies revealed that the rate-determining step is the surface reaction of adsorbed hydrogen and the ethoxy radical (EtO-). A kinetic model is proposed and a comparison of the observed and calculated conversions showed that the rate expressions are of rather high confidence. 相似文献