钒/钛复合氧化物催化剂用于二氧化碳气氛中乙苯氧化脱氢

 采用改进的酸催化溶胶-凝胶法制备了以TiO2为基体的钛基复合氧化物催化剂, 并将该催化剂用于低温下二氧化碳气氛中乙苯氧化脱氢制苯乙烯反应. 采用X射线衍射、 表面物理吸附、 X射线光电子能谱和热重-质谱等分析手段对反应前后的催化剂进行表征. 结果表明, 催化剂在一定反应条件下具有较好的催化活性. 催化剂失活原因主要是反应过程中产生了积炭和高价钒被还原成低价钒. 反应过程中产生的积炭可以通过空气氧化消除,再生后的催化剂其活性基本上能得到恢复.     

CO2 气氛下 MCF 负载氧化钒催化剂上乙苯脱氢反应

 以介孔氧化硅泡沫 MCF 为载体合成了一系列负载型氧化钒催化剂 (V 含量为 2%?10%). 采用 N2 吸附、X 射线衍射和 H2 程序升温还原对 V/MCF 催化剂的结构和织构性质进行了表征, 并评价了催化剂在 CO2 气氛下的乙苯脱氢性能. V/MCF 催化剂具有较高的乙苯脱氢活性, 其中 V 含量为 6% 的催化剂具有最高的反应活性. V/MCF 催化剂的乙苯脱氢活性显著高于 V/MCM-41, 这是由于前者具有较高的可还原性以及较好的扩散性能. CO2 气氛下的乙苯转化率明显高于 N2 气氛下的, 这归因于 CO2 与乙苯发生氧化脱氢, 并通过逆水煤气变换反应在线除去脱氢反应生成的氢.     

Physico-Chemical and Catalytic Properties of Fe-Bi-Mo-Ox Catalysts in the Oxidative Dehydrogenation of Ethylbenzene

The Fe-Bi-Mo-O_x system has been studied in the oxidative dehydrogenation of ethylbenzene to styrene by a pulse-chemisorption method. The two forms of adsorption for ethylbenzene and styrene suggest a non-uniform structure of the catalysts surfaces.     

CO2气氛下负载型Cr2O3催化剂上乙苯脱氢制苯乙烯反应

 采用浸渍法制备了负载型Cr2O3/Al2O3和Cr2O3/SiO2催化剂,并考察了催化剂在CO2气氛下催化乙苯脱氢制苯乙烯反应的活性. 结果表明,Cr2O3/Al2O3的催化活性高于Cr2O3/SiO2. 这可能是由于Cr2O3在Al2O3载体表面的分散度大大高于在SiO2表面的分散度. 催化剂的催化活性与Cr2O3的负载量有关,在w(Cr2O3)=25%时,Cr2O3/Al2O3的催化活性最高. CO2气氛对乙苯脱氢反应有明显的促进作用; 在CO2气氛下,Cr6+物种可能是催化乙苯脱氢反应活性位的前驱体.     

铈在乙苯脱氢氧化铁基催化剂中的助催化作用

研究了铈在Fe_2O_3-K_2O-CeO_2乙苯脱氢催化剂中的助催化作用。铈源为硝酸铈时助催效果明显,但CeO_2则不佳。助催化效果还与催化剂中的钾量有关。铈明显增进高钾催化剂的活性,但对催化剂的选择性无明显影响。     

微量吸附量热技术在ZnxCo1-xCr2O4催化剂筛选上的应用

采用共沉淀法制备了一系列ZnxCo1-xCr2O4催化剂,并将其进行了微量吸附量热技术测定,及苯酚与甲醇邻位烷基化反应的应用性实验。结果证明,ZnxCo1-xCr2O4催化剂上苯酚和甲醇邻位烷基化反应的活性中心应是酸碱的协同作用产生的,ZnxCo1-xCr2O4系列催化剂中的Zn／Co的最佳比例为Zn／Co=1。运用微量吸附量热技术实现了对ZnxCo1-xCr2O4系列催化剂的优化。     

铁系催化剂上乙苯与CO2氧化脱氢反应

采用浸渍法和溶胶-凝胶法制备了三种含Mg,Fe和Al量相同的Fe2O3-MgO/γ-Al2O3,Fe2O3/MgAl2O4和MgFe0.1Al1.9O4催化剂,在580°C考察了它们催化乙苯与CO2氧化脱氢反应性能,并采用X射线衍射,表面元素分析,H2-程序升温还原和CO2-程序升温脱附等技术对催化剂体相及表面性质进行了表征.结果表明,催化剂制备方法影响Fe物种的存在形态,进而影响催化剂的稳定性和活性.采用浸渍法制备的Fe2O3/MgAl2O4催化剂含有高度分散的Fe2O3活性物种,该物种具有较好的初活性,但是稳定性较差;而采用溶胶-凝胶法制备的MgFe0.1Al1.9O4催化剂中,Fe物种主要以同晶取代的形式存在于尖晶石骨架中,因而具有较高的乙苯与CO2氧化脱氢催化活性和稳定性.     

Cr/C催化剂的催化性能与表面酸性的微量吸附热技术分析

以NH3作为吸附探针分子，定量地分析了Cr／C固体表面酸性中心的强度、数量和分布状态，并探讨了表面酸性对催化性能的影响关系。结果表明适当强度的酸性位有利于CO2氧化乙烷脱氢制乙烯反应。     

Dehydrogenation of Ethylbenzene to Styrene with Carbon Dioxide Over ZrO<Subscript>2</Subscript>-based Composite Oxide Catalysts

We have been exploring various new catalyst systems for the utilization of carbon dioxide as a soft oxidant in the catalytic dehydrogenation of ethylbenzene (EB) to styrene. The utilization of CO₂ as a soft oxidant for the commercially important catalytic dehydrogenation of EB to styrene has received enormous attention recently due to its several attractive features. This review summarizes the results of our most recent findings on zirconia-based composite oxide catalyst systems exploited for this reaction. Under this systematic and comprehensive investigation various zirconia-based composite oxide catalysts namely, TiO₂-ZrO₂, MnO₂-ZrO₂, CeO₂-ZrO₂, K₂O/TiO₂-ZrO₂, B₂O₃/TiO₂-ZrO₂ and CeO₂-ZrO₂/SBA-15 have been synthesized, characterized by various techniques and evaluated for the title reaction. Most of these composite oxide catalysts were found to exhibit very interesting physicochemical characteristics and exceptionally better catalytic properties for this reaction. As revealed by characterization results, a large number of acid–base sites with moderate strength are essential for a high conversion and product selectivity of this reaction with CO₂ as the soft oxidant.     

纳米Fe2O3-K2O催化剂的制备及其催化乙苯脱氢性能

采用浸渍-热分解法制备了纳米Fe2O3-K2O催化剂,并在常压和520～580℃的条件下,考察了其对乙苯催化脱氢反应的催化性能.结果发现,纳米Fe2O3-K2O催化剂表现出很好的活性和稳定性.在550℃,N2/H2O/乙苯摩尔比为30.7/10/1和WHSV=0.43h-1的条件下,纳米Fe2O3-K2O催化乙苯脱氢的转化率为71.9%,苯乙烯选择性为91.1%.透射电子显微镜和X射线衍射测试结果表明,氧化铁的粒径为10～14nm.催化剂的尖晶石结构和高比表面积是其表现出高催化性能的主要原因.     

焙烧温度对乙苯脱氢催化剂Fe2O3-K2O性能的影响

用混合法制备了Fe2O3-K2O乙苯脱氢催化剂,并用压汞法、X射线衍射、穆斯堡尔谱、程序升温还原和热重-差热分析等表征手段,考察了焙烧温度对催化剂的催化活性、比表面积、体相结构和还原性能的影响.结果表明,随着焙烧温度的升高,催化剂的比表面积逐渐减小,平均孔径逐渐增大;尖晶石K2Fe22O34中正四面体Fe3 的含量逐渐减少,正八面体Fe3 的含量逐渐增多,催化剂逐渐变得容易被还原;催化剂的催化活性差别不大,但达到平稳时所需的诱导期逐渐缩短.过高的焙烧温度不利于催化剂的稳定性.     

负载型VOx／SBA-15催化剂催化CO2气氛下乙苯脱氢反应的研究

利用浸渍法制备了系列不同钒含量的VOx/SBA-15乙苯脱氢催化剂.并采用BET、UV-vis、XRD、TPO和O2脉冲等物理化学表征手段对催化剂进行了表征.二氧化碳气氛下的乙苯氧化脱氢反应结果表明,在550℃,当V2O5的含量为20%时,催化剂表现出最好的脱氢性能.乙苯的转化率达到74.1%,同时也获得95.7%的苯乙烯选择性.20VOx/SBA-15具有较高的比表面积、较多的酸性、较少的积碳,这可能是该催化剂表现出较好的催化性能的原因.     

高价小分子型分散剂在Al2O3表面的吸附研究

采用5-硝基水杨酸合铁()分光光度法测定了2-膦酸丁烷-1,2,4-三羧酸(PBTCA)及柠檬酸在Al₂O₃表面的等温吸附线,发现二者的饱和吸附量均随pH值的升高而减小,且PBTCA比柠檬酸的饱和吸附量高.ζ电位及沉降实验亦表明,与柠檬酸相比,PBTCA的吸附使Al₂O₃表面的有效负电荷量更高,且其分散作用也更佳.采用FTIR及AES研究了PBTCA在Al₂O₃表面的吸附机理.膦酸基的存在提高了PBTCA在碱性条件下的吸附能力.     

介孔氧化铝负载Ni-Co氧化物催化剂上丙烷氧化脱氢制丙烯

以非离子型三嵌段共聚物作为模板剂, 异丙醇铝为氧化铝的前驱物, 采用一锅法合成了一系列介孔氧化铝负载镍氧化物、钴氧化物以及镍-钴双金属氧化物催化剂, 并以介孔氧化铝为载体, 采用浸渍法制备了负载Ni-Co 氧化物催化剂. 采用N₂吸附-脱附、高分辨透射电镜(HRTEM)、X射线粉末衍射(XRD)、H₂程序升温还原(H₂-TPR)以及激光拉曼光谱(LRS)等技术对催化剂的结构与性质进行表征, 并考察了催化剂的丙烷氧化脱氢反应性能. 结果表明: 一锅法制备的各催化剂均有大的比表面积和规整的孔道结构, 且负载的金属氧化物高度分散; 而浸渍法制备的催化剂, 其载体的介孔结构被破坏并有Co₃O₄晶相生成. 在考察的催化剂中, 一锅法合成的介孔氧化铝负载Ni-Co 氧化物催化剂表现出最佳的丙烷氧化脱氢性能. 在450 °C、C₃H₈:O₂:N₂的摩尔比为1:1:4和空速(GHSV)为10000 mL·g^-1·h^-1条件下, 该催化剂上丙烯产率为10.3%, 远高于浸渍法制备的催化剂上所获得的丙烯产率(2.4%). 关联催化剂表征和反应结果, 讨论了催化剂结构与性能之间的关系.     

二氧化碳氧化丙烷制丙烯催化反应的研究铬镁铝复合氧化物催化剂的制备、表面微量吸附量热及催化性能

以共沉淀法合成的铬镁铝类水滑石为前体,制备了一系列不同原子比的铬镁铝复合氧化物,研究了其对二氧化碳氧化丙烷制丙烯反应的催化性能.采用微量吸附量热技术,以CO2和NH3为探针分子定量地表征了样品表面酸碱中心的强度和数量,并与其催化性能进行了关联.结果表明,Cr:Mg:Al原子比为1:1:1的催化剂具有较大的比表面积(94.5m2/g),样品中Mg(Al1.5Cr05)O4物相的含量最多.样品表面存在数量较多强度较强的酸性中心和数量最少强度较弱的碱性中心,对NH3吸附,它的吸附热为145 kJ/mol,吸附覆盖度为3.55μmol/m2;对CO2吸附,它的吸附热为115kJ/mol,吸附覆盖度为0.063μmol/m2.该样品的催化活性最高,在温度为650℃,CO2/C3H8摩尔比为3.6,GHSV(C3H8)为3000 h-1时,C3H8的转化率为22.8%,C3H6的选择性为83.5%,收率为19.1%.     

TG study on real role of active carbon support in propane dehydrogenation with CO2

Active carbon was used as a support for chromium(III) oxide phase. The synthesized materials appeared to be very active catalysts of the propane dehydrogenation in the presence of CO₂. An influence of the Cr content on the catalytic activity and selectivity was observed. The best results were achieved over the sample containing about 5 wt.% of Cr. A negative effect of activity decay with time-on-stream was found. The reasons of the observed deactivation were explained using the thermal analysis method. A behavior of the fresh and used samples was tested in a temperature range of 25–1000 °C in different atmospheres (inert gas, air or CO₂). It was found that the catalytic runs resulted in a partial decomposition of surface O-containing groups, which together with CrO_x species play a role of active centers. Moreover, a formation of inactive carbonaceous deposit on the catalyst surface was observed.     

含Cu复合氧化物对NO和CO吸附和活化的TPSR研究

利用MS－TPD法并结合XRD、化学分析等对催化剂进行了表征，探讨了K2NiF4结构La2-x(Sr，Th)xCuO4±λ系催化剂中三个典型样品LaSrCuO4、La2CuO4和La1.7Th0．3CuO4对NO、CO及CO＋NO等小分子的吸附性能和活化规律。结果表明：NO吸附量的大小与催化剂中氧空位含量有关，吸附强度和脱附峰种类与金属离子氧化态有关。CO在氧缺陷复合氧化物催化剂上的吸附是首先变为碳酸根，并在高温以CO2物种脱出．在NO和CO的共吸附过程中，有关NO的吸、脱性能与单独NO－TPD中NO的吸脱附规律相似，表明NO在NO＋CO共吸附的竞争吸附过程中，优先吸附起决定作用，而受CO的影响较小．NO的吸附是NO活化分解的必要条件．     

Formation of an active surface on oxide systems containing vanadium used for dehydrogenation of hydrocarbons in the presence of hydrogen acceptors. 4. Catalytic and physicochemical properties of vanadium-zirconium and vanadium-titanium catalysts for the oxidative dehydrogenation of ethylbenzene in the presence of nitrobenzene

A study has been made of the catalytic and physicochemical properties of vanadium-zirconium and vanadium-titanium oxide systems in the oxidative dehydrogenation of ethylbenzene in the presence of nitrobenzene. The degree of conversion to styrene was less than 10% and to aniline 60%. The methods used to study the physicochemical properties of the catalysts were diffuse reflection electron spectroscopy (DRES), x-ray and differential thermogravimetric analysis. The presence of surface V _Td ⁵⁺ , V _Oh ⁵⁺ , and V _Q ⁴⁺ ions has been established, their ratios depending on the initial vanadium concentrations, the nature of the carrier, and the thermal treatment conditions. In the vanadium—zirconium systems V _Td ⁵⁺ predominate, but in the vanadium-titanium ones V _Q ⁴⁺ . The V _Oh ⁵⁺ ions appear to be present in the form of clusters. A chemical compound between the active components and ZrO₂ and a V₂O₅ phase have been detected, which take no part in the dehydrogenation reaction.V. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117334. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 557–561, March, 1992.     

MgO和CaO助剂在Fe-K催化剂中的作用

制备了以MgO和CaO为助剂的乙苯脱氢制苯乙烯用Fe-K催化剂,并考察了助剂对催化剂催化性能的影响.应用SEM、XRD、TPR和Mssbauer谱等手段表征了MgO和CaO对活性前驱体K2Fe22O34晶相形成及其表观体相结构的影响.结果表明,引入MgO助剂,半径相近的Mg2 与Fe3 极易发生取代形成固溶体,使活性前驱体K2Fe22O34晶相的形成温度有所降低,同时给体相结构引入氧空位,从而有利于乙苯发生晶格氧转移机理的脱氢反应,使催化剂活性提高.引入CaO助剂,提高了K2Fe22O34晶相的结晶度和苯乙烯选择性,但催化剂活性有所下降.CaO对Fe-K催化剂的还原有一定的阻碍作用,是催化剂的稳定性助剂.     

Theoretical and Experimental Study on Reaction Coupling： Dehydrogenation of Ethylbenzene in the Presence of Carbon Dioxide

Dehydrogenation of ethylbenzene (EB) to styrene (ST) in the presence of CO2, in which EB dehydrogenation is coupled with the reverse water-gas shift (RWGS), was investigated extensively through both theoretical analysis and experimental characterization. The reaction coupling proved to be superior to the single dehydrogenation in several respects. Thermodynamic analysis suggests that equilibrium conversion of EB can be improved greatly by reaction coupling due to the simultaneous elimination of the hydrogen produced from dehydrogenation. Catalytic tests proved that iron and vanadium supported on activated carbon or Al2O3 with certain promoters are potential catalysts for this coupling process. The catalysts of iron and vanadium are different in the reaction mechanism, although ST yield is always associated with CO2 conversion over various catalysts. The two-step pathway plays an important role in the coupling process over Fe/Al2O3, while the one-step pathway dominates the reaction over V/Al2O3. Coke deposition and deep reduction of active components are the major causes of catalyst deactivation. CO2 can alleviate the catalyst deactivation effectively through preserving the active species at high valence in the coupling process, though it can not suppress the coke deposition.