纳米TiO2负载钯催化剂的性能研究

采用浸渍法制备了纳米TiO2负载钯催化剂,以乙炔选择催化加氢制备乙烯为反应模型考察了稀土元素La、空速对纳米Pd／TiO2催化剂性能的影响,并与纳米SiO2为载体的Pd—La／SiO2催化剂的性能做了比较。实验结果表明,纳米Pd／TiO2催化剂具有良好的催化活性和性能稳定性,La的加入显著提高了乙烯的选择性、增幅达加％左右。与Pd—La／SiO2催化剂相比,Pd—La／TiO2催化剂具有更高的选择性。     

化学包覆法制备TiO_2/SiO_2复合物

与TiO2光催化剂相比,以SiO2为载体或内核制备的TiO2/SiO2复合催化剂,其表面活性、光催化活性和热稳定性都更高。以粉煤灰为原料制备的沉淀SiO2为硅源,钛酸四丁酯为钛源,采用化学包覆法制备TiO2/SiO2复合物,采用扫描电镜(XRD)、红外光谱(FT-IR)和差热分析(TG-DTA)等测试手段对该复合物进行表征。FT-IR和TG-DTA分析证实,SiO2被TiO2有效包覆。复合物热稳定性较高,经700℃焙烧4 h后,SiO2仍为无定形,TiO2以锐钛矿相为主;在900℃焙烧后,TiO2大部分由锐钛矿相转变为金红石相。     

Promotion Effect of Lantanum ions on Co／SiO2 Catalysts Prepared via Solvated Metal Atom Impregnation Method

In order to assess the promotional effects of La^3 on CO hydrogenation of Co/SiO2 catalyst, solvated metal atom impregnation (SMAI) method was used to prepare unpromoted 10% (mass fraction) Co/SiO2 and a series of La^3 -promoted 10% (mass fraction) Co/SiO2 catalyst with different La/Co atomic ratios (0.1, 0.3, 0.5). X-ray diffraction (XRD), and CO chemisorption measurements show that the cobalt particle size decreases as the La/Co ratios increase. X-ray photoelectron spectrescopy indicates that cobalt is in zero-valent state for all the samples. Catalytic test shows that the catalytic activity of La^3 -promoted Co/SiO2 in CO hydrogenation is higher than that of unpromoted Co/SiO2, and enhances with the La/Co ratios increase. La^3 promotion also causes the enhanced selectivity of Co/SiO2 catalyst for higher hydrocarbon products.     

Synergistic Effect of N and Ni2+ on Nanotitania in Photocatalytic Reduction of CO2

Nitrogen and nickel codoped nanotitania (N-Ni/TiO2) photocatalysts for producing methanol by photocatalytic reduction of CO2 were prepared by an improved sol-gol method. The catalysts were characterized by XRD, HRTEM, DES, FTIR, TG-DSC, and UV-Vis, respectively. The experimental results indicated that nano-N-Ni/TiO2 had better properties than the pure nanotitania (TiO2), N doped titania (N/TiO2), and Ni2+ doped titania (Ni/TiO2), considering their performance of photoresponse and photocatalytic reduction of CO2. The methanol yield could reach 482.0μmol/g-cat under optimal conditions. Additionally, the synergetic effect of N and Ni2+ on nano-TiO2 in photocatalytic reduction of CO2 was explained, and the mechanism of photocatalytic reduction CO2 on N-Ni/TiO2 catalyst was proposed.     

Synthesis of cerium-doped MCM-48 molecular sieves and its catalytic performance for selective oxidation of cyclohexane

Cerium-doped MCM-48 molecular sieves were synthesized hydrothermally and characterized by X-ray diffraction, nitrogen adsorption, transmission electron microscope, FT-IR spectroscopy, UV-visible spectroscopy, and Raman spectroscopy. The results showed that all the samples held the structure of MCM-48, and Ce could enter the framework of MCM-48. However, when Ce/Si molar ratio in the sampies was high （0.04 or 0.059）, there were CeO2 crystallites as secondary phase in the extraframework of MCM-48. Ce-doped MCM-48 was a very efficient catalyst for the oxidation of cyclohexane in a solvent-free system with oxygen as an oxidant. In the conditions of 0.5 MPa 02 and 413 K for 5 h, the conversion of cyclohexane was 8.1% over Ce-MCM-48-0.02, the total selectivity of cyclohexanol and cyclohaxnone was 98.7%. With an increase of Ce content, the conversion of cyclohexane and the selectivity to cyclohexanol decreased somewhat, but the selectivity to cyclohexanone increased.     

Role of cerium as a promoter and process optimization studies for dehydration of glycerol to acetol over copper chromite catalyst

Cerium-promoted silica supported copper chromite catalyst was synthesized from acid hydrolysis of sodium silicate by sol-gel method.The catalyst was characterized by Brunauer-Emmett-Teller(BET)method,field-emission scanning electron microscopy(FESEM),X-ray diffraction(XRD),H₂-temperature programmed reduction(H₂-TPR),NH3-temperature programmed desorption(NH3-TPD)and pyridine adsorbed Fourier transform infrared spectroscopy(Py-FTIR).Among cerium doped catalysts,5 wt%of Ce promoted copper chromite supported by 40 wt%of silica(SiCuCr40-Ce5)shows the largest BET surface area.XRD analysis of the reduced form of the catalyst shows both CeO₂/Ce₂O₃ redox system and CuO/Cu₂O/Cu redox system.Py-FTIR shows the maximum number of Lewis acid sites for SiCuCr40-Ce5 than others.The highest acetol selectivity with analytical reagent(AR)grade glycerol conversion is observed for SiCuCr40-Ce5 at 200℃for 3 h in a batch reactor at atmospheric pressure.Cerium promotion lowers the reaction te mperature with enhanced glycerol conve rsion and increased acetol selectivity.Though the above catalyst shows higher conversion for laboratory reagent(LR)grade glycerol but it reduces acetol selectivity.The addition of glucose into the LR grade glycerol further reduces glycerol conversion and decreases the acetol selectivity to zero.This may be due to the presence of iron as impurity in LR grade glycerol.XRD analysis of spent catalyst shows the absence of redox catalytic system and the pore volume reduces identified by BET analysis.Raman analysis of the spent catalyst shows graphite-like carbon deposition in the spent catalvst.     

Preferential Oxidation of CO in H2 over CuO／CeO2 Catalysts

Over the past few years, the design and researchon fuel cells have been made a great development. Avariety of fuel cells for different applications has beenunder development[1,2]: solid polymer fuel cells(SPFC), also know as proton exchange …     

Rare earth oxide modified Cu-Mn compounds supported on TiO₂ catalysts for low temperature selective catalytic oxidation of ammonia and in lean oxygen

Selective catalytic oxidation(SCO) of ammonia was carried out over Cu-Mn compounds catalysts modified with trivalent rare earth oxide Ce2O3 and La2O3 respectively.TiO2 was used as support and different ratio of O2 were tested in order to find an appropriate O2 concentration(vol.%),and the results showed that 1%O2(vol.%) was propitious to SCO of ammonia.The effects of the two rare earth oxides modified catalysts Ce2O3-Cu-Mn/TiO2 and La2O3-Cu-Mn/TiO2 on the catalytic activity and selectivity of ammonia oxidation were investigated under the reaction condition of 500 ppm ammonia,1%O2(vol.%),at the temperature from 125 to 250 oC.The results revealed the beneficial role of Ce2O3 and La2O3 in catalytic activity at low temperature and lean oxygen concentration,while the modification with Ce2O3 and La2O3 led to the negative influence on N2 selectivity.For the catalysts modified with Ce showed lower NO and N2O selectivity than the catalysts modified with La,then the effects of different Ce loadings on catalytic activity and selectivity were also considered,in combination with catalysts preparation methods,which include incipient wet impregnation,sol-gel method and co-precipitation.Results revealed that the catalysts prepared by sol-gel method obtained preferable catalytic activity compared with the others,reaching 99% ammonia at 200 oC,whereas 96% NO was detected.It also indicated that different catalyst preparation method significantly determined production distribution.     

高活性PtMo_2C/Al_2O_3催化剂的研究进展

叙述了高活性PtMo2C/Al2O3催化剂的制备、性能和在水气位移反应中的应用。由于制备出的PtMo2C/Al2O3催化剂中,其铂离子呈几个纳米分散态显微结构,分布十分均匀,它比传统的催化剂如CuZn/Al2O3、Pt/C、Pt/Al2O3和PtCeO2等的催化活性高,选择性好,WGS速率高,反应温度低。     

Partial Oxidation of Methane to Syngas over Monolithic Ni/γ-Al2O3 Catalyst——Effects of Rare Earths and Other Basic Promoters

A series of monolithic Ni/γ-Al2O3 catalysts with and without basic promoters (Na, Sr, La, Ce) were prepared. Partial oxidation of methane (POM) to syngas was carried out in a continuous-flow, fixed-bed reactor. The influences of reaction conditions, including temperature, CH4/O2 ratio and space velocity, on the performance of the catalyst were investigated. The results show that at a high space velocity of 1×105 h-1, optimal CH4 conversion can be obtained. Effects of promoters such as Na, Sr, Ce, La were also investigated, and the catalyst samples were characterized by means of temperature-programmed reduction and XRD techniques. XRD suggests that the addition of promoters has no influence on the crystal structure of Ni/γ-Al2O3 catalyst. The results show that the addition of a small amount of promoters improves the reducibility and activity of the catalyst. The side reaction CH4 2 O2→CO2 H2O, is fully restrained and 100% H2 selectivity is achieved when Ce and La are used as promoters, respectively.     

Zr对Pt-Sn/γ-Al2O3脱氢性能的影响

通过H2-TPR、H2化学吸附和O2-脉冲等物理化学表征手段,并结合丙烷脱氢催化性能测试,考察了助剂Zr对Pt-Sn/γ-Al2O3催化剂反应性能的影响,结果表明：少量Zr的添加可显著改善Pt-Sn/γ-Al2O3催化剂的脱氢稳定性,同时可提高丙烯选择性,降低催化剂表面积碳量.Zr的存在可能加强了Pt与助剂和载体之间的相互作用,提高Pt粒子抗烧结的能力.     

Au-Pd/ZnO-CeO_2催化剂甲醇部分氧化制氢性能的研究

采用聚合物保护乙醇还原法制备了Au-Pd/ZnO-CeO_2催化剂,考察了CeO_2对Au-Pd/ZnO催化剂甲醇部分氧化制氢反应性能的影响,并运用BET、XRD、TPR、H_2-TPD和CH_3OH-TPD等手段对催化剂进行了表征.结果表明,CeO_2对Au-Pd/ZnO催化剂具有较好的改性效果,CeO_2的引入能提高Au-Pd/ZnO催化剂的活性和氢气的选择性,归结于CeO_2的加入增加了催化剂的比表面积、分散度和对反应物甲醇的吸附,同时减少了对生成物H_2脱附,这些均有利于甲醇部分氧化制氢反应.     

Zr对Pt-Sn/γ-Al2O3脱氢性能的影响

通过H₂-TPR、H₂化学吸附和O₂-脉冲等物理化学表征手段,并结合丙烷脱氢催化性能测试,考察了助剂Zr对Pt-Sn/γ-Al₂O₃催化剂反应性能的影响,结果表明:少量Zr的添加可显著改善Pt-Sn/γ-Al₂O₃催化剂的脱氢稳定性,同时可提高丙烯选择性,降低催化剂表面积碳量. Zr的存在可能加强了Pt与助剂和载体之间的相互作用,提高Pt粒子抗烧结的能力.      

高钛型高炉渣渣钛分离研究

针对攀钢高钛型高炉渣,采用高温熔滴炉模拟焦炭反应器研究高钛型高炉渣熔融滴落穿过焦炭层时渣焦、渣气反应过程,生成物与焦炭的粘结情况,滴落渣的成分和性能,并探讨渣钛分离的影响因素.通过实验得出焦炭层滞留有大量橘红色和古铜色的TiC、TiN;滴落渣中的TiO2降到了9.0 %左右.     

Hydroxylation of Benzene to Phenol via Hydrogen Peroxide in Hydrophilic Triethylammonium Acetate Ionic Liquid

A new Fenton-like system in a medium of hydrophilic triethylammonium type of ionic liquid(IL) was used for the hydroxylation of benzene to phenol. The triethylammonium acetate([Et<,3>NH][CH<,3>COO]) IL exhibited re- tardation performance for the decomposition of H<,2>O<,2> and protection performance for the further oxidation of phenol, thus the yield and selectivity to phenol were promoted greatly. The acidity of the system was proved to be an impor- tant factor for the selectivity to phenol. The utilization of H<,2>O<,2> and the selectivity to phenol, as well as the Turnover number(TON) of the catalyst were effectively enhanced by a benzene-[Et<,3>NH][CH<,3>COO] bi-phase system. The cata- lyst with [Et<,3>NH][CH<,3>COO] IL was recycled with stable catalytic performance.     

铕掺杂固载超强酸催化合成三醋酸甘油酯的研究

分别以粘土制成的陶瓷球、分子筛为载体,四氯化钛和三氯化铕为原料,采用液相沉积法制备了掺杂铕的T iO2/SO42-/陶瓷球固载超强酸(ETT)和掺杂铕的T iO2/SO42-/分子筛固载超强酸(ETS)。通过正交试验优选了催化剂制备条件,并以甘油与醋酸的酯化反应考察了催化剂的催化性能。实验结果表明,T iO2等化合物在载体上的沉积速度是影响催化剂活性的关键因素,且载体不同时会影响到催化剂对酯化反应的催化活性。在适宜的条件下,即原料配比n甘油∶n乙酸∶n乙酸酐为1∶4∶0.2,催化剂(ETT)用量2.5g(为总投料量的2.6%),反应时间7h时,三醋酸甘油酯的收率可达到98.3%。     

Hydrogen production by steam reforming of ethanol over copper doped Ni/CeO2 catalysts

High surface area CeO2 was prepared by the surfactant-assisted route and was employed as catalyst support. The 0-3 at.% Cu doped Cu-Ni/CeO2 catalysts with 10 wt.% and 15 wt.% of total metal loading were prepared by an impregnation-coprecipitation method. The influence of Cu atomic content on the catalytic performance was investigated on the steam reforming of ethanol (SRE) for H2 production and the catalysts were characterized by N2 adsorption, inductively coupled plasma (ICP), X-ray diffraction (XRD), transmission electron microscopy (TEM), temperature-programmed rerduction (TPR) and H2-pulse chemisorption techniques. The activity and products distribution behaviors of the catalysts were significantly affected by the doped Cu molar content based on the promotion effect on the dispersion of NiO particles and the interactions between Cu-Ni metal and CeO2 support. Significant increase in the ethanol conversion and hydrogen selectivity were obtained when moderate Cu metal was doped into the Ni/CeO2 catalyst. Over both of the 10Ni98.5Cu1.5/CeO2 and 15Ni98.5Cu1.5/CeO2 catalysts, more than 80% of ethanol conversion and 60% of H2 selectivity were obtained in the ethanol steam-reforming when the reaction temperature was above 450 ℃.     

Role of cerium dopants in MoVNbO multi-metal oxide catalysts for selective oxidation of ethane

The effect of Ce on the structure of MoVNbCeO multi-metal oxide catalysts and the performance of ethane selective oxidation was investigated. These multi-metal oxide catalysts with superior oxidizability exhibit high catalytic activity, and vanadium acts as the active center for ethane oxidation reaction. The improved catalytic activity is related to the increased V⁵⁺ content on the catalyst surface, which results from the enhanced transformation of the electrons between V and Ce. Moreover, Ce effectively promotes oxygen adsorption, activation, and mobility. And the presence of Ce can also prevent MoO₃ formation and stabilize the Mo₅O₁₄-like structure. In addition, the catalyst with a moderate amount of Ce exhibits outstanding catalytic performance. Especially, the MVN-Ce catalyst with a Ce/V ratio of 0.1 exhibits the best performance: the total selectivity of the catalyst toward C₂H₄ and CH₃COOH is the highest (72%) at the ethane conversion of 31%. Therefore, MoVNbCeO multi-metal oxides are promising candidates for selective oxidation.     

Influence of preparation method on performance of Ni-CeO2 catalysts for reverse water-gas shift reaction

This study investigated 1 wt.% Ni-CeO₂ catalysts that were prepared using co-precipitation, deposition-precipitation, and impregnation methods for the reverse water-gas shift (RWGS) reaction. Characterizations of the catalyst samples were conducted by Brumauer-Emmett-Teller (BET), atomic absorption spectrophotometer (AAS), X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM) and temperature programmed reduction (TPR). The results showed that the Ni-CeO₂ catalyst prepared using the co-precipitation method exhibited the best catalytic performance. In the Ni-CeO₂ catalyst prepared using co-precipitation method, a combination of highly dispersed NiO and abundant oxygen vacancies was assumed to play a crucial role in determining the catalytic activity and selectivity of the RWGS reaction.     

氯化稀土改性Ag/CaCO3催化剂对丙烯环氧化反应的影响

本文对用氯化稀土改性Ag/CaCO3催化剂催化丙烯直接环氧化反应进行了研究,实验结果表明加入改性剂后,催化剂活性大幅度降低,但其对环氧丙烷(PO)的选择性明显增加,总的对PO的收率提高。催化剂的活性、选择性与催化剂的组成、反应温度、接触时间以及原料组成有很大关系。在富氧和富烯原料气中,催化剂的催化性能截然不同,在富氧原料气中由于在催化剂表面易形成氯化银而使催化剂对PO的选择性随反应时间急剧下降;在富烯原料气中进行反应则随反应时间变化不大。