Cu/Zn/Al/Mn催化剂上CO/CO2加氢合成甲醇特性研究

利用共沉淀法制备了四组分的Cu-Zn-Al-Mn和Cu-Zn-Al-Ce催化剂以及三组分的Cu-Zn-Al催化剂。利用组成H2/CO/CO2/N2=66/27/3/4(体积比)的富CO原料气对催化剂进行了活性评价，并研究了温度、压力和空速等反应条件对催化剂活性的影响。结果发现添加适量的锰助剂能显著提高催化剂的活性和热稳定性。利用SEM和XRD方法进行了催化剂的结构和形貌表征，同样表明锰助剂可以起到阻止CuO晶粒长大和促进CuO分散作用。利用富CO2的生物质原料气体积比为H2/CO/CO2/N2=50/25/20/5对Cu-Zn-Al-Mn催化剂进行的评价表明：Cu-Zn-Al-Mn催化剂上CO/CO2加氢合成甲醇的甲醇产率和选择性均有下降，在试验范围内，甲醇产率下降11％～25％，选择性为93％～95％。     

光照对Pt/Al2O3光热CO2加氢反应的增强作用（英文）

在传统热催化材料的研究领域中,光照技术已经得到了广泛的应用,从而使传统热催化剂的催化反应活性和选择性得到优化.然而,在光热协同催化反应过程中,光照因素对催化反应过程的影响尚未得到很好地研究和理解.本文通过浸渍法制得Pt/Al2O3催化剂,并应用于光热协同催化CO2加氢反应.结果证明,在光热协同CO2加氢催化反应中, Pt/Al2O3催化剂表现出光热协同效应.本文结合原位漫反射红外光谱(operandoDRIFTS)和密度泛函理论计算(DFT)对光照因素对该催化反应过程的作用机制进行了进一步深入研究.结果表明, CO气体分子从Pt纳米颗粒上的脱附过程为CO2加氢反应的重要步骤;CO气体分子在Pt纳米颗粒上脱附的位置包含台阶位置(Ptstep)和平台位置(Ptterrace).结果表明,反应过程中CO气体分子从Pt表面的脱附有利于催化剂暴露出Pt反应活性位点.值得注意的是,在光热协同催化CO2加氢反应过程中,光照和温度因素对CO气体分子的脱附过程具有不同影响.吸附能的计算结果证明, CO气体分子吸附在Ptstep和Ptterrace上的吸附能分别为-1.24和-1.43eV.由此可见, CO气体分子与Pt纳米颗粒上的Ptstep吸附位点之间相互作用更强.在无光照作用的条件下对催化剂进行加热, CO气体分子更容易从Ptterrace吸附位点发生脱附;但是在对应的温度下加入光照作用后,吸附在Ptstep位点上的CO气体分子会先转移到Ptterrace吸附位点上,随后脱附,从而促进CO2加氢反应的进行.     

Effects of pretreatment and reduction on the Co/Al2O3 catalyst for CO hydrogenation

The purpose of this study was to investigate the effect of preadsorbed CO at different temperatures, calcination temperatures, the combined influence of reduction temperature and time, and pretreatment using hydrogen or syngas as reduction agents on the F-T synthesis （FTS） activity and selectivity of Co/Al2O3 catalyst. The reactivity of the carbon species at higher preadsorption temperature with H2 in TPSR decreased, whereas the carbon-containing species showed higher reactivity over Co/Al2O3 catalyst with low calcination temperature. This agreed well with the order of catalytic activity for F-T synthesis on this catalyst. The catalytic activity of the catalyst varied with reduction temperature and time remarkably. CODEX optimization gave an optimum reduction temperature of 756 K and reduction time of 6.2 h and estimated C5＋ yield perfectly. The pretreatment of Co/Al2O3 catalyst with different reduction agents （hydrogen or syngas） showed important influences on the catalytic performance. A high CO conversion and C5＋ yield were obtained on the catalyst reduced by hydrogen, whereas methane selectivity on the catalyst reduced by syngas was much higher than that on the catalyst reduced by hydrogen.     

Effect of reaction conditions and kinetic study on the Fischer-Tropsch synthesis over fused Co-Ni /Al_2O_3 catalyst

Co-Ni/Al2O3catalyst was prepared by the fusion method and used in Fischer-Tropsch synthesis(FTS).The catalysts were characterized by means of nitrogen sorption and scanning electron microscopy.The effect of some reaction conditions such as temperature,pressure and H2/CO feed ratio on the catalytic performance of Co-Ni/Al2O3in CO hydrogenation was investigated in a fixed-bed reactor.The results indicate that the optimum reaction conditions are 250℃,0.3 MPa,H2/CO feed ratio of 2.0,and GHSV of 3 000 h-1.Kinetically,the reaction rate was correlated with the Langmuir-Hinshelwood-Hougen-Watson type models.The activation energy for the best fitted model is 88.41 kJ/mol,suggesting that the intra-particle mass transport is not significant.     

Ni/Al2O3-SiO2催化剂对C4单烯烃加氢的催化性能

利用XRD、H2 TPR和孔结构的分析对C4馏分加氢催化剂Ni/Al2O3 SiO2进行了表征,在固定床反应器内对催化剂的活性进行了评价,并对加氢机理进行了讨论。结果表明,在Ni/Al2O3 SiO2催化剂表面至少存在两种活性中心,分别由体相NiO和高度分散的NiO还原产生。研制的催化剂对C4馏分加氢具有很高的活性和良好的稳定性,进口温度18.6℃时就可进行加氢,属于低温型加氢催化剂。在 C4单烯烃质量分数为74.85%、加氢压力为2.0MPa~2.7MPa、液时空速为1.0h－1~2.0h－1、氢油体积比为 300~450下,原料中单烯烃转化率在98%以上。催化剂连续运行342h,其活性基本保持不变。     

H2-induced CO adsorption and dissociation over Co/Al2O3 catalyst

The activation of adsorbed CO is an important step in CO hydrogenation. The results from TPSR of pre-adsorbed CO with H2 and syngas suggested that the presence of H2 increased the amount of CO adsorption and accelerated CO dissocia-tion. The H2 was adsorbed first, and activated to form H* over metal sites, then reacted with carbonaceous species. The oxygen species for CO2 formation in the presence of hydrogen was mostly OH*, which reacted with adsorbed CO subsequently via CO*+OH* → CO2*+H*; however, the direct CO dissociation was not excluded in CO hydrogenation. The dissociation of C-O bond in the presence of H2 proceeded by a concerted mechanism, which assisted the Boudourd reaction of adsorbed CO onthe surface via CO*+2H* → CH*+OH*. The formation of the surface species (CH) from adsorbed CO proceeded as indicated with the participation of surface hydrogen, was favored in the initial step of the Fischer-Tropsch synthesis.     

Liquid phase hydrogenation of naphthalene in the presence of CO over supported Ni catalyst

The liquid phase hydrogenation of naphthalene was performed in the presence of CO over a commercial Ni/SiO₂-Al₂O₃ catalyst. Naphthalene was hydrogenated even in the presence of CO at elevated temperatures, accompanying the hydrogenation of CO. Two activation energy values were obtained for the naphthalene hydrogenation depending on the reaction temperature. FT-IR measurement of the adsorbed CO was also carried out. Hydrogenation of the adsorbed CO created sites active for naphthalene hydrogenation.     

Pd-Cu-Clx/Al2O3催化剂对CO氧化的稳定性

CO催化氧化广泛应用于空气净化、机动车尾气治理和CO气体传感器中.在CO氧化催化剂设计与制备过程中,催化剂与使用环境密切相关.例如工业和机动车尾气净化需要在高温(200–600°C)下进行,而对于半密闭空间(隧道或者地下停车场)空气净化需要在室温和高相对湿度下进行.频繁冷启动导致半密闭空间CO浓度累积而超过排放控制标准,因此制备室温、高相对湿度下CO氧化催化剂是面临的重要问题之一.负载型Wacker催化剂对于CO低温催化氧化的研究一直受到广泛关注.环境中少量水的存在会促进负载型Wacker催化剂对CO的低温氧化性能,但随着水沉积量的增加,活性位点将被覆盖,并且Pd和Cu活性组分之间的紧密结构被破坏,从而导致催化剂的失活,即催化剂的稳定性变差.因此,为了提高催化剂在高相对湿度下的稳定性,利用二乙氧基二甲基硅烷对Al2O3载体进行硅烷化处理,以增加载体的疏水性,考察载体疏水改性对CO低温氧化过程中催化剂稳定性的影响.催化剂的稳定性测试结果表明,在0°C,100%相对湿度条件下,未改性催化剂在约20 h内CO转化率由81%下降到50%;载体硅烷化后制备的催化剂在反应进行150 h后,CO转化率仍保持在78%,即反应活性未见降低.由此表明催化剂载体经有机硅烷改性后,可显著增强催化剂在低温、高相对湿度下的稳定性.N2吸附/脱附和水吸附实验结果表明,载体硅烷化改性并未对催化剂的比表面积产生影响,但显著降低了催化剂上水沉积速度和沉积量,未改性催化剂的初始吸水速度是改性后催化剂的4倍,但改性后催化剂的饱和吸水率仅占未改性催化剂的1/3.X射线衍射结果表明,载体预处理后活性物种Cu2(OH)3Cl晶粒尺寸有所增加.氢气程序升温还原、X射线光电子能谱结果表明,载体硅烷化预处理改善了催化剂中Cu和Pd物种的化学分布及接触状态,增加了与Pd物种紧密接触的Cu物种的量,从而促进了Cu物种的还原.与此同时,载体硅烷化显著降低了催化剂表面Cl离子的浓度,从而影响到对CO吸附.为了进一步研究水与催化剂稳定性之间的关系,采用原位红外漫反射(In situ DRIFT)对催化剂进行表征.负载型Wacker催化剂对CO氧化反应机理为:Pd是CO氧化反应的活性中心,通过Pd和Cu物种之间的氧化还原循环来实现CO氧化,且Pd+比Pd2+具有更高的CO氧化性能.反应气氛中水的存在,有利于CO在Pd+上氧化、以及金属态Pd被Cu2+物种再氧化的过程,同时水也显著促进了催化剂表面碳酸盐的生成以及抑制了活性物种Pd+生成.与表面碳酸盐累积相比,水对于活性物种Pd+生成的抑制作用是导致催化剂活性降低的主要原因.     

NiW/Al_2O_3催化剂酸性与加氢活性的调变及对重油加氢脱氮性能的影响

以Ni、W为催化剂的活性金属组分,采用等体积浸渍法制备了NiW/Al2O3加氢脱氮催化剂,考察了Al2O3载体表面经硼酸修饰后对催化剂酸性的影响,以及活性金属与柠檬酸络合后对催化剂加氢反应性能的影响。NH3-TPD、HRTEM、H2-TPR、XPS等表征结果表明,Al2O3载体表面硼酸修饰增加了催化剂表面的中强酸量,减少了强酸量,且削弱了金属与载体之间的强相互作用,但活性中心数目减少。金属与柠檬酸络合可以减小活性相晶粒长度、提高活性相分散性及硫化程度。催化剂的反应评价结果表明,硼酸修饰与柠檬酸络合共同作用可以增强催化剂的重油加氢处理能力,促进芳环与胶质的加氢饱和;具有适宜的氢解与加氢活性,兼顾碱性氮与非碱性氮的脱除,体现了催化剂良好的重油加氢脱氮性能。     

Ni/Al2O3催化2-甲基呋喃加氢制2-甲基四氢呋喃性能的研究

采用浸渍法制备了不同NiO含量的Ni/Al₂O₃催化剂,并进行了2-甲基呋喃加氢制2-甲基四氢呋喃性能的考察。结果表明,在制备的NiO负载量为10%、20%、25%、30%和40%的Ni/Al₂O₃催化剂中,随着NiO负载量增加,加氢反应的选择性与2-甲基呋喃的转化率均呈现出先增加后减小的趋势。其原因是由于适当增加NiO负载量有利于催化剂表面活性中心的形成,有利于加氢反应的进行;但是过度负载的NiO容易堵塞Al₂O₃载体中的介孔通道,降低反应的转化率与选择性。在釜式反应器中进行反应,对加氢反应条件进行了优化,发现在反应压力为3 MPa、反应温度150℃、机械搅拌速率为1000 r/min时,Ni/Al₂O₃催化2-甲基呋喃加氢制2-甲基四氢呋喃具有较高的选择性。当NiO负载量为25%时,2-甲基四氢呋喃的选择性最高为97.1%,2-甲基呋喃的转化率达到99.4%。     

Co-Mo/Al2O3催化剂上裂解汽油中单烯烃加氢宏观动力学

采用绝热管式固定床积分反应器,在2.0MPa~4.0MPa、524K~644K、氢/裂解汽油摩尔比1.5~3.5和反应器入口环戊烯、3 乙基 1 戊烯、苯乙烯和1 己烯的分压分别为0.87kPa~5.60kPa、1.09kPa~7.01kPa、1.14kPa~7.35kPa和0.25kPa~0.97kPa下,对Co Mo/Al2O3催化剂上裂解汽油中单烯烃催化加氢的宏观动力学特性进行了系统研究。以Powell优化法和Merson迭代法对动力学实验数据进行非线性参数估值,建立了与实验数据吻合良好、裂解汽油中单烯烃催化加氢的幂函数型宏观动力学模型。其中,环戊烯、3 乙基 1 戊烯、苯乙烯和1 己烯的反应级数分别为1.725、0.685、0.7和0.655,对应的加氢反应宏观活化能依次为63455 J·mol－1, 61781 J·mol－1, 52105 J·mol－1和54181 J·mol－1。实验所用Co Mo/Al2O3催化剂对环戊烯、3 乙基 1 戊烯和苯乙烯加氢具有明显的催化作用,对1 己烯加氢具有一定的催化作用,但对1 庚烯加氢基本无催化活性。加氢反应压力控制在3.5MPa左右更为适宜。     

Infrared spectroscopic study on the reaction mechanism of CO hydrogenation over Pd/CeO2

In situ infrared spectroscopy was applied to elucidate the reaction mechanism of CO hydrogenation over Pd/CeO₂. Instead of direct dissociation of CO, a new reaction pathway is proposed for methane formation, involving geminal dicarbonyl intermediates and (HCO)₂(a) intermediates, which may be located on the surface of Pd covered with thin layers of reduced ceria (SMST effect). Transformation of methane formation sites into methanol formation ones by the oxidation with water vapor formed during the CO-H₂ reaction is proposed, which may be located on the Pd (111) planes adjacent to ceria support.     

H2-induced CO adsorption and dissociation over Co/Al2O3 catalyst

The activation of adsorbed CO is an important step in CO hydrogenation. The results from TPSR of pre-adsorbed CO with H2 and syngas suggested that the presence of H2 increased the amount of CO adsorption and accelerated CO dissociation. The H2 was adsorbed first, and activated to form H＊ over metal sites, then reacted with carbonaceous species. The oxygen species for CO2 formation in the presence of hydrogen was mostly OH^＊, which reacted with adsorbed CO subsequently via CO^＊＋OH^＊ → CO2^＊＋H^＊; however, the direct CO dissociation was not excluded in CO hydrogenation. The dissociation of C-O bond in the presence of H2 proceeded by a concerted mechanism, which assisted the Boudourd reaction of adsorbed CO on the surface via CO^＊＋2H^＊ → CH^＊＋OH^＊. The formation of the surface species （CH） from adsorbed CO proceeded as indicated with the participation of surface hydrogen, was favored in the initial step of the Fischer-Tropsch synthesis.     

KOH修饰Au/Al2O3催化剂的低温CO氧化催化反应性能

采用等体积浸渍法制备了KOH-Au/Al<,2>O<,3>系列催化剂,考察了催化剂对低温CO氧化反应的初始活性和干、湿气氛下连续反应的稳定性能,并用电感耦合等离子发射光谱、红外光谱、高分辨透射电镜、紫外漫反射光谱等技术对催化剂进行了结构表征.结果表明:与母体催化剂(Au/Al<,2>O<,3>)相比,修饰催化剂(KOH...     

CO_2加氢制甲醇用高活性和高选择性催化剂的研制

研制了一种CO2加氢制甲醇用高活性和高选择性催化剂Cu-ZnO-Al2O3(简记为RK-11),测定了其催化性能.结果表明,当原料气组成(体积分数)为68.5%H2、2.0%CO、20.5%CO2、9.0%N2,温度为240℃,气体时空速度GHSV=6 000h-1,压力为8.0MPa时,CO2转化率达35.2%,CO转化率达39.8%,甲醇的时空产率达686.1g/(L·h),而甲醇在产物中的选择性达99.3%.     

负载型Cu/Al2O3和Cu/ZnO催化剂上CO2加氢的原位FTIR及准原位XPS/HS-LEIS研究

铜基催化剂是工业合成甲醇中常用的催化剂,其主要包含Cu,ZnO,Al2O3三种组分,研究各组分在催化合成甲醇过程中的本质作用及其相互间的协同作用不仅是一个催化基础科学问题,同时对于设计和合成新型高性能的铜基催化剂也有重要指导作用.以往的研究主要针对Cu和ZnO二元组分,关于Al2O3的作用很少有报道,主要观点认为Al2...     

Partial hydrogenation of adiponitrile to 6-aminocapronitrile over Ni/α-Al_2O_3 catalyst promoted with K_2O and La_2O_3

A novel K2O and La2O3 promoted nickel catalyst supported on a-Al2O3 was prepared by co-impregnation method, and it exhibited higher activity and 6-aminocapronitrile selectivity than Ni/a-Al2O3 during the hydrogenation of adiponitrile in the absence of ammonia, i.e., K2O and La2O3 improved the performance of the nickel-based catalyst.     

Study of CO2 Hydrogenation to Methanol over Cu-V/γ-Al2O3 Catalyst

The effect of vanadium addition to Cu/γ-Al2O3 catalyst used in the hydrogenation of CO2 to produce methanol was studied. It was found that the catalytic performance of the Cu-based catalyst improved after V addition. The influence of reaction temperature, space velocity and the molar ratio of H2 to CO2 on the performance of 12%Cu-6%V/γ-Al2Oa catalyst were also studied. The results indicated that the best conditions for reaction were as follows: 240 ℃, 3600 h-1 and a molar ratio of H2 to CO2 the dispersion of the supported CuO species, which resulted in the enhanced catalytic performance of Cu-V/γ-Al2O3 binary catalyst.     

La2O3对Ni-Mo/γ-Al2O3催化剂CO和CO2甲烷化的影响

采用浸渍法制备了一系列Ｎｉ－Ｍｏ－Ｌａ／γ－Ａｌ２Ｏ３催化剂并测定了催化剂的ＣＯ和ＣＯ２甲 化活性采用ＴＥＭ,ＸＰＳ和ＣＯ化学吸附等手段研究了表面性质。结果表明,Ｌａ２Ｏ３的咖入提高了Ｎｉ－Ｍｏ／γ／Ａｌ２Ｏ３催化剂的ＣＯ和ＣＯ２甲烷化活性,增加了催化剂中Ｎｉ的分散度,活性表面积及催化剂表面Ｎｉ原子的浓度,降低了电子结合能。