Co基费托合成催化剂载体的研究进展

综述了近年来钴(Co)基催化剂载体在费托合成反应中的研究进展.重点评述了柱撑蒙脱土、新型介孔分子筛等载体对钴基催化剂活性和选择性等方面的影响,概述了Co/Al_2O_3催化剂在费托合成反应中的催化机理,对今后Co基费托合成催化剂的研究提出了一点建议.     

不同硅铝比Co/ZSM-5催化剂对费托合成汽油馏分烃选择性的调控

以ZSM-5分子筛为载体,通过等体积浸渍法制备了Co/ZSM-5系列催化剂,用于费托合成反应一步法制汽油馏分烃(C_5~C_(11)烷烃)。考察了不同硅铝比(Si O_2/Al_2O_3=25,38,50,80和200)的ZSM-5分子筛对Co/ZSM-5催化剂费托合成汽油馏分选择性的影响。采用氮气物理吸附-脱附、X射线衍射、氢气程序升温还原(H_2-TPR)和氨气程序升温脱附(NH_3-TPD)等手段对载体和催化剂进行了表征,并在高压固定床反应器上对催化剂的费托合成催化性能进行了测试。结果表明,对比Co/ZSM-5(Si O_2/Al_2O_3=25,38,50和80)催化剂,Co/ZSM-5(Si O_2/Al_2O_3=200)催化剂表现出最高的汽油馏分烃类选择性,高达52.8%,这主要归功于Co/ZSM-5(Si O_2/Al_2O_3=200)催化剂上较小钴颗粒尺寸、较优的还原性能以及适量弱酸位的协同作用。分子筛的酸性为催化剂的加氢裂解转化提供活性位,促进重质烃产物发生裂解和异构等二次反应,较小的钴颗粒尺寸和较优的还原性能有利于提高C_5~+烃选择性。     

不同硅铝比Co/ZSM-5催化剂对费托合成汽油馏分烃选择性的调控

以ZSM-5分子筛为载体,通过等体积浸渍法制备了Co/ZSM-5系列催化剂,用于费托合成反应一步法制汽油馏分烃(C_5^C_(11)烷烃)。考察了不同硅铝比(Si O_2/Al_2O_3=25,38,50,80和200)的ZSM-5分子筛对Co/ZSM-5催化剂费托合成汽油馏分选择性的影响。采用氮气物理吸附-脱附、X射线衍射、氢气程序升温还原(H_2-TPR)和氨气程序升温脱附(NH_3-TPD)等手段对载体和催化剂进行了表征,并在高压固定床反应器上对催化剂的费托合成催化性能进行了测试。结果表明,对比Co/ZSM-5(Si O_2/Al_2O_3=25,38,50和80)催化剂,Co/ZSM-5(Si O_2/Al_2O_3=200)催化剂表现出最高的汽油馏分烃类选择性,高达52.8%,这主要归功于Co/ZSM-5(Si O_2/Al_2O_3=200)催化剂上较小钴颗粒尺寸、较优的还原性能以及适量弱酸位的协同作用。分子筛的酸性为催化剂的加氢裂解转化提供活性位,促进重质烃产物发生裂解和异构等二次反应,较小的钴颗粒尺寸和较优的还原性能有利于提高C_5C_(11)烷烃)。考察了不同硅铝比(Si O_2/Al_2O_3=25,38,50,80和200)的ZSM-5分子筛对Co/ZSM-5催化剂费托合成汽油馏分选择性的影响。采用氮气物理吸附-脱附、X射线衍射、氢气程序升温还原(H_2-TPR)和氨气程序升温脱附(NH_3-TPD)等手段对载体和催化剂进行了表征,并在高压固定床反应器上对催化剂的费托合成催化性能进行了测试。结果表明,对比Co/ZSM-5(Si O_2/Al_2O_3=25,38,50和80)催化剂,Co/ZSM-5(Si O_2/Al_2O_3=200)催化剂表现出最高的汽油馏分烃类选择性,高达52.8%,这主要归功于Co/ZSM-5(Si O_2/Al_2O_3=200)催化剂上较小钴颗粒尺寸、较优的还原性能以及适量弱酸位的协同作用。分子筛的酸性为催化剂的加氢裂解转化提供活性位,促进重质烃产物发生裂解和异构等二次反应,较小的钴颗粒尺寸和较优的还原性能有利于提高C_5⁺烃选择性。     

金属与载体间相互作用及对CO加氢反应的影响

金属钴与载体间相互作用会显著影响催化剂分散度等特性,对调变费托合成反应性能具有重要意义。综述了近年来在金属钴与SiO_2、SiO_2-Al_2O_3载体间相互作用领域的研究进展,为进一步调控催化剂的结构和性能研究提供参考。     

Co/Al_(2)O_(3)固定床费托合成催化剂水热稳定性研究

考察不同水热条件对Al_(2)O_(3)载体、Co/Al_(2)O_(3)催化剂稳定性的影响。表征结果表明,在苛刻水热条件下,即使高温焙烧的Al_(2)O_(3)载体也存在水热不稳定性现象。在接近工业固定床费托合成条件下运行,蛋壳型Co/Al_(2)O_(3)催化剂水热稳定性好。少量Co、Si改性能明显提高载体水热稳定性。     

钛助剂引入方式对钴基费托合成催化剂性能的影响

在费托合成反应中,Ti通常起到助剂的作用,Ti的加入能够有效的改变催化剂的物理化学性质,进而改变催化剂费托合成反应的活性及选择性。本文研究了Ti的引入方式对钴基费托合成催化剂催化性能的影响。制备了Ti修饰载体Al2O3的钴基费托合成催化剂Co3/Ti-Al2O3和Ti修饰活性组分前驱体的钴基费托合成催化剂Co3-Ti/Al2O3,分别对其进行了FT-IR、BET、TG、XRD、TPR、TPD、TEM等表征,并研究了其费托催化性能。结果表明,以两种不同方式引入助剂钛后得到的两个催化剂Co3/Ti-Al2O3和Co3-Ti/Al2O3的选择性和活性情况基本一致。     

氧化铝载体孔结构对长链正构烷烃(C_(16)～C_(19))脱氢Pt-Sn-K/Al_2O_3催化剂性能的影响

通过N_2吸附-脱附法对4种Al_2O_3载体进行孔结构表征,采用等体积真空浸渍法制备Pt质量分数0.5%的Pt-Sn-K/Al_2O_3催化剂,以直链烷烃C_(16)~C_(19)脱氢反应为探针,考察Al_2O_3载体孔结构对催化剂脱氢性能的影响。结果表明,催化剂载体的孔容、平均孔径和比表面积之间存在相互制约的关系。载体孔容和平均孔径大,则其比表面积相对较小。对于直链烷烃C_(16)~C_(19)脱氢催化剂,较大孔容、孔径和一定比表面积的Al_2O_3载体为最佳,孔容和孔径较小的催化剂脱氢活性和稳定性较差。     

Ni负载量对煤油水重整制氢催化剂性能的影响

采用等体积分步浸渍法,以γ-Al_2O_3为载体制备NiLaLi/Al_2O_3催化剂,并在自制装置研究不同Ni负载量对NiLaLi/Al_2O_3催化剂催化性能的影响。采用SEM及BET对NiLaLi/Al_2O_3催化剂的形貌及结构进行表征。结果表明,NiLaLi/Al_2O_3催化剂对煤油水重整制氢有较好的催化性能,并且NiLaLi/Al_2O_3催化剂的比表面积和孔容随着Ni负载量的增大而减小。当Ni的负载质量分数为10%时,煤油水重整制氢的平均氢产率为12.75mol·mol~(-1)。     

费托合成催化剂载体的研究进展

综述了近年来费托合成催化剂载体的研究进展.主要评述了孔结构、比表面积、表面酸性、机械强度和热稳定性等因素在铁、钴基催化剂制备过程中对催化剂活性、寿命和选择性控制等方面的影响,分析了费托合成中催化剂载体的效应及各类载体的特点,并对今后催化剂的研究提出了相关建议.     

铁基费托合成催化剂研究进展

综述了近十年来铁基催化剂在费托合成反应中的研究进展,探讨了铁基催化剂活性组分的确定及影响铁基催化剂活性组分的因素,对比了3种催化剂制备方法（熔融法、沉淀法、负载法）和5种催化剂载体（氧化物、分子筛、碳材料、双孔材料和核壳材料）对费托合成反应性能的影响,从反应活性、选择性和反应稳定性3个方面阐述了助催化剂在费托合成反应中的作用。分析认为：碳化铁是铁基费托合成催化剂的活性组分;在铁基催化剂的制备过程中,选择适宜的制备方法、载体、助催化剂,可以达到提高费托合成反应活性、目的产物选择性和反应稳定性的效果。提出合成特定结构碳化铁、进一步研究铁基催化剂反应机理仍是未来研究的重点。     

Ni/Al_2O_3催化剂的CO_2-TPD表征

Ni/Al_2O_3催化剂是甲烷二氧化碳重整反应制取合成气研究最多、最具应用潜力的一种催化剂。通过对催化剂进行CO_2-TPD研究,考察还原态Ni/Al_2O_3催化剂的CO_2脱附特性。结果表明,浸渍法制备的Ni/Al_2O_3催化剂CO_2脱附曲线呈现双峰,分别在(60~65)℃和(350~380)℃出现高低温两个活性位;高温CO_2吸附量为3.0 cm~3·g~(-1),低温CO_2吸附量为24.0 cm~3·g~(-1)。催化剂的CO_2吸附量与其Ni含量无关。考察选用不同载体的CO_2脱附行为,发现以Al_2O_3为载体的催化剂CO_2吸附量是MgO和SiO_2为载体催化剂的2~4倍,以TiO_2为载体的催化剂几乎不吸附CO_2。     

乙二胺四乙酸对NiMo/Al_2O_3催化剂加氢脱氮性能的影响

以氧化铝为载体,Ni和Mo为金属活性组分,添加不同含量乙二胺四乙酸,采用等体积浸渍法制备系列Ni Mo(x)/Al_2O_3(x为乙二胺四乙酸与Ni物质的量比)重质油加氢处理催化剂,考察乙二胺四乙酸加入量对催化剂加氢脱氮性能的影响,并采用N_2物理吸附-脱附、XRD和HRTEM等对催化剂进行表征。结果表明,乙二胺四乙酸的加入增强了金属组分与氧化铝载体间的相互作用,降低了MoS_2活性相的堆垛层数和片层长度,促进了活性相的分散。乙二胺四乙酸与Ni物质的量比为0.5时,MoS_2活性相堆垛层数和片层长度达到良好的结合,对应的催化剂Ni Mo(0.5)/Al_2O_3具有最优的加氢脱氮性能。     

Support effects on the catalytic behavior of NiO/Al2O3 for oxidative dehydrogenation of ethane to ethylene

Six representative Al₂O₃ supports with different specific surface areas and pore volumes were used to prepare NiO/Al₂O₃ catalysts with two NiO loadings. Oxidative dehydrogenation of ethane (ODE) to ethylene was investigated over these catalysts. The yield of ethylene was found to be approximately proportional to the pore volume/surface area ratio of the support used for that catalyst. X-ray diffraction analysis (XRD), TEM and H₂-TPR were employed to characterize their structure differences. It was found that the physical properties of the Al₂O₃ supports were crucial to the dispersion of NiO. More large crystal NiO was found on the Al₂O₃ supports with lower pore volume, while more highly dispersed NiO was formed on the Al₂O₃ supports with higher pore volume. An interpretation based on the pore volume of the supports and the physical properties of salt precursors was proposed.     

Catalytic performance of a novel ceramic-supported vanadium oxide catalyst for NO reduction with NH3

A novel TiO₂/Al₂O₃/cordierite honeycomb-supported V₂O₅–MoO₃–WO₃ monolithic catalyst was studied for the selective reduction of NO with NH₃. The effects of reaction temperature, space velocity, NH₃/NO ratio and oxygen content on SCR activity were evaluated. Two other V₂O₅–MoO₃–WO₃ monolithic catalysts supported on Al₂O₃/cordierite honeycomb or TiO₂/cordierite honeycomb support, two types of pellet catalysts supported on TiO₂/Al₂O₃ or Al₂O₃, as well as three types of pellet catalysts V₂O₅–MoO₃–WO₃–Al₂O₃ and V₂O₅–MoO₃–WO₃–TiO₂ were tested for comparison. The experiment results show that this catalyst has a higher catalytic activity for SCR with comparison to others. The results of characterization show, the preparation method of this catalyst can give rise to a higher BET surface area and pore volume, which is strongly related with the highly active performance of this catalyst. At the same time, the function of the combined carrier of TiO₂/Al₂O₃ cannot be excluded.     

Selective catalytic reduction of NO by C3H8 over CoOx/Al2O3: An investigation of structure–activity relationships

A series of CoO_x/Al₂O₃ catalysts was prepared, characterized, and applied for the selective catalytic reduction (SCR) of NO by C₃H₈. The results of XRD, UV–vis, IR, Far-IR and ESR characterizations of the catalysts suggest that the predominant oxidation state of cobalt species is +2 for the catalysts with low cobalt loading (≤2 mol%) and for the catalysts with 4 mol% cobalt loading prepared by sol–gel and co-precipitation. Co₃O₄ crystallites or agglomerates are the predominant species in the catalysts with high cobalt loading prepared by incipient wetness impregnation and solid dispersion. An optimized CoO_x/Al₂O₃ catalyst shows high activity in SCR of NO by C₃H₈ (100% conversion of NO at 723 K, GHSV: 10,000 h⁻¹). The activity of the selective catalytic reduction of NO by C₃H₈ increases with the increase of cobalt–alumina interactions in the catalysts. The influences of cobalt loading and catalyst preparation method on the catalytic performance suggest that tiny CoAl₂O₄ crystallites highly dispersed on alumina are responsible for the efficient catalytic reduction of NO, whereas Co₃O₄ crystallites catalyze the combustion of C₃H₈ only.     

Role of CeO2 in Ni/CeO2–Al2O3 catalysts for carbon dioxide reforming of methane

Ni catalysts supported on γ-Al₂O₃, CeO₂ and CeO₂–Al₂O₃ systems were tested for catalytic CO₂ reforming of methane into synthesis gas. Ni/CeO₂–Al₂O₃ catalysts showed much better catalytic performance than either CeO₂- or γ-Al₂O₃-supported Ni catalysts. CeO₂ as a support for Ni catalysts produced a strong metal–support interaction (SMSI), which reduced the catalytic activity and carbon deposition. However, CeO₂ had positive effect on catalytic activity, stability, and carbon suppression when used as a promoter in Ni/γ-Al₂O₃ catalysts for this reaction. A weight loading of 1–5 wt% CeO₂ was found to be the optimum. Ni catalysts with CeO₂ promoters reduced the chemical interaction between nickel and support, resulting in an increase in reducibility and stronger dispersion of nickel. The stability and less coking on CeO₂-promoted catalysts are attributed to the oxidative properties of CeO₂.     

Preparation and structural characterization of Co/Al2O3 catalysts for the ozonation of pyruvic acid

A series of Co/Al₂O₃ catalysts were prepared by the incipient wetness impregnation method using γ-Al₂O₃ support and (CH₃COO)₂Co·4H₂O solutions, followed by calcination at 500–800 °C. Characterization of catalysts was accomplished by several techniques such as thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), physisorption of nitrogen, mercury and helium-based pycnometries, Fourier transform-infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and pH of zero charge (PZC). Impregnation of support produced a moderate decrease of its surface area and pore volume and also led to minor changes of its PZC. Depending on preparation conditions (i.e., calcination atmosphere and temperature and metal loading), one or more of the following Co-containing compounds were identified: CoO, Co₃O₄ and CoAl₂O₄. The support and prepared Co/Al₂O₃ catalysts were tested to catalyze the ozonation of aqueous pyruvic acid at pH 2.5. Pyruvic acid was shown refractory towards single ozonation but the use of γ-Al₂O₃ and Co/Al₂O₃ catalysts resulted in 56–96% pyruvic acid conversion and 41–78% decrease in DOC after 2 h of ozonation of phosphate-buffered solutions. In the absence of the buffer, conversion rate was enhanced likely as a result of pH increase during the course of the process thus giving rise to the indirect way of ozonation through hydroxyl radicals. Acetic acid was found as the main by-product of pyruvic acid ozonation. Depending on the catalyst used, yield of acetic acid varied from 32 to 49%, values noticeably lower that that obtained from the control non-catalytic ozonation experiment (73%). Differences in catalytic activity amongst the various Co/Al₂O₃ catalysts investigated were attributed to the different Co active phases deposited on the γ-Al₂O₃ surface. The following sequence of increasing activity can be inferred from experimental results: CoO, CoAl₂O₄ and Co₃O₄. All the Co/Al₂O₃ catalysts prepared showed good stability as the percentage of cobalt leached out was rather low.     

预处理对Ru/Al_2O_3催化马来酸二甲酯加氢影响

采用吸附-沉淀法制备负载Ru质量分数为1.0%的Ru/Al_2O_3催化剂,以马来酸二甲酯催化加氢合成丁二酸二甲酯为探针反应,详细考察预处理条件对Ru/Al_2O_3催化剂加氢性能的影响,并对其进行XRD、TEM和H2-TPR表征。结果表明,焙烧温度越高,催化剂催化活性越低;直接还原活化所得催化剂活性高于空气中焙烧后还原活化所得催化剂。以甲醇为溶剂,在70℃和1.0 MPa条件下,直接还原活化所得Ru/Al_2O_3催化剂上马来酸二甲酯转化率达100%,丁二酸二甲酯选择性约100%。相同时间内,空气焙烧后还原活化所得Ru/Al_2O_3催化剂上马来酸二甲酯转化率接近25%,继续延长反应时间,马来酸二甲酯转化率几乎不变。经高温焙烧还原后,活性组分Ru烧结;直接还原活化后,活性组分Ru高度分散。     

NiO/Al_2O_3基催化剂的TPR特性研究

NiO/Al_2O_3基催化剂用于替代贵金属催化剂,被广泛应用于石油和石化领域生产过程的加氢、脱硫和脱氮。采用TPR方法,研究不同Ni含量NiO/Al_2O_3及不同载体的催化剂还原特性。结果表明,NiO/Al_2O_3催化剂在10%H_2-Ar气氛下,还原温度范围较宽,为(300~800)℃,其中,(500~600)℃还原速率最大;随着NiO含量的增加,起始还原温度降低,还原耗氢量按比例增加;以MgO为载体的NiO催化剂还原呈现双峰特征,以SiO2和TiO2为载体的NiO催化剂的初始还原温度比NiO/Al_2O_3催化剂降低(100~200)℃。