Novel Ni/CeO2-Al2O3 composite catalysts synthesized by one-step citric acid complex and their performance in catalytic partial oxidation of methane

A series of novel Ni/CeO2-Al2O3composite catalysts were synthesized by one-step citric acid complex method. The as-synthesized catalysts were characterized by N2physical adsorption/desorption, X-ray diffraction(XRD), Fourier transform infrared(FT-IR) spectroscopy, hydrogen temperature-programmed reduction(H2-TPR), X-ray photoelectron spectroscopy(XPS) and thermogravimetry analysis(TGA). The effects of nickel content, calcination and reaction temperatures, gas hourly space velocity(GHSV) and inert gas dilution of N2on their performance of catalytic partial oxidation of methane(CPOM) were investigated. Catalytic activity test results show that the highest methane conversion(85%), the best selectivities to carbon monoxide(87%) and to hydrogen(95%), the excellent stability and perfect H2/CO ratio(2.0) can be obtained over Ni/CeO2-Al2O3with 8 wt% Ni content calcined at 700 ℃ under the reaction condition of 750 ℃, CH4/O2ratio of 2 : 1 and gas hourly space velocity of 12000 mL h-1 g-1. Characterization results show that the good catalytic performance of this composite catalyst can be contributed to its large specific surface area(～108 m2 g-1), small crystallite size, easy reducibility and low coking rate.     

Novel Ni/CeO2-Al2O3 composite catalysts synthesized by one-step citric acid complex and their performance in catalytic partial oxidation of methane

A series of novel Ni/CeO2-Al2O3composite catalysts were synthesized by one-step citric acid complex method. The as-synthesized catalysts were characterized by N2physical adsorption/desorption, X-ray diffraction(XRD), Fourier transform infrared(FT-IR) spectroscopy, hydrogen temperature-programmed reduction(H2-TPR), X-ray photoelectron spectroscopy(XPS) and thermogravimetry analysis(TGA). The effects of nickel content, calcination and reaction temperatures, gas hourly space velocity(GHSV) and inert gas dilution of N2on their performance of catalytic partial oxidation of methane(CPOM) were investigated. Catalytic activity test results show that the highest methane conversion(85%), the best selectivities to carbon monoxide(87%) and to hydrogen(95%), the excellent stability and perfect H2/CO ratio(2.0) can be obtained over Ni/CeO2-Al2O3with 8 wt% Ni content calcined at 700 ℃ under the reaction condition of 750 ℃, CH4/O2ratio of 2 : 1 and gas hourly space velocity of 12000 mL h-1 g-1. Characterization results show that the good catalytic performance of this composite catalyst can be contributed to its large specific surface area(～108 m2 g-1), small crystallite size, easy reducibility and low coking rate.     

助剂对甲烷部分氧化制合成气镍基催化剂性能的影响

考察了添加助剂铈、镧和钙对镍基催化剂反应性能的影响，发现助剂对以α-Al2O3为载体的镍基催化剂的调变作用比以γ-Al2O3为载体的镍基催化剂好，且助剂铈对催化剂的性能改善最好。在此基础上，研究了不同载量的铈对催化剂性能的影响。结果表明，铈的质量分数为1%时对催化剂的性能改善最好。同时采用XRD、XPS、TG等技术，研究了助剂铈对10％Ni/γ-Al2O3催化剂的改性作用。XRD分析表明，铈负载量较低时，催化剂中的CeO2高度分散在催化剂表面，铈负载量较高时，CeO2形成微晶颗粒，降低了催化活性。     

Yttria promoted metallic nickel catalysts for the partial oxidation of methane to synthesis gas

A metallic Ni catalyst was prepared with nickel sponge, followed by acid treatment. It was further promoted with yttria by an impregnation method. The catalysts were characterized by SEM, BET, XRD, TPR, XPS, etc., and studied in the partial oxidation of methane to syngas. The characterization results showed that the yttria promoted metallic Ni catalysts had high specific surface area and more NiO. The reaction results showed that the yttria promoter increased the CH4 conversion and the selectivity for H2 and CO.     

焙烧温度对甲烷催化部分氧化Ni/MgO-Al2O3催化剂结构和性能的影响

采用TPR、BET、XRD、TG及反应性能评价等研究方法,考察了焙烧温度对甲烷催化部分氧化制合成气Ni/MgO-Al2O3催化剂结构和性能的影响。研究结果表明,随焙烧温度的升高, Ni/MgO-Al2O3中的镍物种与载体作用逐渐增强,生成了NiAl2O4尖晶石和NiMgO2固熔体。虽然焙烧温度提高会使催化剂比表面降低,由于尖晶石结构的形成,其热稳定性会明显提高,将有利于抑制催化剂在反应过程中因烧结而失活的可能性。与低温焙烧的催化剂相比,高温焙烧的催化剂仍表现出良好催化反应性能,并具有相对较好的稳定性。高温焙烧的催化剂在反应过程中床层的热点温度相对较低,热点温度波动幅度也较小。低温和高温焙烧的Ni/MgO-Al2O3催化剂在常压、1 083 K、CH4与O2摩尔比为1.8、空速2.66×105 h－1的反应条件下均具有良好的抗积炭性能。     

还原方式及还原温度对甲烷部分氧化镍催化剂结构和反应性能的影响

采用H2 TPR、TEM及活性评价等手段,考察了还原方式（等温和程序升温还原）及还原温度对不同温度（550℃和950℃）焙烧制备的镍基催化剂结构和甲烷部分氧化反应性能的影响。结果表明,与程序升温还原方式相比,等温还原的催化剂中镍物种的还原度较低、Ni晶粒度较小。还原方式对550℃焙烧制备的催化剂（POM-1）的甲烷部分氧化反应性能影响不明显,但等温还原的催化剂反应过程中床层温度较低。随着等温还原温度的提高,POM-1催化剂的镍还原度有所降低,而950℃焙烧制备的催化剂（POM-5）还原度略有增加,且具有较小的镍晶粒。随着等温还原温度的提高,POM-1催化剂反应性能无明显差异,但床层热点温度提高;POM-5催化剂反应性能随还原温度的提高而提高,且床层温度呈现降低趋势。通过分析发现,催化剂床层温度与催化剂镍晶粒大小密切相关,较小的镍晶粒利于床层热点温度的降低,这与较大镍晶粒利于甲烷完全氧化反应有关。     

MgO助剂对甲烷部分氧化Ni/Al2O3催化剂结构和性能的影响

采用分步浸渍法制备了MgO改性的Ni/Al2O3催化剂,采用BET、XRD、H2 TPR、TEM和活性评价等研究方法,考察了MgO助剂对Ni/Al2O3催化剂物化性质和甲烷部分氧化制合成气反应性能的影响。实验结果表明,MgO助剂提高了催化剂镍物种的均一性,抑制了NiAl2O4尖晶石的形成,并且增强了镍物种与载体的相互作用,这与MgO、NiO形成固溶体及与Al2O3形成MgAl2O4有关。同时,适量的MgO助剂可以提高Ni物种在催化剂中分散度,并提高其有效利用率,改性后的催化剂在甲烷部分氧化反应中显示出较好的反应性能。过量的MgO助剂对催化剂的反应性能产生负面影响,MgO的碱性可以促进逆水煤气变换反应,从而导致H2选择性降低和CO选择性提高。     

制备方法对Ni/CeO2-Al2O3催化剂甲烷部分氧化催化性能的影响

采用浸渍-沉淀法、水热合成法、共沉淀法和柠檬酸络合法制备了Ni/CeO₂-Al₂O₃催化剂,考察了制备方法对该催化剂的物理结构和甲烷部分氧化(POM)催化性能的影响。利用N₂物理吸附、X射线粉末衍射(XRD)、H₂-程序升温还原(H₂-TPR)、NH₃-程序升温脱附(NH₃-TPD)、热重(TG)分析等手段对反应前后催化剂的物理化学性质进行了表征。实验结果表明,浸渍-沉淀法制备催化剂的活性和产物H₂和CO的选择性最低。而柠檬酸络合法制备的Ni/CeO₂-Al₂O₃表现出最大的CH₄转化率和最高的CO、H₂选择性。BET和XRD表征结果表明,柠檬酸络合法制备的Ni/CeO₂-Al₂O₃的比表面积最大,且CeO₂晶粒粒径小、分散均匀;H₂-TPR测试表明,该催化剂负载的Ni物种和Ni与Al₂O₃相互作用产生的尖晶石NiAl₂O₄都较容易被还原成金属Ni,产生更多的活性中心;NH₃-TPD和TG分析表明,该催化剂具有较多酸性位点和表面积炭,但相比较于它的高反应活性,积炭速率较低、稳定性较高。     

碱土Sr对Co/Al2O3催化剂甲烷部分氧化反应的影响

以γ-Al₂O₃为载体,采用共浸渍法制备了Sr-Co/Al₂O₃系列催化剂,研究了助剂Sr对Co/Al₂O₃催化剂上甲烷部分氧化(POM)制合成气反应的影响,并利用N₂物理吸附、X射线衍射、H₂-程序升温还原和热重等技术对催化剂的理化性质进行了表征。结果表明,未添加助剂的Co/Al₂O₃和800℃焙烧的Sr-Co/Al₂O₃催化剂在POM反应初期催化活性很低,然而,当添加Sr的质量分数高于2%时,催化剂表现出很好的催化活性和稳定性。焙烧后的新鲜催化剂上主要存在两类Co物种,一类是与载体相互作用较弱、易被H₂还原为单质的Co₃O₄;另一类是与载体相互作用较强、难还原、无催化活性的CoAl₂O₄尖晶石。在焙烧过程中,Sr易形成Sr₄Al₁₄O₂₅,从而削弱Co与Al₂O₃之间的相互作用,能在一定程度上抑制CoAl₂O₄物种的形成,提高催化剂的稳定性和活性。未添加Sr的Co/Al₂O₃在反应时易发生物相改变生成尖晶石,导致催化剂迅速失活;但当焙烧温度达到800℃时,添加有限量的Sr还是无法阻止CoAl₂O₄的产生。     

CeO2、CaO助剂对甲烷部分氧化制合成气Ni/MgOAl2O3催化剂结构和性能的影响

采用BET、H2 TPR、XRD、TEM和活性评价等表征手段，考察了CeO2、CaO助剂对Ni/MgOAl2O3催化剂物化性质和甲烷部分氧化制合成气反应性能的影响。实验结果表明，单独加入CeO2或CaO助剂可以改善Ni/ MgOAl2O3催化剂中镍物种的还原性能，以CaO尤为明显；CaO作为结构助剂可以降低还原态催化剂中的镍晶粒尺寸，使改性的催化剂具有较好的活性，而CeO2对催化剂的活性未产生显著影响。当CeO2与CaO两种助剂同时对Ni/MgOAl2O3进行改性时，虽然催化剂中镍物种的还原性能没有发生明显变化，但仍具有很好的反应性能，这与CeO2与CaO能够形成CaO-CeO2固溶体有关。CaO-CeO2固溶体不仅与镍物种间存在相互作用，提高了镍物种的分散度、减小了镍晶粒尺寸，还可以提高催化剂的储氧能力和晶格氧的流动性，从而有利于改善其甲烷部分氧化反应性能。     

Ni-La/CexZr1-xO2对甲烷部分氧化/CH4-CO2重整耦合制合成气的催化剂制备及反应性能

通过共沉淀法制备铈锆固溶体作为载体,采用等体积、分步浸渍的方法制备了一系列10% Ni-3% La/CexZr1-xO2（X=0、0.16、0.5、0.75、1）催化剂,并将其应用到甲烷部分氧化和甲烷二氧化碳重整耦合制合成气的反应中。对不同Ce/Zr比的催化剂性能展开研究,采用XRD、H2-TPR、SEM手段对载体及催化剂进行了表征。结果表明,铈锆固溶体的形成不仅提高了催化剂表面活性组分的分散度,使催化剂表面NiO晶粒尺寸从26.5 nm减到13.7 nm;而且能够加强活性组分与载体之间的相互作用,提高催化剂的热稳定性能;随着Ce/Zr比的增加,催化剂的转化率、选择性及稳定性随之增强,其关系为：Ni-La/Ce0.75Zr0.25O2 > Ni-La/Ce0.5Zr0.5O2 > Ni-La/Ce0.16Zr0.84O2。     

不同载体Ni基负载型催化剂对甲烷部分氧化制合成气催化行为研究

采用浸渍法制备了单一载体(Al₂O₃、ZrO₂、CeO₂)和ZrO₂、CeO₂改性的Al₂O₃复合载体的Ni催化剂,考察了在甲烷部分氧化制备合成气反应中的催化性能。通过N₂-物理吸附、H₂程序升温还原、X射线衍射、NH₃程序升温脱附和程序升温氧化等技术对催化剂进行了表征。结果表明,在单一载体催化剂中,Ni/Al₂O₃具有较大的比表面积,其初始反应活性较高,但该催化剂表面易形成大量的积炭而快速失活。Ni/ZrO₂和Ni/CeO₂催化剂比表面积较小,活性金属Ni在其表面分散性差,催化剂具有较低的CH₄转化率。而CeO₂和ZrO₂改性的Al₂O₃复合载体催化剂,具有较大的比表面积,反应活性明显高于单一载体催化剂。CeO₂-Al₂O₃复合载体催化剂具有最高的反应活性和较好的反应稳定性。同时表明,含CeO₂催化剂反应后表面积炭较少,CeO₂的储放氧功能增强了催化剂对O₂的活化,提高催化剂活性的同时,可以抑制积炭的生成。     

超高温焙烧的Ni/Al2O3对甲烷部分氧化反应的催化活性

考察了超高温焙烧的Ni/Al2O3对甲烷部分氧化反应的催化性能,发现该催化剂经还原后对甲烷部分氧化反应表现出较高的催化活性.X射线衍射结果显示,Ni/Al2O3催化剂在超高温(1200~1400℃)下焙烧后生成了NiAl2O4,且无相转移,进一步经950℃还原后催化剂中绝大部分Ni以单质Ni0形式存在.透射电子显微镜测试结果表明,不同超高温焙烧的催化剂经950℃还原后Ni晶粒的大小无明显差异.这说明超高温焙烧的Ni/Al2O3对甲烷部分氧化反应的高活性可归结为NiAl2O4的可还原性以及还原后Ni0相似的晶粒尺寸.同时还发现,焙烧温度越高,生成的NiAl2O4的还原温度越高.     

Effects of CeO2 and CaO composite promoters on the properties of eggshell Ni/MgO-Al2O3 catalysts for partial oxidation of methane to syngas

The effects of CeO₂ and CaO composite promoters on the properties of eggshell Ni/MgO-Al₂O₃ catalysts of 1.5 mm diameter for the partial oxidation of methane to syngas were investigated. The addition of 1wt.% promoters could enhance the catalytic performance of the Ni/MgO-Al₂O₃ catalyst, while further increasing the promoter content to 4wt.% results in the decrease of reactivity. The catalytic property is related to the oxidizability of surface nickel species.     

Catalytic properties of Ni/ceria-yttria electrode materials for partial oxidation of methane

The catalytic properties of electrode materials Ni/Ce1-xYxO2-δ (x = 0.05, 0.10, 0.15 and 0.20) were investigated for partial oxidation of methane (POM). The CeO2-Y2O3 solid solutions were prepared by co-precipitaion method. The Ni-based catalysts supported on the solid solutions were obtained using the impregnation method. Structural, surface and redox characteristics of the prepared catalysts were systematically examined by means of X-ray diffraction (XRD), N2 adsorption-desorption (Brunauer-Emmet-Teller BET method), H2 temperature-programmed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS) methods. The results indicated that yttria doped in the ceria system, forming a good solid solution, readily induced more defects and oxygen vacancies that favored the improvement of catalytic activity and coking resistance. In the temperature range of 600-850 ℃, Ni/Ce0.90Y0.10O1.95 catalyst exhibited the best catalytic activity among the four tested catalysts, with the CH4 conversion, CO selectivity and H2 selectivity of 78.8%, 90.6% and 89.8%, respectively, at 850 ℃. And the H2/CO molar ratio in products of Ni/Ce0.90Y0.10O1.95 catalyst was closer to the theoretical value of 2.0. The excellent coking resistant behaviors for all catalysts were clearly manifested by Thermal Analysis.     

Ni/CeO2-SiO2催化剂的制备、表征及其甲烷部分氧化制合成气性能

以硝酸亚铈（Ce（NO₃）₃·6H₂O）和正硅酸四乙酯（C₈H₂₀O₄Si）为前驱体,采用溶胶-凝胶法合成了系列具有大比表面积的xCeO₂-（1-x）SiO₂（x = 0,0.25,0.50,0.75,1）复合氧化物载体,然后浸渍活性组分Ni制得用于甲烷部分氧化制合成气的Ni催化剂。运用N₂物理吸附-脱附、X射线粉末衍射、扫描电镜、紫外-可见漫反射光谱、氢程序升温还原、氨程序升温脱附和热重等手段对所得催化剂的组织结构、还原性、表面酸性和积炭行为等进行了表征;同时考察了催化剂的组成、焙烧温度和反应时间等对催化剂在甲烷部分氧化制合成气中催化性能的影响。表征结果表明,该系列Ni/CeO₂-SiO₂催化剂具有大比表面积,CeO₂晶粒较小,NiO的分散性好且易被还原,表面酸性弱,不容易积炭。当Ce/Si摩尔比为1：1,活性组分Ni的质量分数为10%,焙烧温度为700℃时,所制备的Ni/CeO₂-SiO₂催化剂表现出较好的稳定性、最高的CH₄转化率（~84%）和对产物CO及H₂的选择性（>87%）。     

不同Ni前驱物对Ni催化剂甲烷部分氧化制合成气的影响

考察了由硝酸镍,醋酸镍和氯化镍为前驱物制备的催化剂（分别记为Ｎｉ－Ｎ,Ｎｉ－Ａｃ和Ｎｉ－Ｃｌ）对催化甲烷部分氧化反应的影响,并结合和ＴＧ等手段对催化剂进行了表征,结果表明,Ｎｉ－Ａｃ催化剂在６２５℃就能自引发甲烷部分氧化反应,而在Ｎｉ－Ｎ和Ｎｉ－Ｃｌ催化剂上,直到７５０℃甲烷部分氧化反应仍未能引发,三种催化剂上的反应结果表明,Ｎｉ－Ｎ和Ｎｉ－Ｃｌ的催化活性较低。９００℃下的高温反应结果表明,Ｎｉ－     

Modeling of microreactor for syngas production by catalytic partial oxidation of methane

Fixed-bed reactors for the catalytic partial oxidation of methane (CPOM) to produce synthesis gas still pose hot spots problems. Microreactor is a good alternative reactor proposed to resolve these problems. In this paper, synthesis gas (hydrogen and carbon monoxide) production was investigated by a two-dimensional numerical model of single microchannel. CFD modeling with detailed chemistry was conducted to understand the CPOM on platinum (Pt) catalyst. Gas inlet velocity, microchannel pressure, and fuel to air ratio (F/A) are selected as the effective parameters on microchannel performance. Study results show that Reynolds number has considerable effect on methane conversion, hydrogen to carbon monoxide ratio (H2/CO), and product distribution. Increasing gas inlet velocity causes all the above parameters to decrease. It is noted that increasing microchannel pressure and decreasing the ratio of fuel to air cause the decrease of the H2/CO ratio.     

Ni/Al2O3催化剂上甲烷部分氧化制合成气

本研究了Ｎｉ／Ａｌ２Ｏ３催化剂的表面特征以及其与ＣＨ４部分氧化制合成气反应性能的关系。ＴＰＲ，ＸＲＤ和评价结果表明，催化剂Ｎｉ组分含量在９．０％时反应性能最佳，反应过程中催化剂表面上部有部分镍氧化物在５２０～５４０℃就还原，反应条件实验表明，在１１．５２×１０＾５ ｍｌ．ｇ＾－１下，随着反应管外控制温度的升高，ＣＨ４转化率，ＣＯ和Ｈ２选择性及收率增加，在７００℃下，随着原料气空速的增加，ＣＨ４转