Rh doping effect on coking resistance of Ni/SBA-15 catalysts in dry reforming of methane

A series of SBA-15 supported bimetallic Rh–Ni catalysts with different weight ratio of Rh/Ni in the range of 0–0.04 were prepared for carbon dioxide reforming of methane. The doping effect of Rh on catalytic activity as well as carbon accumulation and removal over the catalysts was studied. The characterization results indicated that the addition of a small amount of Rh promoted the reducibility of Ni particles and decreased the Ni particle size. During the dry reforming reaction, the carbon deposition was originated from CH4 decomposition and CO disproportionation. The Rh–Ni catalyst with small metallic particle size inhibited the carbon formation and exhibited high efficiency in the removal of coke. In comparison with bare Ni-based catalyst, the Rh–Ni bimetallic catalysts showed high activity and stability in the dry reforming of methane.     

Ni/Al2O3 catalysts for syngas methanation: Effect of Mn promoter

Ni/Al2O3 catalysts with different amounts of manganese ranging from 1 to 3 wt% as promoter were prepared by co-impregnation method. The catalysts were characterized by N2 physisorption, XRD, TPR, SEM and TEM. Their catalytic activity towards syngas methanation reaction was also investigated using a fixed-bed integral reactor. It was demonstrated that the addition of manganese to Ni/Al2O3 catalysts can increase the catalyst surface area and average pore volume, but decrease NiO crystallite size, leading to higher activity and stability. The effects of reaction temperature, pressure and weight hourly space velocity (WHSV) on carbon oxides conversion and CH4 formation rate were also studied. High carbon oxides conversion, CH4 selectivity and formation rate were achieved at the reaction temperature range of 280 300℃.     

Ni-Co/Mg-Al catalyst derived from hydrotalcite-like compound prepared by plasma for dry reforming of methane

Ni-Co bimetallic catalysts with different Ni/Co content were derived from cold plasma jet decomposition and reduction of hydrotalcite-like compounds containing Ni,Co,Mg and Al,and their catalytic performance was investigated with dry reforming of methane.Experimental results showed that the hydrotalcite-like precursors could be completely decomposed and partly reduced by cold plasma jet,and the Nicontained catalysts exhibited much higher activity than the catalyst without Ni.Especially,the catalyst with Ni/Co ratio of 8/2 achieved not only the highest conversions of 80.3%and 69.3%for CH4 and CO2,respectively,but also the best stability in 100 h testing.The catalysts were characterized by XRD,XPS,TEM and N2 adsorption techniques,and the results showed that the better performance of the 8Ni2Co bimetallic catalyst was attributed to its higher metal dispersion,smaller metal particle size,as well as the interaction effect between Ni and Co,which were brought by the special catalyst preparation method.     

Comparative study of fluidized-bed and fixed-bed reactor for syngas methanation over Ni-W/TiO₂-SiO₂catalyst

In this work,syngas methanation over Ni-W/TiO2-SiO2catalyst was studied in a fluidized-bed reactor(FBR)and its performance was compared with a fixed-bed reactor(FIXBR).The effects of main operating variables including feedstock gases space velocity,coke content,bed temperature and sulfur-tolerant stability of 100 h life were investigated.The structure of the catalysts was characterized by XRD,N2adsorptiondesorption and TEM.It is found that under same space velocity from 5000 h 1to 25000 h 1FBR gave a higher CH4yield,lower coke content,and lower bed temperature than those obtained in FIXBR.Ni-W/TiO2-SiO2catalyst possessed excellent sulfur-tolerant stability on the feedstock gases less than 500 ppm H2S in FBR.The carbon deposits formed on the spent catalyst were in the form of carbon fibers in FBR,while in the form of dense accumulation distribution appearance in FIXBR.     

用于甲烷水蒸气重整的镍基催化剂的失活和再生

The deactivation of nickel catalysts used in Arak and Razi petrochemical complexes followed by catalyst regeneration was evalu-ated. The characterization of the different structures was made by powder X-ray diffraction(XRD),scanning electron microscopy(SEM),energy dispersive X-ray spectroscopy(EDS),transmission electron microscopy(TEM),and carbon & sulfur analyzer. The Ni particle size was estimated from XRD patterns and TEM graphs. The agglomeration of nickel particle and the poison by sulfur components were recognized as the main reasons in deactivation of Arak and Razi catalysts,respectively. The activity of the used catalysts before and after regeneration was measured on methane steam reforming at a CH4:H2O ratio of 1:3 at 850 oC. The regeneration processes for Arak and Razi samples were performed with CO2 as an oxidative atmosphere and steam as a regenerating agent,respectively. The results show that,(1) no residual sulfur components were on the regenerated Razi catalyst surface without changing the structure of the catalyst and the regenerated catalyst has gained 80% of its catalytic activity,and that(2) the nickel particle size of regenerated Arak specimen decreased remarkably as measured by Debye-Scherrer equation from XRD patterns. TEM images were in agreement with the XRD results and indicated a decrease in nickel particle size of regenerated catalyst. Additionally,in both regenerated catalysts all the coke on the surface of the support was eliminated after regeneration.     

MgO纳米晶负载镍催化剂用于甲烷蒸汽重整反应(英文)

Nanocrystalline MgO with a relatively high surface area and mesoporous structure was synthesized by a surfactant assisted precipitation method for use as the support of nickel catalysts for steam reforming of methane. The samples were characterized by X‐ray diffraction, N2 adsorption, temperature‐programmed reduction, temperature‐programmed oxidation, scanning electron microscopy, and transmission electron microscopy. The catalysts showed high catalytic activity and good stability in the steam reforming of methane. Increasing the nickel loading up to 10 wt% gave increased activity. Catalysts with higher nickel loadings showed more deposited carbon after reaction. The excellent anti‐coking performance of the catalysts was attributed to the formation of a nickel‐magnesia solid solution, basicity of the support surface, and nickel‐support interaction.     

析因设计结合响应面法分析甲烷干重整过程中通过形成碳纳米管进行二氧化碳减排(英文)

A factorial experimental design was combined with response surface methodology(RSM) to opti-mize the catalyzed CO2 consumption by coke deposition and syngas production during the dry re-forming of CH4. The CH4 /CO2 feed ratio and the reaction temperature were chosen as the variables, and the selected responses were CH4 and CO2 conversion, the H2 /CO ratio, and coke deposition. The optimal reaction conditions were found to be a CH4 /CO2 feed ratio of approximately 3 at 700 °C, producing a large quantity of coke and realizing high CO2 conversion. Furthermore, Raman results showed that the CH4 /CO2 ratio and reaction temperature affect the system's response, particularly the characteristics of the coke produced, which indicates the formation of carbon nanotubes and amorphous carbon.     

Carbon-Supported Silver Catalysts for CO Selective Oxidation in Excess Hydrogen

Carbon materials were used as supports for Ag catalysts that are prepared using the conventional wet impregnation method, and their catalytic properties for CO selective oxidation in excess hydrogen at temperatures below 483 K were tested. A variety of techniques, e.g. N2 adsorption, XPS, TPD, UV-Vis DRS, TEM and SEM, were used to determine the influence of physical and chemical properties of the carbon on the properties of Ag catalyst. It was found that defects on the carbon surface served as nucleation sites for silver ions, while functional groups on carbon surface induced their reduction to the metallic form. The formation of silver particles on carbon was governed by homogeneous and/or heterogeneous nucleation during the impregnation and subsequent activation processes. The best catalytic performance was obtained with a Ag/carbon black catalyst with a uniform size distribution of silver nanoparticles (about 12 nm), moderate BET surface area (with a mesoporous structure), and a limited amount of carbon-oxygen groups. The research indicates that carbon materials are potentially good supports for silver catalysts for preferential oxidation of CO in excess hydrogen.     

Performance of a tubular oxygen-permeable membrane reactor for partial oxidation of CH_4 in coke oven gas to syngas

A gas-tight BaCo 0.7 Fe 0.2 Nb 0.1 O 3-δ(BCFNO) tubular membrane was fabricated by hot pressure casting.And a membrane reactor with BCFNO tubular membrane and Ag-based sealant was readily constructed and applied to partial oxidation of CH4 in coke oven gas.At 875 ℃,95% of methane conversion,91% of H 2 and as high as 10 ml cm-2·min-1 of oxygen permeation flux were obtained.There was a good match in the coefficient of thermal expansion between Ag-based alloy and BCFNO membrane materials.The tubular BCFNO membrane reactor packed with Ni-based catalysts exhibited not only high activity but also good stability in hydrogen-enriched coke oven gas(COG) atmosphere.     

Performance of a tubular oxygen-permeable membrane reactor for partial oxidation of CH4 in coke oven gas to syngas

A gas-tight BaCo0.7Fe0.2Nb0.1O3-δ (BCFNO) tubular membrane was fabricated by hot pressure casting. And a membrane reactor with BCFNO tubular membrane and Ag-based sealant was readily constructed and applied to partial oxidation of CH4 in coke oven gas. At 875 ℃, 95% of methane conversion, 91% of H2 and as high as 10 ml·cm-2·min-1 of oxygen permeation flux were obtained. There was a good match in the coefficient of thermal expansion between Ag-based alloy and BCFNO membrane materials. The tubular BCFNO membrane reactor packed with Ni-based catalysts exhibited not only high activity but also good stability in hydrogen-enriched coke oven gas (COG) atmosphere.     

热重-质谱联用研究焦炭在甲烷气氛下的热行为

利用热重-质谱联用技术对焦炭在甲烷气氛下的热行为及气体逸出情况进行了初步研究。考察了温度、停留时间、甲烷体积分数及流量、焦炭品质等因素对焦炭增重的影响,同时对焦炭在甲烷气氛下及惰性气氛下加热时的气体逸出情况进行了分析。结果表明,在实验进行的时间范围内焦炭的增重随着温度的升高、停留时间的增长、甲烷体积分数的提高而增加;实验采用的两种气体流量对焦炭增重影响不大;焦炭品质越差,增重程度越明显。质谱分析的结果表明,焦炭在惰性气氛下加热时的失重主要是由于CO2和H2O的逸出引起的;甲烷在焦炭存在下800 ℃以后开始分解析出H2,在恒温停留阶段H2的逸出速率变化不大,同时焦炭的质量增加,说明甲烷分解成碳和氢气。焦炭对甲烷的分解存在一定的催化作用。     

双金属镍-锰／γ-Al2O3催化剂对甲烷二氧化碳重整反应的影响

用浸渍法制备γ-Al2O3负载的Ni-Mn双金属催化剂．在500-700。C按照17：17：2的C02／CHa／N2比例,以36mL／min的载气流速进行甲烷二氧化碳重整反应,利用甲烷二氧化碳的转化率、生成的合成气H2／CO比例以及长期稳定性等指标评价了催化剂的催化性能．实验表明,添加Mn提高催化性能并使双金属催化剂的稳定性更高,比单金属催化剂更好地抑制焦炭生成,Mn最合适的添加量为0．5wt％．通过BET、C02-TPD、TGA、XRD、SEM、EDX和FTIR各种技术对催化剂进行了表征．     

La-Ni-Al钙钛矿氧化物中Sr和Ca取代La对甲醇重整的影响

Mixed perovskite oxides with CaxLa1-xNi0.3Al0.7O3-d and SrxLa1-xNi0.3Al0.7O3-d(x=0,0.2,0.5,0.8,and 1.0;d=0.5x)components have been prepared by a sol-gel method.The effects of the partial substitution of La by Ca and Sr in dry CH4 reforming were investigated at 500-800 ℃ and 101 kPa.The resulting oxides were examined by Fourier-transform infrared spectroscopy,X-ray diffraction,temperature-programmed reduction,scanning electron microscopy,energy dispersive X-ray spectrometry,and BET surface area analysis.Studies following the catalytic tests by carbon analysis show some carbon deposition on this catalytic system.The results indicate that all initial salt entered into a propionate structure,and that most of the solid solution has well defined perovskite structure with surface areas between 3.5 and 9.5 m2/g.Most of the catalysts performed well in the dry reforming,with CH4 conversions up to 90%,H2 yields up to 80%,and H2 selectivity up to 90%.Among the samples,Sr0.2La0.8Ni0.3Al0.7O2.9 showed an excellent catalytic performance in CH4 dry reforming,with a H2/CO ratio of 1,whereas Ca0.8La0.2Ni0.3Al0.7O2.6 showed the lowest coke formation(approximately 0.71%).     

Ni/MgO-Al2O3催化剂上高温焦油组分的催化转化

采用分步浸渍法制备了MgO-Al2O3负载的Ni基催化剂, 并运用N2吸附、载射线衍射(XRD)、透射电子显微镜(TEM)等手段进行表征. 该催化剂用于甲苯或萘为焦油模拟化合物的高温焦炉煤气(COG)的常压加氢裂解反应, 并考察了H2浓度、H2S对催化剂活性的影响. 结果表明: 催化剂还原后, 表面形成均匀分散、直径为8-14 nm的金属Ni纳米颗粒; 在较低的水碳摩尔比(nH2O/nC=0.28)时, 甲苯就能完全转化并选择性地加氢裂解形成CH4, 测试的时间内(480 min), 催化剂没有明显的失活和积炭现象, 显示出好的反应活性、稳定性和耐硫能力. 制得的Ni/MgO-Al2O3催化剂有望应用于较低水含量(10%-15%(φ, 体积分数))的高温焦炉煤气中焦油的直接转化.     

Ni/Al~2O~3催化剂上CH~4分解生成的碳物种的转化

本文利用顺序脉冲实验技术,对CH~4在Ni/Al~2O~3催化剂上分解生成的碳物种及其在实验条件下的转化行为进行研究,以探索催化剂上积炭形成的原因。     

焙烧温度对有色金属尾矿载体及Ni基催化剂的性能影响

以尾矿为载体原料,经不同温度焙烧预处理、等体积浸渍制备了一系列负载型Ni/SiO2-CaO-Fe2O3催化剂并用于CO2重整CH4制合成气,重点考察了载体原料的焙烧温度对催化剂性能的影响.用ICP-AES,XRD测定了有色金属尾矿的成分,用H2-TPR,CO2-TPD,TPO等对催化剂的还原性能、吸附性能、抗积炭性能进行了表征.结果表明,载体原料经850℃焙烧后所负载的镍催化剂在800℃条件下CO2转化率为78.5%,CH4转化率为71.2%,CO和H2选择性分别达到92.2%,89.5%.     

甲烷与二氧化碳重整制取合成气反应的研究 (I)Sr_(1-x)La_xNiAl_(11)O_(19)催化活性表征

对具有磁铅石结构的Ｓｒ１－ｘＬａｘＮｉＡｌ１１Ｏ１９对甲烷与二氧化碳重整反应的催化活性、积炭量和稳定性进行了研究．不同还原温度下催化剂的ＸＲＤ和催化活性的实验结果表明，金属镍是ＣＨ４＋ＣＯ２重整反应的活性组分，金属镍含量越大，反应活性越高．反应后催化剂积炭量的分析结果说明，在相同镍含量和分散度的情况下，Ｌａ３＋离子对Ｓｒ２＋离子调变，可以降低催化剂的表面酸性，提高催化剂的抗积炭能力．ＬａＮｉＡｌ１１Ｏ１９是一种具有较好催化活性、稳定性和抗积炭性能的催化剂．     

负载离子对型酞菁钴双功能硫醇氧化催化剂

将分别带有正、负电荷基团的季铵盐酞菁钴ＣｏＰＣ「Ｎ（ＣＨ３）３Ｉ」４和碘酸盐菁然ＣｏＰｃ（ＳＯ３Ｎａ）４溶解在一起,负载在由水滑石热分解而成的ＭｇＡｌ复合氧化物碱性载体上,制成负载离子对型酞菁钴催化剂,其所具有的碱经性双功能的特征能够有效地催化１－辛硫醇氧化,当这两种酞菁钴配合物的摩尔比为１时,催化活性最高,并且稳定性也有较明显的改善,这种双功能催化剂体系具有酶催化的特点,即遵循双底物（１－Ｃ８Ｈ