Ca and Sr co-doping induced oxygen vacancies in 3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts for boosting low-temperature oxidative coupling of methane

It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(A_(2)B_(2)O_(7)-type)catalysts with disordered defective cubic fluorite phased structure were successfully prepared by a colloidal crystal template method.3DOM structure promotes the accessibility of the gaseous reactants(O2and CH4)to the active sites.The co-doping of Ca and Sr ions in La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts improved the formation of oxygen vacancies,thereby leading to increased density of surface-active oxygen species(O_(2)^(-))for the activation of CH4and the formation of C2products(C2H6and C2H4).3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts exhibit high catalytic activity for OCM at low temperature.3DOM La1.7Sr0.3Ce1.7Ca0.3O7-δcatalyst with the highest density of O_(2)^(-)species exhibited the highest catalytic activity for low-temperature OCM,i.e.,its CH4conversion,selectivity and yield of C2products at 650℃are 32.2%,66.1%and 21.3%,respectively.The mechanism was proposed that the increase in surface oxygen vacancies induced by the co-doping of Ca and Sr ions boosts the key step of C-H bond breaking and C-C bond coupling in catalyzing low-temperature OCM.It is meaningful for the development of the low-temperature and high-efficient catalysts for OCM reaction in practical application.

Methane Oxidation to Synthesis Gas Using Lattice Oxygen of La_(1-x)Sr_xMO_(3-λ)(M =Fe,Mn) Perovskite Oxides Instead of Molecular Oxygen

In this paper, the partial oxidation of methane to synthesis gas using lattice oxygen of La1- SrxMO3-λ (M=Fe, x Mn) perovskite oxides instead of molecular oxygen was investigated. The redox circulation between 11% O2/Ar flow and 11% CH4/He flow at 900℃ shows that methane can be oxidized to CO and H2 with a selectivity of over 90.7% using the lattice oxygen of La1- SrxFeO3-λ (x≤0.2) perovskite oxides in an appropriate reaction condition, while the lost lattice x oxygen can be supplemented by air re-oxidation. It is viable for the lattice oxygen of La1- SrxFeO3-λ (x≤0.2) perovskite x oxides instead of molecular oxygen to react with methane to synthesis gas in the redox mode.

Selective catalytic methanation of CO in hydrogen-rich gases over Ni/ZrO_2 catalyst

Ni/ZrO2 catalysts were prepared by the incipient-wetness impregnation method and were investigated in activity and selectivity for the selective catalytic methanation of CO in hydrogen-rich gases with more than 20 vol% CO2. The result showed that Ni loadings significantly influenced the performance of Ni/ZrO2 catalyst. The 1.6 wt% Ni loading catalyst exhibited the highest catalytic activity among all the catalysts in the selective methanation of CO in hydrogen-rich gas. The outlet concentration of CO was less than 20 ppm with the hydrogen consumption below 7%, at a gas-hourly-space velocity as high as 10000 h-1 and a temperature range of 260 °C to 280 °C. The X-ray diffraction （XRD） and temperature programmed reduction （TPR） measurements showed that NiO was dispersed thoroughly on the surface of ZrO2 support if Ni loading was under 1.6 wt%. When Ni loading was increased to 3 wt% or above, the free bulk NiO species began to assemble, which was not favorable to increase the selectivity of the catalyst.

Double perovskite oxides Sr_2Mg_(1-x)Fe_xMoO(6-δ) for catalytic oxidation of methane

The double perovskite oxides Sr2Mg1-xF exMoO6-δ were investigated as catalysts for the methane oxidation.The structural properties of catalysts were characterized in detail by X-ray diffraction,X-ray photoelectron spectroscopy and X-ray absorption spectroscopy.The catalytic property was strongly influenced by the Fe substitution.The relation between catalytic performance and the degree of Fe substitution was examined with regard to the structure and surface characteristics of the mixed oxides.The Fe-containing catalysts exhibited higher activity attributable to the possible（Fe2＋,Mo6＋） and （Fe3＋,Mo5＋）valency pairs,and the highest activity was observed for Sr2Mg0.2Fe0.8MoO6-δ.The enhancement of the catalytic activity may be correlated with the Fe-relating surface lattice oxygen species and was discussed in view of the presence of oxygen vacancies.

CO selective methanation in hydrogen-rich gas mixtures over carbon nanotube supported Ru-based catalysts

Series of carbon nanotube supported Ru-based catalysts were prepared by impregnation method and applied successfully for complete removal of CO by CO selective methanation from H2-rich gas stream conducted in a fixed-bed quartz tubular reactor at ambient pressure. It was found that the metal promoter, reduction temperature and metal loading affected the catalytic properties significantly. The most excellent performance was presented by 30 wt% Ru-Zr/CNTs catalyst reduced at 350 ℃. Since it decreased CO concentration to below 10 ppm from 12000 ppm by CO selective methanation at the temperature range of 180-240 ℃, and kept CO selectivity higher than 85% at the temperature below 200 ℃. Characterization using XRD, TEM, H2-TPR and XPS suggests that Zr modification of Ru/CNTs results in the weakening of the interaction between Ru and CNTs, a higher Ru dispersion and the oxidization of surface Ru. Amorphous and high dispersed Ru particles with small size were obtained for 30 wt% Ru-Zr/CNTs catalyst reduced at 350 ℃, leading to excellent catalytic performance in CO selective methanation.

Long-term and combined effects of N-[2-(nitrooxy)ethyl]-3-pyridinecarboxamide and fumaric acid on methane production,rumen fermentation, and lactation performance in dairy goats

Background:In recent years,nitrooxy compounds have been identified as promising inhibitors of methanogenesis in ruminants.However,when animals receive a nitrooxy compound,a high portion of the spared hydrogen is eructated as gas,which partly offsets the energy savings of CH4mitigation.The objective of the present study was to evaluate the long-term and combined effects of supplementation with N-[2-(nitrooxy)ethyl]-3-pyridinecarboxamide(NPD),a methanogenesis inhibitor,and fumaric acid(FUM),a hydrogen sink,on enteric CH4production,rumen fermentation,bacterial populations,apparent nutrient digestibility,and lactation performance of dairy goats.Results:Twenty-four primiparous dairy goats were used in a randomized complete block design with a 2×2factorial arrangement of treatments:supplementation without or with FUM(32 g/d)or NPD(0.5 g/d).All samples were collected every 3 weeks during a 12-week feeding experiment.Both FUM and NPD supplementation persistently inhibited CH4yield(L/kg DMI,by 18.8%and 18.1%,respectively)without negative influence on DMI or apparent nutrient digestibility.When supplemented in combination,no additive CH4suppression was observed.FUM showed greater responses in increasing the molar proportion of propionate when supplemented with NPD than supplemented alone(by 10.2%vs.4.4%).The rumen microbiota structure in the animals receiving FUM was different from that of the other animals,particularly changed the structure of phylum Firmicutes.Daily milk production and serum total antioxidant capacity were improved by NPD,but the contents of milk fat and protein were decreased,probably due to the bioactivity of absorbed NPD on body metabolism.Conclusions:Supplementing NPD and FUM in combination is a promising way to persistently inhibit CH4emissions with a higher rumen propionate proportion.However,the side effects of this nitrooxy compound on animals and its residues in animal products need further evaluation before it can be used as an animal feed additive.

CH_3OH在Ga-rich GaAs(001)-(4×2)表面上的吸附与解离:团簇模型的密度泛函计算

采用简单团簇模型结合密度泛函理论研究了CH3OH在Ga-rich Ga As(001)-(4×2)表面上的吸附与解离过程.计算结果表明,CH3OH在Ga-rich Ga As(001)-(4×2)表面上首先会形成两种化学吸附状态,然后CH3OH经解离生成CH3O自由基和H原子吸附在表面不同位置上.通过比较各个吸附解离路径,发现解离后的H原子相对更容易吸附在位于表面第二层紧邻的As原子上.

Selective Oxidation of Methane to Methanol Using Molecular Oxygen on MoOx/(LaCoO3+Co3O4)Catalysts

Comparatively high CH3OH selectivity (60.0%) and yield (6.7%) were obtained on MoOx/(LaCoO3+Co3O4) catalysts in selective oxidation of methane to methanol using molecular oxygen as oxidant. The interaction between MoOx and La-Co-oxide modified the molecular structure of molybdenum oxide and the ratio of O7O ' on the catalyst surface, which controlled the catalytic performance of MoOx/(LaCoO3+Co3O4) catalysts.

溶胶-凝胶法制备镍基CO选择性甲烷化催化剂

提出采用溶胶-凝胶法制备镍基催化剂的工艺,考察了NiO的担载量、焙烧温度等制备条件在氢气纯化中对催化活性的影响,利用SEM、BET等手段对催化剂进行了表征。在一定条件下,CO可以降至0,H2对CO选择性大于99%,完全可以满足质子交换膜燃料电池对氢源的要求。

微通道反应器内Ni-Ru/ZrO_2催化剂上CO选择性甲烷化

利用微通道反应器,对富氢重整气在Ni-Ru/ZrO2催化剂上的CO选择性甲烷化反应进行了研究;考察了反应温度、原料气中CO含量和CO2含量对Ni-Ru/ZrO2催化剂活性的影响,并考察了Ni-Ru/ZrO2催化剂的稳定性。实验结果表明,在微通道反应器中,Ni-Ru/ZrO2催化剂对CO选择性甲烷化反应具有良好的活性,当原料气中CO体积分数不大于1.0%时,在260～300℃内可将CO出口体积分数降至1×10-4以下;CO出口体积分数的最低值随原料气中CO含量的增加而增大,当原料气中CO含量增加到一定程度时,需采用温度梯级甲烷化法才能将CO出口体积分数降至1×10-4以下;120h的稳定性实验结果表明,Ni-Ru/ZrO2催化剂具有良好的稳定性,CO转化率均保持在99.50%以上。

Kinetic Modeling the Formation of Low-mature Gases and Analysis of the Possibility to Be Accumulated

At present, shallow gases have received much attention due to low cost in exploration and production. Low-mature gases, as one significant origin to shallow gas, turns to be an important research topic. The present understanding of low-mature gases is confined within some geological cases, and few laboratory studies have been reported. Therefore, the potential and characters of low- mature gases are not clear up to now. Here, two premature samples （one coal and the other shale） were pyrolyzed in a gold confined system. The gaseous components including hydrocarbon gases and non-hydrocarbon gases were analyzed. Based on kinetic modeling, the formation of low-mature gases was modeled. The results showed that during low mature stage, about 178 mL/gTOC gas was generated from the shale and 100 mL/gTOC from the coal. Two third to three fourth of the generated gases are non-hydrocarbon gases such as H2S and CO2. The total yields of C1-5 for the two samples are almost the same, 30-40 mL/gTOC, but individual gaseous hydrocarbon is different. The shale has much lower C1 but higher C2-5, whereas the coal has higher C1 but lower C2-5. Hydrocarbon gases formed during low-mature stage are very wet. The stable carbon isotope ratios of methane range from -40‰ to -50‰ （PDB）, in good consistence with empiric criterion for low-mature gases summed up by the previous researchers. The generation characters suggest that the low-mature gases could be accumulated to form an economic gas reservoir, but most of them occur only as associated gases.

多手段表征富油煤微生物厌氧发酵孔隙结构变化特征及机制

煤层气生物工程技术是实现富油煤绿色、低碳开发的有效手段之一。为探究微生物厌氧发酵作用下富油煤孔隙结构演化特征,以鄂尔多斯盆地南部黄陵矿区富油煤为研究对象,在实验室条件下开展微生物厌氧发酵(降解)富油煤生烃模拟实验,采用场发射扫描电镜、3D形貌仪、CT扫描、孔隙度/渗透率测试等手段,对微生物降解前后的富油煤表面形貌、粗糙度和内部孔隙进行表征,并探讨微生物降解作用下富油煤的孔渗结构演化规律及生烃机制。结果表明:不同规格大小的煤样甲烷生成潜力与煤的质量(或接触面积)呈正相关关系;微生物降解作用具有显著的扩孔、增孔、增容、造缝等效果,以及降低煤体表面粗糙度,使其变得平滑,有利于煤层气的解吸和运移;微生物还可沿着节理、裂隙系统进入富油煤内部,改造煤体孔隙结构及其连通性;同时微生物降解作用还可提高富油煤的孔隙度和渗透率,为煤层气的渗流和运移提供了良好的通道。微生物主要作用于富油煤中脂肪族上的支链,打破小分子间连接较弱的氢键,降低脂肪族的分支程度和煤结构的交联度,进而生成甲烷。微生物作用还可改变富油煤芳香度和芳香环的缩合程度,进而改变富油煤大分子结构与孔隙结构。微生物厌氧发酵富油煤与非富油煤的生烃机制差异性问题值得后续深入研究。

炭催化富CH_(4)气CO_(2)重整制合成气及动力学研究

以UGI煤气发生炉为基础,在实验室设备装置上模拟气化炉上吹阶段,通入模拟混合气制备合成气,开发了一套新的制备合成气工艺。通过实验研究发现,反应温度和半焦粒度对甲烷转化率具有重要影响。加入水蒸气可以提高炭材料催化剂的稳定性和甲烷转化率,这主要是由于加入水蒸气可以气化半焦表面生成的积碳,同时生成新的活性位给甲烷二氧化碳重整反应提供活性,从而促进甲烷和二氧化碳转化。另外,通过对水蒸气条件下富甲烷气二氧化碳重整动力学研究,得到了炭催化富甲烷气二氧化碳重整的表观活化能为199.7 kJ·mol^(-1)。

Effect of Substitution of Cobalt for Iron in Sr4Fe6O13-δon the Catalytic Activity for Methane Combustion

A series of mixed oxides Sr4Fe6-xCoxO13-δ （x=0, 1, 2, 3, or 4） were prepared by sol-gel method and used for catalytic combustion of methane. The structural properties of oxides were characterized by XRD, TGA, and XPS. The layered intergrowth perovskite-like oxide Sr4FesCoO13 8 exhibits the highest catalytic activity for methane combustion under the experimental conditions. The enhanced catalytic activity of Sr4FesCoO13-δfor methane combustion could be attributed to the increased amount of oxygen vacancy caused by the partial substitution of cobalt for iron in the Sr4Fe6O13, which was confirmed by TGA and XPS.

沁水盆地南部15号煤层顶板灰岩特征对煤层气开采的影响

煤层顶板的含水性对煤层气的开采有重要影响。沁水盆地南部上石炭统太原组15号煤层直接或间接顶板多为灰岩,其中以K2灰岩为主,连续分布。顶板泥岩较少,呈零散分布。灰岩的富水性对煤层气的排水降压有影响。因此,主要从灰岩的厚度展布、裂隙发育、与煤层的接触关系以及区域水文地质条件讨论其含水性对煤层气产能的影响。研究结果表明:(1)灰岩的含水性一般较弱,但当遇到断层或岩溶陷落柱较发育的部位,可能与其他含水层沟通,富水性较强。(2)15号煤层顶板灰岩的厚度与煤层气井的产水量并无直接关系,其裂隙较发育,但大多被方解石充填,导水和储水性能较差。(3)灰岩与15号煤层的接触关系有两种:一种是直接接触型,灰岩直接覆于15号煤层之上;另一种是间接接触型,灰岩与15号煤之间夹有泥岩、砂岩或14号煤层。直接接触型煤层气井的产水量、产气量比间接接触型高。间接接触型15号煤层直接顶板的岩性、厚度对产气、产水都没有太大影响。

不同煤阶煤层气选区评价参数的研究与应用

目前,国外煤层气开发主要以中低煤阶为主,而我国则以中高煤阶为主;不同煤阶具有不同的煤层气地质特点与选区评价标准。为此,通过对国内外重点煤层气盆地的煤层气评价参数对比研究,提出了不同煤阶的煤层气选区评价参数,包括:煤层气资源规模及丰度、煤层厚度、煤层含气量、煤层气吸附饱和度、煤层原始渗透率、有效地应力、地解比、构造发育状况及水文地质条件。在此基础上,通过对重点煤层气区的类比分析,初步建立了我国煤层气选区评价标准,并优选出煤层气有利富集区16个:其中Ⅰ类最有利富集区6个,包括沁水盆地南部、阜新盆地刘家区块、鄂尔多斯盆地东部、宁武盆地南部、准噶尔盆地东南部、二连盆地霍林河地区;Ⅱ类有利富集区4个,包括沁水盆地北部、鄂尔多斯盆地乌审旗地区、黔西盘关地区、川南古蔺—叙永地区;Ⅲ类较有利富集区6个。

高丰度煤层气富集区地球物理识别

为预测煤层气富集区,通过地震反演和地震属性分析,获得了煤层含气量、地质构造、煤层厚度、煤层结构、煤层顶、底板岩性和裂隙等地震地质参数,基于地球物理信息融合方法对煤层气富集区进行了预测。研究结果表明:随着埋藏深度增加,煤层厚度增加,煤层含气量呈增加趋势;向斜轴部隆起带煤层含气量大,背斜轴部凹陷区煤层含气量相对较多;构造煤分布区一般煤层气较富集;煤层直接顶底板为泥岩,则煤层含气量一般较高;裂隙的存在会对煤层气含量有一定影响。研究认为,煤层埋深、煤层厚度、结构、构造和顶底板岩性等参数是控制研究区煤层气富集的主要地震地质因素,基于地球物理信息融合对煤层气富集区进行预测,可以避免单一地震地质因素预测的局限性,有助于提高预测精度。

汾渭盆地富氦天然气成因及成藏条件初探

20世纪70年代,前人在汾渭盆地进行石油勘探时,于新近—古近系钻遇氦、甲烷、氮等天然气,由于当时以新生界石油勘探为目的,所以未能开展进一步工作。20世纪90年代以来,汾渭盆地地热资源得到了充分的利用,在地热水开采中,发现普遍含天然气。笔者通过盆内对不同构造单元、不同层位的地热井采集的天然气样品进行组分及同位素分析,发现汾渭盆地天然气为国内外少有的以壳源氦为主,有少量幔源氦加入的富氦天然气,并具有较高含量的幔源甲烷。综合前人资料成果,对形成天然气藏的气源条件、储盖组合条件、圈闭条件及运移与保存条件进行了的初步分析,认为汾渭盆地具有形成富氦天然气的地质条件和良好的勘探前景。

纳米ZrO_2负载Ni催化剂催化CO选择性甲烷化

利用表面活性剂辅助模板机理,结合水热法合成出纳米有序的多孔 ZrO_2载体,采用等体积浸渍法制备了 Ni/ZrO_2催化剂;采用固定床微反装置评价了 Ni/ZrO_2催化剂对富氢气体中低含量 CO 选择性甲烷化反应的催化性能;采用 X 射线衍射和程序升温还原等方法对载体和催化剂进行了表征。实验结果表明,利用模板剂十六烷基三甲基溴化铵(CTAB)制备的 ZrO_2载体再负载质量分数4%Ni 的 Ni/ZrO_2催化剂具有优异的催化活性,可将 CO 体积分数从1.1%降至0.01%以下,且该催化剂在220～260℃内均能保持较高的活性和选择性。表征结果显示,以 CTAB 为模板剂制备的多孔性纳米 ZrO_2具备优良的载体性能,能促进活性组分 Ni 的分散,载体与活性组分 Ni 之间存在较强的相互作用,提高了催化剂的活性。

沁水盆地煤地质与煤层气聚集单元特征研究

通过对沁水盆地煤层气聚集单元分析,可以看出煤层气聚集单元划分需要查明影响煤层气成藏的各种地质因素。煤层气聚集成藏是天然气成藏中的特殊情况,其特殊的成因机制使得聚集单元分析不能套用常规石油天然气聚集单元的划分原则,其中煤地质基础研究特别是煤层气基础研究是煤层气聚集单元分析的基础;对于一个完整盆地,煤聚积规律研究对煤层气最为重要,因此应该在高分辨率层序地层单元划分的基础上进行精细的富煤单元分析;对于指导煤层气勘探与开发,盆地内部次级单元的划分是实用的,也是难度更大的;沁水盆地煤层气聚集单元可以用以下"富气区"描述,即沁南极富气区、东翼斜坡带富气区、西翼斜坡带低富气区、西山较低富气区和高平-晋城低富气区,因此沁南区是煤层气成藏有利区。