Comparison of three methods for natural gas dehydration

This paper compares three methods for natural gas dehydration that are widely applied in industry:(1) absorption by triethylene glycol, (2) adsorption on solid desiccants and (3) condensation. A comparison is made according to their energy demand and suitability for use. The energy calculations are performed on a model where 105 Nm3/h water saturated natural gas is processed at 30 °C. The pressure of the gas varies from 7 to 20 MPa. The required outlet concentration of water in natural gas is equivalent to the dew point temperature of -10 °C at gas pressure of 4 MPa.     

Conventional processes and membrane technology for carbon dioxide removal from natural gas:A review

Membrane technology is becoming more important for CO 2 separation from natural gas in the new era due to its process simplicity,relative ease of operation and control,compact,and easy to scale up as compared with conventional processes.Conventional processes such as absorption and adsorption for CO 2 separation from natural gas are generally more energy demanding and costly for both operation and maintenance.Polymeric membranes are the current commercial membranes used for CO 2 separation from natural gas.However,polymeric membranes possess drawbacks such as low permeability and selectivity,plasticization at high temperatures,as well as insufficient thermal and chemical stability.The shortcomings of commercial polymeric membranes have motivated researchers to opt for other alternatives,especially inorganic membranes due to their higher thermal stability,good chemical resistance to solvents,high mechanical strength and long lifetime.Surface modifications can be utilized in inorganic membranes to further enhance the selectivity,permeability or catalytic activities of the membrane.This paper is to provide a comprehensive review on gas separation,comparing membrane technology with other conventional methods of recovering CO 2 from natural gas,challenges of current commercial polymeric membranes and inorganic membranes for CO 2 removal and membrane surface modification for improved selectivity.     

Hydrate capture CO2 from shifted synthesis gas,flue gas and sour natural gas or biogas

CO₂ capture by hydrate formation is a novel gas separation technology, by which CO₂ is selectively engaged in the cages of hydrate and is separated with other gases, based on the differences of phase equilibrium for CO₂ and other gases. However, rigorous temperature and pressure, high energy cost and industrialized hydration separator dragged the development of the hydrate based CO₂ capture. In this paper, the key problems in CO₂ capture from the different sources such as shifted synthesis gas, flue gas and sour natural gas or biogas were analyzed. For shifted synthesis gas and flue gas, its high energy consumption is the barrier, and for the sour natural gas or biogas (CO₂/CH₄ system), the bottleneck is how to enhance the selectivity of CO₂ hydration. For these gases, scale-up is the main difficulty. Also, this paper explored the possibility of separating different gases by selective hydrate formation and reviewed the progress of CO₂ separation from shifted synthesis gas, flue gas and sour natural gas or biogas.     

分子印迹技术在天然产物有效成分分离纯化中的应用

天然产物体系复杂,大分子和小分子、生命和非生命物质共存,多存在结构相近的异构体,且有效成分含量低,采用一般的分离方法富集难度较大。分子印迹技术是制备高选择性分离介质的有效技术手段,分子印迹聚合物(MIP)的选择性强,分离操作简单,在各种分离纯化中展现了良好的应用前景。本文对近年来分子印迹技术在天然产物活性组分(如生物碱、甾体、多元酚、黄酮等)的分离纯化中的应用进行了综述,并介绍了本课题组利用MIP从天然产物中分离纯化莽草酸等活性成分的研究进展。     

高硫石油焦制备高储气性能天然气吸附剂

以高硫石油焦为原料,KOH为活化剂,十二烷基苯磺酸钠（SDBS）为表面活性剂制备天然气吸附剂,分析了高硫焦基吸附剂的孔结构和孔分布特征,讨论了高硫焦制备吸附剂的活化机理。结果表明,预活化中加入表面活性剂SDBS可提高KOH与原料的混合均匀度,对活化效果有利。最优活化条件下制备的吸附剂样品GSR3和GSR4的微孔容积分别达到1.0985cm3·g－1 和1.3193cm3·g－1,孔径分布集中在0.9nm~1.5nm;在25℃、充放气压力3.5MPa和0.1MPa下,GSR3、GSR4对甲烷的质量吸附量分别达到0.139和0.145,有效体积脱附量达到111和115。粉体高硫焦基吸附剂的性能非常接近于低硫焦基吸附剂。     

Catalytic methanation reaction over alumina supported cobalt oxide doped noble metal oxides for the purification of simulated natural gas

A series of alumina supported cobalt oxide based catalysts doped with noble metals such as ruthenium and platinum were prepared by wet impregnation method.The variables studied were difference ratio and calcination temperatures.Pt/Co(10∶90)/Al2O3 catalyst calcined at 700 ℃ was found to be the best catalyst which able to convert 70.10% of CO2 into methane with 47% of CH4 formation at maximum temperature studied of 400 ℃.X-ray diffraction analysis showed that this catalyst possessed the active site Co3O4 in face-centered cubic and PtO2 in the orthorhombic phase with Al2O3 existed in the cubic phase.According to the FESEM micrographs,both fresh and spent Pt/Co(10∶90)/Al2O3 catalysts displayed small particle size with undefined shape.Nitrogen Adsorption analysis showed that 5.50% reduction of the total surface area for the spent Pt/Co(10∶90)/Al2O3 catalyst.Meanwhile,Energy Dispersive X-ray analysis(EDX) indicated that Co and Pt were reduced by 0.74% and 0.14% respectively on the spent Pt/Co(10∶90)/Al2O3catalyst.Characterization using FT-IR and TGA-DTA analysis revealed the existence of residual nitrate and hydroxyl compounds on the Pt/Co(10∶90)/Al2O3 catalyst.     

Pt-Rh/CeZrYLa+LaAl催化剂用于理论空燃比天然气汽车尾气净化

采用共沉淀法制备了CeZrYLa+LaAl纳米复合载体,以三种方法制备了一系列Pt-Rh/CeZrYLa+LaAl催化剂.对所制样品进行了N2吸附-脱附、粉末X射线衍射、X射线光电子能谱和H2程序升温还原的表征.并考察了三种方法所制得催化剂的理论空燃比天然气汽车尾气净化性能.结果表明,三个催化剂的活性顺序为Cat3≈ Cat2> Cat1,其中Cat3具有最低的CO和NO起燃温度(T50),分别为114oC和149 oC,最低的CH4和CO完全转化温度(T90),分别为398 oC和179 oC,以及最佳的CH4和CO温度特性,ΔT (T90–T50)值分别为34 oC和65 oC. Cat2具有最低的CH4起燃温度(342°C)和最低的NO完全转化温度(174°C). Cat1具有最差的转化活性,说明物理混合法制备的催化剂(Cat3和Cat2)性能优于共浸渍法制备的催化剂(Cat1).这是由于物理混合法制备的催化剂, Pt和Rh均匀分散在载体表面,两者物理接触共同参与CH4/CO/NO三种污染物的转化.相反,共浸渍法制备的催化剂, Pt和Rh之间存在较强的相互作用,改变了Pt的电子状态,而且形成了表面Pt富集的Pt-Rh双金属颗粒覆盖了Rh活性位,从而降低催化活性;同时,对于通过物理混合法并进一步添加助剂所制备的Cat3, XRD结果显示助剂Zr4+进入了铈锆固溶体晶格,产生晶格缺陷; XPS结果显示Cat3具有最高的Ce3+/Ce比例.这些都有利于提高催化剂的氧流动性,从而提高催化剂活性并拓宽空燃比窗口.     

Pt-Rh/CeZrYLa+LaAl催化剂用于理论空燃比天然气汽车尾气净化

采用共沉淀法制备了CeZrYLa+LaAl纳米复合载体,以三种方法制备了一系列Pt-Rh/CeZrYLa+LaAl催化剂.对所制样品进行了N2吸附-脱附、粉末X射线衍射、X射线光电子能谱和H2程序升温还原的表征.并考察了三种方法所制得催化剂的理论空燃比天然气汽车尾气净化性能.结果表明,三个催化剂的活性顺序为Cat3≈ Cat2> Cat1,其中Cat3具有最低的CO和NO起燃温度(T50),分别为114oC和149 oC,最低的CH4和CO完全转化温度(T90),分别为398 oC和179 oC,以及最佳的CH4和CO温度特性,ΔT (T90–T50)值分别为34 oC和65 oC. Cat2具有最低的CH4起燃温度(342°C)和最低的NO完全转化温度(174°C). Cat1具有最差的转化活性,说明物理混合法制备的催化剂(Cat3和Cat2)性能优于共浸渍法制备的催化剂(Cat1).这是由于物理混合法制备的催化剂, Pt和Rh均匀分散在载体表面,两者物理接触共同参与CH4/CO/NO三种污染物的转化.相反,共浸渍法制备的催化剂, Pt和Rh之间存在较强的相互作用,改变了Pt的电子状态,而且形成了表面Pt富集的Pt-Rh双金属颗粒覆盖了Rh活性位,从而降低催化活性;同时,对于通过物理混合法并进一步添加助剂所制备的Cat3, XRD结果显示助剂Zr4+进入了铈锆固溶体晶格,产生晶格缺陷; XPS结果显示Cat3具有最高的Ce3+/Ce比例.这些都有利于提高催化剂的氧流动性,从而提高催化剂活性并拓宽空燃比窗口.     

预混天然气在多孔介质燃烧器中的燃烧与传热

在一台小型渐变型多孔介质燃烧器上进行了预混天然气燃烧与传热试验研究,探讨了天然气速度和多孔介质厚度对多孔介质燃烧室的温度分布、排烟温度和流动阻力的影响。结果表明,天然气在渐变型多孔介质燃烧器中燃烧稳定,燃烧室与水冷夹套间的换热受天然气速度和多孔介质厚度影响,换热效果比空管中燃烧明显增强,同时预混天然气通过多孔介质的进出口压差随着天然气速度和多孔介质厚度的增加而增加。     

Application of chromatography in purification and structural analysis of natural polysaccharides: A review

Polysaccharides are widely distributed in natural sources from monocytic microorganisms to higher animals, and are found in a variety of biological activities in recent decades. Natural polysaccharides have the characteristics of large molecular weight, diverse composition, and complex structure, so their purification and structural analysis are difficult issues in research. Chromatography as a powerful separation technique, plays an irreplaceable role in the separation and structural analysis of natural polysaccharides, especially in the purification of polysaccharides, the separation of hydrolysates, and the analysis of monosaccharide composition. The separation mechanisms and application of different chromatographic methods in the studies of polysaccharides were summarized in this review. Moreover, the advantages and drawbacks of various chromatography methods were discussed as well.     

基于金属氧化物脱硫剂的天然气深度脱硫

确立了基于GC-MS和GC-SCD的天然气中超微量硫化物定性定量分析方法与条件,并分析了北京城市天然气中的硫化物。结果表明,天然气中含有三种硫化物,主要成分为四氢噻吩(THT),占总硫的94.2%。采用共沉淀法制备了ZnO/Al₂O₃脱硫剂,采用浸渍法制备了ZnO/γ-Al₂O₃、CuO/γ-Al₂O₃和CuO-ZnO/γ-Al₂O₃脱硫剂,并进行了天然气中THT深度脱除的实验研究。结果表明, 采用浸渍法制备的CuO/γ-Al₂O₃和CuO-ZnO/γ-Al₂O₃脱硫剂同时具有良好的低温活性和高温活性,可在50~500℃的宽温下将THT脱除至物质的量分数10×10^-9以下,从而能够满足以天然气为燃料的分布式质子交换膜燃料电池电站对脱硫深度和脱硫温宽的要求。     

Excellent complete conversion activity for methane and CO of Pd/TiOz-Zro.sA10.5O1.75 catalyst used in lean-bum natural gas vehicles

Palladium catalysts are supported on TiO2, ZrO2, A12O3, Zro.sAlo.501.75 and TiO2-Zro.sAlo.501.75 prepared by co-precipitation method, re- spectively. Catalytic activities for methane and CO oxidation are evaluated in a gas mixture that simulated the exhaust from lean-burn natural gas vehicles （NGVs）. Pd/TiO2-Zro.sAlo.501.75 performs the best catalytic activity among the tested five catalysts. For CH4, the light-off temperature （Tso） is 254 ℃, and the complete conversion temperature （Tgo） is 280 ℃; for CO, Tso is 84 ℃, and Tgo was 96 ℃. Various techniques, including N2 adsorption-desorption, X-ray diffraction （XRD）, H2-temperature-programmed reduction （H2-TPR）, X-ray photoelec- tron spectroscopy （XPS）, and scanning electron microscopy （SEM） are employed to characterize the effect of supports on the physicochemical properties of prepared catalysts. N2 adsorption-desorption and SEM show that TiO2-Zro.5Al0.501.75 expresses uniform nano-particles and large meso-pore diameters of 26 nm. H2-TPR and XRD indicate that PdO is well dispersed on the supports and strongly interacted with each other. The results of XPS show that the electron density around PdO and the proportion of active oxygen on TiO2-Zro.sAl0.501.75 are maxima among the five supports.     

固定床天然气与煤共气化火焰区温度影响因素的研究

用实验室固定床反应器模拟合成气制备炉，考察了该工艺中不同因素对火焰区温度的影响。实验中首先确定了使火焰区温度最低时的甲烷和氧气相对入口位置，然后在此条件下分别考察了进料中H2O/O2和CH4/O2摩尔比变化对火焰区温度的影响。结果表明，甲烷和氧气相对入口位置平齐时火焰区温度最低，火焰区温度均随进料中CH4/O2和H2O/O2摩尔比的增大而降低。     

Excellent complete conversion activity for methane and CO of Pd/TiO2-Zr0.5Al0.5O1.75 catalyst used in lean-burn natural gas vehicles

Palladium catalysts are supported on TiO₂, ZrO₂, Al₂O₃, Zr_0.5Al_0.5O_1.75 and TiO₂-Zr_0.5Al_0.5O_1.75 prepared by co-precipitation method, respectively. Catalytic activities for methane and CO oxidation are evaluated in a gas mixture that simulated the exhaust from lean-burn natural gas vehicles (NGVs). Pd/TiO₂-Zr_0.5Al_0.5O_1.75 performs the best catalytic activity among the tested five catalysts. For CH₄, the light-off temperature (T₅₀) is 254 °C, and the complete conversion temperature (T₉₀) is 280 °C; for CO, T₅₀ is 84 °C, and T₉₀ was 96 °C. Various techniques, including N₂ adsorption-desorption, X-ray diffraction (XRD), H₂-temperature-programmed reduction (H₂-TPR), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) are employed to characterize the effect of supports on the physicochemical properties of prepared catalysts. N₂ adsorption-desorption and SEM show that TiO₂-Zr_0.5Al_0.5O_1.75 expresses uniform nano-particles and large meso-pore diameters of 26 nm. H₂-TPR and XRD indicate that PdO is well dispersed on the supports and strongly interacted with each other. The results of XPS show that the electron density around PdO and the proportion of active oxygen on TiO₂-Zr_0.5Al_0.5O_1.75 are maxima among the five supports.     

Nanoporous carbons as promising novel methane adsorbents for natural gas technology

Nanoporous carbons were synthesized using furfuryl alcohol and sucrose as precursors and MCM-41 and mordenite as nanoporous templates.The produced nanoporous carbons were used as adsorbent for methane storage.The average pore diameter of the samples varied from 3.9 nm to 5.9 nm and the BET surface area varied from 320m2/g to 824m2/g.The volumetric adsorption experiments revealed that MCM-41 and sucrose had better performance compared with mordenite and furfuryl alcohol,correspondingly.Also,the effect of precursor to template ratio on the structure of nanoporous carbons and their adsorption capacities was investigated.The nanoporous carbon produced from MCM-41 mesoporous molecular sieve partially filled by sucrose shows the best methane adsorption capacity among the tested samples.     

Comparison of three solid-phase extraction processes in quantification of ciprofloxacin and enrofloxacin in pork meat

Due to strong implications for food safety, control of fluoroquinolones residues in swine meat should be undertaken to verify compliance of the contamination levels with the maximum residue limits recently updated by Commission Regulation (EU) No. 37/2010 of 22 December 2009. Solid-phase extraction is widely used in antibiotic analysis in food of animal origin. In this study, the results of a comparative study using different types of solid-phase extraction columns, HLB, MCX, and MAX, for ciprofloxacin and enrofloxacin analysis, in pork meat, are presented. In addition, diverse sample treatments for defatting, precipitate proteins, eliminate cations, and increase the ionic strength, were used to obtain the most suitable method of analysis. Only the MCX's use followed by liquid chromatography with fluorescence detection resulted in chromatograms that allow the quantification at maximum residue limits. The validation method, in terms of CCα and CCβ, recovery and precision determination, was according to the EU Decision 2002/657/EC. This procedure was used in the analysis of 50 samples of pork meat of Portuguese origin. Only two samples presented residues of enrofloxacin at 30 and 42 μg/kg, values under the legal maximum residue limit.     

Excellent complete conversion activity for methane and CO of Pd/TiO_2-Zr_(0.5)Al_(0.5)O_(1.75) catalyst used in lean-burn natural gas vehicles

Palladium catalysts are supported on TiO2, ZrO2, Al2O3, Zr0.5Al0.5O1.75 and TiO2-Zr0.5Al0.5O1.75 prepared by co-precipitation method, respectively. Catalytic activities for methane and CO oxidation are evaluated in a gas mixture that simulated the exhaust from lean-burn natural gas vehicles(NGVs). Pd/TiO2-Zr0.5Al0.5O1.75 performs the best catalytic activity among the tested five catalysts. For CH4, the light-off temperature(T50) is 254℃, and the complete conversion temperature(T90) is 280℃; for CO, T50 is 84℃, and T90 was 96℃. Various techniques, including N2adsorption-desorption, X-ray diffraction(XRD), H2-temperature-programmed reduction(H2-TPR), X-ray photoelectron spectroscopy(XPS), and scanning electron microscopy(SEM) are employed to characterize the effect of supports on the physicochemical properties of prepared catalysts. N2adsorption-desorption and SEM show that TiO2-Zr0.5Al0.5O1.75 expresses uniform nano-particles and large meso-pore diameters of 26 nm. H2-TPR and XRD indicate that PdO is well dispersed on the supports and strongly interacted with each other. The results of XPS show that the electron density around PdO and the proportion of active oxygen on TiO2-Zr0.5Al0.5O1.75 are maxima among the five supports.     

对比3种不同的QuEChERS前处理方式在气相色谱-串联质谱检测分析烟草中上百种农药残留中的应用

以气相色谱-串联质谱(GC-MS/MS)技术为基础,建立了适合烟草中上百种农药残留分析的3种QuEChERS前处理方法:溶剂转换法、提取液稀释法和正己烷液液萃取法。以烟草中的有机磷、有机氯、拟除虫菊酯类、酰胺类、氨基甲酸酯类、二硝基苯胺类等共155种农药为研究对象,从基质效应、共萃取基质、色谱峰干扰、回收率和定量限等方面对3种前处理方式进行对比分析。经考察发现,3种方法各有优缺点,正己烷液液萃取法得到的提取液中共萃取基质含量最少,但只能保证约100种目标物的回收率在70%~120%;溶剂转换法和提取液稀释法对绝大部分目标物都能保证回收率在70%~120%,适合用于多农药残留分析检测。对不同种类农药进行对比,发现有机磷、酰胺类和氨基甲酸酯类农药的基质效应相对较强,而有机氯和拟除虫菊酯类目标物的基质效应相对较弱,因此,对有机磷农药单独分析时,建议使用提取液稀释法;对有机氯和拟除虫菊酯类农药单独分析时,建议使用正己烷液液萃取法。     

Phenolic natural products of the wines obtained from three new Merlot clone candidates

This work aimed to evaluate the total contents of polyphenolics (the Ribereau-Gayon–Maurié procedure), anthocyanins (using pH differential method) and tannins (the Nègre procedure) as well as the content of phenolic acids (using UPLC/MS chromatography), respectively of the wines obtained from three new Merlot clone candidates in the perennial clonal selection. The aforementioned chemical parameters were determined in the samples covering the period 2009–2012. In comparison both with the standard Merlot wine (mother vine) and the wines obtained from other two clone candidates, the Merlot wine of the clone candidate No. 022 was found to have the highest total content of all three examined components 1.89 ± 0.05 g/L (polyphenolics), 185.59 ± 5.00 mg/L (anthocyanins) and 1.11 ± 0.03 g/L (tannins), as well as six phenolic acids including gallic acid (25.49 ± 0.27 mg/L). These findings are in good agreement with the observed trend for the viticultural parameters indicating the clone candidate No. 022 as more promising than mother.