新型炭／T型分子筛复合膜材料的设计、制备及应用

以聚酰胺酸为有机前驱，两种不同形貌的T型分子筛为杂化物经高温热解制备了新型的炭／T型分子筛复合膜材料。利用TG、XRD、SEM等分析手段对所制备的复合膜的微结构进行了研究。结果表明，T型分子筛在炭相中分散良好，其晶体结构在热解过程中没有被破坏，同时形成了稳定的无机，无机复合结构。单组分气体（CO2，O2，N2和CH4）以及混合气体（CO2／CH4，O2／N2）的渗透实验表明，分子筛减小了气体分子在膜中的扩散阻力从而大大提高了复合膜对气体分子的渗透能力，其中，复合膜对CO2和O2渗透系数可达1302Barrer[1Barrer=1×10^-10cm^3（STP）·cm／cm^2·s·cmHg]和334Barrer，同时CO2／CH4混合气体分离系数达到62，O2／N2分离系数达到8左右。这些数据表明该复合膜是一种可实现大规模二氧化碳以及空气分离的理想膜材料。     

用于分离CH4/CO2的分子筛型PAN-ACF的制备和性能

以聚丙烯腈基预氧纤维毡（PAN－OF）为原料，经过空气氧化和CO2活化制备出对CO2／CH4具有较好筛分性能的分子筛型聚丙烯腈基活性碳纤维毡（PAN－ACF），采用电子天平，变压吸附（PSA）技术，XPS分析表征了分子筛型PAN－ACF的吸附性能和表面结构，结果表明，所制PAN－ACF样品对CO2／CH4吸附的选择性为7－11，当吸附压力为0.15MPa时，所产CH4的浓度达到99．9％，随着吸附的压力升高甲烷气的浓度下降，XPS结果表明经该法处理的样品，其类石墨微晶间以sp^3杂化碳氧单键相联，并出现腈类及酰胺类基团。     

CO_2与CH_4膜分离的发展与现状

通常化石燃料的燃烧会向大气中排放大量高浓度的CO2,其燃烧后对CO2处理减轻温室效应具有重要的环保意义。对于气体分离来说方法众多,基于膜的分离技术已经成为分离方法中极具竞争力的一种,并且成为CO2/CH4分离的有效手段之一,许多膜都能对CO2/CH4进行分离,其中主要可分为3三种:高分子膜、无机膜和混合基质膜。高分子膜通过传递性质更进一步可分为:渗透膜、促进传递膜。介绍了用于CO2/CH4气体分离的几种膜的工作原理、发展现状、瓶颈因素和解决途径,对比了各种膜的操作条件、分离效能和成本,最后提出了未来的研究方向和目标的建议。     

炭分子筛的结构和表面性质对其吸附分离CH4/N2和CO2/N2的影响

对日本Takeda(CMS-1)、Kuraray(CMS-2)和德国BF(CMS-3)3种炭分子筛(CMS)的孔结构和表面官能团进行了表征,分析了它们对CH4/N2和CO2/N2的吸附平衡和吸附动力学分离性能,以及CMS的结构与表面性质对吸附性能的影响。结果表明,CMS-1和CMS-2可实现CH4/N2的动力学分离,还可实现N2/CO2的平衡分离;CMS-3平衡分离CH4/N2和CO2/N2的效果要优于动力学分离。孔结构是影响炭分子筛分离性能的直接因素,孔径分布的差异使CMS-1和CMS-2对CH4/N2的位阻-动力学分离效应表现得更为明显;表面含氧官能团有利于提高炭分子筛的吸附分离性能。     

CO2对MPCVD制备金刚石膜的影响研究

应用微波等离子体化学气相沉积（MPCVD）技术,以CH4／H2／N2为主要气源,通过添加CO2辅助气体,并与未添加CO2辅助气体进行对比,进行了金刚石膜沉积。研究了添加不同浓度CO2对生长金刚石膜的影响。结果表明：当CO2流量在0～25cm3／min范围变化时,金刚石膜表面粗糙度分别为8．9nm、6．8nm、9．2nm、9．6nm。表明适量引入CO2可以降低膜面粗糙度,但是进一步提高CO2流量,膜面粗糙度反而上升。同时当CO：流量在0～15cm3／min范围变化时,金刚石膜的品质和生长都表现出上升趋势,但是超过该流量,其品质和生长率都出现下降趋势。另外,当CO2流量为15cm3／min,生长的金刚石膜不仅品质好,而且生长率也较高。     

乙硼烷混合气中微量杂质的分析

介绍了以美国GOW-MAC592型氦放电检测器气相色谱仪分析乙硼烷与氢气混合气中O2、N2、CH4、CO等微量杂质的色谱条件及定量方法。     

不同等离子体体系中纳米金刚石薄膜制备的研究

利用微波等离子体化学气相沉积（MPCVD）法分别在CH4／H2／Ar体系、CH4／H2／O2体系和C2H5OH／H2体系中进行纳米金刚石（NCD）薄膜的制备研究。采用原子力显微镜（AFM）和激光拉曼光谱（Raman）等方法对不同体系中制备得到的NCD薄膜的表面形貌及其质量进行了检测。结果表明：在CH4／H2体系中添加O2对于促进高平整度NCD薄膜的效果明显优于添加At;C2H5OH／H2体系更有利于制备颗粒更细、金刚石相含量更高的NCD薄膜。利用等离子体CVD技术的相关理论对上述结论进行了理论分析。     

CO_2/CH_4分离膜技术在沼气提纯中的应用研究进展

生物天然气(BNG)是近年来新兴的一种可再生清洁能源.制备生物天然气的核心是去除沼气中的二氧化碳.CO2/CH4分离膜技术被认为是未来沼气提纯领域最有潜力的一项技术.本文对CO2/CH4分离膜技术在沼气提纯中的应用研究和发展现状进行综述,包括CO2/CH4分离膜材料的最新发展;膜法沼气提纯工艺过程的设计;欧美膜法沼气提纯工业化装置的近况等;最后对膜法沼气提纯技术的主要困难及未来发展方向进行分析与讨论.     

乙醇水蒸气重整制氢催化材料的制备及其性能研究

用浸渍法制备了以 CeO2 为助剂的镍基乙醇水蒸气重整制氢催化剂(Ni/CeO2/γ Al2O3)。该种催化剂在较低的温度下具有较高的氢气产率和较高的CO2 选择性,并使副产物 CH4 和 CO的选择性限制在较低水平。在 600℃,催化剂 16% Ni/CeO2/γ Al2O3的氢气产率可达4.8,生成 CO2、CO和 CH4 的选择性分别为70.7%、21%和7%。     

使用改装的SP-2305型气相色谱仪测定气体中的微量杂质

使用氢火焰离子化检测器时,通过加装镍触媒转化管的方法,实现高纯气体中微量CO,CO2,CH4的测定.     

惰性介质对甲烷/空气预混气体爆炸极限的影响?

以化学平衡和吉布斯自由能为基础,采用Chem Kin数值模拟软件并选取临界温度1 450 K作为混合气体是否可燃的判别标准,研究了氮气、二氧化碳惰性介质对混合气体爆炸极限的影响。并在7 L爆炸容器内,对瓦斯和空气的混合气体的爆炸极限进行实测,得到了甲烷与二氧化碳(或氮气)按不同比例混合时在空气中的爆炸极限。结果表明:当甲烷与二氧化碳体积比为0.294时,爆炸上下限重合,当体积比小于0.294时,任何配比下均不被点燃。同时得出二氧化碳的抑爆能力强于氮气。     

聚醚共聚酰胺多层复合气体分离膜的制备及其分离性能

采用浸渍涂覆法,以聚醚共聚酰胺PEBA1074嵌段高分子为选择层膜材料制备具有超薄分离层的PEI/PDMS/PEBA1074/PDMS多层复合气体分离膜,探讨了操作条件对H2、N2、CH4和CO2等在多层复合膜中的渗透性能的影响.多层复合膜对极性气体具有较高的渗透通量,并且对极性/非极性气体分离体系具有较高的选择性.CO2对多层复合膜存在增塑作用,其渗透通量随操作压力的增加而增加;随着操作温度的升高,H2、N2、CH4和CO2在复合膜中的渗透通量显著增大,而CO2/非极性气体(H2、N2和CH4)的分离系数减小.气体渗透通量与温度的关系在PEO链段熔点的上下分别满足不同的Arrhenius方程.当操作温度大于PEO链段熔点温度时,气体的渗透活化能减小.     

Permeation of binary gas mixtures in ultramicroporous membranes

High-quality nanometer thick ultramicroporous membranes were prepared from silica sol-gel processes and tested for the permeation of binary gas mixtures of He, H2, CO2, and CH4 across different temperature and partial pressure regimens. Pore size distribution by molecular probing showed that the majority of pore sizes had dimensions below 2.9 A. In 50:50 binary mixtures, the fluxes of gases increased as a function of temperature, indicating an activated transport mechanism. The ultramicroporous membranes showed high selectivities at 150 degrees C for He/CO2 (30), He/CH4 (93), H2/CO2 (10), and H2/CH4 (9) with lower selectivities for CO2/CH4 (5). High activation energies (Ea) were observed for the permeance of 50:50 binary mixtures containing He and H2 of 22.1-27.5 and 17.6-23.1 kJ.mol-1, respectively. The Ea for the permeance of the total mixture approached the Ea for the permeance of the molecule with the smaller kinetic diameter (He or H2).     

KH-570修饰的SiO2膜制备及CH4/CO2的分离

采用KH-570代替部分TEOS为前驱物,共水解缩聚反应制得疏水性SiO2膜,通过IR、DTG、SEM、接触角测试仪等手段对KH-570修饰后的SiO2膜进行表征,并对CH4和CO2渗透和分离进行研究。实验结果表明,修饰后(0.8KH-570)SiO2膜接触角达到94.2°,红外光谱分析表明修饰后SiO2膜疏水性增强;(0.8KH-570)SiO2膜具有完整性及在400℃水热稳定性;压差30kPa,分离因子随涂膜次数增加先增大后减小,涂膜5次达最大值2.13,超越了努森扩散理论分离因子1.66,此时分离效果好;对于涂膜5次的SiO2膜,CH4渗透通量随压差增加呈现非线性微增趋势,CH4/CO2分离因子几乎不变。     

Precision trace gas analysis by FT-IR spectroscopy. 1. Simultaneous analysis of CO2, CH4, N2O, and CO in air

We report the development of a method of trace gas analysis based on 1-cm-1 resolution Fourier transform infrared (FT-IR) spectroscopy, deployable in both laboratory and field applications. Carbon dioxide, methane, nitrous oxide, and carbon monoxide may be analyzed simultaneously in a single air sample using this method. We have demonstrated that the method can provide analytical precision of the order of +/- 0.15 mumol mol-1 for CO2, +/- 0.9 nmol mol-1 for CH4, +/- 0.3 nmol mol-1 for N2O, and +/- 0.3 nmol mol-1 for CO, expressed as mole fractions in dry air. The analytical precision is in all cases competitive with or superior to that of the more usual methods of analysis for these trace gases, namely, nondispersive infrared spectroscopy for CO2 and gas chromatography-based techniques for CH4, N2O, and CO. The novel FT-IR method relies on calibration using synthetically calculated absorbance spectra and a chemometric multivariate calibration algorithm, classical least squares.     

Decomposition of benzene in the RF plasma environment. Part I. Formation of gaseous products and carbon depositions

This study employed radio-frequency (RF) plasma for decomposing benzene (C6H6) gas, and examined both gaseous products and solid depositions after reaction. The reactants and products were analyzed mainly by using both an on-line Fourier transform infrared (FT-IR) spectrometer and a gas chromatography. The analyses for solid deposition included electron spectroscopy for chemical analysis (ESCA), element analysis and heat value analysis. The C2H2, C2H4, C2H6, CH4, CO2 and CO were detected and discussed. The analytical results demonstrate that in the C6H6/Ar plasma, C2H2 is the sole gaseous product being detected. The fraction of total carbon input converted into C2H2 YC2H2 increased with increasing C6H6 feed concentration, but decreased with increasing input power. In the C6H6/H2/Ar system, besides C2H2, CH4, C2H4 and C2H6 were also detected, and their yields increased with increasing H2/C6H6 ratio. The above results indicated that the addition of H2 (auxiliary gas) achieves the benefit of creating hydrogen-rich species like CH4, C2H4 and C2H6. In the C6H6/O2/Ar system, C6H6 could be totally oxidized into CO2, CO and H2O, and no measurable phenol was found. Analyses of solid depositions revealed that the carbon depositions were similar to those of Anthracite. The carbon deposition has a heat value of 7000 kcal/kg. Additionally, the possible reaction pathways were also built up and discussed.     

KOH活化法制备气体分离用炭分子筛膜

选用KOH为活化剂,利用化学活化法制备炭分子筛膜,考察在热塑性酚醛树脂(PFNR)涂膜液中添加不同质量分数的KOH对炭分子筛膜的影响.结果表明,在炭化过程中,KOH的加入可促进炭分子筛膜孔径的均匀分布,使炭分子筛膜具有发达的孔隙结构.当KOH在PFNR中的添加量从0％增加到4％时,H2的渗透速率由23.68×10-10 mol·m-2·s-1·pa-1提高到28.6×10-10 mol·m-2·s-1·Pa-1;但H2/N2和H2/CH4的分离系数明显下降,分别从471.3下降到147.5、540下降到270.CO2/CH4和O2/N2的分离系数只有轻微下降.     

A gas chromatographic separation for the h and C stable isotope ratio determination of coal compounds

A new, completely automated gas chromatography technique has been developed to separate the different gaseous compounds produced during underground coal gasification for their (13)C/(12)C and D/H isotope ratio measurements. The technique was designed for separation and collection of H(2), CO, CO(2), H(2)O, H(2)S, CH(4), and heavier hydrocarbons. These gaseous compounds are perfectly separated by the gas-phase chromatograph and quantitatively sent to seven combustion and collection lines. H(2), CO, CH(4), and heavier hydrocarbons are quantitatively oxidized to CO(2) and/or H(2)O. The isotopic analyses are performed by the sealed-tube method. The zinc method is used for reduction of both water and H(2)S to hydrogen for D/H analysis. Including all preparation steps, the reproducibility of isotope abundance values, for a quantity higher than or equal to 0.1 mL of individual components in a mixture (5 mL of gases being initially injected in the gas chromatograph), is ±0.1‰ for δ(13)C(PDB) and ±6‰ for δD(SMOW).     

新型CO2分离膜的结构和性能

研制成功一种对ＣＯ２具有促进传递作用的新型膜材料－聚乙烯胺,将此膜材料覆盖在聚砜膜表面复合膜,考察了复合膜的多层结构,复合膜对ＣＯ２、ＣＨ４、Ｎ２等的吸着性能,及复合膜对ＣＯ２和ＣＨ４的分离进透过性能。结果表明,该复合膜对ＣＯ２有很高的吸着量,而对其他测试气体仅有极微弱的吸着;对ＣＯ２／ＣＨ４体系该复合膜具有良好的分离的能力。