原位合成分子筛膜毛细管色谱柱的研制

吸附型多孔层毛细管柱既耐高温又对气体及烃类异构体有选择性，同时又具有毛细管色谱快速、高效等优点，是解决难分离组分的重要柱型．常用作气一固吸附色谱固定相的有强极性的硅、中极性的氧化铝、非极性的碳质及特殊吸附作用的分子筛．其中分子筛以其独特的吸附作用，在永久性气体和烃类碳数族组成分析中有重要地位．Pruecell和Soulages[1，2]等制备了涂渍型5A和13X型分子筛的毛细管柱，对低碳烃类化合物显示了良好的分离能力，分析柱温较填充柱降低约100℃．邹乃忠等[3～5]也先后制备了分子筛层的毛细管柱用来作直馏汽油的分析．由于通…     

双柱串联色谱一次分析甲烷部分氧化制合成气产物

采用ＰｏｒａｐａｋＮ色谱柱，延迟空管和１３Ｘ分子筛色谱柱串联方法，用一个ＴＣＤ，通过ＡｎａＳｔａｒ色谱工作站实时采集信号进行在线分析，可成功地一次性和分析ＰＯＭ产品气听ＣＨ４，ＣＯ，ＣＯ２，Ｏ２等几处可能组分，消除了两台色谱仪无法同时取样分析和在两个不同ＴＣＤ检测器上采集数据引起的实验误差，提高了分析的可靠性。     

气相色谱法用于煤油轻镏分烃类组成分析

用氰乙基化反应合成的强极性固定液制成强极性色谱柱!与分子筛柱串联,结合分子筛扣减技术,测定了几种航空煤油油样中正烷烃、芳烃、异构烷加环烷三个烃族组成。进一步用一种弱极性色谱柱与分子筛柱串联,由分子筛扣减法可测定各单体正构烷烃的含量,对所提出的方法的准确度和重复性进行了讨论。@汪燮卿$用氰乙基化反应合成的强极性固定液制成强极性色谱柱!与分子筛柱串联,结合分子筛扣减技术,测定了几种航空煤油油样中正烷烃、芳烃、异构烷加环烷三个烃族组成。进一步用一种弱极性色谱柱与分子筛柱串联,由分子筛扣减法可测定各单体正构烷烃的含量,对所提出的方法的准确度和重复性进行了讨论。     

高聚物气液固毛细管柱的制备及液相对柱性能的影响

以乙基乙烯苯为单体,二乙烯苯为交联剂,加入不同极性和不同量的固定液,在引发剂存在下可原位一步反应制备成高聚物气液固毛细管柱。通过对柱子等量吸附热（Ｑ＿（ｓｔ））等色谱参数的测定和计算,可以研究高聚物气液固毛细管柱制备过程中形成气液固分离机理所需的液相量。用制备的高聚物气液固柱,对某些异构体的分离进行了考察。     

毛细管多维气相色谱法分析炼厂气

用ＨＰ６８９０气相色谱仪,使用多孔层空心毛细管柱（ＰＬＯＴ）,选用ＨＰ－ＰＬＯＴ／Ｐｏｒａｐａｃｋ Ｑ色谱柱测定ＣＯ２;ＨＰ－ＰＬＯＴ ５Ａ分子筛柱测定Ｏ２,Ｎ２,ＣＨ４;ＨＰ－ＰＬＯＴ／Ａｌ２Ｏ３柱测定有机烃类。采用３阀４柱色谱运行系统,用ＦＩＤ及ＴＣＤ分别检测烃类及无机气体组分。用色谱工作站控制气动切换阀切换气样走向及两种检测器数据的转换校正和归一化定量计算,用已知物对照法定性,测定了炼厂气中     

硅钨杂多酸在中孔全硅分子筛HMS上的固载及其催化性能

用十二烷基胺代替传统的季铵盐合成了中孔全硅分子筛ＨＭＳ，并将硅钨杂多酸浸渍固载在ＨＭＳ上，用ＸＲＤ，ＦＴ－ＩＲ以及ＮＨ３－ＴＰＤ等手段对ＨＭＳ及不同负载量的焙烧温度的负载论剂进行了表征，即使在固载量为５０％的ＳｉＷ１２／ＨＭＳ中，ＳｉＷ１２仍保持其Ｋｅｇｇｉｎ结构产均匀分布在载体表面上，没有ＳｉＷ１２晶相生成，同时，在气－固相反应体系中研究了固载在ＨＭＳ上的ＳｉＷ１２在合成乙酸丁酯中的催化性能，实     

高硅ZSM-5分子筛和二次合成Ti-ZSM-5分子筛的结构

运用度角旋转（MAS）和交叉极化（CP）等核磁共振波谱和红外光谱技术，分别对采用不同模板剂制备的高硅ZSM－5分子筛和以此为母体，经气固同晶取代法得到Ti－ZSM－5分子筛的结构特性进行了研究．结果表明：在水热法合成高硅ZSM-5分子筛过程中，模板剂明显制约着所制得的分子筛的结构特性．通过选用合适的模板剂，可直接获得具有正交晶系结构的高硅ZSM－5分子筛．在随后的气固相同晶取代过程中，钛原子通过占据分子筛骨架中的缺陷位进入骨架，形成具有一定Ti／Si比例的钛硅分子筛（Ti－ZSM－5）。骨架结构中缺陷位的含量直接影响分子筛的载钛量。     

天然气制取的浓乙炔中微量杂质气体的色谱分析

为测定天然气制取的浓乙炔中的微量杂质气体,采用氢作载气,自制热导池为鉴定器,国产大华电子电位计为记录仪的气液色谱及气固色谱法,以水杨醛和液体石蜡混合固定液的色谱柱分离测定其中的丙二烯、甲基乙炔、丁二烯、乙烯基乙炔、丁二炔等五个组分,一次分析时间为18分钟。另以活性炭柱和5A分子筛柱串联及活性炭柱和硅胶柱串联,两次进样,分离测定其中氧、氮、甲烷、一氧化碳、二氧化碳、乙烯等组分,一次分析时间20分钟,本法的最低检出浓度为1.16至36.0×10~(-6),杂质气体含量在0.5至0.005％范围内的分析重复性以相对平均偏差表示<±10％,准确度以相对平均误差表示<±5％。     

仿生手性介孔硅作为气相色谱固定相的性能研究

从帝王蟹几丁质膜中剥离出纳米纤维甲壳素膜,经过处理,将膜中的矿物质去除后作为模板,制备手性向列型介孔硅。热重曲线测试表明手性向列型介孔硅具有很好的热稳定性,适合作气相色谱固定相。将仿生手性向列型介孔硅作为气相色谱固定相,采用动态涂敷的方法制备手性毛细管气相色谱柱,该柱子能够对6种外消旋体(1-甲氧基-2-丁醇、2-甲基戊醛、2-苯基丙醛、香茅醇、3-羟基丁酸甲酯、3-丁炔-2-醇)进行拆分。主要还讨论了6种位置异构体、正构烷烃、正构醇类在该柱的分离情况,同时对柱子的柱效和极性进行了评价。     

3，5-二硝基苯甲酰化β-环糊精键合硅胶手性固定相的合成及高效液相色谱中的手性分离研究

合成了3,5-二硝基苯甲酰化β-环糊精键合硅胶手性固定相,并用红外光谱和X射线光电子能谱进行了表征.制备了相应的高效液相色谱柱,在高效液相色谱中,考察了该手性柱的柱效和对于一些位置异构体和对映异构体的手性分离能力.结果表明,该固定相对于一些位置异构体和对映异构体具有较好的分离能力.     

Preparation and evaluation of OV-240-OH coated glass capillary columns for isomer specific determination of PCDDs and PCDFs

Glass capillaries were leached, dehydrated, persilylated with 1, 3-bis (3-cyanopropyl) tetramethyldisiloxane, and coated with OV-240-OH. After crosslinking and binding the phase to the glass surface the columns showed high separation efficiency, high temperature stability, and inertness comparable to persilylated apolar columns. Column performance is shown to be superior to liquid phase cyanopropyl columns such as SP 2330. The excellent separation capabilities together with the selectivity of the phase makes OV-240-OH coated columns a valuable tool for the determination of toxic isomers in complex mixtures of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). The order of elution of individual TCDD isomers was found to be similar to that described for SP 2330 or Silar 10c. The detection of PCDDs and PCDFs in a fly ash extract further illustrates the utility of OV-240-OH coated columns. The high temperature limit of these columns opens the way for the analysis of high boiling compounds such as mixed brominated/chlorinated dibenzo-p-dioxins and dibenzofurans.     

Gas Chromatography on Zeolite-Based Adsorbents

The adsorption and gas chromatographic properties of zeolites, both modified with carbon and supported as a surface-porous layer, have been studied. Carbonization of zeolites changes the chemical nature of their surface and their molecular sieve properties. In comparison with other adsorbents (carbons, polymers, etc.), modified and supported zeolites are characterized by better selectivity for separation of light-boiling compounds formed in many catalytic reactions. Zeolite-based adsorbents have been used for gas chromatographic analysis of mixtures the analysis of which was a problem or was impossible with traditional chromatographic columns.     

Preparation of High Performance Alumina PLOT Columns and Analysis of Light Hydrocarbons

With the introduction of new capillary column coating technique.It has been realized to prepare gas chromatograph of very high resolution. There has been continued interest in extending the use of GSC adsorbent to capillary chromatography. Currently the film built up on the inner surface of the capillary column can be quite homogeneous and the separation efficiency of the column is increased as well. There have been numerous papers that describe the preparation of PLOT columns in detail. However, Owing to the complexity of the preparation of porous layer for capillary GSC. It is still urgently need to extensively study the preparation process in order to get desired capillary columns of high quality and good reproducibility. This paper describe a new coating method of high performance PLOT columns with alumina by means of liquid phase deposition other than dynamic or static coating techniques. The selectivity, reproducibility and separation power of the column in analysis of light hydrocarbons were examined.     

Gas chromatography for in situ analysis of a cometary nucleus. II. Analysis of permanent gases and light hydrocarbons with a carbon molecular sieve porous layer open tubular column

Considering the severe constraints of space instrumentation, a great improvement for the in situ gas chromatographic (GC) determination of permanent and noble gases in a cometary nucleus is the use of a new carbon molecular sieve porous layer open tubular (PLOT) column called Carbobond. No exhaustive data dealing with this column being available, studies were carried out to entirely characterize its analytical performances, especially when used under the operating conditions of the cometary sampling and composition (COSAC) experiment of the European Space Agency (ESA) Rosetta space mission to be launched in 2003 for a rendezvous with comet 46 P/Wirtanen in 2011. The high efficiency and speed of analysis of this column at both atmospheric and vacuum outlet column pressure is demonstrated, and the kinetic mass transfer contribution of this carbon molecular sieve adsorbent is calculated. Besides, differential adsorption enthalpies of several gases and light hydrocarbons were determined from the variation of retention volume with temperature. The data indicate close adsorption behaviors on the Carbobond porous layer adsorbent and on the carbon molecular sieve Carboxen support used to prepare the packed columns. Moreover, taking into account the in situ operating conditions of the experiment, a study of two columns with different porous layer thicknesses allowed one to optimize the separation of the target components and to select the column parameters compatible with the instrument constraints. Comparison with columns of similar selectivity shows that these capillary columns are the first ones able to perform the same work as the packed and micro-packed columns dedicated to the separation of this range of compounds in GC space exploration.     

Fundamental characteristics of synthetic adsorbents intended for industrial chromatographic separations

With the aim of obtaining comprehensive information on the selection of synthetic adsorbents for industrial applications, effect of pore and chemical structure of industrial-grade synthetic adsorbents on adsorption capacity of several pharmaceutical compounds was investigated. For relatively low molecular mass compounds, such as cephalexin, berberine chloride and tetracycline hydrochloride, surface area per unit volume of polystyrenic adsorbents dominated the equilibrium adsorption capacity. On the contrary, effect of pore size of the polystyrenic adsorbents on the equilibrium adsorption capacity was observed for relatively high molecular mass compounds, such as rifampicin, Vitamin B12 and insulin. Polystyrenic adsorbent with high surface area and small pore size showed small adsorption capacity for relatively high molecular mass compounds, whereas polystyrenic adsorbent with relatively small surface area but with large pore size showed large adsorption capacity. Effect of chemical structure on the equilibrium adsorption capacity of several pharmaceutical compounds was also studied among polystyrenic, modified polystyrenic and polymethacrylic adsorbents. The modified polystyrenic adsorbent showed larger adsorption capacity for all compounds tested in this study due to enhanced hydrophobicity. The polymethacrylic adsorbent possessed high adsorption capacity for rifampicin and insulin, but it showed lower adsorption capacity for the other compounds studied. This result may be attributed to hydrogen bonding playing major role for the adsorption of compounds on polymethacrylic adsorbent. Furthermore, column adsorption experiments were operated to estimate the effect of pore characteristics of the polystyrenic adsorbents on dynamic adsorption behavior, and it is found that both surface area and pore size of the polystyrenic adsorbents significantly affect the dynamic adsorption capacity as well as flow rate.     

Extending the scope of enantiomer separation on diluted methylated β-cyclodextrin derivatives by high-resolution gas chromatography

High-resolution open-tubular columns coated with solutions of heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin (Phase I) or heptakis(2,6-di-O-methyl-3-O-trifluoroacetyl)-β-cyclodextrin (Phase II) in moderately polar polysiloxanes such as OV-1701 (5% cyanopropyl/7% phenyl/88% methylpolysiloxane) and OV-225 (25% cyanopropyl/50% phenyl/25% methylpolysiloxane) are used for the gas chromatographic enantiomer separation of volatiles belonging to different classes of compounds. No derivatization procedures are necessary for most of the resolved chiral molecules. The chiral stationary phases can be operated between 25 and 190°C for extended periods of time. The enantiomer separation of saturated, unfunctionalized hydrocarbons clearly demonstrates the importance of molecular inclusion in chiral recognition using cyclodextrins for this class of compounds. The different, and in some cases complementary, selectivity of the Phases I and II is demonstrated.     

煤直接液化油中混合酚的分离研究

利用分子筛择形特点，对煤直接液化油中的混合酚实施高效分离。本研究选取间甲酚和对甲酚作为分离煤直接液化油馏分段混合酚的模型化合物，采用化学液相沉积法对HZSM-5吸附剂的孔口结构进行改变，分析分子筛硅铝比及颗粒粒径对模型化合物间甲酚和对甲酚吸附分离性能的影响，以获得高性能固相吸附剂，并将其应用于180-190℃馏分段混合酚分离。结果表明，当分子筛硅铝比为25、粒径为3-5 μm时，分子筛的孔口结构调节效果最优；当正硅酸乙酯的最小用量为0.2 mL/g时，固相吸附剂的吸附量为0.03 g/g，对甲酚选择性高于95%。由于外表面沉积物对吸附剂的孔口结构变化，导致对甲酚选择性的提高。进一步采用HZSM-5（1）吸附剂对真实煤直接液化油混合酚的分离中发现，苯酚和对甲酚的选择性均达到100%。     

吸附法脱除乙烯中少量氮气的研究

采用重量法在电子天平上，研究了C2H4和N2单组分在5A、13X、丝光沸石和炭分子筛不同吸附剂上的吸附平衡性质和扩散动力学性质。单柱模拟变压吸附评价了炭分子筛吸附脱除C2H4-N2（N2为4．7％）混合组分中N2的性能，并对流速和压力的影响进行了考察。研究表明，该炭分子筛是吸附脱除C2H4中少量N2的理想吸附剂。     

Purification of OV-17 by supercritical fluid fractionation for fused silica capillary gas chromatography

Commercially available OV-17 was partitioned into a low and a higher molecular weight fraction by supercritical fluid extraction with carbon dioxide. This higher molecular weight fraction is more thermally stable than the original OV-17 due to its more viscous and gum-like nature. Based on the growing evidence in the literature that a deactivating agent for fused silica open tubular columns should be compatible with the stationary phase, a precoat of 1,3,5-trimethyl-1,3,5-triphenylcyclotrisiloxane was applied prior to the static coating of high molecular weight OV-17. Fused silica OV-17 columns prepared in this fashion are stable up to 300°C.     

Determining the vinyl alcohol distribution in poly(vinyl butyral) using normal-phase gradient polymer elution chromatography

The application of film-forming organic polymers, which are in common use in membrane technology, as chromatographic adsorbents for packed and capillary columns has been suggested. The chromatographic characteristics of poly[1-(trimethylsilyl)-1-propine] (PTMSP) as an adsorbent were studied. The film-forming properties of PTMSP simplify manufacturing of capillary and packed gas–solid columns. It was shown that separation of C₁–C₄ hydrocarbon gases on the columns with PTMSP is of practical interest. In the authors’ opinion, PTMSP is also promising for the separation of inorganic gases.