Selective partial oxidation of light paraffins with hydrogen peroxide on thin-layer supported Nafion-H catalysts

Thin-layer carbon supported Nafion-H catalysts were found to be active and highly selective (S>98%) for the partial oxidation of C₁-C₃ alkanes, in a three phase catalytic membrane reactor (3PCMR), under mild conditions and in the presence of H₂O₂. The influences of the catalyst teflon loading and H₂O₂ concentration on the reaction rate have been evaluated. A reaction pathway, based on the electrophilic hydroxylation of the C-H bond of alkanes with protonated hydrogen peroxide (H₃O ₂ ⁺ ), is discussed.     

气相色谱法测定石脑油中含氧化合物含量

本文论述了利用气相色谱法检测石脑油中含氧化合物的方法,考察了无阀切换技术、分离模式的设计、操作条件的优化等方面的问题。提出利用多维气相色谱法,采用一根非极性柱和一根极性柱进行独立和串联分离,通过改变辅助载气压力的无阀切换方式进行柱分离,应用双FID检测器进行信号检测,数据利用Agilent的chemestation工作站采集和输出。该方法操作简单,分析时间在23 min以内,重复测定结果的相对标准偏差(RSD)小于1.5%,标准加入回收率在95～105%范围内,方法准确可靠。     

Partial oxidation of ethane by in situ generated H2O2

Selective partial oxidation of ethane to ethanol and acetaldehyde by in situ generated H₂O₂ has been achieved under cathodic current passing through a carbon supported Nafion-H catalytic membrane. A correlation between H₂O₂ generation rate and reaction rate has been found.     

On the nature of catalyst promotion by manganese in CO hydrogenation to oxygenates over RhMn/NaY

CO hydrogenation over Mn promoted Rh/NaY catalysts was studied at 10 bar and 250°C. Significant selectivity to oxygenates, mainly ethanol and ethyl acetate, was obtained after neutralizing the protons that are formed during reduction of Rh ions. Layered bed experiments show that protons act as sites catalyzing secondary reactions. Protons also convert Mn(OH)₂ to Mn²⁺ ions; the catalysts with highest selectivity to oxygenates contain MnO particles and Rh clusters. The results suggest chemical interaction of adsorbates on Rh_n clusters with those on MnO.     

微乳液在制备C_2含氧化合物合成催化剂中的应用

对微乳液法在制备C2含氧化合物合成催化剂中的应用做了较为详细的综述。从制得纳米粒子与载体的结合方式,主要有3种方法:微乳液同步合成法,微乳液沉积法和微乳液浸渍法。目前报道较多的是第一种方法,制得的Rh/SiO2催化剂具有较好的CO加氢生成C2含氧化合物的活性和选择性,但存在金属包埋的问题。微乳液沉积法可部分解决金属包埋问题,但金属与载体之间的化学作用力不强而导致催化剂热稳定性较差。微乳液浸渍法可以通过保持水核中金属离子在浸渍过程中处于未还原状态从而避免上述这些问题,虽然该法仅用于F-T合成催化剂的制备,但催化性能优越,产物中甲烷选择性非常低,值得尝试用于C2含氧化合物合成催化剂的制备。     

Pyrolysis studies of organic oxygenates: 3. High temperature rearrangement of aryl alkyl ethers

Thermal chemistry pathways of aryl alkyl ethers have been investigated under coal conversion-like conditions. Anisole is a thermally reactive compound having an oxygen functionality found in such coal precursors as lignins. Pyrolysis of anisoles was carried out using small batch autoclaves. Under thermolysis conditions anisole yielded a product distribution strongly dependent upon experimental parameters. Phenol, methane, CO and benzaldehyde are the low molecular weight products and polyphenyls and polyethers are the predominant high molecular weight products. The generation of CO is explained by a high temperature rearrangement of the phenyl group from O- to C- followed by rapid thermal decarbonylation of the benzaldehyde. Carbon monoxide formation from aryl alkyl ethers can thus be an important mechanistic pathway in coal conversion processes. By investigating the rearrangement using para-fluoroanisole it was shown that this rearrangement proceeds via a three-centered intermediate to para-fluorobenzaldehyde. No meta isomer was observed.     

气质联用仪测定汽油中含氧化合物、苯和甲苯的含量

利用选择离子法（SIM）对汽油中含氧化合物、苯和甲苯进行定量分析,可以简化分析步骤,缩短分析时间,有效消除汽油中复杂成分对目标组分分析结果的影响,提高了分析结果的准确性。15种组分标准曲线的线性相关系数均大于0.998 8,最低检测限为2~5 μg•g^-1,回收率为90%~103%,保留时间相对标准偏差小于0.5%,峰面积相对标准偏差小于11.05%。     

氧选择性检测器测定汽油中醇醚类含氧化合物的研究

采用氧选择性火焰离子化检测器，用一根非极性毛细管色谱柱作为分析柱，测定无铅汽油中含氧化合物的含量及总氧含量。本文对仪器各种部件的性能进行了考察，选择了最佳分析条件，建立了完善的分析方法。这套系统操作简单，分析时间短，数据准确，原理合理，符合国际上的发展趋势，便于技术推广，也为今后各炼厂及汽车行业控制无铅汽油中含氧化合物的含量创造了技术条件。     

多维气相色谱法测定车用汽油含氧化合物方法改进研究

一直以来车用汽油中含氧化合物分析基本均采用ASTMD4815或SH/T0663的方法,但随着车用汽油产品标准GB/T17930-2006版的出台,ASTMD4815和SH/T0663两种方法存在着部分含氧化合物分离效果较差、甲醇检测限达不到要求的问题,因此该分析方法迫切需要改进。该文提出采用多维气相色谱,利用经过硅烷化处理后的约1mTCEP微填柱和30mHP-1弹性毛细管柱,TCD和FID双检测器进行样品分离及检测,经过对柱系统和操作条件的优化,可准确地分析车用汽油中C1～C4醇类和醚类含氧化合物,甲醇检测限达到0.05%。方法重复性的相对标准偏差(RSD)≤0.827%,标准样品回收率在90%～110%之间。     

Undesired components in the transformation of biomass pyrolysis oil into hydrocarbons on an HZSM‐5 zeolite catalyst

The results of the catalytic transformation on HZSM‐5 zeolite of mixtures of components of biomass pyrolysis oil in the 673–723 K temperature range are evidence of the need for previously separating certain components (aldehydes, oxyphenols and furfural) that undergo severe thermal degradation by forming carbonaceous deposits at the reactor inlet ducts and on the catalyst itself. The deactivation of the catalyst is a consequence of the deposition of two different types of coke: one of catalytic origin (similar to that generated in the transformation of methanol and bioethanol) and the other of thermal origin, which is produced by the aforementioned degradation. The remaining oxygenate components react to each other with synergistic effect, which means that their reactivity is higher than that of the pure components. The results show that the aqueous fraction of biomass pyrolysis oil may be transformed into hydrocarbons on acid catalysts similarly to the more familiar transformation of methanol and bioethanol. Copyright © 2005 Society of Chemical Industry