建立了铁基催化剂费托合成反应水相产物中低碳（C1~C8）醇、醛、酮的气相色谱测定方法。对色谱分离条件进行了优化，确立了以乙醇为基准物质并结合各组分校正因子的定量方法；考察了方法的精密度和准确度，并对费托合成反应水相产物样品进行了测定。结果表明，乙醇在不同的含量范围内呈现良好的线性关系，相关系数均大于0.99。费托合成水相产物中的加标回收率在93.4％~109.6％之间，准确性可以满足实际分析的需要。实际费托合成水相产物的分析结果表明，费托合成水相产物中主要的低碳醇、醛、酮的总质量分数约为3％~12％，乙醇含量最高（约为1.7％~7.3％），且正构醇、异构醇和醛酮类化合物所占的总比率依次降低。该方法简单、快速，对费托合成水相产物中重要组分的分析有重要意义。

A method for the determination of low-carbon(C1-C8)alcohols,aldehydes and ketones in aqueous products of Fischer-Tropsch synthesis was developed by gas chromatogra-phy. It included the optimization of separation conditions,the precision and accuracy of deter-mination,and the use of correction factors of the analytes to ethanol for quantification. The aqueous products showed that the correlation coefficients for ethanol in different content ranges were above 0. 99,which means it had good linear correlations. The spiked recoveries in the aqueous samples of Fischer-Tropsch synthesis were from 93. 4% to 109. 6%. The accuracy of the method can satisfy the requirement for the analysis of the aqueous samples of Fischer-Tropsch synthesis. The results showed that the total mass fractions of the major low-carbon alcohols, aldehydes,ketones in aqueous products of Fischer-Tropsch synthesis were about 3%-12%,and the contents of ethanol were the highest( about 1. 7%-7. 3%). The largest sha

费托合成通常被认为是个动力学控制的反应过程，因此对其热力学平衡的研究很少报道。本文基于 Aspen Plus 软件建立了费托合成产物物性数据库和热力学平衡分析模型，对费托合成的全局和局部热力学平衡进行了详细研究。结果表明：热力学上乙烯较其它长链烯烃更难生成，是解释实验观察乙烯偏低的重要原因；热力学平衡预测的总产物分布及烯烃、烷烃、醇的各组分分布均符合 ASF 分布规律，与实验观察的产物分布非常相似；若假定反应处于局部热力学平衡，则预测的产物分布链增长因子和烯烷比很接近实验观察值；热力学预测的反应条件对产物分布的影响也与实验结果基本一致。由此可见，热力学平衡是影响费托合成产物分布的重要因素，对反应机理研究至关重要。

Fischer-Tropsch synthesis (FTS) has been generally considered as a kinetic-controlled reaction and thus its thermodynamic equilibrium investigations were seldom reported. Based on Aspen Plus software, a physical properties database and a thermodynamic equilibrium model for FTS were established in this study. The simulated results show that ethylene formation is not favored in thermodynamics compared to other long chainα-olefins, which may be a reason to explain the lower ethylene content in experimental product distribution. The estimated product distributions of total hydrocarbons, olefins, paraffins and alcohols are similar to experimental ones and essentially follow Anderson-Schulz-Flory distribution pattern. As a local thermodynamic equilibrium is assumed for the formation of hydrocarbon product, the chain growth parameter and olefin/paraffin ratio are very close to their experimental values under same reaction conditions. Accordingly, thermodynamic equilibrium is highly important

利用Benson基团贡献法和ABWY法计算了费托合成油品的标准摩尔生成焓、标准熵及摩尔定压热容等基础数据,在298—750 K,对费托合成油品加氢裂化异构化反应体系的反应焓、吉布斯自由能以及平衡常数等热力学数据进行了计算;对体系中各反应的热力学可能性与生成顺序进行了判断以及各反应的热力平衡与限度进行了分析。结果表明:费托合成油品加氢裂化异构化反应是放热反应,低温时大部分反应在热力学上均能够自发的进行,且平衡常数均较大,能够进行到较高的程度;从热力学上看,升高温度不利于加氢裂化异构化反应的进行,适宜反应温度的选择应兼顾各种反应的进行;烯烃比烷烃更容易发生加氢裂化异构化反应;所获得的热力学数据可为费托合成油品加氢裂化异构化工艺研究、反应器开发以及新型催化剂研制等提供理论依据。

The standard molar enthalpy of formation,the standard entropy and isobaric molar heat capacity of Fischer-Tropsch syncrude were estimated by Benson group contribution method and ABWY method.The enthalpy change,Gibbs free energy change and equilibrium constant of hydrocracking and isomerization reaction of Fischer-Tropsch syncrude were calculated as a function of the temperature from 298 K to 750 K.The thermodynamic possibility and formation sequences of hydrocracking and isomerization reaction of Fischer-Tropsch syncrude were judged.Meanwhile,the thermodynamic equilibrium and the limit of different reaction steps were also analyzed. The results show that the hydrocracking and isomerization reaction of Fischer-Tropsch syncrude is an exothermic reaction,most of which are spontaneous at low temperature and can reach to a deep extent.Improving the temperature is not good for hydrocracking and isomerization reaction from a thermodynamic point of view.The choice of the suitable temperature s

采用水热法在Co/Al2O3球形催化剂外表面原位包裹了一层SAPO-34分子筛膜,制备了具有核(Co/Al2O3)-壳(SAPO-34)结构的复合型催化剂.用X-射线衍射和扫描电镜对其结构进行了表征,并考察了其费-托合成直接制取低碳烯烃的反应性能.结果表明:此复合型催化剂外层的SAPO-34膜对核心Co/Al2O3球形催化剂上的费-托合成反应提供了特殊的限域环境、孔道择型选择性和酸性,显著地改变了费-托合成产物分布,抑制了重质烃的生成,极大地提高了低碳烯烃的选择性.

A well-designed zeolite capsule catalyst with a Core (Co/Al2O3)-Shell (SAPO-34) structure was prepared by zeolite shell growing via in situ hydrothermal method. XRD and SEM were used to investigate the structure of the capsule catalyst. The catalyst was used to directly synthesize light alkenes from syngas via Fischer-Tropsch synthesis ( FTS ) reaction. The cesults indicated that the core-shell structure provided a tailor-made confined reaction environment with spatially confined effect, shape selectivity of channels and acidity. Thus the distribution of products from FTS was altered, the formation of long-chain hydrocarbons was suppressed, and the selectivity of light alkenes was significantly improved.

分别采用一步合成法和常规共沉淀法制备了Fe/SiO2催化剂,通过N2物理吸附、X射线衍射、透射电镜、傅里叶变换红外光谱和程序升温还原等方法对催化剂进行了表征,并在固定床反应器中对其费托合成制低碳烯烃的催化性能进行了评价。结果表明,与共沉淀铁基催化剂不同,采用一步合成法制备的纳米复合物主要由Fe3O4相构成,形貌呈规则球形,平均粒径为30 nm,尺寸分布窄,更容易还原。一步合成法制得的Fe/SiO2催化剂对费托合成反应具有较高的活性和低碳烯烃选择性、较低的甲烷选择性和良好的稳定性。

A series of Fe / SiO2 catalysts were prepared by one-pot synthesis and conventional co-precipitationmethods; they were characterized by N2 physisorption, X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, and temperature-programmed reduction. The performances ofthe Fe / SiO of light olefins from syngas. The results showed that in the Fe / SiO 2 catalysts in Fischer-Tropsch synthesis (FTS) were evaluated in a fixed-bed reactor for the production 2 catalyst prepared by one-pot synthesis method, the iron oxide is present as iron-silica nanocomposite in the form of Fe3 O4(magnetite). Compared withthe catalyst prepared by conventional co-precipitation method , the magnetite-silica nanocomposite by one-pot synthesis exhibits a more uniform spherical-like morphology, narrower size distribution (30 nm in average) andbetter reducibility. In FTS and selectivity to light olefin as well as lower selectivity to methane and better stability. , the Fe / SiO2