费-托合成制液态烃研究进展

天然气先转化为合成气, 再经F ischer-Trop sch 反应合成液体烃类(GTL ) 是近年来天然气转化利用研究的主流。Shell、Sasol、Exxon、Syntroleum 等公司都分别开发了各自的GTL 专利技术。GTL 产品中液体燃料基本上由直链烷、烯烃组成, 具有无硫、无氮、无金属、无芳烃等特点, 是对环境友好的燃料油和化学品。由于合成气生成技术、F-T 合成催化剂和反应工艺的不断改进, 用GTL 技术开发利用边远地区和分散的中小气田的天然气资源在价格上已能和原油竞争。本文对F-T 合成催化剂、反应器及GTL 技术发展动态等方面做了综述, 讨论了其今后的发展趋势, 并指出在我国开展GTL 技术研究的必要性。     

The Future of Gas to Liquids as a Gas Monetisation Option

The paper introduces gas to liquids (GTL) as a monetising option from a technology, marketingand project perspective. GTL is complementary to LNG and pipelines. At the same time, using naturalgas as a source for fuels in the form of GTL helps countries around the world to diversify their energysupplies. Furthermore, gas-based products are inherently cleaner than oil products. Shell‘s proprietary GTL technology or SMDS (Shell Middle Distillates Synthesis), is discussed in some detail. The paperalso covers the challenges for successful implementation of GTL projects and why Shell is well positionedto take a lead in the industry on the basis of its long standing and broad experience in GTL research,plant operations, marketing and excellent track record in mega projects in the last thirty years. Shell‘scommitment to GTL is best demonstrated by the recent signing of a Heads of Agreement with Qatar Petroleum for the construction of the world‘s largest GTL plant. A key success factor is Shell‘s experiencewith marketing quantities of high quality GTL products from its 12,500 barrels per day plant at Bintulu,Malaysia since 1993. Further marketing opportunities will arise when new GTL capacity comes on-streamin the middle east when more quantities will become available to bulk users. Amongst the most interesting market will be automotive transportation, where clean GTL fuels can be positioned as an ‘alternativefuel beyond oil‘ providing energy security to host countries. Shell is actively engaging with a numberof regulators, automotive companies and governments worldwide including China, to demonstrate theperformance of GTL and its cost effectiveness in reducing local emissions. An added benefit is that GTLcan use existing infrastructure and requires no investment. Finally, the paper briefly discusses the coal toliquids (CTL) process as an alternative route to produce high quality GTL products and the key issuesrelating to the process.     

2002—Emergence of the Gas—to—Liquids Industry： a Review of Global GTL Developments

This paper reviews the status of the gas-to-liquids(TGL) industry-including current commercial plants,announced projects and the technologies that are are likely to be implemented in these future projects.Today,only 35,000 B/D of GTL products (0.1% of market) are manufactured from commercial gas-based plants,Advances in technology have lowered the cost of plants to the point where GTL phants can be profitable at crude oil prices of $16/B ,The advanced stage of development of several proposed GTL projects and attractive integrated economicws,for both the gas field and plant ,show that GTL can be a significant alternative for monetizing natural gas in the 21st centruy,GTL technologies includes more than Fischer-Tropsch technology and extends to other liquid fuels,especially in the oxygenate family (methanol,dimethyl ether ,etc.).     

Chromatographic determination of total hydrocarbons in ethanolamine employed in sweetening process of natural gas

Summary A rapid and easy gas chromatographic method is proposed for the determination of condensate content in monoethanolamine employed in the sweetening process of natural gas in the petroleum industry. This method covers a wide range of heavy hydrocarbons (condensate) content by using a short conventational column. A comparative study has been carried out and the advantages of the gas chromatographic technique have been demonstrated.     

The determination of chlorinated aliphatic hydrocarbons in air, natural waters, marine organisms, and sediments

A gas Chromatographic procedure is described for the determination of chlorinated aliphatic hydrocarbons in the atmosphere, natural waters, aquatic organisms and sediments. Air samples are passed through activated carbon traps and the chloro compounds are later desorbed by heating in a current of nitrogen. Chloro compounds are stripped from water samples by bubbling with nitrogen and from bio-materials and sediments by heating in a current of nitrogen. In each instance, the chlorinated compounds are trapped in copper columns packed with Chromosorb coated with silicone oil, and cooled to -78°. The chloro compounds are subsequently swept off these columns into a gas chromatographic column with a current of argon. Detection of the Chromatographic peaks is performed with an electron-capture detector. The procedure gives near quantitative recoveries of a range of chlorinated hydrocarbons from natural samples.     

Analysis of C10-C20 hydrocarbons in natural gas by solid phase extraction and CGC

A method is described for the determination of C10-C20 hydrocarbons in natural gas. Enrichment by solid phase extraction on ODS followed by liquid desorption was found to give better results than adsorption on Tenax or charcoal followed by liquid or thermal desorption.     

Methane—the Promising Career of a Humble Molecule

Methane, CH4, here represents natural gas (NG) of which it is the main constituent. Routes ofchemical utilisation of NG — as opposed to energy usage — are discussed. A main step is the conversion of NG to synthesis gas, a mixture of CO and H2. Simple molecules derived from synthesis gas, like methanol,can be further reacted to longer-chained hydrocarbons like propylene and other olefins and even to gasoline and diesel.     

A New Model for the Genesis of Natural Gases--Multi-source Overlap, Multi-stage Continuity, Type Controlled by Main Source and Nomenclature by Main Stage (Ⅰ)--Multi-source Overlap and Type Controlled by Main Source

Based on the geochemical studies of natural gases in the past ten years in China, the authors have proposed a new model for their genesis--multi-source overlap, multi-stage continuity, main source-controlling type and nomenclature by the main stage.Multi-source refers to a diversity of material sources involved in the formation of natural gases, including abiogenic and biogenic material sources. In regard to biogenic sources, either oil-generating or coal-generating organic matter would produce gaseous hydrocarbon reservoirs of commercial importance. Generally, natural gases originating from these sources can overlap to form gas reservoirs. Under specific circumstances mantle-source abiogenic gases could overlap biogenic gases to form gas reservoirs. In nature, natural gases predominated by gaseous hydrocarbons may be formed from a single end-member source. However, multi-source overlap is more typical of the genesis of natural gases.     

Mathematical algorithm for qualitative and semiquantitative analysis of petroleum hydrocarbons in solid wastes using on-line gas chromatography

Non-degradated mineral-oils like gasoline, solvent naphtha, diesel fuel, fuel and lubricating oils provide a characteristic fingerprint gas chromatogram. This visual classification, e.g. in solid wastes, is complicated due to the simultaneous presence of several mineral-oils. Therefore, a mathematical algorithm for the separation of gas chromatographic fingerprint of “single mixtures” of aliphatic hydrocarbons is developed. The technique ¶is essential for analysis of time-overlapping “single mixtures” of petroleum hydrocarbons (so-called “complex mixtures”) and it relies on the concentration-varying hydrocarbons during evaporation. It is possible to separate the data from the gas chromatogram of a “complex mixture” of hydrocarbons into the chromatograms of the pure “single mixtures” and to give their respective concentrations. A synthetic ?complex mixture” of kerosene, diesel fuel and lubricating oil is used to illustrate the method.     

Mathematical algorithm for qualitative and semiquantitative analysis of petroleum hydrocarbons in solid wastes using on-line gas chromatography

Non-degradated mineral-oils like gasoline, solvent naphtha, diesel fuel, fuel and lubricating oils provide a characteristic fingerprint gas chromatogram. This visual classification, e.g. in solid wastes, is complicated due to the simultaneous presence of several mineral-oils. Therefore, a mathematical algorithm for the separation of gas chromatographic fingerprint of "single mixtures" of aliphatic hydrocarbons is developed. The technique is essential for analysis of time-overlapping "single mixtures" of petroleum hydrocarbons (so-called "complex mixtures") and it relies on the concentration-varying hydrocarbons during evaporation. It is possible to separate the data from the gas chromatogram of a "complex mixture" of hydrocarbons into the chromatograms of the pure "single mixtures" and to give their respective concentrations. A synthetic "complex mixture" of kerosene, diesel fuel and lubricating oil is used to illustrate the method.     

喷气燃料裂解产物中芳烃的全二维气相色谱-质谱分析

采用全二维气相色谱-质谱联用仪(GC×GC-MS),通过优化程序升温和调制周期,建立了喷气燃料裂解产物中芳烃的定性定量分析方法。该方法对多环芳烃(PAH)同分异构体具有良好的分离能力。利用MS检测器谱库检索结果、芳烃标准品及相关的文献报道,对喷气燃料裂解产物中常见的单环芳烃、二环芳烃、三环芳烃及四环芳烃等共27种芳烃进行了准确定性,并利用外标GC×GC-FID法对其进行定量。定量结果表明,芳烃含量均随着裂解产气率的增加而增大,当裂解产气率达到22%时,二环芳烃开始产生,且其含量随着裂解产气率的增加呈指数形式增加。该方法与传统的气相色谱-质谱相比,具有更好的分离及定性能力,可应用于复杂样品的分离及其定性定量分析。     

Conversion of natural gas to C_2 hydrocarbons through dielectric-barrier discharge plasma catalysis

The experiments are carried out in the system of continuous flow reactors with dielectric-barrier discharge (DBD) for studies on the conversion of natural gas to C2 hydrocarbons through plasma catalysis under the atmosphere pressure and room temperature. The influence of discharge frequency, structure of electrode, discharge voltage, number of electrode, ratio of H2/CH4, flow rate and catalyst on conversion of methane and selectivity of C2 hydrocarbons are investigated. At the same time, the reaction process is investigated. Higher conversion of methane and selectivity of C2 hydrocarbons are achieved and deposited carbons are eliminated by proper choice of parameters. The appropriate operation parameters in dielectric-barrier discharge plasma field are that the supply voltage is 20-40 kV (8.4-40 W), the frequency of power supply is 20 kHz, the structure of (b) electrode is suitable, and the flow of methane is 20-60 ml · min-1. The conversion of methane can reach 45%, the selectivity of C2 hydrocarbons i     

Influence of the Feed Gas Composition on the Fischer-Tropsch Synthesis in Commercial Operations

Key technical challenges relating to the Fischer-Tropsch(F-T)synthesis applied in the commer- cialization of coal/gas-to-liquids(CTL/GTL)technolo- gies have been reviewed.Based on the experiences ac- cumulated from pilot plant,semi-work test and lab re- searches,the influences of the H_2/CO ratio and the CO_2 in the feed gas on the F-T process as well as on CTL/GTL complex in terms of product yields,energy efficiency and carbon utilization efficiency have been studied.Being contrary to the current design schemes for F-T process using the coat derived syngas and the iron-based cata- lyst,it is suggested to feed the F-T synthesis unit with a syngas having a H_2/CO ratio of 0.5 and then adjusting to 1.4 via the recycling process.As a result,the carbon efficiency of the whole plant could be reached to as high as 50%.For the issue of CO_2 addition to the feed gas, it is proved that only a diluting role is played under the current commercial slurry phase F-T process.     

Characterization of waxes used in pictorial artworks according to their relative amount of fatty acids and hydrocarbons by gas chromatography

A study attempted to characterize natural waxes used in pictorial works of art was carried out by means of gas chromatography. The analytical treatment requires prior hydrolysis of the waxes to release the fatty acids (FA) (myristic (myr), palmitic (pal), oleic (ole), stearic (ste), araquidic (ara), behenic (beh), lignoceric (lig), cerotic (cer)) from the main esters of the waxes. The formation of volatile derivatives of the fatty acids was carried out by derivatization with ethyl choroformate (ECF). This derivatization reagent was chosen due to the speed, safety and quantitativity of the reaction. The analyzed hydrocarbons were n-eicosane, n-heneicosane, n-docosane, n-tricosane, n-tetracosane, n-pentacosane, n-hexacosane, n-heptacosane, n-octacosane, n-nonacosane, n-tricontane n-hentriacontane, n-dotriacontane, n-tritriacontane, n-tetratriacontane, n-pentatriacontane, main constituents of the waxes. No derivatization is needed to analyze the hydrocarbons. Ethyl ester derivatives and hydrocarbons are adequately separated by gas chromatography, identified by flame ionization detection and confirmed by mass spectrometry. To characterize natural waxes, peak area ratios of each fatty acids with respect to the palmitic acid and peak area ratios of each hydrocarbons with respect to n-heptacosane were calculated. The proposed method provides a good characterization of different waxes most frequently used in artworks, such as beeswax, carnauba wax and ceresin, and has been successfully applied to real samples. This is the first report on the application of ECF to the analysis of fatty acids in wax.     

电场增强等离子催化反应由天然气合成碳二烃

本研究借助电场作用通过交流或直流等离子催化反应在常压、低下将天然气（甲烷）直接转一烃。甲烷被等离子场激活后直接和催化剂活性位作用生成乙烷、乙烯等碳二烃，由气相色谱在线分析其组成。考察了反应条件和催化剂的影响。得到了本实验较适宜反应条件下的碳二烃选择性在９０％以上的结果。     

静电自组装聚电解质/有机染料插层蒙脱土光致变色纳米复合膜

从构筑静电自组装聚电解质／有机染料插层蒙脱土光致变色纳米复合膜所必需 的基本纳米构件--有机染料插层蒙脱土光致变色纳米复合物的设计出发，制备了具有光致 变色功能的蒙脱土／阳离子偶氮染料（GTL）均插层纳米复合物现，插人蒙脱土层 间的GTL热稳定性大幅度提高．由于GTL在纳米受限空间的超分子有序结构共轭，使 偶氮基发生了高达91 nm的显著红移．使用该插层纳米复合物构件与阳离子聚电解 质（PDAC）通过静电自组装得到了生长均匀、排列规整有序的光致变色聚电解质／ 阳离子偶氮染料插层蒙脱土纳米复合膜.     

Distribution of Hydrocarbons in Soil Through Contamination from a Leaking Natural Gas Pipeline

Abstract

A plume of hydrocarbon contamination in soil from a leaking natural gas pipeline located at a depth of 80 cm was defined on the basis of discoloration of soil at 3 to 7 cm depth. Eleven sites were selected randomly on a grid superimposed on a map of the 240 m² plume and 48 soil samples at depths from 7 cm to 150 cm were collected. Samples were individually extracted using cyclohexane in a Soxhlet extraction apparatus. Condensed extracts were analyzed using capillary GC and GC/MS techniques to determine quantitatively the dinstribution of C₁₀ to C₃₅ hydrocarbons in soil. In solvent extracts of the soils, over 150 organic compounds were resolved and detected at total concentrations from 0.1 to 2700 ppm. The vertical distribution of hydrocarbons was consistent throughout the plume with higher concentrations of all components with increased proximity to the surface. The hydrocarbons moved vertically from the leak and diffused horizontally along an interface created at 15 to 30 cm by the addition 20 years earlier of a dense clay soil to a naturally high-gypsum base. Ratios of soil concentrations in three size ranges for the hydrocarbons were used to evaluate the physical mechanism for gaseous migration and environmental fate of the hydrocarbons. These ratios were not uniform at every site and depth throughout the plume. Results were consistent with differences in mobility and fate of the hydrocarbons in the soil based on volatility and adsorption. Polycyclic aromatic hydrocarbons present in the natural gas and in the pipeline residue were also found in some but not all soil samples under the conditions of extraction and analyses which were not optimized in the soil-extraction of the aromatic compounds.     

Recent advances in understanding the key catalyst factors for Fischer-Tropsch synthesis

Catalytic conversion of synthesis gas (CO+H₂) into hydrocarbons, also known as Fischer-Tropsch (FT) synthesis, is a crucial reaction for the transformation of non-petroleum carbon resources such as coal, natural gas, shale gas, coal-bed gas and biogas, as well as biomass into liquid fuels and chemicals. Many factors can influence the catalytic behavior of a FT catalyst. This review highlights recent advances in understanding some key catalyst factors, including the chemical state of active phases, the promoters, the size and the microenvironment of active phase, which determine the CO conversion activity and the product selectivity, particularly the selectivity to C₅₊ hydrocarbons.     

Selective Coke Combustion by Oxygen Pulsing During Mo/ZSM‐5‐Catalyzed Methane Dehydroaromatization

Non‐oxidative methane dehydroaromatization is a promising reaction to directly convert natural gas into aromatic hydrocarbons and hydrogen. Commercialization of this technology is hampered by rapid catalyst deactivation because of coking. A novel approach is presented involving selective oxidation of coke during methane dehydroaromatization at 700 °C. Periodic pulsing of oxygen into the methane feed results in substantially higher cumulative product yield with synthesis gas; a H₂/CO ratio close to two is the main side‐product of coke combustion. Using ¹³C isotope labeling of methane it is demonstrated that oxygen predominantly reacts with molybdenum carbide species. The resulting molybdenum oxides catalyze coke oxidation. Less than one‐fifth of the available oxygen reacts with gaseous methane. Combined with periodic regeneration at 550 °C, this strategy is a significant step forward, towards a process for converting methane into liquid hydrocarbons.     

天然气与硫酸盐热化学还原反应的模拟实验研究

为探讨天然气中高含量硫化氢形成的化学机制，利用高温高压反应装置，对天然气与固态硫酸钙反应体系进行了热模拟实验研究。使用气相色谱仪、微库仑仪、傅里叶变换红外光谱仪和X射线衍射仪对产物进行了分析，探讨了硫酸盐热化学还原反应的热力学特征，并进行了反应动力学研究。结果表明，高温下天然气与固态硫酸钙可以发生反应，产物主要为硫化氢、二氧化碳、碳酸钙、水和炭。热力学研究表明，天然气与固态硫酸钙的反应可行，升高温度对反应有利，同一温度下长链烷烃与固态硫酸钙发生反应的可能性要比短链烷烃大。根据动力学模型得到反应活化能为96.824kJ/mol。