渣油、煤、水三元合成燃料

使用适当的分散剂和乳化剂研制成功两种渣油、煤、水三元混合燃料（水包油型和油包水型），并对两种混合燃料的流变性能进行了初步研究．     

Production of Oil by Hydrogenation of Coal

A survey of coal hydrogenation processes revealed that, despite a wealth of experience gathered in Germany up to 1945 some of which served as a basis for further work in the USA, there is at present no process available anywhere in the world for the commercial production of oil from coal. Approaches suitable for further development are the noncatalytic one-step limited hydrogenation and catalytic hydrogenation. Under the most favorable conditions production of oil from coal should become technically feasible some time between the early and mid-1980's. In view of the price of heavy fuel oil the commercial prerequisites for production of synthetic fuel oil from coal are presumably fulfilled only in those countries with low coal prices.     

煤制油的化学原理及其应用前景

煤制油属于新型煤化工的一部分。在人类面临能源短缺、国际石油价格剧烈波动的情况下,煤制油逐渐进入了公众的视野。介绍煤制油的化学原理及其应用过程中面临的挑战。     

1H NMR和GC-MS法分析表征煤液化油

采用经典柱色谱法对煤液化循环油和“加氢”后的循环油进行族组成分离,将其分离成饱和烃、芳香烃和极性物3个组分,并用核磁共振波谱仪对各个组分进行定性分析,同时用气质联用分析方法初步确定了饱和烃和芳香烃两个馏分的主要物质组成。结果表明:循环油饱和烃部分主要由C12~C27直链烷烃组成,芳香烃部分主要组成是烷基取代的氢化单环芳烃及少量的多环芳烃。而循环油经420℃“加氢”后饱和烃部分除了含C12~C27的直链烷烃,还有一些直链烷烃的异构体和环烷烃,芳香烃部分主要是双环、三环、四环芳烃,单环芳烃则完全消失。     

煤基费托合成油中微量总铁的测定

铁系催化剂的残留污染一直是煤间接液化技术生产费托合成油工艺生产和产品质量控制的重点关注问题之一。准确分析合成油中微量残留铁的含量已成为工艺开发过程中至关重要的手段。该文对不同检测方法进行了对比,以燃烧灰化样品等离子体发射光谱检测铁含量的方法对不同沸点的合成油样品进行了验证,并通过实验数据优化了检测方法中的关键步骤。经验证费托合成油样品前处理最优条件为称样量5 g,马弗炉于500℃灰化1 h。该法对铁含量测定的回收率大于95%,相对标准偏差(RSD)不大于5.7%,检出限及定量下限分别为0.15 mg/kg和0.50 mg/kg。     

Isotope Dilution Analysis of Exchangeable Water in Coal,Coal Char,and Activated Coal Char

Abstract

Isotope dilution analysis techniques were employed for the determination of the quantity of exchangeable water in moist subbituminous coal, non-activated coal and activated coal char; the latter two products were prepared from the subbituminous coal used in this study.     

中心切割GC-MS法分析煤液化油中的酚类化合物

使用碱洗提酚法提取煤液化油中的酚类化合物,然后结合Deans Switch装置和LTM色谱柱模块,采用中心切割气相色谱(GC)-质谱(MS)法对提取的酚类化合物进行定性。采用GC建立标准曲线,对煤液化油中主要酚类化合物的质量分数进行测定,并测定了煤液化油中邻甲基苯酚、2-乙基苯酚、4-丙基苯酚和5-茚酚4种酚类化合物的加标回收率。结果表明,在煤液化油中共定性出51种酚类化合物,测定了其中的35种酚类化合物的质量分数,其量占煤液化油总量的2.54(wt)%,苯酚和烷基苯酚占35种酚类化合物的88.2(wt)%。煤液化油中4种酚类化合物的加标回收率高,重复性好。     

中心切割二维GC-MS法测定煤直接液化加氢改质油组成

采用SYD-6536C石油产品蒸馏试验器取煤直接液化加氢改质全馏分油55.2～138.2℃的馏分段,建立了一种运用中心切割二维GC-MS法研究其单体烃组成的分析方法。实验采用PONA毛细管气相色谱柱(50m×200μm×0.5μm)对色谱条件进行优化,找到煤直接液化加氢改质油55.2～138.2℃馏分段的最佳分离条件。被测样品首先在第一根色谱柱上进行分离,然后使用Dean Switch微流控制系统把目标化合物切割至第二根色谱柱(DB-35MS 30m×250μm×0.25μm)上,进一步分离。实验将烃类化合物在PONA柱上的色谱保留规律、化合物保留指数、标准化合物保留值及质谱谱库检索等多种方法联合对煤直接液化加氢改质油在55.2～138.2℃的馏分段中66种化合物进行定性分析。鉴于被测油样中化合物的结构性质相近,忽略化合物相对校正因子的影响,采用面积归一化法NORM%进行定量分析。该方法方便快捷、精确度高,适用于低馏分段的煤直接液化加氢改质油的分析,同时也为高馏分段煤直接液化加氢改质油和其他种类油样的单体烃组成分析提供了参考。     

Polyurethane Dispersions Based on Sardine Fish Oil,Soybean Oil,and Their Interesterification Products

Alkyd resins were synthesized from different ratios of sardine fish oil and soybean oil. Three alkyd resin samples were styrenated. The styrenated alkyd resins and alkyd resins were subsequently converted into the polyurethane dispersions. The physicochemical properties, such as iodine value, saponification value, and specific gravity were determined. Infrared spectroscopy and nuclear magnetic resonance techniques were used for structural elucidation of newly synthesized resins. The coating properties, such as adhesion, flexibility, scratch hardness, pencil hardness, impact, solvent, and chemical resistance were evaluated. Thermogravimetric analysis was used to investigate the thermal stability of alkyd resin and polyurethane dispersions. Cost effective volatile organic components (VOC) compliant coatings for various applications can be synthesized successfully by partly replacing soybean oil with commercially available, inexpensive sardine fish oil.     

Determination of Organophosphorus Pesticides in Soybean Oil, Peanut Oil and Sesame Oil by Low-Temperature Extraction and GC-FPD

A low-temperature clean-up method for residue determination was developed and validated for 14 organophosphorus pesticides in soybean oil, peanut oil and sesame oil by gas chromatography with flame photometric detector (GC-FPD). A different matrix influenced the response and retention time of pesticides. Hence matrix-matched calibration standards were used to counteract the matrix effect. The pesticide responses in blank samples of soybean oil, peanut oil and sesame oil were within the linear range of 0.02–1 mg kg⁻¹ and the correlation coefficients were higher than 0.9989. Average recoveries obtained from different oil samples at three fortified levels were higher than 50% with relative standard deviations (RSDs) of less than 15%. The limit of detections (LODs) of studied pesticides ranged from 2 to 5 μg kg⁻¹. Thirty-nine commercial samples were analyzed, and the results were confirmed by gas chromatography–mass spectrometry (GC–MS) in selective ion monitoring (SIM) mode.     

准噶尔盆地陆梁油气田原油的生物降解作用与油气成藏

1原油的生物降解现象 陆梁油气田原油可按饱和烃色谱图上正构烷烃的完整程度和m/z 177质量色谱图上25-降藿烷的存在与否,分为3类.第1类:饱和烃分布完整,不存在25-降藿烷,主要分布于中侏罗统西山窑组X4段;第2类:饱和烃分布完整但存在25-降藿烷,主要分布于中侏罗统西山窑组X1段;第3类:饱和烃分布差异较大,从仅缺损部分低碳数正构烷烃到几乎完全缺损正构烷烃,而且存在25-降藿烷,主要分布于下白垩统吐谷鲁群.原油中25-降藿烷的存在,表示了该原油曾经遭受过"严重"级别的生物降解.     

煤在合成气、氢气和氮气气氛下的热解研究

采用固定床反应器，在合成气气氛下对中国寻甸褐煤、蒙古Shiveeovoo褐煤和Khoot油页岩进行了热解研究。升温速率10 ℃/min，褐煤热解温度400 ℃～800 ℃，油页岩热解温度300 ℃~600 ℃，研究结果与氢气和氮气气氛下的热解进行了比较。结果表明,与加压热解不同，褐煤在不同气氛下常压热解半焦和焦油收率差别不大，但对油页岩，合成气和氢气气氛下热解焦油收率高于氮气，气体收率低于氮气。黄铁矿硫在不同气氛下热解均极易脱除，并部分转化为有机硫。油页岩的总硫脱除率远低于褐煤，与油页岩的高灰分含量有关。与氮气甚至氢气相比，合成气下寻甸褐煤的高总硫脱除率和低有机硫含量与合成气中的CO有关。但CO在油页岩热解脱硫中不起作用，也与油页岩高灰分含量有关。研究结果也表明合成气可代替氢气进行加氢热解。     

微波消解-微波等离子体炬原子发射光谱法测定原油和渣油中的铁、镍、铜和钠

采用微波消解技术消解原油和渣油,利用微波等离子体炬原子发射光谱法测定原油和渣油中的Fe、Ni、Cu、Na。考察了原油和渣油的最佳消解条件、各元素测定条件及共存元素对测定的影响。方法对Fe、Ni、Cu和Na元素的检出限分别为22、42、2．0和1．0μg/L;线性范围分别为0．1-100、0．15-50、0．01-5．0和0．006-2．0mg／L,应用该方法测定实际样品中Fe、Ni、Cu和Na的相对标准偏差分别为3．9％、3．6％、5．5％和3．4％。微波消解样品的测定结果与常规干法灰化法的测定结果相吻合。本方法省时、省酸、简便、快速,没有环境污染,具有一定的实际应用价值。     

香茅油纳米乳剂的构建、表征、抗菌性能和细胞毒性

化学合成杀菌剂的大量、不合理使用对人类健康造成危害的同时也会导致严重的环境污染。因此,迫切需要寻找低毒、高效、无残留的天然杀菌剂。植物精油因其优良的杀菌活性、良好的生物相容性和丰富的来源,已成为农业病害防控领域的研究热点。香茅油是一种具有趋避、杀虫和抗菌活性的天然植物精油,主要包括香茅醛、香叶醇和香茅醇。目前,关于香茅油的研究主要集中于卫生害虫的驱避和防治,而用于农业致病菌防治的相关报道相对较少。在实际应用中,香茅油的疏水性和挥发性导致其生物利用度低,不能充分发挥生物活性。因此,构建一种改善香茅油疏水性、降低挥发性的递送系统十分必要。纳米乳剂因具有液滴细微均匀、物理稳定性好、渗透能力强以及生物利用度高等优点,已成为疏水农药的重要递送系统。本研究通过观察样品的外观和微观结构,并且测量样品液滴大小,考察了乳化剂种类(亲水亲油平衡值,HLB)、用量和乳化时间对纳米乳剂形成及稳定的影响,在此基础上筛选了香茅油纳米乳剂的优化配方。同时本研究还调查了香茅油纳米乳剂的生物活性和生物安全性。结果表明,以蓖麻油聚氧乙烯醚EL-40 (HLB = 13.5)为乳化剂的纳米乳剂性能最佳,且乳化剂用量从3%增加到7% (w,质量分数)时,纳米乳剂稳定性提高。此外,高速剪切3 min获得的纳米乳剂稳定性最高。基于此,确定了香茅油纳米乳剂的优化配方为：5% (w)香茅油,6% (w)乳化剂(EL-40),89% (w)去离子水,高速剪切3 min。香茅油纳米乳剂对菠萝泛菌(Pantoea ananatis)具有良好的抑制作用,抑制中浓度(EC₅₀)为74.85 mg·L⁻¹。纳米乳剂(低于100 mg·L⁻¹)处理人体正常肝细胞(L02) 24 h后,细胞存活率仍高于83%,凋亡率仅为6.93%,表明香茅油纳米乳剂具有较低的细胞毒性。本研究有助于设计和构建稳定、高效、安全的农业纳米乳剂,同时为植物精油作为农业杀菌剂提供了切实可行的解决方案。     

Characterization of Kangxi Coins of Tsing Empire by SEM-EDS

 The major and minor elements Cu, Zn, Sn, Pb and Fe of coins issued in the Kangxi dynasty of Tsing Empire were analyzed by X-Ray energy dispersive spectrometry using a scanning electron microscope (SEM-EDS). This paper presents the characteristic concentration of elements in the coins, and may act as a criterion for other coins dating back to the Kangxi dynasty. The 73 coins were classified in three groups according to the results. Group 1 with good fineness represents the coins minted in ‘Yunnan’ province and some coins for special purpose such as the celebration of Kangxi emperor’s birthday; groups 2 and 3 represent the coins issued before and after 1684 AD, respectively. At a concentration range of 0.23%∼6.11%, the distribution of lead is not homogeneous in the coins, and the largest diameter of lead inclusion is less than 15 μm. Regional difference is not evident except with coins showing the mintmark ‘Yun’. The official degradation of fineness was supported. Author for correspondence. E-mail: jmhu@whu.edu.cn Received September 10, 2002; accepted March 12, 2003 Published online June 5, 2003     

微波消解试样-火焰原子吸收光谱法测定原油和渣油中铁、镍和铜

采用微波消解技术消解原油和渣油样品,研究了微波消解-火焰原子吸收光谱法测定原油和渣油中铁、镍和铜的方法。考察了最佳样品用量、酸用量、微波消解时间、消解压力、消解功率,确定了微波消解原油和渣油的最佳程序。此法样品损失少,酸用量少,降低了环境污染,所用时间缩短了3.5倍。测定结果与灰化法结果一致,铁、镍和铜的相对误差分别为1.6%,1.4%和1.6%。该方法简便、快速、准确,是一种绿色环保的分析方法。