煤基高能量密度燃料的合成及表征

高能量密度燃料是为新型高性能飞行器提供动力保障的关键,其合成及应用研究具有重要的前瞻性和重大战略意义。煤炭是我国的主体能源和重要原料,通过煤直接转化获取的煤基油,充分保留了煤中特有的环状分子化学结构,具有良好的热安定性和较高的能量密度,被认为是高超音速飞行器的优选燃料。以煤直接液化工艺生产的煤液化石脑油馏分为起始原料,通过富集轻质芳烃、化学合成、催化加氢稳定和产物分离提纯等方法制备煤基高能量密度燃料,并对其产物进行分子结构表征和性能评价。结果表明,煤直接液化生产的石脑油馏分是一种优异的催化重整原料,经催化重整富集轻质芳烃后,其轻质芳烃质量分数高达71.05%。Diels-Alder化学合成主产物是由多个封闭环平面组成且具有空间立体构型的二环或三环烃类物质,质量分数为46.18%,因分子内存在较大的张力能,结构紧凑,其拥有更大的密度和体积热值。煤基高能量密度燃料的密度和体积热值分别为0.8990 g/cm3与38.06 MJ/L,均大大超过现行的国内石油基喷气燃料(RP-3和RP-6)、煤基大比重喷气燃料、美国和俄罗斯军用标准。与单一纯物质合成高能量密度燃料(JP-10和T-10)比较,其密度与体积热值偏小。究其原因主要是轻质芳烃的富集度仅为71.05%,需进一步提高其轻质芳烃质量分数。另外,制备的煤基高能量密度燃料种类复杂,其主产物质量分数仅46.18%,下一步可重点调控合成产物的分子构型和纯化分离。     

The assessment of commercial beef and chicken bouillons in terms of heterocyclic aromatic amines and some of their precursors

Herein, the assessment of commercial beef and chicken bouillons in terms of heterocyclic aromatic amines (HAAs) and some of their precursors was evaluated. Creatine and creatinine levels were ranged between 0.57–0.80 and 0.28–0.94 mg g⁻¹, respectively. Glutamic acid was found to be the most abundant amino acid in both bouillons. 2-amino-3,7,8-trimethylimidazo[4,5-ƒ]quinoxaline (7,8-DiMeIQx, up to 0.03 ng g⁻¹) was the only quantified analyte in beef bouillons, whereas it (up to 0.08 ng g⁻¹) was determined in addition to 2-amino-3-methylimidazo[4,5-ƒ]quinoxaline (IQx, up to 0.08 ng g⁻¹) in chicken bouillons. Creatine, creatinine and free amino acid composition did not have the capacity to initiate the formation of HAAs. Therefore, bouillons do not pose risk in terms of HAAs. However, it should be noted that multiple factors, such as the substrate amount and production conditions, may affect the results. Glutamic acid content is remarkable in commercial bouillons sold in Turkey.     

分子印迹-气相色谱-串联质谱法检测烤肉中的14种多环芳烃

目的比较5种不同萃取净化法结合气相色谱-串联质谱法检测烤肉中14种多环芳烃含量的效果。方法样品经提取后,比较中性氧化铝柱、HLB小柱、分子印迹技术、GPC凝胶色谱净化技术、QuEChERS法5种不同萃取净化法的净化效果,确定烤肉中14种多环芳烃检测的最合适前处理技术。结果比较5种净化技术,分子印迹柱和GPC方法在烤肉制品中平均回收率为80%～100%,其他技术的回收率偏低,不符合实验要求。使用分子印迹柱作为前处理方法时, 14种多环芳烃在5～200 ng/mL范围内呈良好线性,相关系数均大于0.995,平均回收率在76.42%～106.8%之间,相对标准偏差为0.8%～7.8%,方法定量限为0.76～1.21μg/kg。结论比较5种方法的净化结果,分子印迹柱和GPC凝胶色谱均能满足检测需求,但分子印迹柱稳定性更好,成本更低,更适用于烤肉中14种多环芳烃残留的检测。     

THE OLIGOCENE–MIOCENE MENILITE FORMATION IN THE UKRAINIAN CARPATHIANS: A WORLD‐CLASS SOURCE ROCK

This study investigates the hydrocarbon potential of Oligocene–Miocene shales in the Menilite Formation, the main source rock in the Ukrainian Carpathians. The study is based on the analysis of 233 samples collected from outcrops along the Chechva River in western Ukraine in order to analyse bulk parameters (TOC, Rock‐Eval), biomarkers and maceral composition. In Ukraine, the Menilite Formation is conventionally divided into Lower (Lower Oligocene), Middle (Upper Oligocene) and Upper (Lower Miocene) Members. The Early Oligocene and Early Miocene ages of the lower and upper members are confirmed by new nannoplankton data. The Lower Menilite Member is approximately 330 m thick in the study area and contains numerous chert beds and turbidite sandstones in its lower part together with organic‐rich black shales. The shales have a high content of silica which was probably derived from siliceous micro‐organisms. The TOC content of the shales frequently exceeds 20 wt.% and averages 9.76 wt.%. HI values range between 600 and 300 mgHC/gTOC (max. 800 mgHC/gTOC). The Middle Member contains thin black shale intervals but was not studied in detail. The Upper Member is about 1300 m thick in the study area and is composed mainly of organic‐rich shales. Chert layers are present near the base of the Member, and a prominent tuff horizon in the upper part represents a volcanic phase during shale deposition. The member grades into overlying molasse sediments. The average TOC content of the Upper Menilite succession is 5.17 wt.% but exceeds 20 wt.% near its base. Low T_max and vitrinite reflectance measurements for the Lower (419°C and 0.24–0.34 %R_r, respectively) and Upper (425°C and 0.26–0.32 %R_r, respectively) Menilite Member successions indicate thermal immaturity. Biomarker and maceral data suggest a dominantly marine (Type II) organic matter input mixed with varying amounts of land‐plant derived material, and indicate varying redox and salinity conditions during deposition. Determination of the Source Potential Index (SPI) shows that the Menilite Formation in the study area has the potential to generate up to 74.5 tons of hydrocarbons per m². The Chechva River outcrops therefore appear to have a significantly higher generation potential than other source rocks in the Paratethys realm. These very high SPI values for the Menilite Formation may explain why a relatively small area in Ukraine hosts about 70% of the known hydrocarbon reserves in the northern and eastern Carpathian fold‐thrust belt.     

CARBONATE RESERVOIR ROCKS AT GIANT OIL AND GAS FIELDS IN SW IRAN AND THE ADJACENT OFFSHORE: A REVIEW OF STRATIGRAPHIC OCCURRENCE AND PORO‐PERM CHARACTERISTICS

SW Iran and the adjacent offshore are prolific petroleum‐producing areas with very large proven oil and gas reserves and the potential for significant new discoveries. Most of the oil and gas so far discovered is present in carbonate reservoir rocks in the Dehram, Khami and Bangestan Groups and the Asmari Formation, with smaller volumes in the Dashtak, Neyriz, Najmeh, Gurpi, Pabdeh, Jahrum, Shahbazan, Razak and Mishan (Guri Member) Formations. The Permo‐Triassic Dehram Group carbonates produce non‐associated gas and condensate in Fars Province and the nearby offshore. The Jurassic – Lower Cretaceous Khami Group carbonates are an important producing reservoir at a number of offshore fields and in the southern Dezful Embayment, and are prospective for future exploration. Much of Iran's crude oil is produced from the Oligo‐Miocene Asmari Formation and the mid‐Cretaceous Sarvak Formation of the Bangestan Group in the Dezful Embayment. This review paper is based on data from 115 reservoir units at 60 oil‐ and gasfields in SW Iran and the adjacent offshore. It demonstrates that the main carbonate reservoir units vary from one‐another significantly, depending on the particular sedimentary and diagenetic history. Ooidal‐grainstones and rudist‐ and Lithocodium‐bearing carbonate facies form the most important reservoir facies, and producing units are commonly dolomitised, karstified and fractured. In general, reservoir rocks in the study area can be classified into six major types: grainstones; reefal carbonates; karstified, dolomitised and fractured carbonates; and sandstones. The stratigraphic distribution of these reservoir rocks was principally controlled by the palaeoclimatic conditions existing at the time of deposition. A comparative reservoir analysis based on core data shows that dolomitised and/or fractured, grain‐dominated carbonates in the Dehram Group, Lower Khami Group and Asmari Formation typically have better reservoir qualities than the Cretaceous limestones in the Upper Khami and Bangestan Groups.     

高效液相色谱法测定多环芳烃的出峰顺序探讨

目的探讨水﹑气﹑土壤中多环芳烃检测标准(HJ 478-2009﹑HJ 647-2013、HJ 784-2016)的正确出峰时间和顺序。方法用高效液相色谱来对苊烯、芴、苊、?、苯并(a)蒽进行定性分析,并与3个标准中的出峰顺序进行比较。结果苊烯、苊、芴、苯并(a)蒽、?的出峰时间分别为6.450、7.923、8.233、17.760、18.740min,与标准HJ478-2009﹑HJ647-2013的出峰顺序存在差异。结论在使用标准HJ478-2009﹑HJ647-2013、HJ 784-2016同时测定16种多环芳烃时,多环芳烃的出峰顺序及时间应以HJ 784-2016为准。     

地理标志产品镇江香醋标准符合性验证分析

目的从理化指标、特征有机酸以及检验方法等对2018年江苏镇江地理标志产品镇江香醋进行标准验证。方法对5个质量等级,共计20批次镇江香醋样品进行抽检,采用GB/T 18623-2011标准对特征性成分进行分析检测,并对检验标准进行验证。结果镇江香醋5个等级产品理化特性均符合标准规定,未检测到致病菌,菌落总数以及大肠菌群均未超过标准规定的限量要求;重金属铅和总砷、真菌毒素黄曲霉毒素B_1以及食品添加剂苯甲酸和山梨酸均符合标准规定技术限量要求;具有镇江香醋标志性特征有机酸(乳酸、乙酸、焦谷氨酸和琥珀酸),且随着等级要求越高,其有机酸含量越高。结论镇江香醋特征性成分完全符合其标准规定要求,镇江香醋标准与国家强制性标准一致,建议可对有机酸的液相检测方法进行优化,尝试离子排斥色谱柱或耐酸C_(18)柱,以满足镇江香醋有机酸液相检测更高的分析要求。     

Mineral Oil Hydrocarbons (MOSH/MOAH) in Edible Oils and Possible Minimization by Deodorization Through the Example of Cocoa Butter

Mineral oil hydrocarbons (MOH) are present in many fats and oils as well as foods prepared thereof. A survey of mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH) in different types of vegetable fats and oils is reported. Contents of MOSH/MOAH were quantified using liquid chromatography online‐coupled to gas chromatography with flame‐ionization detection (LC‐GC‐FID). Cocoa butter (n = 142) showed levels from <LOQ (2.5 mg kg^?1) to 162 mg kg^?1 ΣMOSH (sum of C10–C50) and <LOQ to 55 mg kg^?1 ΣMOAH, in palm oil (n = 21) ΣMOSH were quantified from <LOQ to 124 mg kg^?1 and ΣMOAH from <LOQ to 39 mg kg^?1. Sunflower oil showed lower levels: ΣMOSH were determined in the range of <LOQ to 17 mg kg^?1 and MOAH were not observed at all. A possible influence of deodorization and a subsequent minimization of MOSH/MOAH was investigated. Systematic model‐experiments were performed on laboratory scale using spiked cocoa butter. Significant minimization of volatile MOH subfractions ≤C24 were observed at a deodorization temperature of 210 °C. Deodorization can be considered as an important processing step to reduce or even remove volatile MOSH/MOAH ≤C24. Practical Applications: Regardless of their possible entry routes into the food chain, volatile fractions of MOSH/MOAH can be removed by deodorizing vegetable fats and oils. This model‐study identifies the temperatures of deodorization that provide a significant improvement toward minimization of undesired MOSH/MOAH.