Reactive ball-milling synthesis of Co-Fe bimetallic catalyst for efficient hydrogenation of carbon dioxide to value-added hydrocarbons

Catalytic hydrogenation of CO_(2) using renewable hydrogen not only reduces greenhouse gas emissions,but also provides industrial chemicals.Herein,a Co-Fe bimetallic catalyst was developed by a facile reactive ball-milling method for highly active and selective hydrogenation of CO_(2) to value-added hydrocarbons.When reacted at 320℃,1.0 MPa and 9600 mL h^(-1) g_(cat)^(-1),the selectivity to light olefin(C_(2)^(=)-C_(4)^(=)) and C_(5)+ species achieves 57.3% and 22.3%,respectively,at a CO_(2) co nversion of 31.4%,which is superior to previous Fe-based catalysts.The CO_(2) activation can be promoted by the CoFe phase formed by reactive ball milling of the Fe-Co_(3)O_(4) mixture,and the in-situ Co_(2)C and Fe_(5)C_(2) formed during hydrogenation are beneficial for the C-C coupling reaction.The initial C-C coupling is related to the combination of CO species with the surface carbon of Fe/Co carbides,and the sustained C-C coupling is maintained by self-recovery of defective carbides.This new strategy contributes to the development of efficient catalysts for the hydrogenation of CO_(2) to value-added hydrocarbons.

Determination of Trace Amount of Polycyclic Aromatic Hydrocarbons in Urban Sewage by Solid-phase Extraction Coupled with High Performance Liquid Chromatograph

[Method] This study aimed to determine trace amount of polycyclic aromatic hydrocarbons(PAHs) in urban sewage by using solid-phase extraction(SPE) coupled with high performance liquid chromatograph(HPLC).[Method] From the aspects of solid-phase extraction column,elution solvent,elution volume,elution speed and so forth,the test conditions of SPE-HPLC method were optimized,and trace amount of PAHs in urban sewage was determined.[Result] The optimized solid-phase extraction conditions were SUPELCLEAN LC-18 solid-phase extraction column,methylene dichloride as elution solvent,15 ml elution volume,2 ml/min elution speed,5 ml/min loading speed,1 000 ml water with 200 ml methanol loading volume.Under the optimized extraction conditions,the recovery was high,namely 76.3%-105.2%;relative standard deviation was 3.8%-6.0%,showing good precision;detection limit was low,only 0.000 8-0.048 0 μg/L.[Conclusion] This method is user-friendly,with high sensitivity and good precision,and suitable for continuous determination of a large volume of water samples.

Low organic matter abundance and highly efficient hydrocarbon generation of saline source rock in the Qaidam Basin,NW China

The geochemical analysis and experimental simulation are comprehensively used to systematically study the hydrocarbon generation material,organic matter enrichment and hydrocarbon generation model of Paleogene source rock in the Western Qaidam Depression,Qaidam Basin,NW China.Three main factors result in low TOC values of saline lacustrine source rock of the Qaidam Basin:relatively poor nutrient supply inhibits the algal bloom,too fast deposition rate causes the dilution of organic matter,and high organic matter conversion efficiency causes the low residual organic carbon.For this type of hydrogen-rich organic matter,due to the reduction of organic carbon during hydrocarbon generation,TOC needs to be restored based on maturity before evaluating organic matter abundance.The hydrocarbon generation of saline lacustrine source rocks of the Qaidam Basin is from two parts:soluble organic matter and insoluble organic matter.The soluble organic matter is inherited from organisms and preserved in saline lacustrine basins.It generates hydrocarbons during low-maturity stage,and the formed hydrocarbons are rich in complex compounds such as NOS,and undergo secondary cracking to form light components in the later stage;the hydrocarbon generation model of insoluble organic matter conforms to the traditional“Tissot”model,with an oil generation peak corresponding to Ro of 1.0%.

On-line enrichment and determination of polycyclic aromatic hydrocarbons in atmospheric particulates using high performance liquid chromatography with fluorescence as detector

Seven polycyclic aromatic hydrocarbons （PAHs） in atmospheric particulates were determinated by high performance liquid chromatography （HPLC） with fluorescence detector using direction injection and an on-line enrichment trap column. The method simplified the sample pretreatment, saved time and increased the efficiency. With the on-line trap column, PAHs were separated availably even underground injecting 1.0 ml sample with relatively high column efficiency. The recoveries of the seven PAHs were from 85% to 120% for spiked atmospheric particulate sample. The limit of detection was 15.3-39.6 ng/L （S/N=3.3）. There were good linear correlations between the peak areas and concentrations of the seven kinds of PAHs in the range of 1-50 ng/ml with the correlation coefficients over 0.9970. Furthermore, it also indicated that the method is available to determine PAHs in atmospheric particulates well.

Optimization of Ultrasonic Extraction and Clean-up Protocol for the Determination of Polycyclic Aromatic Hydrocarbons in Marine Sediments by High-performance Liquid Chroma-tography Coupled with Fluorescence Detection

The procedures of ultrasonic extraction and clean-up were optimized for the determination of polycyclic aromatic hydrocarbons (PAHs) in marine sediments. Samples were ultrasonically extracted, and the extracts were purified with a miniaturized silica gel chromatographic column and analyzed with high performance liquid chromatography (HPLC) with a fluorescence detector. Ultrasonication with methanol-dichloromethane (2:1, v/v) mixture gave higher extraction efficiency than that with dichloromethane. Among the three elution solvents used in clean-up step, dichloromethane-hexane (2:3, v/v) mixture was the most satisfactory. Under the optimized conditions, the recoveries in the range of 54.82% to 94.70% with RSDs of 3.02% to 23.22% for a spiked blank, and in the range of 61.20% to 127.08% with RSDs of 7.61% to 26.93% for a spiked matrix, were obtained for the 15 PAHs studied, while the recoveries for a NIST standard reference SRM 1941b were in the range of 50.79% to 83.78% with RSDs of 5.24% to 21.38%. The detection limits were between 0.75 ng L-1 and 10.99 ng L-1for different PAHs. A sample from the Jiaozhou Bay area was examined to test the established methods.

Influence of Magmatic Intrusion on Abnormal Hydrocarbon Generation and Expulsion of Source Rock:A Case Study of the Dongying Sag,Bohai Bay Basin

How gabbro affects the generation and expulsion of hydrocarbons in muddy surrounding rocks is clarified by analyzing thin section,major and trace elements,total organic carbon(TOC),pyrolysis,extracts and vitrinite reflectance data from source rocks in the Chunxi area the Dongying Sag,Bohai Bay Basin,eastern China.The results show that a magma intrusion brings copious heat to the source rocks,which promotes abnormal maturation of organic matter(OM)and rapid hydrocarbon generation.The CH_(4)and H_(2)produced by gabbro alteration play a role in hydrocarbon generation of source rocks.The hydrothermal process during magma intrusion provides many different minerals to the source rock,resulting in carbonate-rich surrounding mudstone.The carbonate and clay minerals produced by volcanic mineral alteration jointly catalyze the hydrocarbon generation of the source rock.The high-temperature baking of the intrusion results in hydrothermal pressurization and hydrocarbon generation pressurization,causing many fractures in the surrounding rock.The generated oil and gas are discharged through the fractures under diffusion and pressure.Mantle-derived CO_(2)is also conducive to the expulsion of hydrocarbons because of its strong enrichment capacity for hydrocarbons.

Efficient upcycling of high-density polyethylene into separable cyclic hydrocarbons

This highlight is inspired by a recent article in Nature Nanotechnology in which Zeng and co-workers[1]from the University of Science and Technology of China reported a strategy for upcycling high-density polyethylene(HDPE)into separable cyclic hydrocarbons under solvent-and hydrogen-free condition.This work made a significant progress in plastic recycling.

Reservoir characteristics and hydrocarbon accumulation of Carboniferous volcanic weathered crust of Zhongguai high area in the western Junggar Basin, China

Based on the drilling,cores,logs,seismic,laboratory analysis and so on,reservoir characteristics and hydrocarbon accumulation of Carboniferous volcanic weathered crust in Zhongguai high area are studied.Volcanic rocks were formed in an island arc environment.The lithology is mainly andesite and tuff;Reservoir spaces are mainly secondary pore,fracture and their combination forms,fractures have a better effect on reservoir seepage;There are four layer structures of volcanic weathered crust,weathered clay layer,strongly weathered zone,weakly weathered zone and unweathered zone and strongly weathered zone is the best,which is the main reservoir development zone;The development of reservoir is mainly affected by weathering-leaching,lithology and lithofacies,and fault(fracture);Effective reservoirs could reach to 480 m thickness(high quality reservoirs are within 240 m).Carboniferous volcanic reservoirs are distributed along three zones,which are near the fault zone,high structural part,favorable lithofacies development zone,and one plane,which is near the unconformity.

Exposure of university students to polycyclic aromatic hydrocarbons measured from urinary monohydroxy metabolites

Internal exposure of university students to polycyclic aromatic hydrocarbons (PAHs) was assessed through urinary PAHs metabolites. Eight monohydroxylated PAHs (OH-PAHs) were detected with high performance liquid chromatography (HPLC). The detectable frequencies were 59%-100% for different analytes. Major components in the subjects’ urine were 2-hydroxynaphthalene (2-OHNap, 0.60 μg/mmol creatinine), followed by hydroxyphenanthrene (ΣOH-Phe, 0.38 μg/mmol creatinine) and 2-hydroxyfluorene (2-OHFlu, 0.25 μg/mmol creatinine). Excretion of 1-hydroxypyrene (1-OHPyr, 0.08 μg/mmol creatinine) was almost one order of magnitude lower than the 2-OHNap level in the urine samples. Phenanthrene can be metabolized to five monohydroxy metabolites in human urine. In the present study, 1-or 9-hydroxyphenanthrene (1-or 9-OHPhe) was the dominant component (79%), followed by 2-+3-OHPhe (18%) and 4-OHPhe (3%). The study indicates that 1-OHPyr may not be a good marker for total PAHs exposure, and monitoring of 2-OHNap, 2-OHFlu, 1-or 9-OHPhe and 1-OHPyr as multiple biomarkers are more suitable than only using 1-OHPyr. The levels of OH-PAHs detected in urines of students living in Shanghai are higher those of people in other countries or regions. The concentrations of urine OH-PAHs are directly related to the exposure to PAHs in the environment, indicating that Shanghai residents are at high health risk.

Effect of Cu-ZnO-Al_2O_3 supported on H-ferrierite on hydrocarbons formation from CO hydrogenation

Methanol synthesis catalysts based on Cu, Zn and Al were prepared by three methods and subsequently mixed with H-ferrierite zeolite in an aqueous suspension to disperse the catalysts over the support. These materials were characterized by X-ray diffraction, N2 adsorption, transmission electron microscopy, temperature programmed reduction, NH3 and H2 temperature-programmed desorption, and X-ray photoelectron spectroscopy. They were also applied to the CO hydrogenation reaction to produce dimethyl ether and hydrocarbons. The catalysts were prepared by coprecipitation under low and high supersaturation conditions and by a homogeneous precipitation method. The preparation technique was found to affect the precursor structural characteristics, such as purity and crystallinity, as well as the particle size distribution of the resulting catalyst. Low supersaturation conditions favored high dispersion of the Cu species, increasing the methanol synthesis catalyst＇s metallic surface area and resulting in a homogeneous particle size distribution. These effects in turn were found to modify the zeolite properties, promoting both a low micropore volume and blockage of the zeolite acid sites. The effect of the methanol synthesis catalyst on the reaction was verified by the correlation between the Cu surface area and the CO conversion rate.

Pre-Drilling Prediction Techniques on the High-Temperature High-Pressure Hydrocarbon Reservoirs Offshore Hainan Island,China

Decreasing the risks and geohazards associated with drilling engineering in high-temperature high-pressure(HTHP) geologic settings begins with the implementation of pre-drilling prediction techniques(PPTs). To improve the accuracy of geopressure prediction in HTHP hydrocarbon reservoirs offshore Hainan Island, we made a comprehensive summary of current PPTs to identify existing problems and challenges by analyzing the global distribution of HTHP hydrocarbon reservoirs, the research status of PPTs, and the geologic setting and its HTHP formation mechanism. Our research results indicate that the HTHP formation mechanism in the study area is caused by multiple factors, including rapid loading, diapir intrusions, hydrocarbon generation, and the thermal expansion of pore fluids. Due to this multi-factor interaction, a cloud of HTHP hydrocarbon reservoirs has developed in the Ying-Qiong Basin, but only traditional PPTs have been implemented, based on the assumption of conditions that do not conform to the actual geologic environment, e.g., Bellotti's law and Eaton's law. In this paper, we focus on these issues, identify some challenges and solutions, and call for further PPT research to address the drawbacks of previous works and meet the challenges associated with the deepwater technology gap. In this way, we hope to contribute to the improved accuracy of geopressure prediction prior to drilling and provide support for future HTHP drilling offshore Hainan Island.

Determination of Hydrocarbon Potentials Using High Resolution Aeromagnetic Data over Sokoto Basin, Northwestern Nigeria

Aeromagnetic method of exploration is famed for its suitability for locating buried magnetic ore bodies because of their magnetic susceptibility. This method has been used in the early stage of petroleum exploration to determine depth and major structures of crystalline Basement rocks underlying the sedimentary basin. In this study, high resolution aeromagnetic data were used to ascertain the viability for hosting hydrocarbon potentials of the study area which forms part of the Illummeden Basin (also known locally as the Sokoto embayment) of West Africa. This was largely carried out through Spectra analysis to determine sediment thickness. The results of the analysis of the aeromagnetic data show that, deeper magnetic source ranges from 0.41 km to 2.69 km, shallow magnetic sources from 0.17 km to 0.97 km. Areas with shallow sediment thickness could not allow the thermal maturation of the sediments, since temperature increase with depth and a depth of two kilometers and above has a temperature range of 60°C and above. Areas with sediment thickness of 1.5 km and above were delineated and considered as sub-basins and hence potential areas for hydrocarbon exploration.

Association between polycyclic aromatic hydrocarbons and human rectal tumor or liver cancer

Objective: The aim of this study was to investigate the effect of polycyclic aromatic hydrocarbons (PAHs) in rectal carcinoma and hepatocarcinoma genesis. Methods: The PAHs in the human rectal cancer and liver cancer tissues, the adjacent tissues and homologous tissues without rectal cancer or liver cancer were extracted by ultrasonic wave. The extracts were then cleaned up and enriched by solid phase extraction, analyzed by high performance liquid chromatography (HPLC) with fluorescence spectroscopy. Results: Four kinds of PAHs were detected in human rectal and hepatic tissues. The contents of pyrene, 2-methylanthracene and benzo (a) pyrene in both rectal cancer tissues and adjacent homologous tissues were higher than rectal tissues without rectal cancer, the differences were statistically significant (P < 0.05). The contents of phenanthrene in the three kind of tissue were not significant (P > 0.05). The differences of the content of each PAHs between rectal cancer and adjacent tissue were not significant (P > 0.05). The contents of the four PAHs in the three kinds of liver tissues were not statistically significant (P > 0.05). Conclusion: PAHs are found in human rectal tissues or hepatic tissues. The contents of PAHs in human rectal tissue may have an effect on the occurrence of human rectal cancer while the contents of PAHs in human hepatic tissues may have not ones.

The detection and significance of polycyclic aromatic hydrocarbons in human pancreatic cancer

Objective:The aim of this study was to investigate the effect of polycyclic aromatic hydrocarbons (PAHs) on the occurrence of human pancreatic cancer.Methods:PAHs in human pancreatic cancer,adjacent pancreatic cancer tissues and tissues without pancreatic cancer were extracted by ultrasonic extraction (UE).And then the extracts were cleaned up by solid phase extraction and analyzed by high performance liquid chromatography (HPLC) with fluorescence spectroscopy.Results:Four kinds of PAHs were detected,which were chrysene,2-methylanthracene,pyrene and benzo (a) pyrene.The contents of the four PAHs were not statistically significant between pancreatic cancer and adjacent tissues (P > 0.05).The contents of 2-methylanthracene,pyrene and benzo (a) pyrene in pancreatic cancer and adjacent tissues were higher than tissues without pancreatic cancer,the differences were statistically significant (P < 0.05).The contents of chrysene in the three kinds of pancreatic tissues were not statistically significant (P > 0.05).Conclusion:PAHs were found in human pancreatic tissues.Human pancreatic tissues have extremely strong ability of bio-concentrating PAHs.PAHs might play an important role in the occurrence of human pancreatic cancer.

碳氢树脂高频覆铜板的研究进展

本文综述了高频覆铜板的特点,并对其基体树脂的介电性能进行对比,重点介绍了碳氢树脂(PCH)高频覆铜板的研究进展。通过对目前碳氢树脂高频覆铜板研究的总结,找出现存的问题并对其未来发展趋势进行展望。

陆相中高成熟页岩油“组分流动”条件及其在提高页岩油产量中的作用

基于中国陆相页岩油区重点试采井的生产曲线、生产制度、烃产物数量和产出烃构成随时间的变化等资料,开展页岩油精细馏分切割和页岩油组成变化对宏观流动性影响的试验以及分子动力学数值模拟,提出页岩油“组分流动”概念,并对组分流动的形成机理与条件进行探讨。研究表明:(1)在地下页岩微纳米孔隙中,轻烃、中质烃和重烃会按相似相溶原理发生混相,使重烃等难流动组分以分子聚集体方式“悬浮”在轻烃和中质烃溶剂中,从而显著降低其黏度并增加流动性和流动量;(2)小分子芳烃是组分流动发生的载体,气态烃和轻烃含量越高,越利于抑制胶质和沥青等重组分形成尺寸更大的聚集体,并增加其塑性变形能力,组分流动效果越好;(3)较高的地层温度可降低蜡质等重烃组分黏度,提高其流动性;(4)保存条件、地层能量和生产制度对控制轻烃组分含量、流出速度和形成稳定的“组分流动”都有重要作用,是页岩油多组分烃形成最优配伍和最大流动量的重要影响因素。地下页岩油“组分流动”概念的提出对于提高页岩油单井产量和累计采出量具有重要意义。

溶剂提取-高效液相色谱法测定大气颗粒物中18种多环芳烃

建立大气颗粒物PM2.5中18种多环芳烃的样品快速溶剂提取结合高效液相色谱的测定方法。将1/2玻璃滤膜剪碎后加入2.0 mL乙腈,于20℃水浴超声提取30 min,提取液经0.22μm有机相滤膜过滤,多环芳烃C18专用柱分离,以乙腈-水作为流动相进行梯度洗脱,采用紫外串联荧光检测器-高效液相色谱仪检测,以色谱峰面积外标法定量。18种PAHs的质量浓度在0.01~0.50μg/mL范围内与色谱峰面积线性关系良好,相关系数不小于0.999,检出限为0.03~0.47 ng/m^(3),样品加标平均回收率为75.6%~114.7%,相对标准偏差为0.09%~3.78%(n=7)。该方法简便、快速、准确、灵敏,可应用于大气颗粒物PM2.5中18种多环芳烃的测定。

准噶尔盆地东道海子凹陷二叠系平地泉组烃源岩特征及热演化史模拟

基于钻井、录井、测井及烃源岩分析测试等资料,对准噶尔盆地东道海子凹陷二叠系平地泉组烃源岩的生烃潜力和热演化史进行了系统研究。研究结果表明:(1)准噶尔盆地东道海子凹陷二叠系平地泉组烃源岩主要为深灰色、灰黑色泥岩,颜色深且厚度普遍较大,自东北部斜坡区向凹陷中部厚度逐渐增大,并向西部莫索湾凸起逐渐减小,最大泥岩厚度可达536 m。(2)研究区平地泉组烃源岩有机质丰度综合评价为中等—极好,纵向上以平一段有机质丰度最高,平面上以凹陷东北部滴南7井区和滴南19井区最高;平地泉组有机质类型主要为Ⅱ_(2)—Ⅲ型,少部分为Ⅱ_(1)型,纵向上以平二段有机质类型最好,平面上凹陷区烃源岩有机质类型主要为Ⅱ_(1)—Ⅱ_(2)型。(3)热演化史模拟结果显示,凹陷区和斜坡区烃源岩分别在晚三叠世和晚侏罗世达到生烃高峰,现今分别处于高成熟阶段和成熟阶段。(4)研究区发育“下生上储”和“自生自储”2类油气藏,其中平地泉组烃源岩与上乌尔禾组储集层形成“下生上储”油气藏,平二段和平一段的优质烃源岩与湖盆边缘的小型扇三角洲沉积在平地泉组内部形成“自生自储”油气藏,二者油气勘探潜力均较大。

液液萃取--超高效液相色谱串联质谱法同时测定尿中11种羟基多环芳烃

目的建立可同时测定尿中11种羟基多环芳烃(hydroxy-polycyclic aromatic hydrocarbons,OH-PAHs)的超高效液相色谱串联质谱分析(ultra-high performance liquid chromatography tandem with mass spectrometry,UPLC-MS/MS)法。方法尿液样品在pH=5.5条件下,在37℃水浴中经β-葡萄糖苷酸酶—芳基硫酸酯酶避光水解16 h,3.0 mL正己烷萃取、涡旋、离心,取上层有机相,重复萃取两次,合并萃取液,氮吹至近干,再复溶于20%乙腈水溶液中。流动相为水和10%异丙醇甲醇溶液,梯度洗脱模式洗脱,CORTECS C18色谱柱分离,ESI-模式测定尿液中11种羟基多环芳烃浓度,内标法定量分析。结果11种羟基多环芳烃线性关系良好,相关系数(r)均大于0.997。方法的检出限为0.01~0.10 ng/mL;日间回收率为79.8%~97.3%,精密度为1.9%~4.7%(n=3);日内回收率为78.6%~92.3%,精密度为3.7%~7.1%(n=3)。结论该方灵敏度高,准确可靠,适用于人群中多种羟基多环芳烃的监测。

天然气中掺氢对计量物性参数的影响分析

在天然气管道中掺入氢气是进行大规模天然气输送的有效途径,但氢气会对管输水力和热力特性造成影响,进而影响与计量相关的物性参数。基于此,以常规天然气、页岩气及伴生气等三种典型气质组成为基础,系统分析了不同掺氢条件对管输温度、压力的影响及天然气物性参数的变化规律,探讨了天然气掺氢对计量分析的影响。结果表明,掺氢浓度与掺氢天然气温度呈反比,升高温度或降低压力可以减少掺氢天然气的沿程温降;采用GERG-2008方程计算压缩因子的结果准确度明显高于AGA8-92DC方程,随着温度降低、氢气浓度增加,计算结果误差明显增大。建议管道中掺氢浓度不应超过10%;并从改造气相色谱仪、加速标准气体制备、完善量值溯源和标准体系建设等方面入手,逐步实现掺氢天然气计量的标准化和工业化。