Effect of petroleum chemical fraction and residual oil content in saline lacustrine organic-rich shale: A case study from the Paleogene Dongpu Depression of North China

Halite and gypsum minerals in saline shale make the retention mechanism and chemical fractionation of residual oil unique. The Dongpu Depression in North China is a typically saline lacustrine basin with developing halite and gypsum. The effect of gypsum minerals on residual oil content and chemical fractionation remains unclear. In this study, shale samples with different gypsum contents were used in organic geochemical experiments, showing that the high total organic matter (TOC) content and type II kerogen leads to a high residual oil content, as shown by high values of volatile hydrocarbon (S1) and extractable organic matter (EOM). XRD and FE-SEM result indicate that the existence of gypsum in saline shale contributes to an enhanced pore space and a higher residual oil content in comparison to non-gypsum shale. Additionally, the increase in the gypsum mineral content leads to an increase in the saturated hydrocarbon percentage and a decrease in polar components percentage (resins and asphaltene). Furthermore, thermal simulation experiments on low-mature saline shale show that the percentage of saturated hydrocarbons in the residual oil is high and remains stable and that the storage space is mainly mesoporous (> 20 nm) in the oil expulsion stage. However, the saturated hydrocarbons percentage decreases rapidly, and oil exists in mesopores (> 20 nm and < 5 nm) in the gas expulsion stage. In general, gypsum is conducive to the development of pore space, the adsorption of hydrocarbons and the occurrence of saturated hydrocarbon, leading to large quantities of residual oil. The data in this paper should prove to be reliable for shale oil exploration in saline lacustrine basins.

Void Fraction Measurement in Oil-Gas Transportation Pipeline Using an Improved Electrical Capacitance Tomography System

To measure the void fraction online in oil-gas pipeline, an improved electrical capacitance tomography (ECT) system has been designed. The capacitance sensor with new structure has twelve internal electrodes and overcomes the influence of the pipe wall. The data collection system is improved by using high performance IC (integrated circuit). Static tests of bubble flow, stratified flow and annular flow regime are carried out. Measurements are taken on bubble flow, stratified flow and slug flow. Results show that the new ECT system performs well on void fraction measurement of bubble flow and stratified flow, but the error of measurement for slug flow is more than 10%.

Migration Fractionation of Neutral Nitrogen Compounds of Crude Oils from Tabei Oilfield in the Tarim Basin, China

The absolute amounts and relative distributions of neutral nitrogen compounds in the Tabei oilfield (e.g. blocks Ln1-Ln11) showed remarkable migration fractionation in the vertical direction. From Ordovician reservoirs (O) to oil legs T-Ⅲ and T-Ⅰ of Triassic reservoirs in blocks LN1-LN11, the concentrations of + decreased from {1.59}μg/g, {0.49}μg/g to {0.17}μg/g (oil). The ratios of various alkylcarbazole isomers, such as 1,8-dimethylcarbazole/nitrogen-partially shielded isomers and 1,8-dimethylcarbazole/nitrogen-exposed isomers, were adopted as the indicators of petroleum migration. The ratios increased from {0.13}, {0.20} to {0.67} and from {0.42}, {0.87} to {3.30}, corresponding to those of Ordovician oil leg and oil legs T-Ⅲ and T-Ⅰ. In going from the south to the north of the Tabei oilfield, the absolute concentrations of neutral nitrogen compounds decreased drastically, and the nitrogen-shielded isomers were enriched relative to nitrogen-exposed isomers and nitrogen-partially shielded isomers. Crude oils in the Tabei oilfield migrated laterally from the Jilake structure to the Sangtamu fault uplift and Lunnan fault uplift, and crude oils in the same fault uplift migrated and remigrated vertically from Ordovician reservoirs, to oil legs T-Ⅲ to T-Ⅰ of Triassic reservoirs.

Phytochemical Profile and <i>In Vitro</i>Antioxidant Properties of Essential Oils from Powder Fractions of <i>Eucalyptus camaldulensis</i>Leaves

Dried leaves of Eucalyptus camaldulensis were finely grinded and fractionated by sieving into four granulometric classes (<100 μm, 100 - 200 μm, 200 - 355 μm and >355 μm). The obtained powder fractions were used for essential oil (EO) extraction by hydrodistillation and their phytochemical profile and in vitro antioxidant activities were evaluated. The mother powder (unsieved powder) was used for comparison. Particle size exerted a significant influence (p < 0.05) on the phytochemical composition and in vitro antioxidant properties of the EOs. Comparatively, the mother powder had the highest contents of α-pinene (55.6%), camphene (3.4%) and limonene (3.7%), while 1,8-cineole (26.6% and 22.4%), exo-fenchol (5.6% and 3.5%), α-campholenol (4.2% and 3.4%), L-trans-pinocarveol (5.5% and 2.7%), L-borneol (12.6% and 6.8%) and α-terpineol (16.4% and 7.6%) are the main compounds of EOs from the <100 μm and 100 - 200 μm fractions, respectively. The antioxidant activities of the EOs revealed higher radical-scavenging activities DPPH (90.62% and 70.46%) and ABTS (89.59% and 73.31%) for finer fractions (<100 μm and 100 - 200 μm, respectively). The best reducing power (36.15% and 34.27%) were also found in these finer powder fractions which improved by more than 2 times the value of mother powder (reducing power of 17.01%). These results suggest that grinding followed by sieve fractionation concentrates the majority of antioxidant phytochemicals in the EOs of the finer powder fractions of E. camaldulensis leaves. Finer powders could be used as functional ingredients in food formulations for the management of chronic diseases.

Fractional pyrolysis of Cyanobacteria from water blooms over HZSM-5 for high quality bio-oil production

Fractional pyrolysis and one-step pyrolysis of natural algae Cyanobacteria from Taihu Lake were comparatively studied from 200 to 500 ℃. One-step pyrolysis produced bio-oil with complex composition and low high heating value （HHV〈30.9 MJ/kg）. Fractional pyrolysis separated the degradation of different components in Cyanobacteria and improved the selectivity to products in bio-oil. That is, acids at 200 ℃, amides and acids at 300 ℃, phenols and nitriles at 400 ℃, and phenols at 500 ℃, were got as main products, respectively. HZSM-5 could promote the dehydration, cracking and aromatization of pyrolytic intermediates in fractional pyrolysis. At optimal HZSM-5 catalyst dosage of 1.0 g, the selectivity to products and the quality of bio-oil were improved obviously. The main products in bio-oil changed to nitriles （47.2%） at 300 ℃, indoles （51.3%） and phenols （36.3%） at 400 ℃. The oxygen content was reduced to 7.2 wt% and 9.4 wt%, and the HHV was raised to 38.1 and 37.3 MJ/kg at 300 and 400 ℃, respectively. Fractional catalytic pyrolysis was proposed to be an efficient method not only to provide a potential solution for alleviating environmental pressure from water blooms, but also to improve the selectivity to products and obtain high quality bio-oil.

Flow Characteristics of Crude Oil with High Water Fraction during Non-heating Gathering and Transportation

In order to ensure the safety of the non-heating gathering and transportation processes for high water fraction crude oil,the effect of temperature,water fraction,and flow rate on the flow characteristics of crude oil with high water fraction was studied in a flow experimental system of the X Oilfield.Four distinct flow patterns were identified by the photographic and local sampling techniques.Especially,three new flow patterns were found to occur below the pour point of crude oil,including EW/O&W stratified flow with gel deposition,EW/O&W intermittent flow with gel deposition,and water single-phase flow with gel deposition.Moreover,two characteristic temperatures,at which the change rate of pressure drop had changed obviously,were found during the change of pressure drop.The characteristic temperature of the first congestion of gel deposition in the pipeline was determined to be the safe temperature for the non-heating gathering and transportation of high water cut crude oil,while the pressure drop reached the peak at this temperature.An empirical formula for the safe temperature was established for oil-water flow with high water fraction/low fluid production rate.The results can serve as a guide for the safe operation of the non-heating gathering and transportation of crude oil in high water fraction oilfields.

Measurement of oil volume fraction and velocity distributions in vertical oil-in-water flows using ERT and a local probe

This paper presents the use of a high performance dual-plane electrical resistance tomography (ERT) system and a local dual-sensor conductance probe to measure the vertical upward oil-in-water pipe flows in which the mean oil volume fraction is up to 23.1%. A sensitivity coefficient back-projection (SBP) algorithm was adopted to reconstruct the flow distributions and a cross correlation method was applied to obtain the oil velocity distributions. The oil volume fraction and velocity distributions obtained from both measurement techniques were compared and good agreement was found, which indicates that the ERT tech- nique can be used to measure the low fraction oil-water flows. Finally, the factors affecting measurement precision were discussed.

Control Scheme Discussion for Bottom Oil Slurry System of FCCU Fractionator

流化催化裂化装置（FCCU）分馏塔底油浆系统的控制效果对整个装置的平稳安全运行具有重要意义。近年来国内新建了许多大型FCCU，既包含国内各设计院自己的技术，也有部分引进国外的工艺包，其分馏塔底油浆系统的控制方案也有多种形式。总结了近年来国内新建FCCU常用的三种较为典型的油浆系统控制方案，阐述了各方案的特点，对其进行了简要的对比和分析。在此基础上尝试性地提出了这三种方案的适用场合，方便设计人员根据每个项目的特点设计合理的控制方案，达到最佳控制效果。

Research on Synthesizing Disperser with Fraction of Anthracene Oil for Coal Water Slurry

Experiment of synthesizing a disperser for coal water slurry (CWS) by using fractions of anthracene oil from high-temperature coal tar was performed. The orthogonal test was used to investigate the influence of temperature, time, quantity of sulfonation agent and condensation agent and the interaction of these factors on properties of the disperser. The result shows that the influence of temperature, time, quantity of sulfonation agent and condensation agent, and the interaction of sulfonation time and sulfonation agent has a significant influence on the properties of disperser. The optimal condition of synthesis is that in 150g of the fractions of anthracene oil, 40 mL of sulfonation agent is added and sulfonated for 3 h at 130℃, then, 10 mL of condensing agent is added and condensated for 1.5 h at 115 ℃.

GEANT4 simulation of water volume fraction measurement in dehydrated crude oil

Online measurement of water volume fraction (WVF) in dehydrated crude oil is a difficult task due to very little water in dehydrated crude oil and high precision requirements. We presents a method to measure water volume fraction in dehydrated crude oil with γ-ray densitometry. The Monte Carlo computer simulation packet GEANT4 was used to analyze the WVF measuring sensitivity of the γ-ray densitometry at different γ-ray energies, and effects of temperature, pressure, salinity and oil components on WVF measurement. The results show that the γ-ray densitometry has high sensitivity in γ-ray energy ranges of 16~25keV, and it can distinguish WVF changes of 0.0005. The calculated WVF decreases about 0.0002 with 1℃ of temperature increase and they have approximately linear relation with temperature when water volume fraction remains the same. Effects of pressure, salinity and oil components on water volume fraction can be neglected. Experiments were done to analyze sensitivity of the γ-ray densitometry. The results , as compared with simulations, demonstrate that simulation method is reliable and it is feasible to gauge low water volume fraction using low energy γ-rays.

Biomarker responses in the bivalve Chlamys farreri to the water-soluble fraction of crude oil

To investigate the effect of the water soluble fraction of crude oil(WSF) on marine bivalves, the scallop C hlamys farreri was exposed to three WSF concentrations(0.18 mg/L, 0.32 mg/L, and 0.51 mg/L, respectively) in seawater. Petroleum hydrocarbon contents in scallops and a suite of enzymes [7-Ethoxyresorufin-O-deethylase(EROD), aryl hydrocarbon hydroxylase(AHH), glutathione S-transferase(GST), and glutathione peroxidase(GPx)] in gills and digestive glands were monitored over 10 days. The results revealed that WSF affected the activity of the four enzymes in the gills and digestive glands. EROD activity in the gills was significantly induced in most individuals of the three test groups, while in the digestive gland it was significantly induced in the low-concentration group within 4 days but was inhibited in the middle- and high-concentration groups on days 1, 4, and 10. AHH activity in the gills of all treatment groups was significantly induced on day 1. In the digestive gland, AHH activity was induced in most individuals from the treatment groups. In all treatment groups, GST activity was significantly inhibited from days 2 to 10 in the gills and was induced after day 4 in the digestive gland. GPx activity in the gills was significantly inhibited throughout the exposure period in all treatment groups. There was no overall significant difference in GPx activity in the digestive gland between the control and treatment groups. Our results also revealed that petroleum hydrocarbon concentrations in the tissues increased linearly with exposure time. EROD activity in the digestive gland and GST and GPx activity in the gill tissue were negatively correlated with petroleum hydrocarbon body burden. These enzymes play important roles in detoxification and can act as potential biomarkers for monitoring petroleum hydrocarbon contaminants in the marine environment.

Production of Cocoa Butter Replacer by Dry Fractionation, Partial Hydrogenation, Chemical and Enzymatic Interesterification of Tea Seed Oil

Production of cocoa butter replacer (CBR) from tea seed oil through common modification methods of oils (dry fractionation, partial hydrogenation, chemical and enzymatic interesterification) was evaluated. Some physico-chemical properties (iodine, saponification, acid and peroxide values) and fatty acid composition (FAC) of modified samples were analyzed and compared with a reference cocoa butter (CB). Solid and liquid fractions for large amounts of unsaturated fatty acids (approx. 80%) and thereby lower iodine values (81 - 85 gI2/100g) than that of CB (37% and 34 gI2/100 g, respectively), are not suitable as CBR. Among all ratios of chemically and enzaymatically interesterified oil blends (20%, 25% and 30% of hydrogenated tea seed oil with 80%, 75% and 70% of tea seed oil/liquid fraction/solid fraction), the samples with ratio of 30:70 from both chemical and enzymatic interesterification had FAC and iodine value closer to that of CB. A comparision between chemically and enzymatically interesterified samples (CISs and EISs, respectively), in terms of solid fat content (SFC) indicated that although the SFC values in EIS were much lower than that of CB, but the thermal behavior of this sample is comprable to CB at 20℃- 30℃ (sharp melting point of CB).

Fractional Yield, Extract Composition and Variability from Jordanian Oil Shales

Surface and subsurface oil shale (OS) rocks in Jordan have potential economic value for the country and still unutilized. This research paper focuses on central and southern OS deposits in Jordan. Brief characterization of four OS deposits is presented. Size distribution test and elemental analysis were performed. Shale oil was extracted via three solvation methods: Soxhlet extraction, extraction via mixing and stirring, and lastly super-critical fluid extraction. Major shale oil fractions were obtained from extract fractionation on chromatographic column. The nuclear magnetic resonance spectroscopy technique was used to study qualitatively the fractional composition of OS extract. Results show that all studied OS deposits have quite similar trend in their particle size distribution and their elemental composition. These OS deposits are found to be varying in their solvation behavior, fractional yield, and shale oil composition. Highest yield is obtained from polar solvents. The OS extraction via solvation processes is promising under certain extraction conditions such as super-critical conditions. The solvation variability of Jordanian OS indicates that different extraction techniques suit different OS deposits. Such variability should be considered in any future extraction options.

Investigation of oil-air two-phase mass flow rate measurement using Venturi and void fraction sensor

Oil-air two-phase flow measurement was investigated with a Venturi and void fraction meters in this work. This paper proposes a new flow rate measurement correlation in which the effect of the velocity ratio between gas and liquid was considered. With the pressure drop across the Venturi and the void fraction that was measured by electrical capacitance tomography apparatus, both mixture flow rate and oil flow rate could be obtained by the correlation. Experiments included bubble-, slug-, wave and annular flow with the void fraction ranging from 15% to 83%, the oil flow rate ranging from 0.97 kg/s to 1.78 kg/s, the gas flow rate ranging up to 0.018 kg/s and quality ranging nearly up to 2.0%. The root-mean-square errors of mixture mass flow rate and that of oil mass flow rate were less than 5%. Furthermore, coefficients of the correlation were modified based on flow regimes, with the results showing reduced root-mean-square errors.

原油直接催化裂解UPC工艺过程模拟与反应参数多目标优化

原油直接催化裂解技术可以实现从原油到三烯(乙烯、丙烯、丁烯)、三苯(苯、甲苯、二甲苯)的一步跨越,对我国炼化行业的转型升级具有重要意义。以全馏分石蜡基中原原油(159~780℃)为原料,采用混合馏分结构与分子组成集总建模策略,对原油直接催化裂解制烯烃(UPC)反应过程进行建模与工艺参数校准,并基于工业试验数据验证了其准确性。以多产烯烃、控制焦炭生成为目的,利用NSGA-Ⅲ多目标优化算法对模型进行了优化,得到优化后的操作参数。采用优化后的操作参数,即在第一段预热闪蒸温度为194.32℃、第二段预热闪蒸温度为228.16℃、第一段提升管反应器出口温度为615.73℃、第二段提升管反应器出口温度为622.59℃的条件下,UPC工艺得到的乙烯和丙烯收率之和为53.367%,焦炭收率为8.311%。此外,由于现行税费体系燃料型工艺路线税收贡献明显高于化工型工艺路线,UPC工艺参数优化后,烯烃收率大幅度提升,燃料油收率大幅度下降,原油生产总值降低44.30元t。

沙粒质量分数对油气混输泵过流部件磨损的影响

为研究沙粒质量分数对油气混输泵过流部件磨损的影响规律,基于DPM模型对油气混输泵内部的沙粒运动进行数值计算,并采用Finnie磨蚀模型计算油气混输泵过流部件的磨蚀率.研究结果表明:在沙粒质量分数较小时,沙粒与流体介质混合均匀;随着沙粒质量分数的增大,增压单元内的沙粒局部质量浓度显著增大,沙粒集中在叶轮压力面及导叶流道中部;沙粒质量分数增大会使磨损区域和磨损率急剧增大;在叶轮域中,磨损首先发生在压力面出口处,吸力面则在进口外缘发生点状和条状磨损;在导叶域中,压力面的磨损主要发生在外缘处,吸力面的磨损主要发生在进口轮毂处;从定量分析看,叶轮叶片表面的磨蚀率普遍大于导叶叶片表面的磨蚀率,磨损最严重的位置为叶轮叶片进口靠近轮毂处.研究结果可为改善油气混输泵抗磨损性能以及提高油气混输泵实际运行寿命提供一定参考依据.

乙酸和富芳香组分对生物油电化学提质中聚合结焦的影响

生物油是唯一的液体含碳可再生资源,因其成分复杂、热值低、酸度高、粘度大等特点,必须经过提质才能进一步利用。生物油电化学提质是一种条件温和、易于控制的新兴提质方法,但仍面临生物油聚合结焦的问题,降低了提质生物油的品质和收率。通过对含有不同浓度乙酸和富芳香组分(Aromatic-Rich Fraction,ARF)的调制生物油分别进行电化学提质实验,对电化学反应后的溶液和焦表征分析,研究了乙酸和ARF对焦产率的影响规律,探讨了乙酸和ARF对生物油聚合结焦的影响机制。结果表明,乙酸能抑制生物油聚合结焦,加入浓度1%的乙酸可降低焦产率约25%,继续增加乙酸浓度会进一步降低焦产率;而ARF则会促进生物油聚合结焦,当ARF浓度从60%升到70%时,焦产率增加了约70%,当ARF浓度升到80%后,焦产率增加了约150%。乙酸能抑制生物油中酚类物质自缩合,降低了聚合结焦反应的速率,而ARF则增强了羟醛缩合反应,提高了聚合结焦反应的速率。

超声波辅助棕榈油分提工艺研究

为提升棕榈油分提工艺,采用超声波对结晶罐中的油液进行辅助处理。以分提所得低度液油碘值为指标,研究超声时间、超声时油脂的结晶时间、超声频率、超声功率对分提工艺的影响,并在单因素试验的基础上设计正交试验方案。结果表明,超声波辅助分提最佳设置条件为超声处理时间10 min、超声结晶时间600 min、超声频率28 kHz和超声功率400 W。同时对所得低熔点棕榈液油进行了品质测定,结果显示,超声处理并不会改变所得液油的品质。优化的超声工艺条件加快了棕榈油冷却结晶的进程,缩短了工艺时间,增强了生产运行的稳定性,提升了液油产率,具有良好的应用前景。

起伏地形下油气管道水合物生成规律研究

针对油气水混输在一定条件下会生成天然气水合物的问题,采用OLGA建立了某爬坡油气水混输管道流动模型,分析了开发前期、中期、后期生产变化,研究了水合物的生成规律。结果表明,随着天然气流量的增大,管道内天然气水合物体积分数峰值降低。长庆油田该区块前期产量较大,应主要在管道出口位置设置水合物解堵设施,而在开发后期产量下降后,应注意在翻越高点、低洼处附近设置水合物解堵设施。随着气液比的增大,管道内水合物体积分数明显增加,在气液比为140∶1时,管道里程5812 m处水合物体积分数达到最大峰值17%,应注意此时管道低洼处的水合物积聚问题,提前采取加热等措施防止水合物堵塞造成生产事故。