Molecular composition of low-temperature oxidation products of the heavy oil

Low-temperature oxidation(LTO)is the main reaction that affects fuel formation in the in-situ combustion process,which has important significance for the subsequent combustion propulsion and the successful extraction of crude oil.In this study,heavy oil was subjected to LTO reactions at different temperatures.Three types of reaction products with varying oxidation depths were characterized in terms of the number of oxygen atoms and the polarity of the molecule to reveal the low-temperature oxidation process of the heavy oil.Ketone compounds and acid polyoxides in the oil phase and deep oxidation products with a higher number of oxygen atoms in the coke were identified with increasing oxidation depth.The experimental results showed that the oxidation reaction of the heavy oil changed from kinetic-controlled to diffusion-controlled in the open oxidation system of the heavy oil as the oxidation depth increased.The oxidation reaction of the oil phase reached a maximum and stable value in oxygen content.The molecular compositions of the ketone compound and acid polyoxide did not change significantly with further increase in reaction temperature.The molecular compositions of the deep oxidation products with a higher number of oxygen atoms in the coke phase changed significantly.The coke precursor molecules with a lower oxygen content and condensation degree participated in the coke formation,and the oxidation reaction pathway and the complexity of the oxidation product component also increased.

In situ catalytic upgrading of heavy crude oil through low-temperature oxidation

The low-temperature catalytic oxidation of heavy crude oil（Xinjiang Oilfield,China） was studied using three types of catalysts including oil-soluble,watersoluble,and dispersed catalysts.According to primary screening,oil-soluble catalysts,copper naphthenate and manganese naphthenate,are more attractive,and were selected to further investigate their catalytic performance in in situ upgrading of heavy oil.The heavy oil compositions and molecular structures were characterized by column chromatography,elemental analysis,and Fourier transform infrared spectrometry before and after reaction.An Arrhenius kinetics model was introduced to calculate the rheological activation energy of heavy oil from the viscosity-temperature characteristics.Results show that the two oil-soluble catalysts can crack part of heavy components into light components,decrease the heteroatom content,and achieve the transition of reaction mode from oxygen addition to bond scission.The calculated rheological activation energy of heavy oil from the fitted Arrhenius model is consistent with physical properties of heavy oil（oil viscosity and contents of heavy fractions）.It is found that the temperature,oil composition,and internal molecular structures are the main factors affecting its flow ability.Oil-soluble catalyst-assisted air injection or air huff-n-puff injection is a promising in situ catalytic upgrading method for improving heavy oil recovery.

Low-temperature oxidation of light crude oil in oxygen-reduced air flooding

Light crude oil from the lower member of the Paleogene Xiaganchaigou Formation of Gaskule in Qinghai Oilfield was selected to carry out thermal kinetic analysis experiments and calculate the activation energy during the oil oxidation process.The oxidation process of crude oi l in porous medium was modeled by crude oil static oxidation experiment,and the component changes of crude oil before and after low-temperature oxidation were compared through Fourier transform ion cy-clotron resonance mass spectrometry and gas chromatography;the dynamic displacement experiment of oxygen-reduced air was combined with NMR technology to analyze the oil recovery degree of oxygen-reduced air flooding.The whole process of crude oil oxidation can be divided into four stages:light hydrocarbon volatilization,low-temperature oxidation,fuel deposition,and high temperature oxidation;the high temperature oxidation stage needs the highest activation energy,followed by the fuel deposition stage,and the low-temperature oxidation stage needs the lowest activation energy;the concentration of oxygen in the reaction is negatively correlated with the activation energy required for the reaction;the higher the oxygen concentration,the lower the average activation energy required for oxidation reaction is;the low-temperature oxidation reaction between crude oil and air generates a large amount of heat and CO,CO_(2) and CH4,forming flue gas drive in the reservoir,which has certain effects of mixing phases,reducing viscosity,lowering interfacial tension and promoting expansion of crude oil,and thus helps enhance the oil recovery rate.Under suitable reservoir temperature condition,the degree of recovery of oxygen-reduced air flooding is higher than that of nitrogen flooding for all scales of pore throat,and the air/oxygen-reduced air flooding de-velopment should be preferred.

The occurrence characteristics of oil in shales matrix from organic geochemical screening data and pore structure properties:An experimental study Author links open overlay panel

The occurrence characteristics of shale oil are of great significance to the movability of shale oil.In this study,the occurrence characteristics of oil in the shale matrix at Funing Formation shale in Subei Basin were quantitatively evaluated by organic geochemistry and microscopic pore structure characterization experiments.The Multiple Isothermal Stages Pyrolysis(MIS)experiment results show that the content of total oil,adsorbed oil,and free oil in the shales are 3.15-11.25 mg/g,1.41-4.95 mg/g,and 1.74-6.51 mg/g,respectively.among which the silicon-rich shale has the best oil-bearing.The relative content of free oil shows an increasing trend in pores with pore diameters greater than 3 nm.When the relative content of free oil reaches 100%,the pore size of silicon-rich shale is about 200 nm,while that of calcium-rich shale,clay-rich shale,and siliceous mixed shale is about 10 nm.The occurrence law of adsorbed oil is opposite to that of free oil,which indicates that shale oil will occur in the pores and fractures in a free state in a more extensive pore size range(>200 nm).This study also enables us to further understand the occurrence characteristics of shale oil under the interaction of occurrence state and occurrence space.

Analysis of Retorted Water Produced from Partial Combustion of Sultani Oil Shale

Oil shale samples from Sultani oil shale mine, south of Jordan, were pyrolyzed by a partial combustion to generate shale oil. The produced water was sent for analysis. The different samples were analyzed for carbon content, and results showed that the TOC was 2010 mg per liter of retorted water. Phenol and arsenic contents were measured and found to be 64 mg and 0.18 mg per liter respectively. Phosphate and sulfate were also determined and found to be 35.7 and 5022 mg per liter. On the other hand, ammonium was also found to be 2831 mg per liter. Several elements were traced and reported in the present work, in which arsenic, chrome and nickel are the most important, and the retorted water was found to contain 0.18, 0.7 and 0.5 mg per liter.

Study on the Catalytic Reforming Law of Solid-Phase Carbon and Nitrogen Sources Loaded with MnO_(2)at Low Temperatures in Tahe Heavy Oil

MnO_(2)/Melem composites were synthesized with MnO_(2)nanoparticles loaded onto the Melem using the hydrothermal method.As raw materials for C and N carriers,Melem was prepared from melamine roasted at 354℃,and KMnO_(4)as a raw material for Mn,MnO_(2)nanoparticles were prepared using the hydrothermal synthesis of KMnO_(4).Scanning electron microscopy(SEM),transmission electron microscopy(TEM),X-ray diffraction(XRD),and a laser particle size analyzer were used for structural characterization,and the catalytic oxidation performance of the heavy oil was investigated at different reaction temperatures(100℃to 180℃)using MnO_(2)/Melem with an oxidant and donor protonic acid.The results showed that the synthesizedβ-MnO_(2)nanoparticles were successfully loaded onto the Melem surface;the oil samples before and after the reaction at different temperatures were subjected to SARA analysis using Fourier transform infrared(FT-IR),elemental analysis,gas chromatography-mass spectrometry(GC-MS)and viscosity tests,respectively.It was determined that the hydrocarbons in the crude oil were converted to heavy mass by oxidation reactions with the oxidant mainly through a low-temperature oxidation process below 140℃in the heavy oil when the temperature exceeds 140℃,in addition to the oxidation reaction with the oxidant,a cleavage reaction in the carbon chain occurs to form hydrocarbon substances with lower molecular weights.

页岩干馏渣制备多孔材料及其吸附性能的研究

为了处理油页岩炼油过程中产生的大量页岩干馏渣以及页岩干馏废水,本文对页岩干馏渣进行酸化改性,采用优化的改性条件制备了多孔吸附材料,以实现废物的资源化利用。采用X射线荧光光谱(XRF)、X射线粉末衍射(XRD)、N_(2)吸附-脱附等手段对所得样品进行了表征分析。将制得的吸附剂用于吸附页岩干馏废水,考察了吸附剂的改性条件、吸附剂用量、吸附温度、pH和吸附时间等因素对油去除率的影响。由XRF分析结果可知,页岩干馏渣样品的主要成分为SiO_(2)和Al_(2)O_(3),含量分别为61%和23.5%。N_(2)吸附-脱附表征分析结果表明,酸化改性前后,页岩干馏渣的比表面积分别为59.412m^(2)·g^(-1)和76.276m^(2)·g^(-1),孔径分别为3.056nm和2.271nm。吸附实验表明,酸化处理提高了页岩干馏渣的吸附性能,酸化页岩渣对油的去除率提高了22%。最佳吸附条件为:用8%硝酸酸化的页岩干馏渣吸附100mL页岩干馏废水,在55℃下吸附3h,油去除率能达到61.74%。

基于RF-PSO-SVM的油页岩干馏工艺粉尘爆炸风险评估

为准确预测油页岩干馏工艺过程粉尘爆炸风险等级,以加强油页岩粉尘爆炸事故防范能力,提出了一种快速精准的风险评估模型。按照4M分类原则将评价指标分为人、物、管理和环境4大类和30小项,采用随机森林(RF)对30项特征指标进行属性约简,进而提取关键指标;使用粒子群算法(PSO)对支持向量机(SVM)进行更新全局寻优,合理优化SVM的参数。通过随机选择30组评价数据进行测试,进行了RF-PSO-SVM模型与SVM模型、RF-SVM模型以及PSO-SVM模型对比。结果表明:该模型风险预测结果正确率最高且运行时间较短,识别准确率达93.33%,体现出该模型对油页岩干馏工艺粉尘爆炸风险预测的精准性和及时性。

油页岩干馏废水中氨氮利用的工程化研究

针对油页岩干馏废水中高浓度氨氮的处理难题,本文采用吹脱-吸收法脱除油页岩干馏废水中的高浓度氨氮。工艺条件为:温度40℃,气液比2300∶1,用碱调节废水pH为10~11。经循环吸收可得到浓度15%以上的氨水。氨水可应用到油页岩干馏工艺的加热炉烟气脱硫单元,氨法脱硫后的副产品硫铵可用于矿山复垦绿化工程,由此开发了一条将污染物资源化利用的新型工艺循环处理路线。

Pyrolysis characteristics of a North Korean oil shale

Pyrolysis characteristics of a North Korean oil shale and its pyrolysates were investigated in this paper. The pyrolysis experiments were conducted below 600 ℃ at a heating rate of 10, 15, 20 and 25 ℃/min, respectively. The kinetics data were calculated using both integral and differential methods with the assumption of first order kinetics. The results show that the averaged oil content of the North Korean oil shale is about 12.1 wt% and its heat value is 13,400 kJ/kg. The oil yields at different retorting temperatures show that the higher the retorting temperature the greater the oil and retorting gas yields. The optimal retorting temperature for the North Korean oil shale is about 500 ℃. The properties of the North Korean shale oil including density, viscosity, flash point and freezing point are found to be relatively low compared with those of shale oil from FuShun, China. The gasoline fraction, diesel fraction and heavy oil fraction account for 11.5 wt%, 41.5 wt% and 47 wt%, respectively. The major pyrolysis gases are ca4 （the most abundant）, H2, CO2, H2S, CO, and C2-C5 hydrocarbons. The heat value of retorting gas is more than 900 kJ/mol, and the retorting gas has high sulfur content.

Reaction mechanism and kinetics of pressurized pyrolysis of Chinese oil shale in the presence of water

A study of reaction mechanisms and chemical kinetics of pressurized pyrolysis of Chinese Liushuhe oil shale in the presence of water were conducted using an autoclave for simulating and modeling in-situ underground thermal degradation.It was found that the oil shale was first pyrolyzed to form pyrobitumen,shale oil,shale gas and residue,then the pyrobitumen was further pyrolyzed to form more shale oil,shale gas,and residue.It means that there are two consecutive and parallel reactions.With increasing temperature,the pyrobitumen yield,as intermediate,first reached a maximum,then decreased to approximately zero.The kinetics results show that both these reactions are first order.The activation energy of pyrobitumen formation from oil shale is lower than that of shale oil formation from pyrobitumen.

A New Method for Predicting Wall Sticking Occurrence Temperature of High Water Cut Crude Oil

In crude oil transportation, adhesion of oil on pipe wall can cause partial or total blockage of the pipe. This process is significantly affected by wall sticking occurrence temperature(WSOT). In this work, an efficient approach for estimating WSOT of high water-cut oil, which can agree well with the actual environment of multiphase transportation pipeline, is proposed. Based on the energy dissipation theory, it is possible to make comparison of average shear rates between the stirred vessel and the flow loop. The impacts of water content and shear rate on WSOT are investigated using the stirred vessel and the flow loop. Good agreement has been observed between the stirred vessel and the flow loop results with the maximum and the average absolute deviations equating to 3.30 °C and 2.18 °C, respectively. The development of gathering scheme can enjoy some benefits from this method.

Extraordinary Compatibility to Mass Loading and Rate Capability of Hierarchically Porous Carbon Nanorods Electrode Derived from the Waste Tire Pyrolysis Oil

The conversion of waste tire pyrolysis oil(WTPO)into S-doped porous carbon nanorods(labeled as WPCNs)with hierarchical pore structure is realized by a simple template-directed approach.The specific surface area of as-obtained porous carbon nanorods can reach up to 1448 m^(2) g^(−1) without the addition of any activating agent.As the capacitive electrode,WPCNs possess the extraordinary compatibility to capacitance,different electrolyte systems as well as long-term cycle life even at a commercial-level areal mass loading(10 mg cm^(−2)).Besides,only an extremely small capacitance fluctuation is observed under the extreme circumstance(−40 to 80℃),reflecting the excellent high-and low-temperature performance.The relationship between the pore structure and capacitive behavior is analyzed by comparing WPCNs with mesopores-dominated asphalt-derived porous carbon nanorods(APCNs)and micropores-dominated activated carbon.The molecular dynamics simulation further reveals the ion diffusion and transfer ability of the as-prepared carbon materials under different pore size distribution.The total ion flow(NT)of WPCNs calculated by the simulation is obviously larger than APCNs and the N_(T) ratio between them is similar with the experimental average capacitance ratio.Furthermore,this work also provides a valuable strategy to prepare the electrode material with high capacitive energy storage ability through the high value-added utilization of WTPO.

Evaluation and Analysis of Oil Shale in Quseir-Safaga and Abu-Tartur Western Desert, Egypt

Seeking ways to diminish Egypt’s dependency on foreign oil imports, we had to look for the obvious resources to exploit. Oil shale is one of Egypt’s resources that are left abandoned and not used. This project is aiming at introducing both experimental analysis for oil shale in Egypt and the best production technique for it. This study is about experimentally analyzing different samples of potential oil shale fields in Egypt. Samples that are analyzed in this project are from two locations in Egypt: Quseir-Safaga and Abu-Tartur Western Desert, and they are compared to one of the best oil shale fields in the world, which is from Green River Formation Colorado. The experiments were done using AUC lab retort to experimentally determine the critical temperature that will lead to the maximum production using sudden and gradual change in temperatures, which turned out to be sudden change at 500°C. Thereafter, the degree of API gravity was calculated for each run. Then the oil samples were determined for impurities and liquid chromatography results in the Egyptian Petroleum Research Institute. Part two of the study plan has been included to determine the ultimate ways of producing efficiently, ecologically and economically.

不同杀菌处理对秋刀鱼软罐头营养及滋味的影响

本文评估了橄榄油油浸结合超高压杀菌应用于秋刀鱼软罐头加工的潜力,设置了五种处理方式:不加橄榄油的未杀菌组、橄榄油油浸的超高压杀菌(UHPSO)组、不加橄榄油的超高压杀菌(UHPS)组、橄榄油油浸的传统热杀菌(RSO)组以及不加橄榄油的传统热杀菌(RS)组,并对不同处理组秋刀鱼软罐头营养(基本营养成分、氨基酸和脂肪酸)及滋味(游离氨基酸和呈味核苷酸)的相关指标进行对比分析。结果表明:UHPSO组的粗脂肪、粗蛋白含量高于其他杀菌处理组,营养价值更高;不同杀菌处理的秋刀鱼软罐头氨基酸组成均符合FAO/WHO推荐模式且不存在限制性氨基酸,UHPSO组氨基酸评分最高,尤其是补充含硫氨基酸及赖氨酸的优质来源;与传统热杀菌相比,超高压杀菌可以更好抑制不饱和脂肪酸的氧化降解,结合橄榄油油浸处理的秋刀鱼软罐头是补充n-3多不饱和脂肪酸的优质来源。与未杀菌组相比,4种杀菌处理均导致游离氨基酸和呈味核苷酸含量增加,结合滋味活性值和味精当量值,发现谷氨酸、苏氨酸、天冬氨酸、丙氨酸和次黄嘌呤对秋刀鱼软罐头鲜美滋味的形成具有重要的贡献作用,其中UHPSO组鲜味最强。综合分析,与传统热杀菌相比,橄榄油油浸结合超高压杀菌处理的秋刀鱼软罐头营养丰富,滋味更加鲜美。

油页岩原位开采技术现状及建议

本文详细介绍了国内外油页岩原位开采的技术特点,并对电加热、对流加热、辐射加热、燃烧加热等4种加热方式具有代表性的技术进行了归纳整理,对其优缺点进行了比较分析,提出了存在的主要问题及建议。结合当前的研究进展,如何使油页岩的开发和利用变得更加高效、便捷和绿色,将是未来研究的发展方向,本文为进一步开发油页岩资源提供了一定参考。

生化系统处理高氨氮废水关键参数研究

本文研究了生化系统处理页岩炼油干馏污水的主要运行参数。结果发现,高pH值能够促进氨氮的降解,保证硝化反应进行彻底;溶解氧是亚硝酸盐菌和硝酸盐菌的主要竞争基质;硝化菌在水温不超过36℃的条件下可保持有效活性。

油页岩自热干馏——无热载体技术的提出背景及进展

阻碍油页岩(OS)成为主流能源的技术瓶颈是其要经干馏(热解)才能采出,需用大量的650℃以上的高温热载体将灰分占主体的油页岩矿石加热到约500℃,能耗高、操作难度大。研究证实,在干馏过程中引入适量氧可形成放热的、自发裂解的自热干馏技术(SHR),也称有氧低温干馏技术、氧化热解和自热热解等。SHR极大地简化了干馏过程,相对于传统需用大量高温热载体或在发展之中的电加热等工艺,SHR自身原位生热用于油页岩自裂解,因此一定程度上可视为无热载体法的干馏工艺。SHR在地下干馏中也优势极大。笔者论述了SHR的研究进展,旨在推动更多的研究者关注SHR工艺,促进油页岩资源的高效利用。

Directional preparation of naphthalene oil-rich tar from Beisu low-rank coal by low-temperature catalytic pyrolysis

Low-rank coal(LRC)can be converted to high value-added naphthalene and its alkylated derivatives through low-temperature catalytic pyrolysis.In this paper,the catalytic pyrolysis of Beisu LRC in a fixed-bed at low temperature was investigated.And the catalytic effects of HZSM-5,low-temperature carbocoal(LtC),and LtC-HZSM-5 on the content and yield of naphthalene oil were examined.The results showed that the generation of naphthalene oil in low-temperature LRC pyrolysis(LT-LP)process could be improved when LtC(prepared at 550℃)or HZSM-5 was individually used as a catalyst.Compared with sole pyrolysis of raw LRC,the addition of the LtC-HZSM-5 catalyst increased the content of naphthalene oil from 11.19 wt.%to 31.49 wt%.And the yield of naphthalene oil was increased from 1.07 wt%to 5.31 wt%.The reactions of micromolecular hydrogen-containing radicals(⋅MHCR)were optimized by LtC.⋅MHCR could be captured in relatively low-temperature region(200-400℃)and released at high temperature by LtC.The generation of phenolics was inhibited by HZSM-5.As a result,the naphthalene oil-rich tar was obtained through low-temperature LtC-HZSM-5 catalytic pyrolysis of Beisu LRC.

油页岩干馏废水中高氨氮回收处理技术

油页岩干馏废水中氨氮浓度均值在4000 mg/L,属于高氨氮废水,为了寻求适合油页岩干馏工艺特点的废水处理方案,分析了该废水水质特点,开展空气吹脱法和蒸汽汽提法对比工艺分析。结果表明:空气吹脱法为传统脱氮工艺,需补充大量碳源和碱度,污水处理厂运行成本极高,同时造成氨氮资源浪费;蒸汽汽提法结合干馏工艺特点,将废水中的氨氮提炼浓缩为15%以上浓氨水,再应用到干馏工艺的脱硫单元,实现污染物质在系统内部再利用。