油砂沥青超临界水热改质研究进展

油砂沥青超临界水热改质技术作为一种新型的绿色工艺,具有原料转化率高,体系结焦量少,脱硫、脱硝、脱重金属效果明显等优点;但迄今为止学术界对该过程的机理及相态变化情况仍无法进行准确的描述,尤其是对超临界水在体系中的作用仍存在争议。本文总结了油砂沥青超临界水热改质技术的机理,重点分析了超临界水在体系中的作用,简述了供氢剂和催化剂的研究情况,同时从相行为方面提出了提高体系改质效果的方法。分析表明超临界水在体系中的供氢效果并不显著,而更多的是以催化剂的作用存在。固体催化剂在该体系中的应用存在诸多缺陷,供氢剂的开发将成为油砂沥青超临界水热改质技术的发展方向,且供氢剂和自由基引发剂的应用将极大缓和工艺条件、降低设备要求,有利于促进该工艺的工业化。     

油砂资源现状及其开采分离方法浅谈

世界油砂矿藏主要沿环太平洋带和阿尔卑斯带展布,目前大约95%所探明的油砂矿藏分布于加拿大、委内瑞拉及美国。油砂的可采资源量约为6510亿桶,占世界石油可采总量的近三分之一。露天开采的油砂要经过油砂分离,沥青改质和废物处理三个环节。其中油砂分离包括热碱水法、溶剂萃取法以及干馏法等。     

重油改质技术获进展

据美国《化学工程》2008年5月26日报道，加拿大油砂产品沥青典型情况下的API度小于10，并且高含硫、金属和总酸值（TAN）。先经焦化再经加氢处理是改质重油的常用方法。这些过程可在当地或在炼油厂中应用。     

油砂沥青质对油砂沥青中甲苯残留的影响

利用热重质谱联用仪（TG-MS）分析了三种油砂沥青（印尼油砂沥青、伊朗油砂沥青、加拿大油砂沥青）中的甲苯残留以及油砂沥青质含量对油砂沥青中甲苯残留的影响,并在此基础上,进一步研究了油砂沥青质中的甲苯残留。结果发现,不同油砂沥青中甲苯残留量存在一定差异,其中印尼油砂沥青中的甲苯残留量最多。进一步对沥青质质量分数分别为10%、19%、30%的油砂沥青样品进行热重质谱实验,发现随着油砂沥青中沥青质含量的增加,甲苯的残留量会成倍增加。以加拿大油砂沥青质为例,研究了油砂沥青质对溶剂残留的影响,发现油砂沥青质具有对甲苯分子的夹带能力,导致甲苯分子在超过自身沸点40℃以上才能从沥青质中分离出来。油砂沥青中其他组分的存在也会加剧沥青质对甲苯的夹带作用。此外,研究还发现,在350~650℃时,油砂沥青质可以热解产生甲苯,而且油砂沥青中的沥青质含量越高,热解生成的甲苯越多。     

废塑料化学转化制燃料的催化剂研究进展

在简要介绍和比较热裂解、催化裂解、热裂解-催化改质和催化裂解-催化改质4种废塑料化学转化制燃料基本方法的基础上,综述了近年来国内外在废塑料裂解催化剂和废塑料裂解产物改质催化剂的研究进展,重点讨论了催化剂酸性、比表面积、孔径以及负载金属离子的类型等对废塑料催化裂解和催化改质反应性能的影响,并介绍了聚烯烃（包括聚乙烯和聚丙烯）废塑料和聚苯乙烯废塑料热裂解和催化裂解的反应机理。最后对废塑料化学转化制燃料技术的研究与开发提出了一些建议,指出采用催化裂解-催化改质组合技术是未来废塑料化学转化制燃料过程的发展趋势,其今后的研究重点将是开发具有较强酸性和有利于大分子扩散与传质性能孔道结构的分子筛催化剂。     

加拿大油砂生产成本上升

<正>加拿大能源研究院(CERI)发布的最新年度报告中表示,在过去的一年,加拿大阿尔伯塔省的沥青和合成原油生产成本上涨。采用蒸汽辅助重力驱油生产工艺的油砂生产成本(调和与运输前)上涨4.4%,升至50.89美元/桶;未经改质的油砂采矿成本上涨1.6%,升至71.81美元/桶;采矿和改质集成生产的成本上涨     

油砂沥青处理技术研究现状

为了实现油砂沥青的无害化处理,提高处理效率和综合效益,对油砂沥青现行处理技术的机理、工艺流程、优缺点和适用范围进行了概述和总结。通过分析表明,各种油砂沥青现行处理技术都有各自的优缺点及适用范围。因此,在选择油砂沥青处理技术时要综合考虑技术本身的特点、适用范围、油砂性质及具体工艺要求等诸多因素,必要时要多种处理技术联合操作以实现综合效益的最大化。     

油砂沥青质分离纯化及其热裂解研究

为更好地开采并利用油砂,以新疆某油田油砂沥青质为研究对象,在分离纯化后进行热裂解实验研究,探寻油砂沥青质的转化规律。实验结果表明,超声震荡可以快速将沥青质包裹组分释放出来,缩短沥青质的分离纯化时间;沥青质中3种重要物质生烃、生气、生焦含量变化与温度和时间的关系非常密切;沥青质裂解具有明显的一级反应动力学特征,随着温度的升高,时间逐渐缩短,而其表观速率常数总体呈增加的趋势。     

改质沥青生产工艺的比较与应用

介绍了改质沥青的生产原理及我国目前改质沥青的生产现状,分析了各种改质沥青生产工艺的优缺点。改质沥青有多种生产方法,国内大部分厂家目前仍采用釜式连续加热聚合法,日本及欧美等国家则采用比较先进的热沥青循环聚合法和真空闪蒸法。通过对比,指出了焦油连续加热聚合法和真空闪蒸法是适合我国国情的发展趋势较好的两种工艺。     

釜式热缩聚工艺生产改质沥青存在的问题及对策

通过对釜式热缩聚工艺生产改质沥青过程中存在的反应釜管道易堵塞、反应釜使用周期短和反应釜倒釜操作生产中温沥青等问题进行分析,提出了由三釜串联改为四釜串联、增加排焦流程、改造闪蒸油集气管结构和改善倒釜操作流程等措施。通过以上措施的实施,使改质沥青反应釜使用周期得以延长,改质沥青收率得以提高。     

Understanding bitumen partial upgrading through process modelling and simulation

Partial upgrading is an emerging direction in the processing of Canadian oil sands bitumen in response to the economic and environmental challenges in the oil sands industry. Partial upgrading aims to improve bitumen quality only to the level at which pipeline specifications are met without use of diluent. Given that partial upgrading technologies have not yet reached commercial deployment, there is a lack of technical data to assess the expected benefits in terms of energy input and greenhouse gas emissions reduction. In this study, we present an assessment of a partial upgrading scheme using detailed process simulation. We developed a conceptual process scheme considering visbreaking, solvent deasphalting, and naphtha hydrotreating as the core partial upgrading processes. Reactor models were assembled using experimental data from CanmetENERGY's pilot plant facilities and from the literature and integrated into a plant‐wide simulation model. Simulations allowed the examination of trends in partial upgrader product yields and quality and enabled a comparison with traditional bitumen upgrading.     

Potential for hydrogen generation from in situ combustion of Athabasca bitumen

The volume of heavy oil and bitumen in Alberta, Canada is estimated to be about 1.7 trillion barrels. The majority of the produced heavy oil and bitumen in Alberta is converted in surface upgraders to synthetic crude oil, a crude oil with API gravity typically between 31 and 33° API, which in turn can be converted to fuel, lubricant, and petrochemical products in standard refineries. To upgrade bitumen requires hydrogen. In current practice, much of this hydrogen is generated from catalytic steam reforming of methane together with the water-gas shift reaction. This means that heavy oil and bitumen upgrading, as is currently done, requires large amounts of natural gas to generate hydrogen. The potential for in situ generation of hydrogen by gasification of bitumen reservoirs offers an attractive alternative which can also have both economic and environmental benefits. For example, hydrogen generated from bitumen gasification can also be used for in situ upgrading as well as feedstock for ammonia and other chemicals. The water-gas shift reaction also generates carbon dioxide which could be potentially sequestered in an in situ gasification process so that emissions to the atmosphere are reduced. This technology provides a potential clean method to produce fuel and feedstock material from bitumen, a relatively “dirty” fuel and feedstock oil, in addition to more energy efficient ways of extracting in situ heavy oils. However, to design in situ bitumen gasification processes requires a reaction model that provides a reasonable representation of the gasification reactions. Here, a new kinetic model is developed to examine the potential for hydrogen generation from Athabasca bitumen. The kinetic model consists of thermal cracking, oxidation/combustion, hydrogen generation and hydrogen consumption reactions. A comparison of the simulation results and experimental data from the published literature reveal that the new model can predict hydrogen generation from gasification of methane, Athabasca bitumen, and coke.     

A comparison of fluidized bed pyrolysis of oil sand from Utah,USA, and Alberta,Canada

Characterization and thermal pyrolysis of oil sand was conducted. The experiment was performed on Circle Cliffs, Utah, U.S.A. and the results were compared with the data from Alberta, Canada. The reaction character identified by TGA was dual mode of vaporization of light hydrocarbon and thermal cracking of high molecular hydrocarbon. The pyrolysis experiment was performed in a 2 kg/h capacity fluidized bed externally heated by electricity. The process variables investigated were a temperature range of 723-923 K, fluidization gas velocity of 1.5-2 times of the minimum fluidization velocity, solid retention time of 15-30 minutes, and average particle size of 435 microns. The results of TGA and elemental analysis of bitumen provided necessary information regarding maximum liquid yield from the pyrolysis prior to pyrolysis experiment. The oil yield was maximum at 823 K. The yield of liquid was not exceeding the weight percent of maltenes in original bitumen. The optimum reaction condition should be fast vaporization of light hydrocarbon and minimizing thermal cracking of high molecular hydrocarbon. To maximize the liquid yield, fast heating and vaporization of oil sand bitumen and then the rapid removal of the vaporized product from the heating zone is recommended, i.e., operation in a fluidized bed reactor.     

Gas evolution from the aquathermolysis of heavy oils

Aquathermolysis experiments were performed on core samples taken from three large bitumen and heavy oil deposits found in Alberta, to investigate gas evolution over the temperature range 360 to 420°C. Experiments conducted on Athabasca included runs with an initially pre-oxidized oil sample and runs with a change in core mineralogy. Pre-oxidizing the oil was found to substantially increase the amount of carbon monoxide and molecular hydrogen generated. Core mineralogy played an important role in the generation of carbon dioxide, and the amount of hydrogen sulphide produced was dependent on oil composition, mineralogy and time. Although substantial amounts of gaseous products are produced by simple thermolysis reactions (i.e., without water present), the main thermal recovery methods, steam injection and in-situ combustion, bring the oil phase and its host rock into direct contact with water. As water has been shown to take part in thermal cracking reactions, these experiments provide usful data for the estimation of produced gas composition during thermal recovery projects.     

Microwave applications to oil sands and petroleum: A review

This review provides a general overview of microwave applications in oil sands bitumen or shale oil production in petroleum upgrading. The vast oil reserves in the oil sands of Alberta will become a major source of petroleum products in the near future and a number of alternative technologies have been explored for the production and upgrading of oil sands and heavy oil. This study is based primarily on the unique selective heating capacity associated with exposure of materials to microwaves. Of particular interest are applications of microwaves for bitumen extraction, upgrading heavy oils, removing heteroatoms, and the underground heating of oil sands to reduce bitumen viscosity and allow it to be pumped to the surface. The fundamentally different method of transferring energy from the source to the sample is the main advantage of utilizing microwave energy. By directly delivering energy to microwave-absorbing materials, conventional issues such as long heating periods and energy loses can be minimized. Microwave energy was shown to be effective in some applications; however, it is not used commercially at the present time.     

裂解原料的优化

通过分析扬子石化裂解原料结构和裂解性能,优化裂解原料配置,实施原油分贮分炼,提高自产石脑油品质和轻质裂解原料比例,同时利用石脑油吸附分离技术,进一步改善石脑油品质,提高乙烯收率。     

沥青砂油页岩的开发技术与应用

沥青砂和油页岩属于非常规能源,储量均大于常规石油储量。当今世界越来越面临能源资源匾乏的严峻挑战,开发沥青砂和油页岩越来越引起人们的重视。本文在调研了国内外沥青砂和油页岩现状的基础上,研究了沥青砂油页岩开发的主要技术原理,分析了各种异地开采和就地开采技术应用现状及其发展趋势。研究表明,我国大多数沥青砂油页岩资源埋藏较浅,适合采用异地开采技术,可移动式矿区开采技术将是异地开采技术的发展趋势,就地开采技术是未来沥青砂油页岩开采技术的重点。     

Effect of Operating Temperature on Water‐Based Oil Sands Processing

Operating temperature is one of the most important controlling parameters in oil sands processing. Considering the massive energy consumption and green house gas emission, lowering the processing temperature is highly desirable. To achieve such an ambitious goal requires a comprehensive understanding on the role of temperature in oil sands processing. This paper provides an overview of major findings from existing studies related to oil sands processing temperature. The relation between temperature and bitumen recovery is discussed. The effect of temperature on the physiochemical properties of oil sand components, such as bitumen viscosity, bitumen surface tension and surface potentials of bitumen and solids, is analyzed. The interactions between bitumen and solids and between bitumen and gas bubbles as a function of temperature are recounted. Also discussed is the role of chemical additives in oil sand processing. It has been found that temperature affects nearly all properties of oil sands among which bitumen viscosity and bitumen‐solids adhesion impose a prominent impact on bitumen recovery. The use of selected chemical additives can reduce bitumen viscosity and/or the bitumen‐solids adhesion, and thus provide a possible way to process oil sands at a low temperature while maintaining a high bitumen recovery.     

油砂沥青分离技术研究进展

油砂作为一种储量丰富的非常规石油资源,越来越受到世界各国的广泛关注。对于油砂的加工利用,其前提就是油砂沥青的分离,因此对其技术的研究十分必要。本文首先介绍了油砂的组成及分类,然后着重对几种主要油砂分离技术（热水洗法、有机溶剂萃取法、超临界流体萃取法、超声波辅助萃取法、离子液体萃取法和热解干馏法）的优缺点进行了汇总,并详细分析了它们各自的分离流程。其中,热水洗法、有机溶剂萃取法和热解干馏法是目前研究相对成熟的3种方法,而其他方法虽然分离效果相对高,但是对工艺条件和设备的要求较高,导致较高的投资和运行成本,因此还需要对这些油砂沥青分离工艺进行更加深入的研究,以满足工业化应用的要求。最后,对油砂沥青分离技术的发展前景进行了展望。     

Hydrotreating the bitumen-derived hydrocarbon liquid produced in a fluidized-bed pyrolysis reactor

The pyrolysis of bitumen-impregnated sandstone produces three primary product streams: C₁---C₄ hydrocarbon gases, a C₅⁺ total liquid product, and a carbonaceous residue on the spent sand. The bitumen-derived hydrocarbon liquid was significantly upgraded relative to the native bitumen: it had a higher API gravity, lower Conradson carbon residue, asphaltene content, pour point and viscosity, and a reduced distillation endpoint relative to the native bitumen. The elemental composition was little different from that of the native bitumen except for the hydrogen content, which was lower. Thus, integration of the bitumen-derived liquid into a refinery feedstock slate would require that it be hydrotreated to reduce the nitrogen and sulphur heteratom concentrations and to raise the atomic hydrogen-to-carbon ratio. The bitumen-derived liquid produced in a fluidized-bed reactor (diameter 10.2 cm) from the Whiterocks tar sand deposit has been hydrotreated in a fixed-bed reactor to determine the extent of upgrading as a function of process operating variables. The process variables investigated included total reactor pressure (11.0–17.2 MPa (1600–2500 psig)); reactor temperature (617–680 K; (650–765 °F)) and liquid hourly space velocity (0.18-0.77 h⁻¹). The hydrogen/oil ratio was fixed in all experiments at 890 m³ m⁻³ (5000 scf H₂/bbl). A sulphided Ni-Mo on alumina hydrodenitrogenation catalyst was used in these studies. The extent of denitrogenation and desulphurization of the bitumen-derived liquid was used to monitor catalyst activity as a function of process operating variables and to estimate the extent of catalyst deactivation as a function of time on-stream. The apparent kinetics for the nitrogen and sulphur removal reactions were determined. Product distribution and yield data were also obtained.