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.     

In situ upgrading of bitumen and heavy oils via nanocatalysis

Thermal in situ bitumen production has introduced a different engineering approach compared to conventional oil exploitation. Steam injection for example, allows the development of a relatively confined liquid and gas chamber surrounding and along the length of the production wells. This heated place can be converted into a reactor for upgrading processes founding expectations of extensive reservoir upgrading of unconventional oils reducing the total energy currently required to both exploit the reservoir and surface upgrade the produced bitumen. These could also selectively transform contaminants into harmless products remaining in the reservoir. This article highlights the nanocatalytic in situ upgrading paths that may result in economical and environmentally efficient oil sands exploitation. © 2012 Canadian Society for Chemical Engineering     

A benchmark assessment of residues: comparison of Athabasca bitumen with conventional and heavy crudes

Compared to benchmark crude oils, bitumen does not respond well to conventional upgrading processes. In order to improve our understanding of this problem, we compare the chemical and physical properties of fractions from super critical fluid extraction of bitumen pitch with the corresponding fractions of residua from Venezuelan heavy oil, a Saudi Arabian light crude and a Chinese Daqing conventional crude.Relatively minor differences in chemical structure were observed between the corresponding residua fractions from Athabasca bitumen, Venezuelan heavy oil and Saudi Arabian light crude. Only the Chinese Daqing showed significant variance; this sample is much more aliphatic and has greater geometrical dimensions than the corresponding samples from the other residua.The end-cut from Athabasca bitumen pitch contained ultra-fine solids together with much higher levels of nickel, vanadium and nitrogen than the conventional crude end-cuts. These components are among the most intractable in upgrading and could be responsible for the problems encountered in bitumen upgrading, especially by catalytic processes.     

MODELLING AND SCALEUP OF DISPERSED PHASE LIQUID-LIQUID REACTORS

The problem of modelling dispersed phase liquid-liquid reactors is discussed from a global view. The two major areas of microscopic and macroscopic problems are addressed. The microscopic problem is concerned with the determination of the local rate of transfer of reactants and/or products between the two phases. Attention is focussed on approaches to obtain kinetic data; and results on recent important chemical systems such as nitrations, metal chelation reactions, and phase transfer catalytic reactions are discussed. The liquid jet recycle reactor is pointed out as a useful tool for obtaining laboratory data. Recent works employing the classical film and penetration theories to obtain flux expressions for complex reactions are described. The macroscopic problem deals with the reactor design question. Various models proposed to account for macromixing and/or micromixing effects are categorized into noninteraction and coalescence- dispersion or interaction models. The former approach includes the axial dispersion and CSTR models and can predict conversions at the extremes of micromixing. (See the previous paper in this series by Nauman for complete discussion of these models.) The basic formulations of these models and results are discussed in this paper, The latter approach discussed here includes population balance equations and Monte Carlo simulation methods. The ability of Monte Carlo simulation techniques to predict the effect of intermediate degrees of micromixing on conversion is demonstrated. The potential of the Monte Carlo simulation technique to account for local variations in dispersion properties, model droplet rate processes, and model complex reaction systems is also shown. (See the paper by Patterson in this series for more discussion of the application of Monte Carlo stimulation to complex reactions.)     

Inference of reaction kinetics for supercritical water heavy oil upgrading with a two-phase stirred reactor model

We present the development and application of a two-phase stirred reactor model for heavy oil upgrading in the presence of supercritical water (SCW), with coupled phase-specific thermolysis reaction kinetics and multicomponent hydrocarbon–water phase equilibrium. We demonstrate the inference of oil and water phase kinetics parameters for a compact lumped reaction kinetics scheme through the application of this model to two different sets of batch reactor experiments reported in the literature. We infer that, although SCW can suppress the formation of newer polynuclear aromatics (PNA) from distillate range species, it is broadly ineffective in deterring the combination of pre-existing PNA fragments in the oil feed. Quantification of the conversion to distillate liquids before the onset of coke formation helps arrive at a clear conclusion on whether the use of SCW in the batch reactor leads to better product outcomes for different oil feeds and operating conditions.     

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.     

Kinetic studies on extra heavy crude oil upgrading using nanocatalysts by applying CFD techniques

Regarding the growth of global energy consumption and the paucity of light crude oil,extracting and using heavy and extra heavy crude oil has received much more attention,but the application of this kind ofoil is complicated due to its very high molecular weight.High viscosity and low flowability complicate the transportation of heavy and extra heavy crude oil.Accordingly,it is essential to reduce the viscosity of heavy and extra heavy crude oil through in-situ operations or immediate actions after extraction to reduce costs.Numerical simulations are influential methods,because they reduce calculation time and costs.In this study,the cracking of extra heavy crude oil using computational fluid dynamics is simulated,and a unique kinetic model is proposed based on experimental procedures to predict the behavior of extra heavy crude oil cracking reaction.Moreover,the hydrodynamics and heat transfer of the system and influence of nanocatalysts and temperature on the upgrading of crude oil are studied.The geometry of a reactor is produced using commercial software,and some experiments are performed to examine the validity and accuracy of the numerical results.The findings reveal that there is a good agreement between the numerical and experimental results.Furthermore,to investigate the main factors affecting the process,sensitivity analysis is adopted.Results show that type of catalyst and concentration of catalyst are the parameters that influence the viscosity reduction of extra heavy crude oil the most.The findings further revealed that when using a 25 nm SiO2 nanocatalyst,a maximum viscosity reduction of 98.67％ is observed at 623 K.Also,a catalyst concentration of 2.28wt％ is best for upgrading extra heavy crude oil.The results obtained through sensitivity analysis,simulation model,and experiments represent effectual information for the design and development of high performance upgrading processes for energy applications.     

Estimation of parameters in monte carlo modelling

This paper presents a general method for estimating model parameters from experimental data when the model relating the parameters and input variables to the output responses is a Monte Carlo simulation. From a statistical point of view a Bayesian approach is used in which the distribution of the parameters is handled in discretized form as elements of an array in computer storage. The stochastic nature of the Monte Carlo model allows only an estimate of the distribution to be calculated from which the true distribution must then be estimated. For this purpose an exponentiated polynomial function has been found to be useful. The method provides point estimates as well as joint probability regions. Marginal distributions and distributions of functions of the parameters can also be handled. The motivation for exploring this alternative parameter estimation technique comes from the recognition that for some systems, particularly when the underlying process is stochastic in nature, Monte Carlo simulation often is the most suitable way of modelling. As such, the Monte Carlo approach increases the range of problems which can be handled by mathematical modelling. The technique is applied to the modelling of binary copolymerization. Two models, the Mayo-Lewis and the Penultimate Group Effects models, are considered and a method for discriminating between these models in the light of sequence distribution data is proposed.     

稠油和沥青VAPEX技术影响因素的研究进展

由于常规稀油石油资源逐渐枯竭,作为非常规石油资源的稠油和沥青的开采日益重要,稠油和沥青的蒸气萃取（VAPEX）技术已经成为一项非常有前途的开采工艺。本文讨论了影响稠油和沥青VAPEX技术的各种因素,包括稠油黏度,溶剂在稠油中的扩散系数,溶剂的分散度,溶剂注入时的温度、压力,溶剂的注入速度,地质因素等。列出了这些因素之间重要的数学关系式以及这些因素与稠油和沥青质产量之间的数学模型,对VAPEX技术发展前景和未来研究方向进行了总体展望：由于模型与实际油藏的差异造成结果偏差因而需修正实验模型;VAPEX和SAGD的混合使用;不同温度、压力下溶剂的扩散系数;混合溶剂的使用。     

The effect of bitumen molecular fractions on diffusivity and rheology of bitumen under high-temperature conditions: Molecular dynamics (MD) simulation study

Heavy oil and bitumen play an incredible role in Canada's energy resources. The main processes that have already been applied to produce heavy oil and bitumen are in-situ thermal methods. The primary mechanism of production in these reservoirs is a reduction in heavy oil and bitumen viscosities via heat transfer. Having deep knowledge about the rheological behaviour of heavy oil and bitumen is crucial to designing a more accurate and efficient in-situ thermal recovery method. In this work, molecular dynamics (MD) simulation was used to model the rheological behaviour of bitumen under different temperatures. According to MD outputs, the highest diffusion coefficient between bitumen fractions belongs to saturate fractions. On the other hand, the lowest diffusion coefficient belongs to asphaltene fractions. The size of asphaltene, its polarity, and the polarity of a resin fraction affect the diffusion coefficient of asphaltene in a bitumen sample and its rheological behaviour. The MD simulation aims to provide molecular insights and essential information about the rheological trend of bitumen under different thermodynamic conditions. The results of the current work provide essential information about the effect of bitumen fractions on its rheological behaviour.     

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。     

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.     

Heavy oil upgrading in the presence of high density water: Basic study

Heavy oil (Canada oil sand bitumen) upgrading in high density water (100 and 200 kg/m³) at 723 K was performed by a batch reactor. Yields of asphaltene, maltene, and coke were evaluated. With increasing water density, the rate of coke formation was promoted. To get some hints of coke formation mechanism, the formed coke was observed by scanning electron microscope (SEM). The most part of the coke formed st neat pyrolysis (pyrolysis in the absence of high density water) was coalescent structure of some small coke particles, while that at pyrolysis in the presence of water (200 kg/m³ of water density) was porous structure that indicated occurrence of phase inversion of coke precursors. Based on the results, the reaction mechanism of the heavy oil upgrading was considered: lighter oil was extracted in high density water and the concentration of light hydrocarbon decreased in a heavier oil phase, while the concentration of heavier oil in the oil phase increased. Thus, the lighter oil decomposed further in high density water phase and the heavier oil in the oil phase combined together to form coke due to its higher concentration.     

Radiation absorption and rate constants for carbaryl photocatalytic degradation in a solar collector

We discuss an analytical model for the evaluation of radiation absorption in a tubular photocatalytic reactor. The model has no adjustable parameters and takes into account scattering in all directions. We compare the results of this model with those of Monte Carlo (MC) simulations and of a Lambert–Beer (LB) approximation, for a reactor illuminated by a parabolic solar concentrator. A good correspondence is found with the MC simulations. In particular, the model displays the correct saturation behavior of absorption for large catalyst particle concentrations, which is not obtained with the LB approximation. We have carried out experiments for the degradation of carbaryl in a solar parabolic collector (PC). The model is used to calculate the rate constant for this degradation from the experimental data. The theoretical model predictions reproduce well, the trends observed in the experiments.     

下行床内提高颗粒浓度及改善颗粒分布研究进展

重质油高效转化和优化利用是国民经济发展的重大需求,具有十分重要的现实意义和战略意义。提升管催化裂化一直是重油轻质化的重要手段,但提升管的不均匀环核结构及气固返混特性降低了重油转化率和产品选择性。相对于提升管,下行床具有近平推流流型及气固短停留时间的优点,处理重油具有潜在优势。但下行床内颗粒浓度过低且气固初始接触较差限制其推广及应用。本文综述了提高下行床颗粒浓度及改善颗粒初始分布的相关文章,指出了深入研究下行床的颗粒增浓机制及气固初始混合可以丰富下行床的基础研究并推动其工业应用。     

Through a glass,darkly: Kinetics and reactors for complex mixtures syncrude innovation award lecture

The concepts of chemical reaction engineering are powerful, because the most basic design equations are applicable to a wide range of physical phenomena. For example, the applicability of the ideal continuous-flow stirred tank reactor goes far beyond chemical reactors to include biological, medical and environmental processes. The difficulty in analyzing these processes is not in formulating an appropriate reactor equation, but in modeling the chemical kinetics. The challenge is to define kinetic rate equations that allow for the mixtures of reactants and mixtures of catalysts, especially given incomplete information. Examples drawn from biology and medicine illustrate reaction kinetics that are complex due to the nature of the catalyst. In contrast, processes for upgrading of bitumen to more valuable products exhibit ill-defined reaction chemistry and mixtures of thousands of reactants and products. The need to define kinetics for such mixtures has given rise to several distinct approaches, including empirical rate equations, simplification to model reactions, lumped kinetics and Monte Carlo simulation. A summary of these methods shows that the key element for successful kinetic modeling is creative definition of a model, followed by vigorous testing of the model to determine its ability to predict performance.     

Monte Carlo Simulation of Coalescence Processes in Oil Sands Slurries

Conditioning of an oil sand slurry is a critical step in the extraction of bitumen from oil sand ore. To model the conditioning process, a constant‐number Monte Carlo algorithm is used to simulate the mean‐field kinetics of coalescing bitumen drops and air bubbles. The coalescence rate of drops and bubbles is described by the model of Coulaloglou and Tavlarides (1977). Simulations yield results that are consistent with aerated bitumen drop sizes and conditioning times reported in the literature. The effects of turbulent energy, bitumen concentration, and initial bitumen drop size on the evolution of drop size distributions are investigated.     

Effect of supercritical water on upgrading reaction of oil sand bitumen

The advantages of supercritical water (SCW) as a reaction medium for upgrading oil sand bitumen were investigated through a comprehensive analysis of the output product, which includes gaseous products, middle distillate, distillation residue, and coke. Canadian oil sand bitumen mined by the steam assisted gravity drainage method was treated in an autoclave at 420-450 °C and 20-30 MPa for up to 120 min with three kinds of reaction media: SCW, high-pressure nitrogen, and supercritical toluene. The yields of gaseous products indicated that a very small amount of water was involved in the upgrading reaction. The analytical results of the middle distillate fractions were almost the same using water and nitrogen at 450 °C. The distillation residues produced in SCW had lower molecular weight distributions, lower H/C atomic ratios, higher aromaticities, and consequently more condensed structures compared to those produced in nitrogen. The coke produced using SCW also had lower H/C values and higher aromaticities. Judging from all the analytical results, the upgrading of bitumen by SCW reaction was primarily considered to be physical in nature. As a result, it is possible to highly disperse the heavy fractions by SCW. This dispersion effect of SCW led to intramolecular dehydrogenation of the heavier component and prevention of recombination reactions, and consequently gave the highest conversion.     

Monte Carlo simulation of sequential structure control of AN-MA-IA aqueous copolymerization by different operation modes

The regulation of polyacrylonitrile (PAN) copolymer composition and sequence structure is the precondition for producing high-quality carbon fiber high quality. In this work, the sequential structure control of acrylonitrile (AN), methyl acrylate (MA) and itaconic acid (IA) aqueous copolymerization was investigated by Monte Carlo (MC) simulation. The parameters used in Monte Carlo were optimized via machine learning (ML) and genetic algorithms (GA) using the experimental data from batch copolymerization. The results reveal that it is difficult to control the aqueous copolymerization to obtain PAN copolymer with uniform sequence structure by batch polymerization with one-time feeding. By contrary, it is found that the PAN copolymer with uniform composition and sequence structure can be obtained by adjusting IA feeding quantity in each reactor of a train of five CSTRs. Hopefully, the results obtained in this work can provide valuable information for the understanding and optimization of AN copolymerization process to obtain high-quality PAN copolymer precursor.     

Kinetic study of crude oil-to-chemicals via steam-enhanced catalytic cracking in a fixed-bed reactor

This study presents new experimental results on the direct conversion of crude oil to chemicals via steam-enhanced catalytic cracking. We have organized the experimental results with a kinetics model using crude oil and steam co-feed in a fixed-bed flow reactor at reaction temperatures of 625, 650, and 675°C over the Ce-Fe/ZSM-5 catalyst. The model let us find optimum conditions for crude oil conversion, and the order of the steam cracking reaction was 2.0 for heavy oil fractions and 1.0 for light oil fractions. The estimated activation energies for the steam cracking reactions ranged between 20 and 200 kJ/mol. Interestingly, the results from kinetic modelling helped in identifying a maximum yield of light olefins at an optimized residence time in the reactor at each temperature level. An equal propylene and ethylene yield was observed between 650 and 670°C, indicating a transition from dominating catalytic cracking at a lower temperature to a dominating thermal cracking at a higher temperature. The results illustrate that steam-enhanced catalytic cracking can be utilized to effectively convert crude oil into basic chemicals (52.1% C2-C4 light olefins and naphtha) at a moderate severity (650°C) as compared to the conventional high-temperature steam cracking process.