PSCDSHREP1001 - Hydrocarbon and Renewable Energy Production

Items of discussion in the course include:

This five-day course offers a unified framework from classical equilibrium and irreversible thermodynamics, and statistical thermodynamics, and molecular simulations to investigate bulk phases, interfaces, and thin liquid films. Rheology of bulk and interfaces is an integral part of the intensive course. The focus of the topics will be on molecule structure in bulk phase, adsorption at the fluid-solid and fluid-fluid interfaces, interfacial energy density of fluid-fluid and fluid-solid interfaces, wettability, viscosification of CO2, hydraulic fracturing by water and by CO2 in tight hydrocarbon and geothermal formations, and interfacial rheology. Many topics are covered in relation to efficient hydrocarbon energy and renewable energy production from the subsurface and environmental stewardship. Molecular structure in fluid phases and at the interface and molecular engineering of functional molecules are covered to emphasize the advances that can lead to efficient processes. The context of presentations is shale light oil and gas reservoirs, low salinity water injection, improved oil recovery from fluid-fluid interface elasticity increase, flow assurance in relation to asphaltenes, waxes, and hydrates and use of low concentration of functional molecules, CO2 fracturing in shale and in in geothermal formations, and CO2 viscosification (in relation to mobility control in CO2 injection and sequestration and CO2 fracturing). Various structures in bulk phases from micelles and emulsions in hydrocarbon production are covered. We will also cover efficient and robust phase-split computations in relation to CO2 and fluid hydrocarbons and asphaltene rich-phase, and CO2 and water, CO2-brine, hydrogen-water, and hydrogen-brine. Past climate changes are covered to the level that computations can be performed. The course will go beyond nano-particles; at the atomic scale the vast opportunities that functional molecules can offer for process improvement, efficiency, and safety will be explored. Efficient molecular dissolution of asphaltenes, and colloidal stabilization will be discussed. A new improved oil recovery that may only require a concentration of 100 ppm functional molecules in brines of high salinity will be presented in detail. Various advantage of CO2 fracturing of tight oil and gas formations and hot dry rock in geothermal formations will be discussed in detail. The need for combining molecular simulations and molecular thermodynamics will be demonstrated in prediction of molecular structure and adsorption at the fluid-solid interfaces.  The concepts will be presented through cartoons to facilitate understanding of a broad range of topics. All presentations and discussions will be based on materials (book, papers, and prepared write-ups) that will be proved to participants. 

A topic of major emphasis will be use of CO2 : in CO2 sequestration, CO2-IOR,and CO2 fracturing based on fundamentals. Direct CO2 viscosification will facilitate the widespread use.

• Unique properties of CO2 in comparison to nitrogen and methane and water in relation to improved oil recovery in fractured and unfractured reservoirs and fracturing of tight formations and geothermal formations. Lab results and field experiences from different parts of the world will be discussed.
• Efficient and safe CO2 sequestration in saline aquifers.
• Multicomponent Fickain diffusion and diffusion coefficient calculation based on irreversible thermodynamics.
• The strong connection between the Lagrangian and phase-field simulation of fracturing
• Mechanisms of low salinity water injection and effect of salinity and salts on wettability, dissolution, and in micellization and microemulsions
• Why a low lab recovery may give a high recovery in large scale and vice versa.
• Shale-gas and shale-light oil reservoirs and unique features of shale rocks
• Strength of cubic-plus-association EOS for a variety of complex problems in aqueous mixtures and asphaltene precipitation and variety of reservoir fluids. Basic concepts in electrolytes. E-CPA EOS.
• Predictive capability of EOS and reservoir fluid characterization
• CO2 mixing with reservoir fluids; Modeling of diffusion flux in reservoir simulators based on gradient of chemical potentials.
• Asphaltene and resin molecular structure and interaction with water
• Formation of nano-particles of asphaltenes and hydrates, and advantage of surface property changes to bulk phase property changes
• Why adsorption measurements at high pressure (say by gravimetric methods) do not provide relevant data and should be combined with molecular simulations to interpret the instrument measurements. Why shale swells from the contact with hydrocarbons and CO2. 
• Why flow in shale nano-pores is by diffusions. Why flow in nano-pores is one to three orders of magnitude higher than the calculations based on classical expressions.  
• Effect of size of nano-particles on melting and on saturation pressure 
• Efficient two- and three- and four-phase split computations
• The link between irreversible thermodynamics and complex diffusion processes and past climate change modeling
• Asphaltene removal from pipes and from rocks by efficient molecular dissolution
• Species distribution in hydrocarbon reservoirs from irreversible thermodynamics 
• Thermal diffusion in CO2-water and CO2-brine in CO2 sequestration in aquifers
• Hydrate particle stabilization and advancing hydrate flow assurance by small amounts of functionalized molecules.
• Basic level understanding of microemulsion and micellization and application to a variety of problems in hydrocarbon energy production.
• Interfacial Rheology
• Interfacial rheology measurement interpretation in relation to improved oil recovery
• New IOR by increase in interfacial elasticity.
• Thermodynamics of fracturing in rocks. Solid-fluid interfacial energy density. Phase field method
   

Daily sessions will be from 9:0 a.m. to 4:30 p.m. with a lunch break from 12:30 p.m. to 1:30 p.m. A lunch will be provided. Part of the  last session in the afternoon, will be devoted to discussions.

Day 1

• Brief class introduction. Overview of molecular structures in petroleum fluids and fluid-fluid and fluid-solid systems and use of basic knowledge, modeling, and modern techniques from thermodynamics and rheology in efficient oil and gas and geothermal energy production and stewardship of the environment.
• Use of thermodynamic principles in the study of shale gas, shale-light oil, flow assurance, and improved oil recovery
• Use of functional molecules and drastic change of properties
• Property changes with size in the nm range
• Solubility increases in CO2 at constant temperature and pressure with increase in size of one group of hydrocarbons!

• Brief review of bulk phase equilibrium thermodynamics
• Unique features of the thermodynamics function grand potential in comparison to other thermodynamic functions.
• Removal of fluids from a constant -volume container at constant temperature and observation of pressure increase
• Isobaric heating of a liquid and freezing

• General theory of bulk-phase equilibrium thermodynamics with gravity and interfacial effects
• How we increase or decrease normal boiling by the size of the confinement and type of fluids?
• Why condensation and vaporization can be drastically different in single components and in multicomponents? Sometimes the opposite of each other!

• Phase behavior and volumetric description of fluids and fluid mixtures and petroleum fluids from cubic equations of state (EOS) including waxes and asphaltenes
• Nature of delay and kinetics in various processes including vaporization, condensation, crystallization, and melting
• Why kinetics of vaporization is so different from condensation: the same is true in crystallization and melting
• Why the PR-EOS works so well for reservoir fluids

• Concept of molecular association  
• Phase behavior of water and water-CO2 mixtures by the cubic-plus-association (CPA) EOS  
• Phase behavior in asphaltene precipitation by CPA-EOS

• Phase behavior of bitumen with CO2 and normal alkanes by CPA-EOS and PR-EOS
• Characterization of reservoir fluids for modeling of various processes, including equilibria of vapor-liquid, vapor-liquid-liquid, wax precipitation, and asphaltene precipitation
• Discussions of various topics of the day

Day 2

• Thermodynamic stability, and criticality concepts and criteria, and applications in problems of hydrocarbon reservoirs and production; Gibbs free energy surface analysis; How rugged is Gibbs free energy surface? Tangent plane distance analysis
• Two- and three- and four-phase phase split computations; Stability testing; How to perform phase-split computations with any number of phases with large number of components
• Brief presentation on phase behavior calculations in UNV space and major difference with the PTVN space

• General theory of irreversible thermodynamics; Fickian, thermal, and pressure diffusion flux expressions; How can oil float on top of lighter gas forever! Example is Yufutsu field in Japan. This is possible through thermal diffusion.
• Species distribution in hydrocarbon reservoirs; Past climate changes from irreversible thermodynamics

• Interfacial thermodynamics; Gibbs adsorption equation; New phase formation and driving force; Induction time; Line tension; Effect of size on contact angle; Bubble nucleation; Induction time; Thermodynamics of adsorption in fluid solid interfaces

• Defining parameters of deformable media; thermodynamics of deformable solids
• Discussion of the topics of the day

Day 3

• Solution-gas drive in permeable media
• Thermodynamics of thin liquid films; thin film description
• Effect of size on melting point due to thin films

• Introduction to micellization and emulsions
• Thermodynamics of micellization and microemulsion; Effect of different salts; Why different salt molecules are so different in their effectiveness?
• Emulsion flow in porous media. Higher flow rates give lower pressure drops. This makes use of Darcy's law inappropriate in some coreflloding! Detrimental effect of water-in-oil emulsion on flow.
• Introduction to molecular simulation

• Molecular and atomistic simulations: basic concepts of statistical thermodynamics. Thermodynamic and molecular models. Molecular dynamics simulations. Monte Carlo simulations

• Molecular and atomistic simulations (continued): Various algorithms and ensembles. Potential functions. Basic concepts in conducting molecular and atomistic simulations
• Linear viscoelasticity

• Griffith’s idea of deformable media failure from tension; critical energy release rate
• Lagrangian and the Euler-Lagrange equation
• Phase field formulation of fracturing and fracture propagation
• Fluid-solid interfacial energy density. Molecular simulations
• Comparison of hydraulic fracturing by CO2 and by water: breakdown pressure, fracture intensity

• CO2 viscosifcation and effectiveness in displacement of brine and oil by viscosified CO2
• Why some oligomers may be effective in CO2 solubility and viscosification

• Introduction to flow assurance: waxes, hydrates, and asphaltenes
• Discussions

Day 4

• Asphaltene colloidal stabilization in petroleum fluids by functional molecules; Molecular dissolution of asphaltenes in petroleum fluids at very low concentration of functional molecules; Dissolution of deposited asphaltene molecules back into petroleum fluids
• Effect of water and brine on asphaltene precipitation and deposition and mitigation
• Wax mitigation by crystal modifiers and dispersant. Effect of water

• Natural gas hydrates
• Driving force in hydrate formation
• Hydrate anti-agglomeration; Hydrate slurry and hydrate powder by functional molecules at low concentrations

• Low salinity water injection; Mechanisms

• Improved oil recovery by effective functional molecules at 100 ppm concentration through increase in interface elasticity
• Introduction to shale-gas and shale-light oil reservoirs  

• Condensation and vaporization in nano-pores more than 10 nm
• Phase behavior in shale nano-pores more than 10 nm
• Adsorption and desorption in shale and kerogen media. Swelling from hydrocarbons in kerogen media

• Flow and Separation of species in shale nano-pores. Flow in shale media.

• MD simulation of hydrates and hydrate anti-agglomeration; Effect of salt and hydrocarbons on hydrate anti-agglomeration;
• Effect of droplet size on contact angle. MD simulations of contact angle
• Discussions

Day 5

• The class will be introduced to the science of rheology, which concerns the flow and deformation of complex, non-Newtonian liquids. This subject, which links together fluid mechanics and material science, has great application in the recovery of oil from porous media, wax and hydrate flow assurance, drilling operations that employ complex muds, the design of fracturing fluids, and the stability of oil-water emulsions. Introduction to rheology, the stress tensor in flowing liquids and the rate of strain tensor. Definition of rheological material functions (viscosity, normal stress differences, compliance, dynamic moduli). Shear rheometry and constitutive models.

• Linear viscoelasticity

• Application of rotational shear rheometry to fluids in the production of oil
• Extensional rheometry. The extensional viscosity of mobile liquids. The design of extensional rheometers and their application to liquids used in enhanced oil recovery.

• Interfacial rheology. Classification of complex fluid interfaces. Interfacial rheological material functions.

• Application of bulk and interfacial rheology to problems in oil production and manufacturing
• Discussions

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