OPTIMIZATION OF IN-SITU COMBUSTION: MAXIMIZING PRODUCTION AND REDUCING CO2 FOOTPRINT

by

Zhenshuo Liu

A Dissertation Presented to the FACULTY OF THE USC GRADUATE SCHOOL UNIVERSITY OF SOUTHERN CALIFORNIA In Partial Fulfillment of the Requirements for the Degree DOCTOR OF PHILOSOPHY (CHEMICAL ENGINEERING)

August 2011

Copyright 2011

Zhenshuo Liu

UMI Number: 3477948

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Dedication

To Daisy For Everything

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Acknowledgements

First and foremost, I would like to thank my advisors, Dr. Kristian Jessen and Professor Theodore Tsotsis for all the guidance they have provided me over the years. They have been the Sun and the North Star in my research journey. Without them I would have been lost long ago. Moreover, I would like to thank them for giving me the courage to endure all the challenges along the way. They have sacrificed much for me and I will forever be grateful.

I am also thankful for the guidance provided by Professor Fokion Egolfopoulos while serving on my dissertation committee. His challenges of what I have known have led me to greater understanding and new findings. I would also like to thank Dr. Katherine Shing and Professor Iraj Ershaghi who served on my qualifying exam committee. Their input has been an invaluable roadmap. In addition, I would like to give a heartfelt thanks to Professor Ershaghi for assisting me with finding an internship.

I am deeply appreciative of the Energy Corporation of America for the internship opportunity in West Virginia. The field knowledge I acquired there complimented my education at USC perfectly, and has honed my skills in ways that cannot be acquired in the classroom or lab. In particular, I would like to thank Bryce Yeager, Ryan Deadrick, and Kyle Mork for their mentorship.

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For their camaraderie, I thank Arthur Xu, Yu Wang, and Mini Basabdatta, my office- and lab-mates. Working with them has never been dull, and the struggles and triumphs we have had together are an education in themselves.

Equally important, I would like to express my pleasure in working with Karen Woo, Idania Takimoto, Tina Silva, Aimee Barnard, and the rest staff in MFD. Without their help, I would have never successfully navigated the mundane complications of life in academia.

I thank CMG for providing access to their reservoir simulation software suite.

Mom and Dad, I love you and thank you for always encouraging me to go the distance. Ive always been very proud to call you my parents, and I hope this goes some ways to making you proud to call me your son.

And thank you Daisy, my love, for giving me a reason to take this journey.

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Table of Contents Dedication Acknowledgements List of Tables List of Figures Abstract Chapter 1: Introduction 1.1 Importance of heavy oil 1.2 How can we address the need to more EOR 1.3 Description of ISC processes 1.4 The chemistry of ISC processes 1.4.1 Pyrolysis 1.4.2 High temperature oxidation 1.4.3 Low temperature oxidation 1.5 CO2 cycling 1.6 Simulations with CMG STARS Chapter 2: Theory, physical models and numerical simulation 2.1 Equations 2.1.1 General mass conservation equations 2.1.2 General energy conservation equation 2.2 Simplifications and assumptions used in STARS 2.2.1 Porosity calculations 2.2.2 Representation of phase equilibrium 2.2.3 Component and phase densities 2.2.4 Mass advection and calculation of phase velocities 2.2.5 Reactions rates 2.2.6 Wells equations 2.2.7Enthalpy and internal energy 2.2.8 Thermal conductivity 2.2.9 Specific heat of reaction 2.3 Dimensionless Equations 2.3.1 Introduction of characteristic values 2.3.2 Dimensionless mass conservation equations 2.3.3 Dimensionless energy equation Chapter 3: Procedure for Modeling ISC in a 1-D Combustion Tube Scenario 3.1 The Model 3.2 Oil Composition ii iii viii x xv 1 1 2 4 7 8 9 12 13 16 17 17 17 19 21 21 22 23 24 26 27 28 31 31 31 32 33 34 39 39 40

3.3 Relative permeability tables 3.4 Reaction kinetics 3.5 System dimensions 3.6 Initial settings 3.7 Well settings Chapter 4: The Effects of CO2 Recycling in a 1-D Combustion Tube 4.1 Overview of numerical experiments 4.2 Definitions used to report the results of the numerical experiments 4.3 Standard in situ combustion process: adiabatic conditions 4.4 Series 1: CO2 recycling with constant total injection rate in an adiabatic setting 4.5 Series 2: CO2 recycling with increased total injection rate in an adiabatic setting 4.6 CO2 recycling with constant total injection rate under non-adiabatic setting 4.6.1 Non-adiabatic ISC processes at an increased injection rate of 0.512 PVI/min 4.6.2 Operation of non-adiabatic ISC at an increased injection rate of 0.681 PVI/min 4.6.3 Operation of non-adiabatic ISC processes with O2 enriched injection 4.7 CO2 recycling with an increase in the total injection rate in a nonadiabatic setting 4.8 Summary Chapter 5: ISC in a Field Scale Pseudo 2-D Environment 5.1 Introduction 5.2 Results and discussion 5.3 Summary Chapter 6: Parameter Space for Pseudo-2D ISC Operation 6.1 Introduction 6.2 Results and discussion 6.3 Summary Chapter 7: ISC with CO2 Recycling in 3-D Configurations 7.1 Introduction 7.2 Pattern selection 7.2.1 Inverted 9 spot 7.2.2 Line drive pattern 7.3 Results discussion 7.3.1 Inverted 9 spot pattern discussion 7.3.2 Line drive pattern discussion 7.4 Gravity override

42 44 47 48 49 51 52 53 50 57 62 66 70 74 79 83 87 90 90 94 100 102 102 103 119 121 121 123 124 126 128 128 132 137

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7.5 Cost analysis 7.6 Comparison with steam injection 7.7 Summary Chapter 8: Conclusions and future work 8.1 Future work References

142 143 144 147 151 153

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List of Tables Table 3-1. Component Properties: Critical Properties, Molecular Weight and Density Table 3-2. Component Properties: viscosity enthalpy and K values Table 3-3: Relative Permeability: water-oil Table 3-4: Relative Permeability: liquid-gas Table 3-5. Reaction rates and enthalpies Table 3-6. Reaction concentration factors Table 3-7. System properties

41 42 43 44 45 46 48

Table 4-1. Comparison of Ro and net moles CO2 for recycle of CO2 in lieu of air at adiabatic condition 60 Table 4-2. Comparison of Ro and Net moles CO2 for recycle of CO2 in addition 65 to air at adiabatic conditions Table 4-3. Comparison of Ro and net moles of CO2 for recycle of CO2 in lieu to 72 air in at non-adiabatic conditions with an injection rate of 0.512 PVI/min Table 4-4. Comparison of Ro and net moles of CO2 for recycle of CO2 in lieu to 77 air in an adiabatic system with an injection rate of 0.681 PVI/min Table 4-5. Comparison of Ro and net moles of CO2 for recycle of CO2 in lieu of 80 air in at non-adiabatic conditions with initial injection of 80% enriched O2 Table 4-6. Comparison of Ro and net moles of CO2 for recycle of CO2 in addition to air in a non-adiabatic system with an initial injection of air of 41 85 PVI/h Table 5-1. Reservoir characteristics Table 5-2. Ro and CO2D at constant PVI with varying recycle rates. Table 5-3. Ro and CO2D at constant time with varying recycle rates. Table 5-4. CO2D at constant Ro with varying recycle rates. 92 100 100 100 viii

Table 6-1. Rate expression terms Table 6-2. Reference values of the dimensionless groups Table 7-1. Reservoir details for inverted 9-spot system Table 7-2. Reservoir details for line drive system

103 103 126 127

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List of Figures Figure 1-1. Mechanistic characterization of ISC processes Figure 3-1. Water-oil relative permeability Figure 3-2. Gas-liquid relative permeability Figure 3-3. Schematic of the model system 4 43 44 49

Figure 4-1. Cumulative oil produced for standard ISC simulation under adiabatic conditions 54 Figure 4-2. Temperature profiles for a standard ISC process at adiabatic conditions 55

Figure 4-3. Coke concentration profiles for a Standard ISC process at adiabatic conditions 55 Figure 4-4. Oil recovery for a standard ISC process at adiabatic condition Figure 4-5. Net moles of CO2 produced for a standard ISC process at adiabatic conditions 56 57

Figure 4-6. Comparison of Ro for 30% and 50% CO2 recycle in lieu of air with the standard ISC process at adiabatic conditions 58 Figure 4-7. Comparison of Ro for 70% and 90% CO2 recycle in lieu of air with the standard ISC process at adiabatic conditions 58 Figure 4-8. Comparison of net moles of CO2 produced for 30% and 50% CO2 recycle in lieu of air injection with the standard ISC process at adiabatic conditions 59 Figure 4-9. Comparison of net moles of CO2 produced for 70% and 90% CO2 recycle in lieu of air injection with the standard ISC process at adiabatic conditions. 59 Figure 4-10. Comparison of Ro for 30% and 50% CO2 recycle in addition to air injection with the standard ISC at adiabatic conditions 63 Figure 4-11. Comparison of Ro for 70% and 90% CO2 recycle in addition to air injection with the standard ISC at adiabatic conditions 63

Figure 4-12. Comparison of net moles of CO2 produced for 30% and 50% CO2 recycle in addition to air injection with the standard ISC at adiabatic conditions 64 Figure 4-13. Comparison of net moles of CO2 produced for 70% and 90% CO2 recycle in addition to air injection with the standard ISC at adiabatic conditions 64 Figure 4-14a. Comparison of Ro between non-adiabatic and adiabatic standard ISC for an injection rate of air of 0.000933 m3/min (0.157 PVI/min) 67 Figure 4-14b. Comparison of temperature profiles between non-adiabatic and adiabatic standard ISC at injection rate of air of 0.000933 m3/min (0.157 PVI/min) 68 Figure 4-15. Comparison of oil recovery at various air injection rates in a nonadiabatic ISC process 69 Figure 4-16. Comparison of Ro for 30% and 50% CO2 recycle in lieu of air injection with the standard ISC at diabatic conditions for an injection rate of 0.880 PV/hr 70 Figure 4-17. Comparison of Ro for 70% and 90% CO2 recycle in lieu of air injection with the standard ISC at non-adiabatic conditions for an injection rate of 0.880 PV/hr 71 Figure 4-18. Comparison of net moles of CO2 for 30% and 50% CO2 recycle in lieu of air injection with the standard ISC at non-adiabatic conditions for an injection rate of 0.880 PV/hr 71 Figure 4-19. Comparison of net moles of CO2 for 70% and 90% CO2 recycle in lieu of air injection with the standard ISC at non-adiabatic conditions for an injection rate of 0.880 PV/hr 72 Figure 4-20. Comparison of Ro for 30% and 50% CO2 recycle in lieu of air injection with the standard ISC at non-adiabatic conditions with an injection rate of 0.681 PVI/min 75 Figure 4-21. Comparison of Ro for 70% and 90% CO2 recycle in lieu of air injection with the ISC at non-adiabatic conditions with an injection rate of 0.681 PVI/min 75 Figure 4-22. Comparison of moles of CO2 for 30% and 50% CO2 recycle in lieu of air injection with the standard ISC at non-adiabatic conditions with an injection rate of 0.681 PVI/min 76

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Figure 4-23. Comparison moles of CO2 for 70% and 90% CO2 recycle in lieu of air injection with the standard ISC at non-adiabatic conditions with an injection rate of 0.681 PV at RC/hr 76 Figure 4-24. Comparison of oil recovery at various percent recycle for an 80% enriched O2 ISC process in a non-adiabatic setting 79 Figure 4-25. Comparison of net moles of CO2 produced at various percent recycle for an 80% enriched O2 ISC process in a non-adiabatic setting 80 Figure 4-26. Comparison of Ro for 30% and 50% CO2 recycle in addition to air with the standard ISC at adiabatic conditions. 83 Figure 4-27. Comparison of Ro for 70% and 90% CO2 recycle in addition to air with the standard ISC at adiabatic conditions 84 Figure 4-28. Comparison of net moles of CO2 for 30% and 50% CO2 recycle in addition to air with the standard ISC at adiabatic conditions 84 Figure 4-29. Comparison of net moles of CO2 for 70% and 90% CO2 recycle in addition to air with the standard ISC at adiabatic conditions 85 Figure 5-1. Schematic of the ISC system. Figure 5-2.Water-oil relative permeability curve for 2-D and 3-D systems Figure 5-3.Liquid-gas relative permeability curve for 2-D and 3-D systems Figure 5-4. Fractional cumulative oil production vs. PVI Figure 5-5. Fractional cumulative oil production vs. time Figure 5-6.Dimensionless net CO2 emission vs. pore volumes injected of gas Figure 5-7. Dimensionless net CO2 emission vs. time Figure 5-8. Pore volumes of gas injected vs. time Figure 6-1. Oil recovery vs. time for various values of PeMass. Figure 6-2. Oil recovery vs. PVI for various values of PeMass Figure 6-3. Comparison of CO2 emissions (CO2D) vs. time for various values of PeMass. 91 91 92 95 95 96 99 99 108 108 109

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Figure 6-4. Comparison of CO2 emissions (CO2D) vs. Ro for various values of PeMass Figure 6-5. Comparison of oil recovery vs. time for various values of PeHeat Figure 6-6. Comparison of CO2 emissions (CO2D) vs. time for various values of PeHeat Figure 6-7. Time needed to recover 90 % of the oil in place vs. PeHeat Figure 6-8. Comparison of oil production vs. time for various Dacoke burning Figure 6-9. Comparison of CO2 emissions (CO2D) vs. time for various Dacoke burning Figure 6-10. Comparison of oil recovery vs. time for various Dacoke forming Figure 6-11. Comparison of CO2 emissions (CO2D) vs. time for various Dacoke forming Figure 6-12. Comparison of oil recovery vs. time for various initial water saturation Figure 6-13. Comparison of CO2 emissions (CO2D) vs. time for various initial water saturation Figure 7-1.Permeability distribution of the inverted 9-spot pattern Figure 7-2.Permeability distribution for the line-drive pattern of the top layer Figure 7-3.Gas saturation after 4000 days for a standard, inverted 9-spot ISC run Figure 7-4.Comparison of cumulative oil recovery between a standard and a CO2-recycle run for an inverted 9-spot pattern Figure 7-5.Gas saturation after 4000 days for an inverted 9-spot run with CO2 recycle Figure 7-6.Comparison of CO2 emissions for the inverted 9-spot pattern between the standard and the CO2-recycle runs Figure 7-7.Comparison of net CO2 emissions vs. Oil recovery for the inverted 9spot pattern Figure 7-8.Cumulative oil comparison for the line-drive pattern

109 111 111 112 114 114 115 116 117 117 125 127 129 129 130 131 132 135

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Figure 7-9.Net CO2 production comparison for the line-drive pattern Figure 7-10.Net CO2 production versus recovery of oil for the line-drive simulation Figure 7-11.Gas saturation at the conclusion of the standard line-drive ISC Figure 7-12. Gas saturation at the conclusion of the line drive recycle CO2 into row 1 Figure 7-13.Ngv parameter study for the inverted 9-spot well configuration Figure 7-14. Ngv parameter study for the line-drive well configuration Figure 7-15.Ngv Parameter study for line drive well configuration, Ro vs. PVI Figure 7-16. Comparison of air versus steam injection for the first section of line drive

135 136 136 137 139 141 142 144

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Abstract

The in-situ combustion (ISC) process is an enhanced oil recovery (EOR) method that utilizes fuel in place to upgrade and displace the hydrocarbons in heavy oil reservoirs. In ISC processes, air is injected into a heated section of the reservoir. Upon reaching a threshold temperature, oxygen from the injected air reacts with the oil in place to generate heat, steam and reaction products such as CO2. This process drives oil towards production wells, but at the same time produces large amounts of CO2.

In this research project we investigate the potential of recycling produced CO2back into the reservoir simultaneously with the ISC process. We attempt to maintain the advantages of the ISC process while at the same time reduce emissions of CO2. Numerical simulations have been performed using CMGs STARS, a commercial thermal recovery simulator. To validate the model and the software we first simulated a lab-scale combustion tube experiment, following Belgrave et al. (1990) who previously modeled combustion tube experiments done by Hayashitani (1978). Following initial model

validation, we then investigated the effect of CO2 recycle in both adiabatic and nonadiabatic settings. Our simulations show that net CO2 productions can be reduced significantly, but this reduction, however, comes at the cost of lower oil production rates, higher injection rates and/or both. In the most optimal adiabatic setting, CO2 production is reduced by 62% while the oil production is reduced by 10.5%. In the most optimal non-adiabatic setting, CO2 production is reduced by 42% while oil production remains

xv

the same. However, in the non-adiabatic case, an additional 60% increase in total injection rate is necessary.

Leveraging on our findings from the initial modeling/simulation work, a field scale pseudo 2-D model of the hybrid ISC process was developed. Using this model we showed that recycling of the CO2 back into the reservoir, to replace some of the air that would be otherwise injected, can be beneficial for both reducing the CO2 production as well as for increasing the oil production. We observed that the CO2that is recycled back into the system dissolves readily into the oil phase thus resulting in lower oil viscosity and in improved production rates. The results of our numerical calculations provide justification for the proposed combined ISC/CO2-flood process. In this process the ISC itself provides on-site the gas that is needed for the CO2 flood, and a substantial fraction of the total CO2 produced can be permanently sequestered in the subsurface.

The pseudo 2-D model was utilized to study the process for a wide range dimensionless parameters (e.g., Peclet and Damkhler numbers), and initial saturations. Favorable trends induced by CO2 recycling are observed over a broad range of the dimensionless parameters. Under a set of realistic conditions, an increase in the oil recovery of ~33% for a fixed time of operation was observed when comparing the ISC process with CO2 recycle to the more conventional ISC process. In addition, at the time when 80% of the total oil in place had been produced, the simulations showed that the CO2 emissions were consistently lower by 18-22 % for the case when CO2 was recycled back into the formation.

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Following our2-D investigations, we initialed oil displacement simulations of full 3-D systems. We have studied two different cases, an inverted 9-spot and a line-drive configuration. Simulations in these 3-D settings were on a much larger scale and were performed with a shared-memory parallel machine available through HPCC at USC. The results of our numerical calculations show that, due to the naturally-occurring heterogeneity in the 3-D reservoir, the displacement behavior resembles an array of channels that are very similar to those observed in the simulation of the 1-D and pseudo 2-D models. Large well-to-well distances, as in the case of the inverted 9-spot configuration lead to poor overall sweep and performance (e.g., only 11% overall recovery). Recycling of CO2 under these circumstances widens the transport channels and improves the oil sweep and recovery to a value of ~20%. However, due to the still low sweep efficiency, CO2 emissions savings were observed to be negligible.

In the line-drive scenario, with a relatively shorter well-to-well distance, the performance of the standard ISC process was noticeably improved with an overall oil recovery of 32%. Recycling of the CO2 was not as effective as in the 9-spot configuration in increasing oil production, largely because flow channels were well developed, leaving little room for further improvement. However, because much more oil was produced relative to the 9-spot case, a large amount of void volume was available for CO2 storage. With recycling, up to 30% reduction in CO2 emissions was observed.

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In summary, this research has demonstrated the potential for reducing CO2 emissions from ISC processes via efficient recycling strategies. The proposed mode of operation is a first step towards application of ISC in areas with strict emission regulations. Additional research, at various scales, is warranted in order to further test and validate the ideas developed in this work.

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Chapter 1: Introduction 1.1 Importance of heavy oil At the turn of the 21st century petroleum resources are being depleted rapidly while the demand for petroleum is steadily increasing. Since exploration for new oil reserves is not sufficient to meet such rising demand, attention is being paid towards recovering additional oil from existing heavy oil reservoirs using enhanced oil recovery (EOR) techniques (Mahinpey et al., 2007).

California is one of the states where heavy oil recovery is important. In fact, the state ranks 4th in the USA among states with the most abundant crude oil reserves, with an estimated 3,389 million barrels of proven reserves in 2006, roughly 1/6th of the total U.S. proven reserves (Energy Information Administration, 2009). While California in the past was a self-sufficient state in terms of its crude oil needs, in recent years the decline in crude oil production has forced it to rely on importing crude from other areas such as the Middle East, Central America, and South America (Sheridan, 2006). For example, from 1996 to 2006, crude oil production in California dipped by 23% (Sheridan, 2006), and in 2006, foreign crude imports accounted for more than 1/3 of Californias consumption. It is, of course, in the states (but also the nations) best interest, for it once again to become independent of foreign oil imports.

One major problem lies in Californias crude oil reserves themselves: 51% of all California crude is heavy oil. (Heavy oil is defined here as oil with an API gravity of 18 or less). In addition, the California heavy crudes are, typically, also fairly viscous; for 1

example, the viscosities of Huntington Beach and West Newport crudes range from 0.032 to 0.201 Pa S at 65 oC (Abu-Khamsin et al., 1988). Because of its gravity and viscosity, heavy crude is difficult to produce, and typically Thermally Enhanced Oil Recovery (TEOR) is implemented in California in order to improve recovery beyond the primary recovery limits (Sheridan, 2006). The vast majority of TEOR in California utilizes steam or cyclic steam injection. Unfortunately, even with steam injection and cycling, reports continue to show an annual decline in oil production in California. Unless aggressive new TEOR methods are implemented, annual declines of 3.5% a year are expected.

1.2 How can we address the need for more EOR? One option, of course, would be to simply increase the use of steam EOR. While that may be reasonable for now, steam methods are not without limitations of their own. For one thing, steam generation requires a significant amount of energy; and second, steam injection is difficult to operate in deep reservoirs, as the energy in the steam is lost to the surroundings before it can reach the target oil. The declining trends in oil production in California, clearly point out the need for exploring and developing other future alternatives to steam TEOR.

An alternative TEOR process that may be suitable for heavy oils is the In Situ Combustion (ISC) process(Sarathi, 1999). This TEOR process is the focus of the research reported in this Thesis. In the ISC process, air is injected into a reservoir and ignited in the subsurface using a fraction of the crude oil in place as a fuel. One advantage of ISC over steam TEOR processes is the potential energy savings, since no steam generation is

necessary. A second advantage is that deeper reservoirs may be targeted by the ISC processes as the heat is generated in-situ and does not need to be provided externally as in the steam TEOR processes.

ISC has already been shown to be viable for California crudes (Ramey et al., 1992). Recently, the ISC technology was also applied successfully at a commercial scale in India (Doraiah et al., 2007). In the latter case, oil recovery values increased from 6-12% to 3945%. Accordingly, one may wonder why ISC is not being employed more commonly in the U.S. One of the major issues that currently prevent the use of ISC processes in this country is the stringent pollution regulations (National Emissions Standard, 2007 and Environmental Protection Agency, 2009). Unlike steam EOR, the ISC process produces a number of gaseous by-products, including H2S, NOx, CO, CO2 and volatile hydrocarbons alongside with the oil(Sarathi, 1999). Because of these potentially hazardous pollutants, ISC, as things now stand, is a very difficult process to adopt and operate in the U.S. (in contrast, for example, to other countries, where pollution regulations are not, as yet, as strict).

Hence, the focus of this research is not on developing ISC processes in the traditional sense, as that has already been shown to be viable. Instead, the author focuses on capturing the hazardous gases produced in ISC and either sequestering or re-injecting them as part of the ISC process so that the emissions are significantly reduced or even eliminated. The ultimate goal of this project is to reduce emissions to the level where ISC processes can be operated in compliance with the current U.S. emission regulations.

1.3 Description of ISC processes Before discussing the details of the current work, it is important to discuss in some detail the basics and the background of ISC processes. As noted previously, ISC is an enhanced oil recovery method that is effective at recovering heavy crude (Mahinpey et al., 2007).The process involves injecting air or oxygen-enriched air into a reservoir in an effort to enhance oil recovery through in-situ upgrading. The key mechanisms involved are fuel formation and burning. A typical ISC process involves first heating of the reservoir near the injection well. This, then, causes the oil in place to undergo pyrolysis (defined as the transformation of a substance into one or more other substances by heat alone without oxidation), leaving behind a lighter oil and coke. The lighter oil is the targeted product.

Figure 1.1. Mechanistic characterization of ISC processes(Mahinpey et al., 2007). 4

The coke formed from the pyrolysis of the oil, on the other hand, serves as the fuel for the underground combustion process, as mentioned previously. The coke combustion with the oxygen in the injected air is an exothermic reaction resulting in the formation of gas products such as CO2 and steam, as well as heat -- this is the fuel burning mechanism. The CO2 and the steam formed in the combustion reactions displace the lighter oil towards the production well. The heat generated travels downstream of the combustion front and causes additional fuel formation/deposition via pyrolysis, i.e., the formation of more light oil and coke. This process continues until this burning front reaches the production well. Accordingly, the key challenge of an ISC process is to provide sufficient oxygen to maintain the combustion front. Figure 1.1 illustrates a traditional mechanistic representation of an ISC process (Mahinpey et al., 2007) including up to 7 distinct zones.

Zone 1 is where the oil has already been displaced. This zone contains mostly reservoir rock saturated with air and possibly water (depending on whether you inject dry or wet air). In most cases there will still be some residual coke left in zone 1, on the order of up to 2% by mass(Mahinpey et al., 2007). Zones 2 and 3 represents the regions where the key mechanism of ISC processes plays out. In zone 2 one finds the burning front. In this zone, injected oxygen reacts with the coke fuel to generate combustion products such as CO2, steam as well as heat. Compared to the rest of the reservoir, this zone is very narrow. Immediately downstream of the combustion front is zone 3, the coking zone. Here, the fuel formation mechanism plays out. Heat generated from zone 2 advances to zone 3 faster than the oxygen. This heat then causes the oil in zone 3 to pyrolyze, forming coke and a lighter oil fraction. The fuel coke deposited in zone 3 directly relates to the

amount of combustion that occurs in zone 2. Similarly, the amount of heat propagated to zone 3 from zone 2 is proportional to the amount of combustion that occurs in zone 2. These two zones are very closely coupled, and a delicate balance is struck between the fuel (coke) formation and combustion processes.

Further downstream one finds the steam and water zones (zones 4 and 5, respectively). The energy generated from the combustion reactions is dispersed through the water and steam, formed from the combustion process, into the oil reservoir via these zones. The increase in temperature reduces the viscosity of the oil and increases its mobility, an important feature that is key to the effectiveness of the ISC process. Downstream from the water zone is the oil-bank zone 6. This zone represents the lighter oil that is generated and displaced by the upstream processes. Last is zone 7, which is an area sufficiently downstream from the combustion zone so that the effects of the ISC process have not yet changed the properties of the original oil. The only disturbances in zone 7 are due to gases, such as CO2, that travel downstream rapidly as a result of their high mobility. This gas is generally at a lower temperature by the time it reaches the production well due to the heat transfer in zones 4 through 7.

While a mechanistic model is good for gaining qualitative insight into the dynamics of ISC processes, reality is more complicated. Zones can be inter-dispersed and not easily distinguishable. The sequence of the zones can also be altered (from that of Figure 1.1), due to the heterogeneity that exists in the reservoir. Nonetheless, the zone model of Figure 1.1, serves an important purpose in the initial overview of the process.

1.4 The chemistry of ISC processes After the general overview of ISC process, the chemistry and reactions of ISC processes are now reviewed. Because the goal of this work is to control gaseous pollution, it is important to understand the reactions that take place during ISC first, as these reactions produce the gaseous by-products in the first place. Therefore, before going into more details on how this research proposes to handle gaseous pollution, the ISC reactions and their chemistry are discussed.

Despite decades of research and the efforts of many scientists and engineers, the exact chemistry and kinetics of crude combustion and pyrolysis are still unknown. It is, generally, accepted that the reaction network is highly complex, with each individual hydrocarbon in the crude undergoing multiple partial and full oxidations, as well as pyrolysis. ISC offers an additional challenge as the reactions occur in the subsurface, where the soil heterogeneity, crude composition variations, and the air and fuel concentrations throughout the reservoir are not known in great detail. Much work has been done in trying to understand and to simplify these reactions and systems, so that studies and simulations can be done efficiently. Since working with a detailed reaction model is not feasible, reactions and components are commonly lumped. The common approach to ISC reaction chemistry and kinetics is explored below. Virtually all the important reactions of ISC processes occur in zone 2, the combustion zone, and zone 3, the coking zone (Mahinpey et al., 2007). While steam flooding and CO2 flooding are EOR techniques in their own right, the unique characteristic of ISC processes is the combustion and pyrolysis that generate heat in situ. The chemical

reactions involved can be divided into 3 categories: Pyrolysis, High-Temperature Oxidation (HTO), and Low-Temperature Oxidation (LTO).

1.4.1 Pyrolysis Pyrolysis is the set of reactions that describes the effects of heat on the oil in the absence of oxygen. Pyrolysis reactions are also known as the intermediate-temperature zone and the fuel-deposition reactions in the ISC literature. From its name one could infer that pyrolysis occurs in an intermediate temperature range, and that it is responsible for coke formation. This turns out to be true. While the temperature of pyrolysis varies from case to case, it falls in between the LTO and HTO temperatures. Generally, in ISC processes, LTO occurs between 300 and 450 oC, pyrolysis between 450 and 600 oC, and HTO occurs above 600 oC. As noted previously, pyrolysis reactions are the main mechanism for fuel (coke) deposition (Burger and Sahuquet, 1972; Lin et al., 1987). They occur in the absence of oxygen, and are mostly found in zone 3, the coking-zone.

Abu-Khamsin et al. (1988) describe pyrolysis as a combination of three overlapping processes: distillation, visbreaking, and coking. They indicate that coke is not formed in one step, but rather in a series of steps. In the distillation step, the light components of the crude are first separated. At higher temperatures, in the visbreaking step, mild cracking of the oil occurs, and the oil becomes less branched and more viscous. At even higher temperatures, the oil separates into a volatile and a non-volatile fraction. The non-volatile fraction is the coke, which is deposited in the subsurface and serves as fuel for the oxidation reactions. The visbreaking and coking reactions are described as follows:

Crude oil visbroken oil gas visbroken oil coke gas

1.1

1.2

Alternatively, Belgrave et al. (1990) describe the coking process of Canadian bitumen as follows: bitumen maltenes maltenes asphaltenes asphaltenes gas asphaltenes coke

1.3

1.4

1.5

1.6

This reaction network has been utilized repeatedly in studies by the University of Calgary.

1.4.2 High-temperature oxidation Following the formation of coke in zone 3, this coke is burnt in zone 2. Generally, the burning of coke constitutes the great majority of the HTO reactions. While it may seem intuitive that the oil should burn more readily than solid coke, because the oil is downstream, in zone 6, very little oxygen makes it to that zone in a well-behaved ISC operation. Hence, the HTO that occurs in ISC processes involves only the burning of the 9

coke (Burger and Sahuqet, 1972).The stoichiometric reaction scheme for such a reaction is as follows: 2 21 4

1 1 1 2

1.7

where is the volume fraction of in the exhaust gas (Burger and Sahuquet, 1973).

The (C/H) ratio x can be determined via elemental analysis of the coke (fuel) or by material balance of the gas phase produced in the high-temperature combustion zone alone (Mahinpey et al., 2007). Alternately, it can also be expressed as: 2 1 21 4

1 1 1 2

1.8

Where m is the volume fraction of

in the exhaust gas = .

The high temperature oxidation is a heterogeneous surface reaction that can be divided into the following steps(Scarborough and Cady, 1982): 1. Diffusion of oxygen from the bulk gas stream into the coke pore structure and surface. 2. Adsorption of the oxygen onto the surface. 3. Chemical reaction with the fuel (coke). 4. Desorption of the combustion products from the surface. 10

5. Diffusion of the products through the pore structure and away from the surface and into the bulk gas stream.

Whether this process is diffusion-limited or reaction-limited is still a topic of debate (Islam et al., 1989). Work by Dabbou et al. (1974), and Lin et al. (1982), for example, have suggested that the HTO reactions are diffusion-limited. Studies by Fassihi et al., (1984), and Burger and Sahuquet (1973), on the other hand, have suggested that the HTO phenomena are reaction-limited. For the HTO reaction, the rates utilized in this study are in the following form(Islam et al., 1989):

1.9

Where C is the concentration of fuel (coke), k is the rate constant, PO2 is the oxygen partial pressure, and m and n are the corresponding reaction rate orders. In addition to coke combustion, in this study we include two additional reactions for direct HTO of the oil. These reactions were not included in Belgraves model, but were recommended therein (1990). The stoichiometry for the oil HTO is based on the work of Coats (1980): 1 Asphaltene 102.6 O 74.87 CO 8.356 CO 47.02 H O 1 Maltene 38.17 O 27.85 CO 3.108 CO 17.49 H O 1.10 1.11

It is interesting to note, that the general consensus among the technical literature studies on ISC is that little hydrogen is formed during the process, and can therefore be ignored in the reaction scheme. Sarathi (1999), for example, catalogs combustion tube effluent analysis, where negligible H2 is formed. Models old and new, while varying in reaction 11

schemes, all exclude H2(Benham and Potemann, 1958; Burger and Sahuquet, 1973; Belgrave et al., 1990; Jain et al., 2010).

1.4.3 Low-temperature oxidation LTO reactions occur at lower temperatures than the HTO, but the exact range of temperatures is wide and varies from crude to crude. Generally, these reactions are known to occur in the range of 300-450 oC (Alexander et al., 1962; Moore 1993). Unlike HTO, LTO reactions do not produce CO2 and CO but rather cyclic and partially oxygenated hydrocarbons. These reactions also deposit coke, which increases fuel availability (Mahinpey et al., 2007; Belgrave et al., 1990), but at the same time the hydrocarbons that are formed by LTO have been shown to increase the oil viscosity (Dabbous and Fulton, 1974; Alexander et al., 1962). Significant reduction in oil recovery has been reported by Dabbous and Fulton (1974)when LTO was present in addition to HTO. On the other hand, Belgrave et al. (1990)demonstrated that fuel deposition via pyrolysis alone (without LTO) was not sufficient to sustain HTO in the preceding zone. The above studies obviously offer no clues whether LTO reactions offer benefits or are detrimental to oil recovery during ISC. They do emphasize the complexity of the problem, however, whereby different experimental techniques lead to different conclusions.

This work takes into consideration the LTO reactions, as we agree that they play an important role in the ISC process. As previously noted, LTO reactions are necessary for sufficient fuel production and deposition in order to maintain the combustion front;

12

however, LTO reactions, on the other hand, may result in low air flux and to poor combustion characteristics, and can cause the oil to become permanently trapped in the pores (Mahinpey et al., 2007). The LTO reactions included in this study are: 1 Maltene 3.431 O 0.4726 Asphaltenes 1 Asphaltene 7.513 O 101.537 Coke 1.12 1.13

In summary, LTO reactions are of the utmost importance when it comes to understanding the mechanism of the ISC process, as they have a direct and significant impact on air flux and on the combustion characteristics of the process.

1.5 CO2 cycling The previous section discussed the importance of the proper balance among pyrolysis, LTO, and HTO reactions. It is of the utmost importance to maximize HTO in order to maintain high temperatures and to have a complete combustion. The more complete the combustion process is, the greater is the likelihood of success. However, more HTO leads to the production of more gaseous pollutants. It must be emphasized that this research does not propose to modify the complex ISC process, but rather to reduce the emissions of the gases that are generated. We propose that gases that are produced after breakthrough are cycled back into the reservoir. This idea combines ISC with CO2-EOR and sequestration, first presented by Kovscek and Wang(2005). In their papers they discuss the possibility of simultaneous CO2 geological sequestration alongside a typical CO2-EOR process.

13

In ISC processes, the majority of the gas produced is CO2 (Mahinpey et al., 2007).In this preliminary investigation of the process, we have therefore assumed that we only cycle the CO2 from the gases that are produced, initially without consideration of the costs of separating the CO2. This simplification is made because accounting for CO2 is straightforward, as the HTO reaction that produces the majority of the CO2 can be easily described by reactions (1.7 1.11). At later stages of this work we will address issues relating to the presence of other gases, some of which may be valuable products in their own right (e.g., low MW hydrocarbons), and others may be objectionable pollutants. Currently, for example, very little work exists on the production of H2S, NOx and light hydrocarbons during ISC processes, particularly relating to the reactions and other processes that are responsible for the generation of these compounds during the ISC process. This is not surprising, as most ISC research up to now has been focused on the oil recovery alone, and more often than not, the gases produced are simply lumped into a single component. In the future, there will be great need for accounting for the physicochemical processes resulting in the formation of other gases (in addition to CO/CO2 and water), and for documenting their reaction kinetics.

The proposed operation mode is as follows: Operate ISC normally by injecting air compressed to the reservoir pressure until gas breakthrough. After breakthrough of gases, separate the gases and re-inject a portion back into the reservoir. Operate until a target recovery is reached and then shut the wells in order to trap the gases in the subsurface. In theory, there should be no real additional difficulty in operating this way compared to a standard ISC process. Separation of gases is a common (albeit costly) task in oil and gas

14

operations, but a necessary step in the future application of ISC, mandated by the need to minimize the carbon foot-print of the process. Compression of the CO2is not significantly different (or more costly) from compression of air. Concerns about gases escaping through the earth are an important issue when operating the ISC process, but a wise operator needs to account for this and to choose a field where upward gas mobility is negligible.

It is important to note here, that the goal is not to sequester 100% of the produced CO2 in the reservoir, but rather a significant portion of it. Most reservoirs are not completely isolated. Gases produced can also be sequestered into other geological formations nearby, for example, in deep saline aquifers. Or, they could even be used for other EOR processes, such as CO2-flooding of a nearby lighter crude, or even a gas reservoir (Sim et al., 2008). Light hydrocarbon gases can also be eliminated by injecting them further downstream of the combustion front, thereby prepping the oil for ISC. These factors will vary from location to location and must be included in the process of selecting a specific mode of ISC operation. The goal of this work, therefore, is to investigate how much of the produced CO2 can be stored in the target reservoir. If the answer is 20%, then there needs to be a lot of consideration for what to do with the other 80%. On the other hand, if it is shown that 80% of the CO2 produced can be kept in the reservoir, then only 20% of the CO2 now needs to be sequestered elsewhere. That scenario could very well be feasible, and may convince the operators to apply the ISC processes.

15

1.6 Simulations with CMG STARS The first stage of the research includes model development and simulation of the ISC process, and an investigation of the impact of CO2cycling on process performance. A model similar to that of Belgrave et al. (1990) was chosen and implemented in the commercial thermal recovery simulator STARS (Steam, Thermal, and Advanced Processes Reservoir Simulator). The initial goal is to show that in simple 1-D and pseudo 2-D models cycling of CO2 is feasible and to understand the impact on the ISC process performance. Key issues addressed in the preliminary investigations include: (i) (ii) What is the level of CO2 cycling that will not interfere with the ISC process? What is the level of CO2 reduction and sequestration that is potentially feasible? (iii) What are the impacts on the economics of the ISC process (e.g., cost-savings because of the enhanced recovery vs. costs associated with CO2 separation)? With this background and these goals in mind, we have set-forth to explore the possibilities of cycling CO2 in ISC processes.

16

Chapter 2: Theory, Physical Models, and Numerical Simulation 2.1 Equations We begin by describing the basic conservation equations used to describe flow through a porous media.

2.1.1 General mass conservation equations The conservation of mass of the individual species in our ISC model can be described as 1, . . . , 2.1

the dispersive/diffusive molar flux, and Ri the reaction rate. This form of the flux, conservation equations is valid away from sources and sinks (wells). In Eq. 2.1, the overall molar concentration of component i can be expanded as:

the advective molar where t is the time, , the overall molar concentration of species i,

1, . . . ,

2.2

where xij is the mole fraction of component i in phase j, j the molar density of phase j, the volume of fluid per unit of bulk volume, Sj, the saturation of phase j (w, water; g,

component i in the void volume. Saturation is defined as volume of a phase (e.g. water) divided by total fluid volume. Void volume is defined as volume of fluid divided by total overall volume (including rock). 17

gas; o, oil), the void volume fraction , and Csi the solid-phase molar concentration of

The overall advective flux of component i is defined as

1, . . . ,

2.3

The overall dispersive flux of component i can be defined as

where is the Darcy velocity of phase j.

2.4

1, . . . ,

where is the dispersivity of phase j and is the magnitude of the interstitial velocity in phase j (Darcian velocity divided by porosity). The overall reaction rate of component i is given by

1, . . . ,

2.5

equation rk is defined as

where is the net stoichiometric coefficient of component i for reaction k. In the above

1, . . . ,

2.6

18

wherekk is the reaction constant for reaction k, Xi is the molar concentration or partial pressure of component i in the phase where reaction k occurs, and Pik is the reaction rate order for component i in reaction k. The activation energy AEk is defined by where Ek is the activation energy for reaction k.

2.7

2.1.2 General energy conservation equation In addition to the mass conservation equations, we consider an energy conservation equation in the following form

2.8

represents the enthalpy flow, In Eq. 2.8, E is the internal energy, is the heat conduction term, G is the heat generation due to the reactions, and L is the heat loss to surroundings. Note, that there is no viscous dissipation term in Eq. 2.8, as this is not explicitly represented in STARS. While we do consider very viscous fluids, the velocity gradients in our system are rather small, and consistent with this assumption. In analogy to the mass conservation equations, we expand the individual terms, and define the combined energy density as 1

2.9

19

where, is the specific internal energy of phase j, Cs is the total solid molar

the solid phase. In Eq. 2.9, is the volumetric internal energy of the rock and 1 is the rock fraction in a unit volume. The combined convective energy flux is defined by:

concentration in the void volume = , and is the specific internal energy for

2.10

Where is the specific enthalpy of phase j. No enthalpy term is included for the solid Fouriers law as

phase as the coke is assumed to be immobile. The conductive heat flux is defined by

2.11

Where Kj is the thermal conductivity of phase j and T is the temperature. The total generation of energy by the chemical reactions can be written as:

2.12

Where Hrk is the heat of reaction for reaction k. The heat loss to over- and under-burden is modeled semi-analytically as heat transfer to or from an adjacent formation of infinite extent (Lin et al., 1987; Islam et al. 1989). It assumes a temperature profile in the base or cap rock as a function of time and

20

distance from the reservoir interface. Heat loss is a function of thermal conductivity and heat capacity of the over- and under-burden. ,

2.13

2.2 Simplifications and assumptions used in STARS The general conservation equations are valid for all systems, but representation of the variables can be complicated. Simplifications and assumptions are a necessity for efficient simulation. In this section we review the implementation of the above equations in the commercial simulator STARS.

2.2.1 Porosity calculations We begin by describing how the simulator quantifies volume. The simulator divides the system volume into a number of grid blocks. These grid blocks are defined by the user. In our numerical calculations the system was defined in either Cartesian or radial coordinates. Each of these grid blocks serves as a unit volume. The volume of each grid block is divided into rock volume (r), and void volume (v). The void volume is divided into solid volume (s) and fluid volume (f). Furthermore, fluids are divided into gas volume (g), oil volume (o), and water volume (w). The void porosity, , is defined as
Total volume Void volume Fluid volume

, this value must be user specified for each grid block. While the void volume

of a grid never changes, the fluid porosity, , defined as Total volume, varies with changing solid (coke) concentration. The simulator represents fluid porosity as:

21

2.14

that

Where Csi is the concentration and is the density of the solid component i. We note

represents the total solid volume. Lastly, the fluid volume is divided into

three phases, namely gas, oil, and water. Each phase has its own respective saturation Sg, So, and Sw, as defined in eq. 2.2.

2.2.2 Representation of phase equilibrium Now, we proceed to discuss how components are distributed between existing phases. The rock volume is assumed to be inert and stationary. The solid phase is treated identically to the rock except that it can react. There are no flow terms associated with the solid phase and the mass balance is simply accumulation = net reaction. (Note that STARS also supports an adsorbed phase, which is in equilibrium with the fluid phases. We however, do not include any adsorbed phases in this work.)

For the overall fluid compositions, components are assumed to be in instantaneous equilibrium among the gas, oil, and water phases. The simulator uses a K-value approach in order to determine equilibrium phase compositions. K values are defined by the ratios of mole fraction between two phases. For three fluid phases, there exist three K values for each component. These K values are defined as: ;

2.15

22

 ; ;

2.16

2.17

We note that only 2 of the 3 K-values are independent; hence, the user must provide 2 sets of K values, e.g. gas-liquid and liquid-liquid. Gas-liquid K values can be set either via the use of tables or by applying a correlation. The correlation used in the simulator is given by:

2.18

Where P is pressure and T is temperature and kvi1 thorough kvi5 are user-provided parameters. Liquid-liquid K values, on the other hand, are specified by a table.

2.2.3 Component and phase densities Next we discuss how the density of a fluid varies with composition. For a component existing in the solid or liquid phase, the user must provide a pure component density. While density may depend on temperature and pressure, the oil and coke data adapted in this work did not provide any such parameters, and therefore were reported as constants. For water, STARS provides default temperature and pressure dependence based on Phys. Chem. Ref. data, Vol. 16, No. 4, 1987. The actual calculations are fairly involved and are detailed in the STARS manual(CMG, 2008). Liquid phase densities are calculated assuming ideal mixing:

23

1 1 and

2.19

Gas phase density is calculated based on an equation of state (EOS), , where the compressibility Z is calculated from the Redlich-Kwong EOS with no binary interaction coefficients. The author notes that the ideal liquid phase mixing rule and the lack of interaction coefficients may, potentially, lead to inaccurate representation of the physics.

2.2.4 Mass advection and calculation of phase velocities Sections 2.2.1 through 2.2.3 detailed the calculations needed to represent an isolated volume of known overall composition. Next we will discuss how the simulator models the commutation of these components by advection, diffusion, reactions, and wells. To evaluate the advective flux from eq. 2.3 we need mole fractions, phase densities, and phase velocities. Phase velocities are calculated using the multi-phase version of Darcys law:

2.20

Where is the absolute permeability, is the relative permeability of phase j, is the viscosity of phase j, and is the potential of phase j. To evaluate a phase velocity, we describe the new terms starting with absolute permeability, a representation of the ease of flow through a porous material. This parameter is provided by the user for each point in the computational domain. In our simulations, absolute permeability was held constant.

24

For a multi-phase system, the permeability of a given phase is not simply the absolute permeability but rather the effective permeability, expressed as the absolute permeability multiplied by the relative permeability; .

Relative permeability, which ranges between zero and one, must be provided by the user via tables. Two tables are needed, one for water-oil relative permeability, and one for liquid-gas relative permeability. The relative permeability tables used in our simulations are from Belgrave et al. (1990). They are presented in the next chapter, in Tables 3-3 and 3-4. Stones second method(Stone, 1973) is used to calculate the effective three-phase permeability of a given phase from the two tables. While permeability and relative permeability describe the ease of flow through a porous material, viscosity describes a fluids innate resistance to flow. For both the water phase and the oil phase components, a correlation is used for calculating the pure component viscosity: 2.21

In our system we assume the great majority of the organic phases will be either in the oil and gas phase (in addition, Belgraves model does not include adsorption or organics into the aqueous phase. As of to date, no liquid-liquid K-values were found in the literature involving these specific pseudo components). Thus, no mixing rule is needed for the aqueous phase. For an oil phase, the default mixing rule used in the simulator given by:

2.22

25

This mixing rule is simple, namely linear logarithmic. A more complex non-linear version can be implemented, based on user-provided functions. However, at this stage of the investigation, the default mixing rule was used. Gas phase viscosity is calculated using the internal correlation: 0.0136 3.8 10

2.23

Note that this internal correlation does not take composition or pressure into account. This is a very computationally inexpensive choice for representing gas phase viscosity, and is often sufficient for ISC processes (CMG, 2008). A component-based viscosity calculation is also available, but is not used in this work. The phase potential is defined as: P where P is the pressure and is the

vector. Pressure is a primary variable that the simulator solves for and the initial pressure of the computational domain must, therefore, be provided by the user.

, where g is gravitational acceleration and is the vertical unit gravity term:

2.2.5Reaction rates Reaction rates are expressed in the simulator in the general form:

2.24

is the pre-exponential factor, a scaling constant, Eak is the activation energy, which

determines the effect of temperature on reaction rate, R is the gas constant and is the 26

concentration raised to an exponential power (the order of the reaction for that particular component). Eq. 2.4 assumes that the reaction rate is only a function of temperature and component concentration. The concentration factor can be expressed in three ways, depending on the phase. For a liquid phase:

2.25

Alternatively, concentrations for the solid phase are expressed as 2.26

Lastly, for a gas phase, partial pressure may be used

2.27

Wherexigas is the mole fraction of i in the gas phase and Pgas is the gas phase pressure.

2.2.6 Well equations Having detailed the calculation of mass transfer within the numerical simulator, this section discusses the equations governing flow in and out of the reservoir through wells. The general governing equations are defined away from wells, but for a discretized domain that includes a well, an additional well term must be included into the equation (through boundary conditions). For a given component, the molar flow through a well can be represented as:

2.28

27

Where is the well volumetric flow rate of phase j. Note, that because we have a discretized system the units are in, and we consider the effects the well has in a grid block of volume Vgrid. The well volumetric flow rate of phase j is given by: 2.29

Where Pgrid is the pressure of the grid-block, Pwell is the flowing well-bore pressure, and Iwell is a well index, a proportionality parameter that accounts for the geometry of the system. The well index used in STARS is derived from the work done by Peaceman (1983). Note, that we have represented our well in a mobility un-weighted fashion. Mobility-weighted fashion, which introduces another term describing viscosity and density, can also be used.

2.2.7 Enthalpy and internal energy In addition to mass we must also keep track of the energy in our system. There are only a few additional terms needed to describe energy conservation, namely specific enthalpy, specific internal energy, thermal conductivity, and the heat of reaction. In this section we discuss enthalpy and specific internal energy. To define enthalpy, the temperature derivative of enthalpy for a component i in a fluid phase j is calculated as: 2.30

28

Cpij is calculated for each component in each phase using the equation:

1 2 3 4

2.31

Wherecpg1 through 4 are user-provided coefficients. Substituting eq. 2.31 into eq. 2.30 and integrating from Tref to T obtains H(T) (Tref is a user-provided reference temperature). The total phase enthalpy is calculated in the following manner:

2.32

This ideal mixing rule, which defines Hj in terms of individual Hij, and in turn T, is questionable, however currently there are no other options provided in the simulator used in this work. Lastly, there are no enthalpy calculations for the solid phase and the rock matrix as they do not flow. For the flowing phases, internal energy is calculated from: 2.33

Where P is the phase pressure and is the phase density (mass). For the solid phase, the solid phase heat capacity and a user-provided reference temperature: since there is no flow term, internal energy is simply calculated from user-provided , 2.34

29

Lastly, the simulator calculates the rocks internal energy on a volume basis as: 1 2 2.35

Where a and b are user-provided parameters. From the above definitions, we see that fluid enthalpies, solid-phase internal energy, and rock internal energy are readily converted into terms that are dependent on temperature. We now convert specific internal energy of a fluid phase into enthalpy, so that all energy terms can be expressed in terms of temperature. We start by substituting eq. 2.33 into eq. 2.9 to arrive at: 1

2.36

If no capillary forces are included, the phase pressures are equal and, therefore,
. Since the sum of saturations over all fluid phases equals 1, the

expression reduces to , and the internal energy E can be expressed as:

2.37

In this form all fluid phase internal energy terms are expressed in terms of enthalpy, which can be written in terms of temperature. Us and Ur can also be written in terms of temperature using eq. 2.34 and 2.35.

30

2.2.8 Thermal conductivity While the enthalpy is needed to describe energy convection, the thermal conductivity is needed to express the thermal conduction, .The thermal conductivity of each phase is 1

provided by the user. An internal mixing rule is then used to calculate K:

2.38

While other more complex mixing rules are available, this simple mixing rule was chosen for the preliminary numerical simulations. The more complex mixing rules will be explored in future work.

2.2.9 Specific heat of reaction Lastly, the specific heat of reaction, which appears in the G term in eq. 2.12 above, needs to be provided by the user for the individual reactions.

2.3 Dimensionless equations While it is important to fully understand how the simulator solves a problem, it is equally important to understand how to interpret the results. To facilitate the interpretation of the simulation results, we now convert the equations presented in section 2.1 into their dimensionless forms, so that results can be reported and compared in more general way.

31

2.3.1 Introduction of characteristic values First, we present a general version of the dimensionless equations. Assuming a characteristic length lo for our system, we define dimensionless lengths (for a cylindrical coordinates system) as follows: ;

2.39

Substituting the above definitions into the del operator we obtain:

Then, we can define a dimensionless , as follows:

2.40

Next, given a characteristic velocity vo , we define a dimensionless velocity as: 2.41

Using vo, we can also make time dimensionless as: 2.42

32

 . Lastly, we define a characteristic density, , and a characteristic activation energy, From these characteristic values we then define the following dimensionless terms: 2.43

2.44

2.3.2 Dimensionless mass-conservation equations We now return to our general mass conservation equations: 1, . . . ,

2.1

we can rewrite Eq. 2.1 in the following form

1, . . . ,

2.45

with

1, . . . ,

2.46

and

1, . . . ,

2.47

We introduce the Peclet number for mass transfer defined by 2.48

33

As well as a characteristic activation energy given by

2.49

Where To is a characteristic temperature. Finally, we introduce the Damkhler number for reaction k as

2.50

To arrive at a set of dimensionless mass conservation equations in the form 1 1, . . . ,

2.51

In this work, we focus on Dak for the coke oxidation reaction (Dacb) and Dak for the coke forming (pyrolysis) reaction (Dacf).

2.3.3 Dimensionless energy equation Having made the mass conservation equations dimensionless, we perform the same manipulations for the energy conservation equation:

2.8

34

term, G is the heat generation due to the reactions, and L is the heat loss to surroundings.

represents the enthalpy flow, In eq. 2.8, E is the internal energy, is the heat conduction

In analogy to the mass conservation equations, we expand the individual terms, and define the combined energy density as (see section 2.12) 1

2.9

As with the mass conservation equations, we introduce dimensionless variables and rewrite the dimensionless energy density as: 1

2.52

By introducing , a characteristic enthalpy and define: 2.53

and Similarly we define as:

2.54

2.55

35

2.56

Combining all the terms we find:

2.57

Which reduces to 1

2.58

Finally, we can define a Peclet number for heat transfer as 2.59

where Ko is the conductivity of the rock, T1 is a characteristic reaction temperature, To is a characteristic ambient temperature, and Ho is the enthalpy of the injection stream. This allows us to arrive at the final form of the dimensionless energy conservation equation. 1 1

2.60

36

The reference (base) values of the various dimensionless groups were obtained by the following considerations: We choose a characteristic length,
lo ,

to represent the inter-well

distance of 100 m. The value of dispersivity is provided by (Lake,1989), 0.3 , value of California dolomite(Sarathi, 2009) and an observed lab-scale

which results in 333. The characteristic rock conductivity is based on the average

conductivity(Belgrave et al., 1990), Ko = 70 J/m-min. The two reference temperatures (To and Ta) are selected as 600 K for To, representing a temperature at the combustion front, and 298 K for Ta, a temperature that represents the surface conditions. The characteristic velocity is defined as the maximum surface injection rate, multiplied by the characteristic length and divided by the pore volume 0.2727

2.61

The characteristic density and enthalpy are the air density and enthalpy at surface conditions, (1 atm, 290 K) resulting in 1.18 , 481 . Since reservoir

conditions are constantly changing, surface conditions were used to ensure constant

values were chosen to determine the Damkhler numbers. For both the coke oxidation and formation reactions, the characteristic activation energy is set at To, the reference temperature at the combustion front. For the coke burning reaction (4), the coke density was chosen as a reference concentration, and the partial pressure of O2 was chosen to be that in air at atmospheric conditions, in order to be consistent with the other characteristic terms that involve gases (density, enthalpy, and velocity). For the coke forming reaction

characteristic values. This results in 25.2. Finally, the following characteristic

37

(2), the asphaltene density was chosen as a reference concentration. These selections result in Dacb = 14,840, and Dacf= 2,740

38

Chapter 3: Modeling ISC in a 1-D Combustion Tube 3.1 The model The first task of this research was to simulate a set of combustion-tube experiments. Our simulations followed on the steps of an earlier publication by Belgrave et al. (1990). Their publication is one of very few that utilizes a complete reaction network for the ISC including pyrolysis, HTO and LTO reactions. In addition, the model parameters utilized by Belgrave et al. (1990) were shown to substantially reproduce the observations from a prior combustion tube experiment (Hayashitani, 1978). As noted previously, the original set of HTO reactions of Belgrave et al. (1990) was modified by adding a reaction accounting for the burning of the crude oil (in the original model, the only HTO reaction included was the burning of coke), as Belgrave et al. (1990) had also recommended (as a step to improve their model). In principle, for a well-designed ISC processes, HTO reaction of the crude oil should not be necessary. In such a process, as previously described, injected oxygen must first traverse the burning zone (zone 2, Figure 1-1) before ever reaching the oil. In the burning zone high coke concentrations and temperature promote HTO reactions between the coke and the oxygen, are expected to consume virtually all the oxygen thus never allowing it to reach the oil zone (Figure 1-1). However, for ISC processes operating under sub-optimal conditions this may not be the case, so to account for this in this work, HTO oil combustion reactions were included into the model for completeness.

39

To the best of the our knowledge, no oil burning kinetics was ever published for the specific crude oil that was investigated by Belgrave et al., and therefore parameters for this HTO reaction had to be estimated. We assumed that the stoichiometry of the HTO reactions, whether for coke or oil, should still follow that of eq. 1.7. In addition, we assume the CO2/CO ratio for the oil HTO reaction to be identical to the coke HTO reaction, namely 8.94. Activation energy and frequency factors were estimated based on oil oxidation parameters presented by Coats, (1984) by fitting the oil fractions presented by Belgrave et al. (1990) based on their molecular weight.

3.2 Oil composition The study by Belgrave et al. (1990) simulates the experiments reported in the PhD dissertation of Hayashitani(1978). Their model employs two components to describe an Athabasca Bitumen, namely a light maltene fraction, and a heavy asphaltene fraction. This was based on the fractions separated via filtration by Hayashitani using n-pentane to separate the maltenes in the bitumen from asphaltenes and coke, followed by using benzene to separate asphaltenes from coke. In addition to the two oil components and coke, the ISC model includes water, CO2, CO, O2 and N2. Coke is commonly reported simply as CHx. Belgrave et al. (1990) used a C:H ratio of 1:1.13, and we ourselves model coke as CH1.13.

Water is the system results in two different ways. There is water initially in the porous media (known as connate water) and water that is formed as a combustion product. The simulator makes no distinction in the properties of the two different types of water. Air is

40

described as a mixture of O2 and N2, and is injected into the system via the injection wells. CO2 and CO are formed by the ISC process. As mentioned before, H2S and NOx and light hydrocarbons are also produced, however, we know of no prior studies that explicitly include these components in the calculations. For example, the study of Belgrave et al. (1990) accounts for the production of CO2 (which occurs in the HTO reaction) but lumps all other gases that may form (e.g., CH4 and H2S) into a single component, namely CO. Since the production rate of CO is much larger than the production rate of CH4 and H2S(Sarathi, 1999), lumping them together into a single component appears to be a reasonable approximation. The fraction of CO that is formed (vs. CO2) in the HTO reaction is small, namely 1:8.94, so in fact the vast majority of the gas that forms is CO2. In our own study (since we assume that we only recycle the CO2) we have also followed the convention of Belgrave et al. (1990), lumping all gases formed into CO. The components and their properties are summarized below in Tables 3-1 through 3-4.
Pcrit kPa 22107 792 1478 7376 3496 5046 3394 Tcrit K 647 1177 892 304.2 132.9 154.6 126.2 MW kg/mol 0.018 1.0928 0.4067 0.04401 0.02801 0.031999 0.028013 0.01313 Mass Density kg/m3 1000 1158 983.2 984.84 788.6 1141 808.607 1280

H 2O Asphalt Maltene CO2 CO O2 N2 Coke (solid)

Table 3-1. Component Properties: Critical Properties, Molecular Weight and Density

41

H 2O Asphalt Maltene CO2 CO O2 N2 Coke

Liquid Viscosity AVISC cp BVISC C 0.00752 1384.86 4.89E-25 33147 1.94E-05 5369.2 0.044126 578.08 0.146092 94.06 0.189439 85.68 0.141269 90.3

Enthalpy J/mol oC at 100 oC 1800 2516.267 994.7837 25.531 16.247 18.568 16.247

K value correlation KV1 kPa KV4 C 1.18E+07 -3.82E+03 0 0 1.42E+08 -6.56E+03 8.62E+08 -3103.39 2.32E+05 -530.22 6.55E+05 -734.55 4.16E+05 -588.72

KV5 K 4.61E+01 0 1.93E+02 0.16 13.15 6.45 6.6

Table 3-2. Component Properties: viscosity enthalpy and K values

Note that only a gas-liquid K-value correlation was provided and no liquid-liquid K-value table was provided. We chose not to estimate our own liquid-liquid K-value table, but rather only allow gases to only dissolve in the oil phase: It is reasonable to neglect gas solubility in the aqueous phase due to the high temperature associated with ISC processes.

3.3 Relative permeability tables The relative permeability tables provided by Belgrave et al. (1990) for their experiments are presented below in Tables 3.3 and 3.4 and Figures 3.1 and 3.2.These curves are very atypical and are based on history matching of an initial gas flooding/pressurization step before ignition. Belgrave et al. (1990) explained that the very low values of gas and water relative permeabilities were required to respectively obtain high enough oil production and to limit calculated water produced during this displacement period. While the values and methodology are somewhat questionable, we still wish to reproduce their work as closely as possible and therefore retained their relative permeability model.

42

Sw 0.05 0.1 0.15 0.25 0.35 0.45 0.65 0.75 0.85 0.95 1

krw 0 0.00039 0.00156 0.00625 0.01406 0.025 0.03906 0.05625 0.07656 0.1 0.12656

krow 1 0.88581 0.77855 0.58478 0.41869 0.28028 0.08651 0.03114 0.00346 0 0

Table 3-3. Relative Permeability: water-oil

1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 0.2 0.4 Sw krw krow 0.6 0.8 1

Figure 3-1.Water-oil relative permeability

kr

43

Sl 0.07 0.16 0.21 0.31 0.41 0.51 0.61 0.71 0.8 0.95 1

Krg 0.1 0.08615 0.06632 0.03711 0.01881 0.00829 0.00296 0.00073 0.00011 0 0

Krog 0 0.00316 0.01262 0.0505 0.11362 0.20199 0.31562 0.45449 0.6 0.8908 1

Table 3-4. Relative Permeability: liquid-gas

1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 0.2 0.4 Sl krg krog 0.6 0.8 1

Figure 3-2. Gas-liquid relative permeability

3.4 Reaction kinetics The reactions used in this work are divided into 3 classes: pyrolysis, HTO, and LTO. The pyrolysis reaction consists of 3 steps:

kr

44

1 Maltenes 0.372 Asphaltenes 1 Asphaltenes 83.223 Coke 1 Asphaltenes 37.683 Gas

3.1 3.2 3.3

Belgrave et al. (1990) reported a good agreement between this model and the experimental work done by Hayashitani (1978). This model was converted to a STARS input deck with the exception that non-CO2 gases were lumped into CO. Belgrave et al. (1990) report the molecular weight for the gas produced from cracking to be 29 g/mol. This gas is most likely a combination of CH4 and C2-type hydrocarbons (with molecular weights of 16 and 32 for ethane, respectively). However, since we are not cycling this portion of the gas, it was lumped into CO for simplicity. The reaction rate expressions, the rate constants, and the corresponding enthalpies are reported below in Tables 3-5 and 3-6.
Reaction number 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 Enthalpy Joules/mole 0 0 0 1300000 2860000 428000 38030000 14540000 Pre-exponential constant Units 1/min 1/min 1/min (1/kPa)0.4246/min (1/kPa)4.7627/min (1/kPa)/min (mol/m3) -1/min (mol/m3)-1/min Activation energy J/mol -177000 -235000 -176000 -86700 -186000 -34800 -137000 -137000

Value 2.44E+11 5.46E+14 8.17E+10 7.69E+06 2.48E+06 3.72E-03 8.35E+08 6.90E+07

Table 3-5. Reaction rates and enthalpies

45

Reaction number 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8

Concentration factors phi * So * densityo * x(Asphalt) phi * So * densityo * x(Maltene) phi * So * densityo * x(Asphalt) phi * So * densityo * x(Maltene)* (Pg * y(O2)) 0.4246 phi * So * densityo * x(Asphalt)* (Pg * y(O2)) 4.7627 Pg * y(O2)* phi * solidconc(Coke) phi * So * densityo * x(Asphalt)* phi * Sg * densityg * y(O2) phi * So * densityo * x(Maltene)* phi * Sg * densityg * y(O2)

Table 3-6. Reaction concentration factors There are three HTO reactions included in our model. The first represents the coke burning reaction of Belgrave et al. (1990). The second and third reactions represent the complete oxidation of maltene and asphaltene. The stoichiometric values for these reactions were estimated from the data reported by Coats (1984), based on HTO reactions with components of similar molecular weights. The three reactions are: 1 Coke 1.232 O 0.899 CO 0.1003 CO 0.565 H O 1 Asphaltene 102.6 O 74.87 CO 8.356 CO 47.02 H O 3.4 3.5 3.6

1 Maltene 38.17 O 27.85 CO 3.108 CO 17.49 H O

The reaction rates and enthalpies are also reported in Tables 3-5 and 3-6 above. Finally, there is a two-step LTO reaction that results in the creation of asphaltenes from maltenes and coke from asphaltenes. These reactions are considered oxygen additive, and thus no significant amount of gases is formed. Belgrave et al.(1990) make the assumption that partially oxygenated asphaltene and coke behave the same way as these formed during pyrolysis. They claim that in their experiments, that cracking of pre-oxygenated bitumen does not regenerate oxygen. While the author is not completely convinced of the validity of modeling coke and partially oxygenated coke as the same component, he wishes to 46

stay consistent with one model, and has decided to maintain the proposed reaction stoichiometry for the LTO reactions. The two reactions then are: 1 Asphaltene 7.513 O 101.537 Coke 1 Maltene 3.431 O 0.4726 Asphaltenes 3.7 3.8

The reaction rates are included in Tables 3-5 and 3-6 above as well.

3.5 System dimensions The simulation replicates the dimensions and initial conditions provided by Belgrave et al. (1990), representing a combustion process in a vertical tube of length 1.83 m and diameter 0.0994 m. Because the system is represented by a 1-D model, the crosssectional area of 0.0078 m2 was created by x and y dimensions of 0.0881 m. The 1.83 m vertical direction is represented by 200 grids-blocks, each representing a length of 0.00915 m. In addition, in the x direction, zero porosity grid-blocks of variable width were added on both sides of the porous media. These impermeable sections were used to simulate heat loss to the surroundings. The model can accordingly be used to simulate adiabatic and non-adiabatic processes. In the adiabatic case, the impermeable section of the model has the thermal conductivity set to zero, while in the non-adiabatic case, the impermeable zone has the thermal conductivity set to 100 W/mK, the same value as the porous section. Figure 3-1 below illustrates the system, and Table 3-7 summarizes the parameters used in the simulations. Note that the permeability of 1200 mD is somewhat high for a reservoir, but is common for laboratory work with unconsolidated porous materials.

47

3.6 Initial settings The pressure in the combustion tube was initially set at 4100 kpa. There are four initial temperatures representing four different zones. The initial temperature of the porous zone is 100 oC. There are two different temperature regions for the impermeable section, a far and a near region. In the near region, the initial temperatures is 67 oC, having felt some effect from the elevated temperature of the porous zone; in the far region initial temperatures is 32 oC, which is considered ambient subsurface conditions. The last zone is the heated zone. The temperature of the first 5% of the porous medium is initially set to 500 oC. This is in order to simulate electrical heating that is necessary to initiate the combustion process. A wide range of initial temperatures were tested. While the behavior of the system was never identical, the qualitative results were similar for all but the most extreme cases.

Length Width and depth Cross sectional area Porosity (primary zone) Total volume Pore volume Axial grid blocks Initial water saturation Initial oil saturation Initial gas saturation Pressure Initial mole frac. Maltene Initial mole frac. Asphaltene Volumetric heat capacity Thermal Conductivity Permeability Initial injection rate

1.83 0.0881 0.00776 0.412 0.014201 0.005857 200 0.118 0.882 0 4100 0.9151 0.0849 2.28E+06 100 1200 0.004

M M m2 m3 m3

kPa

J/(m3oC) J/m-min-K mD m3/min

Table 3-7. System properties

48

Injector 0.0881 meters 1.313 meters

0.0881 meters

Heated zone 500 C

1.83 meters

Zero porosity zone, far 32 oC Figure 3-3. Schematic of the model system 3.7 Well settings

Zero porosity zone, close 67 oC

Ambient zone 100 oC Producer

There are two wells in our 1-D system, an injector and a producer well. The injector is located at the top of our system and the producer well at the bottom. The initial gas injected is air: 21% O2, 79% N2. The injector operates at a constant gas injection rate of 0.004 m3/min at surface conditions for the non-adiabatic scenario, and at 0.000933 m3/min for the adiabatic scenario. A higher injection rate is needed for the non-adiabatic scenario in order to sustain a high-temperature front. However, using the same injection rate for the adiabatic scenario resulted in igniting the tube, and thus the injection rate was reduced. No water or oil is injected. The producer operates at constant pressure of 4100

49

kPa, the initial pressure of the tube. We also used a constant well index (see Eq. 2.29)of Iwell=5.54for both wells.

50

Chapter 4: The Effects of CO2 Recycling in an 1-D Combustion Tube

4.1 Overview of simulations This chapter presents the initial investigation of the feasibility of CO2cycling for the 1-D combustion tube case. Four series of numerical experiments were conducted in order to study the potential for recycling of CO2 in ISC processes. These experiments are as follows: 1. Adiabatic system, recycle CO2 by replacing a portion of the injected air net injection rate constant. 2. Adiabatic system, recycle CO2 by adding it to the injected air net air injection rate constant. 3. Non-adiabatic system, recycle CO2 by replacing a portion of the injected air net injection rate constant. 4. Non-adiabatic system, recycle CO2 by adding it to the injected air net air injection rate constant.

For each of the four series of simulations, five different cases were investigated. First, a simulation of a standard ISC process was performed to serve as a reference point. Four additional simulations were then performed whereby 30%, 50%, 70%, and 90% of the produced CO2 was recycled. The results reported in this section are in terms of the oil recovery and the net CO2 produced.

51

4.2 Definitions used in the numerical experiments We first define the key quantities that we will use in order to gauge the process performance in the various modes of operation. The total volume in the system is 0.0142 m3 and the total pore volume is 0.00585 m3. With an initial oil saturation of 0.882, the total volume of oil is 0.00493 m3. This volume of oil is denoted as the initial oil in place. The recovery of oil will be reported as the volume of oil produced relative to the initial oil in place: Volume of oil produced Original oil in place

Due to the low compressibility of the crude oil used in our model, the volumes of oil produced at reservoir conditions (RC) and surface conditions (SC) are almost identical and a single definition of Ro is sufficient. Volumetric CO2 production, on the other hand, varies greatly based on whether it is measured at SC or RC. To avoid confusion, CO2 production will, therefore, be reported in moles. Lastly, the dimensionless time, , will

be reported in terms of pore volumes injected (PVI).

time, is volumetric injection well rate at SC (101 kPa and 290 K) and Vtotal is the

, where t is standard

total pore volume. In practice it is easiest to measure the cumulative as follows:

Total gas volume injected at STD Pore volume of the reservoir

It is important to clarify that the definition of PVI used here is in terms of volume at surface condition. The standard practice would be to report PVI at reservoir conditions. However, because in the ISC process the temperature and pressure of the system change, 52

reservoir conditions vary with time and location. Therefore, for consistency, we report the PVI at surface conditions.

4.3 The standard in situ combustion process: Adiabatic conditions Utilizing the definitions of section 4.2, we examine first the results from the standard ISC process without recycling of any of the produced CO2. In the adiabatic case, air was injected at 0.000933 m3(0.157 PVI)/min continuously until the temperature front reached the production well. The calculated oil production is first reported in Figure 4-1, and later in terms of recovery factor in Figure 4-4. In Figure 4-1 we note that a high rate of oil production is observed at early times. This is a very typical behavior before breakthrough. After approximately 240 min, we observe a drop in production rate corresponding to the time where gas breaks through to the production well. At that point, a large fraction of the total volume produced is gas, and thus the oil production rate is reduced. For gas recycling runs, this is where the measurement of gas production rate begins and the CO2 recycling is initiated.

53

0.005 Volume Oil Produced (m^3) 0.004 0.003 0.002 0.001 0 0 500 1000 1500 Time (min) 2000 2500

Figure 4-1. Cumulative oil produced for a standard ISC simulation under adiabatic conditions We see from Figure 4-1 that approximately 2,500 min are needed to complete the displacement process (when the combustion front reaches the producer). The volume of oil produced at the end of the run is 0.00475 m3. Since the initial oil in place was 0.00493 m3, the recovery factor of oil, Ro, at this point is 0.9635. Of the un-recovered fraction of oil, 0.46% still remains in the reservoir and the rest, a little more than 3%, was consumed by the combustion front and converted into heat and gaseous products that either have been produced alongside with the oil or remain in the pore space. This initial result provides evidence that the standard ISC process is highly effective, since only a small fraction of the oil is being consumed by the reactions and very little residual oil remains in the system, although the losses will increase for systems of higher dimensionality (see further discussions in this Thesis). To verify that ISC is, indeed, initiated and maintained, we report the temperature profiles and solid fuel (coke) deposition profiles in Figures 4-2 and 4-3.

54

1000 Temperature (K)

800

600

400 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 Distance from injector (m) T at 600 min T at 1200 min T at 1800 min

Figure 4-2. Temperature profiles for a standard ISC process at adiabatic conditions

Coke conc. (gmole/m^3)

3000

2000

1000

0 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 Distance from injector (m) Coke Conc. at 600 min Coke Conc. at 1200 min Coke Conc. at 1800 min

Figure 4-3. Coke concentration profiles for a standard ISC process at adiabatic conditions

Figures 4-2 and 4-3 verify that the ISC process is taking place, as expected. A hightemperature peak develops due to the HTO reactions. Downstream of the temperature peak, coke is produced in what is zone 3 (Figure 1-1), the intermediate temperature coking zone. It is important to note, that all the coke is reacted with oxygen. For example, 55

after 1,800 min, aside from the coke peak generated in zone 3, no coke is found throughout the system as it is consumed in the HTO zone 2 immediately preceding zone 3. These results demonstrate that we have established a benchmark of a typical ISC process under adiabatic conditions. We proceed next by reporting dimensionless data for the oil production in terms of the oil recovery factor and the CO2 production in net moles of CO2produced, (Figures 4-4 and 4-5), standardizing them for comparisons with the subsequent CO2 recycling simulation runs.

1 Ro, fraction oil recovery 0.8 0.6 0.4 0.2 0 0 50 100 150 200 250 300 350 400 450 td, Pore volumes injected

Figure 4-4. Oil recovery factor for a standard ISC process at adiabatic conditions.

56

Net moles of CO2 produced

14 12 10 8 6 4 2 0 0 50 100 150 200 250 300 350 400 450 td, pore volumes injected

Figure 4-5. Net moles of CO2 produced for a standard ISC process at adiabatic conditions. From Figures 4-4 and 4-5 we see that the discontinuity in the oil recovery curve does, indeed, correspond to the breakthrough and production of CO2. Breakthrough occurs at approximately 26 PVI.

4.4 Series 1: CO2 recycling with a constant total injection rate in an adiabatic setting We now examine the effects of CO2 recycling in the combustion tube. In the first series of simulations, we explore the effects of recycling 30%, 50%, 70%, and 90% of CO2 in lieu of air, under adiabatic conditions. Recycling is conducted by monitoring the production rate of CO2 and changing the injection conditions to include the recycled CO2. In the case of recycling CO2 in lieu of air, the total injection rate is kept constant and the molar fraction of air is lowered to accommodate the added CO2. In Figures 4-6 through 4-9, we report the oil recovery and net CO2 production. A comparison of cumulative oil production and net CO2 production at various PVI is given in Table 4-1. 57

Ro, Fraction oil recovered

1 0.8 0.6 0.4 0.2 0 0 50 100 150 200 250 300 350 400 450 500 td, pore volumes injected Std ISC 30% CO2 50% CO2

Figure 4-6. Comparison of Ro for 30% and 50% CO2 recycle in lieu of air with the standard ISC process at adiabatic conditions.

Ro, Fraction oil recovered

1 0.8 0.6 0.4 0.2 0 0 50 100 150 200 250 300 350 400 450 500 td, pore volumes injected Std ISC 70% CO2 90% CO2

Figure 4-7. Comparison of Ro for 70% and 90% CO2 recycle in lieu of air with the standard ISC process at adiabatic conditions.

58

Net moles of CO2 produced

14 12 10 8 6 4 2 0 0 100 200 300 400 500 td, pore volumes injected

standard ISC 30% recycle 50% recycle `

Figure 4-8. Comparison of net moles of CO2 produced for 30% and 50% CO2 recycle in lieu of air injection with the standard ISC process at adiabatic conditions.

Net moles of CO2 produced

14 12 10 8 6 4 2 0 0 100
standard ISC

200
70% recycle

300

400
90% recycle

500

td, pore volumes injected

Figure 4-9. Comparison of net moles of CO2 produced for 70% and 90% CO2 recycle in lieu of air injection with the standard ISC process at adiabatic conditions.

59

Table 4.1 reports Ro and the net moles of CO2 produced at 210, 280, and 350 PVI. This covers the latter half of the operation timeline. We are most interested in this portion of the process as the effects of CO2 recycling are more evident.
Run Standard ISC 30% recycle 50% recycle 70% recycle 90% recycle Ro 0.64 0.63 0.62 0.61 0.59 net moles of CO2 produced 6.6 6.1 5.4 4.4 2.5 % Ro compared with standard ISC 100% 98 % 97% 95% 92 % % net moles of CO2 compared with Std. ISC 100% 91% 82% 67% 37%

Table 4-1a. Comparison of Ro and net moles CO2 for recycle of CO2 in lieu of air under adiabatic condition at 210 PVI

Run Standard ISC 30% recycle 50% recycle 70% recycle 90% recycle

Ro 0.78 0.77 0.75 0.73 0.70

net moles of CO2 produced 9.0 8.3 7.6 6.2 3.4

% Ro compared with standard ISC 100% 98 % 96 % 93% 89 %

% net moles of CO2 compared with Std. ISC 100% 92% 83% 68% 38%

Table 4-1b. Comparison of Ro and net moles CO2 for recycle of CO2 in lieu of air under adiabatic conditions at 280 PVI
net moles of CO2 produced 11.4 10.6 9.6 8.0 4.4 % Ro compared with standard ISC 100% 98.1% 96.4% 93.0 % 87.3% % net moles of CO2 compared with Std. ISC 100% 92.6% 84.4% 70.0% 38.9%

Run Standard ISC 30% recycle 50% recycle 70% recycle 90% recycle

Ro 0.90 0.89 0.87 0.84 0.80

Table 4-1c. Comparison of Ro and net moles CO2 for recycle of CO2 in lieu of air under adiabatic conditions at 350 PVI As expected, Ro is reduced as the amount of CO2 that is recycled is increased. However, under adiabatic conditions, regardless of the fraction of CO2 that is recycled, the reduction in produced CO2 is always greater than the reduction in Ro. At all times, the 60

30% and 50% recycle cases show a reduction in both Ro and net moles of CO2produced. However, at 280 PVI, the reduction in oil production is only 2% and 4 % respectively while the reduction in net moles CO2 produced is 8% and 16.5% respectively. For lower recycling rates (30% and 50%) the ratio between reduction in oil production and the reduction in CO2 produced, , is approximately 1:4, a very promising result. When recycling reaches 70% and 90%, we see an increase in the reduction of CO2 produced. Again, after 280 PVI, the reduction in oil production is 7% and 11%, and correspondingly the reduction in CO2 produced is 31% and 61% for 70% and 90% recycle, respectively. As we increase the amount of CO2 that is recycled, increases from 1:4.5 at 70% recycle to 1:5.5 at 90% recycle. These initial results for an adiabatic ISC process show that virtually all the CO2 can be recycled, and that a relatively small fraction of the oil remains un-recovered in the porous media.

While the behavior tends to not vary much between the 3 selected times, a consistent trend is observed, namely that the improvement in performance diminishes as the PVI increases. Regardless of the amount of CO2 that is recycled, as operation time increases, the oil production rate decreases while the rate of CO2 production increases. This is something to keep in mind as we discuss further the trends of the various operation modes.

This first series of numerical experiments provides a positive initial result. We observe that in an adiabatic combustion tube displacement process we are able to sequester a large amount of the CO2 with a relatively small reduction in oil production. That is not to say

61

that operation should always take place at 90% recycle. Maximizing the oil production is still the priority, and recycling needs only to sequester enough CO2 to meet the environmental regulations. In addition, other available sites may be available to sequester CO2as well. As mentioned in the introduction, deep saline aquifers, light oil reservoirs and gas reservoirs are all potentially alternate candidates for storing any produced CO2. However, these alternate candidates may not be available within a reasonable distance. A key additional observation from these initial numerical experiments is that in adiabatic 1D ISC processes, recycling even a large fraction of CO2 does not extinguish the combustion front.

4.5 Series 2: CO2 recycling with increased total injection rate in an adiabatic setting In a second series of numerical experiments at adiabatic conditions, CO2 is also being recycled at levels of 30%, 50%, 70% and 90% of the produced amount. In this case, however, the recycled CO2 is added to the injection stream, and the total injection rate increases. Therefore, the rate of air injection is constant throughout the numerical experiments; however, due to the addition of CO2, the mole fraction of oxygen in the injection stream is still lower. To compare this mode of operation with that of the previous section, we present a similar sequence of numerical experiments. Figures 4-10 through 4-14, show the oil recovery and net CO2 production as a function of PVI. A quantitative comparison of cumulative oil production and net CO2 production is reported in Table 4-2.

62

Ro, fraction oil recovery

1 0.8 0.6 0.4 0.2 0 0 50 100 150 200 250 300 350 400 450 500 td, pore volumes injected Standard ISC 30% recycle 50% recycle

Figure 4-10. Comparison of Ro for 30% and 50% CO2 recycle in addition to air injection with the standard ISC at adiabatic conditions.
1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 100 200 300 td, pore volumes injected
Standard ISC 70% recycle 90% recycle

Ro, fraction oil recovery

400

500

600

Figure 4-11. Comparison of Ro for 70% and 90% CO2 recycle in addition to air injection with the standard ISC at adiabatic conditions.

63

Net moles of CO2 produced

14 12 10 8 6 4 2 0 0 100 200 300 400 500 td, pore volumes injected

standard ISC 30% recycle 50% recycle

Figure 4-12. Comparison of net moles of CO2 produced for 30% and 50% CO2 recycle in addition to air injection with the standard ISC at adiabatic conditions.

Net moles of CO2 produced

14 12 10 8 6 4 2 0 0 100 200 300 400 500 td, pore volumes injected

standard ISC 70% recycle 90% recycle

Figure 4-13. Comparison of net moles of CO2 produced for 70% and 90% CO2 recycle in addition to air injection with the standard ISC at adiabatic conditions. Ro and net moles of CO2 produced are tabulated in Table 4.2 below for the same dimensionless times as series 1, namely 210, 280 and 350 PVI. 64

Run Standard ISC 30% recycle 50% recycle 70% recycle 90% recycle

Ro 0.64 0.63 0.61 0.60 0.58

net moles of CO2 produced 6.6 6.0 5.4 4.5 2.9

% Ro compared with standard ISC 100% 97% 95% 93% 90%

% net moles of CO2 compared with Std. ISC 100% 92% 83% 68% 44%

Table 4-2a. Comparison of Ro and net moles CO2 produced for recycle of CO2 in addition to air at adiabatic conditions at 210 PVI

Run Standard ISC 30% recycle 50% recycle 70% recycle 90% recycle

Ro 0.78 0.76 0.74 0.71 0.68

net moles of CO2 produced 9.0 8.3 7.6 6.3 4.0

% Ro compared with standard ISC 100% 98% 95% 91% 87%

% net moles of CO2 compared with Std. ISC 100% 93% 84% 70% 45%

Table 4-2b. Comparison of Ro and net moles CO2 produced for recycle of CO2 in addition to air at adiabatic conditions at 280 PVI

Run Standard ISC 30% recycle 50% recycle 70% recycle 90% recycle

Ro 0.90 0.89 0.86 0.83 0.78

net moles of CO2 produced 11.4 10.6 9.7 8.0 5.1

% Ro compared with standard ISC 100% 97% 95% 91% 86%

% net moles of CO2 compared with Std. ISC 100% 93% 85% 70% 45%

Table 4-2c. Comparison of Ro and net moles CO2 produced for recycle of CO2 in addition to air at adiabatic conditions at 350 PVI The results from the series 2 of simulations show similar trends to those of the series 1. At 280 PVI, Ro was 2.5%, 5%, 8.5%, and 13% lower for the 30%, 50%, 70% and 90% recycle cases, respectively, when compared to the standard ISC without recycle. In comparison, for series 1 they were 2%, 4%, 7% and 11% lower respectively. for the series 2 simulations remained fairly constant at 1:3.5, while for the series 1, ranged

65

from 1:4 to 1:5.5. While the trends are similar, the above results show that at adiabatic conditions it is generally more beneficial to operate by recycling CO2 in lieu of air than by adding produced CO2 to the injected air stream. Even though injection of CO2 in addition to air results in higher oil production rates, the increase in the injection rate can be on the order of 50-100% at 70% and 90% CO2 recycle, requiring proportionally increased compression costs. Also, during the operation of CO2 recycle as an add-on to air injection, one must be careful not to exceed the maximum injection rate possible in a given a well.

From the initial numerical experiments, it appears that CO2 cycling is capable of reducing net CO2 production in adiabatic processes. Whether the CO2 cycled replaces the air injected or is added to the injection stream, significant reductions in net CO2 production can be achieved. In both cases, at the same PVI as a standard ISC operation, an oil production penalty was incurred. This penalty, naturally, increased with increasing the CO2 recycle rate. In all modes of operation, a higher oil production rate and a lower net CO2 production rate are observed when CO2 is cycled in lieu of air. These results support that, under adiabatic conditions, it is preferable to inject air at the maximum well rate and recycle CO2 produced by replacing a portion of that air.

4.6 CO2 recycling with constant total injection rate under non-adiabatic conditions In the previous sections, we investigated the behavior of the ISC process under adiabatic conditions. In the following sections we investigate the more realistic, non-adiabatic case. For series 1 and 2, heat loss to the surrounding rocks was not included. In the next two

66

series of numerical experiments, the thermal conductivity in the impermeable zone is set equal to that of the primary zone, 100 J/m-min-K.

Initially the ISC process was investigated for the same injection rate as used in Series 1 and 2, namely 0.000933m3/min (0.157PVI/min). Figure 4-14 compares the oil production and temperature profiles for the adiabatic and non-adiabatic processes. It is clear, that when heat loss is included in the simulations, the temperature front is not sustained, and as a result the recovery of oil is greatly diminished.
1 Ro, recovery fraction 0.8 0.6 0.4 0.2 0 0 100 200 300 400 500 600 700 800 900 1000 td, pore volumes injected Non-Adiabatic Std. ISC Adiabatic Std. ISC

Figure 4-14a. Comparison of Ro between the non-adiabatic and the adiabatic standard ISC for an injection rate of air of 0.000933 m3/min (0.157 PVI/min).

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900 Temperature K 800 700 600 500 400 300 0 0.05 0.1 0.15 0.2 Distance, x/L Non-adiabatic Temp. at 28 PVI Adiabatic Temp. at 28 PVI Non-adiabatic Temp. at 192 PVI Adiabatic Temp. at 192 PVI 0.25 0.3 0.35 0.4

Figure 4-14b. Comparison of temperature profiles between non-adiabatic and adiabatic standard ISC at injection rate of air of 0.000933 m3/min (0.157 PVI/min). The temperature profiles in Figure 4-14b show that a zone of high temperature due to HTO reactions cannot be sustained under non-adiabatic conditions. At 192 PVI, while the adiabatic case has a temperature front that has already traveled 10% of the 1-D domain, no similar temperature front is sustained for the non-adiabatic case. The consequence of this is clear from Figure 4-14a, as production from the adiabatic process is much greater than that from the non-adiabatic process.

Based on these simulations, and in order to continue our numerical investigations, the initial settings were changed so that a standard ISC could proceed. Two cases were explored, either increasing the injection rate, or increasing the oxygen concentration in the injection stream. The fundamental idea behind both options is to deliver oxygen into the system more rapidly. First, we consider the impact of increasing the injection rate. A series of standard ISC processes at non-adiabatic conditions were simulated where the 68

injection rate was gradually increased. The cumulative oil recovery from these experiments is shown in Figures 4.15.

Figure 4-15. Comparison of oil recovery at various air injection rates in a non-adiabatic ISC process. From Figure 4-15, we see that an increase in injection rate can alleviate the production issue. At each incremental PVI/min, we see an improvement in the production rate. At an injection rate of 0.157 PVI/min, a combustion front is not developed, while for a rate of 0.342 PVI/min a small increase in temperature in the burning zone was observed (not shown here). The oil production is very low in both cases, however. At 0.512 PVI/min we appear to reach/exceed a threshold and a sustained ISC process is then observed. This can be observed from the relatively fast oil recovery at injection rates of 0.512 PVI/min and 0.681 PVI/min (0.003 m3/min and 0.004 m3/min) in Figure 4.15, as well as the temperature profiles (not shown here). Compared to the adiabatic case, this process, even with a four times higher injection rate, recovers oil slower on a PVI basis. While the

69

improvement from carrying out the ISC under adiabatic conditions is obvious, carrying out a field ISC process under adiabatic conditions is not a feasible mode of operation.

4.6.1 Non-adiabatic ISC processes at an increased injection rate of 0.512 PVI/min Having established that an air injection rate of .512 PVI/min is sufficient to sustain a combustion front, simulations with30%, 50%, 70%, and 90% of CO2 recycled were performed. Oil production rates and net CO2 production are shown in Figures 4.16-4.19, supplemented by a comparison of Ro and net moles of CO2 in Table 4-3.

0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 500 1000 1500 2000 2500 td, pore volumes injected Std ISC 30% recycle 50% recycle

Figure 4-16. Comparison of Ro for 30% and 50% CO2 recycle in lieu of air injection with the standard ISC at non-adiabatic conditions for an injection rate of 0.512 PVI/min.

Ro, fraction oil recovered

70

0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 500 1000 1500 2000 2500 3000 3500 4000 td, pore volumes injected Std ISC 70% recycle 90% recycle

Figure 4-17. Comparison of Ro for 70% and 90% CO2 recycle in lieu of air injection with the standard ISC at non-adiabatic conditions for an injection rate of 0.512 PVI/min.

Ro, fraction oil recovered

Net moles of CO2 produced

70 60 50 40 30 20 10 0 0 500 1000 1500 2000 2500 td, pore volumes injected standard ISC 30% recycle 50% recycle

Figure 4-18. Comparison of net moles of CO2 for 30% and 50% CO2 recycle in lieu of air injection with the standard ISC at non-adiabatic conditions for an injection rate of 0.512 PVI/min.

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Net moles of CO2 produced

70 60 50 40 30 20 10 0 0 500 1000 1500 2000 2500 3000 3500 4000 td, pore volumes injected standard ISC 70% recycle 90% recycle

Figure 4-19. Comparison of net moles of CO2for 70% and 90% CO2 recycle in lieu of air injection with the standard ISC at non-adiabatic conditions for an injection rate of 0.512 PVI/min. We note that the observations at 210, 280 and 350 PVI reported in Table 4-1 for the adiabatic settings are a poor choice in the non-adiabatic case as the total PVI required for the runs are significantly larger. Instead, data is reported at 875, 1225 and 1575 PVI, to more appropriately reflect the timeline of these runs.
Run Standard ISC 30% recycle 50% recycle 70% recycle 90% recycle Ro 0.58 0.56 0.55 0.55 0.54 net moles of CO2 % Ro compared with standard % net moles of CO2 compared produced ISC with Std. ISC 27.5 100% 100 % 25.4 97% 92% 23.3 95% 84 % 19.3 94% 70% 10.9 94% 39%

Table 4-3a. Comparison of Ro and net moles of CO2 for recycle of CO2 in lieu to air in at non-adiabatic conditions with an injection rate of 0.512 PVI/min at 875 PVI.

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Run Standard ISC 30% recycle 50% recycle 70% recycle 90% recycle

Ro 0.71 0.68 0.64 0.62 0.60

net moles of CO2 % Ro compared with standard % net moles of CO2 compared produced ISC with Std. ISC 39.4 100% 100.00% 36.6 95% 93% 33.5 90% 85% 28.7 86% 72% 14.3 84% 36%

Table 4-3b. Comparison of Ro and net moles of CO2 for recycle of CO2 in lieu to air at non-adiabatic conditions with an injection rate of 0.512 PVI/min at 1225 PVI.

Run Standard ISC 30% recycle 50% recycle 70% recycle 90% recycle

Ro 0.84 0.79 0.74 0.68 0.63

net moles of CO2 % Ro compared with standard % net moles of CO2 compared produced ISC with Std. ISC 50.6 100 % 100% 47.3 95% 94% 43.6 89% 86% 37.7 81% 75% 15.4 75% 31%

Table 4-3c. Comparison of Ro and net moles of CO2 for recycle of CO2 in lieu to air at non-adiabatic conditions with an injection rate of 0.512 PVI/min at 1575 PVI. The results from these non-adiabatic numerical simulations show similar trends as the adiabatic simulations at 30% and 50% CO2 recycle. For these two cases, we again see a linear behavior of ; however, the reduction in oil production is higher, resulting in a of 1:1 rather than 1:4. This is attributed to the combination of heat loss and reduced oxygen concentrations resulting in a lower temperature in the non-adiabatic cycling scenario. The lower temperatures result in mixtures of coke and oxygen that are unable to ignite. Furthermore, unreacted oxygen travels through the burning zone and into the oil zone (Figure 1-1) causing excess LTO reactions, which increases the oil viscosity. The combination of these effects reduces the mobility of the oil much more than lowering the oxygen concentration would do alone (i.e., the adiabatic case).

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These effects are even more pronounced when 70% and 90% of the produced CO2 is recycled, with oil production rates dropping even more sharply. At a recycle rate of 70%, the burning zone is extinguished after 2,200 pore volumes are injected, while at a recycle rate of 90% this occurs after approximately 1,250 pore volumes are injected. The viscosity of the crude oil is greatly increased due to the LTO reactions causing a larger fraction of the oil to be left in the subsurface. In the 90% recycle scenario, the maximum recovery attainable is 0.75 after 1,575 PVI. This oil trapping behavior has been documented in DOEs In-Situ Combustion Handbook(Sarathi, 1999).

4.6.2 Operation of non-adiabatic ISC at an increased injection rate of 0.681 PVI/min Operating at 0.512PVI/min, 30% and 50% CO2 recycle caused moderate reduction in oil production. However, increasing CO2 recycle up to 70% and 90% resulted in dramatically lower oil production rates that we attribute this to the lack of a sustained burning front. To further study this effect, a second set of non-adiabatic ISC processes with CO2 recycling in lieu of air was conducted, this time at an increased injection rate of 0.681 PVI/min.

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Ro, fraction oil recovered

1 0.8 0.6 0.4 0.2 0 0 200 400 600 800 1000 1200 1400 td, pore volumes injected Std. ISC 30% recycle 50% recycle

Figure 4-20. Comparison of Ro for 30% and 50% CO2 recycle in lieu of air injection with the standard ISC at non-adiabatic conditions with an injection rate of 0.681 PVI/min.

Ro, fraction oil recovered

1 0.8 0.6 0.4 0.2 0 0 200 400 600 800 1000 1200 1400 td, pore volumes injected Std. ISC 70% recycle 90% recycle

Figure 4-21. Comparison of Ro for 70% and 90% CO2 recycle in lieu of air injection with the ISC at non-adiabatic conditions with an injection rate of 0.681 PVI/min.

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Net moles of CO2 produced

45 40 35 30 25 20 15 10 5 0 0 200 400
standard ISC

600

800
30% recycle

1000

1200

1400

td, pore volumes injected

50% recycle

Figure 4-22. Comparison of moles of CO2 for 30% and 50% CO2 recycle in lieu of air injection with the standard ISC at non-adiabatic conditions with an injection rate of 0.681 PVI/min.

Net moles of CO2 produced

45 40 35 30 25 20 15 10 5 0 0 200 400
standard ISC

600

800
70% recycle

1000

1200

1400

td, pore volumes injected

90% recycle

Figure 4-23. Comparison moles of CO2 for 70% and 90% CO2 recycle in lieu of air injection with the standard ISC at non-adiabatic conditions with an injection rate of 0.681 PV at RC/hr.

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At higher injection rates, the operation time is reduced as the combustion front travels faster through the porous material. Accordingly, Table 4.4 reports oil and CO2 productions at 875, 1,050, and 1,225 PVI.
Run Standard ISC 30% recycle 50% recycle 70% recycle 90% recycle Ro 0.70 0.67 0.65 0.63 0.62 net moles of CO2 % Ro compared with % net moles of CO2 compared with produced standard ISC Std. ISC 27.7 100% 100% 25.8 96% 92% 23.6 93% 85% 19.8 90% 71% 12.1 89% 43%

Table 4-4a. Comparison of Ro and net moles of CO2 for recycle of CO2 in lieu to air in an adiabatic system with an injection rate of 0.681 PVI/min at 875 PVI

Run Standard ISC 30% recycle 50% recycle 70% recycle 90% recycle

Ro 0.80 0.76 0.73 0.70 0.69

net moles of CO2 % Ro compared with % net moles of CO2 compared with produced standard ISC Std. ISC 33.8 100% 100% 31.6 95% 93% 28.9 91% 85% 24.3 86% 71% 14.6 86% 43%

Table 4-4b. Comparison of Ro and net moles of CO2 for recycle of CO2 in lieu to air in an adiabatic system with an injection rate of 0.681 PVI/min at 1050 PVI

Run Standard ISC 30% recycle 50% recycle 70% recycle 90% recycle

Ro 0.88 0.85 0.81 0.77 0.77

net moles of CO2 % Ro compared with % net moles of CO2 compared with produced standard ISC Std. ISC 39.3 100% 100% 36.8 96% 93% 33.9 92% 86% 28.5 86% 72% 16.9 87% 43%

Table 4-4c. Comparison of Ro and net moles of CO2 for recycle of CO2 in lieu to air in an adiabatic system with an injection rate of 0.681 PVI/min at 1225 PVI Increased injection rates show promising results in counter-balancing the detrimental effects of CO2 cycling. Oil recovery is much higher for the 30% and 50% CO2 recycle

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cases when injection rates are .681PVI/min. This causes to approach 1:2, an 100% improvement from the 0.512 PVI/min displacement process, where this ratio was 1:1. Ro is significantly higher for the .681PVI/min displacement as well. Compared to a rate of 0.512 PVI/min, at 35 PVI, Ro was higher by approximately 0.15 in all case. We attribute this to a hotter temperature front being developed. Another improvement caused by the increased injection rate is that at the higher recycling rates of 70% and 90% the temperature front is still sustained. While recovery is still reduced, Figure 4-21 shows that eventually the oil is still produced.

One noteworthy observation is that oil production for the displacement calculations where 70% and 90% of the produced CO2 is recycled are almost identical, even though a recycle rate of 90% results in a significantly higher reduction in CO2 emissions. The coke-oxygen interaction can be used to explain this behavior. When a large fraction of the produced CO2 is recycled, a fraction of the coke is left un-reacted in the burned zone (zone 1, Figure 1-1). Elevated temperatures cause the injected oxygen and coke that was not consumed at the combustion front to react and hence to partially consume the injected O2. When the injected O2 mole fraction is ~13.5% and ~10.5% for the 70% and 90% CO2 recycling respectively, the gas that reaches the burning zone, has an O2 concentration of 8%. In the burning zone, oxygen is completely consumed, releasing energy that lowers the viscosity of the oil. Oxygen that reacts coke behind the burning front, however, produces heat in zone 1. This energy dissipates in all directions and has only a moderate influence on the oil production at the leading edge of the displacement. The additional oxygen that is injected in the system when 70% of the produced CO2 is recycled relative

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to 90% is accordingly wasted. This, in turn, results in similar oil production rates for the 70% and 90% CO2 recycling scenarios with additional CO2production in the latter..

4.6.3 Operation of non-adiabatic ISC processes with O2 enriched injection After exploring the option of increasing the injection rates, we now consider the option of increasing the O2 mole fraction in the injection stream. Here, the injection rate was held constant at 0.000933 m3/min (0.157 PV/min), and the O2 mole fraction in the injection stream was increased until the ISC process could sustain a high temperature combustion front. This was achieved at 80% O2. The produced CO2 was then recycled at rates of 30%, 50%, 70%, and 90%. Figures 4-24 and 4-25 show the oil production and the net CO2 production for these modes of operation. Table 4-5 compares Ro and net moles of CO2 injected at 210, 280, and 350 PVI.
1 0.8 0.6 0.4 0.2 0 0 100 200 300 400 500 600 700 800 900 1000 td, pore volumes injected standard ISC 30% recycle 50% recycle 70% recycle 90% recycle

Figure 4-24. Comparison of oil recovery at various recycle fractions for an 80% enriched O2 ISC process in a non-adiabatic setting.

Ro, fraction oil recovery

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Net mols of CO2 Produced

80 70 60 50 40 30 20 10 0 0 100 200 300 400 500 600 700 800 900 1000 td, pore volumes injected standard ISC 30% recycle 50% recycle 70% recycle 90% recycle

Figure 4-25. Comparison of net moles of CO2 produced at various recycle fractions for an 80% enriched O2 ISC process in a non-adiabatic setting.

Run Standard ISC 30% recycle 50% recycle 70% recycle 90% recycle

Ro 0.48 0.44 0.43 0.42 0.41

net moles of CO2 produced 26.0 22.2 18.9 14.7 10.1

% Ro compared with standard ISC 100% 92% 89% 87% 86%

% net moles of CO2 compared with Std. ISC 100% 85% 72% 56% 38%

Table 4-5a. Comparison of Ro and net moles of CO2 for recycle of CO2 in lieu of air in at non-adiabatic conditions with initial injection of 80% enriched O2 at 210 PVI

Run Standard ISC 30% recycle 50% recycle 70% recycle 90% recycle

Ro 0.61 0.52 0.48 0.46 0.44

net moles of CO2 produced 36.1 30.4 25.6 19.3 11.7

% Ro compared with standard ISC 100% 86.% 79% 75% 72%

% net moles of CO2 compared with Std. ISC 100% 84% 70% 53% 32%

Table 4-5b. Comparison of Ro and net moles of CO2 for recycle of CO2 in lieu of air in at non-adiabatic conditions with initial injection of 80% enriched O2 at 280 PVI

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Run Standard ISC 30% recycle 50% recycle 70% recycle 90% recycle

Ro 0.76 0.62 0.53 0.49 0.46

net moles of CO2 produced 47.2 38.8 32.3 23.9 12.9

% Ro compared with standard ISC 100% 81% 70% 64% 60%

% net moles of CO2 compared with Std. ISC 100% 82% 68% 50% 27%

Table 4-5c. Comparison of Ro and net moles of CO2 for recycle of CO2 in lieu of air in at non-adiabatic conditions with initial injection of 80% enriched O2 at 350 PVI We note that for the non-adiabatic case we failed to get ignition with standard air injection at 0.157 PV/min. However, both injection of air at 0.681 PV/min (referred to as case 1) and the injection of 80% O2 enriched air at 0.157 PV/min (case 2) resulted in ignition. The obvious question to ask is whether it is more efficient to enrich the oxygen content of air or to simply increase its injection rate. Because the ratio between the two injection rates is 1:4.28, we choose to compare data between 1,225 PVI for case 1 and 280 PVI for case 2, since they correspond to roughly the same real time. Ro and net moles CO2 produced for case 1 were 0.879 and 39.3 respectively while for case 2 they were 0.612 and 36.2 respectively. This means that case 1 had a higher Ro (a difference of ~ 0.27) but also 8.5% more CO2 production. A comparison of operation of case 1 at 90% CO2 recycle, which has a Ro of 0.769 and production of 17.0 moles of CO2, with the 90% CO2 recycle of case 2 shows the former case having a Ro which 0.327 higher than that of case 1, but also produces 44% more net moles of CO2. The Ro value of 0.442 for the 90% CO2 recycling example in case 2 highlights the problem of attempting to recycle CO2 during enriched O2 ISC.

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From these simulations we observe that both increasing the injection rate and the oxygen mole fraction in the injection stream are capable of sustaining the ISC process. However, increasing the injection rate is the more viable route for the case with CO2 recycling. Using oxygen-enriched air to sustain ISC for an operation with CO2 recycling resulted in production rates of CO2 that were too high. Recycling even a small fraction of the CO2 greatly reduces the O2 mole fraction, severely affecting the oil production. Recycling a moderate to high fraction of CO2, in fact, resulted in complete interruption of the ISC process.

To summarize, from the third series of numerical experiments, we observe that once heat loss is included into the model, significantly higher injection rates or oxygen mole fractions are needed in order to initiate and sustain an ISC process. Figure 4-15 suggests that it takes at least three times the injection rate of the adiabatic case in series 1 in order to sustain a standard ISC process when heat loss is included. CO2 recycling at the injection rate of 0.512 PVI/min, performed poorly; the recycling of CO2 could not reach 70% as the combustion front would extinguish. Increasing the injection rate to 0.681 PVI/min had a positive effect. At the same PVI, an increase in Ro of approximately 0.15 was observed and an increase in of 100% was observed, for 30% and 50% CO2 recycling respectively. Furthermore, the combustion front did not extinguish when 70% and even 90% of the CO2 was recycled. We also noted that recycling CO2 at rates of 70% and 90% resulted in the same oil recovery. This was attributed to oxygen reacting prematurely with residual coke resulting in approximately equal oxygen rates being

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delivered to the burning zone. Finally, we observed that injecting enriched oxygen air was not as effective as increasing the total injection rate.

4.7 CO2 recycling with an increase in the total injection rate in a non-adiabatic setting In this last series of numerical experiments we explore the recycling of CO2 as an add-on to injected air under non-adiabatic conditions. Based on our previous observations that operating at low injection rates or by using enriched air is not beneficial for CO2 recycling, we decided to conduct Series 4 of numerical simulations with an initial injection rate of 0.681 PV/min of standard air. Figures 4-26 through 4-29 illustrate the oil fraction recovered and the net CO2 moles produced when CO2 is cycled at rates of 30%, 50%, 70% and 90%, as well as for the standard ISC process. Table 4-6 supplements these Figures with a breakdown of oil production.
1 0.8 0.6 0.4 0.2 0 0 200 400 600 800 1000 1200 1400 td, pore volumes injected standard ISC 30% recycle 50% recycle

Figure 4-26. Comparison of Ro for 30% and 50% CO2 recycle in addition to air with the standard ISC at adiabatic conditions.

Ro, fraction oil recovery

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Ro, fraction oil recovery

1 0.8 0.6 0.4 0.2 0 0 200 400 600 800 1000 1200 1400 td, pore volumes injected standard ISC 70% recycle 90% recycle

Figure 4-27. Comparison of Ro for 70% and 90% CO2 recycle in addition to air with the standard ISC at adiabatic conditions.

45 40 35 30 25 20 15 10 5 0 0 200 400 600 800 1000 1200 1400 td, pore volumes injected standard ISC 30% recycle 50% recycle

Figure 4-28. Comparison of net moles of CO2 for 30% and 50% CO2 recycle in addition to air with the standard ISC at adiabatic conditions.

Net mols of CO2 Produced

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45 40 35 30 25 20 15 10 5 0 0 200 400 600 800 1000 1200 1400 td, pore volumes injected standard ISC 70% recycle 90% recycle

Figure 4-29. Comparison of net moles of CO2 for 70% and 90% CO2 recycle in addition to air with the standard ISC at adiabatic conditions. Figures 4-26 through 4-29 show that the PVI needed for the burning front to traverse the combustion tube decreased as the recycle rate increased. To cover this new range of PVI, Table 4-6 shows results at 700, 875 and 1050 PVI.

Net mols of CO2 Produced

Run Standard ISC 30% recycle 50% recycle 70% recycle 90% recycle

Ro 0.60 0.60 0.60 0.60 0.60

net moles of CO2 produced 21.8 20.2 18.6 15.8 11.7

% Ro compared with standard ISC 100% 99% 99% 99% 100%

% net moles of CO2 compared with Std. ISC 100.00% 92% 85% 72% 53%

Table 4-6a. Comparison of Ro and net moles of CO2produced for recycle of CO2 in addition to air in a non-adiabatic system with an initial injection of air of 41 PVI/h at 700 PVI

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Run Standard ISC 30% recycle 50% recycle 70% recycle 90% recycle

Ro 0.69 0.68 0.68 0.68 0.70

net moles of CO2 produced 27.7 25.8 23.7 20.2 15.2

% Ro compared with standard ISC 100% 98% 98% 98% 100%

% net moles of CO2 compared with Std. ISC 100% 92% 85% 72% 54%

Table 4-6b. Comparison of Ro and net moles of CO2produced for recycle of CO2 in addition to air in a non-adiabatic system with an initial injection of air of 41 PVI/h at 875 PVI
net moles of CO2 produced 33.7 31.5 28.9 24.9 19.6 % Ro compared with standard ISC 100% 98% 97% 97% 105% % net moles of CO2 compared with Std. ISC 100% 93% 85% 73% 58%

Run Standard ISC 30% recycle 50% recycle 70% recycle 90% recycle

Ro 0.80 0.78 0.77 0.78 0.84

Table 4-6c. Comparison of Ro and net moles of CO2produced for recycle of CO2 in addition to air in a non-adiabatic system with an initial injection of air of 41 PVI/h at 1050 PVI

This series of numerical experiments shows a trend surprisingly different from that of Series 2. Rather than a decrease in oil production with increased recycling, for the most part, production remains constant and in addition, at 90% CO2 recycle, the production of oil is observed to increase. At 875 PVI, the net moles of CO2 produced are reduced to 48%, and production Ro increased to 100.7%. While this CO2 production reduction comes at no cost in oil production, there is still a compression cost, as previously noted, since 90% CO2 recycling means that the total injection rate should increase by 60%.

The results from this section suggest that optimal operation of CO2 recycling in a nonadiabatic case involves injecting air at a high enough rate to sustain a strong burning 86

zone, and then recycling CO2 in addition to the air to the maximum allowable well rate. While this trend is intriguing, we have yet to discover any errors in the simulation, data entry, or data extraction. Additional simulations with different boundary conditions may be needed to shed added light into these results. The author is currently exploring the parameter space as well as possibilities for optimization of this operation mode in combination with increased initial oxygen mole fractions (which performed poorly when CO2 replaced the air injected). There may be an operational mode of a high initial oxygen concentration and CO2 recycling as an add-on to the air injection that is economical.

4.8 Summary The numerical study, presented in the previous sections, investigating the potential for CO2 circulation in ISC processes show promising results: In a combustion tube, a significant portion of CO2 that is produced from the ISC process can be re-injected into the porous material while still maintaining a good performance in terms of oil production, The commercial thermal enhanced oil recovery simulator, STARS, by CMG, has been used to create a model based primarily on work published by Belgrave et al. (1990) After verifying that the model successfully reproduces the combustion-tube ISC process, the effects of cycling CO2 after breakthrough in four different modes of operation have been studied systematically.

The displacement process of series 1 was initiated with injection of air at 0.157 PVI/min. In addition to a standard ISC process without recycling of produced gases, four additional modes of operation were investigated, where produced CO2 was recycled at rates of 30%,

87

50%, 70%, and 90% back into the injection well. This recycled CO2 replaced air that would have been injected, lowering the amounts of oxygen injected as well. The results showed a decrease in oil production rates, but also a relatively large reduction in the CO2 production.

In the second series of numerical experiments, the displacement process was carried out in a very similar fashion to series 1, except that the CO2 that was recycled was injected as an add-on to the injected air, this increasing the total injection rate. While the results were similar to that of series 1, in all operational modes, CO2 cycling in lieu of air performed better when measurements were taken at the same PVI. Based on these observations, we concluded that under adiabatic conditions, it is better to operate at the maximum injection rate and recycle CO2 in lieu of air.

Two additional series of numerical experiments were performed for operating under nonadiabatic conditions, in order to study the effect of heat loss on the process performance. Initial attempts to simulate a standard ISC process at in injection rate of 0.157 PVI/min were unsuccessful. In order to sustain a burning zone, an increase in injection rate to 0.512 PVI/min or an increase in the O2 mole fraction was found to be necessary. While an injection rate of air at 0.512 PVI/min was capable of sustaining ISC under nonadiabatic conditions, recycling of CO2 was found to perform poorly. By increasing the injection rate to 0.681 PVI/min, however, it was possible to recycle up to 90% of the produced CO2 in lieu of air without extinguishing the combustion front.

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Series 4 investigated the impact of cycling CO2 as an added stream to air injection at a total rate of 0.681/min under non-adiabatic conditions. A surprising result from this numerical experiment was that CO2 recycling did not lower the oil production rates significantly. In fact, oil production rates actually increased slightly when 90% of the produced CO2 was recycled. At the same time, CO2 production was also reduced by 48%. This result is opposite that of the adiabatic cases, suggesting that it is better to recycle CO2 in addition to air rather than in lieu of air as is the case for the non-adiabatic operation.

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Chapter 5: ISC in a Field-Scale Pseudo 2-D Environment 5.1 Introduction After completing the investigation of ISC in a lab-scale combustion tube, we expanded our simulations to study field-scale ISC. In these simulations we kept the HTO, LTO and coke burning reaction model in order to describe the intrinsic characteristics of the ISC process (e.g., oil composition, reaction kinetics, and equilibrium behavior), and have added field-scale data, primarily from the Belridge field(Ramey et al., 1992), and the Videlefield in Romania(Turta and Pantazi, 1986) to describe relevant reservoir properties (e.g., thickness, length, permeability, porosity and injection rates). Our model was improved to include the effects of heat loss to the overburden and underburden, which is expected to be a key parameter in ISC. Additionally, we utilized the generic relative permeability curves of Maini and Kokal (1989) over the experiment-specific relative permeability data of Belgrave et al., (1990) for the purpose of generality. Phase behavior calculations in STARS are based on temperature dependent K-values despite the fact that Kristensen et al. (2008) have suggested that K-values may be inappropriate and that an equation of state (EOS) based model may be more appropriate. We note, however, that EOS-based calculations may also be associated with significant uncertainties due to the lack of experimental observations at conditions of relevance to the ISC processes. Finally, using the dispersivity correlations presented in Lake(1989), we chose component dispersivities that are appropriate for the length scale of our study. Figure 5-1 and Table 5-1 summarize the model parameters.

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30 meters Injection well, 12000 kPa 100 meters

Heat loss to overburden and underburden

Initial: 353 K 4100 kPa

Production well, 4100 kPa Figure 5-1. Schematic of the ISC system.

1 0.9 krw 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 0.1 0.2 0.3 0.4 0.5 Sw 0.6 0.7 0.8 0.9 1 krow

Figure 5-2. Water-oil relative permeability curve for 2-D and 3-D systems

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1 0.9 0.8 krg 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 0.1 0.2 0.3 0.4 0.5 Sl 0.6 0.7 0.8 0.9 1 krog

Figure 5-3. Liquid-gas relative permeability curve for 2-D and 3-D systems
Initial temperature 353 Initial oil viscosity 1630 Initial pressure 4100 Initial oil saturation 0.8 Initial water saturation 0.2 Production well boundary pressure condition 4100 Injection well boundary pressure condition 12000 Porosity 0.32 Rock thermal conductivity 70 Mass dispersivity 1 K Cp kPa

kPa kPa J/m-min-K m

Table 5-1. Reservoir characteristics

The model formation we simulate is a pseudo 2-D cylindrical system. The length of the system is 100 m, and the diameter is 30 m. We use 200 cells in our numerical calculations. A single injector well is placed at the top, and a single producer well is placed at the bottom of the system. Mass transport occurs in one direction only. However, 92

heat losses to the overburden and underburden are included in the model, in addition to the longitudinal energy transport. The model initialization begins with the injection well closed while the two topmost grid blocks are heated to reach 600 K. Once this temperature is reached, the heater is turned off and injection begins at a fixed pressure of 12,000 kPa. For the remainder of the simulation, the pressure boundary conditions are not changed. In addition, we use a 60 m3/s maximum flow condition. Note, that using this fixed pressure boundary condition means that the injection rates are not constant during the simulations, but will adjust themselves accordingly to the conditions prevailing in the subsurface. At the time of breakthrough when CO2 production begins, recycling is initiated. Because the current version of CMG STARS does not support recycling of a single component (CO2), a Visual Basic script was used to read the output file, calculate the effluent concentration of CO2, and to create a restart file to adjust the composition of the injection stream to include a fraction of the produced CO2. CO2 production rates were measured every 250 min, and a restart was written every 750 min based on the average of three measurements.

Recycling rates of 20%, 40%, 60% and 80% of the produced CO2 were studied. For a given recycle fraction, the composition of the injection stream was altered so that the injection rate of CO2 was equal to the production rate of CO2 times the selected recycle fraction.

93

5.2 Results and discussion Comparison of fractional cumulative oil production and CO2 production for 20, 40, 60 and 80% recycling rates are reported in Figs. 5-4 through 5-8. In Figs. 5-4 and 5-6, the variable in the x-axis is the number of pore volumes of total gas (CO2+air) injected at standard conditions (std), PVI, defined as:
Total gas volume injected at STD Pore volume of the reservoir

For Figs. 5-5 and 5-7, the variable in the x-axis is true time (days). Figures 5-4 and 5-5 report the fractional cumulative oil production, Ro, defined as:

Volume of oil produced Original oil in place

Figs. 5-5 and 5-6 report the scaled net cumulative volumetric CO2 production at std conditions defined as:
Pore volume of the reservoir Volume of emitted

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1 0.9 0.8 0.7 0.6 Ro 0.5 0.4 0.3 0.2 0.1 0 0 100 200 300 400

40% recycle 20% recycle 60% recycle No recycle 80% recycle

500

600

700

800

PVI Gas PVI Injected No recycle 20% Recycle 40% Recycle 60% Recycle 80% Recycle

Figure 5-4. Fractional cumulative oil production vs. PVI

1 0.9 0.8 0.7 0.6 Ro 0.5 0.4 0.3 0.2 0.1 0 0 100 200 300 Time (days) No recycle 20% Recycle 40% Recycle

40% recycle 60% recycle 20% recycle 80% recycle No recycle

400

500

600

60% Recycle

80% Recycle

Figure 5-5. Fractional cumulative oil production vs. time

95

80 70 60 CO2D 50 40 30 20 10 0 0 100 200 300 400 500

No recycle 20% recycle 40% recycle 60% recycle 80% recycle

CO2D

600

700

800

PVI gas injected PVI No recycle 20% recycle 40% recycle 60% recycle 80% recycle

Figure 5-6. Dimensionless net CO2 emission vs. pore volumes injected of gas

The volume of gas is reported here at std conditions, because the reservoir conditions are constantly changing; therefore, the reported volumes are large, since considerable expansion occurs from the reservoir conditions to the std conditions.

Fig. 5-8 shows PVI vs. time (days) for various recycle ratios. Table 5-2 compares oil recovery (in terms of Ro) and the scaled net volumetric CO2 production for different recycle rates at two fixed PVI = 400 and 500. Table 3 shows the same comparisons in real time at 365 and 425 days. Table 5-4 compares scaled net volumetric CO2 production for three fixed Ro levels, and for different recycle ratios.

When comparing fractional cumulative oil production as a function of PVI, the general trend (Fig. 5-4) is that Ro decreases as the recycling ratio of CO2 increases. However, 96

CO2Dalso decreases with increasing recycle (Fig. 5-6), and at a much higher rate. Table 52 shows that at PVI=500, for an 80% CO2 recycle rate CO2D is reduced by 50% at a cost of a 7% reduction in Ro. One, under such conditions, may opt to sacrifice a fraction of the oil production in order to reduce the CO2 production considerably.

When fractional cumulative oil production is plotted as a function of real time (Fig. 5-5), we observe that CO2 recycling actually improves the oil production rate. This is attributed to the increased amounts of CO2 being dissolved into the oil phase as a result of the increase in the CO2 molar fraction in the reservoir. This, in turn, lowers the viscosity of the oil, and therefore increases the production rate (for a given pressure drop). The combination of CO2 dissolving and increasing the oil mobility actually allows for more gas to be injected over the same time period. Fig. 5-8, for example, shows that the higher the CO2 recycle ratio is the faster the gas is being injected into the reservoir. While the O2 concentration of the injected gas is lower than that in air, under the fixed pressure boundary condition and for the kinetics of Belgrave et al. (1990), lowering the oxygen levels in the injection stream does not appear to extinguish the combustion front.

Fig. 5-7, reports the CO2D vs. time, and indicates that increased recycle ratios of CO2 initially (<~425 days) have a beneficial effect in terms of decreasing the scaled net cumulative volumetric CO2 production. However, that is not true at larger times where increased recycle ratios appear to have a negative impact resulting in larger CO2D. This behavior appears also to be at odds with Fig. 5-6, which plots CO2Dvs.PVI and shows no similar cross-over type of behavior. This unique behavior is due to the use of the fixed

97

pressure (rather than constant injection rate) boundary condition. Using Fig 5-6, when comparing the 80% recycle rate case with the no recycle case at 425 days, one discovers that over the same period they have injected approximately 300 more pore volumes. As expected then, over the same period (see Fig. 5-5) the Ro for the 80% recycle case (~0.8) is much larger than the corresponding Ro (~0.45) for the no recycle case. This is shown more clearly in Table 5-4, where for a fixed target value of Ro the 80% recycle ratio simulation run has produced significantly less CO2D than the no recycle case. In conclusion, for the same target value of Ro, recycling of CO2 increases the PVI, and significantly decreases the time needed to attain the desired levels of oil recovery.

98

80 70 60 CO2D 50 40 30 20 10 0 0 100 200 300 Time (days) No recycle 20% recycle 40% recycle 400

No recycle 20% recycle 40% recycle 60% recycle 80% recycle

CO2D

500

600

60% recycle

80% recycle

Figure 5-7. Dimensionless net CO2 emission vs. time

800 700 600 500 PVI 400 300 200 100 0 0 100 200 300 Time (days) No recycle 20% recycle 40% recycle 60% recycle 400

80% recycle 60% recycle 40% recycle 20% recycle No recycle

500

600

80% recycle

Figure 5-8. Pore volumes of gas injected vs. time

99

PVI no recycle 20% recycle 40% recycle 60% recycle 80% recycle

Ro 400 0.624 0.618 0.612 0.604 0.598

CO2D 400 49.81 46.89 42.69 35.94 23.91

Ro 500 0.749 0.740 0.728 0.714 0.696

CO2D 500 63.01 59.54 54.50 46.48 31.63

Table 5-2. Ro and CO2D at constant PVI with varying recycle rates.
Ro 365 days 0.351 0.366 0.388 0.424 0.482 CO2D 365 days 22.52 22.32 21.61 19.91 16.13 Ro 425 days 0.466 0.489 0.530 0.599 0.753 CO2D 425 days 33.72 34.04 34.7 35.52 36.35

Time no recycle 20% recycle 40% recycle 60% recycle 80% recycle

Table 5-3. Ro and CO2D at constant time with varying recycle rates.
CO2D PVI 0.7 57.81 55.38 51.63 45.32 31.85 CO2D PVI 0.75 63.01 60.50 57.02 50.16 36.35 CO2D PVI 0.8 68.46 65.69 62.08 55.77 41.40

Ro no recycle 20% recycle 40% recycle 60% recycle 80% recycle

Table 5-4. CO2D at constant Ro with varying recycle rates.

5.3 Summary This chapter expands ISC and CO2 recycling from lab scale combustion tube simulation into field scale simulation. We have designed a pseudo 2-D field-scale system to mimic a channel between an injector and producer. Flow is allowed to travel along the channel, and energy is allowed to both travel along the channel as well as escape to the surroundings. Five different simulations were carried out, a control standard ISC

100

operation, and ISC in the presence of 20%, 40%, 60%, and 80% CO2 recycle. The results suggest that recycling of CO2 in an ISC operation is both viable and beneficial. For the conditions of these simulations, the burning front temperature was not compromised by reducing the O2 concentration in the injection stream, regardless of the fraction of CO2 recycled. Because CO2 dissolves much more readily into the oil phase compared to N2, and because we use a constant pressure boundary condition, the rate of O2 being injected into the system was not significantly reduced by CO2 recycle. Thus, despite the lower concentration, the high temperatures in the burning zone allowed combustion to continue as enough O2 was being delivered. As we increased the CO2 recycle rate, oil recovery rate also increased. Additionally, increasing CO2 recycling reduces the net CO2 emission for a given amount of oil recovery. At an oil recovery of 0.8, the 80% CO2 recycling simulation had a net CO2 emission that is 40% less than the standard ISC simulation.

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Chapter 6: Parameter Space Study for the Pseudo-2D ISC Operation

6.1 Introduction In this chapter we present a parametric analysis of the relevant reaction and transport phenomena for the pseudo-2D ISC case over a broad range of physical parameters. Four key dimensionless groups are identified, as follows: PeM = PeH =

6-1 6-2 6-3 6-4

Dacb = Dacf=

They include PeM - the Peclet number for mass transfer, PeH - the Peclet number for heat transfer, Dacb - the Damkhler number for the oxidation of coke, and Dacf the Damkhler number for coke formation by pyrolysis. Table 6-1 summarizes the primary parameter associated with each dimensionless group, i.e., the parameter that when varied it only affects that particular group. A range of values for each of the dimensionless groups was selected in order to study the impact of the relevant parameter space on the performance of the proposed hybrid ISC process. Table 6-2 lists the reference values of these dimensionless groups selected from the available technical literature (see the Chapter 2.3.3 for further discussion). For example, the reference value of PeM is based on the field data reported by Lake(1989), and reflects a case of moderate dispersivity. For PeH, the reference value was selected based on the conductivity data reported for a field in San Joaquin Valley (Coats, 1984)as well as the lab-scale work of Belgrave et 102

al.(1990). For Dacf and Dacb the reference values are based on the work of Belgrave et al. (1990). The range of values of PeM, and PeH investigated in this work spans 3 log-cycles. A much broader range of values was investigated for Dacb and Dacf in order to completely explore the impact of these reactions on the performance of the ISC process.

Primary adjusted parameter Mass dispersivity Rock thermal conductivity Reaction pre-exponential value: coke burning Reaction pre-exponential value: coke forming

Associated dimensionless group PeM PeH Dacb Dacf

Table 6-1. Parameters uniquely associated with each dimensionless group

Dimensionless group PeM PeH Dacb Dacf Reference Value 333 25.2 1.48E4 2.73E3

Table 6-2. Reference values of the dimensionless groups

In the following section, we report the results of our parametric study, and we compare the performance of the proposed ISC process, incorporating CO2 recycle, with the performance of a conventional ISC process.

6.2 Results and discussion We have previously studied(Liu et al., 2009 see also Chapter 3) the impact on ISC operation of varying the CO2 recycling rates. As expected, the performance of ISC with CO2 recycle is similar to that of a standard ISC process for low values of the recycling 103

rate. Conversely, it was observed that an ISC process operated at very high recycle rates performs similarly to N2 and CO2 flooding, but with in-situ upgrading and heat generation both absent since a) the oil fails to ignite or b) the in-situ heat generation becomes insufficient for maintaining a combustion front. It was found that a moderate recycling rate of ~60 % provides for an optimal performance both in terms of oil recovery and CO2 emissions. In this parametric study, we have investigated a similar crude and, therefore, we have selected a reference recycling rate of 60 %.

We report results using the same terminology as in section 5-2. The impact of mass dispersivity on the production of oil and on the generation of CO2 is investigated initially by varying the value of PeM,(the ratio of advective to dispersive mass transport, see Eq. 6-1) while keeping the values of the other dimensionless groups constant. This is done by changing the dispersivity, , as per our prior discussion. Figures 6-1through6-4 report the oil recovery vs. real time, the oil recovery vs. PVI, CO2Dvs. real time and CO2Dvs. oil recovery. For all values of PeM, we observe the same trend, namely that recycling of CO2 significantly increases oil recovery in real time, but that the trend reverses when oil recovery is plotted versus PVI. This behavior is because dissolution of the recycled CO2 into the oil phase and the associated reduction of the oil viscosity allows for higher gas injection rates (for a fixed injection pressure boundary condition), and because CO2 at reservoir conditions has a higher density than air. As a result, recovery rates increase in real time because more gas can be injected in a given time frame. In terms of pore volumes injected, however, recycling of CO2 is observed to be somewhat less efficient. In field applications, the more efficient mode of operation, from an economic point of view,

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will depend on whether the savings resulting from having to operate for fewer days exceed the costs of separating and re-compressing the CO2. In a business environment where CO2 is a regulated pollutant, however, the latter costs will be mandatory, and the advantage of the ISC process with CO2 recycle is clear.

In Fig. 6-1 we see distinct changes in the rate of oil production (around 220 days and again at ~300 days). The first change in the rate of oil production is observed prior to the breakthrough of gas (see Fig. 6-3). The change in the oil production rate reflects the transition from the production of original oil to the production of oil that has been contacted and saturated by the gas (primarily CO2) from the combustion process. This oil will invariably have a lower viscosity than the original oil in the system resulting in an increased flow rate for a given pressure drop. This increase in flow rate due to the reduction of the oil viscosity ends with the arrival of the gas at the production well. Oil and gas are now produced simultaneously resulting in a gradually lower mobility of the oil phase. However, due to the continuous gas phase between the injection well and the production well, the volumetric flow rate of gas increases allowing for additional oil production, although the gas saturation is now steadily increasing in the porous material near the production well. Subsequent oil production is maintained through viscosity reductions (by both thermal and compositional means) and by the formation of upgraded oil (also with lower viscosity) downstream of the combustion front combined with a steadily increasing flow rate of gas in the reservoir.

105

The emissions of CO2 from the ISC operation with CO2 recycle relative to those of the standard ISC process (Fig. 6-3) are lower at early times for the recycle process, as the reinjected CO2 initially accumulates in the subsurface. However, at later times, the CO2 emissions for the ISC process with recycle overtake those of the standard ISC process. This is because as the reinjected CO2 gradually fills the pore space in the subsurface, the storage rate declines, causing more of the injected CO2 to circulate back to the production well. Combined with the CO2 generated by the combustion process itself, emissions finally overtake those of the standard ISC process (in Fig. 6-3, this happens between 400 and 500 days). However, since oil recovery rates significantly increase when CO2 is recycled back into the formation, the ISC process with recycle always results in significantly reduced CO2 emissions for a given target value of the oil recovery, as shown in Fig.6-4.

Over the range of the PeM values investigated, ISC processes (both with and without CO2 recycle) are found to perform better when dispersive mixing is relatively high (i.e., for low values of PeM). Figure 6-1, for example, shows a somewhat faster oil recovery, at a given time, as the PeM decreases (i.e., as dispersivity increases). This can be attributed to an extended mixing zone, where the injected gas dissolves into the oil phase and, as a result, reduces the oil viscosity. The differences, as expected, are more magnified in Fig. 6-2 where recovery is plotted vs. PVI, indicative of the fact that for higher dispersivities less gas needs to be injected in order to attain the same oil recoveries. It follows, therefore, that higher dispersivities also mean reduced CO2 emissions, as can be seen in Figs. 6-3 and 6-4.

106

Production of oil reaches slightly over 90% for all values of PeM. Because the system is 1-D, in terms of mass transport, no channeling or viscous instabilities can occur, and as a consequence, oil cannot be bypassed. Therefore, one would expect very little oil to remain in the porous material at the end of the displacement process. This, in turn, suggests that approximately 10% of the original oil in the formation is consumed in the ISC process. This, of course, is one of the downsides of the ISC approaches, but the partial consumption of the original oil is more than compensated by the increase in the oil recovery rates. This finding is consistent with combustion tube experiment performed at the University of Calgary(Sarathi, 1999), which report an 88% recovery of OOIP in a dry forward combustion in Athabasca Oil Sands. Also, coke combustion and O2 consumption are consistent with the model of Belgrave(1990). As the burning zone has traversed 44% of the system length, average coke combustion for the reference run was 23.2 kg/m3 and O2 consumption was 65.6 std m3/m3. Belgrave reports, at 44% traversed, an average coke combustion of 23.09 kg/m3 and an O2 consumption of 64 std m3/m3,

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1 0.9 0.8 0.7 0.6

10x Reference value, no recycle Reference value, no recycle 0.1x Reference value, no recycle 10x Reference value, with recycle Reference value, with recycle 0.1x Reference value, with recycle

Ro

0.5 0.4 0.3 0.2 0.1 0 0 100 200 300 Time (days) 400 500 600

Figure 6-1. Oil recovery vs. time for various values of PeMass
1 0.9 0.8 0.7 0.6
10x Reference value, no recycle Reference value, no recycle 0.1x Reference value, no recycle 10x Reference value, with recycle Reference value, with recycle 0.1x Reference value, with recycle

Ro

0.5 0.4 0.3 0.2 0.1 0 0 100 200 300 400 PVI 500 600 700 800 900

Figure 6-2. Oil recovery vs. PVI for various values of PeMass. 108

120
10x Reference value, no recycle Reference value, no recycle 0.1x Reference value, no recycle 10x Reference value, with recycle Reference value, with recycle 0.1x Reference value, with recycle

100

CO2 Emissions (CO2D)

80

60

40

20

0 0 100 200 300 Time (days) 400 500 600

Figure 6-3. Comparison of CO2 emissions (CO2D) vs. time for various values of PeMass
120
10x Reference value, no recycle Reference value, no recycle 0.1x Reference value, no recycle 10x Reference value, with recycle Reference value, no recycle 0.1x Reference value, no recycle

100

CO2 Emissions (CO2D)

80

60

40

20

0 0 0.2 0.4 Ro 0.6 0.8 1

Figure 6-4. Comparison of CO2 emissions (CO2D) vs. Ro for various values of PeMass 109

The impact of varying the PeH (the ratio of advective to conductive energy transport) without altering the other dimensionless groups is illustrated in Figs. 6-5 and 6-6, which report the oil recovery and CO2 emissions (CO2D) vs. real time. The value of PeH is changed by adjusting the conductivity of the porous material. CO2 recycle is again shown to be effective both in terms of increasing the oil production rates as well as reducing the CO2 emissions. Unlike the case when varying the PeM, however, the behavior with respect to PeH is non-monotonic, as indicated in Figure 6-7 that reports the time required to reach a 90% oil recovery for various values of PeH. For high values of PeH(low rock conductivity) heat conduction is low and the formation loses little energy to the surroundings. A reduced heat loss results in a higher formation temperature and increased reaction rates in the burning zone. On the other hand, a low thermal conductivity also prevents the heat from travelling rapidly downstream, and from increasing the production rate through a reduction of the oil viscosity. Increasing the conductivity (lowering the value of PeH), enhances the heat loss to the surroundings and reduces the temperature in the formation and the reaction rates in the burning zone, and initially has a negative impact on oil production. However, under such conditions the heat that is generated propagates downstream faster, thus increasing the production rate through a reduction of the oil viscosity. For high enough values of the thermal conductivity (low enough PeH values) the latter beneficial effect outweighs the negative impact of reduced temperatures and burning rates, and oil production begins to increase as the PeH value reduces further from that point.

110

Figure 6-5. Comparison of oil recovery vs. time for various values of PeHeat
120
10x Reference value, no recycle Reference value, no recycle 0.1x Reference value, no recycle 10x Reference value, with recycle Reference value, with recycle 0.1x Reference value, with recycle

100

CO2 Emissions (CO2D)

80

60

40

20

0 0 100 200 300 Time (days) 400 500 600

Figure 6-6. Comparison of CO2 emissions (CO2D) vs. time for various values of PeHeat

111

565

Time needed to recover 90% of OOIP (days)

560

555

550

545

540

535

530 0 2 4 6 8 10 12

PeH

Figure 6-7. Time needed to recover 90 % of the oil in place vs. PeHeat

Next, we study the significance of the reaction rates on the performance of ISC processes. In particular, we investigate the impact of varying the rate of coke formation by pyrolysis (reaction 3.2) and the rate of coke oxidation in the HTO regime (reaction 3.4) on oil production, and the viability of CO2 recycling. The impact of these two reactions was studied via the corresponding Damkhler numbers, namely Dacf and Dacb(see Eqs. 6-3 and 6-4 for definitions). We focus primarily on these reactions for two reasons: First, Dacb was selected because the rate of coke oxidation in the HTO regime and the energy release associated with it is well-known to play a central role in the success of the ISC processes. Second, Dacf was selected because coke oxidation cannot occur without, first, coke formation. While it is arguable whether pyrolysis or LTO is the main source of coke formation, our preliminary studies showed (Liu et al., 2009) that once a burning zone was 112

established, very little oxygen makes contact with the downstream oil. While without doubt, LTO is very important for establishing a burning zone, pyrolysis is what sustains ongoing coke formation; thus variation of coke formation via pyrolysis was chosen over coke formation via LTO in this study. Figures 6-8 and 6-9 report the oil recovery and CO2 emissions (CO2D) vs. real time for various values of Dacb, while Figs. 6-10 and 6-11 report the recovery and emissions for different values of the Dacf.

We study the impact of changing the value of Dacb over a much larger range than that for the heat- and mass-transfer Peclet numbers, as the coke oxidation kinetics for the reference value of Dacb are so fast that an increase/decrease of the value of Dacb by a factor of 10 does not change the observed behavior. At the reference condition, any coke that is formed is oxidized immediately provided that sufficient oxygen is present. A reduction in the value of Dacb by several orders of magnitude is required before any impact on the oil recovery and CO2 emissions is observed. As extreme cases we report here the behavior of the process for values of Dacb that are 10-5 and 10-6 times the reference value (see Figs. 6-8 and 6-9). At these conditions, the kinetics are so slow that very little coke is oxidized, and the majority of energy is generated from burning the oil directly either via the LTO or the HTO reactions. This is, of course, a highly undesirable mode of operation with large concentrations of coke left unreacted on the surface of the porous material accompanied by lower oil production rates (as well as lower overall recoveries), and a significant increase in CO2 emissions.

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1
1E-6x Reference value, no recycle

0.9 0.8 0.7 0.6

1E-5x Reference value, no recycle Reference value and 10x Reference value, no recycle 1E-6x Reference value, with recycle 1E-5x Reference value, with recycle Reference value and 10x Reference value, with recycle

Ro

0.5 0.4 0.3 0.2 0.1 0 0 100 200 300 400 Time (days) 500 600 700 800

Figure 6-8. Comparison of oil production vs. time for various Dacoke burning
160
1E-6x Reference value, no recycle 1E-5x Reference value, no recycle

140 120

Reference value and 10x Reference value, no recycle 1E-6x Reference value, with recycle 1E-5x Reference value, with recycle Reference value and 10x Reference value, with recycle

CO2 Emissions (CO2D)

100 80 60 40 20 0 0 100 200 300 400 Time (days) 500 600 700 800

Figure 6-9. Comparison of CO2 emissions (CO2D) vs. time for various Dacoke burning

114

Figures 6-10 and 6-11 show the effect on ISC performance of varying the value of Dacf. Decreasing the value of Dacf from the reference value has a significant impact on the oil production rates. As Dacf decreases, the rate of coke formation also decreases and a gradually larger fraction of the coke is formed by the LTO reaction 8. The reduction in the amount of coke that is formed results in a reduced formation temperature due to a reduction in heat generation by the oxidation of coke. As a result, as seen from Fig. 6-12, lower values of Dacf are also associated with significant reductions in CO2 emissions. However, recycling of CO2 continues to have a beneficial effects on the ISC process performance. Figure 6-10, for example, shows that that recycling of CO2 significantly improves the oil production rate, while Fig. 6-11 indicates that the CO2 emissions are consistently lower than those in the standard ISC process.

Figure 6-10. Comparison of oil recovery vs. time for various Dacoke formation

115

Figure 6-11. Comparison of CO2 emissions (CO2D) vs. time for various Dacoke formation The primary focus of this work is oil reservoirs with relatively high oil viscosities that are not suitable for water flooding. Accordingly, our base model has a relatively low initial water saturation of 5%. We have also investigated the impact of initial water saturation on the performance of the proposed hybrid ISC process. Figures 6-12 and 6-13 compare ISC processes for the base reservoir (5% initial/5% critical water saturation) with three alternate reservoirs settings. The first alternate reservoir has a 20% initial/20% critical water saturation, the second reservoir has a 35% initial/30% critical water saturation, and the third reservoir has a 60% initial/30% critical water saturation. Water saturation below the critical saturation value is considered immobile and cannot be further reduced by convective forces. Additional water may still be evaporated, however.

116

1 0.9 0.8 0.7 0.6

Ro

0.5 0.4 0.3 0.2 0.1 0 0 100 200 300 400 500 600

Time (days)
5% water saturation, no recycle 35% water saturation, 30% water critical, no recycle 5% water saturation, 5% water critical, recycle 35% water saturation, 30% water critical, recycle 20% water saturation, 20% water critical, no recycle 60% water saturatin, 30% water critical no recycle 20% water saturation, 20% water critical, recycle 60% water saturation, 30% water critical, recycle

Figure 6-12. Comparison of oil recovery vs. time for various initial water saturations
140 120 100 80

Net CO2D

60 40 20 0 0 100 200 300 400 500 600

Time (days)
5% water saturation, 5% water critical, no recycle 35% water saturation, 30% water critical, no recycle 5% water satureation, 5% water critical, recycle 35% water saturation, 30% water critical, recycle 20 % water saturation, 20% water critical, no recycle 60% water saturation, 30% water critical, no recycle 20% water saturation, 20% water critical, recycle 60% water saturation, 30% water critical, recycle

Figure 6-13. Comparison of CO2 emissions (CO2D) vs. time for various initial water saturations 117

We observe that a higher initial water saturation (particularly mobile water), accelerates the oil recovery process. This is a consequence of the increase in overall mobility and, as a result, breakthrough of gas occurs earlier. An additional benefit from the higher initial water saturation is that more steam is produced which stimulates the oil production. However, for the third case with 60% initial water saturation, both a standard ISC process and an ISC process with recycle of CO2 perform poorly: Initial oil production rates are poor (high water cut) despite high injection rates and the oil recovery is significantly reduced ( ~ 20%) relative to the cases with a lower initial water saturation. In terms of CO2 emissions, an increase is observed for higher initial water saturations (5% - 35%). This is, primarily, due to higher production rates, but also the result of operating with a constant pressure boundary condition at the injector well. Since oil is produced faster, the pressure in the subsurface decreases faster and the injection rate increases. This, in turn, facilitates combustion and the associated CO2 production. At 60% initial water saturation, we observe a different behavior. CO2 production is accelerated with gas breakthrough an order of magnitude faster, and a comparison of the oil production to the amount of gas injected reveals a less efficient ISC process.

For all cases except the one with 60% initial water saturation, the trend of faster oil production and reduced CO2 emissions with CO2 recycle (for a given recovery) remains unchanged. These results demonstrate that in the very unfavorable setting of 60% water saturation, neither a standard process nor a hybrid ISC process are likely to be successful. However, in settings with a low to moderate initial water saturation, ISC is a viable process, and ISC with recycling of CO2 increases the process performance.

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While ISC with CO2 recycle appears technically feasible the economics of the process need to be further investigated. In providing a preliminary estimate of the increase in operational costs, it appears that the primary additional cost will primarily related to the separation of CO2 from the produced gas. This is based on the assumption that in conventional ISC use will be made of an oil-gas separator, and that the compression of CO2 will not significantly add to the operational cost (relative to the compression of air). CO2 separation costs vary widely, depending on the technique chosen and the degree of separation (which in this case is not a critical factor, as the process can tolerate a moderately pure CO2 stream). These additional costs must be then balanced by operational savings that result from the increased oil production rates during ISC with CO2 recycle. Of course, the above discussion is for the business as usual scenario, whereby the assumption is that conventional ISC operations will not be required in the future to separate and sequester the CO2 produced. If such environmental regulations (e.g., carbon tax) were to be imposed worldwide, there would be no downside in applying ISC with CO2 recycle, because then one would be required to separate the CO2 even for the conventional ISC.

6.3 Summary For the range of PeM and PeH values investigated in this work, we observe increases in the oil recovery of ~33% for a fixed time of operation when comparing the ISC process with CO2 recycle with the conventional ISC process. In addition, at the time when 80% of the total oil in place has been produced, the CO2 emissions are consistently lower by

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18-22 % when CO2 is recycled back into the formation. Similar gains in oil recovery and reductions in CO2 emissions are observed in our parametric study of the coke formation kinetics (effect of Dacf). We find that Dacf plays an important role with significant decreases in oil recovery observed for lower values of Dacf where a transition from the HTO to the undesirable LTO regime takes place.

A key conclusion of this study is that CO2 recycling is beneficial for ISC processes both in terms of enhanced oil recovery rates and in terms of reduced CO2 emissions. Reductions in CO2 emissions, for a fixed oil recovery target value, are observed over a broad range of operational conditions based on displacement calculations for a large range of mass- and heat-transfer Peclet numbers, and of Damkhler numbers for the coke formation and oxidation reactions. Even in cases where the ISC process is performing sub-optimally due to poor reaction kinetics, reduced oil viscosity due to CO2 recycling can still improve oil production while at the same time reducing the associated CO2 emissions. These results are applicable to wide range of initial water saturations, from the extreme case of 95% oil saturation to the moderate case of 65% oil saturation.

ISC processes with CO2 recycle show substantial promise. A more detailed analysis of the economics of the overall process including the costs of separation and recycling of CO2 is clearly warranted, however. The engineering implications related to the operation of the hybrid ISC process in a more realistic 3-D reservoir setting are discussed in the next chapter.

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Chapter 7: ISC with CO2 Recycling in 3-D Configurations

7.1 Introduction In the previous chapters, we have studied the potential for recycling of produced CO2 in 1-D and pseudo 2-D configurations. The focus of this chapter is on expanding our model to 3-D ISC processes and to verify the validity of the displacement dynamics observed in the 1-D and 2-D simulations. Two well patterns were selected: an inverted 9-spot pattern and a line-drive pattern. To investigate the potential of recycling CO2 in more realistic 3-D ISC processes, we have made some modifications to our previous mode of operation: 1. We initiate the ISC process by injecting air into a preheated section of the reservoir, and continuing the injection until gas arrives at the production wells. 2. After gas breakthrough, we measure the rate of production of CO2 and we change the injection stream through recycling of a fraction of the produced CO2 back into the reservoir. In the inverted 9-spot pattern, all re-injected CO2 is combined into the single injection well. In the line-drive pattern, CO2 produced from a given well is recycled into an injection well upstream, either in the first row of the system or the current injector row. 3. We continue this mode of operation until the temperature at the production well exceeds 600 K, signaling that the burning zone has reached that well. 4. When a well reaches 600K, the well is shut-in; if not all wells are shut-in, the process continues. 5. When all wells are shut-in, the simulation concludes for the inverted 9-spot. For the line drive, producers are converted into injectors and a new row of producers is introduced. 121

In this chapter, we continue utilizing CMG STARS(CMG, 2008)and the ISC kinetics reported by Belgrave et al. (1990) as discussed in precious sections. While recent works have shown that compositional modeling based on an equation of state (Jain et al., 2010, Kristensen et al., 2007) produces results significantly different from models that are based on temperature dependent equilibrium K-values, the current version of CMG STARS only allows for the use of T-dependent K-values. The Virtual Kinetic Cell proposed by Kristensen et al. (2007), is not commercially available and is not designed to handle larger scale 3-D simulations that are of primary interest in this study. Accordingly, CMGs STARS remains the best option for the purpose of this work. Furthermore, more complex pseudo-component reaction kinetics based on SARA fractions have been devised (Jain et al 2010, Freitag and Exelby, 2006), but the larger number of reactions greatly increases the CPU time required to handle large-scale 3-D ISC simulation. Therefore, to allow for 3-D computations, the simpler model of Belgrave et al. (1990) was used, with the added benefit of allowing for direct comparisons with our previous 1D and 2-D work.

Due to the number of grid-blocks needed to run a meaningful 3-D model, simulations with CMG STARS were performed on parallel Unix machines at USCs High Performance Computing Center. CMG STARS uses shared-memory parallel processing, and simulations were conducted therefore with both 12-parallel and 16-parallel sharedmemory systems in order to reduce the run-times.

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As in the previous sections, a standard ISC process is compared with the proposed operational mode where a portion of the produced CO2 is recycled back into the reservoir by replacing a fraction of the injected air. Constant pressure boundary conditions were used both at the injection wells and the production wells. Past work both in the laboratory (Awoleke et al., 2010) and numerical calculations (Fadaei et al., 2010) have shown that heterogeneity and/or fractures can affect ISC processes significantly in terms of both air delivery and oil recovery. We expect results that are quantitatively different from 1-D and pseudo 2-D models and our studies are intended to understand whether heterogeneity and gravity override occurring in 3-D settings will alter the results only marginally, or qualitatively change the conclusions concerning the benefits and drawbacks of CO2recycling during ISC reached in the 1-D and 2-D studies.

7.2 Pattern selection As noted above, the two applications of ISC processes studied in this chapter are the 9spot pattern and the line-drive, which are the most traditional and well understood ISC operations. In this study we simulate an isolated inverted 9-spot pattern based of the South Belridge field(Ramey et al., 1992), and a line-drive pattern based on the Romanian Suplacu de Barcau field (Turta et al., 2005). Pilot patterns like the one in the Belridge field are often used to determine the viability of ISC at larger-scales, both in a contiguous sequence of 9-spot patterns as well as in line-drive operation. Hence, understanding the viability of ISC with CO2 recycling in these typical ISC configurations is important for practical field design and implementation.

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Beyond pilot projects, ISC has also been commercially successful globally, with a lot of data available, particularly for in line-drive ISC (Turta et al., 2005).. This configuration is thought to have a number of advantages over the contiguous 9-spot patterns In the following sections we investigate the dynamics of both patterns in order to further expand our understanding of the effects of heterogeneity, gravity and CO2 recycling on ISC operation.

7.2.1 Inverted 9 - spot pattern The inverted 9-spot pattern mimics the South Belridge pilot pattern 528(Ramey et al., 1992). In this setting we have 1 injector in the center and 8 producers along the perimeter. Figure 7-1 shows the permeability distribution and well placements, and Table 7-1 reports additional relevant field data. Permeability fields were generated based upon the average permeability observed in the South Belridge field with data from Ramey et al. (1992) and the permeability distribution from Jessen and Orr (2002).The dimensions of the model are (300 m x 300 m x 25 m), with grid-block size of (6 m x 6 m x 5 m) (25,000 active cells).

The model initialization begins with the heating of the injection well until a temperature of 600 K is reached. Once this temperature is reached, the heater is turned-off and injection of air begins at a fixed pressure of 10,000 kPa. We note, once more, that the use of a fixed injection pressure results in injection rates that are not constant during the displacement process, and that rates will adjust accordingly to the conditions prevailing in the subsurface. At the time of gas breakthrough at the production well, the recycle

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operation is initiated. In order to adjust the injection gas composition dynamically in the CMG STARS, we use a Fortran script to calculate the effluent concentration of CO2 based on output from the simulator, and to create a restart file in order to adjust the composition of the injection stream to include a fraction of the produced CO2. CO2 production rates were measured every 1000 min, and the injection stream composition was changed every 3000 min, based on the average of the last three rate observations. We note that the recycle streams from all production wells are combined into the single injection well.

Once the temperature at a producer well reaches 600 K we conclude that the burning front has reached the well and the well is shut-in.

Figure 7-1. Permeability distribution (mD) of the inverted 9-spot pattern

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Initial temperature Initial oil viscosity Initial pressure Initial oil saturation Initial water saturation Production well boundary condition Injection well boundary condition Porosity Rock thermal conductivity Mass dispersivity

310 22000 2895 0.73 0.27 2895 10000 0.36 700 .03

K cP kPa

kPa kPa J/m-min-K m

Table 7-1. Reservoir details for the inverted 9-spot system

7.2.2 Line-drive pattern The line-drive model mimics the Suplacu de Barcau field in Romania (Turta et al., 2005). The Suplacu line-drive is roughly 50 wells wide, and in order to reduce simulation runtimes, our line-drive model simulates a strip of the field which is 4-well wide. Figure 7-2 shows the chosen permeability distribution of the field (from Seto et al., 2003) and the well placement, and Table 7.2 reports relevant field data. The dimensions of the system are (150 m x 225 m by 5 m) with grid-block sizes of (5m x 2.5 m x 1m) for a total of 13,500 active cells. In the simulations, the 4 initial injection wells are heated to 600 K. Then, injection begins at a pressure of 5,000 kPa. As the burning zone propagates slowly towards the first row of production wells, gas will break-through. CO2 is then recycled back into the reservoir with production well 1 recycling to injection well 1 and so forth. When the burning zone reaches a production well it is shut-in. After all four wells are shut-in, the first stage of the line-drive ends. A restart file has been written which converts the producer wells into injector wells. A new row of 4 production wells is then introduced downstream and operation continues as before. This process is repeated until we traverse the entire domain. 126

In later phases of the line-drive operation (when the injection wells have moved into the 2nd row and beyond), two modes of CO2 recycling were investigated, namely either recycle back to row 1 of injection wells, or recycle back to the current active injector row.

Figure 7-2. Permeability distribution (mD) for the line-drive pattern

Initial temperature Initial oil viscosity Initial pressure Initial oil saturation Initial water saturation Production well boundary condition Injection well boundary condition Porosity Rock thermal conductivity Mass dispersivity

291 2200 550 0.85 0.15 550 5000 0.32 700 .03

K cP kPa

kPa kPa J/m-min-K M

Table 7-2. Reservoir details for the line-drive system

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7.3 Results and discussion 7.3.1 Inverted 9-spot pattern The inverted 9-spot-pattern simulations show that a combustion zone is established and that the development of the burning zone is similar to previous 1-D and 2-D simulations but also that the effects of heterogeneity are significant. Large horizontal sections of the reservoir are not swept and production is mostly limited to one or two wells at a time.

Gravity plays a significant role in the overall efficiency of the 3-D ISC process, as bottom layers of the reservoir appear to remain largely untouched. This leads to a reduced sweep efficiency, as compared to previous 2-D simulations (Liu et al., 2009). Figure 7-3, for example, shows the gas saturation after 4000 days of operation. For the uppermost layer the sweep is relatively efficient, but in contrast, the bottom layer remains largely unswept. Overall, the standard ISC process recovery reaches only 11% of the oil in place after 4000 days of operation without CO2 recycling, and 13% when CO2 recycling is included, see Figures 7-4 and 7-5, and further discussion below.

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Figure 7-3. Gas saturation after 4000 days for a standard, inverted 9-spot ISC run

0.14

0.12

0.10

Oil Production (Ro)

0.08

0.06 ISC without CO2 recycle ISC with CO2 Recycle 0.04

0.02

0.00 0 500 1000 1500 2000 2500 3000 3500 4000 4500 Time (days)

Figure 7-4. Comparison of cumulative oil recovery between a standard and a CO2-recycle run for an inverted 9-spot pattern

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With CO2 recycling, after breakthrough, we see similar benefits in the 3-D ISC process as we did in the 1-D and 2-D configurations. This is not surprising, as each gas conduit behaves essentially as a pseudo 2-D section. Like in our previous simulations, 60% of the CO2 produced is recycled back into the central injector. This cools the burning front somewhat, but also increases the width of the gas channels and, thus, improves the sweep efficiency. Figure 7-5 below shows the gas saturation at 4000 days in the ISC process with CO2-recycling.

Figure 7-5. Gas saturation after 4000 days for an inverted 9-spot run with CO2 recycle

Figure 7-4 shows that the improved sweep from CO2 recycling increases recovery of oil by ~20% relative to the oil recovery of the standard ISC process. As with the 1-D and 2D ISC processes, this is because CO2 dissolves more readily than N2 into the oil phase and reduces its viscosity. This, in turn, results in a widening of the low-viscosity and mobile oil phase conduits.

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In terms of CO2 emissions, as Figure 7-6 indicates, CO2 recycle has a beneficial effect though in real time (days) the behavior is rather complex, with cross-over events at intermediate times due to shut-in of various production wells. The beneficial effect of CO2 recycle is more prominently and clearly indicated in Figure 7-7 where oil recovery is plotted vs.CO2 emissions. When CO2 is recycled, for the same level of CO2 emission, more oil is produced. CO2 reduction is significant, on the order of 30%, meaning potentially large saving in downstream emission reduction costs.
35.00

30.00

Net CO2 Emission (CO2D)

25.00

20.00 standard run recycle run 10.00

15.00

5.00

0.00 0 500 1000 1500 2000 2500 3000 3500 4000 4500

Time (days)

Figure 7-6. Comparison of CO2 emissions for the inverted 9-spot pattern between the standard and the CO2-recycle runs

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35.00

30.00

Net CO2 Emission (CO2D)

25.00

20.00

15.00 ISC without CO2 recycle ISC with CO2 recycle 10.00

5.00

0.00 0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14

Oil Production (Ro)

Figure 7-7. Comparison of net CO2 emissions vs. Oil recovery for the inverted 9-spot pattern 7.3.2 Line-drive pattern As previously noted, the line-drive process investigated in this work, mimics the Suplacu de Barcau field in Romania (Turta et al., 2005). The line-drive process significantly outperforms the base 9-spot pattern discussed in the previous section in terms of oil recovery. The shorter well to well distance, and higher formation permeability result in an improved horizontal displacement efficiency of the ISC process.

In the line-drive configuration shown in Figure 7-2, the well-to-well distance is 75 m. Operation was continued until the burning zone reached all production wells at the end boundary of the pilot domain, 225 m downstream of the initial row of injectors. As Figure 7-8 indicates, the line-drive process results in higher oil recovery relative to the 9132

spot pattern. Two different cases of CO2 recycle are shown in Figures 7-8 and 7-9, the first being a mode of operation where CO2 is recycled always back into the first row of injectors, while in the other mode of operation CO2 is recycled back into the current row of injectors. Unlike recycling of CO2 in the 9-spot configuration, for the line-drive system it does not appear that CO2 recycle (for either mode of operation) has any impact on the recovery of oil in real time. Both the standard and the CO2 recycle ISC operations reach similar oil recoveries (~ 32% of oil in place) by the time the combustion front reaches the formation boundary, albeit at a somewhat shorter time for the latter mode of operation.

In terms of CO2 emissions, the line-drive results also differ from the inverted 9-spot results. Significant reductions in CO2 emissions is observed in real time. After 650 days of operations, as shown in Figure 7-9, we observe ~23% less CO2 production for the recycle case over the standard operation. It is valuable to compare oil recovery versus net CO2 emissions (Figure 7-10). The behavior in Figure 7-10 is similar with that in Figure 77 for the inverted 9-spot. For the line-drive case, we again see a roughly 30% improvement in oil recovery for the same net CO2 emission when CO2 is recycled back into the subsurface.

For the inverted 9-spot configuration, we observed that recycling CO2 had the effect of widening the production channels. Due to the short well-to-well distances in the line drive scenario, production channels were already wide in the standard ISC operation. The recycling of CO2 is unable to widen these channels significantly. Rather, the main effect of recycling is accumulation of CO2 in the subsurface. In other words, in the inverted 9-

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spot case, recycling of CO2improvesthe oil recovery vs. CO2 emission response by promoting the rate of oil production, while in the line-drive case, the a similar result is achieved by reducing the net CO2 emission.

Key factors for the effective storage of CO2 in the line-drive scenario are high overall sweep and the geometry of the system. Having an effective displacement of oil provides more void space available for CO2 storage. And because gas in later sections can migrate upstream, additional volume is available for storage. Figures 7-11 and 7-12 compare gas saturation at the end of the standard and recycle runs. For the recycle process, gas saturation is clearly higher and spread further. The solid red sections with high gas saturation highlight the original channels where the burning fronts have traversed. The yellow and orange sections adjacent to these channels in Figure 7-12 are areas where CO2 has diffused into the oil as we recycle, providing for additional storage in the subsurface.

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0.35

0.3

0.25
Oil production (Ro)

0.2

0.15

No recycle Recycle to First Row Recycle to Current Injectors

0.1

0.05

0 0 100 200 300 400 Time (days) 500 600 700 800

Figure 7-8. Cumulative oil comparison for the line-drive pattern

140

120

Net CO2 Emission (CO2D)

100

80

60 No recycle 40 Recycle to First Row 20 Recycle to Current Injectors 0 0 100 200 300 400 500 600 700 800

Time (days)

Figure 7-9. Net CO2 production comparison for the line-drive pattern

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140

120

Net CO2 Emission (CO2D)

100

80

60

40

No recycle Recycle to First Row

20 Recycle to Current Injectors 0 0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35

Oil production (Ro)

Figure 7-10, Net CO2 production versus recovery of oil for the line-drive simulation

Figure 7-11. Gas saturation at the conclusion of the standard line-drive ISC.

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Figure 7-12. Gas saturation at the conclusion of the line drive with recycling of CO2 into row 1. 7.4 Gravity override While general trends in the 3-D simulations show similar benefits from CO2 recycling compared to our 1-D and 2-D simulation studies (Liu et al., 2009), and sweep efficiency and eventual oil recovery are significantly lower for the 3-D simulations. To gauge the effects of gravity forces on the process performance, the dimensionless gravity number (Zhou et al., 1994), Ngv, was calculated for both the 9-spot and line-drive examples. In addition, a parametric study was conducted by varying Ngv and observing the effect on overall sweep efficiency. The details and derivation of Ngv can be found in Zhou et al. (1994). For our system we adapt the following definitions:

7.1

horizontal well-to-well distance and kav is the average permeability in the vertical

is the difference between density of oil and gas, g is gravity constant, L is the 137

direction. H is the thickness of the reservoir, while q is the horizontal Darcy flow velocity, calculated by taking average oil production rates and dividing by the crosssectional area. Finally, denotes the viscosity of the oil phase.

In addition to the gravity number, Zhou et al. (1994) define a mobility ratio term

and an aspect ratio term. The mobility ratio terms is defined as follows:

7.2

In our case the mobility ratio term is negligible as the difference in viscosity makes this value close to unity. The aspect ratio is defined as :

7.3

where khan is the average permeability in the horizontal direction.

In the work of Zhou et al. (1994), 5 regions are defined for Ngv. For Ngv>>1, we expect a strong influence of gravity and the development of a single-gravity tongue. For Ngv ~1, a transition zone occurs and while a single-gravity tongue may not be developed, gravity will still play a noticeable role. For Ngv<<1, three zones are possible depending on the aspect ratio, Rl2. For Rl2<<1, no vertical communication occurs. For Rl2~1, flow is viscous-dominated, and for Rl2>>1 a viscous-cross-flow equilibrium is established.

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For the 9-spot configuration we compare three different cases, and use the Belridge field model as the reference case. The other two cases include an example where the reservoir thickness is reduced by a factor of 5, and one example where the well-to-well distance was reduced by a factor of 2. Figure 7-13 compares fractional oil recovery vs. time for these three cases.
0.12 Standard reservoir Reservoir thickness reduced by factor of 5 0.10 Well to well distance reduced by factor of 2 NGV= 0.02 RI2 = 5.2 NGV= 11 RI2 = 128 NGV= 0.004 RI2 = 1.3

Oil Production (Ro)

0.08

0.06

0.04

0.02

0.00 0 500 1000 Time (days) 1500 2000 2500

Figure 7-13. Ngv parameter study for the inverted 9-spot well configuration

From Figure 7-13, we observe three distinct types of behavior. When the well-to-well distance is reduced, production greatly improves, but when the reservoir thickness is reduced, production sharply declines. The standard case, with an Ngv of 0.02, is in either the transition zone or in the viscous-cross-flow equilibrium zone, by the definition of Zhou et al. (1994). The reduced well-to-well distance example is in the viscousdominated zone. The reduced thickness example is in the gravity-dominated zone. The 139

original work by Zhou et al. (1994) was mainly focused on non-reactive two-phase flow configurations. Because in ISC one deals with reactive flows, accurate estimates of the horizontal Darcy flow velocity, density difference, and the average viscosity are difficult. Therefore, it is not clear that our systems will fall neatly into the same regions of behavior(same values of Ngv and Rl2), as defined by Zhou et al., (1994), but this is not as critical, as these zones serve primarily as guidelines, after all. However, the results above emphasize the need to minimize Ngv and choose systems with low Rl2 in order to ensure a successful ISC operation.

Figure 7-14 below shows a similar comparison for the line-drive scenario. Here, we study four different cases here: the standard configuration, representing the Suplacu de Barcau field, a case where the reservoir thickness is increased 5 times, a case where the well-towell distance is doubled, and a case where well-to-well distance is reduced by a factor of 2.

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0.35

0.3

0.25

Oil production (Ro)

0.2

0.15
Standard reservoir NGV= 0.12 RI2 = 22 NGV= 0.02 RI2 = 0.9

0.1

Reservoir thickness increased by factor of 5

Well to well distance increased by factor of 2 NGV= 0.63 RI2 = 90

0.05

Well to well distance decreased by factor of 2 NGV=0.034 RI2 =5.625

0 0 100 200 300 400 Time (days) 500 600 700

Figure 7-14. Ngv parameter study for the line-drive well configuration

The Ngv of the standard case for the line-drive has a similar value to that of the 9-spot. Using the relative values of Ngv to delineate different types of behavior appear to be a valuable undertaking for the line-drive configuration as it is for the 9-spot case. However, when oil recovery is plotted vs. real time, comparing the behavior based on the Ngv values alone is not as straightforward. For example, the cases where the formation thickness was increased 5 fold, and well-to-well distance are reduced by a factor of 2 have values of Ngv that are close, yet recovery rates are quite different. Again, this is an indication of the high degree of complexity of ISC as compared to the non-reactive flows studied by Zhou et al. (1994). Ngv appears to be a more sensitive indicator of distinct behavior when oil recovery is plotted as a function dimensionless time, i.e., pore volumes injected (PVI), as. Figure 7-15 below indicates.

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0.35

0.3

0.25

Oil production (Ro)

0.2

0.15

0.1

Standard reservoir Reservoir thickness increased by factor of 5

NGV= 0.12 RI2 = 22.5 NGV= 0.02 RI2 = 0.9

0.05

Well to well distance increased by factor of 2 NGV= 0.63 RI2 = 90 Well to well distance decreased by factor of 2 NGV=0.034 RI2 =5.625

0 0 200 400 600 PVI 800 1000 1200 1400

Figure 7-15. Ngv parameter study for line drive well configuration, Ro vs. PVI

In Figure 7-14, we see that for a given value of PVI the recovery of oil is higher for lower values of NGV and Rl2, as expected. The distinction between the thick reservoir example and the short well-to-well distance example is clear. The thick reservoir, with the lowest values of NGV and Rl2 has the most efficient recovery. A short well-to-well distance performs second best, ahead of the standard case, which performs better than the high Ngv example that represents a large well-to-well distance. These results (together with those from the inverted 9-spot) show that the gravity number and aspect ratio can be valuable tools for the better understanding and the more effective design of ISC processes.

7.5 Cost analysis During one of our line-drive CO2recycle simulations, we produced 92 925 barrels of oil and injected 1.28E7 kg CO2 back into the subsurface. The cost of separation by 142

membranes (Matsumiya et al., 2005) has been estimated to be roughly 0.037 $/kg of CO2. For each barrel of oil produced, we must then spend an additional $5.13. The viability of this process will improve with improving separation technology as well as the stringency of CO2 emissions regulations.

7.6 Comparison with steam injection To put ISC and ISC with recycle in perspective, an additional simulation was conducted for the first section of the line-drive where 600 K steam was injected at a constant pressure instead of air. The production profile of a steam drive is compared with air injection in Figure 7-16 below. Steam injection results in a less eventful and constant production, but is always less effective than an ISC process in this calculation example. While steam injection does not produce significant byproducts (from the subsurface) and avoids the costs associated with separation of the production gas, the steam generation and the associated energy requirement plus emissions must also be factored into the comparison. This work provides evidence that ISC processes combined with CO2 recycling can be an economically viable alternative to more traditional thermal EOR processes (e.g., steam).

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0.16

0.14

0.12

Oil production (Ro)

0.1 Air Injection 0.08 Steam Injection

0.06

0.04

0.02

0 0 50 100 150 Time (days) 200 250 300

Figure 7-16. Comparison of air versus steam injection for the first section of line drive 7.7 Summary The results and analysis presented in the previous sections demonstrate that in 3-D settings, heterogeneity and gravity override reduce the overall efficiency of oil recovery in ISC processes. Because of the heterogeneity, 3-D flow often collapses onto a series of channels (dictated by the heterogeneity) that are similar to pseudo-2D flow. For the 9spot displacement calculations with a large well-to-well distance and associated gravity override, oil sweep was found to be very poor, with only 11% of oil recovery after 4000 days of operation. With the addition of CO2recycling, sweep was observed to improve the recovery to 13% after 4000 days, an increase of approximately 20%. This is primarily attributed to CO2 dissolving into the oil surrounding the flow channels (see discussion above), and through that mechanism increasing the width of the channels. The majority 144

of CO2 dissolved in the oil, however, is produced with the oil and results in marginal reductions in the CO2 emissions in real time.

In the line-drive operation, we observe that the overall sweep is greatly increased and reaches 32% recovery of the oil in place after 650 days. The use of a larger number of injection wells combined with shorter well-to-well distances promotes a more effective sweep of the formation, particularly of the lower layers. In real time, CO2 recycling had a different effect than that for the 9-spot case, not accelerating oil production, but rather reducing CO2 emissions. Because the burning front has a shorter distance to travel, the production wells are shut in (and converted to injection wells) relatively fast and only a marginal increase in oil production was observed in response to the recycling of CO2. However, the elongated shape of the reservoir used in the line-drive example, promotes a reduction of the CO2 emissions. CO2 concentrations build-up in the upstream portions of the reservoir (behind the burning front). This build-up reduces the net CO2 emissions by 23% at the end of the line-drive process.

When recovery of oil is plotted versus net CO2 emissions we observe similar results from the two well configurations: In both cases, for a given level of CO2 emission, oil recovery is increased with CO2 recycling. In both scenarios, recovery was increased roughly 30% for the same magnitude of the CO2 emissions at the end of operations.

The additional cost of the hybrid ISC process (with recycling) was estimated to be approximately $5 per barrel of oil produced. Also, it was demonstrated that ISC

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processes, under the conditions studied in this work are able to produce more oil than a steam-drive, and this suggests that ISC may be a cost effective alternative. Lastly, a study of the effect of gravity number was conducted. The results show that operations with small gravity numbers, NGV, and small values of the aspect ratio, Rl2, improves oil production rate, both in real and dimensionless (PVI) time.

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Chapter 8: Conclusions and Future Work The U.S. domestic energy sector currently faces a unique set of challenges. On one hand, the U.S. domestic market and demand is steadily growing. It is, therefore, desirable to increase the domestic reserves in order to promote independence from external crude oil sources. Unfortunately, a vast portion of untapped oil deposits in the U.S. is heavy oil. In the last few decades, a large effort has been undertaken in order to tap into these domestic resources. There substantial technical literature on EOR techniques, including the in-situ combustion process that is exceptionally complex in nature both in a fundamental and in an applied context. However, the growing national concern about environmental pollution has increased the challenges associated with the successful development of the U.S. domestic oil resources.

CO2 emissions, greenhouse gases, and global warming are today common topics of the technical and well as non-technical literature. Despite the past studies and progress in modeling ISC processes and in the delineation of the reactions involved in these

processes, very limited literature exists on how to address the effluents resulting from the ISC operations. This work is dedicated to the challenge of extracting existing heavy oil reserves with emphasis on simultaneously addressing their energy and environmental aspects. The decision to explore simultaneous ISC and CO2 sequestration has substantial merit, in our opinion. Compressors and separators are, for example, necessary for the standard ISC operations. A large challenge economically for CO2 sequestration is the transportation from major point sources to candidate storage sites. Sequestering of CO2 at the source can, therefore, eliminate additional costs associated with these operations. All

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these considerations motivated us, therefore, to study scenarios whereby CO2 recycling could benefit ISC not only in terms of enhancing the oil production, but also in terms of reducing its environmental impacts.

In the first three chapters of this Thesis, we described the numerical aspects of CMG STARS used for our displacement calculations, and demonstrated that we could reproduce simulation results of past works involving in-situ combustion in a combustion tube. In chapter 4 we demonstrated that it is viable to recycle CO2 in a combustion tube. Recycling of CO2 was conducted for both adiabatic and non-adiabatic settings. In an adiabatic setting, CO2 recycling was successful even at low injection rates. While oil production rates decreased slightly, net CO2 emissions decreased more significantly. At the extreme case of 90% recycling of produced CO2, the oil production was reduced by 11%, but the net CO2 emissions were reduced by 61%. The performance was observed to be enhanced further when CO2 was recycled in lieu of N2 (as opposed to air), in order to keep the O2 concentrations high.

In non-adiabatic settings, we observed that a threshold injection rate of 0.68 PVI/min was needed to sustain a burning zone. However, once we reached this rate, we were able to recycle CO2 at the same levels as for the adiabatic setting. The performance for the nonadiabatic settings was observed to be better than for the adiabatic settings, with oil recovery rates decreasing only slightly (and in the case of 90% CO2 recycle, increasing), and the net CO2 reducing as much as 42%.

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In chapters 5 and 6 we expanded the concept of recycling from the combustion tube model to pseudo 2-D field-scale models. In chapter 5 we designed a cylindrical system in order to mimic a channel between an injection and a production well in settings that are similar to the well documented Belridge field. CO2 recycling was conducted at a fraction of 20%, 40%, 60%, and 80% of the production rate. With increasing CO2 recycle, oil production rates were observed to increase. This is attributed to CO2 dissolving into the oil phase and hereby reducing the oil viscosity. Eventually, CO2 saturates in the oil phase and CO2 production increases. However, for a given oil recovery, the net CO2 emissions are always reduced. For 80% CO2 recycling and an oil recovery of 80%, the net CO2 emissions were reduced 40% compared to a standard ISC process.

In chapter 6 we further expanded these ideas by introducing a set of relevant dimensionless parameters. We studied the dynamics of ISC with 60% recycling of produced CO2 over a wide range of Peclet mass and heat numbers, as well as for the Damkhler numbers for the coke burning and the coke formation reactions, and initial oil saturations. In all cases where a standard ISC process operated reasonably, the findings of chapter 5 were verified for the hybrid operations incorporating CO2 recycling. Furthermore, even in cases characterized by a very low coke formation activation energy, where ISC performs sub-optimally, recycling of CO2 can still be beneficial. In such a case, despite operating primarily in an LTO regime, recycling of CO2 did not completely extinguish the burning zone, and was demonstrated to reduce the oil phase viscosity significantly. From chapter 6, we gained confidence that CO2 recycling could benefit oil production and reduce CO2 emissions for a large range of oil field settings.

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Chapter 7 explores the application of ISC processes in realistic3-D field-scale settings including an inverted 9 spot pattern and a line-drive. In both cases, shared memory parallel processing was required to perform the numerical calculations in a reasonable time frame. The numerical displacement calculations demonstrate that 3-D displacements breaks down into a series of pseudo 1-D channels and that the observations from chapters 5 and 6 carry over to 3-D models. For the inverted 9 spot pattern, because of a large wellto-well distance and long range correlation in the heterogeneities of the subsurface, sweep can be very poor. Recycling of CO2 diminishes this problem somewhat and widens the channels that are formed in the course of the displacement and hereby improves the overall recovery by 20%. However, CO2 does not have unlimited opportunity to dissolve into the oil-phase, and hence CO2 savings were not significant. For the line-drive configuration, sweep is significantly better due to shorter well-to-well distances, combined with the utilization of multiple injection wells. When the produced CO2is recycled, the established flow channels do not widen significantly before production wells are shut-in (when compared to the inverted 9-spot pattern), and thus additional oil recovery is marginal. However, because more of the oil is displaced (better sweep), there is significant room for CO2 to accumulate and be stored in the subsurface (as well as diffuse into the un-swept oil phase). This results in a reduction in the net CO2production on the order of 23%. In terms of recovery of oil vs. CO2 emissions, both scenarios had the positive result of producing 30% more oil for a given level of CO2 emissions when CO2 was recycled.

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In summary, this work has explored the application of ISC and hybrid-ISC processes from lab-scale to field-scale with emphasis on improving oil recovery while at the same time reducing emissions. For each case, we have verified the applicability of CO2 recycling, and have confirmed a range of reasonable parameters that describe potential field-scale applications. The observations and analysis presented in this thesis provide a framework for expanding the applicability of ISC processes with CO2 recycling as a commercially-viable and environmentally-responsible EOR process.

8.1. Future work Four areas have been identified that are both much needed and would facilitate future research activities and advances related to ISC processes. These include: Improving computational performance of the ISC simulations Integrating compositional modeling Improving representation of reaction mechanisms Optimizing well pattern/locations in pilot and field scale applications

Improving the computational efficiency of ISC simulation tools is key to the latter three areas of future work. Gaining either access to larger shared-memory computation centers or access to a simulator that uses a cluster parallelism paradigm will be of utmost importance. With more efficient simulation frameworks, the integration of more complex and realistic physical models can become a reality.

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Compositional modeling of ISC has been investigated for small scale computations by Kristensen et al. (2007). It will only be a matter of time before thermal EOR begins to embrace it as well. This should lead to more confidence in the results, as generally compositional modeling is considered a more realistic representation of the fluid interactions as compared to the K-value approach that is currently being used in CMG STARS.

More detailed reaction mechanisms have been introduced recently (Freitag and Exelby, 2006;Jain et al. 2010). Inclusion of SARA models could be beneficial to building more confidence in ISC modeling efforts. Again, a key issue is run-time; with better numerical performance we have more options for including additional relevant details.

Finally, optimization of well placements and operational modes in ISC processes is a largely unchartered territory. For example, there must exist a well configuration between the 9 spot and the line-drive that maximize sweep, and minimizes net CO2 production. Optimization techniques/strategies must be developed to explore and understand for which well configurations we will find the best compromise between energy and environmental needs.

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