Hydrocarbon Classification and EOR 101

Table of Contents

TABLE OF CONTENTS........................................................................................... 1 ABSTRACT .......................................................................................................... 3 TABLE OF APPENDICES ........................................................................................ 3 INTRODUCTION.................................................................................................... 4 HUBBERT’S “PEAK” AND BELL CURVE ................................................................ 4 GEOPOLITICS OF INTERNATIONAL HO & BITUMEN DEPOSITS ............................... 5 ENVIRONMENTAL BITUMEN & HO ISSUES ........................................................... 7 OILFIELD JARGON AND PROFESSIONS ................................................................... 8 GEOSCIENCES, ACCOUNTING, LAND, LEGAL........................................................ 8 DRILLING AND PETROPHYSICAL ENGINEERS ........................................................ 9 PRODUCTION AND RESERVOIR ENGINEERS ........................................................... 9 CRUDE OIL CLASSIFICATION ..............................................................................11 INTERMEDIATE HYDROCARBONS ........................................................................11 SINGLE-PHASE FLOW IN POROUS MEDIA.............................................................13 DRY GAS RESERVOIRS .......................................................................................13 LNG AND ENERGY POLICY ................................................................................14 WET GAS RESERVOIRS .......................................................................................16 2-PHASE RELATIVE PERMEABILITY AND FRACTIONAL FLOW ...............................16 RELATIVE PERMEABILITY AND MOBILITY RATIO ................................................17 RETROGRADE GAS RESERVOIRS .........................................................................18 VOLATILE OILS ..................................................................................................18 CRUDE “BLACK” OILS........................................................................................20 CONVENTIONAL (LIGHT & INTERMEDIATE) CRUDE OIL ......................................20 API GRAVITY AND HEAVY CRUDE OILS (HO) ....................................................21 HO & BITUMEN, ACCORDING TO USGS:............................................................22 SHALES, ACCUMULATIONS, AND “OIL SHALES”..................................................23 RESERVOIR CONDITIONS AND FLUID DENSITIES ..................................................24 RESERVOIR CONDITIONS AND OIL VISCOSITIES ...................................................24 RESERVOIR CONDITIONS, POROSITIES & WETTABILITIES ....................................25 PRIMARY OIL RECOVERY DRIVE MECHANISMS ...................................................25 ORIGINAL OIL IN PLACE AND RECOVERY EFFICIENCY .........................................26 CONSEQUENCES OF OIL RESERVOIR DEPLETION ..................................................28 WATERFLOOD AND EOR (IOR) UNITS ...............................................................28 SCREENING PRODUCING OIL FIELDS FOR WF & EOR..........................................29 WATER DRIVE, DISPOSAL AND SUPPLY...............................................................29 WATERFLOODING & HOT WATER INJECTION ......................................................30 WHY WATERFLOODS UNDER-PERFORM ..............................................................31

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CHEMICAL FLOODING (CF) INTRODUCTION ........................................................32 ALKALINE FLOODING AND ASP..........................................................................32 SURFACTANTS, MICELLES, TYPE I MICRO-EMULSIONS .......................................32 MICRO-EMULSION TYPES II & III .......................................................................33 SURFACTANTS IN E&P .......................................................................................34 POLYMERS, GELS, AND GELATION ......................................................................34 OILFIELD POLYMERS AND GELS ..........................................................................35 MICROBIAL EOR................................................................................................36 CF EOR SUMMARY ...........................................................................................37 MISCIBLE EOR (CO2) PROCESSES:.....................................................................37 CO2 FLOOD LOGISTICS & OPERATIONS...............................................................38 SCREENING OIL-CO2 MISCIBILITY ......................................................................39 EOR FOR HO FIELDS: TRHO............................................................................40 CYCLIC STEAM INJECTION (CSI).........................................................................41 STEAMFLOODING (SF)........................................................................................41 IN-SITU COMBUSTION (I-SC, OR FIRE FLOOD) .....................................................42 TOE TO HEEL AIR INJECTION (THAI™)..............................................................42 DILUTION OF HO FOR PIPELINES.........................................................................43 SURFACTANTS, HO, & BITUMEN ........................................................................44 “DEAD” OIL AND RECOVERY EFFICIENCY...........................................................44 STRIPPER WELLS IN THE US ...............................................................................45 AN EMERGING EOR CHEMICAL FLOODING PROCESS ..........................................45 EOR AND CO2 SEQUESTRATION ........................................................................46 FLUE GAS & GREENHOUSE GASES......................................................................47 US FLUE GAS LOCATIONS ..................................................................................47 US LOCATIONS FOR GEOLOGICAL CO2 SEQUESTRATION .....................................49 FLUE GAS COMPOSITION ....................................................................................50 FLUE GAS PROCESSING ......................................................................................50 PROCESSING FLUE GAS NOX ...............................................................................51 PROCESSING FLUE GAS SO2 ...............................................................................51 PROCESSING FLUE GAS MERCURY, HG ...............................................................52 GREENHOUSE GAS SEQUESTRATION ...................................................................52 CO-OPTIMIZATION FAILURE ................................................................................53 HORIZONTAL DRILLING IN PROVEN OILFIELDS....................................................54 MICRO HOLE DRILLING ......................................................................................56 SUMMARY: LIGHT OIL LEGACY, HEAVY OIL DESTINY .......................................57 US ENERGY POLICY ISSUES................................................................................59 REFERENCES ......................................................................................................60

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Abstract The Global Industry of Exploration & Production (E&P), refining, transportation, distribution, and sales of hydrocarbons (oil & gas) give and take tremendous influence from and upon International geopolitical economics and logistics. Based upon environmental, ecological, personal and national economics, 2009 may mark the beginning of the end of the “Hydrocarbon Age” of Man. May this Age conclude with as little torment as the Stone Age, ages of Bronze, Iron, Coal, etc... Should this End be near, exit strategies for individuals, companies, provinces, and nations will be required. New information and technologies are available to assist with this eventual shift from reliance upon hydrocarbons to fuel our vehicles, heat and cool our buildings, and generally support commerce and culture on all scales. Inventory and study of these data and technologies is vital to promote progress, control human convenience, prevent human tragedy, preserve flora and fauna, foster sustainable ecology and environment, and preserve political stability. Traditional and alternative energy resources must be balanced in delicate compromise and interplay. This document focuses upon some aspects of the science, engineering and technologies of E&P, at a college freshman level. The overall role of E&P in upcoming events will not be to solve the many problems now in view. Opportunities to forestall identified problems, mitigate their intensity, and reduce their consequences seem apparent, however. Transition to the New Energy Economy will benefit from efforts to sustain and implement good ideas, maximum identification of practical oil & gas resources, and quest for sustainable modifications to current systems. Enhanced oil recovery (EOR), especially as applied to heavy oil (HO) and bitumens, is perhaps the most powerful tool E&P can wield in the near future. Improved national energy policies and environmental policies for many nations may be attainable through careful study and collaboration between nations. Our citizens and companies would certainly benefit from application of foresight, practicality, and timing to enact genuine US National Energy Policy and US National Environmental Policy. Table of Appendices
APPENDIX 1. DARCY’S LAW..................................................................................................62 APPENDIX 2. PITCH (ASPHALT) LAKES ..................................................................................63 APPENDIX 3. FAIRWAY JAMES LIME FIELD, EAST TEXAS .......................................................63 APPENDIX 4. EXXON MOBIL ADDS 1.5B BARRELS TO PROVED RESERVES ................................64 APPENDIX 5. OIL FROM CANADA’S TAR SANDS CAN BE MADE ‘CLEAN,’ OBAMA SAYS.........64 APPENDIX 6. ANWR RESIDENTS FAVOR DEVELOPMENT.........................................................66 APPENDIX 7. REVIEWS OF HUBBERT'S PEAK: THE IMPENDING WORLD OIL SHORTAGE ..........66 APPENDIX 8. REVIEWS OF MATTHEW R. SIMMONS’ TWILIGHT IN THE DESERT:........................71 APPENDIX 9. RADIAL JET ENHANCEMENT..............................................................................74 APPENDIX 10: ........................................................................................................................75 “SURFACTANT-BASED PHOTORHEOLOGICAL FLUIDS: EFFECT OF THE SURFACTANT STRUCTURE” .............................................................................................................................................75

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Introduction A definition: petroleum, pe·tro·le·um (pə-trō'lē-əm) A thick, flammable, yellow-to-black mixture of gaseous, liquid, and solid hydrocarbons that occurs naturally beneath the earth's surface, can be separated into fractions including natural gas, gasoline, naphtha, kerosene, fuel and lubricating oils, paraffin wax, and asphalt and is used as raw material for a wide variety of derivative products. [Middle English, from Medieval Latin petrōleum: Latin petra, rock; see petrous + Latin ōleum, oil; see oil.] Hubbert’s “Peak” and Bell Curve M. King Hubbert was a Shell geologist who in 1956 predicted that US oil production would peak in the early 1970s and then begin to decline. Hubbert was dismissed by many experts inside and outside the oil industry. Pro-Hubbert and anti-Hubbert factions arose and persisted until 1970, when US oil production peaked and started its long decline. The Hubbert method is based on the observation that oil production in any region follows a bell-shaped curve. Production increases rapidly at first, as the cheapest and most readily accessible oil is recovered. As the difficulty of extracting the oil increases, it becomes more expensive and less competitive with other fuels. Production slows, levels off, and begins to fall. This can be observed in any sedimentary basin producing oil. Hubbert demonstrated that total US oil production in 1956 was tracing the upside of such a curve. To know when the curve would most likely peak, however, he had to know how much oil remained in the ground. Underground reserves provide a glimpse of the future: when the rate of new discoveries does not keep up with the growth of oil production, the amount of oil remaining underground begins to fall. That's a tip-off that a decline in production lies ahead. Kenneth S. Deffeyes is the son of a petroleum engineer; he was born in Oklahoma, "grew up in the oil patch," became a geologist and worked for Shell Oil before becoming a professor at Princeton University. In Hubbert's Peak, Kenneth S. Deffeyes, writes with good humor about the oil business, but he delivers a sobering message: the 100-year petroleum era is nearly over. Global oil production will peak sometime between 2004 and 2008, and the world's production of crude oil "will fall, never to rise again." If Deffeyes is right--and if nothing is done to reduce the increasing global thirst for oil--energy prices will soar and economies will be plunged into recession as they desperately search for alternatives. It's tempting to dismiss Deffeyes as just another of the doomsayers who have been predicting, almost since oil was discovered, that we are running out of it. But Deffeyes makes a persuasive case that this time it's for real. This is an oilman and geologist's assessment of the future, grounded in cold mathematics. And it's frightening. Deffeyes used a slightly more sophisticated version of the Hubbert method to make the

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global calculations. The numbers pointed to 2003 as the year of peak production, but because estimates of global reserves are inexact, Deffeyes settled on a range from 2004 to 2008. Three things could upset Deffeyes's prediction. One would be the discovery of huge new oil deposits. A second would be the development of drilling technology that could squeeze more oil from known reserves. And a third would be a steep rise in oil prices, which would make it profitable to recover even the most stubbornly buried oil. Above summary is adapted from Scientific American review (See Appendix 7.) of Deffeyes’ book. While exact dates are unknown, analysis of International sedimentary basins indicates that a peak in International oil producing capacity is in the very near future, if not already past. Simmons’ Twilight in the Desert (See Appendix 8.), also disturbing, dwells on Saudi reserves and deliverability. The American Petroleum Institute estimated in 1999 that the world's oil supply would be depleted between 2062 and 2094, assuming total world oil reserves at between 1.4 and 2 trillion barrels and consumption at 80 million barrels per day. Geopolitics of International HO & Bitumen Deposits An abundance of information on heavy and extra-heavy oils and what USGS calls “bitumens” was published at http://pubs.usgs.gov/fs/fs070-03/fs070-03.html. Table 1 is excerpted from this publication: Table 1. 2003 USGS Summary: International distribution of estimated technically
recoverable heavy & extra-heavy oil and natural bitumen in billions of barrels (BBO). The total estimated petroleum in these known accumulations is about equal to remaining conventional (light) oil reserves, and is concentrated in the Western Hemisphere. recovery factor* North America South America W. Hemisphere Africa Europe Middle East (ME) Asia Russia E. Hemisphere GLOBAL TOTAL 0.19 0.13 0.13 0.18 0.15 0.12 0.14 0.13 0.13

recoverable
Heavy Oil, BBO 35.3 265.7 301.0 7.2 4.9 78.2 29.6 13.4 133.3 434.3

recovery factor* 0.32 0.09 0.32 0.10 0.14 0.10 0.16 0.13 0.13

recoverable Natural Bitumen, BBO

530.9 0.1
531.0

43.0 0.2 0.0 42.8 33.7
119.7

650.7

*Recovery factors were based on published estimates of technically recoverable and in-place oil or bitumen by accumulation. Where unavailable, recovery factors of 10 percent and 5 percent of heavy oil or bitumen in place were assumed for sandstone and carbonate accumulations, respectively.

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Especially for assignment to various classes of oil refineries, crude oils are classified according to their API Gravities, sulfur content, and other measured characteristics. Thus the implications of downstream Refining and Marketing components of the Oil and Gas Industry have influenced the Exploration and Production components’ (E&P) view of crude oil classification. Before quickly reviewing the definition of API Gravity and the International classifications of various classes of hydrocarbon reservoirs, a quick introduction to the International setting of the known Heavy Oil (HO) and Bitumen deposits and their potential geopolitical significance is provided. An abundance of information on heavy and extra-heavy oils and what USGS calls “bitumens” was published at http://pubs.usgs.gov/fs/fs070-03/fs070-03.html. Table 1 is excerpted from this publication: In addition, 212.4 billion barrels of natural bitumen in place is located in Russia but is either in small deposits or in remote areas in eastern Siberia. The USGS article excerpted here is a clear patriotic and scientific call for official and public awareness. HO and bitumens, as strategic domestic resources concentrated in the Western Hemisphere, could be key elements in a National Energy Policy. Environmental Bitumen & HO Issues In 2003, the USGS lumped light and intermediate crude oils together as “conventional” or “light,” and pointed out:
“Because conventional light oil can typically be produced at a high rate and a low cost, it has been used before other types of oil. Thus, conventional oil accounts for a declining share of the Earth's remaining oil endowment. In addition to assessing conventional oil resources, scientists of the US Geological Survey's Energy Resources Program collect data on the abundant energy resources available as heavy oil (including extra-heavy oil) and natural bitumen... Historically, heavy oil was found incidentally during the search for light oil and was produced by conventional methods when economically feasible. However, to sustain commercial well production rates, heavy and extra-heavy oil production almost always requires measures to reduce oil viscosity and to introduce energy into the reservoir... Natural bitumen (often called tar sands or oil sands) and heavy oil differ from light oils by their high viscosity (resistance to flow) at reservoir temperatures, high density (low API Gravity), and significant contents of nitrogen, oxygen, and sulfur compounds and heavy-metal contaminants. They resemble the residuum from the refining of light oil… The Western Hemisphere has 69 percent of the world's technically recoverable heavy oil and 82 percent of the technically recoverable natural bitumen. In contrast, the Eastern Hemisphere has about 85 percent of the world's light oil reserves.”

Many environmental issues are associated with recovery of heavy oil and bitumens. Traditional thermal recovery processes include consumption of water, fuels, and solvents. Tar sand recovery may also involve surface mining and, similarly, use water, fuels and solvents, and is often unsightly on profoundly grander scales. Tar sand recovery involves strips and open pits of Canadian land.

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Please note that Canada has huge quantities of oil, gas, minerals, timber, etc. These are on monumental expanses of abundant land remote from population centers, environmental political success, and tourist attractions. Canadian government has legitimate, sound, and fortunate jurisdiction over exploitation and their fiscal attitude might be named. Call it “needy,” “greedy,” pragmatic, or statesmanlike, it is very profitable to the government and perhaps a vital benefit to citizens of the Great White North. The ownership of Canadian mineral royalties by the Crown will always outweigh environmentalism. Canada is perfect for study of exploitation technical issues without undue environmental and political restraint. US E&P professionals face greatly enhanced ethical, moral, and legal issues overprinting those technical issues. Oilfield Jargon and Professions The oil and gas (O&G) industry contains several sectors: “upstream” exploration and production (E&P) sector, midstream gas processing and transmission (pipeline) sector, and “downstream” refining and distribution sectors. In E&P, shallower rock formations and equipment are called “uphole” from those deeper; deeper ones are called “downhole” from shallower ones. Equipment on the ground surface may also be called “uphole,” and those below the surface are usually called “downhole.” All the operations of drilling and producing oil and gas wells are recorded in the well history, a vital administrative tool. Additional detailed records reside in various documents (permits, notices) legally required by regulatory agencies. Lease Net Revenues of each Lease are shared by Joint Venture (JV) holders of Working Interests (WI’s) in the Lease, after subtraction of taxes, overriding royalty interests (ORRI’s), and other operating expenses from the Lease’s Gross Revenue. Geosciences, Accounting, Land, Legal Accounting and bookkeeping performs normal and exotic accounting for accounts payable and receivable, taxes, and especially Division Orders (DO’s) by which owners of working interests (WI’s). Legal contracts and procedures are performed by attorneys, their clerks and assistants, including lease operating agreements (LOA’s). Geoscience and Exploration: exploration geologists and geophysicists, also called explorationists, pick targets with hopeful potential to discover new oil and gas reservoirs underground. Geophysical data, including seismic, gravity, magnetic, and x-ray fluorescence surveys are used along with data from existing wells (“well control”) in these processes. Geoscience and land services may be performed by operating company employees or by outside consultants, which may be freelance partnerships between geoscientist and landmen. Land: “landmen” meet owners of downhole mineral rights and uphole surface property, and negotiate leases which control payment of ORRI’s and surface rentals and liabilities. Before a lease can be drilled, an LOA must be signed by WI holders to assign a state-

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licensed operating company to “operate” the lease. Later in the lease development process, exploitation and development geologists and geophysicists pick additional well locations to capitalize on existing properties and/or new discoveries. Locations are picked for downhole geology and uphole considerations and prepared, numerous other rentals and services are paid, and drilling expenses and liabilities are borne by Operating Companies registered with State regulators and other WI holders. After all WI holder’s finalize and approval the LOA, each lease expense for geoscience labor, data, or processing, drilling, workover, recompletion, and stimulation is submitted by operating company to WI holders in an authority for expenditure (AFE), requiring each WI to consent or non-consent. Actual drilling and production operations are performed in the field using procedures detailed in a prognosis for the operations. Drilling and Petrophysical Engineers Drilling Department: Drilling managers, drilling engineers, and wellsite foremen (“company men”) track the progress of each wells while it is being drilled. Drilling rigs are commonly owned by drilling contractors. First penetration of ground surface is called “spudding,” occurring on “spud date.” Drillpipe is generally lowered in 30’ “joints,” turned to the right by a kelly bushing in a rotary table which is like a giant motorized wrench, as drilling fluid is pumped through the entire “string” of drillpipe to lubricate the drillbit and return rock cuttings to wellsite surface. Drillpipe is occasionally withdrawn in 60-90’ “stands”; this operation is called “tripping drillpipe.” Geoscientists and/or petroleum engineers evaluate each well is evaluated after reaches its Total Depth (TD). An openhole wireline unit is dispatched to wellsite to run electric porosity and resistivity logs. Petrophysical engineers (petrophysicists) specialize in casing point evaluation of wells, using well logs, mud logs, cores, well tests, and other data acquired during drilling process. During the casing point decision the opportunity for an attempt to produce hydrocarbons, a “completion” is sought. A casing election made according the LOA with consent or non-consent of WI holders. If incremental economics are deemed to allow the expense to set production casing, a casing crew arrives to assemble the long string of steel production pipe reaching to TD. Cement trucks then arrive to mix oilfield cement, pump it down the drillpipe to return behind the casing, providing a hopefully strong seal between formation rock layers and production pipe. This “cement job” may be the drilling personnel’s last wellsite duty. Petrophysicists also assist other petroleum engineers and geoscientists to further scrutinize well data for additional opportunities, especially recompletions uphole of the deepest completion, which is almost always performed first. Production and Reservoir Engineers Production engineers: Many petroleum production engineers hand both downhole completion and uphole facilities work, but these activities are discussed separately here. After running a wireline cement bond log to confirm a successful cement job, completion engineers design the downhole system the packers, plugs, and tubing, submersible

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pumps, gas lift valves, and/or rods. They call out a wireline perforating unit, which blasts controlled perforations in the production casing by electrically detonating shaped charges downhole. Perforated interval will probably be acidized, and a swabbing unit may then check the wellbore for liquid entry. Facilities engineers specialize in the uphole meters, compressors, separators, dehydrators, treaters, pumps, pipes, valves, tanks or tank batteries, often served with stairs and walkways for safety. Reservoir engineers assist in justifying the choice of a drilling location and, with petrophysicists, to evaluate a well’s success at TD. They then monitor the data in each field to watch for problems and opportunities. They project the oil, gas, and water anticipated from fields for many years into the future. Economic forecasts of oil and gas prices are used with these production forecasts to estimate the economic performance of these assets. Reservoir engineers have primary responsibilities for the 10-k Reports required by the SEC for public corporations. Ultimately these activities combine to set a present value (PV) on each asset, employing discounted net cash flow (DCNF) method. Reservoir engineers use computer programs called reservoir simulators to match the production histories of fields and for numerical experimentation to plan waterfloods (WF), enhanced oil recovery (EOR) projects, and reservoir gas cycling to enhance recovery in retrograde gas and volatile oil reservoirs. They use other programs to analyze the pressure-volume-temperature (PVT) behavior of complex reservoir fluid systems. Along with production engineers, they use “nodal analysis” software to analyze and predict the pressure drops that occur in every interval from the perforations at a completion through downhole and uphole equipment all the way to the stock tanks or gathering lines. In the 1970’s, the Environmental Protection Agency (EPA) and Occupational Safety and Health Administration (OSHA) were created just in time for the Oil Boom following the OPEC oil embargo of 1973. Since then the O&G industry has evolved the merging of these priorities with security to create the acronym “HSSE” for health, safety, security, and environmental emphasis.

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Crude Oil Classification Crude oil is classified as light, medium, heavy, or extra-heavy, according to its measured API Gravity, based on this crude oil’s specific gravity (SAG), its gravimetric density compared to that of water, at 60°F. API Gravity = (141.5 / SG@60°F) - 131.5, so SG = 141.5 / (API Gravity +131.5). This temperature of 60°F is a component of Standard Temperature and Pressure (STP). The exact temperature of STP has been numerically redefined regularly since the STP concept was introduced. Currently the North America petroleum Industry uses predominantly STP of 60°F and 14.73 psi (to define the natural gas sales unit MCF @STP, for example). Natural gas companies in Europe and South America have adopted 15 °C (59 °F) and 101.325 kPa (14.696 psi) as their STP. Light crude oil is defined as having an API Gravity higher than 31.1°API. Gasoline’s API Gravity averages 50°, so its SG= 141.5 / (50° + 131.5) = 0.778. Intermediate crude oil or Medium crude oil is defined as having an API Gravity between 22.3°API and 31.1°API. Note the EU defines medium crude gravity between 25.7° API and 31.1°API. Heavy crude oil is defined as having an API Gravity between or 10° and 22.3° API. The EU has a slightly different definition of ‘heavy'. Their cutoff between ‘heavy' and ‘intermediate' lies at 25.7° API Gravity. This causes there to be more “heavy” crude oil in their view. Extra-heavy crude oil is generally defined as having an API Gravity below 10°.
Graphic copyright Schlumberger "Oilfield Review.” From Carl Curtis and others, 2002, Oilfield Review, v. 14, no. 3, p. 50.

Intermediate Hydrocarbons The continuum of hydrocarbons is best understood within the unified concepts of fractionation and equilibria related to deposits of natural gas, volatile oils, and crude oils. These will be discussed in sections below.

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When a wellsite geologist uses a wellsite gas chromatograph (GC) to analyze the combustible gases, these hydrocarbon gases are fractionated to methane (CH 4), ethane (C2H6), propane (C3H8), and the butanes (C4H10’s). The 5 gases are reported as C1, C2, C3, C4, and C5. C4 and C5 are the butanes; pentane is often a liquid and thus not always logged.

Figure 1. Gas Chromatograph display, showing a retrograde gas or wet gas response. The butanes are liquids at many winter temperatures. The pentanes would be liquids at all common uphole temperatures. All might gaseous in situ, depending upon downhole temperature and pressure. http://www.srigc.com/

Please note that methane is CH4, ethane is C2H6, propane is C3H8, butanes are C4H10’s, pentanes are C5H12’s, and hexanes are C6H14’s. Methane occurring alone is often called natural gas or dry gas; a more inclusive definition of dry gas is provided below. The collection of ethane through the hexanes, CH4- C6H14’s, is called intermediate hydrocarbons, or intermediates. The intermediates are discussed regularly in classification of hydrocarbon gases and liquids. Butane, also called n-butane, is the unbranched alkane with four carbon atoms, CH3CH2CH2CH3. Butane is also used as a collective term for n-butane together with its only other isomer, isobutane (also called methylpropane)(CH 3)3;; the isobutane molecule is triangular. When the butanes are blended with propane and other hydrocarbons, it is referred to commercially as liquefied petroleum gas (LPG). For decades the butane’s, C4H10’s, were commonly used as fuels, especially in agricultural engines. Propane, C3H8, and LPG have replaced the butanes in these routine rural applications, and propane now commonly used in motor vehicles, outdoor cooking, and home heating. This replacement avoids the problem of butane condensing to a vaporless liquid during cold weather. Liquid hydrocarbons do not burn; only hydrocarbon vapors burn under control by design. Likewise, pentanes, C5H12, and hexanes, C6H14, are liquids at STP.

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All these heavier hydrocarbons require vaporization by some process such as carburation or fuel injection to fuel controlled combustion. Single-Phase Flow in Porous Media Darcy's law is a simple proportional relationship between the instantaneous discharge rate through a porous medium, the viscosity of the fluid and the pressure drop over a given distance. The rate at which a fluid flows through a permeable substance per unit area is equal to the permeability, which is a property only of the substance through which the fluid is flowing, times the pressure drop per unit length of flow, divided by the viscosity of the fluid. Darcy’s Law is presented below in its 1D form:
The total discharge, Q (units of volume per time) is equal to the product of the permeability of the medium, the crosssectional area (A) to flow, and the pressure drop (Pb − Pa), all divided by the fluid’s dynamic viscosity µ, and the length. Figure 2. Schematic view of Darcy’s Law for single-phase fluid flow through a porous medium.

Q = - κ A (Pb – Pa) / µ L.
The total discharge, Q (units of volume per time, e.g., m³/s) is equal to the product of the permeability (κ units of area, e.g. m²) of the medium, the cross-sectional area (A) to flow, and the pressure drop (Pb − Pa), all divided by the dynamic viscosity µ (in SI units e.g. kg/(m·s) or Pas), and the length L the pressure drop is taking place over. The negative sign is needed because fluids flow from high pressure to low pressure. So if the change in pressure is negative (in the x-direction) then the flow will be positive (in the xdirection). Dividing both sides of the above equation by the Area A results in a more general notation for the differential form of Darcy’s Law:

q = - κ  p / µ.
This simple law, detailed in Appendix 1., is completely adequate to formulate numerical simulations of saturated groundwater movement. It also describes the movement of dry gas and wet gas in downhole reservoirs lacking oil or water, and is completely adequate for their numerical simulation. Darcy’s Law is perhaps the most unavoidable buzzword in subsurface reservoir engineering. Dry Gas Reservoirs Virtually all petroleum reservoirs contain some accumulation of methane, CH 4. This methane may be dissolved in crude or volatile oil. It may have accumulated as a gravitystable gas “cap” above a bank of saturated oil. Most oil deposits also contain some intermediates. Methane in a cap above oil is usually rich in intermediates. Methane

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found without oil may be almost pure (dry) or may be dissolved with intermediates. Methane, ethane, and propane, with their small molecules, are gases at STP and at all common surface atmospheric conditions. If a petroleum reservoir contains only water, methane, ethane, and/or propane, the deposit is called dry gas. The dry gas may also contain butane, C4H10’s, but these will condense at the surface during cold weather.
Dry gas is primarily methane, perhaps including some intermediates. This is the phase diagram of a typical dry gas. Both the line of isothermal reduction and separator condition point are outside the phase envelope. The looping lines within the phase envelope represent constant liquid volume as fractions of total volume. They are called iso-vols or quality lines. The dry gas hydrocarbon mixture is 100% gas in the reservoir, the tubing, at surface, and even at separator conditions. The very light intermediates, C2H6, and/or C3H8, will require processing equivalent to refrigeration for separation from methane. Figure 3. Dry Gas (methane, ethane, and/or propane) McCain, 1990.

Local or remote offsite processing of the ethane, propane, and/or butane enrichments to methane can be very profitable, however. These are generally called “plant products.” The “gas plants” which separate them from methane may be owned by the E&P venture, the pipeline transmission company, or a 3rd-party midstream specialist. Ethane and butane may have markets as petrochemical feedstocks or heavy oil diluent. Butane and propane and LPG are also commercial fuels, of course. These most convenient gases can also remain dissolved in natural gas and contribute to the heat value of the gas. Their contribution should be honored when negotiating gas unit sales value. Specification and timing of the heat value measurement will help optimize pipeline sales contracts. The International oil markets which swirl with superstition and uncertainty are not completely reproduced in the Continental markets for natural gas. Thus some additional stability occurs in the natural gas markets. For the first 100 years of E&P, markets for natural gas were very limited; many gas discoveries were plugged as disappointments, and much gas associated with oil wells was wasted by flaring. Great abundance, low prices, gathering, transmission, and distribution pipeline systems combined with oil rationing and labor shortage to accelerate heating with gas during WW2. LNG and Energy Policy Before this dry (natural) gas can be moved overseas it must be liquefied cryogenically. Liquefied natural gas (LNG) technology is mature but only applied to specific isolated

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deposits and markets. Methane is refrigerated to –163°C, -258°F, reducing the methane’s volume below STP by approximately the factor 600. LNG is about half as dense as water, so it is suited to transport by sea to locations without adequate domestic natural gas supplies. LNG is a “transparent, odorless, non-toxic, noncorrosive,” very cold, very flammable liquid, stored and transported in insulated pressure containers. About 200 LNG transport vessels are in service, and at least 13 nations export to 17 nations importing LNG. LNG prices are sometimes more than twice those for natural gas. In absence of very long pipelines and/or LNG shipments, natural gas supplies are huge geopolitical issues, especially in Eurasia. Europe and Asia rely upon former Soviet Republics for natural gas supplies. Hopefully the gas markets on other Continents will perform less brutally than has Eurasia’s market. About 84% of the US natural gas supply, about 19.3 TCF annually, comes from the approximately 500,000 US natural gas wells and associated gas from a similar number of US oil wells. About 83% of US gas imports, 3.3TCF annual, come from Canada. Slightly more US gas is exported to Mexico than is imported from Mexico. The 2% balance of US natural gas needs, 771BCF annual, is met by importing LNG from Trinidad/Tobago (58%), Algeria, Egypt, Nigeria, Equatorial Guinea, and Qatar. The 8 US LNG import terminals are located on the Gulf of Mexico coast (4), in Massachusetts (2), in Maryland and Georgia. Mexico has terminals at Altamira and Baja California. The US exports LNG to Japan, Mexico, and Russia. The oldest marine terminal has been in service at Kenai, Alaska since 1969, exporting mostly to Japan and other Pacific Rim customers. At least 12 LNG import terminal proposals are now before the FERC, including Atlantic, Pacific, and Gulf Coasts, including the Pacific Northwest region. Compared to 2005 demand, International LNG import demand will double in the next few years. With Total’s commitment to develop a terminal in Yemen, that nation is posed to become the World’s newest exporter of LNG. The US natural gas Industry has underwritten moderate product cost increases by its aggressive replacement of reserves since 2000. The bulk of these new reserves have been provided by offshore oil and gas fields and unconventional gas reservoirs (“tight gas” from low-permeability reservoirs like shales, coal bed methane (CBM), and gas hydrates. Natural gas and LNG deserve detailed attention in the US Energy Policy as a domestic strategic resource.

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Wet Gas Reservoirs
Wet gas reservoirs produce condensate stock tank liquids, with GOR’s above 5,000 (even 50,000) scf/STB. The gravity of the stock tank liquid is in the 40-50°API range and does not change during reservoir life; GOR is also constant during reservoir life. This liquid is usually clear as water. No hydrocarbon liquid exists in the wet gas reservoir downhole. The pressure path line in a wet gas phase diagram does not enter the liquid phase envelope. Separator conditions lie within the phase envelope, however, causing liquid to be formed at the surface.

Figure 4. Phase diagram for a wet gas reservoir. McCain, 1990.

The hydrocarbon accumulations in most petroleum reservoirs are saturated with water due to their contact and equilibrium with water. Luckily the solubility of water in hydrocarbons is low. As a classification, the term “wet gas reservoir” is named, not for water, but for their rich cocktails of downhole hydrocarbons in gaseous form. Those downhole gases that condense in separators at surface facilities are called condensates. These volatile, (brown, orange, or green) translucent and perhaps almost transparent stock tank liquids may contain hexanes and above, pentanes, butanes and limited evaporating propane. In the early oil and gas business these were sometimes called “drip gas” because they might be burned as gasoline in a vehicle. Gasoline’s API Gravity averages 50°, so its SG= 141.5 / (50° + 131.5) = 0.778. 2-Phase Relative Permeability and Fractional Flow The Buckley–Leverett equation or the Buckley–Leverett displacement can be interpreted as a way of incorporating the microscopic effects due capillary pressure in two-phase flow into Darcy's law. In a 1D sample (control volume), let S(x,t) be the water saturation; f is the fractional flow rate, Q is the total flow, Ф (φ, phi) is porosity and A is area of the cross-section in the sample volume. Forward in this primer, subsequent types of oil and gas accumulations will require concepts of 2-phase reservoir flow. Interfacial tension (IFT) forces are responsible for wettability (hydrophilic (water-wet), lipophilic or hydrophobic (oil-wet), or amphiphilic (mixed or “dalmation” wettability)) between oil and rock, and capillarity and gravity segregation between oil, gas, and water and water. In fluid dynamics, the Buckley–Leverett equation is a transport equation used to model two-phase flow in porous media[1] . The Buckley–Leverett equation or the Buckley–

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Leverett displacement can be interpreted as a way of incorporating the microscopic effects due to capillary pressure in two-phase flow into Darcy's law. The Buckley–Leverett equation is derived for a 1D sample given  mass conservation  capillary pressure pc(S) is a function of water saturation S only  dpc / dS = 0 causing the pressure gradients of the two phases to be equal. General solution: The solution of the Buckley–Leverett equation has the form S(x,t) = S(x − U(S)t) which means that U(S) is the front velocity of the fluids at saturation S. Relative Permeability and Mobility Ratio Especially during the development of reservoir engineering for secondary recovery (waterflooding), the relative permeability concept received generations of empirical and theoretical research. A reservoir mobility gas-liquid mobility ratio, Mg-l, of gas to liquid, can be defined as

M g-l = kg µl / kl µg
where M= µl and µg. are the viscosities of the liquid and gas phases, kg and kl are the 2-phase reservoir relative permeabilities to gas and liquid.

Figure 5. 2-phase oil-water relative permeability curves measured in laboratory (2004, L. Qingjie, L. Li, Manli).

A similar mobility ratio can be formulated for water to oil, M w-o, gas to oil, Mg-o, etc. The

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most interesting relative permeability considerations are in 3-phase reservoir circumstances, where Herb Stone’s 3-phase relative permeabilities equations are required to estimate 30-phase data from 2-phase data for use in numerical reservoir simulation programs. Retrograde Gas Reservoirs An initial producing GOR of 3,300 to 5,000 indicates a very rich retrograde gas. Without pressure maintenance, such a rich gas will condense sufficient retrograde liquid to represent a saturation of 35%. Even such a large quantity of retrograde liquid normally cannot be produced, due to its unfavorable mobility ratio as compared to reservoir gas. Economics incentive pressure maintenance and/or gas cycling to keep this valuable solvent/gas in its gaseous phase! GOR > 50,000 indicates negligible retrograde effect. Retrograde gas reservoirs produce lightly colored, brown, orange, greenish, or waterwhite stock tank condensates with the same range of API Gravity, 40-50° API, as the liquids from wet gas reservoirs. The surface gas is very rich in intermediates; it is usually processed to remove propane, butanes, pentanes, and/or heavier hydrocarbons. These are often called plant liquids or plant products.
Retrograde gas reservoir phase diagrams have the critical point on the left side. Critical temperature is less than reservoir temperature; the cricondentherm is greater. Initially retrograde gas is totally gas downhole (1); under production pressure may drop to dew point (2). Then liquid condenses downhole. This liquid is called retrograde liquid. Laboratory phase diagrams indicate lower pressures (3) where retrograde liquid revaporizes. This effect is uncertain in producing reservoirs due to downhole fluid composition changes during production. Figure 6. Phase diagram for a retrograde gas reservoir. McCain, 1990.

GOR’s increase and stock tank liquid gravity increase after reservoir pressure drops below the dew-point (2). Retrograde gas reservoirs are cycled with reinjection of miscible gases (especially methane) to facilitate surface liquid recovery. They may also undergo water injection to maintain pressure and retard the retrograde process. Volatile Oils The class of light petroleums that are 100% liquids under initial downhole reservoir conditions, those in the 40-50° API Gravity range, is called volatile oils. Volatile oils contain fewer heavy molecules and more intermediates (ethane through hexanes) than

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crude oils. Note that volatile oils, wet gas, and retrograde gas/condensate reservoirs all have very low viscosity and high API Gravity and very low fractions of very large heavy hydrocarbon molecules. The distinction between downhole liquids and gases can be arbitrary and/or academic among such light hydrocarbons. Laboratory-determined compositions of volatile oils will have mole 12.5-20% heptanes and above. The dividing line between volatile oils and retrograde gases at 12.5% mole percent heptanes plus is fairly definite. When the mole concentration of heptanes-plus is below 12.5%, the reservoir fluid is almost always gas and exhibits a dew point. When this concentration is above 12.5%, the reservoir fluid is almost always a liquid and exhibits a bubble point. Any exceptions to this rule normally do not meet the rules of thumb regarding stock-tank oil gravity and color. Laboratory observation of a volatile oil will reveal an initial formation volume factor greater than 2.0 RB/STB. The oil produced at point 2. of the Figure will shrink by more than 0.5, often 0.75, on its journey to the stock tank (3 or more stages of surface separation are recommended). Volatile oils have also been called “high-shrinkage crude oils” and “near-critical oils.”
The volatile oil reservoir phase envelope critical point is low and close to reservoir temperature. The iso-vols are not evenly spaced; they are shifted upwards toward the bubble-point line. The vertical line shows the path taken by the constant-temperature pressure reduction during production, releasing a large proportion of gas for a small pressure drop. A volatile oil may become as much as 50% reservoir gas at only a few hundred psi below the bubble-point pressure. Also, an iso-vol with even lower gas proportion crosses the separator condition point. Figure 7. Phase diagram for a volatile oil reservoir. McCain, 1990.

As reservoir pressure drops to point 2 in Figure 4, creation of a secondary gas saturation begins. The secondary downhole gas associated with a volatile oil reservoir is very rich, usually a retrograde gas; also, often over 50% of stock tank liquid produced from a volatile oil reservoir entered the wellbore as a gas. Remember the favorable mobility ratio allowing gas to flow preferentially due to its low viscosity. The critical temperature of a volatile oil is always greater than the reservoir temperature; its initial production GOR is between 2,000 and 3,3000 scf/STB. Producing GOR and stock tank API Gravity increases with primary production.

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Literature is slight on volatile oil deposits. The largest accumulation I personally observed is the Fairway James Lime Field, East Texas with 410 MMBOIP, of which 213 MMBO had been recovered in 2007 after 4 decades of gas cycling and water injection to maintain reservoir pressure. (Appendix 3.) Another noteworthy volatile oil accumulation is in Eugene Island, Block 99, Lease OCSG 21637, 20 miles offshore of Louisiana in the Gulf of Mexico. The extremely poor characterization and operation of this field by Columbia Gas Development Corp. left many millions of barrels of volatile trapped at abandonment despite the extremely low price and high availability of natural gas to optimize recovery by gas cycling. The Properties of Petroleum Fluids By William D. McCain states: “Volatile oils contain relatively fewer heavy molecules and more intermediates, ethane-hexanes [methane is CH4, ethane is C2H6, propane is C3H8, butane’s are C4H10’s, pentane’s are C5H12, hexanes are C6H14]. Their critical temperatures are much lower than for black oils and are close to reservoir temperatures. Their gas-oil ratios (GOR’s) are in the range of 2,000-3,3000 scf/STB.” Crude “Black” Oils Note that Dr. McCain wrote the Book, and refers to the non-volatile light oils as “black,” low-shrinkage crude oils, or ordinary oils. So, black oil is a synonym for crude oil, and is expected to have a GOR < 2,000scf/STB, an API Gravity < 45, and to be dark due to presence of heavy hydrocarbons. Black, or crude oils contain a wide variety of chemical species, including those large, heavy, molecules resistant to evaporation. Black, or crude, oils contain more heavy molecules and less intermediates (ethane through hexanes) than volatile oils. As the reservoir pressure drops below bubble point, a secondary gas saturation is created. The lower viscosity of gas eventually allows it to be preferentially drained during production. Oil volumes shrink slightly as their dissolved gases evaporate from this hydrocarbon mixture downhole. Conventional (Light & Intermediate) Crude Oil Intermediate crude oil or Medium crude oil is defined as having an API Gravity between 22.3°API and 31.1°API. Note the EU defines medium crude gravity between 25.7° API and 31.1°API. Especially the most economically favorable crude oils are classified by API Gravity and sulfur content and given names. For example, Brent Crude is actually a combination of crude oil from 15 different North Sea oil fields with API Gravity of 35.5°. The Permian Basin’s West Texas Intermediate (WTI) has an API Gravity of around 39.6 (specific gravity of around 0.827), lighter than Brent Crude. It contains about 0.24% sulfur, rating it a sweet crude, less sulfurous and thus “sweeter” than Brent. WTI properties and production sites make it ideal for being refined in the United States, mostly in the Midwest and Gulf Coast regions where demand for gasoline and petrochemical products is high. Thus its listed market price is often higher than Brent crude. WTI is extensively stockpiled at locations like Cushing, Oklahoma.

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From January 1, 1987 to June 15, 2005, OPEC calculated an arithmetic average of seven crude oil streams (known as the OPEC Basket). This basket included Algeria's Saharan Blend, Indonesia Minas, Nigeria Bonny Light, Saudi Arabia Arab Light, Dubai Fateh, Venezuela Tia Juana and Mexico Isthmus (a non-OPEC oil) to estimate the OPEC basket price. Effective June 16, 2005, OPEC's new reference basket consists of eleven crude streams representing the main export crudes of all member countries, weighted according to production and exports to the main markets. The crude oil streams in the basket are: Saharan Blend (Algeria), Minas (Indonesia), Iran Heavy (Islamic Republic of Iran), Basra Light (Iraq), Kuwait Export (Kuwait), Es Sider (Libya), Bonny Light (Nigeria), Qatar Marine (Qatar), Arab Light (Saudi Arabia), Murban (UAE) and BCF 17 (Venezuela). According to OPEC, the API Gravity for the new basket is heavier (32.7º compared to 34.6º). In addition, the sulfur content of the new basket is more sour (1.77% compared to 1.44%).
The black (crude) oil phase envelope has the critical point higher above reservoir temperature. Iso-vols are spaced rather evenly within the envelope. Line 123 indicates the reduction in pressure during primary production. Along Line 12, the oil is undersaturated; if more reservoir gas were present, it would dissolve at these higher pressures. Along Line 23, the gas is saturated, and pressure reduction releases gas from the crude oil to form a volumetric pore system saturation of a free gas phase. Figure 8. Phase diagram for a “black,” or “crude” oil reservoir. McCain, 1990.

API Gravity and Heavy Crude Oils (HO) Heavy crude oil is defined as having an API Gravity between or 10° and 22.3° API. The EU has a slightly different definition of ‘heavy'. Their cutoff between ‘heavy' and ‘intermediate' lies at 25.7° API Gravity. This causes there to be more “heavy” crude oil in their view. Extra-heavy crude oil is generally defined as having an API Gravity below 10°. The USGS definition of natural bitumens, which are yet denser than extra-heavy crude oils, is presented below. This indication of oil specific gravity at temperature 60°F places the heaviest of the HO class, with API Gravity = 10°, at the specific gravity (SG) of 1.0 (identical to water at 60°F).

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The lightest HO, at a SG= 141.5 / (22.3° + 131.5) = 0.922, floats on water. Asphalt, in the extra-heavy class, on average has an API Gravity of 8° (sinks in water). Its high viscosity makes it seem more solid than liquid; hence its desirability for pavement composites. The heaviest crude oils and natural bitumens, composed of very large complex carbonrich hydrocarbon molecules, have very high heat contents. They were originally refined to produce fuel oil, but require specialized refining to yield the petrochemical products in highest demand today. Some of the rarest and most profitable petroleum refineries today are those devoted specifically to processing heavy and extra-heavy crude oils. A memorable example is Valero’s Bill Greehey Refinery in Corpus Christi, TX; one of the most profitable refineries in the USA is refining very heavy oils to produce gasoline and other topprice petrochemicals! The properties of heavy and extra-heavy crude oil and bitumens are very strongly influenced by temperature. Their form as perhaps solids, perhaps liquids, is much different depending upon temperature. The crude oil may be on the surface at 0.0° C, or at 100.0° C also on location, or at 100.0° C in a thermal recovery process at a depth of 2,000’. These Celsius temperatures convert to 32° and 212° Fahrenheit. The very high kinematic viscosities of these heaviest crude oils and bitumens are especially strongly affected by their temperatures in their various environments.
Cumulative percentage of annual production (blue) and cumulative percentage of technically recoverable resources (brown) of heavy oil as a function of oil density (API Gravity) in 2000. Less than 10 percent of the heavy oil produced annually is extra-heavy oil (API Gravity of 10° or less), whereas 33 percent of the technically recoverable heavy oil has an API Gravity of 10° or less. Figure 9. Cumulatives production and recoverable vs. API Gravity, USGS.

HO & Bitumen, According to USGS: Many “liquid” hydrocarbons in this class are found in tar sands, such as the Athabasca Tar Sands in Canada. These tar sands are shallow, and due to their northern latitude these shallow deposits are rather cool. When the Tar Sands are sampled in core barrels, only the tar consolidates the core, and the core falls into a blob when warmed! For some of their discussions, USGS lumps the Light and Heavy crude oil classes together as …:

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“(USGS) Light oil, also called conventional oil, has an API Gravity of at least 22° and a viscosity less than 100 centipoise (cP). Heavy oil is an asphaltic, dense (low API Gravity), and viscous oil that is chemically characterized by its content of asphaltenes (very large molecules incorporating most of the sulfur and perhaps 90 percent of the metals in the oil). Although variously defined, the upper limit for heavy oil has been set at 22° API Gravity and a viscosity of 100 cP. Extra-heavy oil is that portion of heavy oil having an API Gravity of less than 10°. Natural bitumen, also called tar sands or oil sands, shares the attributes of heavy oil but is yet more dense and viscous. Natural bitumen is oil having a viscosity greater than 10,000 Centpoise (cP).” Water has a kinematic viscosity of 1.0 cP at 60°F. Natural bitumen (often called tar sands or oil sands), extra-heavy and heavy crude oils differ from lighter oils by their high viscosity (resistance to flow) at reservoir temperatures, high density (low API Gravity), and significant contents of nitrogen, oxygen, and sulfur compounds and heavy-metal contaminants. They resemble the refinery residuum from the refining of light oil.”

Shales, Accumulations, and “Oil Shales” As a rock type, a shale is a fine-grained sedimentary rock whose predominant original constituents were clay minerals or muds. It is “fissile,” its thin laminae breaking with an irregular curving fracture, often splintery. Non-fissile rocks of similar composition are mudstones. Related rocks but with less clay and more very fine-grained silica are siltstones. Shale beds are of immense importance in E&P as sources, seals, and reservoirs. Their study is also part of the “shaly sands problem” in petrophysics. Every hydrocarbon accumulation relies on its resident reservoir porosity system, a seal and trap to confine the oil and/or gas, and migration of the hydrocarbons from the source formation in which the hydrocarbons were geochemically created. Those are classically defined as the basic elements required creating a hydrocarbon accumulation. Shale is the most common sedimentary rock; it is deposited in beds of all thicknesses, from tiny laminae to vertical sequences of thicknesses of thousands of feet extending over huge areas. By virtue of their very limited hydraulic permeabilities and huge volumes, shale beds are the most common “seals” above oil and gas reservoir rocks, serving along with structural and stratigraphic “traps” to confine accumulations of hydrocarbons. Halite (table salt) formations are also excellent seals by virtue of their low permeability and flowing behaviors of plastic deformation. Since organic-rich shale beds are the predominant “sources” of hydrocarbons, few of these beds are lacking in hydrocarbon content. Unlike the focused limited definition of shale as a rock type, a thick shale bed’s depositional cycles commonly included silty and sandy episodes, resulting in laminae of sufficient primary porosity containing natural gas to allow these massive beds to serve as gas reservoirs after horizontal drilling and hydraulic fracture treatments. Thinner shale beds and those with inferior organic content do not offer similar potential for gas production.

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An 'oil shale' is neither oil, nor shale. Oil shale contains kerogens (immature precursors to oil and gas), and theoretically can be burnt without processing as a fuel. In a documented episode, a personally built mountain cabin was constructed with a fireplace built from “oil shale.” The first fire in that fireplace was a real house warming, and the cabin was destroyed. First Exxon in the 1970’s, then more recently Shell Oil, have invested $ billions attempting to create synthetic oil and gas from “oil shale” in the Rocky Mountain states. Huge technological and environmental challenges remain, and these will be some of the final energy resources exploited in North America. Reservoir Conditions and Fluid Densities The oil and gas Industry’s exploration and production (E&P) activities, a legacy of observational context based on gravimetric density permeates the views of the geoscientist and engineer. In this legacy, gas floats on oil, and oil floats on water. Innumerable geologic crossections, areal maps, and well log breakdowns are thus aligned. The maps show primary and secondary gas “caps” perched upon rings of light and intermediate oils. The oil rings very often float on aquifers or smaller deposits of formation water. The Yates Field Unit of Pecos Co., Texas, is an example: After generations of injection of possibly every available fluid, including nitrogen, CO2, heated and unheated water, this is still a $billion property. The oil accumulation is now described as a “seven-foot oil column,” above a water column, below a gas “cap.” Subsurface accumulations of heavy and especially extra-heavy crude oils challenge this gravimetric stereotype. The lightest of the extra-heavy crudes have neutral buoyancy in fresh waters. Formation brines have specific gravities up to about 1.1, but low-salinity connate waters may be gravity-stable above heavy oils. This density contrast defies the Industry stereotype of the oil-water contact, replacing it with a water-oil contact. Reservoir Conditions and Oil Viscosities The API Gravity a crude oil and its basis in specific gravity (SG), based on the density of water, reflect the molecular weights of their constituent liquid hydrocarbons. Generally liquid hydrocarbon viscosities increase as do their densities, but this correlation exhibits considerable statistical scatter, especially when the various international occurrences of these very heavy hydrocarbons are examined. Note that while API Gravities of reservoir oils and their gravimetric implications are themselves of interest in thermal recovery of heavy oil (TRHO), HO’s very high kinematic viscosities have even more impact on their performance under all recovery processes. The primary recovery characteristics of California’s largest fields benefited greatly from their extreme overpressure, however. This extreme pressure regime temporarily overcame the disadvantage of the very high viscosities of the HO’s, and was probably greatly influenced by the region’s pronounced tectonic stresses. This discussion assumes subject HO’s have viscosities more than 50 times that of water

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under reservoir conditions. This is consistent with real HO’s under recovery using TRHO options. Reservoir Conditions, Porosities & Wettabilities Perhaps the most accessible parameters in reservoir characterization are average porosities. Perhaps the least accessible parameters in reservoir characterization are wettabilities. A reservoir pore may be primary (created during sedimentary deposition) or secondary (created during lithification or diagenesis long after sediments are deposited). The primary porosity systems may be intergranular, especially in sandstones, siltstones, and even in shales (thus the current wave of “shale gas” projects which has added significant US natural gas reserves through combined use of horizontal drilling and hydraulic fracturing technologies). Porosity systems may be intercrystalline, karstic, fractured, or all of the above, especially in carbonate reservoir rocks. Wireline compensated neutron lithodensity combination porosity logs give average reservoir porosity measurements with accuracy ranging from excellent to barely adequate. Generally these nuclear porosity logs provide adequate accuracy for average reservoir porosity evaluation. The surfaces of a reservoir pore may be hydrophobic (repelling water) or hydrophilic (attracting water). Oil will cling electrostaticly to hydrophobic surfaces. Water will cling similarly to hydrophilic surfaces. These concepts are easily demonstrated in simplistic experiments. Many reservoir porosity systems exhibit mixed, checkerboard, or “Dalmatian“ nonuniform wettabilities. Since many techniques to evaluate reservoir systems’ wettability states and distributions unfortunately involve alteration of these states, wettability evaluations are very difficult. Primary Oil Recovery Drive Mechanisms Primary recovery in oil reservoirs depends on a primary reservoir drive mechanism. Hydrostatic and/or lithostatic forces have charged the compressible oil accumulation with potential energy. Gravity drainage occurs when heavy oil "drips" down through the reservoir porosity system into production wells. This is significant in reservoirs with depleted pressures. If the oil is saturated with gas, a primary gas cap may exist gravity-stable above banks of oil and water. If the water bank is small, water drive will not be significant. In gas cap drive, the very high compressibility of natural gas may allow the gas cap’s expansion to significantly support pressure and maintain reservoir energy during production. With great care, oil production may be controlled and limited to prevent premature fingering of a gas bank into production wells. Since gas has very low viscosity and very high mobility ratio, this is a difficult engineering task. Volatile and crude oils without water drive often depend upon dissolved gas drive (DGD). This mechanism, also known as depletion drive, is especially important in the early period of high production rate sometimes called flush production. Above bubble point, the oil enters the wellbore without gas liberation or significant reduction of

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reservoir potential energy.

Figure 10. Schematic cross sections of 3 basic reservoir drive mechanisms: depletion or dissolved gas drive, gas cap drive, and water drive.

As the DGD oil reservoir’s pressure drops during production, it eventually reaches bubble point, and gas is liberated from the oil. Especially near the wellbore, regions of free gas occur. Viscosities and mobility ratios predict preferential flow of gas, and the producing GOR increases. Oil composition is thus changed, and reservoir oil gradually shrinks slightly and loses much of its natural gas and intermediates content. Without pressure maintenance operations the reservoir’s oil loses its potential energy, becomes heavier and more viscous. This undesirable and destructive loss of DGD oil reservoir energy can be prevented by instituting a pressure maintenance plan before reservoir pressure drops significantly below bubble point. Encouragement or requirement of such conservation measures is admirably institutionalized in Canada and China, for example. The US E&P Industry is now super-mature way beyond much benefit from such regulation in any emerging energy policy, however. An oil reservoir with an oil-water contact directly connected to an extensive aquifer may benefit from the aquifer’s advance toward production wells, water drive. Given adequate management to moderate production and minimum heterogeneity regarding reservoir/aquifer permeability, a large aquifer may support reservoir pressure for a generation before the free water impinges upon production wells. These water drives may be considered strong and active (large aquifer moving quickly as oil is produced), moderate, or weak. Original Oil in Place and Recovery Efficiency A reservoir engineer’s evaluation of an oil deposit begins with calculation of original oil in place (OOIP). This calculation is simple: multiply the volume of the oil accumulation by its average porosity by its porosity-weighted oil saturation. After volumetric units like acre-feet are converted to barrels of oil (BO), an estimate of the original oil in place in BO results. The Lower 48 States of the US abounds with counties which have produced over 1 billion BO; some of these records were set before WW2, and very many have followed. The ratio of cumulative oil recovery to OOIP, in BO, is called recovery

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efficiency. In carefully engineered conditions, under the most fortunate drive mechanisms and other reservoir details, more than half of OOIP (50%) may be produced during primary recovery. This is most likely under conditions of strong water drive, very high reservoir porosity, and permeability, with moderate drawdown of bottomhole tubing pressure (BHTP). The bank of water moves toward the oil column as the oil column moves toward the wellbore, maintaining downhole reservoir pressure. Along with oil fields on land where the oil column is in direct contact with a very large aquifer, these conditions are especially likely in marine settings like the Gulf of Mexico (GoM). Occasionally a column of reservoir brine may even outcrop on the marine floor, placing it in direct contact with the marine hydrostatic gradient. Due to the unfavorable mobility ration of gas to oil, oil accumulations with gas cap drive seldom approach such high recovery efficiency as 50%. Accumulations depending upon DGD never approach such a high value of recovery efficiency, and the economics of primary production eventually becomes marginal, leaving most of OOIP remains in the reservoir. Recovery efficiency under primary recovery for DGD reservoirs ranges from 3% to 30%, at an average of around 12%.

Figure 11. Chemical analysis of a Texas intermediate crude oil thought to be Paleozoic in origin, from a reservoir on production for almost 100 years. Note that methane and intermediates are almost absent, with heptane (n7) the lightest component displayed with significant amplitude. This stripping of light HC’s is a common characteristic due to excessive drop of reservoir pressure in a DGD oil reservoir. Because of its increased viscosity and lowered API Gravity, such oil is called “dead” oil.

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Consequences of Oil Reservoir Depletion In the Lower 48 States of the US, during primary recovery, most active oil fields produce by the dissolved gas drive (DGD) primary recovery mechanism, also called depletion drive. As was just mentioned, drawing an oil reservoir’s far below bubble point quickly promotes a premature severe change in downhole reservoir conditions. Several changes in the reservoir’s character are then inevitable:
  Gas is progressively liberated from reservoir oil, forming banks of gas. Due to unfavorable mobility ratio of oil to gas, these banks of free gas flow preferentially to the wellbore. This gas is typically rich in intermediates, having been in contact with oil. Thus methane and intermediates are progressively stripped from the oil, making the oil heavier. Eventually the GOR ratio will vanish to near zero; such remaining oil is called “dead oil.” Consequences of this oil composition change are inevitable: The progressively heavier oil becomes denser, “shrinking” within the reservoir pores. Additional pore space is thus evacuated. Oil may shrink into the less accessible volumes of the porosity system. This reduced oil saturation increases relative permeability to gas, enhancing the already-unfavorable oil-gas mobility ratio. The progressively heavier oil becomes more viscous, “thickening” in viscosity, further enhancing the unfavorable oil-gas mobility ratio. High gas flow rates near the wellbore enhance the stripping of reservoir oil from the completion area, further enhancing the unfavorable oil-gas mobility ratio near the wellbore. Recovery efficiency under this unfavorable scenario is often in the 10% range, and is seldom as high as 20%.

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The largest of the producing oil fields, and those with the largest amounts of original oil in place (OOIP), will institute unitization to implement a waterflood for pressure maintenance. In small accumulations the result of poorly managed reservoir pressure yields a “stripper well,” which produces a few BO/day or less. Waterflood and EOR (IOR) Units Beginning in the 1980’s, WF and EOR processes have been lumped together and discussed as improved oil recovery (IOR) processes to encompass all activities beyond primary production. Generally the formation of a waterflood (WF) or EOR unit is facilitated by the extremely reduced performance of the existing leases in the field under its previous recovery technique. Often the process of elimination makes the decision of leaseholders to participate obvious. In Texas, the Railroad Commission’s energy policy famously incentives leaseholders to unitize. Regardless, the considerations mentioned here and above are necessary to justify and accomplish this transition from primary recovery to a more engineered combination of characterization, development, and recovery methods. Canadian regulators monitor each oil field, and as each fields bottomhole reservoir pressure approaches bubble point, the operator of the field is ordered to shut-in the field until a pressure maintenance plan is approved and being implemented for the field. China’s energy policy is even more aggressive. During field development, before extensive reservoir depletion, programs of water injection to maintain pressure and

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displace oil to producing wells begin. Before launching the complicated study and economic expense of EOR, oil fields may be waterflooded, with all the issues mentioned above. The unfavorable viscosity ratio between water and most crude oils enhances the bypassing of oil banks and premature breakthrough of water banks during WF. This secondary recovery process also provides invaluable information regarding reservoir characterization, however. After economic performance of a waterflood unit becomes inadequate, the operator may propose additional measures to increase the unit’s profit and producing life. These measures are collectively known as enhanced oil recovery (EOR) or tertiary recovery. Screening Producing Oil fields for WF & EOR The bases for planning and organizing a WF or EOR operation can perhaps be divided into these components:
       reservoir rock (depth, permeability, porosity, wettability) characterization oil properties (especially viscosity) reservoir drive mechanism water quality and availability analog field examination pilot projects, and Unitization.

When screening oil fields regarding WF, heterogeneity, continuity, and non-oil-bearing reservoir volumes (“thieves” or “thief zones”) are dominant reservoir characterization issues. The geologic thieves may be connected aquifers below the hydrocarbon column and/or wet areas on its flanks. Due to the limitations of cement jobs, major WFs often inadvertently provide pressure maintenance in uphole and even downhole reservoirs. These unplanned flows can enhance oil well performance, even on relatively distant adjacent leases. These operations problems may also be regarded as thief zones. They are huge windfalls for nearby ventures receiving this free pressure maintenance. The accepted methods to screen a field or lease for secondary recovery (WF) are reservoir characterization and subsequent study of analog fields. Both these steps are best taken in concert between engineering and geosciences. The next step before unitization for WF is the choice of an area of the field for a pilot WF involving a reasonable number of injectors and producers. This and all other decisions preliminary to unitization are best made with input from any leaseholders willing to be involved. Water Drive, Disposal and Supply “Dad” Joiner’s discovery well the East Texas Field, Bradford No. 3, reached a depth of 3,592 feet in the Woodbine sand on September 5, 1930, and flowed 300 barrels of oil per day, and was completed on October 5, 1930. This landmark discovery was followed by multitudinous additional successful wells. 30,340 wells have been drilled within its 140,000 acres. Located in central Gregg, western Rusk, southern Upshur, southeastern

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Smith, and northeastern Cherokee counties in the east central part of the state, is called the largest and most prolific oil reservoir in the contiguous United States. The magnitude of the field’s reserves and productivity set off many unique precedentsetting events in understanding mechanisms of oil recovery (the primary recovery mechanism of water drive, for example), pipeline construction, and production regulation. The price of a barrel of oil dropped from about $1.00 to $0.10 and below during the 1930’s. Roosevelt’s New Deal administration, the US Congress and Supreme Court’s crablike attack of the “hot oil” problem combined with Texas executive, judicial, and legislative steps to provide authority to regulate and limit oil and gas production to the Texas Railroad Commission. These were direct results of overproduction from the East Texas field. By January 1, 1993, cumulative East Texas field oil production from was reported as 5,145,562,000 barrels, perhaps not including huge volumes of “hot oil” stolen in the 1930’s. Originally skeptical operators were convinced by 1938 that ultimate recovery of the field's production depended upon the conservation of its water-drive mechanism. They initiated a pressure maintenance program by re-injecting produced salt water into the aquifer, reducing the rate of pressure decline. Thus produced formation water had advanced from the status of inconvenience or nuisance to become an invaluable resource to sustain and limit decline of production. This was a crucial event in reservoir engineering management. Conservation of produced water can provide massive economic and logistical long-term advantages in operation of oil fields. Early commencement of re-injection of produced water from oil wells, and injection of water from water supply wells is now a hallmark of foresight in reservoir engineering, especially in Canada and China. Waterflooding & Hot Water Injection A waterflood (WF) pilot or unit attempts to mimic the natural strong water drive, which is one of the most efficient drive mechanisms observed in primary recovery operations. Waterflooding is also called secondary recovery. Banks of this injected water can displace banks of oil toward producing wells wholesale. Reservoir rock heterogeneity and wettability cause some oil banks to be bypassed, however, as water banks break through prematurely at production wells. This premature water breakthrough is greatly enhanced when reservoir oil is many times more viscous than reservoir water. This viscosity contrast is called an unfavorable mobility ratio. Hot water injection, the most basic and probably the earliest thermal recovery technique uses water heaters at surface injection facilities to provide hot water for injection. Remember the term “hot” is relative, especially under cold surface conditions. The warming of water for injection can be a vital measure in its overall assistance to field operations. Especially when some heavy oil or fractions are involved, accumulations of paraffin or other solids can be major themes in maintenance. Field facilities professionals routinely

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employ “heater-treaters” to remediate problems with viscous or solid heavy crudes, lubricants, cements, or solids or break emulsions. The viscous/solid problem materials may include whatever crude or oils, solvents, cements, plastics, natural materials combine to contaminate a rental part or operator production component. So, the ability to bring this practicality of heating water at a water injection site is a very important option. Combined with general detergents and industrial chemicals to control injectant properties, heating water is just a routine industrial activity. WF’s can also be augmented by using additives to increase the viscosity of injection water, thus reducing mobility ratio problem and premature water breakthrough, and constituting an element of chemical flooding (CF). Why Waterfloods Under-perform The Petroleum Technology Transfer Council (PTTC) workshop on Permian Basin (PB) waterfloods presented these “top 10” list reasons why waterfloods under-perform:
 Misunderstanding reservoir heterogeneity: The carbonate reservoirs of the PB are notoriously heterogeneous. Petrophysical and geological review of existing and new well logs, including correlation of injection and production data are vital to refine descriptions of these porosity systems. Injecting above formation fracture pressure enhances heterogeneity and premature water breakthrough. It can be avoided by automatic control of water injection systems and automatic monitoring of wellhead pressures using satellite communication. IHS and competing vendors have this technology for hire; in-house networks may be contracted for projects with well-counts above 100. Incorrect perforations are always suspected in the old wells of PB waterfloods. High oil viscosity can result from the stripping of reservoir gas and energy during primary production with depletion drive mechanism. The emerging EPARS technology help to mitigate this with crude oil analysis and well treatments to improve reservoir oil composition. Insufficient lift capacity does not allow sufficient oil production. Early water breakthrough, an element of waterflood conformance, will be the subject of constant study and vigilance. When water breaks through and eliminates oil production, a well is usually shut in and eventually converted to water supply or injection. Out-of-zone injection, related to incorrect perforations, must be suspected. Underestimating fill-up volume when shut-in tubing pressures are about 15psi, all reservoir natural gas will re-dissolve in oil, and waterflood will become effective. Insufficient water supply is related to several other topics above. Scale, bacteria, or other water quality issues that reduce injectivity benefit by analysis of samples of water, scale, and corroded metal and service company consultations, to provide adequate treatment for injection water and employment of optimum well treatments.

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Wells are high-dollar investments that must remain healthy; they benefit from corrosion/chemical treating, material and metallurgy selection, rod handling, tubing and rod inspection services, and careful surface facility design. Design and operation changes can remove moved unnecessary pressure drops in injection systems, thus significantly lowering horsepower requirements for injection pumps to

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reduce power cost. According to PTTC, “When the chemical man, pump supplier, service rig, company man, etc., work together, well failure frequencies of fewer than 0.5 per well per year can be achieved, and some operators actually achieve rates of 0.25 per well per year or less.” Chemical Flooding (CF) Introduction Chemical flooding (CF), involving surfactants to reduce interfacial tension (IFT) between oils and water and polymer gels to increase water viscosity, is an augmentation of the waterflood process. CF has been the subject of major oil company and service company research and development for many decades. Surfactants to reduce oil-water IFT can act similarly to household detergents, dissolving oil fractions in the injected aqueous phase. Engineered aqueous polymers increase water viscosity to reduce unfavorable oil-water mobility ratios. A variety of “recipes” has been researched, and many have had field trials. Perhaps the most proven and successful CF method is the micellar or micro-emulsion flood, in which a slug of a stable solution of oil, water, alkalines or surfactant(s), and salt electrolytes is injected to reduce interfacial and capillary forces. This slug then displaced by a slug of high-viscosity mobility control buffer polymer solution, and finally followed by slugs of water injection. Those micellar flood steps may be preceded by a “preflush” of low-salinity water. Synonyms for this process are micellar/polymer flooding and surfactant /polymer flooding. Alkaline Flooding and ASP Perhaps the most common acronym in CF is ASP for “alkaline surfactant polymer.” Alkaline (caustic) chemicals react with organic acids in certain crude oils in situ to produce surfactants that dramatically lower IFT between oil and water, creating emulsions to entrain and mobilize oil. These caustics also react with reservoir rock surface to modify wettability. Caustic slug injection may be preceded by a “preflush” of low-salinity water and/or followed by a viscous mobility-control slug injection. The alkaline flooding and ASP concepts deserve the increased attention they are currently receiving. Some alkalines, like sodium hydroxide (NaOH, “lye”, or “caustic soda), famous for cleaning drains, dissolving organic matter, making soap, and its extreme solubility in water with liberation of heat, are so inexpensive as to lend themselves to economic performance in well-configured recovery processes. Alkaline industrial waste products are also readily available. Wood ash, for example, can be processed to provide a low cost environmentally friendly alkali. Emerging laboratory and field technologies to refine the designs of chemical floods should be especially effective on alkaline flooding applications due to their potentially low chemical costs. Surfactants, Micelles, Type I Micro-emulsions Surfactants are broadly defined as organic compounds that can enhance cleaning efficiency, emulsifying, wetting, dispersing, solvency, foaming, defoaming, and lubricity of water-based compositions. Surfactants are produced from petrochemical (synthetic)

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feedstocks or oleochemical (biological) feedstocks. They can stabilize mixtures of oil and water by reducing the interfacial surface tension (IFT) at the interface between the oil and water molecules. Because water and oil do not dissolve in each other, a stable homogeneous mixture (emulsion) requires a surfactant to keep it from separating into layers. Soaps and detergents are surfactants. Sodium dodecyl sulfate (SDS) is an example of a regularly studied anionic surfactant. The word "surfactant" is the shortened form of "surface-active agent.” Surfactants accumulate at interfaces due to their amphiphilic natures: The hydrophilic “head” segment (moiety) of a surfactant molecule (monomer) is polar, like water. Another “tail” hydrophobic moiety of the molecule is nonpolar, like oil. Surfactant molecules accumulate at the oil-water interface with their polar moiety in the aqueous phase and their non-polar moiety in the oil phase, minimizing Gibbs free energy. A surfactant solution has three components: surfactant monomers in the aqueous solution, micellar aggregates, and monomers adsorbed as a film at the interface (surface of bubble, oil-water, etc.) The surfactant is in dynamic equilibrium among these components. Each micelle is a dynamic structure. When the aqueous surfactant concentration exceeds critical micelle concentration (CMC), surfactant monomers selfaggregate into spherical or wormlike monomer aggregates called micelles. The micellar aggregate of “n” micelles has stability (relaxation time, n τr) in the range of milliseconds (ms) to seconds, breaking and reforming rapidly. A large relaxation time represents high micellar structure stability. Relaxation time correlates quantitatively strongly with foaming ability, textile wetting time, bubble volume, emulsion droplet size, solubilization of benzene, etc. When discussing the molecular structures of surfactants, micelles, and oil and water phases, an emulsion is called a microemulsion. An oil-in-water (Type I) microemulsion can be formed with micelles’ polar micelle exteriors in contact with water phase, and nonpolar micelle interiors containing oil. Micro-emulsion Types II & III Oil-based drilling fluids are composed primarily of diesel fuel, often configured as a water-in-oil (Type II) microemulsion. Oil-soluble surfactants form inverse micelles with their tails exterior and their heads interior, where water is trapped. In an oil reservoir, a surfactant will partition between oil and water phases according to the monomer’s relative hydrophilicity; surfactant hydrophilic-lipophilic balance (HLB).
   Water-soluble surfactant mixtures with micelles have HLB’ of about 20. For transitional mixtures, 8 < HLB < 12. Oil-soluble mixtures with inverse micelles have HLB’s around 5.

Chemical system conditions can be varied to force water-soluble surfactants to partition into the oil phase. For example, in an ionic surfactant system, increasing water salinity can lower HLB and force surfactant monomers to partition into the oil phase. HLB’s for nonionic surfactant systems are decreased with temperature increases. At aqueous surfactant concentrations >10-20 times CMC, high micelle concentrations

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can produce “middle phase” oil-in-water microemulsions with ultra-low oil-water IFC’s to mobilize oil trapped by IFC in a porous reservoir. To achieve a middle phase microemulsion (Type III) system, HLB is adjusted so surfactant is ready to leave the water phase, but not to enter the oil phase, so the monomers accumulate at the surface. Since all the surfactant cannot fit in the interface, a new “middle” phase forms, containing oil, water, and virtually all the surfactant, in equilibrium with free oil and water phases. Theoretically, these middle phase microemulsions do not break with time, so their achievement under reservoir conditions is a very favorable goal. Surfactants in E&P Other oilfield surfactant applications are:
      demulsifiers to separate oil and water by breaking emulsions, viscosity stabilizers lubricants, petroleum additives, engine-oil additives, fuel additives and dehazers organoclay intermediates, anti-swelling clay hydration inhibitors corrosion control, foam control, anti-fouling, anti-scaling KCl replacement, acidizer additive dispersants and deflocculation agents, wetting and suspending, biocides.

These oilfield surfactants are involved in well stimulation, drilling, cementing completion, production, refining, and pipeline transport, as well as EOR. EOR and other downhole applications require surfactants that meet demanding downhole environmental regulations and performance requirements. Emulsifiers to allow oil and water to mix perhaps require the majority volume of oilfield surfactants. The dramatic rise in oil and gas prices, peaking in 2008, caused significant increases in EOR activity and demand for more effective EOR processes and materials. This has stimulated market demand for specialty, higher cost surfactants such as cationics and amphoterics (anionic or cationic depending on conditions). These are more costly than nonionics and anionics (negative charge on surface-active moiety) but perform more effectively. Interest in use of surfactants for EOR in HO and bitumen reservoirs is beginning to compete with traditional emphasis of thermal recovery of heavy oil (TRHO). Polymers, Gels, and Gelation Polymers, macromolecules, high polymers, and giant molecules are high-molecularweight materials composed of repeating subunits. Natural organic polymers include polysaccharides (or polycarbohydrates) such as starch and cellulose, nucleic acids, and proteins. A gel is a continuous solid network enveloped in a continuous liquid phase; the solid phase typically occupies less than 10-volume % of the gel. Gels can be classified in terms of the network structure. The network may consist of agglomerated particles (formed, for example, by destabilization of a colloidal suspension; a “house of cards” consisting of plates (as in a clay) or fibers; polymers joined by small crystalline regions;

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or polymers linked by covalent bonds. In a gel the liquid phase does not consist of isolated pockets, but is continuous. Consequently, salts can diffuse into the gel almost as fast as they disperse in a dish of free liquid. Thus, the gel seems to resemble a saturated household sponge, but it is distinguished by its colloidal size scale. The dimensions of the open spaces and of the solid objects constituting the network are smaller (usually much smaller) than a micrometer. Thus the interface joining the solid and liquid phases has an area on the order of 1000 m 2 per gram of solid. As a result, interfacial and short-range forces, such as van der Waals, electrostatic, and hydrogen bonding, control the properties of a gel. Factors that influence these forces, such as introduction of salts or another solvent, application of an electric field, or changes in pH or temperature, affect the interaction between the solid and liquid phases. The process of gelation, which transforms a liquid into an elastic gel, may begin with:
   a change in pH that removes repulsive forces between the particles in a colloidal suspension, or decrease in temperature that favors crystallization of a solution of polymers, or the initiation of a chemical reaction that creates or links polymers.

Conversely, the reason that water cannot be gently squeezed out of such a gel is that the network of solids has a strong affinity for the liquid, and virtually all of the molecules of the liquid are close enough to the solid-liquid interface to be influenced by those attractive forces. The most striking feature of a gel is its elasticity. If the surface of a gel is displaced slightly, it springs back to its original position. If the displacement is too large, gels, except those with polymers linked by covalent bonds, may suffer some permanent plastic deformation, because the network is weak. Oilfield Polymers and Gels Commercial oilfield polymers include solid beads to adsorb hydrocarbons as well as gels. The gels are available in both dry powder and very dense and viscous “liquids.” Xanthan Gum, for example, is a polysaccharide biopolymer well known to have excellent performance in high salinity brine. “Standard” EOR polyacrylamides have molecular weights in the >12,000,000 range and are suited for bottomhole temperatures <90 °C. Sulfonated copolymers of acrylamide and sodium salt of acrylamide propyl sulfonated acid, suited for EOR applications with bottomhole temperatures >90 °C, have molecular weights in the <12,000,000 range. Oilfield gels are used to increase viscosity of an aqueous drilling fluid or EOR injectant. Less expensive starch gels are adequate for many routine drilling fluid requirements. When more expensive polymer gels are used, the 5-gallon buckets of polymer gel are heavy; the gel concentrate is dense, very viscous, and very thixotropic (sticky). Working directly with these polymer gels is physical challenging on wellsite; the gel does not want to leave the bucket, sticks to personnel and equipment, and needs specialized

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mixing equipment to be uniformly dispersed in drilling fluid. Emulsion gels have colorful wellsite names like “whale snot.” Microbial EOR Labs are engineering microbes that react in situ with reservoir oils to biochemically generate surfactants and CO2 downhole (see miscible EOR processes below). The microbes can be cultivated underground or in wellsite surface vats; some grow explosively. US DOE and Canadian CERA are funding MEOR research in hopes that MEOR technologies become cost-effective and environmentally advantageous. MEOR is already used in Venezuela, China, Indonesia, and the U.S. to treat HO reservoirs. Researchers hope to develop improved microbial species to inoculate reservoirs and modify the difficult properties of HO and bitumen. Microbial technologies are also proposed to reduce use of harsh chemicals during oil well drilling. Genetic engineer’s goals are more effective bacteria to subsist on abundant inexpensive nutrients. In an MEOR process downhole, conditions for microbial metabolism are supported via injection of nutrients. This may involve injecting a fermentable carbohydrate into the reservoir. Some reservoirs also require inorganic nutrients as substrates for cellular growth or as alternative electron acceptors in place of oxygen or carbohydrates.

Figure 12. Illustration summarizing total US EOR production history indicates that production from thermal recovery, including TRHO to recover heavy oil, is decreasing steadily. EOR production from “gas injection”, including CO2 injection, may increase, but not sufficiently to offset the decrease of thermal recovery production. Emerging priorities for CO2 sequestration, however, may spur additional CO2 injection projects, including those without potential for oilCO2 miscibility to make miscible displacement possible. Chemical flooding (CF) production is not significant.

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MEOR processes are applicable to 40-50% of North American oil reservoirs. Reservoir conditions restricting MEOR applications are:
   high total salinity (above 12%) high reservoir temperatures (above 50 C), and very low permeability.

While some microbes grow inside of these environmental parameter ranges, few successful MEOR projects have been in such reservoirs. Biotechnology may soon take greater advantage of extremophiles — microorganisms that grow in high salt or heavy metal concentrations, or at extremes of temperature, pressure, or pH. These organisms could support process operation over a wider range of conditions. However, extremophiles present challenges for the development of industrial bioprocesses, such as slow growth, low cell yield, and high shear sensitivity. Potential hazards of using microbes for drilling, environmental remediation, and/or EOR include migration of microbes and/or metabolites into groundwater, use of brine and other media and pH adjustment chemicals, emissions of H 2S, and solid waste issues. In addition to steps in “Screening Producing Oil fields for WF & EOR” section above, in an MEOR investigation, reservoir oil and water samples are analyzed to pick microbes and processes supportable in the oil reservoir and augmented cultures which survive and perform desired in situ metabolic function(s) are determined. Field demonstration project is then designed to confirm success of selected MEOR mechanism(s). If demo is successful, laboratory, consultants, and operator can consider an MEOR pilot project.
http://peswiki.com/index.php/Directory:Microbial_Enhanced_Oil_Recovery

CF EOR Summary Historically, CF has perhaps been a stepchild in the family of EOR processes. In 1983, Slider quoted HK van Poollen & Associates, "Although much laboratory work has been done, no field project has as yet been reported as economic." CF has benefited, however, from the intense chemical research of O&G product refining and distribution sectors. These sectors’ development of detergents and polymer gels for their huge array of industrial customers has produced profit centers, which subsidized their development of CF agents. CF importance and interest surges whenever very high oil prices become sustained. A range of laboratory and field technologies is emerging to refine the designs of chemical floods. Miscible EOR (CO2) Processes: The most successful EOR processes for recovery of light and intermediate crudes are various forms of miscible displacement using CO2. An injectant is chosen to mix downhole with residual crude oil. The miscible component of injectant is called a “solvent”; it is usually some combination of CO2 with anything inconvenient for the EOR surface gas processing plant to remove. These additional gases may include methane CH4, and contaminants: hydrogen sulfide (H2S), sulfur dioxide (SO2), and even Nitrogen (N2).

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CO2 flooding processes can be classified as immiscible and miscible, even though CO2 and crude oils are not miscible upon first contact at the reservoir. Recovery mechanisms in immiscible processes involve reduction in oil viscosity, oil swelling, and dissolved-gas drive. In the miscible process, CO2 is effective for improving oil recovery for a number of reasons. While not 1st-contact miscible, CO2 is very soluble in crude oils at reservoir pressures; therefore, it swells the oil and reduces oil viscosity.

Figure . Condensing/vaporizing mechanisms for a multiple-contact miscibility process between compressed CO2 and reservoir crude oil.
http://txspace.tamu.edu/bitstream/handle/1969.1/4138/etd-tamu-2005B-PETEGarcia.pdf?sequence=1

Miscibility between CO2 and crude oil is achieved through a multiple-contact miscibility process. Multiple-contact miscibility starts with dense-phase CO 2 and hydrocarbon liquid. The CO2 first condenses into the oil, making it lighter and often driving methane out ahead of the oil bank. The lighter components of the oil then vaporize into the CO 2rich phase, making it denser, more like the oil, and thus more easily soluble in the oil. Mass transfer continues between the CO2 and the oil until the two mixtures, vaporizing oil and condensing CO2, become indistinguishable in terms of fluid properties. Because of this mechanism, good recovery may occur at pressures high enough to achieve miscibility. Figure illustrates the condensing/vaporizing mechanisms for a multiplecontact miscibility process Marylena Garcia Quijada reviews of the perfect example of successful CO2 flooding in her 2005 Master’s Thesis. In general, high downhole pressures are required to compress CO 2 to a density at which it becomes a good solvent for the lighter hydrocarbons in the crude oil. This pressure is known as minimum miscibility pressure. (MMP) and it is the minimum pressure at which miscibility between CO2 and crude oil can occur. CO2 Flood Logistics & Operations Obtaining a CO2 supply was the first hurdle jumped in the logistics to create CO 2 floods. The development of Bravo Dome in NE New Mexico, with its pipelines to large Permian Basin WF’s, was perhaps the milestone event heralding commencement of full-scale miscible displacement projects. Additional fields in the 4-Corners area and Mississippi have served to swell the ranks and production volumes of CO 2 injection projects.

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Regarding miscible EOR processes and field conformance, major conformance issues I have seen repetitively include these issues: Premature solvent (CO2) breakthrough in volumes so large as to
  overload the surface CO2 processing plant, indicate excessive bypassing of reservoir oil by injected CO2.

Figure . Map illustrating the US States studied by DOE for EOR with CO2. Basin-oriented assessments estimate 89 billion additional barrels recoverable. Schematic cross-section shows the water-alternating-gas (WAG) process.

Note that bypass of oil by injected CO2 is serious; only those volumes of CO2 which actually contact reservoir oil can mix with the downhole oil to accomplish
  lower oil viscosity (thinning) increase oil volume (swelling).

Of course, these are the reasons for the “injecting water” part of water alternating with gas (WAG) studied and employed so widely in simulations, Pilots, and Units include:
   Maintenance of oil reservoir downhole pressure Reduction of downhole miscible gas mobility, thus remediating premature CO2 breakthrough, and Displacement of downhole oil banks by banks of injected water.

Another conformance issue I see frequently is the alteration of reservoir rock at injection wells due to chemical leaching and processes associated with high injection rates, enlarging pores and increasing injectivity. The most constant and frequent issue I have observed in fields using CO 2 WAG is corrosion, both uphole and downhole (especially in production wells and facilities). Brine or brackish water, of course, causes corrosion in a waterflood. The copious water downhole in a waterflood converted to a CO2 flood becomes carbonated, and the resulting carbonic acid is even more corrosive than formation or injection water. Add a little H2S downhole and/or in CO2 stream, and completions & facilities may seem to disintegrate before your eyes! Screening Oil-CO2 Miscibility In addition to operating problems detailed above, establishment of miscible displacement in a WF involves very detailed screening for oil oil-CO 2 miscibility under reservoir conditions.

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In a successful miscible displacement, CO2 is not a gas in the reservoir. To become miscible, CO2 must exist in the reservoir at sufficiently high pressure and temperature to exist in a dense liquid-like phase. Unless an EOR project achieves oil-CO 2 miscibility in the reservoir, CO2 in contact with oil will only achieve some swelling and viscosity reduction and perhaps crude vaporization. Inferior performance is expected when CO2 is injected without miscibility. Emerging priorities for greenhouse gas sequestration might greatly increase the volume of these non-miscible projects, however, and additional oil recovery would be likely. Downhole miscibility of CO2 requires a minimum bottomhole reservoir pressure of about 1500psi. The oil-CO2 minimum miscibility pressure (MMP) correlates inversely with API oil gravity, increasing as oil becomes heavier. Miscibility fails to occur at any pressure at about API gravity < 22. The MMP requirement also fails for reservoirs shallower than about 2,500’, for oils of API gravity > 40. Heavier oils at 22 < API gravity < 32 require reservoir depths of about 4,000’ to 2,800, respectively. Precise experimental oil-CO2 MMP measurements are performed in specialized laboratories, and have required generations of research for their development. Computational estimates of oil-CO2 MMP’s also continue to be topics of intense research. Experience with many CO2 floods in the Permian Basin of West Texas has yielded two Rules of Thumb for recovery efficiency under CO2 flooding. Incremental recovery from miscible CO2 flooding can be estimated as:
   10% of original oil in place, OOIP, or 25% of primary and secondary recovery combined. NOTE: when combined, these estimates predict that 50% of the OOIP is left abandoned in the reservoir after tertiary recovery! Remember, however, that recovery efficiency is sensitive to the price of oil and other economic parameters.

EOR for HO Fields: TRHO Many of the known HO deposits exist in sandstone reservoirs; CA’s most prolific oil fields are examples. Thus, the use of water or steam for downhole injection may activate downhole clay minerals, causing these clays to swell. This swelling is a notorious mechanism to reduce formation permeability by the blocking pore throats by swelling and/or migrating clay crystals. Water must be procured and treated for injection, and motors must be operated to inject the water. Industry introductions of thermal recovery of heavy oil (TRHO), steamfloods (SF) and cyclic steam injection (CSI), were based on waterflood experience and/or use of heat to handle oil on surface production facilities. Steam was generated at the ground surface and substituted for water as an injectant as in a waterflood. When a bank of super-heated steam progresses in an oil reservoir,
  oil viscosity is reduced as temperature increases. Reservoir pressure is increased through

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 

additional water volume partial distillation of the oil.

Whether SF or CSI was introduced first is not clear. The discovery of the SCI process is attributed by at least one source to a steamflooding accident in Venezuela noticed by Shell in 1959. I suspect this was the independent discovery of a secret proprietary and confidential unpatented stimulation treatment already being performed behind locked lease gates in CA and perhaps elsewhere. By 1966 the Kern River Field’s production rate had exceeded its 1904 rate of 47,100 BBL/day. This California achievement almost matched the total daily oil production rate of the entire State of Texas! Cyclic Steam Injection (CSI) The most basic step in TRHO is cyclic steam injection (CSI). This is a single-well stimulation method in which high-pressure steam is generated at the ground surface for injection into 1 or more wells. After a period of injection into each well, the same well is temporarily converted to a period of production. Between steam injection and production periods there is an idle period, allowing additional fluid flow and heat transfer, leading to the term “Steam Soak.” This cycle is repeated while recovery is economic; it is also called “huff ‘n’ puff.” Advances in the details improving the CSI option of TRHO were introduced and developed in prolific HO deposits like the Kern County area of California (CA), Venezuela and Indonesia. Many of the legendary CA producing fields were identified around 1900, so today they are some of the most super-mature assets in the USA, leaving remaining recoverable reserves as low as 20% of Original Oil in Place (OOIP). Regardless, at least 1 billion barrels of oil are likely to remain in these fields. As a single-well stimulation process, CSI requires relatively little increase in petrophysical, geological, and reservoir study over those conducted for primary recovery. CSI is normally applied to wells proved as previous producers under primary recovery. Since it effects a region of limited extent around a single wellbore, its effectiveness eventually declines over its period of application. Wellbore heat absorption limits CSI formation depth to less than 3,000ft (1,000m). The requirement of surface steam generation depends upon the procurement and treatment of water for injection, the use of natural gas to generate steam from said water, and the management of related environmental issues. Steamflooding (SF) CSI has continued as a mainstay of TRHO, holding steady in CA during the period of relatively low oil prices in the Industry slump ending in 2005, for example. During this period WF recovery declined in CA. The employment of more advanced techniques such as Steamflooding (SF) and In-Situ Combustion (I-SC, also called Fireflooding) has been in flux over the same period. The Steamflood rationale combines some waterflooding principles and some CSI principles. Downhole injected steam warms the oil to reduce its viscosity. This effect is

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reduced by absorption of steam heat by the reservoir rock, water, wellbore, and adjacent formations. Employment of SF has gradually increased since 1995; these SF projects often enhance or replace CSI processes. As for CSI, wellbore heat absorption limits formation depth for SF to less than 3,000ft (1,000m). Steam condenses downhole to yield liquid water. As with CSI and WF, these wet processes have dangerous possibilities of clay activation. Their requirement of surface steam generation depends upon the procurement and treatment of water for injection, the use of natural gas and treated water to generate steam, and the management of related environmental issues. Regarding reservoir characterization, SF benefits from all the attention to petrophysics, geosciences, and reservoir study, pilot and unitization required for optimized WF. Conformance of the WF is invaluable characterization data. The financial expenses and the physical issues are so enhanced for SF, however, that characterization must be truly sophisticated during the screening, pilot, and unitization phases. Loss of effective injection to various thieves and injectant bypassing oil no longer involves only treated water and its injection horsepower, but also heating cost and the increased complexity of SF facilities. In-Situ Combustion (I-SC, or fire flood) The incentives to reduce uphole heat loss, clay activation, and various environmental issues have accumulated to motivate research and production personnel to seek alternatives to the wet methods mentioned above. So, the In-Situ Combustion (I-SC) process, also called fire flood or fireflood, has benefited from considerable analysis, experiment, and discussion. In-situ combustion is a flameless dry process. As a bare minimum, oxygen (O2) must be injected. O2 (pure, atmospheric with Nitrogen, staged or otherwise combined) then reacts with a downhole fuel flamelessly to heat the reservoir rock and HO. Reliance upon reservoir HO alone as a downhole fuel is a convenient notion, but probably impractical. Methane, a solvent, and/or other staged and/or optimized additives are probably required to engineer this combustible injectant. Note that CH 4 and O2 combine to form CO2 and H20 in combustion, along with at least traces of CO (carbon monoxide) and perhaps O3 (ozone), so such a process is not completely dry! CO 2 is, of course, desirable since it will dissolve in water and oil at low pressures. Larger fuel molecules would yield more complex combustion product compounds. Theoretically, I-SC avoids wellbore heat loss, most of the water involved with CSI and SF, and some surface environmental issues. I-SC introduces, however, many complex physical issues like ignition method, choice of fuel(s), choice of O 2 or mixture, sources of these, the flameless processes visualized downhole, and the details of their effects on rock and HO. Toe to Heel Air Injection (THAI™) Toe to heel air injection (THAI) is a new method of extracting oil from heavy oil deposits, which may have significant advantages over existing methods, including

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previous I-SC implementations. The method was developed by Malcolm Greaves of the University of Bath and has been patented by Petrobank. THAI™ is an evolutionary new combustion process that combines a vertical air injection well with a horizontal production well. During the process a combustion front is created where part of the oil in the reservoir is burned, generating heat, which reduces the viscosity of the oil, allowing it to flow by gravity to the horizontal production well. The combustion front sweeps the oil from the toe to the heel of the horizontal producing well, recovering an estimated 80 percent of the original oil-in-place, while partially upgrading the crude oil in-situ. Combustion continues as long as air is injected, estimated at about five years. Combustion gasses bring the mobilized oil and water to the surface, so no pumps are needed. Water and natural gas are used during the first three months to create steam injected in vertical injection well. After this initial period, for the estimated 5-year project life, neither water nor natural gas is used. The second quarter test report indicates oil cut is over 50%. No new water is added after the first three months; produced water combines condensed previous steam, reservoir water, and combustion product. Petrobank estimates that THAI will recover 70% to 80% of oil originally in place (OOIP). If 10% of the oil originally in place were burned in the process, this would leave 10% to 20% of the oil originally in place in the ground. According to the Petrobank website, besides yielding 70% to 80% recovery efficiency, THAI can be used in many areas where steam methods cannot:
     Thinner reservoirs, less than 10 meters thick Where top or bottom water is present Where top gas is absent Areas with "shale lenses" that act as barriers to steam, In general, lower pressure, lower quality, and deeper reservoirs than current steam-based processes.

By comparison, recovery using current steam processes is estimated to be 20% to 50% in the high-grade, homogeneous areas where steam methods can be used. Dilution of HO for Pipelines Extra-heavy oil requires addition of diluents (gas condensate, natural gas liquids, or light crude) to enable pipeline transport. Extra-heavy oil must also be chemically upgraded to reduce density and remove contaminants for refinery feedstock. In recent Venezuelan Orinoco heavy oil belt projects, 1 barrel of diluents is required for every 3 or 4 barrels of extra-heavy oil produced. Horizontal wells and optimally positioned lateral branches equipped with improved electrical submersible or progressing cavity pumps can deliver up to 2,000 BO/day in the Venezuela’s Orinoco heavy oil belt. Horizontal well costs dropped in recent years, and this extra-heavy crude oil is commercial. Fuel use for reservoir injection and facilitating transport to upgrading facilities is still significant. In 2001, concession operators still planned to increase Orinoco production to

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600,000 barrels of extra-heavy oil per day by 2005, however, and to sustain that rate for 35 years. (Petroleum Review, 2001, v. 55, no. 653, p. 30). Surfactants, HO, & Bitumen In Venezuela, from 1980 to 1984, PDVSA, jointly with British Petroleum, developed a new method to reduce the high cost of transporting bitumen by pipeline. This effort resulted in new and simple technology to process Cerro Negro bitumen, known as Orimulsion. In this proprietary process the bitumen is mixed with water and a surfactant chemical in order to produce a stable emulsion, which can be transported by pipeline and by ship in a similar way as fuel oil. Orimulsion is an emulsion of approximately 70% natural Cerro Negro bitumen 8.5° API suspended in 30% fresh water by means of mechanical energy and the addition of less than 1% alcohol-based surfactants (emulsifiers) that allow the bitumen droplets to remain suspended in a stable mode. This product can be easily handled at room temperature and with standard equipment. Furthermore, the presence of water improves the combustion characteristics of the natural bitumen. PDVSA’s BITOR division enjoyed massive international success due to Orimulsion’s combination of:
  sufficiently low viscosity to allow routine transportation of Orimulsion extremely successful combustion characteristics, allowing direct use as fuel.

PDVSA decided in August 2003 that it was dissolving BITOR into PDVSA's eastern operating division and not expanding production of Orimulsion because it could make more profits from Venezuelan extra-heavy oil and bitumen selling blends or syncrude instead of Orimulsion. PDVSA intended to fulfill long-term contracts, which BITOR had with utilities in Canada, Denmark, Italy, and Japan, but to discontinue any contracts in negotiation and close UK, UE, and North American operations. This leaves a huge vacuum for related technologies to replace Orimulsion.
www.soberania.org/Articulos/articulo_1375.htm

Recent research (Piero Baglioni et al) indicates that relatively slight modifications to surfactant molecular structure can promote reduction in both viscosity and density in an emulsion. Such research applied to oilfield surfactants could yield valuable applications for surfactant use in EOR for HO and bitumens. See Appendix 10. “Dead” Oil and Recovery Efficiency Over 1,800,000 crude oil wells have been drilled and brought into production in the United States in the past 125 years. Over 90% of the wellheads in the Global well count are in the Lower 48 states. Most of the large oil fields of the US lower 48 states are very old. Many of the smaller oil fields are also quite old. Those not already on waterflood may soon be unitized for this. Recall, however, that many sandstones contain sensitive reservoir clays which migrate and/or swell when contacted with water. Before implementation of waterflood, prolonged and pronounced reduction of reservoir pressure under DGD has rendered the

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crude oil “dead”, lacking methane and intermediate hydrocarbons, and thus more viscous and dense than its original character. Yet, of the 430,000,000,000 barrels of crude oil proven to be in place within the various oil-bearing formations throughout the United States and Canada, no more than 25% of that crude oil, on the average, has actually been recovered, leaving about 325,000,000,00 billion barrels of crude oil still in place within the various rock formations. Stripper Wells in the US In the United States of America, one out of every six barrels of crude oil produced comes from a marginal oil well, and over 78 percent of the total number of US oil wells are now classified as such. There are over 400,000 of these wells in the United States, and together they produce nearly 900 thousand barrels of oil per day, 15 percent of US production. These are known as stripper wells. Many of the huge population of stripper wells lie in these fields; some are tiny accumulations known as “single-well fields.” Until a field reaches a critical size with quite a few wells, unitization for waterflood is not feasible, though many tiny fields, which include water disposal wells, have constituted tiny waterflood pilots. Between 1994 and 2003, approximately 142,000 marginal wells were plugged and abandoned. The resultant loss in oil revenue is significant: more than $3.0 billion in lost oil revenue at the 2003 average world oil price. Until improved economics occurs, especially based on oil pricing, these wells cannot be replaced by drilling replacement wells. During this interminable period local, regional and National payrolls, rental fees, property taxes, and balance of trade are lost. Some may even be temporarily abandoned (TA) or permanently abandoned (plugged and abandoned) (PA, or P&A), “brownfield,” wells. Unitization for waterflood and EOR helps to reverse this trend, but is often not feasible due to geologic or environmental limitations. Industry badly needs new EOR alternatives. Petroleum geochemists have investigated long and hard to provide analysis and operations to bridge the gap between a stripper well and enhancement of its economics and longevity.
http://stripperwells.com

An Emerging EOR Chemical Flooding Process One such bridge is a proprietary technology presented by EPRS Energy. Dr. R C Ropp, VP of Technical Affairs, Fellow and Certified Chemist of The Royal Society of Chemistry (London) has patented this process. EPRS performs the patented chemical analysis to characterize each specific accumulation of crude oil. A concentrated stimulation treatment chemical is then designed specifically for the accumulation at hand, and EPRS sends a team to that specific location to implement that treatment. About a barrel of this aqueous chemical concentrate is injected per well, followed by a “chaser” slug of 15-20 barrels of water to displace and dilute the engineered concentrate. A reaction between heavy components of the crude oil’s hydrocarbon molecular weight

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range and the contents of the engineered concentrate forms natural gas downhole. The result of this effect can be compared to TRHO’s “distillation,” Miscible Recovery’s mixing, or even the catalytic cracking reactions performed in petrochemical refineries. Reservoir crude oil is thus depleted of these unfavorable heavy fractions and restored with light hydrocarbons. Some of the restored methane and intermediates dissolve in the enhanced reservoir crude, and some remains as a free gas phase downhole. The reservoir crude oil is thereby rendered less dense and less viscous. API Gravity is increased. Reservoir and wellhead pressures increase. Post-treatment wellhead pressures as high as 1600psi have been achieved. EPRS has experimented with about 65 different crude oils from all over the US and has generated significant gas volumes from each. The EPRS chemical flooding technology exhibits considerable potential to accomplish these effects in accumulations of heavy and extra-heavy crude oils. This may extend even to tar sands, bitumens, and even the kerogens in “oil shales.” EPARS is one E&P’s newest alternatives in the field of EOR. EOR and CO2 Sequestration New opportunities for environmental remediation, increased oil production, and job creation are emerging due to recently identified global and US priorities to reduce emission of greenhouse gases into the atmosphere. Naturally, CO 2 withheld from such release must be impounded (sequestered) somewhere. The mature and successful EOR technique of miscible displacement relies primarily on programs to inject CO2 into oil reservoirs as a “solvent” to mix and dissolve with reservoir oil, including additional injection of various grades of water for reservoir fluid mobility control. There is a growing inventory of existing CO 2 sequestration EOR (CO2S-EOR) projects, and an expanding volume of related literature on screening for and cooptimization of new CO2-S-EOR opportunities. Energy and environmental agencies have strong interest in co-optimization of EOR by gas injection and greenhouse gas sequestration (EOR-GGS) by disposal of CO2, CO, oxides of nitrogen, H2S, SO2, etc., as exist in flue gases and especially in output of oil and gas processing plants. There are enough EOR-GGS examples around the world (Algeria, Australia, Canada, Norway, etc.) in operation or post-proposal stages to help EPRS avoid previous wrong turns in planning. Two prominent Canadian projects are the widely publicized Weyburn Pilot Project in Saskatchewan and the much more interesting Zama oil field in Alberta. The Zama Field project injects both CO2 and H2S from its nearby processing plant into the top of a Devonian pinnacle reef. Oil is produced from a completion near the reef bottom, making this project somewhat gravity-stable. A shallower well serves to monitor leakage of these “acid gases.” These projects also use the term “carbon sequestration.” E&P companies are prepared to seek industrial sources of CO2 and other greenhouse gases (especially output from gas processing plants which scavenge these gases from crude oil and/or natural gas, and perhaps flue gases from power stations), and to formulate plans to sequester these

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undesirable emissions underground. Flue Gas & Greenhouse Gases New opportunities for environmental remediation, increased oil production, and job creation are emerging due to recently identified global and US priorities to reduce emission of greenhouse gases into the atmosphere. Naturally, CO 2 withheld from such release must be impounded (sequestered) somewhere. The mature and successful EOR technique of miscible displacement relies primarily on programs to inject CO2 into oil reservoirs as a “solvent” to mix and dissolve with reservoir oil, including additional injection of various grades of water for reservoir fluid mobility control. There is a growing inventory of existing CO 2 sequestration (CO2-S) EOR (CO2-S-EOR) projects, and an expanding volume of related literature on screening for and co-optimization of new CO2-S-EOR opportunities.

US Flue Gas Locations Energy and environmental agencies have strong interest in co-optimization of EOR by gas injection and greenhouse gas sequestration (EOR-GGS) by disposal of CO2, CO, oxides of nitrogen, H2S, SO2, etc., as exist in flue gases and especially in output of oil and gas processing plants. There are enough EOR-GGS examples around the world (Algeria, Australia, Canada, Norway, etc.) in operation or post-proposal stages to help EPRS avoid previous wrong turns in planning. Two prominent Canadian projects are the widely publicized Weyburn Pilot Project in Saskatchewan and the much more interesting Zama oil field in Alberta.

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The Zama Field project injects both CO2 and H2S from its nearby processing plant into the top of a Devonian pinnacle reef. Oil is produced from a completion near the reef bottom, making this project somewhat gravity-stable. A shallower well serves to monitor leakage of these “acid gases.” These projects also use the term “carbon sequestration.” E&P companies are prepared to seek industrial sources of CO2 and other greenhouse gases (especially output from gas processing plants which scavenge these gases from crude oil and/or natural gas, and perhaps flue gases from power stations), and to formulate plans to sequester these undesirable emissions underground. So, actual feasibility of co-optimizing EOR, especially the gas-injection processes of immiscible and miscible displacements, is a crucial issue to be questioned in every realistic sense.
 Characterization of flue gas compositions, especially flue gases from the gas-fired and coalfired power plants which dominate the US power utility industry. Can flue gases be directly injected into oil reservoirs for these EOR processes? If processing is required to prepare flue gases for EOR injection, what are the nature, scale, and expense of these processes? Will existing flue gas processing methods be adequate, or must additional techniques be researched?

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US Locations for Geological CO 2 Sequestration

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Flue Gas Composition CO2 is NOT the only greenhouse gas: nitrogen oxides, NOX, are considered MUCH more hazardous, for example. Unprocessed flue gases are seldom good candidates for EOR by gas injection due to their very high (78-80%) atmospheric nitrogen (N2) content.
Fuel Choices & OSHA: Chemical Species Nitrogen, N2 Carbon dioxide, CO2 Oxygen, O2 Carbon monoxide (CO) Nitrogen oxides (NOx) Ammonia, NH3 Sulphur dioxide (SO2) Hydrocarbons (CXHY) Mercury, Hg Fly Ash none minimal 50 NO-25, NO2-5* 50 H2S-20*, SO2-5 5000 OSHA TWA *ceiling, ppm Natural Gas 78-80% 10 – 12% 2-3% 70-110ppm 50-70ppm Fuel Oil 78-80% 12-14% 2-6% 70-160ppm 50-110ppm Used in removal of NOx. 180-250ppm <60ppm >200lb/year/plant 12% >2,000ppm 1% 7% Coal 78-80%

Table. Summary of flue gas composition ranges for power plants fueled by gas, oil and coal. Given these inconvenient contaminants it is no surprise that EOR by flue gas injection has been discontinued, sometimes converted to nitrogen injection, in most projects which attempted that EOR implementation. OSHA’s TWA limits are allowed for 8-hour personnel shifts. OSHA’s Ceiling limits should not be exceeded at any time for personnel.

Flue Gas Processing An example of flue gas processing sequence is:
 While flue gas is still hot, incineration under controlled temperature and pressure in a chamber, which may include a catalyst system, perhaps injecting a reagent, can produce required chemical reactions. Incineration reaction results depend on composition, temperature, pressure, catalysis, and residence time for which these conditions apply. Co-generation heat exchangers can scavenge heat from this hot gas and provide cooling. Sorbents like activated carbon, lime, or sodium salts, can be injected to adsorb mercury or SO2 gases. Electrostatic precipitators (ESP’s), wet or dry, can capture particulates like sorbents, fly ash, or soot, in a wide range of temperatures. These devices have been adapted to “ionic” household air cleaners. Wet scrubbers can accept high-temperature moist flue gas to remove particulates and/or gaseous contaminants. Dry scrubbers (cooling followed by carbon, lime or sodium reagent injection, and fabric “baghouse” filter) can remove particulates.

  

 

Carbon monoxide, CO, is a colorless, odorless gas which is tasteless and non-irritant. It is somewhat less dense than air and, although it is a product of imperfect combustion, it is

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inflammable. Carbon monoxide, like oxygen, has an affinity for iron-containing molecules, and it is about 210 times more effective in binding to iron-containing haemoglobin than oxygen. Blast furnace gas contains 25% carbon monoxide. Coal gas, which was used as a fuel in Europe up until North Sea (natural) gas became plentiful, contains 16% CO. Processing Flue Gas NOx Nitrogen oxides (NOx) occur in all fossil fuel combustion, through oxidation of atmospheric nitrogen (N2) and also from organic nitrogen fuel content, and flue gas NO x concentrations are enhanced by high combustion chamber temperatures. Nitric oxide (NO) oxidizes with time and forms nitrogen dioxide (NO2), a brown, toxic, water-soluble gas that can seriously damage the lungs, contributes to acid rain and helps to form ozone. With or without Selective Catalytic Reduction (SCR), ammonia (NH3) ions react with both species: 4NH3 + 6NO  5N2 + 6H2O, 8NH3 + 6NO2  7N2 + 12H2O. Use of ammonia in NOx reduction technologies or for flue gas conditioning can have a substantial balance-of-plant impact on coal-fired plants. Ammonia adsorbs on fly ash within the flue gas processing system as both free ammonia and ammonium sulfate compounds, however. This ammonia can then desorb during subsequent transport, disposal, or use of the fly ash. This desorption of ammonia presents several technical and environmental concerns as fly ash disposal occurs in surface water and landfills. SCR can optimize the NH 3-NOx reduction with a minimum of downstream problems developed by ammonia slip. Processing Flue Gas SO2 Almost all hydrogen sulfide, H2S (OSHA “ceiling” = 20ppm), oxidizes within a day to SO2. SO2 is smelly, toxic, and contributes to acid rain. SOX can be removed from flue gas by dry alkaline adsorption before particulate removal. Addition of sodium bicarbonate into the flue gas causes it to react in the following manner: 2NaHCO3  Na2CO3 + H2O + CO2. This allows for the sodium carbonate to react with the oxygen and sulfur dioxide in the flue gas to form sodium sulfate and carbon dioxide as follows: Na2CO3 + SO2 + 0.5CO2  Na2SO4 + CO2. With the creation of solid sodium sulfate, the desulfurization of the gas is complete, awaiting capture of solid sodium sulfate particles. In wet limestone scrubbing after particulate removal, limestone slurry in water comes into contact with the flue gas SO2 + CaCO3 + H2O  CaSO3 + H2O + CO2. This calcium sulfite (CaSO3) is then oxidized to form calcium sulfate, CaSO4, gypsum.

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Contaminants in “sheet rock” made from recycled gypsum are suspect household environmental hazards. Processing Flue Gas Mercury, Hg Since the average mid-sized coal-fired plant releases at least 200-300 pounds of mercury per year, and mercury pollution has immense environmental impact, mercury emission control is receiving large “doses” of money and professional attention, and benefits from specialized industry knowledge. Oxidized mercury, Hg2+, and Hg bound to particles is easily removed with ESP’s or wet flue gas desulfurization (FGD); removal of free elemental mercury is more challenging. Technologies that impact mercury speciation include most existing air pollution control methods: Selective Catalytic Reduction (SCR) mercury oxidation is gaining emphasis for mercury removal, since it is often already used to remove NO x; sorbent injection, dry scrubbers, dry and wet ESP's, and wet scrubbers are oldest and most commonly employed methods. The accepted existing activated carbon mercury sorbent process is that it takes many, many times more pounds of carbon per pound of mercury removed. Since the average mid-sized plant releases at least 200-300 pounds of mercury per year, it equates to anywhere from four hundred thousand to almost four and one half millions pounds of injected carbon needed per year. Once polluted with mercury and captured, this carbon is useless, cannot be recycled, and must sit in a landfill. ADA’s patented Mercu-RE process has been introduced to provide a sorbent which can be detached after capture to yield elemental mercury for resale. The Cloric acid laboratory process produces HgOCl: Hg + HClO3  HgOCl + H2O, and can also be used to oxidize NOX pollutants, and those can then pass through the system as nitrogen gas, without the problem of ammonia slip contaminating fly ash.
http://www.wshinton.com/

Greenhouse Gas Sequestration US Federal agencies DOE, DOI (especially USGS), and EPA are showing strong interest in co-optimization of EOR by gas injection and greenhouse gas sequestration (GGS) for disposal of COX, NOX, H2S, SO2, CXHY, etc. There are enough EOR-GGS examples around the world (Algeria, Australia, Canada, Norway, etc.) in operation or post-proposal stages to help researchers, planners, and developers avoid previous wrong turns in planning. Regarding power stations, separation of greenhouse gases from N 2 in flue gases seems a dominant problem, since N2 injection is only favorable for gravity-stable EOR displacement of light oils (API Gravity > 30 °) at depths beyond the common range of oil reservoir depths. So, most US oil fields would be eliminated “out” of screening processes for injection of raw flue gas. A possible example that might screen “in,” regarding depth, reservoir pressure, and

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temperature, is the Hawk Point Field of Campbell County, WY, a complex PermianPennsylvanian Minnelusa interbedding of with eolian sands. Naturally, such a complex reservoir has large variations in vertical permeability, flow barriers, and is generally very heterogeneous. Its reservoir has thickness 50’, porosity 12%, and permeability 60mD reported. Hawk Point reservoir depth is 11,500’, with 260 °F Temperature and 4,472psi initial pressure. Providing its crude oil contents are light enough (API Gravity > 30 °) and temperature is not too high (increases oil viscosity), Hawk Point a good candidate to further screen for a pilot project to investigate EOR using injection of nitrogen or flue gas. On primary production in 1986 and waterflood in 1989, in 2001 Hawk Point Field was already a candidate for abandonment due to economic limit.
USGS: CO2 sequestration “Based on current projections, the United States faces the need to increase its electrical power generating capacity by 40% over the next 20 years and its total energy consumption by 24% by the year 2030. Fossil fuel usage, a major source of carbon dioxide emissions to the atmosphere, will continue to provide the dominant portion of total energy in both industrialized and developing countries. Overall reduction of carbon dioxide emissions will likely involve some combination of techniques, but for the immediate future, sequestration of carbon dioxide in geological reservoirs seems especially promising, as existing knowledge derived from the oil and gas production industries has already helped to solve some of the technological obstacles. The USGS has been studying geologic options for storing CO2 in depleted oil and gas reservoirs, deep coal seams, and brine formations.” http://energy.er.usgs.gov/health_environment/co2_sequestration/

Co-optimization Failure The deepest oil reservoirs are generally shallower than 20,000 feet. The Semitropic Field in California produced oil from an interval between 17,610-18,060 feet. Heat levels at those depths eventually "cook" the oil, converting it to natural gas. Mexico’s Cantarell Field is considered the world’s biggest N 2-injection project, producing 500,000 BO/D incremental in recent reports. Bechtel/IPSI’s 2001 design report explores all the problems with flue gas injection and several other processes, culminating in the choice of N2 injection to provide pressure maintenance, immiscible displacement, and increased production in the huge Cantarell project. That report all but eliminates the practical potential for flue gases as EOR solvents. The extensive contamination of flue gases, reported in Table above, makes their processing to eliminate N2 a chemical engineering design nirvana, but a construction and maintenance infinite nightmare. All those greenhouse contaminants in flue gas, including COX, are associated with corrosion and/or toxicity. In the gas injection EOR processes they would not be processed once; they would be processed indefinitely in cycles for the life of the project.
www.ipsi.com/Tech_papers/cantarell2.pdf

So, without extensive treatment of flue gases, EOR and GGS will not co-optimize except in exceptional and infrequent applications. GGS should then be directed toward storage

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in less valuable reservoirs, like depleted natural gas reservoirs, gas-depleted low-grade coal beds and coal beds too thin or deep for mining, etc. Some pilot projects for EOR-GGS co-optimization would be helpful for research and demonstration purposes, however. Just west of Hobbs, NM, are Xcel’s Maddox and Cunningham gas-fired power stations, for example. Their minor flue gas outputs could be combined for processing, and there are small oil fields nearby perfect for EOR pilot projects. Saline aquifers should be considered with great care, because they may eventually be needed with desalinization technologies to produce fresh water. Contaminating them with flue gas contaminants would render that water useless.
Horizontal Drilling in Proven Oilfields

Figure 13. Geologic cross-section illustrates advantages for reservoir exploitation (increased initial potential, IP, and ultimate recovery, OR) and surface land conservation advantages of directional drilling. http://www.americandirectionaldrill.com.

In the last 10 years the Natural Gas Industry has invested the time and money to perfect most aspects of directional drilling and measurement while drilling (MWD) to replace considerable fractions of US natural gas consumption. This has moderated pricesand exploded the performance of tight gas wells. Along with the “slick water” fracture treatments this has created most of the “unconventional” shale gas plays like the Barnett Shale.

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Figure 14. American Directional Drilling’s VR-500 eliminates many traditional drilling components, such as draw works, cables, manual tongs, and catheads, which reduces injuries and downtime. Standard Operating Procedures limits the need for crewmembers to be on the drilling floor, which contributes to improved jobsite safety. Push/Pull Thrust and Rotary Torque for increased working power and reserve capacity. The Best-In-Industry Top Head Drive equipped with Slip Spindle is rugged and durable yet easy on Pipe Threads. The VR-500 provides optimum bit load from initial surface contact throughout the entire drilling operation. Operators also have the ability to immediately start a horizontal curve after surface penetration resulting in greater access to shallow formations, possibly as shallow as 1,200’. www.americandirectionaldrill.com.

Horizontal drilling technology has equal aptitude for rejuvenating many oil fields, especially those with low permeability and almost all their OOIP still in place to be recovered. Many of these are shaly sands reservoirs, where waterflooding is hazardous

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due to sensitive reservoir clays. Horizontal drilling in such settings has multiple appeals:
  Initial production Potential (IP): Vertical completion, sandstone, vertical thickness 40’, for example, 50,000 BO cumulative, can be completed across a 4,000’ horizontal interval. Ultimate Recovery (OR): Horizontal completion contacts much more formation volume, especially banks of oil bypassed by previous development, and may be expected to produce at least 10 times the vertical completions’ cumulatives. As is already demonstrated for thermal recovery of heavy crudes, low-permeability sands with viscous intermediate crudes are horizontal drilling targets.

New drilling rig designs allow horizontal “kick-off” from vertical wells at much shallower depths, allowing targeting shallower oil reservoirs.

Micro Hole Drilling
Figure 13. Small trailer mounted coiled tubing “Micro Hole” system. DOE and LANL funded design, which uses coiled tubing, mud motor, bent bit sub, reduction gear sub, and ultra-compact steering tool. Horizontal depth can be far less than 1,000’.

Figure 15. Schematic displays its hole diameter range vs. conventional hole sizes.

www.offshoretechnology.com/features/feature758/

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Micro-hole drilling has the potential to greatly reduce the cost of drilling shallow and moderate-depth holes for exploration, field development, long-term subsurface monitoring and, to a limited degree, actual oil and gas production. It also offers greatly enhanced reservoir imaging, making access to data cheaper and more precise, as well as being invaluable during exploration activities. These new low-cost production capabilities are needed to invigorate the domestic oil and gas industry so that more of the petroleum resources in the USA's mature basins can be recovered. Dedicated boreholes with permanent reservoir monitoring systems will provide high-resolution, real-time information while monitoring and optimizing improved oil recovery (IOR) processes. This low-cost, long-term, improved imaging method of monitoring fluids in the reservoir will enhance oil recovery and allow dedicated boreholes for reservoir monitoring, eliminating production interruptions. Summary: Light Oil Legacy, Heavy Oil Destiny
USGS: HO & Bitumen “In spite of an immense resource base, heavy oil and natural bitumen accounted for only about 3 billion barrels of the 25 billion barrels of crude oil produced in 2000. Compared to light oil, these resources are generally more costly to produce and transport. Also, extra-heavy oil and natural bitumen must usually be upgraded by reducing their carbon content or adding hydrogen before they can be used as feedstock for a conventional refinery. The extra production, transportation, and upgrading costs explain why development and production of extra-heavy oil and bitumen are still limited. Their abundance, strategic geographic distribution, quality, and costs will shape their role in the future oil supply.” http://pubs.usgs.gov/fs/fs070-03/fs070-03.html
Stacked pair of horizontal wells for steam-assisted gravity drainage (SAGD), a natural bitumen recovery process. Steam injected through the upper well mobilizes bitumen, and gravity causes the mobilized fluid to move toward the lower well, where the bitumen is pumped to the surface. Figure 16. In Canada, natural bitumen is extracted from Alberta oil sand deposits that are too deep to surface mine by a process known as steamassisted gravity drainage (SAGD). Production wells could produce in excess of 2,000 barrels of bitumen per day. (USGS) Graphic copyright Schlumberger "Oilfield Review.” From Carl Curtis and others, 2002, Oilfield Review, v. 14, no. 3, p. 50.

The legacy of E&P, both Internationally in the USA, is emphasis and expertise devoted to

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the wholesale finding, developing, recovering, transporting, and refining of Light and Intermediate grades of crude oil. Virtually all the Earth’s remaining reserves of these most convenient feedstocks occur in the Eastern Hemisphere. These geopolitical settings include many governments that are unstable and/or unfriendly to the USA and its allies. Emerging technologies and geopolitical pressures are pointing to future enhancement of and reliance upon the recovery of heavy and extra-heavy oils. This same trend applies to large deposits of natural bitumens, especially regarding tar sands. It is time to study and plan for the large potential environmental consequences of commercial recovery of these vast resources. In 2001, about 735,000 barrels per day were extracted by mining and by in-situ production from Alberta oil sands, accounting for 36 percent of Canada's total oil production. Projected 2011 production is 2.2 million barrels per day (Alberta Energy and Utility Board, 2002, Alberta's Reserves 2001 and Supply/Demand Outlook 2002-2011, Statistical Series 2002-98, p. 2-8 to 2-9). On Page 53, McCain mentions that the petroleum engineer is rarely concerned with solid hydrocarbons. This is an example of E&P’s historic unfamiliarity with deposits of heavy and extra-heavy crude oils and bitumens.

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US Energy Policy Issues In review, key issues in formulating a US Energy Policy for the 21 st Century include:
 Excessive reliance upon light and medium crude oils to provide the refined domestic products necessary for domestic commerce, science, health, and welfare continues today. This reliance is despite the heavy concentration of global heavy oil and bitumen resources in California, Canada and South America. A precarious state of up to 250,000 stripper wells continues in the US. These wells produce only a few barrels of oil daily, at most. Economics of these are extremely sensitive to oil price. They contribute significantly to US production, reducing balance of trade problems and reliance upon unreliable International sources. The stripper well aggregate also contributes greatly to their local economies, providing ad valorem tax base, local payrolls, specialty materials purchases, royalty contributions, and surface rentals. New Enhanced Oil Recovery (EOR) alternatives are needed to improve recovery and prolong production of crude oils from old fields with critically low reservoir pressures and/or advanced “deadening” of their original crude oil compositions. At least one of these is available for licensing and implementation today. The “Peak Oil” concept has recently emerged, describing a theory that the International oil production rate is now nearing its peak. The theory is that oil production rate will soon decline and continue its decline indefinitely. If this production rate peak occurs, huge waves of price increases and/or regional shortages are inevitable, with potentially dire economic and logistical effects. This term is adapted from Hubbert’s work (Appendix 7.). Horizontal and micro-hole drilling: Horizontal drilling helped spur the US gas boom in 2000. It is now proven, and new rig designs are ready for US oil fields, perhaps in combination with waterflooding and/or EOR. Micro-holes will also be very helpful. Another anomaly of high oil prices will occur soon: Pricing in 2010 will average about $75/BO. Now is the time to explore and develop the remaining very large structures of Alaska, while existing field activities support healthy infrastructure, lending “critical mass” to moderate the huge costs of such geoscience and engineering projects under such challenging conditions. Residents of Kaktovik, the only people living on the Coastal Plain of ANWR, support oil and gas development in their 'back yard'. (Appendix 6.) Natural gas is a domestically strategic resource. Its use to generate electric power and even power motor vehicles could result in premature depletion in North America. Future generations could have no recourse but to heat their homes with coal. Burning coal in power plants and biofuels in vehicles are examples of available substitutes. Emissions from coal fired power plants can be scrubbed. Use of coal to generate electric power is perhaps the best way to conserve natural gas and assist transition to alternative energy sources like wind, solar, and nuclear technologies. To mitigate pollution, the emissions of plants fired by high-sulfur coals can be scrubbed of their carbon, soot, sulfur, etc., with manageable (25%) impacts on their economics. Emerging technologies: Prolonging stripper production, improving EOR processes, wind, solar and bio-fuel technologies, recycling, and especially for scrubbing the emissions from power plants fueled by high-sulfur coals, are technologies that will experience exploding demand in the coming generations, decades, and even immediately. US technological leadership: If the US is not a pre-eminent provider of at least the design of such technologies, our Nation will have to procure them overseas. Such a circumstance would represent tragic loss of International prestige, National revenue, and a myriad of opportunities both tangible and intangible.

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References Hubbert's Peak: The Impending World Oil Shortage, Kenneth S. Deffeyes, 285 pages, Princeton University Press (October 1, 2001). Twilight in the Desert: The Coming Saudi Oil Shock and the World Economy - Matthew R. Simmons, 448 pages, Wiley (June 10, 2005) Heavy Oil and Natural Bitumen -- Strategic Petroleum Resources, Richard F. Meyer and Emil D. Attanasi: USGS Fact Sheet 70-03, August 2003 - Online Version 1.0.
http://pubs.usgs.gov/fs/fs070-03/fs070-03.html

The Properties of Petroleum Fluids, McCain, William D., Jr., 596 pages, Pennwell Books, 2 Sub edition (April 1990) ISBN-10: 0878143351 ISBN-13: 978-0878143351. “LNG Update”, Maslowski, Andy: Well Servicing Magazine, Nov./Dec. 2008, pages 43-46. Petroleum Reservoir Rock and Fluid Properties by Abhijit Y. Dandekar. “Effect of Wettability Alteration on Relative Permeability Curves for Low Permeability Oil-Wet Reservoir Rocks,” 2004, L. Qingjie, L. Li, Manli, Research Institute of Petroleum Exploration and Development, PetroChina.
http://www.scaweb.org/assets/papers/2004_papers/1-SCA2004-39.pdf

S.E. Buckley and M.C. Leverett (1942). "Mechanism of fluid displacements in sands.” Transactions of the AIME (146): 107–116.
http://stripperwells.com

Standard Handbook of Petroleum and Natural Gas Engineering, Second Edition (Complementary Science) by Ph.D., PE, William C. Lyons and BS, Gary J Plisga (Hardcover - Oct 15, 2004). KGS--Petroleum a primer for Kansas:
http://www.kgs.ku.edu/Publications/Oil/index.html SRI Instruments - GC, HPLC, Data Systems, Hydrogen Generators www.srigc.com/ www.americandirectionaldrill.com www.xtremecoildrilling.com www.offshore-technology.com/features/feature758/

www.rmotc.doe.gov/Pdfs/RSFFeb06.pdf Radial Jet Enhancement (RJE) (www.encapgroup.com) http://en.wikipedia.org/wiki?title=Talk:Tar_sands
http://peswiki.com/index.php/Directory:Microbial_Enhanced_Oil_Recovery

“Orimulsion is the best way to monetise the Orinoco's bitumen,” Carlos Rodriguez, Soberania.org - 17/07/05,
http://www.soberania.org/Articulos/articulo_1375.htm.

Worldwide practical petroleum reservoir engineering methods, H. C. "Slip" Slider, Ed 2, PennWell Books, 1983, 616. Regarding micellar polymer flooding, HK van Poollen &

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Associates point out: "Although much laboratory work has been done, no field project has as yet been reported as economic." OPTIMIZATION OF A CO2 FLOOD DESIGN WASSON FIELD - WEST TEXAS
A Thesis by MARYLENA GARCIA QUIJADA, Texas A&M University

MASTER OF SCIENCE, August 2005, Petroleum Engineering
http://txspace.tamu.edu/bitstream/handle/1969.1/4138/etd-tamu-2005B-PETEGarcia.pdf?sequence=1

Handbook of Detergents, Part D: Formulation (Surfactant Science) by Michael Showell Handbook of Detergents, Part E: Applications (Surfactant Science) by Uri Zoller

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Appendix 1. Darcy’s Law Henri D’Arcy (′där·sēz ′lö) was the French civil engineer who discovered these valuable connections between the porous medium’s porosity and permeability, fluid viscosity, pressure gradient, and fluid flow. Darcy’s Law: Darcy's law is a simple proportional relationship between the instantaneous discharge rate through a porous medium, the viscosity of the fluid and the pressure drop over a given distance. http://www.answers.com/topic/darcy-s-law (fluid mechanics) The law that the rate at which a fluid flows through a permeable substance per unit area is equal to the permeability, which is a property only of the substance through which the fluid is flowing, times the pressure drop per unit length of flow, divided by the viscosity of the fluid. http://www.answers.com/topic/darcy-s-law Darcy's law states that where the Reynolds number is very low, the velocity of flow of a fluid through a saturated porous medium is directly proportional to the hydraulic gradient. For example, the flow of groundwater from one site to another through a rock is proportional to the difference in water pressure at the two sites:
V = hPl

where h is the height difference between the highest point of the water-table and the point at which flow is being calculated (the hydraulic head), V is the velocity of flow, P is the coefficient of permeability for the rock or soil in question, and l is the length of flow. Darcy's law is valid for flow in any direction, but does not hold good for well-jointed limestone, which has numerous channels and fissures. The total discharge, Q (units of volume per time, e.g., m³/s) is equal to the product of the permeability (κ units of area, e.g. m²) of the medium, the cross-sectional area (A) to flow, and the pressure drop (Pb − Pa), all divided by the dynamic viscosity µ (in SI units e.g. kg/(m·s) or Pas), and the length L the pressure drop is taking place over. The negative sign is needed because fluids flow from high pressure to low pressure. So if the change in pressure is negative (in the x-direction) then the flow will be positive (in the xdirection). Dividing both sides of the equation by the area and using more general notation leads to where q is the flux (discharge per unit area, with units of length per time, m/s) and is the pressure gradient vector. This value of flux, often referred to as the Darcy flux, is not the velocity which the water traveling through the pores is experiencing[2]. The pore velocity (v) is related to the Darcy flux (q) by the porosity (φ). The flux is divided by porosity to account for the fact that only a fraction of the total formation volume is available for flow. The pore velocity would be the velocity a conservative tracer would experience if carried by the fluid through the formation.
http://en.wikipedia.org/wiki/Darcy's_law

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Appendix 2. Pitch (Asphalt) Lakes (of Trinidad, Venezuela, and California)
http://www.semp.us/publications/biot_reader.php?BiotID=485

A pitch lake is a deposit of natural asphalt in a “great expanse of more or less mobile character, covering many acres, and resembling in many ways a similar expanse of water”, said petroleum geologist Clifford Richardson in 1917. (1) The most classic of all pitch lakes is Trinidad Lake in the Caribbean West Indies’ Island of Trinidad, but other pitch lakes exist throughout the world, including the Bermudez Lake in Venezuela, and the Rancho La Brea “Tar” Pits in Los Angeles, California. The meanings of the related terms asphalt, petroleum, bitumen, pitch, tar and hydrocarbons, are continuously evolving. Their meanings emanate from certain times and places, for example, the Roman era of “bitumen” and the modern era of “petroleum.” Even the term lake, as applied to natural asphalt deposits, may overstate the reality of these often soggy, belching, smelly, weeping sores of the Earth’s crust. Appendix 3. Fairway James Lime Field, East Texas Still Developing After 48 Years Robert E. Webster, David Luttner, and Lawrence Liu Hunt Oil Company, Dallas, TX Fairway (James Lime) Field, in Henderson and Anderson counties, Texas, trapped volatile 48° oil in the Aptian age James Lime member of the Pearsall Formation. The reservoir is a large patch reef complex of varied carbonate facies that grew on a paleobathometric high in the interior platform of the Lower Cretaceous shelf. For reservoir management purposes, the James is divided into an upper “A” zone with reefderived skeletal grainstone and/or lagoonal facies with moldic and interparticle porosity, a “B” dense zone of non-porous reef core, and a lower “C” zone composed of uniform fine grainstone. Porosity and permeability average 12.5% and 33 mD in the “A” zone and 12.9% and <1 mD in the “C” zone, respectively, at depths of 9,800 to 10,200 ft. Total net pay averages 56 ft. Following discovery in 1960, 157 wells were drilled on 160 acre spacing during the initial development phase. In 1963, a high pressure gas gathering system and gas plant were put into operation, and in 1965 a field-wide unit of 28,518 acres was approved, designed to conduct gas and water pressure maintenance operations. An injection project was then initiated to preserve reservoir energy and increase recovery through use of a WAG (water-alternating-gas) miscible recovery process. Additional infill drilling projects were implemented in 1971, 1980, 1991, and 2006 to optimize recovery; to date 237 wells have been drilled, including 3 recent horizontal wells targeting bypassed pay in the upper “A” and lower “C” zones. A large secondary gas saturation developed over the years as the gas-recycling program was implemented. Gas sales began in 2000, and gas injection was terminated in January, 2005. OOIP in the James was calculated as 410 MMBO, of which 213 MMBO has been produced. As of Aug. 1, 2007, production was 1,220 BOPD, 23,400 BWPD, 70 MMCFD, and 3,360 BNGLPD. Field life is projected

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beyond 2015. AAPG Article #90078©2008 AAPG Annual Convention, San Antonio, Texas Appendix 4. Exxon Mobil adds 1.5B barrels to proved reserves Associated Press, 02.16.09, 03:17 PM EST Exxon Mobil Corp. said Monday it added 1.5 billion barrels of oil equivalent to its proved reserves last year, once again extending a positive trend of replacing more barrels than it produced. The added reserves for the industry's biggest player totaled 103 percent of its 2008 output. The company said it added 2.2 billion oil-equivalent barrels to its resource base in 2008, with reserves additions from the Kearl Phase 1 oil sands project in Canada totaling 1.1 billion oil-equivalent barrels. It said proved additions were also made in the US, Norway, Nigeria, Australia, and Angola. For 2008, the company's resource base - which includes proved and probable reserves grew by 0.3 billion oil-equivalent barrels to 72.4 billion oil-equivalent barrels. That figure includes production, revisions to existing discoveries, asset sales and increased government take, which reduced the base by 0.5 billion oil-equivalent barrels. Last month Exxon reported a US record for annual profit even as its fourth quarter results fell 33 percent to $7.8 billion. Appendix 5. Oil From Canada’s Tar Sands Can Be Made ‘Clean,’ Obama Says Jim Efstathiou Jr. Jim Efstathiou Jr. – Wed Feb 18, 12:00 am ET Feb. 18 (Bloomberg) -- Oil extracted from tar sands in Canada can be made a clean energy source, and the US will work with its northern neighbor to develop the technology, President Barack Obama said. A joint effort by the US and Canada, its biggest trading partner, on ways to capture and store carbon dioxide underground would “be good for everybody,” Obama said yesterday in an interview with the Canadian Broadcasting Corp. Obama will make his first journey as president outside the US tomorrow to meet with Canadian Prime Minister Stephen Harper. Conservationists on both sides of the border have called on Obama to reject any bid to exempt tar-sands oil from proposed climate-protection rules. Government officials in Canada say restrictions on oil-sands exports would increase US dependence on oil from unfriendly countries. The oil is separated from sand and clay with intense heat in a process that releases more greenhouse gases than pumping conventional crude. “The United States is the Saudi Arabia of coal, but we have our own homegrown problems in terms of dealing with a cheap energy source that creates a big carbon footprint,” said Obama, who has backed “clean-coal” technology in the US over skepticism about its prospects from environmentalists such as former Vice President Al Gore. Reducing greenhouse-gas emissions from energy sources such as coal and oil sands will

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promote economic growth in both countries, Obama said. ‘Ceiling’ on Growth “If we don’t, then we’re going to have a ceiling at some point in terms of our ability to expand our economies and maintain the standard of living that’s so important, particularly when you’ve got countries like China and India that are obviously interested in catching up,” the president said. The US imported about 780,000 barrels a day of tar-sands oil in 2008, 60 percent of total production, according to the Canadian Association of Petroleum Producers. PetroCanada, the country’s third-largest oil company, and other producers expect to more than double industry output to 3.3 million barrels a day by 2020. Alberta’s oil sands may hold the equivalent of 173 billion barrels, enough to supply the US for 24 years, according to some government estimates. Only Saudi Arabia, the biggest producer in the Organization of Petroleum Exporting Countries, has more reserves. “Canada’s energy industry is willing to invest money, technology, know-how and time in this effort, but we really can’t do it alone,” Petro-Canada Chief Executive Officer Ronald Brenneman told reporters last week in New York. “It will take the combined efforts of the industry, government, regulators and consumers.” Environment Minister Canadian Environment Minister Jim Prentice has said Canada and the US should work together to develop systems to capture and sequester underground carbon-dioxide emissions. The total “life- cycle” of emissions released, all the way to filling a car’s tank with gasoline, are 20 percent more than conventional oil, the Rand Corp. research organization of Santa Monica, California, said in a 2008 report. Carbon capture would help “transition from a high-carbon present to a low-carbon future while avoiding a disruptive and dislocative period,” Prentice said on Jan. 20. Obama backs slashing emissions of heat-trapping gases to 1990 levels. The new president will have to square his environmental agenda with his call to trim dependence on oil supplies from the Mideast and with the US’s longstanding policy to treat Canada as a commercial and strategic ally. “Would I rather rely on Canada for my energy security or would I rather rely on Hugo Chavez?” Gordon Giffin, US ambassador to Canada during President Bill Clinton’s second term, said in an interview, referring to Venezuela’s president. “What Canada is saying to the United States is we now believe that we ought to be developing a North American approach to energy and to the environment. Our energy issues are not identically connected, but they’re logically connected.” To contact the reporter on this story: Jim Efstathiou Jr. in New York at
jefstathiou@bloomberg.net.

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Appendix 6. ANWR residents favor development The residents of Kaktovik, the only people living on the Coastal Plain of ANWR, support oil and gas development in their 'back yard'. Alaska's indigenous people have benefited greatly from North Slope production. In addition to providing a tax base for the local government, oil development has provided jobs, funding for water and sewer systems and schools. Native and village corporations with oil field-related subsidiaries are working on the North Slope, and the local government has a voice in permitting and environmental regulation. Organizations representing the residents of the Coastal Plain and surrounding area such as the City of Kaktovic, Kaktovik Inupiat Corporation, North Slope Borough, Arctic Slope Regional Corp., Doyon Regional Corporation and Alaskan Federation of Natives have all endorsed development based on their experience with Prudhoe Bay.
http://www.anwr.org/people/people.htm Appendix 7. Reviews of Hubbert's Peak: The Impending World Oil Shortage

232 pages, September 29, 2008 These several reviews can be found on Amazon.com. From Scientific American You have to wonder about the judgment of a man who writes, "As I drive by those smelly refineries on the New Jersey Turnpike, I want to roll the windows down and inhale deeply.” But for Kenneth S. Deffeyes, that's the smell of home. The son of a petroleum engineer, he was born in Oklahoma, "grew up in the oil patch," became a geologist and worked for Shell Oil before becoming a professor at Princeton University. And he still knows how to wield a 36-inch-long pipe wrench. In Hubbert's Peak, Deffeyes writes with good humor about the oil business, but he delivers a sobering message: the 100-year petroleum era is nearly over. Global oil production will peak sometime between 2004 and 2008, and the world's production of crude oil "will fall, never to rise again." If Deffeyes is right--and if nothing is done to reduce the increasing global thirst for oil--energy prices will soar and economies will be plunged into recession as they desperately search for alternatives. It's tempting to dismiss Deffeyes as just another of the doomsayers who have been predicting, almost since oil was discovered, that we are running out of it. But Deffeyes makes a persuasive case that this time it's for real. This is an oilman and geologist's assessment of the future, grounded in cold mathematics. And it's frightening. Deffeyes's prediction is based on the work of M. King Hubbert, a Shell geologist who in 1956 predicted that US oil production would peak in the early 1970s and then begin to decline. Hubbert was dismissed by many experts inside and outside the oil industry. Pro-Hubbert and anti-Hubbert factions arose and persisted until 1970, when US oil production peaked and started its long decline. The Hubbert method is based on the observation that oil production in any region follows a bell-shaped curve. Production increases rapidly at first, as the cheapest and most

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readily accessible oil is recovered. As the difficulty of extracting the oil increases, it becomes more expensive and less competitive with other fuels. Production slows, levels off, and begins to fall. Hubbert demonstrated that total US oil production in 1956 was tracing the upside of such a curve. To know when the curve would most likely peak, however, he had to know how much oil remained in the ground. Underground reserves provide a glimpse of the future: when the rate of new discoveries does not keep up with the growth of oil production, the amount of oil remaining underground begins to fall. That's a tip-off that a decline in production lies ahead. Deffeyes used a slightly more sophisticated version of the Hubbert method to make the global calculations. The numbers pointed to 2003 as the year of peak production, but because estimates of global reserves are inexact, Deffeyes settled on a range from 2004 to 2008. Three things could upset Deffeyes's prediction. One would be the discovery of huge new oil deposits. A second would be the development of drilling technology that could squeeze more oil from known reserves. And a third would be a steep rise in oil prices, which would make it profitable to recover even the most stubbornly buried oil. In a delightfully readable and informative primer on oil exploration and drilling, Deffeyes addresses each point. First, the discovery of new oil reserves is unlikely--petroleum geologists have been nearly everywhere, and no substantial finds have been made since the 1970s. Second, billions have already been poured into drilling technology, and it's not going to get much better. And last, even very high oil prices won't spur enough new production to delay the inevitable peak. "This much is certain," he writes. "No initiative put in place starting today can have a substantial effect on the peak production year. No Caspian Sea exploration, no drilling in the South China Sea, no SUV replacements, no renewable energy projects can be brought on at a sufficient rate to avoid a bidding war for the remaining oil." The only answer, Deffeyes says, is to move as quickly as possible to alternative fuels-including natural gas and nuclear power, as well as solar, wind and geothermal energy. "Running out of energy in the long run is not the problem," Deffeyes explains. "The bind comes during the next 10 years: getting over our dependence on crude oil." The petroleum era is coming to a close. "Fossil fuels are a one-time gift that lifted us up from subsistence agriculture and eventually should lead us to a future based on renewable resources," Deffeyes writes. Those are strong words for a man raised in the oil patch. For the rest of us, the end of the world's dependence on oil means we need to make some tough political and economic choices. For Deffeyes, it means he can't go home again. Paul Raeburn covers science and energy for Business Week and is the author of Mars: Uncovering the Secrets of the Red Planet (National Geographic, 1998). --This text refers to the Hardcover edition. Review "Deffeyes has reached a conclusion with far-reaching consequences for the entire industrialized world.... The 100-year reign of King Oil will be over." -Fred Guterl,

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Newsweek "Deffeyes makes a persuasive case.... This is an oilman and geologist's assessment of the future, grounded in cold mathematics. And it's frightening." Paul Raeburn, Scientific American "Deffeyes writes with the taut reasoning of a scientist and the passion of someone raised in the industry. His background is ideal for this subject, and the book is a gem... Read Hubbert's Peak-it's better to know what lies ahead than to be surprised too late to respond." -Brian J. Skinner, American Scientist The wolf is at the door, November 2, 2001, By Dohn K. Riley (Tahoe City, CA United States) Deffeyes hits the nail on the head when he clearly details what petroleum industry insiders already know - it's not "if" global oil production will peak, it's "when.” After years of warning about the imminent demise of cheap oil supplies, experts are now splitting hairs about whether or not inexpensive oil production will peak in this decade or the next. The author's easy-going, occasionally humorous prose makes the bad news easier to take, but either way, a serious global oil crisis is looming on the horizon. Deffeyes energizes his readers by sweeping us easily through the denser strata of the complexities and developmental progress that built "Big Oil," but he also warns of relying on technology to save us in the future. Unlike many technological optimists, this life-long veteran of the industry concludes that new innovations like gas hydrates, deepwater drilling, and coal bed methane are unlikely to replace once-abundant petroleum in ease of use, production, and versatility. The Era of Carbon Man is ending. A no-nonsense oilman blessed with a sense of humor, Deffeyes deftly boils his message down to the quick. Easily produced petroleum is reaching its nadir, and although they are clean and renewable, energy systems like geothermal, wind and solar power won't solve our energy needs overnight. "Hubbert's Peak" represents an important aspect of the energy crisis, but it is only one factor in this multi-faceted problem that includes biosphere degradation, global warming, per-capita energy decline, and a science/industry community intolerant of new approaches to energy technology research and development. An exciting new book by the Alternative Energy Institute, Inc., "Turning the Corner: Energy Solutions for the 21st Century," addresses all of the components associated with the energy dilemma and is also available on Amazon.com. Anyone who is concerned about what world citizens, politicians, and industry in the United States and international community must do to ensure a smooth transition from dependence on dangerous and polluting forms of energy to a more vital and healthier world, needs to read these books. Future generations rely on the decisions we make today. The Story of Oil, The End of Oil, September 18, 2001, by Ron Patterson (Huntsville, Al USA) Kenneth Deffeyes, Princeton professor and former oil field geologist, tells the story of oil, right up to the beginning of the demise of oil. He takes the methods developed by M. King Hubbert, the man who accurately predicted the peak in US oil production, and

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applies them to world oil production. The book makes absolutely riveting reading. The first few chapters deal entirely with the source and production of oil. I kept wondering, as I was reading these chapters, what has this to do with Hubbert's Peak and the coming decline in oil production? Then it began to dawn on me, one has to know everything about oil to accurately predict the future production of oil. Deffeyes is that man and he covers every possible base. Many say "Just drill deeper" or "There is oil in the deep ocean", but Deffeyes shows why drilling deeper can yield natural gas but not one drop of oil and why oil from deep ocean sediments is impossible. Deffeyes leaves no stone unturned and covers every possible source of oil. Deffeyes expects the peak in world oil production at around 2005 but says it could come as early as 2003 or as late 2006. There is a fair amount of jitter in the year-to-year production so picking the exact peak is difficult. But he reminds us that the center of the US Best-fit curve was 1975 and the actual peak came in 1970. He says however, there is nothing plausible that could postpone the peak until 2009. Of course Kenneth Deffeyes is not the only oil field geologist that is predicting an impending peak in world oil production, Colin Campbell, Jean Laherrere and several others have been doing that for several years. The data supporting the impending peak and decline is sometimes difficult to interpret but Deffeyes lays the data out in undeniable terms and in such a manner that the average layman can understand it. The only problem I had with the book was I felt Deffeyes was overly optimistic as to the effects of the coming decline in world oil production. He sees only a decade or so of difficulties until we get over our dependence on crude oil. Many others however, who have looked more closely at the possibility of alternate sources of energy to replace cheap portable oil, find no possible replacement. And....most of these see nothing short of a worldwide holocaust a few years after the peak. They say the world's six billion people are supported by a network of food production and transport that will be impossible to maintain when oil production begins to drop and the price of the remaining oil begins to rise dramatically. But by all means, BUY THIS BOOK. Not only will it convince you of the inevitability of the impending peak and decline in oil production, but also it will give you the ammunition and data to convince those around you, to convince them and give them time to make preparations for....for something I find too hard to even imagine. Only one more oil crisis, but it'll be a doozy, February 27, 2002, By Royce E. Buehler "figvine" (Cambridge, MA USA) While millions of environmentally concerned Americans are ready to vilify on reflex what Molly Ivins flippantly dubs "the oil bidness," Kenneth Deffeyes thinks of the petroleum fields as a place of high spirits and high romance. But, having spent half his life working for Shell, and half of it training later generations of fossil fuel hunters, he is here to break the bad news to us gently. And the news is, the party's over. The days of derring-do among the derricks are just about done. Thirty years ago, US oil production peaked, and has been declining ever since. Shortly,

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world oil production will hit the same peak, and begin to decline. That doesn't mean there will be no oil left; thirty years after hitting its own peak, the US is still the second largest oil producer in the world. But it does mean that demand will outstrip supply, and that means the economic dislocations of the late 70s - the spiking prices, the long gas lines, the deep recession - will become permanent. Eventually, other sources of energy, both renewables and plentiful fossil fuels like natural gas, will fill in the breach. But it will be a long and painful process, requiring a ton of capital investments in research and in infrastructure that a suddenly poorer first world will be ill able to afford. "Shortly,” Deffeyes argues, means in one to six years, and probably in the early part of that range. One can quibble with some of his arguments for that timing. With luck, he acknowledges, there may be one significant set of oil fields yet to be discovered, in the South China Sea (unexplored so far because the competing jurisdictions of the several nearby island nations have made contracts hard to nail down.) And I don't think he's given sufficient weight to the fact that all the oil recovery in the Middle East (ME) is still "primary,” using old-fashioned pumping technology. But if all the quibbles are granted, it only affords the world economy another five or ten years of grace. So, if Deffeyes is wrong, the time to start making those massive investments and changes is today. If he is right, the time to start making them is ten years ago, and all we can accomplish by swift action is to make the period of intense pain a decade or two shorter. Though Professor Deffeyes isn't political enough or impolite enough to say so, Clinton (for all his green talk) failed to provide any leadership to reduce our dependence on petroleum. And his successor, of course, is providing energetic leadership, but all of it is geared to marching us all double-time into still more rapid consumption of what little oil is left. History will remember neither President Slick, nor President Oil Slick, any more kindly than it now remembers Herbert Hoover for fiddling while the fuse that would set off the Great Depression burned. The book is an easy read, short and set in a conversational style that permits the reader to glide through the more technical portions if so inclined. The technical details and the mathematical arguments could be tighter, and the folksiness, which would be delightful in a lecture room, is occasionally a bit much on the written page. For those reasons, it would be easy to give the book only four stars. But those faults are inseparable from the book's virtues. They're compromises Deffeyes chose to make in order to be accessible to a wide audience, and his book deserves to reach one. If environmentalists take Deffeyes' message seriously, they'll realize that we will soon be so starved for oil that ANWR is certain to be plundered, and that nuclear plants are certain to sprout across the landscape like, well, like mushrooms. If Deffeyes is on or near target, nothing can prevent those developments. Greens today should be using ANWR and an expanded nuclear industry as bargaining chips, to be traded for strict CAFE standards, investment in renewable technologies, non-industry oversight of nuclear safety, and (since the near term alternative will be coal) investment in natural gas pipeline infrastructure.

Jim Myers, MPE

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Appendix 8. Reviews of Matthew R. Simmons’ Twilight in the Desert:
The Coming Saudi Oil Shock and the World Economy

464 pages, Wiley; illustrated Investment banker Simmons offers a detailed description of the relationship between Saudi Arabia and the US and our long-standing dependence upon Saudi oil. With a fieldby-field assessment of its key oilfields, he highlights many discrepancies between Saudi Arabia's actual production potential and its seemingly extravagant resource claims. Parts 1 and 2 of the book offer background and context for understanding the technical discussion of Saudi oil fields and the world's energy supplies. Parts 3 and 4 contain analysis of Saudi Arabia's oil and gas industry based on the technical papers published by the Society of Petroleum Engineers. Simmons suggests that when Saudi Arabia and other ME producers can no longer meet the world's enormous demand, world leaders and energy specialists must be prepared for the consequences of increased scarcity and higher costs of oil that support our modern society. Without authentication of the Saudi's production sustainability claims, the author recommends review of this critical situation by an international forum. A thoughtprovoking book. Mary Whaley Copyright © American Library Association. bad news from the SPE, via a Texas investment banker, June 16, 2005 (excerpts) By R. Hutchinson "autonomeus" (a world ruled by fossil fuels and fossil minds) Matthew R. Simmons analyzes the technical papers of the Society of Petroleum Engineers (SPE) on Saudi oil, shining a light behind the veil of secrecy that has shrouded it since OPEC stopped reporting oil production data in 1982. In short, what the SPE reports reveal is that the official Saudi claims for reserves and production capacity are vastly overstated. Further, tragically, it seems that the fields have been mismanaged, making it unlikely that all the oil will ever be recovered. Are there vast untapped reserves in Saudi Arabia? According to the SPE data, the answer is no. No giant fields have been discovered since 1968, despite intensive exploration. Here is a list of crisp facts about world oil, according to Simmons (p. 331):
  Only a handful of super-giant oilfields have ever been discovered in Saudi Arabia and the ME -- they represent a very significant portion of all ME oil, and they are all very mature. All mature giant oilfields peak and decline (production profiles showing the peaks are shown for 8 fields in Texas, Alaska, the North Sea, and Russia). Implication: sophisticated new technology will not prevent or forestall this from happening. There do not seem to be many giant oilfields left to be discovered in Saudi Arabia or the ME. Non-OPEC oil, excluding the FSU (former Soviet Union) seems to be peaking, or has already peaked.

 

Another dire warning that we must develop energy alternatives, March 28, 2006 By Dennis Littrell (SoCal) Kenneth S. Deffeyes warned us that peak oil is upon us and that what is left in the ground is just about the same as what we have already used. He pointed to Thanksgiving Day,

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2005 as the day oil hit its peak. Now another world renowned expert on oil, Matthew R. Simmons in this densely considered book, is advising us that the estimates of oil left in the ground by the largest producer of oil, Saudi Arabia, are probably inflated, and at any rate cannot be independently confirmed. Furthermore, it is supposed that estimates by almost all oil producing countries are inflated since such inflation improves their ability to influence the market while allowing them (OPEC members at least) to produce more. A question that might be asked is how do we know that there are not great fields of oil somewhere waiting to be discovered? Certainly if there are, the twilight of the oil-based world economy is pushed further into the future leaving us with much less to worry about now. Simmons answers this question for Saudi Arabia at least. He makes it clear that the possibility of any great discoveries on the Arabian peninsula "must now be deemed remote" since the land has been so thoroughly explored. (See Chapter 10 "Coming Up Empty in New Exploration.") Deffeyes answered this question in another way. Using logic from his mentor M. King Hubbert who predicted with startling accuracy when US production would peak (early 1970s) Deffeyes argues that what's left can be inferred from current production curves. Because oil exploration and production has been so extensive worldwide, if the oil were there, it would have been discovered and drilled for. This is not to say that there are not some (small) fields left undiscovered. There are some, no doubt, but like puddles added to a great lake, they won't affect the overall picture. This same sort of logic can be applied to Saudi Arabia, and Simmons does indeed use such logic. However, he goes beyond that because he believes that oil prediction simulation models (see Chapter 12, "Saudi Oil Reserves Claims in Doubt") can fail. Typically, he writes, an oilfield will yield about 75 percent of its oil during the first half of its producing life. (p. 278) Almost all of the great Saudi fields are decades old. The strange thing about this book is that while it is touted as another book predicting the end of oil, it actually argues that the situation is not entirely clear. It is possible that there is still a lot of undiscovered oil left in Saudi Arabia in places such as "the land along the Iraq border, an unexplored area almost as large as California" and a couple of other places. (p. 243) World wide such unexplored places are many. Nonetheless even if a lot of oil is discovered say in the middle of the Pacific Ocean or deep in the Antarctic, the cost of producing that oil will be greater than the cost of producing oil from say the great Ghawar field in Saudi Arabia where the oil gushes out of the ground almost effortlessly. Actually, according to Simmons "effortlessly" is no longer the correct adjective to use. As oil fields grow old some help is needed to get the oil to rise to the top and flow. Water is typically pumped into the field to get the oil to elevate. Simmons reports on the extensive use of saline water in Saudi Arabia--more evidence that there is not as much oil left as the Saudis would like us to believe. Also a distinction must be made between pure "reserves" (actual oil in the ground) and "recoverable reserves" (oil that is cost-effective to produce). And a further distinction

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must be made between grades of oil. It may be cost-effective to pump the sweetest, purest grade of oil out of a field whereas lesser grades would not be worth the expense. A weakness of the book is that, despite the words "and the World Economy" in the subtitle, which suggest an exploration of consequences and what to expect, there is next to nothing about the effect less oil (than expected) will have on the world economy. Clearly, of course, and in the broadest sense, our standard of living will go down as our energy costs rise. The subtitle is probably just a book biz editor's attempt to gain a larger readership. Twilight in the Desert is long and extraordinarily detailed and gives the typical reader more information than perhaps would be desired. This reader came away convinced that Simmons's main argument, that Saudi oil reserves have been exaggerated, is probably correct, but curiously his extremely balanced and careful delineation left me feeling that there is still plenty of doubt about both Saudi reserves and those world wide. Stay tuned. Regardless, one thing is clear, soon or late, within twenty years or fifty, we will have to retool our economies to run on something other than fossil fuels. The sooner we get started on that, the better. If we wait too long the sudden economic shock is likely to be catastrophic. (END of REVIEWS)

Jim Myers, MPE

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Appendix 9. Radial Jet Enhancement Radial Jet Enhancement is a patented technology to daily production of existing marginally producing oil and gas wells. The technology is oriented toward existing oil and gas wells in North America at depths of 4,500 feet and shallower.
Radial Jet Enhancement utilizes patented design and manufacturing technology of the Deflecting Shoe Boot and pressure water jetting. This figure below more precisely illustrates the process. The technology has the ability to drill up to 8 laterals in only two days, as opposed to a typical period of four weeks per well. The figure below demonstrates how Radial Jet Enhancement can drastically expand the production area within a given field. An average well will pull petroleum from an area of up to 120 feet from the well bore.

www.encapgroup.com
Radial Jet Enhancement lateral wellbores extend up to 300 feet from the well bore, thus increasing the area of production several fold.

Traditional well bore configuration, pulling from 120 feet, equates to a total volume of pay zone of 271,296 cubic feet. Each lateral of 300 feet will pull from over 360,000 cubic feet. That’s 1,440,000 cubic feet on four laterals. http://www.texas-energy.org/

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Appendix 10: “Surfactant-Based Photorheological Fluids: Effect of the Surfactant Structure” The effect of the surfactant structure on the mechanical and structural properties of surfactant based photorheological fluids are presented in this paper. Cetyltrimethylammonium bromide (CTABr) mixed with trans-o-methoxycinnamic acid in a basic environment can form photosensitive systems. The driving force is the ability of surfactant molecules to form wormlike micelles in the presence of the anionic photosensitive additive. Taking into account that slight changes in the surfactant monomer’s structure can induce drastic modifications of the micellar aggregate features, the role the of the nature of the counterion (in the CTAX type surfactants) or the headgroup size (CTRABr type surfactants) and its influence on the mechanical properties of surfactant based photorheological fluids using trans-o-methoxycinnamic acid (transOMCA) as additive were investigated. Rheological studies reported in this paper show that the viscosity of these systems drastically varies only by changing the nature of the surfactant counterion. Moreover, by increasing the bulk simply by replacing the three methyl groups with three ethyl groups in the surfactant headgroup moiety, the viscosity drastically decreases. Highly photosensitive PR fluids can be further obtained using cetyltrimethylammonium trans-o-methoxycinnamate (CTAOMC) as surfactant at neutral pH. In addition to the complete rheological characterization carried out by means of the application of both a steady shear and a dynamic shear stress, a 1H NMR and NOESY study was also performed. Piero Baglioni‡, Elena Braccalenti †, Emiliano Carretti‡, Raimondo Germani †, Laura Goracci †, Gianfranco Savelli* † and Matteo Tiecco † †CEMIN, Center of Excellence on Innovative Nanostructured Materials, Department of Chemistry, University of Perugia, Via Elce di Sotto 8, I-06123 Perugia, Italy‡Department of Chemistry and CSGI, University of Florence, Via della Lastruccia 3, Sesto Fiorentino, I-50019 Firenze, Italy Langmuir, 2009, 25 (10), PP 5467–5475 DOI: 10.1021/la900465h Publication Date (Web): April 17, 2009 Copyright © 2009 American Chemical Society
http://pubs.acs.org/doi/abs/10.1021/la900465h

Jim Myers, MPE

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