Definition of EOR Oil recovery -primary -secondary -tertiary(EOR,IOR) Primary Result from the use of natural energy present

in a reservoir as the main source of energy for the displacement of oil to producing wells. -solution gas drive, gas cap drive, natural water drive fluid and rock expansion, gravity drainage. Secondary Result from the augmentation of natural energy through injection of water or gas to displaced oil toward producing well -gas injection is either into a gas cap for pressure maintenance and gas cap expansion or into the oil column to displace oil immiscibly according to relative permeability and volumetric sweepout consideration.

-Gas processes based on other mechanisms, such as oil swelling, oil viscosity reduction, or favorable phase behavior, are considered EOR processes. -The injected fluids does not interact with the reservoir rock/oil system to create conditions favorable for oil recovery

Tertiary -Result from the injection of gases or liquid chemicals and the use of thermal energy. -The use of gas is considered as EOR process if the recovery efficiency significantly depend on a mechanism other than immiscible frontal displacement characterized by high interfacial tension. -EOR processes involve the injection of a fluid or fluids of some type into a reservoir. -The injected fluids and injection processes supplement the natural energy present in the reservoir to displace oil to a producing well.

-The injected fluids interact with the reservoir rock/oil system to create conditions favorable for oil recovery. -These interactions might, for example, result in lower 1FT's, oil swelling, oil viscosity reduction, wettability modification, or favorable phase behavior. Gas-hydrogen,CO2, nitrogen and flue gas. Liquid chemical- polymer, surfactant and hydrocarbon solvent. Thermal- consist of the use of steam or hot water, or rely on the in-situ generation of thermal energy through oil combustion in the reservoir rock.
Practical consideration The size of the fluid slugs that are injected and their unit costs -the nature of flow in porous media and rock/fluid interactions lead to the diminished effectiveness of injected fluid slugs. - Such chemical losses, changes in composition, or losses of thermal energy mean that the injected fluid slug size must be large enough to sustain the losses or changes and still operate effectively. The ease of handling an EOR fluid and its general compatibility with the physical injection/production system. -Highy toxic or corrosive fluids, or fluids that are not readily injected, are not very amenable to use in EOR processes.

The availability of an EOR fluid -If an EOR process is applied in a major reservoir, the fluid requirements for that single reservoir can be quite large. - And if that process is widely accepted for application across the country or the world, the volume requirements can become an important limiting factor for its application.

Efficient microscopic and macroscopic displacement E=EDEv E= overall displacement efficiency Microscopic Displacement Efficiency ED= microscopic efficiency, is a measure of the effectiveness of the displacing fluid in moving the oil at those place in the rock where the contacting fluid contact the oil

The microscopic displacement efficiency is affected by the following factors: Interfacial and surface tension forces Wettability Capillary pressure Relative permeability Macroscopic Displacement Efficiency EV= macroscopic efficiency, is a measure of how effectively the displacing fluid sweep out the volume of a reservoir both areally and vertically,as well how effectively the displacing fluid moves the displaced oil toward production wells. Factors that affect the macroscopic displacement efficiency are the following: Heterogeneities and anisotropy of an oil-bearing formation the mobility of the displacing fluids compared with the mobility of the displaced fluids the physical arrangement of injection and production wells The type of rock matrix in which the oil exists.

General classification of EOR process Mobility control Chemical Miscible Thermal Microbial EOR

Mobility control A solution of partially hydrolyzed polyacrylamide polymer in brine is injected to displace oil (and associated water) toward production wells. Polymer solutions are designed to develop a favorable mobility ratio between the injected polymer solution and the oil/water bank being displaced ahead of the polymer. The purpose is to develop a more uniform volumetric sweep of the reservoir, both vertically and areally

CO2 dynamic miscible process

A volume of relatively pure CO2 is injected to mobilize and displace residual oil. Through multiple contacts between the CO2 and oil phase, intermediate- and higher-molecular-weight hydrocarbons are extracted into the CO2 rich phase. Under proper conditions, this CO2-rich phase will reach a composition that is miscible with the original reservoir oil. From that point, miscible or near-miscible conditions exist at the displacing front interface.

Miscible first-contact-miscible (FCM) process The injected fluid is directly miscible with the reservoir oil at the conditions of pressure and temperature existing in the reservoir. A relatively small slug of a hydrocarbon fluid, such as liquefied petroleum gas (LPG), is injected to displace the oil. Primary slug/oil interfaces are eliminated, and oil drops are mobilized and moved ahead of the primary slug. The LPG slug, in turn, is displaced by a larger volume of a less expensive gas that is high in methane concentration.

The multiple-contact- miscible (MCM) process. The injected fluid is not miscible with the reservoir oil on first contact. Rather, the process depends on the modification of composition of the injected phase, or oil phase, through multiple contacts between the phases in the reservoir and mass transfer of components between them. Under proper conditions of pressure, temperature, and composition this composition modification will generate miscibility between the displacing and displaced phases in situ.

MICIBLE PROCESS

AND

IMMISICBLE

DISPLACEMNT

first-contact-miscible (FCM) process The injected fluid is directly miscible with the reservoir oil at the conditions of pressure and temperature existing in the reservoir. A relatively small slug of a hydrocarbon fluid, such as liquefied petroleum gas (LPG), is injected to displace the oil. Primary slug/oil interfaces are eliminated, and oil drops are mobilized and moved ahead of the primary slug. The LPG slug, in turn, is displaced by a larger volume of a less expensive gas that is high in methane concentration. Multiple contacts miscible Vaporizing gas process Condensing process

Vaporizing gas process The injected fluid contain mostly methane and low molecular weight hydrocarbon The composition of the injected fluid is modified as it move through the reservoir so that it become miscible with the oil The injected fluid is enriched in composition through multiple contact with the oil The intermediate component in the oil are vaporized into the injected fluid Under proper conditions, this enrichment can be such that the injected fluid of modified composition will become miscible with the oil at some point in the reservoir. From that point on, under idealized conditions, a miscible displacement will occur.

Condensing process The injected fluid contain large amount of intermediate molecular weight hydrocarbon The reservoir oil near injected well is enriched in composition by contact with the injected fluid first put in the reservoir The hydrocarbon component are condensed from the injected fluid into the oil Under proper conditions, this enrichment can be such that the oil of modified composition will become miscible with the injected fluid at some point in the reservoir. From that point on, under idealized conditions, a miscible displacement will occur.

MMP and MME MMP- the minimum pressure at which miscibility can be achieved in a MCM process for a specified fluid system MME- the minimum enrichment at which the limiting tie line pass through injected gas phase composition Measurement of MMP and MME slim tube test rising bubble apparatus

Slim tube test

Consists of a stainless-steel tube about 5/16 in. ID and about 40 ft long. The tube is packed uniformly with fine grade sand or glass beads of a size on the order of 100 mesh The tube is coiled in a manner so that the flow is horizontal and gravity effect are insignificant A pump system is provided to force fluids through the porous medium pack, and pressure is controlled by a backpressure regulator. The coiled tube and certain auxiliary equipment are placed inside a constant-temperature bath, usually an air bath. At the effluent end of the tube, fluid collection and measurement systems are provided. A small visual cell also is included at the effluent end so that the fluid product can be observed.

Test procedures MMP the porous medium in tubing is filled with crude oil from a reservoir to be consider for immiscible displacement the system is brought to test temperature the back pressure regulator is set at desire displacement pressure the displacing fluid is injected at constant rate the pressure drop across the system should be set and measured the hydrocarbon recovery at displacing fluid breakthrough, recovery at the time of injection for a specified number of PV and ultimate hydrocarbon recovery are recorded recoveries as a function of displacement pressure are plotted the MMP is assume to be the pressure at the break in the curve MME To measure the minimum gas enrichment necessary to achieve miscibility (MME) at a fixed pressure. Repeated displacements are run with increasingly higher concentrations of an intermediate compound such as C2+ in the displacing solvent.

Rising bubble apparatus Consists of a flat glass tube mounted vertically in a high-pressure sight gauge in a temperature controlled bath. A back light is used on the sight gauge so that behavior can be observed. MMP measurement The tube and the gauge is filled with distilled water The distilled water is displaced with oil except for the bottom part of the tube The temperature is held at desire value Pressure is held at specified test value A small gas bubble is injected into the bottom of the tube The gas bubble rises first through the water column and then through the oil Its behavior is observed as it rises through the region of the sight glass Slightly above the MMP, as the bubble rises, it changes shape and disperses into the oil Far below the MMP, the bubble retains its near spherical shape as it rises but decrease in size as a result of mass transfer. Far above the MMP, the bubble disperses into the oil quite rapidly

MOBILITY CONTROL PROCESS Physical and chemical characteristic of polymers Type of polymer Polyacrylamide Polysaccharide Polyacrylamide Characteristic Produce from the polymerization process of acrylamide monomers Polyacrylamide absorbs strongly on mineral surface Thus, the polymer is partially hydrolyzed to reduce adsorption by reacting polyacrylamide with a base, such as sodium or potassium hydroxide or sodium carbonate. Hydrolysis converts some of the amide groups (NH2) to carboxyl groups (COO-). Polyacrylamides are supplied as a dry polymer or as liquid emulsions with oil- or water external systems.

Xanthan gum is a biopolymer produced commercially by microbial action of the organism Xanthomonas campestris on a carbohydrate feed stock. The polymer acts like a semirigid rod and is quite resistant to mechanical degradation. Average reported molecular weights of xanthan biopolymers used in EOR processes range from 1 million to 15 million

polyvinylpyrrolidone

Was develop for high temp application in harsh environment where polyacrylamide and biopolymers were found not to be applicable.

Polymer stability Oxidative attack

Both polyacrylamides and biopolymers are susceptible to oxidative attack by dissolved oxygen in the injected water. Degradation is detected by the loss of solution viscosity with time The degradation rate increases as temperature increases, The oxidative degradation reaction is catalyzed by dissolved metal ions, such as Fe +++ . Degradation by oxidative attack can be prevented or minimized by reducing the oxygen content of the water or brine to less than a few parts per billion. This usually is done by use of oxygen scavengers or deaeration. A mixture of thiourea, isopropyl alcohol, and sodium bisulfate was found to retard oxidative attack on xanthan biopolymers at temperatures up to 207F.

Temperature
Carbon/carbon backbone of polyacrylamides is stable in the absence of oxygen and divalent ions to temperatures up to 194oF.

Divalent cations
The presence of divalent cations causes stability problems for polyacrylamides at elevated temperatures. As the degree of hydrolysis increases as a result of polyacrylamide reaction with water, the solubility of the polymer decreases in the presence of calcium and magnesium.

Bacterial attack
Polymer degradation also results from bacterial attack. Biopolymers are susceptible to biological attack resulting in the loss of solution viscosity from the destruction of the carbohydrate backbone For this reason, the polymer broth usually contains a bactericide, such as formaldehyde, to control bacterial growth. This effect is consider because bacteria could be transported appreciable distances through porous rock

Flow of polymer through porous media Polymer rentention

Sources of retention: Adsorption on the surface of the porous material and mechanical entrapment in pores that are small relative to the size of the polymer molecule in solution. hydrodynamic retention- Occur when flow rates are suddenly increased after polymer has been injected at a constant rate until a steady state condition has been attained-i.e., until the effluent concentration has reached the injected concentration.

Inacessible PV
Polymer molecules are larger than water molecules and are large relative to some pores in a porous rock. Because of this, polymers do not flow through all the pore space contacted by the brine. The fraction of the pore space not contacted by the polymer solution is called the inaccessible PV.

Flow characteristic permeability reduction

Permeability reduction depends on: The type of polymer The amount of polymer retained The pore-size distribution The average size of the polymer relative to the pores in the rock. Permeability reduction is determined experimentally by first displacing polymer solution through a porous medium and then displacing the polymer with brine and measuring the permeability to brine after all mobile polymer has been displaced.

Residual resistance factor The ratio of the brine mobility before contact with polymer, w to the brine mobility after all mobile polymer has been displaced from the pore space wp.

Frr = residual resistance factor for the porous matrix after Contact with a particular polymer solution, kwp = permeability of the porous matrix to brine after contact with polymer solution kw = initial brine permeability. The permeability to brine after the mobile polymer has been displaced

kwp, is assumed to be the same as the permeability of the porous medium to the flow of polymer, kp

The resistance factor, Fr is the ratio of the brine mobility in the porous medium before polymer contact to the polymer mobility in the same porous medium and is defined by

POLYMER GEL
Applications: To reduce water cut in production well Control profile in injectors

Partially hydrolyzed polyacrylamide In the pure state the polymer is electrically neutral, seeming to prevent any cross linking through ionic bond. By reaction with base these polymer acquire negative charge because some of the amide group is converted to carboxyl group Cross linkers The polymer molecule are bound together into a gel structure through of a crosslinking chemical agent such Cr(III) or Al(III). They can be extracted from chromium acetate or aluminum citrate because they are not exist in the nature. Crosslinking process of polyacrylamide When metal ions such as Cr3+, Fe3+, Al3+, and Zr4+ are added to a partially hydrolyzed polyacrylamide solution, a reaction occurs between the carboxyl group and the metal ion. Polyacrylamide molecules are flexible coils in dilute solutions and are isolated from each other when the polymer concentration is less than C - the critical overlap concentration. If a further reaction occurs between the initial metal ion-carboxyl complex and another carboxyl group on the same polymer chain, intra-molecular crosslinks form. Due to additional metal ion complexes reacting with the polymer chain, the average molecular weight of the metal ion-polymer complex, termed a pregel aggregate, increases slightly. When the polymer concentration exceeds C, intermolecular crosslinks can occur between two or more polymer molecules, and the molecular weight of each complex increases in proportion to the extent of crosslinking. Continued intermolecular crosslinking may lead to the formation of an infinite network of crosslinks between polymer-metal ion complexes, leading to the formation of a gel and the immobilization of the solution.

CHEMICAL FLOODING SURFACTANT

Are chemical substances that adsorb on or concentrate at a surface or fluid/fluid interface when present at low concentrations in a system. Consist of a hydrocarbon portion (nonpolar) and a polar, or ionic, portion The Hydrocarbon portion is often called the "tail" and the ionic portion the "head" of the molecule.

The hydrocarbon portion can be either a straight chain or a branched chain.

 The nonpolar and polar portions are called lipophilic and hydrophilic portion The entire molecule is sometimes called an amphiphile because it contains the nonpolar and polar moieties

Classification and Structure of Surfactants

Surfactants may be classified according to the ionic nature of the head group: Anionic Cationic Nonionic Zwitterionic Anionic: sodium dodecyl sulfate (C12H25 S04Na+). In aqueous solution, the molecule ionizes, and thus the surfactant has a negative charge. This surfactant is classified as anionic because of the negative charge on its head group. Cationic: dodecyltrimethylammonium bromide (C 12H 25 N+Me3Br ). In aqueous solution, ionization occurs and the surfactant head group has a positive charge and is cationic. Nonionic: dodecylhexaoxyethylene glycol monoether (C12H 25[OCH2CH 2]6OH). In this particular molecule, which does not ionize, the head group is larger than the tail group. Zwitterionic: 3-dimethyldodecylamine propane sulfonate, this surfactant has two group of opposite charge.
-

Anionics and nonionics have been used as surfactants in EOR processes Anionic surfactants have been the most widely used because: they have good surfactant properties, are relatively stable, exhibit relatively low adsorption on reservoir rock can be manufactured economically

Nonionics have been used primarily as cosurfactants to improve the behavior of surfactant systems. Nonionics are much more tolerant of high-salinity brine, but their surface-active properties (reduction of IFT) are not generally as good as anionics. Cationics are usually not used because they adsorb strongly on reservoir rocks. Sulfonated hydrocarbons-common surfactant used in polymer flood "Petroleum sulfonates" are sulfonates produced when an intermediatemolecular- weight refinery stream is sulfonated, "synthetic sulfonates" are the product when a relatively pure organic compound is sulfonated. Widely used because: are effective at attaining low IFT relatively inexpensive reported to be chemically stable Problem: Crude oil and petroleum sulfonates have been used for low salinity applications

The characteristics and structure of petroleum sulfonates suitable for EOR applications depend on: The chemical composition of the feedstock, Degree of sulfonation, The average number of sulfonate groups attached to each molecule

Micelles and Microemulsions

When the surfactant is added to solvent at very low concentration , the dissolve surfactant molecule dispersed as monomers As the concentration of the surfactant increases, the molecules tend to aggregate. Above a specific concentration called critical micelles concentration (CMC) further addition of surfactant result in the formation of micelles. The concentration of surfactant as monomers essentially remains constant above the CMC. That is the surfactant added at concentration above CMC result in formation of additional micelles but relatively little change in monomer concentration.

If the solvent is water, the micelles form with the tail portion directed inward and the head (polar) portion outward. Water would be the continuous phase For a hydrocarbon solvent, the orientation of the surfactant molecules is reversed and the hydrocarbon would be the continuous phase.

Micelles characteristic The cores of spherically shaped micelles formed in aqueous solution are capable of solubilizing organics. Under the right conditions, significant amounts of oil can be solubilized into the micelles. Conversely, in hydrocarbon solvents containing micelles, water can be solubilized into the interior of the micelle. Micelles that have solubilized a phase that is immiscible with the solvent often are called swollen micelles or the solutions are called microemulsions.

Phase Behavior of Microemulsions

A microemulsion usually is composed of at least five components: a surfactant, cosurfactant, hydrocarbon, water, and NaCl. Cosurfactant and NaCI are not essential. When brine is a pseudocomponent, the microemulsion system has four components and phase behavior can be represented on a quaternary diagram But another pseudocomponent is needed to reduce the region of investigation to a pseudoternary diagram. In most cases, the surfactant and cosurfactant are treated as a pseudocomponent and subsequently called the "surfactant

Effect of Brine Salinity on Phase Behavior

Type II(-) environment(healy)/Type I microemulsions(Windsor) At relatively low brine salinity, solutions at concentrations within the multiphase region divide into a water-external microemulsion and an excess-oil phase. The microemulsion is saturated with oil at that composition and temperature. Because the microemulsion is the aqueous phase and is more dense than the oil phase, it resides below the oil phase and is call a lower phase microemulsion. Type II(+) environment/Type II microemulsions. At high salinity, the system separates into an oil-external microemulsion (hydrocarbon or oleic phase) and an excess, more dense, water (brine) phase. In this case, the microemulsion is an upper-phase microemulsion. Type Ill phase environment/Type Ill microemulsion. At intermediate salinity, the system is more complex. At lower surfactant concentrations, a three-phase region exists. Solutions with overall concentrations within this region separate into microemulsion, water, and oil phases Because the density of the microemulsion is intermediate to the oil and brine densities, it is called a middle-phase (or midphase) microemulsion and is designated by M*

Alkaline flooding
In alkaline flooding, a high-pH chemical system is injected. If the reservoir crude oil has sufficient' 'saponifiable components," a reaction will occur in which surfactants are formed in situ. In most of the literature, these saponifiable components are described as petroleum acids, even though their structure is not known.

Alkaline agent Sodium hydroxide Ammonium hydroxide Sodium orthosilicate Sodium carbonate Ammonium carbonate

In situ formation of surfactant

Addition of the alkali chemicals results in a high pH because of the dissociation in the aqueous phase

The hydroxide ion must react with a petroleum acid from the crude oil to form a surfactant

Some of the petroleum acid in the crude oil partitions into the aqueous phase

The petroleum acid dissociates in aqueous phase The species A- is an anionic surface-active agent. In effect, caustic uses up the hydrogen ion by the reaction

This result in an increase in [A-]

Chemical formulation and IFT

Several investigators have measured the effect of alkaline chemical type and concentration on IFT between aqueous and oil phases. IFT is plotted as a function of alkali concentration. The minimum IFT value occurs in the concentration range of 0.05 to 0.10 wt%, and the minimum value is about 0.01 dyne/cm. There is little difference between the two alkaline chemicals tested. Other work has also shown that sodium carbonate, sodium hydroxide, and sodium orthosilicate are equally effective at reducing IFT.

FOAM AS AN EOR AGENT

Most foams that have any significant persistence contain: Gas Liquid foaming agent. The foaming agent may comprise one or more of the following: surfactants macromolecules finely divided solids.

Foam structure

LAMELLA: region that encompasses the thin film, the two interfaces on either side of the thin film, and part of the junction to other lamellae PLATEAU BORDER: The connection of three lamellae, at an angle of 120

Application of foam in the petroleum industry

Application of foam in EOR: Blocking or restricting flow of undesired fluids, such as the coning of gas or water in a production well. Blocking or restricting flow of injected fluids in high permeability streaks or fractures (profile modification). Improving the mobility ratio in displacement processes by reducing the mobility of the injected phase.

Foam stability
The stability of a foam is determined by a number of factors involving both bulk solution and interfacial properties: gravity drainage capillary suction surface elasticity viscosity (bulk and surface) electric double-layer repulsion dispersion force attraction steric repulsion Gravity drainage This liquid will drain by flowing downward through the interior of the lamellae. Capillary suction At the Plateau borders the gas-liquid interface is quite curved, and this curve generates a low pressure region in the Plateau area (as shown by the YoungLaplace Equation). Because the interface is flat along the thin-film region, a higher pressure resides here. This pressure difference forces liquid to flow toward the Plateau borders and causes thinning of the films and motion in the foam.

Surface elasticity If a surfactant-stabilized film undergoes a sudden expansion, a local rise in surface tension produces immediate contraction of the surface. The surface is coupled by viscous forces to the underlying liquid layers. Thus, the contraction of the surface induces liquid flow, in the thin-film, from the low-tension region to the hightension region. The transport of bulk liquid due to surface tension gradients provides the resisting force to film thinning. Viscosity The bulk viscosity will most influence the thinning of thick films, and the surface viscosity will be dominant during the thinning of thin films. Stability would vary according to the effect of temperature on the viscosity The addition of a small amount of nonionic surfactant to a solution of anionic surfactant can enhance foam stability because of the formation of a viscous surface layer, which is possibly a liquid-crystalline surface phase in equilibrium with a bulk isotropic solution phase

Electric double-layer repulsion Because the interfaces on each side of the thin-film are equivalent, any interfacial charge will be equally carried on each side of the film. If a foam film is stabilized by ionic surfactants, then their presence at the interfaces will induce a repulsive force that opposes the thinning process. The magnitude of the force will depend on the charge density and the film thickness. Having a charged interface influences the distribution of nearby ions in a polar medium. Ions of opposite charge (counterions) are attracted to the surface, while those of like charge (coions) are repelled. An electric double layer, which is diffuse because of mixing caused by thermal motion, is thus formed.

Dispersion force attraction Neutral molecules exert forces of attraction on each other that are caused by electrical interactions between three types of dipolar configurations. The attraction results from the orientation of dipoles that may be (1) Two permanent dipoles, (2) Dipole-induced dipole (3) Induced dipole-induced dipole (also called London dispersion forces). Disjoining pressure When the two interfaces that bind a foam lamella are electrically charged, the interacting diffuse double layers exert a hydrostatic pressure that acts to keep the interfaces apart. The disjoining pressure represents the net pressure difference between the gas phase (bubbles) and the bulk liquid from which the lamellae extend , and is the total of electrical, dispersion, and steric forces (per unit area) that operate across the lamellae

Foam generation
Foam Formation. Three fundamental pore-level generation mechanisms exist: snap-off, division, and leave-behind. Snap off

The snap off mechanism occur at low capillary pressure when a film or a collar of water accumulate in the throat. The collar swells and bridge the throat blocking gas flow and leading to creation of new lamella

Lamella Division

A translating foam bubble encounters a point where flow branches in two directions (Figure 6a). The interface stretches around the branch point and enters both flow paths. The initial bubble divides into two separate bubbles (Figure 6b) that continue to move downstream.

Effect of oil on foam stability

Film invasion

The oil drop first enters one of the film surfaces and forms a lens. On further thinning of the film the lens enters the opposite film surface and an oil bridge is formed. The bridge is unstable because the capillary forces dewet the film from the bridge and the film ruptures. The arrows in the film indicate the direction of capillary forces. Oil emulsion When the pseudoemulsion film is stable, the oil drop enhance the foam stability; when the film is unstable, the oil act as antifoam

Leave behind

Two gas menisci invade adjacent liquid-filled pore-bodies (Figure 7a). A lens is left behind as the two menisci converge downstream. As long as the capillary pressure of the medium is not too high, and the pressure gradient is not too large, a stationary stable lens emerges (Figure 7b).

MICROBIAL ENHANCE OIL RECOVERY

Refer to: the use of microorganism to retrieve additional oil from existing wells, thereby enhancing the petroleum production of an oil reservoir. Six different type of the microorganisms: Bacteria Fungi Archaea Protists Plankton Planarian

Aerobic microbe: is a microorganism that can survive and grow in an oxygenated environment Aneroabic microbe: is any microorganism that does not require oxygen for growth Nutrient: is a chemical that a microorganism needs to live and grow which must be taken in from its environment such as nitrates, molasses, phosphate Metabolites: are the product of a set of chemical reaction that happen in living microorganism to maintain live. Advantage of using microbe self replicating and relative inexpensive to produce the nutrient are economically priced may produce many chemical (gases, surfactant, acid, solvent, plomers and biomass) microbes do not consume large amount of energy MEOR product are all biodegradable and will not be accumulated in the environment , thus MEOR is environmentally friendly The use of microbes is not dependent on the price of crude oil

Microbial product and their action

Product Biomass microorganism Bacillus licheniformis leuconostoc mesenteroides Xanthomonas campestris Application in oil recovery Selective biomass pluging Viscosity reduction Wet ability alteration Oil degradation Emulsification Decreasing IFT Viscosity reduction Injected profile modification Mobility control

Bio surfactant (emulsion sophorolipids, peptidolipid, rhamnolipid)

Biopolymers (alginate, xanthan, dextran, pullulan)

Solvent (n-butanol, acetone, ethanol)

Acid (acetate,butyrate) Gases (CO2, CH4, H2

Arthrobacter paraffineus Bacillus licheniformis Clostridium pasteurianum Corynebacterium fascines Pseudomonas rebescens Bacillus polymyxa Brevibacterium viscogenes Leuconostoc Mesenteroides Xanthamonas campestris Clostridium acetobutylicum Clostridium pasteurianum Zymomonas mobilis Clostridium spp. Enterobacter aerogenes Clostridium acetobutylicum

Oil dissolution Viscosity reduction

Increase permeability emulsification Increased pressure, oil swelling, decrease of IFT

Oil recovery mechanisms by microorganisms Reduction of oil viscosity Microorganism help breakdown the molecular structure of crude oil making it more fluid and easier to recover from the well Production of carbon dioxide gas The gases are form in-situ due to fermentation of carbon sources such as glucose by usually anaerobic bacteria. This gases dissolve the crude oil and than reduce its viscosity. The gases also increase the pressure of the reservoir. Production of biomass When microorganism metabolize the nutrient they need for survival, they produce organic biomass as a by product. This biomass accumulate between the oil and the rock surface of the well, physically displacing the oil and making it easier to recover from the well. Selective plugging Some microorganism secrete slimy substances called exopolysaccharides to protect themselves from dying out or falling prey to other organism. This substances help bacteria plug the pore found in the rock of the well so that oil may move past the rock substances more easily. Blocking rock pores to facilitate the movement of oil is known as selective plugging. Production of biosurfactant Microorganism produce slippery substances called surfactant as they breakdown oil. Because they are naturally produce by biological microorganism they are referred to a biosurfactant. Biosurfactant act like slippery detergents helping the oil to move more freely away from rock and crevices so that it may travel more easily out of the well.

Production of biopolymer Bacteria reduce the permeability of highly permeable zone or of the water channel that form in heterogeneous reservoir. Thus the unswept formations are invaded by the water and sweep efficiency increase Production of organic acid Production of acid dissolve the rock matrix or carbonates thus increasing the pore size and permeability.

MEOR process wellbore clean up well stimulation enhanced water floods Classification of MEOR Surface MEOR : biosurfactant (rhamnolipid) biopolymer(xantan gum) enzyme Underground MEOR: microorganism nutrients other additive Underground MEOR cyclic microbial recovery (huff and puff) wax removal and paraffin inhibition selective plugging recovery acidizing/fracturing microbial flooding recovery

Microbial flooding process 1. the reservoir is usually conditioned by a water preflush 2. a solution of microorganism and nutrient is injected 3. this solution is pushes through the reservoir by drive water, it form gases and surfactant that help to mobilized the oil 4. the resulting oil and product solution is then pumped out through production wells Limitation of MEOR Parameter Lithology Porosity and permeability Temperature Salinity pH API gravity requirement 10-30% , above 75md Less than 75C Less than 10% W/V Between 4 and 9 Greater than 18

1. Under proper condition of pH and ionic strength, clay and rock posses charge on their surface that act to absorb bacteria and inhibit their migration through the porous media 2. Bacteria have length of 0.5-10m and width of 0.5-2 m. pore size of less than 0.5 m will place severe restriction to the movement of them. Permeability of 75-100md are thought to be lower limit for effective microbial transport 3. Geothermal gradient are commonly 1-2F/100ft. it is found that greater than 90% of the reservoir in all state have temperature of less than 185-210F (8599C using 1000ft as the limiting depth 4. Increasing salinity absorb water from the microbes and negatively effect its growth 5. Microorganism grow optimally between a pH of 4 and 9 6. Crude oils with API gravity of less than 18 are generally consider as heavy. Because the heavier the crude the more difficult it is to recover using chemical means due to unfavorable mobility ratios between brine and oil

Displacement fundamental
Surface tension and IFT Surface tension: The force acting in the plane of the surface per unit length of the surface. Consider the two immiscible, fluids, air (or gas) and water (or oil), as shown schematically in Figure 2-2. A liquid molecule, which is remote from the interface, is surrounded by other liquid molecules, thus having a resulting net attractive force on the molecule of zero. A molecule at the interface, however, has a force acting on it from the air (gas) molecules lying immediately above the interface and from liquid molecules lying below the interface. Resulting forces are unbalanced and give rise to surface tension.

Assuming the radius of the capillary tube is r, the total upward force Fup, which holds the liquid up, is equal to the force per unit length of surface times the total length of surface,

The upward force is counteracted by the weight of the water, which is equivalent to a downward force of mass times acceleration

Rearrange since Fup = Fdown

Capillary pressure

Viscous forces The pressure drop for laminar flow through a single tube

Viscous forces in a porous medium can be expressed in terms of Darcy's law,

For a bundle of equal size capillaries, the permeability is given by

Phase trapping

The trapping mechanism, however, is known to depend on the pore structure of the porous medium fluid/rock interactions related to wettability fluid/fluid interactions reflected in IFT and sometimes in flow instabilities

The system is static, with different pressures existing at Points A and B because of capillary forces. The static pressure difference must be exceeded for flow to occur. For condition in figure 2.13b.

Pressure in the oil phase would exceed the pressure in the water phase by the value of Pc, but there would be no net pressure change across the drop.

If rb < ra, then PA >PB and a pressure drop exists in the direction from Point A to B.

If a > b and cos a < cos b pressure drop exists in the direction from Point A to B.

IFT and contact angles are different at the two interfaces because the fluid systems are different. Again, if go cos b > gw cos a a pressure drop exists from Point A to B when this system is static.

Capillary number Viscous to capillary forces in flow through a capillary.

The dimensionless group, or variations of the group, are called the capillary number. In this text, the capillary number is defined as in Eq. 2.30, but without the cos term. Therefore

If Darcy's law is introduced into Eq: 2.31 and Darcy velocity is used,

Nca could be increased to more than about 10-5 in a flood, then the magnitude of residual oil would decrease. The correlation shows that Nca can be increased by either (1) Increasing the flow rate of the displacing fluid, (2) Increasing the viscosity of the displacing fluid, or (3) Reducing IFT between the displaced and displacing fluids.

Various chemical EOR processes

Micellar/surfactant polymer flooding Alkaline flooding Alkali-surfactant flooding Alkali-surfactant-polymer flooding Polymer flooding

Alkali-surfactant-polymer flooding
In the Alkaline Surfactant Polymer (ASP) process, a very low concentration of the surfactant is used to achieve ultra low interfacial tension between the trapped oil and the injection fluid/formation water. The alkali then reacts with the acidic components in the crude oil to form additional surfactant in-situ, thus, continuously providing ultra low interfacial tension and freeing the trapped oil In the ASP Process, polymer is used to increase the viscosity of the injection fluid, to minimize channeling, and provide mobility control.

Polymer flooding
Polymer flooding where the injection-water is made more viscous in order to push the crude from the injection- to the producing well. This type of EOR is mostly used with crude that have a higher viscosity