Compositions and methods for enhanced oil recovery from low permeability formations

Abstract

The present invention provides compositions and methods for enhancing oil recovery from low permeability subterranean formation using three mechanisms: repressurization; reduction of interfacial tension; and increased permeability. The subject compositions comprise a chelating agent, a biosurfactant, a carbonate or bicarbonate salt, water, and a pH adjusting substance, which when applied to an oil-bearing formation according to the methods of the subject invention, allow for controlled release of carbon dioxide within the formation without complicated machinery or gas-producing microorganisms.

Claims

1. A method for enhancing oil recovery from an oil-bearing subterranean formation, the method comprising obtaining a composition comprising EDTA (ethylenediaminetetraacetic acid), a sophorolipid biosurfactant, sodium bicarbonate, and water, adding an amount of sodium hydroxide to the composition sufficient to adjust the pH of the composition to at least about 9.5; injecting the composition into the formation, injecting an acid solution into the formation, wherein the acid solution is added at a quantity such that the pH of the composition is reduced to 7.0 or below and causes the controlled release of carbon dioxide gas inside the formation, injecting a plugging composition comprising 1.0-1.5% sodium alginate dissolved in water into the formation, and wherein the formation pressure is increased.

2. The method of claim 1, wherein the acid solution is injected prior to injection of the composition.

3. The method of claim 1, wherein the acid solution is injected after injection of the composition.

4. The method of claim 1, further comprising injecting water or brine to push the composition and acid solution deep into the formation.

5. The method of claim 1, wherein the acid solution is water or brine having a pH of 3.0 or below.

6. The method of claim 1, wherein the plugging composition further comprises one or more biopolymers selected from xanthan gum and guar gum.

7. The method of claim 1, further comprising shutting the formation for 3 to 30 days.

8. The method of claim 1, wherein once carbon dioxide release has stopped inside the formation, pumping of oil begins after about 1 to 2 days.

9. The method of claim 1, wherein the formation has a permeability of 10 mD or lower.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) FIGS. 1A-1B show the appearance of the subject EOR composition before (1A) and after (1B) adding 200 ml of 30% citric acid.

(2) FIGS. 2A-2B show the difference between aged sands treated with a standard MEOR treatment (1A) versus sands treated with an EOR composition of the subject invention (1B). The sands treated with the EOR composition (1B) produced more carbon dioxide gas, as can be seen with the pockets of air that formed in the sand

(3) FIGS. 3A-3B show a comparative study of carbon dioxide release from three different treatments of the H-sand in test tubes, shown side-by-side in 3A. The first treatment was a water control, the second treatment was a yeast MEOR product, and the third treatment (magnified in 3B) was an EOR composition of the subject invention. After the addition of citric acid to the tubes, carbon dioxide bubbles immediately released from the sands in the third test tube and continued releasing past 4.5 hours.

(4) FIGS. 4A-4B show oil recovery from aged sands pre-treated with an acid solution and plugged with an alginate solution having holes therein (4A), as well as the oil recovered from the sands after treatment with an EOR composition according to the subject invention (4B).

DETAILED DESCRIPTION OF THE INVENTION

(5) The subject invention provides environmentally-friendly compositions and methods for enhancing oil recovery using three mechanisms: repressurization of an oil formation; reduction of interfacial tension in the formation; and increase of formation permeability through dissolution of scale and solubilization of carbonate rock in the formation. Advantageously, the subject invention can be used to increase the recoverable reserves in a subterranean formation.

(6) In certain embodiments, the subject invention provides a composition for enhanced oil recovery (EOR). Preferably, the EOR composition comprises a chelating agent, a biosurfactant, a carbonate salt, and water. In one embodiment, the EOR composition further comprises a pH adjuster.

(7) In a specific embodiment, the EOR composition comprises EDTA as the chelating agent, a glycolipid, such as a sophorolipid (SLP), as the biosurfactant, sodium bicarbonate (baking soda) as the carbonate salt, and water. Preferably, the SLP is an acidic form SLP. In one embodiment, the pH adjuster is sodium hydroxide (NaOH).

(8) Further provided is a specific process for producing the subject composition for optimal efficacy in enhancing oil recovery, as well as compositions produced according to this process. In general, the process comprises mixing a solution of a chelating agent, a biosurfactant, a carbonate salt, and water, under basic conditions. Advantageously, it has been found that up to 10% sodium bicarbonate can be dissolved in basic solution without releasing carbon dioxide. More specifically, the process can comprise adding a chelating agent, such as EDTA, to water to form a solution; adding a biosurfactant, preferably an acidic sophorolipid (SLP) composition to the solution; adding a carbonate salt, such as sodium bicarbonate, to the solution; and mixing the solution.

(9) In preferred embodiments, the solution is prepared under basic conditions, meaning a pH adjusting composition is added to the solution. Preferably, the pH adjusting substance is added prior to addition of the carbonate salt in an amount that allows for complete dissolution of the chelating agent in the water. This typically requires a pH of 9, 10, 11, 12 or greater. The pH adjusting substance can be, for example, sodium hydroxide.

(10) In preferred embodiments, the biosurfactant is produced by dissolving a biosurfactant, e.g., SLP, in water and adding a pH adjuster, e.g., sodium hydroxide, to bring the pH to 8 and convert the SLP to an acidic form.

(11) The subject invention further provides methods for enhancing oil recovery from an oil-bearing subterranean formation utilizing the subject compositions. In one embodiment, the methods comprise first preparing a composition of the subject invention according to the process described herein; preparing an acid solution; and preparing a plugging composition.

(12) In one embodiment, the acid solution is 30% citric acid. In another embodiment, the plugging composition comprises 1.0-1.5% sodium alginate dissolved in water. The plugging composition can also comprise a biopolymer, such as xanthan gum or guar gum.

(13) Next, the methods comprise steps that can be generally characterized as 1) gas release; and 2) plugging. More specifically, gas release can comprise injecting an EOR composition of the subject invention into the formation. This can either be immediately preceded by or followed by injection of the acid solution in an amount sufficient to reduce the pH of the EOR composition to 7.0 or below, preferably 6.0 or below, which will activate the release of carbon dioxide gas.

(14) Next, the method comprises injecting water and/or brine to push the composition and acid solution deep into the formation. In one embodiment, the need for the acid solution is obviated by, for example, the injection of brine that has an acidic pH (e.g., pH of 3.0, 2.5, 2.0 or lower) sufficient to reduce the pH to 7.0 or lower, preferably, 6.0 or lower.

(15) Finally, the method comprises injecting the plugging composition into the formation to help with gas and pressure buildup, as well as improve flow of oil from the formation. The plugging composition is preferably in liquid form upon injection, but solidifies when it comes into contact with salts present in the brine and formation. The plugging composition will selectively plug larger pores and channels with some non-selective plugging of smaller pores.

Selected Definitions

(16) As used herein, the term “biocorrosive bacteria” or “biocorrosive microorganism” means, any taxonomic grouping of bacteria (or microorganism) known to contribute to microbial induced corrosion (“MIC”) of metallic and/or non-metallic materials. Non-limiting examples include chemoautotrophs, sulfate-reducing bacteria, iron oxidizing bacteria, sulfur oxidizing bacteria, nitrate reducing bacteria, methanogens, and acid producing bacteria. These bacteria are capable of reducing metal directly, producing metabolic products that are corrosive (e.g., hydrogen sulfide gas), and/or leading to the formation of biofilms that can alter the local environment to promote corrosion.

(17) As used herein, a “biofilm” is a complex aggregate of microorganisms, such as bacteria, wherein the cells adhere to each other and/or to a surface by secreting an extracellular polysaccharide matrix. The cells in biofilms are physiologically distinct from planktonic cells of the same organism, which are single cells that can float or swim in liquid medium.

(18) As used herein, the term “enhanced oil recovery, or “EOR,” refers to post-primary recovery of oil from an oil-bearing subterranean formation. Various methods can be utilized in EOR, including, for example, microorganisms, gas and/or water injection and plugging, to increase the movement of oil and/or gas from a formation. EOR can also include well stimulation. As used herein, “harvested” refers to removing some or all of the microbe-based composition from a growth vessel.

(19) As used herein, reference to a “microbe-based composition” means a composition that comprises components that were produced as the result of the growth of microorganisms or other cell cultures. Thus, the microbe-based composition may comprise the microbes themselves and/or by-products of microbial growth. The by-products of growth may be, for example, metabolites, including surfactants and expressed proteins, cell membrane components, and/or other cellular components. The microbes may be intact or lysed. The cells may be present at, for example, a concentration of at least 1×10.sup.4, 1×10.sup.5, 1×10.sup.6, 1×10.sup.7, 1×10.sup.8, 1×10.sup.9, 1×10.sup.10, or 1×10.sup.11 or more CFU per milliliter of the composition. Furthermore, the cells may be separated, i.e., removed, from the broth in which they were cultivated such that the composition comprises cell-free broth with cellular growth by-products.

(20) The subject invention further provides “microbe-based products,” which are products that are to be applied in practice to achieve a desired result. The microbe-based product can be simply the microbe-based composition harvested from the microbe cultivation process. Alternatively, the microbe-based product may comprise further ingredients that have been added. These additional ingredients can include, for example, stabilizers, buffers, appropriate carriers, such as water, salt solutions, or any other appropriate carrier, added nutrients to support further microbial growth, non-nutrient growth enhancers, such as plant hormones, and/or agents that facilitate tracking of the microbes and/or the composition in the environment to which it is applied. The microbe-based product may also comprise mixtures of microbe-based compositions. The microbe-based product may also comprise one or more components of a microbe-based composition that have been processed in some way such as, but not limited to, filtering, centrifugation, lysing, drying, purification and the like.

(21) As used herein, “permeability” of a porous rock formation is the measure of the ability of fluid to pass through the rock. Permeability is measured in darcies (D), wherein 1 D is the permeability of a porous medium with a cross-sectional area of 1 cm.sup.2 and a length of 1 cm, through which the passage of 1 cm.sup.3 of fluid with viscosity of 1 cp, flows in 1 second under a pressure differential of 1 atm. Permeability depends upon the porosity of a formation (the higher the porosity the higher the permeability) and the connectivity of the pore spaces. The size and shape of grains, the grain size distribution, and other factors such as the wetting properties of the rock and the presence of pore-blocking deposits can also influence permeability. Permeability can vary from 1 nanodarcy (nD) to 1 microdarcy (mD) for granites, shales and clays, to several D for extremely permeable reservoir rocks. Reservoir permeability can be classified as low or fair (<10 mD), high (10-100 mD), very high (100-1,000 mD), and exceptional (>1,000 mD), where rock with permeability of 1 mD or less is not considered reservoir rock unless subjected to manipulation (e.g., through fracking).

(22) As used herein, a “stripper well” or “marginal well” refers to a mature oil well that is depleted, or nearing the end of its economically useful life. Marginal oil wells are generally characterized in that their daily production of crude oil has dropped to between 10 and 15 barrels per day, or less, for any twelve-month period. These wells often go abandoned prematurely, leaving behind hundreds or even thousands of barrels of valuable and useful crude oil.

(23) As used herein, “surfactant” refers to a compound that lowers the surface tension (or interfacial tension) between two liquids or between a liquid and a solid. Surfactants can act as, for example, detergents, wetting agents, emulsifiers, foaming agents, and/or dispersants. A surfactant produced by microorganisms is referred to as a “biosurfactant.”

(24) The transitional term “comprising,” which is synonymous with “including,” or “containing,” is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. By contrast, the transitional phrase “consisting of” excludes any element, step, or ingredient not specified in the claim. The transitional phrase “consisting essentially of” limits the scope of a claim to the specified materials or steps “and those that do not materially affect the basic and novel characteristic(s)” of the claimed invention.

(25) Unless specifically stated or obvious from context, as used herein, the term “or” is understood to be inclusive. Unless specifically stated or obvious from context, as used herein, the terms “a,” “and” and “the” are understood to be singular or plural.

(26) Unless specifically stated or obvious from context, as used herein, the term “about” is understood as within a range of normal tolerance in the art, for example within 2 standard deviations of the mean. About can be understood as within 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, or 0.01% of the stated value.

(27) The recitation of a listing of chemical groups in any definition of a variable herein includes definitions of that variable as any single group or combination of listed groups. The recitation of an embodiment for a variable or aspect herein includes that embodiment as any single embodiment or in combination with any other embodiments or portions thereof.

(28) Any compositions or methods provided herein can be combined with one or more of any of the other compositions and methods provided herein.

(29) Other features and advantages of the invention will be apparent from the following description of the preferred embodiments thereof, and from the claims. All references cited herein are hereby incorporated by reference.

(30) Compositions of the Subject Invention

(31) The subject invention provides environmentally-friendly compositions and methods for enhancing oil recovery using three mechanisms: repressurization of an oil formation; reduction of interfacial tension in the formation; and increase of formation permeability through dissolution of scale and solubilization of carbonate rock in the formation. Advantageously, the subject invention can be used to increase the recoverable reserves in a subterranean formation.

(32) In certain embodiments, the subject invention provides a composition for enhanced oil recovery (EOR). Preferably, the EOR composition comprises a chelating agent, a biosurfactant, a carbonate salt, and water. In one embodiment, the EOR composition further comprises a pH adjuster.

(33) In a specific embodiment, the EOR composition comprises EDTA as the chelating agent, a glycolipid, such as a sophorolipid (SLP), as the biosurfactant, sodium bicarbonate (baking soda) as the carbonate salt, and water. Preferably, the SLP is an acidic form SLP. In one embodiment, the pH adjuster is sodium hydroxide (NaOH).

(34) Advantageously, when injected into a subterranean, oil-bearing formation, the composition allows for enhanced oil recovery through three mechanisms. These include delayed production of pressurizing gas, e.g., carbon dioxide, with pH-controlled reaction of a carbonate salt; reduction of interfacial tension with inclusion of a biosurfactant, e.g., SLP; and increased permeability of the formation with inclusion of a scale-dissolving and carbonate rock-solubilizing chelating agent, e.g., EDTA.

(35) In preferred embodiments, the EOR composition comprises a chelator or chelating agent. As used herein, “chelator” or “chelating agent” means an active agent capable of removing a metal ion from a system by forming a complex so that, for example, the metal ion cannot readily participate in or catalyze oxygen radical formation.

(36) Examples of chelating agents suitable for the present invention include, but are not limited to, dimercaptosuccinic acid (DMSA), 2,3-dimercaptopropanesulfonic acid (DMPS), alpha lipoic acid (ALA), thiamine tetrahydrofurfuryl disulfide (TTFD), penicillamine and ethylenediaminetetraacetic acid (EDTA).

(37) Advantageously, the chelating agent enhances the efficacy of the EOR composition by dissolving mineral scale build-up that can clog pores and oil well equipment, as well as solubilizing carbonate rock to increase the permeability of a formation.

(38) The concentration of chelating agent in the composition can be about 5 g/L to 50 g/L or more, about 10 g/L to about 30 g/L, or about 15 g/L to about 25 g/L. In specific embodiments, the chelating agent is EDTA at a concentration of about 20 g/L.

(39) The subject EOR composition can further comprise a substance for reducing the interfacial tension within a subterranean formation, thereby promoting formation wettability and flow of oil. Preferably, the substance is one or more biosurfactants.

(40) Biosurfactants are a structurally diverse group of surface-active substances produced by microorganisms. Biosurfactants are amphiphiles. They consist of two parts: a polar (hydrophilic) moiety and non-polar (hydrophobic) group. Due to their amphiphilic structure, biosurfactants increase the surface area of hydrophobic water-insoluble substances, increase the water bioavailability of such substances, and change the properties of bacterial cell surfaces.

(41) Biosurfactants accumulate at interfaces, thus reducing interfacial tension and leading to the formation of aggregated micellular structures in solution. This, combined with the characteristics of low toxicity and biodegradability, means that biosurfactants are advantageous for use in the oil and gas industry.

(42) Biosurfactants include low molecular weight glycolipids, lipopeptides, flavolipids, phospholipids, and high molecular weight polymers such as lipoproteins, lipopolysaccharide-protein complexes, and polysaccharide-protein-fatty acid complexes. The hydrocarbon chain of a fatty acid acts as the common lipophilic moiety of a biosurfactant molecule, whereas the hydrophilic part is formed by ester or alcohol groups of neutral lipids, by a carboxylate group of fatty acids or amino acids (or peptides), an organic acid in the case of flavolipids, or, in the case of glycolipids, by a carbohydrate.

(43) Microbial biosurfactants are produced by a variety of microorganisms such as bacteria, fungi, and yeasts. Exemplary biosurfactant-producing microorganisms include those listed below, including, and/or in addition to, Pseudomonas species (P. aeruginosa, P. putida, P. florescens, P. fragi, P. syringae); Flavobacterium spp.; Starmerella spp., Bacillus spp. (B. subtilis, B. pumillus, B. cereus, B. licheniformis); Psueudozyma spp.; Pichia spp.; Wickerhamomyces spp.; Candida spp. (C. albicans, C. rugosa, C. tropicalis, C. lipolytica, C. torulopsis); Rhodococcus spp.; Arthrobacter spp.; Campylobacter spp.; Cornybacterium spp. and so on. The biosurfactants may be obtained by fermentation processes known in the art.

(44) In one embodiment, the biosurfactants utilized according to the subject invention are obtained through cultivation processes ranging from small to large scales. These cultivation processes include, but are not limited to, submerged cultivation/fermentation, solid state fermentation (SSF), and hybrids, modifications and/or combinations thereof.

(45) In some embodiments, the biosurfactants of the subject composition are in a purified form. In some embodiments, the biosurfactants are utilized in crude form. Crude form biosurfactants can take the form of a liquid mixture comprising biosurfactant sediment in fermentation broth resulting from cultivation of a biosurfactant-producing microbe. This crude form biosurfactant solution can comprise from about 0.001% to about 99%, about 1% to about 90%, about 5% to about 80%, about 25% to about 75%, about 30% to about 70%, from about 35% to about 65%, from about 40% to about 60%, from about 45% to about 55%, or about 50% pure biosurfactant.

(46) Preferably, cultivation is performed in a system that is distributed to a location that is at or near the site of application. For example, a local production facility can be installed at, or within 100 miles of, the oil well where the subject invention will be applied.

(47) In certain embodiments, the one or more biosurfactants of the EOR composition can include glycolipids such as, for example, sophorolipids (SLP), rhamnolipids (RLP), mannosylerythritol lipids (MEL), trehalose lipids (TL), cellobiose lipids, or a combination thereof. The biosurfactants can also include lipopeptides, such as, for example, surfactin, lichenysin, fengycin, arthrofactin and iturin.

(48) In certain embodiments, the biosurfactant is a glycolipid, preferably a SLP. Sophorolipids consist of a hydrophobic fatty acid tail of 16 or 18 carbon atoms and a hydrophilic carbohydrate head comprising sophorose. One terminal or sub terminal hydroxylated fatty acid is f3-glycosidically linked to the sophorose molecule. The carboxylic end of this fatty acid is either free (acidic or open form) or internally esterified at the 4″, or in some rare cases, at the 6′- or 6″-position (lactonic form). The properties of the SLP can be significantly influenced by the form of the SLP (i.e., acidic or lactonic).

(49) The concentration of biosurfactant(s) in the composition can be about 1 g/L to 30 g/L or more, about 5 g/L to about 20 g/L, or about 10 g/L to about 15 g/L. In specific embodiments, the biosurfactant is SLP at a concentration of about 10 g/L.

(50) Preferably, the SLP is in an acidic form. Acidic SLP can be produced by dissolving the SLP in water and adding a pH adjuster, e.g., sodium hydroxide, to bring the pH to 8.

(51) In some embodiments, the composition further comprises a carbonate salt. Carbonates are made from reaction between carbonic acid (aqueous carbon dioxide) and a base (or alkali). Carbonate salts, which herein include bicarbonate salts, are generally considered weak bases. Examples of carbonate salts useful according to the present invention include but are not limited to ammonium bicarbonate, barium carbonate, cesium bicarbonate, calcium bicarbonate, magnesium bicarbonate, magnesite, potassium bicarbonate, sodium percarbonates, sodium carbonate, sodium bicarbonate.

(52) In preferred embodiments, the carbonate salt is sodium bicarbonate. Preferably, the concentration of sodium bicarbonate is about 20 g/L to 200 g/L, about 50 g/L to 150 g/L, or about 75 g/L to about 125 g/L. In a specific embodiment, the sodium bicarbonate concentration is 100 g/L.

(53) In one embodiment, the FOR composition further comprises a pH adjuster. Suitable pH adjusting substances can include, for example, potassium hydroxide, ammonium hydroxide, potassium carbonate or bicarbonate, sodium hydroxide, or mixtures thereof. In preferred embodiments, the pH adjuster is sodium hydroxide. The amount of sodium hydroxide in the composition depends upon the quantity needed to dissolve the chelating agent completely.

(54) The subject invention further provides a specific process for producing the subject EOR composition for optimal efficacy in enhancing oil recovery, as well as compositions produced according to this process. In general, the process comprises mixing a solution of a chelating agent, a biosurfactant, a carbonate salt, and water, under basic conditions. Advantageously, it has been found that up to 10% of sodium bicarbonate can be dissolved in basic solution without releasing carbon dioxide.

(55) More specifically, the process can comprise adding a chelating agent, such as EDTA, to water to form a solution; adding a biosurfactant, preferably an acidic sophorolipid (SLP) composition to the solution; adding a carbonate salt, such as sodium bicarbonate, to the solution; and mixing the solution.

(56) In preferred embodiments, the solution is prepared under basic conditions, meaning a pH adjusting composition is added to the solution prior to addition of the carbonate salt. Preferably, the pH adjusting substance is added in an amount that allows for complete dissolution of the chelating agent in the water, which typically requires a pH of at least 9, 10, 11, 12 or greater. The pH adjusting substance can be, for example, sodium hydroxide.

(57) In preferred embodiments, the biosurfactant is produced by dissolving a biosurfactant, e.g., SLP, in water and adding a pH adjuster, e.g., sodium hydroxide, to bring the pH to 8 and convert the SLP to an acidic form.

(58) In a specific embodiment, preparation of the composition comprises: 1) dissolving 20 g/L EDTA in water to form a solution; 2) adding 10 g/L of acidic form SLP to the solution; 3) adding 100 g/L sodium bicarbonate to the solution; 4) mixing the solution for 40 minutes; and 5) letting the solution rest for 20 more minutes. Preferably, the method comprises, sometime after 1) but before 3), adjusting the pH of the solution to at least 9.5, up to pH 10, 11, 12 or greater, by adding an appropriate amount of sodium hydroxide to completely dissolve the EDTA.

(59) Normally, a carbonate salt will ionize in water and will produce carbon dioxide and water when reacted with an acid. The subject composition, however, is prepared in such a way that any reactions can be timed specifically for a controlled release of gas within a formation. Sodium bicarbonate, for example, will not react to form gas when the pH is above 7. When gas production is desired, the composition with the carbonate salt can be mixed with an acid or with acidic brine water to lower the pH.

(60) Methods for Enhanced Oil Recovery

(61) The subject invention further provides methods for enhancing oil recovery from an oil-bearing subterranean formation utilizing the subject compositions. In preferred embodiments, the formation has fair or low permeability, such as that found in diatomite formations, or is heterogeneous with certain areas of fair or low permeability. In a specific embodiment, the formation has a permeability of 10 mD or lower.

(62) In one embodiment, the methods comprise first preparing a composition of the subject invention according to the process described herein; preparing an acid solution; and preparing a plugging composition.

(63) In one embodiment, the acid solution is 30% citric acid. In another embodiment, the plugging composition comprises 1.0-1.5% sodium alginate dissolved in water. The plugging composition can also comprise a biopolymer, such as xanthan gum or guar gum.

(64) Next, the methods comprise steps that can be generally characterized as 1) gas release; and 2) plugging.

(65) More specifically, gas release can comprise injecting an EOR composition of the subject invention into the formation. This can either be immediately preceded by or followed by injection of the acid solution in an amount sufficient to reduce the pH of the EOR composition to 7.0 or below, preferably 6.0 or below, which will activate the release of carbon dioxide gas. The time in between application of the EOR composition and the acid solution can be, for example, 5 minutes or less, 2 minutes or less, or even 30 seconds or less.

(66) Next, the method comprises injecting water and/or brine to push the composition and acid solution deep into the formation. Preferably, the injection of water and/or brine is performed quickly (e.g., immediately, or within 5 minutes or less) after the EOR composition comes into contact with the acid solution in order for the reaction that produces carbon dioxide gas to occur as deep into the formation as possible.

(67) The amount of acid solution injected into the formation can vary depending upon the amount of EOR composition that is injected and the acidity of the brine. In one embodiment, no acid solution is injected, for example, when the brine has an acidic pH (e.g., pH of 2 to 3 or lower) that is sufficient to reduce the pH to 7.0 or lower, preferably, 6.0 or lower.

(68) Finally, the method comprises injecting the plugging composition into the formation to help with gas and pressure buildup, as well as improve flow of oil from the formation. The plugging composition is preferably in liquid form upon injection, but solidifies when it comes into contact with salts present in the brine and formation. The plugging composition will selectively plug larger pores and channels with some non-selective plugging of smaller pores.

(69) Over time, the plugging composition will wash out on its own throughout the oil production process; however, if desired, the plugging composition can be deliberately washed out using known methods.

(70) In one embodiment, the shut-in time for the EOR composition is dependent upon the time it takes for carbon dioxide to be released, which can depend upon, for example, the porosity of the formation and the speed at which citric acid and the treatment composition diffuse throughout the formation. Preferably, the shut-in time for the subject methods ranges from 1-50 days, more preferably from 3-30 days.

(71) Once carbon dioxide production stops, pumping of oil from the formation can resume after about one or two days.

(72) In one embodiment, the method can be performed in multiple locations within the formation at one time, for example, if it is desirable to have an increased amount of gas or to have more than one area in the formation with increased pressure.

(73) Advantageously, the subject method utilizes microbial metabolites and non-toxic biochemicals for delayed release of carbon dioxide. The carbon dioxide that is dissolved in the subject EOR composition remains dissolved, until the composition reacts with the acid to produce carbon dioxide gas. This occurs only once and in a short period of time. This is advantageous over continuous injection and/or production of carbon dioxide because it reduces the potential for carbonic acid production and corrosion associated therewith.

(74) As used herein, “applying” a composition or product refers to contacting it with a target or site such that the composition or product can have an effect on that target or site. The effect can be due to, for example, microbial growth and/or the action of a biosurfactant or other growth by-product. For example, the microbe-based compositions or products can be injected into oil wells and/or the piping, pumps, tanks, etc. associated with oil wells and the transmission, storage and/or refining of oil and/or gas.

(75) The composition can be applied in an amount of at least 1,000 barrels, preferably in amounts of at least 500 barrels, even more preferably in the amount of 80 barrels total. In some embodiments, the composition is applied in a range between 80 and 1,000 BBLS, depending on, for example, the depth of the well and the amount of carbon dioxide release is desired.

(76) The subject methods and compositions advantageously can replace current methods of pressurization that utilize pumping of gas into formations, or CO.sub.2-producing bacteria, which can lead to establishment of sulfate-reducing bacteria or other potentially corrosive or deleterious microorganisms. Additionally, the subject invention can be used without releasing large quantities of inorganic compounds into the environment. Furthermore, the subject compositions and methods utilize components that are biodegradable and toxicologically safe. Thus, the present invention can be used in oil and gas production (and other industries) as a “green” treatment.

EXAMPLES

(77) A greater understanding of the present invention and of its many advantages may be had from the following examples, given by way of illustration. The following examples are illustrative of some of the methods, applications, embodiments and variants of the present invention. They are not to be considered as limiting the invention. Numerous changes and modifications can be made with respect to the invention.

Example 1—Determination of Solubility of Sodium Bicarbonate

(78) Initial experiments were performed to determine the solubility of sodium bicarbonate in different solutions and to find the most suitable acid for converting an amount of dissolved sodium bicarbonate into carbon dioxide gas. It was determined that citric acid is acceptable for initiating the reaction. The process takes place according to the formula:
H3C6H5O7(aq)+3NaHCO.sub.3(aq).fwdarw.Na3C6H5O7(aq)+3H2O(l)+3 CO2(g)

(79) Accordingly, 1 mole of citric acid reacts with 3 moles of sodium bicarbonate to produce 3 moles of carbon dioxide, meaning that 1 kg of sodium bicarbonate fully reacts with 762.7 g citric acid to produce 270.25 L of carbon dioxide. From these calculations, it was determined that sodium bicarbonate can be dissolved in basic solution up to 10% without releasing carbon dioxide.

Example 2—Preparation of the Treatment Composition

(80) The EOR composition of the subject invention is prepared according to the following steps:

(81) 1. 20 g/L EDTA is added to water;

(82) 2. 10 g/L acidic SLP is added to the water;

(83) 3. Sodium hydroxide is added until all remaining EDTA is dissolved

(84) 4. 100 g/L sodium bicarbonate is added to the water;

(85) 5. The solution is mixed for 40 minutes;

(86) 6. The solution is left to rest for 20 minutes;

(87) The solution has a pH of approximately 9.5, which is crucial for the proper timing of carbon dioxide release when injected into a well. The color is colorless to slightly yellow, and the solution is clear, with no dispersion.

Example 3—Release of Carbon Dioxide with Addition of Acid

(88) As shown in FIG. 1A, there is no release of carbon dioxide with the EOR composition as it is prepared in Example 2. In FIG. 1B, however, where 200 ml of 30% citric acid is added into 4 L of the EOR composition, a powerful release of carbon dioxide takes place.

(89) The addition of 200 ml of 30% citric acid was repeated 11 times, and gas was released after each of these repetitions. It was concluded that the formulation is stable (with no release of carbon dioxide) and mixing with citric acid produces large amounts of carbon dioxide from sodium bicarbonate.

Example 4—Gas Release Compared with Meor

(90) Experimental work was conduction using aged sand containing oil with API gravity of 32.3. To produce the aged sands, 700 ml of oil are mixed with 5.5 kg of sand (13%) in cylinders and “aged” at 60° C. for 3 days.

(91) An EOR composition of the subject invention is added to one cylinder having aged sands therein. The other cylinder comprises an MEOR, yeast-based treatment. The gas releasing capabilities of the two treatments are tested by adding citric acid to the cylinders.

(92) FIG. 2B shows the carbon dioxide release from sands treated with an EOR composition of the subject invention, whereas FIG. 2A shows the sands treated with the MEOR treatment. The EOR test tube displays large pockets of air, indicating carbon dioxide release, whereas the MEOR test tube displays more compact sands, indicating less carbon dioxide release.

Example 5—Comparative Study of Oil Recovery

(93) Three different treatments are compared for recovery of oil from aged sands prepared as described in Example 4:

(94) 1. 30 g of sand added to 20 ml of water.

(95) 2. 30 g of sand added to 20 ml of yeast fermentation product.

(96) 3. 30 g of sand added to 20 ml of EOR composition.

(97) Citric acid (30%, 3 ml) is added to each. Carbon dioxide was released immediately after contacting the test tubes with citric acid. After 4.5 hours (FIGS. 3A-3B), the EOR composition continued to release carbon dioxide in the third treatment tube.

Example 6—Gas Release Using Pre-Treatment with Acid and Alginate Plugging

(98) Experiments were conducted to mimic oil movement through a capillary system to increase permeability and determine the effect of adding acid into an oil well prior to application of the EOR composition of the subject invention. The experiments also aimed to determine a suitable plugging composition that would help promote lateral release of carbon dioxide in the formation and prevent back-channeling of carbon dioxide after the treatment formulation mixes with the acid.

(99) A cylinder was filled with 60 g of aged sand as prepared in Example 4. Citric acid (6 ml) was added through a silicone tube to make the sand acidic. The cylinder was then plugged by a 1.5% alginate solution, which was not completely dissolved. Two holes were made in the alginate “cup” that formed to allow for gas release. The plugging material proved effective to handle the pressure produced by the carbon dioxide.

(100) Finally, 20 ml of EOR solution were added through the silicone tube, after which gas release continued for more than 4 hours. The sample was left overnight and afterwards, produced 8 ml, or about 90% of the oil, on top of the alginate cup through the holes.

(101) FIG. 4A shows the gas release after addition of the EOR composition through the holes in the alginate cup, while FIG. 4B shows the oil recovered on top of the plug after about 4 hours.