foaming composition with wetting capacity modification and corrosion inhibiting properties for high

专利摘要:
FOAMING COMPOSITION WITH MODIFICATION PROPERTIES OF MODIFICATION AND CORROSION INHIBITORS FOR HIGH TEMPERATURES AND ULTRA-HIGH SALINITY The present invention relates to the obtainment and use of foaming compositions with wetting capacity modification and corrosion inhibiting properties that control fluid channeling in naturally fractured carbonate reservoirs, they favorably alter the wetting capacity of the rock in intensified crude oil recovery processes and control the uniform corrosion problems that occur in production equipment under conditions of high temperature and ultra-high salinity; through the synergistic effect resulting from the supramolecular interaction of alkyl amido propyl hydroxysultains or alkyl hydroxysultains with sodium alkyl hydroxysulphonates and sodium alkenyl sulphonates (1). The foaming compositions with wetting capacity modification and corrosion inhibiting properties are characterized by being tolerant to high concentrations of divalent ions such as calcium, magnesium, strontium and barium and by the fact that for their application in the reservoir, sea water and/or the congenital water characteristic of the reservoir can be used as a means of transport.
公开号:BR102013024720B1
申请号:R102013024720-0
申请日:2013-09-26
公开日:2021-05-25
发明作者:Raúl HERNÁNDEZ ALTAMIRANO；Luis Silvestre Zamudio Rivera；Violeta Yasmín Mena Cervantes；Erick Emanuel Luna Rojero；Enrique Serrano Saldaña；José Manuel Martínez Magadán；Raúl OVIEDO ROA；David Aarón Nieto Alvarez；Eduardo Buenrostro González；Rodolfo CISNEROS DEVORA；María Del Pilar Arzola García；Mirna PONS JIMÉNEZ；América Elizabeth Mendoza Aguilar；Sung Jae Ko Kim；Jorge Francisco Ramírez Pérez；Tomás Eduardo Chávez Miyauchi；Yosadara Ruiz Morales
申请人:Instituto Mexicano Del Petróleo；
IPC主号:

专利说明:

DESCRIPTION TECHNICAL FIELD OF THE INVENTION
[0001] The present invention is related to the obtainment and use of foaming compositions with wetting capacity modification and corrosion inhibiting properties that control the channeling of fluids in fractured carbonate reservoirs in a natural way, favorably altering the wetting capacity of rock in intensified crude oil recovery processes and control uniform corrosion problems that occur in production equipment under conditions of high temperature and ultra-high salinity; through the synergistic effect resulting from the supramolecular interaction of alkyl amido propyl hydroxysultains or alkyl hydroxysultains with sodium alkyl hydroxysulphonates and sodium alkenyl sulphonates (1). Foaming compositions with wetting capacity modification and corrosion inhibiting properties are characterized by being tolerant to high concentrations of divalent ions such as calcium, magnesium, strontium and barium, and by the fact that their application in the reservoir, water sea and/or congenital water, characteristics of the reservoir, can be used as a means of transport.
FUNDAMENTALS OF THE INVENTION
[0002] One of the biggest technological challenges currently around the world in naturally fractured carbonate reservoirs (NFCR) with the conditions of high temperature and ultra high salinity is to increase the recovery factor of hydrocarbons using chemical products. NFCRs are characterized by having a low porosity, having preferential flow areas, due to the existence of fractures and dissolution cavities, and by presenting wetting capacities of oil or intermediates; therefore, the chemicals used in it in order to increase the recovery factor must be able to control fluid channeling and change the wetting capacity of the rock from wetting oil and wetting water. In addition, if NFCRs have high temperature and salinity conditions, the chemicals to be used in enhanced recovery processes must be tolerant of high salinity and divalent ion concentrations and control the corrosion problems that occur in production equipment.
[0003] The traditional way to control fluid channeling in NFCRs has been through the use of foaming agents and/or gels [SPE 145718, 2011, Development of a new foam EOR model from laboratory and field data of the naturally fractured Cantarell Field; SPE 130655, 2010, High-temperature conformance field application through coiled tubing a successful case history; SPE 129840, 2010, Application of gas for mobility control in chemical EOR in problematic carbonate reservoirs] and its performance is a function of the reservoir temperature, salinity and concentration of divalent ions present in the injection water and/or formation water, and the type of crude oil present in the reservoir. In addition, the benefits of using foaming agents with wetting capacity modification properties that control gas pipeline problems and increase the recovery factor in NFCRs have recently been demonstrated in Mexico [AIPM, 13-33, 2012, Gas mobility control in the cap in the wells of the Akal field belonging to Complejo Cantarell; SPE 145718, 2011, Development of a new foam EOR model from laboratory and field data of the naturally fractured Cantarell Field;] and the development of foaming agents with improved stabilities with wetting capacity modification properties and the ability to control Corrosion problems that occur in production equipment have been established as a challenge.
[0004] The main chemical families of surfactants that have been used to generate foams that have application in intensified recovery processes include: 1) alkyl aryl sulfonates (US Patent 5,273,682; Viscosity control additives for foaming mixtures), 2) alkoxy alkyl benzenesulfonates (US Patent 5,049,311, Alkoxylated substituted alkyl phenol sulfonates, compounds and compositions, the preparation thereof and their use in various applications), 3) alpha olefin sulfonates (US Patent 4,607,695; High sweep efficiency steam drive oil recovery method) , 4) alkyl starch betaines (US Patent 7,104,327; Methods of fracturing high temperature subterranean zones and foamed fracturing fluids therefor), 5) alkyl starch hydroxysultaines (US Patent 7,407,916; Foamed treatments fluids and associated methods) and 6) alkyl ether sulfates (Report DE-FC26-03NT15406 by the Department of Energy of the United States of America Surfactant-Based Enhanced Oil Recovery Processes and Foam Mobilit and Control). However, when temperature conditions in the reservoirs are high (higher than 70 °C), the salinity is higher than 30,000 ppm total solids and the concentration of divalent ions such as calcium and magnesium is higher than 2000 ppm, the stability of the foam generated by this class of chemical families of surfactants dramatically decreases.
[0005] In order to increase the stability of foams and, therefore, their tolerances to high concentrations of divalent ions and/or temperature, formulations of foaming agents with accentuated properties have been developed, including as follows:
[0006] The US patent 3,939,911 (Surfactant oil recovery process usable in high temperature formations containing water having high concentrations of polyvalent ions) describes a system of three surfactants applied to intensified recovery processes in reservoirs with high temperature and formation water containing 200 to 14000 ppm dissolved polyvalent ions such as calcium or magnesium. The three-surfactant system is composed of: 1) a water-soluble salt of an alkyl or alkyl aryl sulfonate, where the alkyl chain may have from 5 to 25 carbon atoms, 2) a phosphate ester surfactant with a molecular weight medium not exceeding 1000 AMU and 3) a sulfobetain-based surfactant having the structural formula (2) and wherein R is an alkyl group of 12 to 24 carbon atoms. The combination is stable up to a temperature of 107 °C and resistant to bacterial attack and inhibits scale formation.

[0007] Patent 4,703,797 (Sweep improvement in enhanced oil recovery) mentions a new improved method for sweeping during intensified hydrocarbon recovery processes. The method comprises generating foam by dispersing the removal fluid in an aqueous solution containing a surfactant formulation. Said surfactant formulation comprises a lignosulfate-based foaming agent and a foaming surfactant. The foaming surfactants that are mentioned include the group comprising anionic, nonionic and amphoteric surfactants.
[0008] US Patent 5,295,540 (Foam mixture for steam and carbon dioxide drive oil recovery method) mentions a foam-based method to increase the production of hydrocarbon in underground formations that consists of: 1) injection of steam and fluids produced in the formation and 2) injection of a mixture of steam, a non-condensable gas and an aqueous mixture of surfactant and polysaccharides. The mentioned surfactants that can be used include linear toluene sulfonates, alkyl aryl sulfonates, dialkyl aryl sulfonates, alpha olefin sulfonates and alpha olefin sulfonate dimers.
[0009] US Patent 5,542,474 (Foam mixture for carbon dioxide drive oil recovery method) refers to a foam-based method to improve performance during the delivery of steam or carbon dioxide into underground formations containing crude oil and which comprises at least one production well and one injection well. Sweeping efficiency in the oil recovery process via steam supply is increased by: 1) injecting steam until it begins to appear in the production well and 2) subsequently adding a mixture of steam, non-condensable gas and an aqueous solution of a surfactant-polypeptide. The aqueous surfactant-polypeptide solution forms stable foam with the forming oil under reservoir conditions. Surfactants used as the base for the foaming agent include sodium and ammonium salts of sulfated alcohol ethoxylates, linear alcohol ethoxylates and linear toluene sulfonates.
[0010] The article "Improving the foam performance for mobility control and improved sweep efficiency in gas flooding" (Ind. Eng. Chem. Res. 2004, 43, 4413-4421) mentions that the apparent stability and viscosity of a foam generated by alpha olefin sulfonates in brine having concentrations of 30,000 and 120,000 ppm total dissolved solids are substantially enhanced when formulated with partially hydrolyzed polyacrylamide based polymers or xanthan gum type biopolymers. Furthermore, the article mentions that the stability of foams generated by twelve carbon alpha olefin sulfonates is substantially increased when formulated with amine oxide type surfactants.
[0011] The US patent 5,911,981 (Surfactant blends for generating a stable wet foam) mentions a mixture of surfactants that generates stable spherical foams. The surfactant blend contains a nonionic surfactant or an amphoteric surfactant as the main foaming agent, and sufficient amounts of an acyl lactylate to increase the foam volume and to provide excess foam in a spherical shape for periods of time. approximately forty minutes. Amphoteric surfactants which are mentioned include betaines, sultains and aminosultaines and the use of cocodimethylpropylsultaine, stearyldimethylpropylsultaine, lauryl-bis(2-hydroxyethyl)propylsultaine and cocoamidopropylhydroxysultaine is specifically mentioned.
[0012] US patent 7,104,327 provides methods for fracturing high temperature underground zones and aqueous and viscous foam fracturing fluids for this purpose. The fracture fluid of said invention comprises water, a terpolymer of 2-acrylamide-2-methylpropane sulfonic acid, acrylamide and acrylic acid or its salts, a gas, a foaming agent and a viscosity breaker to control and reduce the viscosity of the fracture fluid. The foaming agent in said invention is selected from the group comprising C8-C22 alkyl starch betaine, alpha olefin sulfonate, taloyl trimethyl ammonium chloride, ethoxylated C8-C22 alkyl sulfate and trimethyl coconut ammonium chloride and special mention is made from cocoamidopropyl betaine as a foaming agent.
[0013] The synergistic effect of alkyl amido propyl betaines with sodium alkyl ether sulfate type surfactants and sodium alkyl sulfate has been studied in the literature (Langmuir 2000, 16, 1000-1013, Langmuir 2004, 20, 565-571, Langmuir 2004, 20, 5445-5453) and mainly suggests the ability of alkyl amido propyl betaines to stabilize and improve the rheological properties (viscosity) of foams generated by said anionic surfactants and which have application in shampoos and hair conditioners. Furthermore, the article “Synergistic sphere-to-rod micelle transition in mixed solutions of sodium dodecyl sulfate and cocoamidopropyl betaine” (Langmuir 2004, 20, 565-571) indicates that the synergistic effect between aa cocoamidopropyl betaine and sodium dodecyl sulfate it is due to an electrostatic attraction between the main surfactants (3).

[0014] US Patent 7,134,497 (Foamed treatment fluids and associated methods) mentions foam treatment fluids comprising water, a gas and a foam and foam stabilizing surfactant mixtures comprising an alkaline salt of an alkyl ether sulfate, in whereas the alkaline salt of alkyl ether sulfate comprises an alkaline salt of a C 6-10 alkyl ether sulfate and an alkaline salt of a C 4 alkyl ether sulfate, an alkyl amidopropyl amphoteric surfactant selected from the group consisting of an alkyl amidopropyl hydroxysulfaine, an alkyl amidopropyl betaine and a combination thereof, and an alkyl amidopropyl dimethylamine oxide. The patent comprises methods for generating fluids for foam treatments and for introducing them into underground formations. Furthermore, US patent 7,134,497 does not mention the use of sodium alkyl hydroxy sulfonates and/or sodium alpha olefin sulfonates, or that foam treatment fluids have wetting capacity modification and corrosion inhibiting properties.
[0015] US Patent 7,287,594 (Foamed Treatment Fluids and Associated Methods) relates to treatment methods for underground formations using foam fluids comprising water, a gas and a foam, and foam stabilizing surfactant mixtures comprising a range of alkali salts of alkyl ether sulfates, wherein the alkyl group on each of the alkyl ether sulfates is in the range of 4 carbon atoms to 10 carbon atoms, an alkyl amido propyl hydroxysultaine or an alkyl amido propyl betaine and an alkyl starch propyl dimethylamine oxide. The patent does not mention the use of sodium alkyl hydroxy sulfonates and/or sodium alpha olefin sulfonates or that foam fluids have wetting capacity modifying or corrosion inhibiting properties.
[0016] US Patent 7,373,977 (Process for Oil Recovery Employing Surfactant Gels) protects a hydrocarbon recovery composition and the process, which comprises injecting an aqueous solution into a hydrocarbon-containing formation through one or more injection wells , remove the solution within the formation and recover the hydrocarbon through one or more production wells. The aqueous solution contains one or more amphoteric surfactants of the alkyl amide betaine type (4) which form a viscoelastic surfactant gel which can reduce interfacial tension and increase the viscosity of the injection fluid simultaneously in certain oils and brines. Viscoelastic gels are tolerant to electrolytes and polyvalent cations and are particularly useful within reservoirs with medium to high temperature, high salinities, high concentrations of divalent ions and low porosity. The application mentions that the hydrocarbon recovery compound contains one or more amphoteric surfactants selected for their ability to reduce interfacial tension and simultaneously increase the viscosity of an aqueous medium, a secondary surfactant and optionally one or more polymers to provide residual viscosity. The patent application indicates that the secondary surfactant can be selected from the anionic, cationic or nonionic group and that the polymer providing residual viscosity is selected from the group of polyacrylamide, partially hydrolyzed polyacrylamide, xanthan gum, hydroxyethyl cellulose or guar gum. Additionally, the patent application mentions that the combination of alkyl amido betaines with linear type sodium dodecyl benzene sulfonate secondary surfactants and sodium arylalkyl xylene sulfonate reduces the interfacial tension and increases the viscosity of the system.

[0017] US Patent 7,407,916 (Foamed treatment fluids and associated methods) mentions foam treatment fluids containing water, a gas and a foam and foam stabilization surfactant mixtures comprising an alkaline salt of an alkyl ether sulfate, in whereas the alkali salt of alkyl ether sulfate comprises an alkaline salt of a C 6-10 alkyl ether sulfate and an alkaline salt of a C 4 alkyl ether sulfate, an amphoteric alkyl amido propyl surfactant selected from the group comprising an alkyl amido propyl hydroxysultaine, an alkyl propyl betaine starch and a combination thereof, and an alkyl propyl starch dimethylamine oxide. The patent includes methods for generating fluids for foaming treatments and for introducing them into underground formations. Additionally, US Patent 7,407,916 does not mention the use of sodium alkyl hydroxy sulfonates and/or sodium alpha olefin sulfonates, or that foam treatment fluids have wetting capacity modification and corrosion inhibiting properties.
[0018] Mexican patent MX 297297 refers to a foaming composition with improved stability that controls the gas channeling in naturally fractured carbonate reservoirs with conditions of high salinity and temperature, through the synergistic effect resulting from the supramolecular interaction of sodium alpha olefin sulfonates with alkyl starch propyl betaines (5),
wherein R and R1 are independent straight or branched alkyl chains with a length ranging from 1 to 30 carbon atoms. The patent application mentions that supramolecular complexes resulting from the interaction of sodium alpha olefin sulfonates with alkyl amido propyl betaines can be combined with anionic surfactants, preferably of the 3-hydroxy-alkyl sodium sulfonate type, with cationic surfactants such as salts of alkyl quaternary ammonium, preferably of the alkyl trimethyl ammonium chloride or bromide type, with divalent ion scavengers, preferably oligomers or copolymers derived from itaconic acid and whose average molecular weight is within the range of 200 to 20000 Daltons, with derived gels of copolymers selected from the group comprising polyacrylamides, partially hydrolyzed polyacrylamide, xanthan gum, poly(itaconic acid), poly(acrylic acid), poly(itaconic acid-co-acrylic acid), poly(itaconates) and poly(acrylates). Additionally, the patent application indicates that foaming compositions with enhanced stability have applications in recovery and/or enhanced production assurance processes. The patent application does not mention the use of compositions based on alkyl amido propyl hydroxysultaine or alkyl hydroxysultaine or that these have applications as wetting capacity modifiers and corrosion inhibitors.
[0019] Regarding their use as wetting capacity modifiers with applications in intensified recovery processes, the specialized literature mentions that the main surfactant families that were used are: 1) tetra-alkyl quaternary ammonium salts (Energy & Fuel 2011, 25, 2083-2088; Combined Surfactant-Enhanced Gravity Drainage (SEGD) of Oil and Wettability Alteration in Carbonates: The Effect of Rock Permeability and Interfacial Tension (IFT)), 2) ethoxylated alcohols (Energy & Fuel 2002, 16, 1557 -1564; An Evaluation of Spontaneous Imbibition of Water into Oil-Wet Carbonate Reservoir Colors Using a Nonionic and a Cationic Surfactant), 3) Alkaline salts of alkyl ether sulfates (Patent Application US 2011/0071057; Method of Manufacture and Use of Large Hydrophobe Ether Sulfate Surfactants in Enhanced Oil Recovery (EOR) Applications; Langmuir 2008, 24, 1409914107; Mechanistic Study of Wettability Alteration Using Surfactants with Applications in Naturally Fractur ed Reservoirs), 4) sodium alkyl aryl sulfonates (US Patent 4,836,283, Divalent Ion Tolerant Aromatic Sulfonates), 5) internal sodium olefin sulfonates (SPE 115386, Recent Advances in Surfactant EOR), 6) Betaines (Energy & Fuel 2011, 25, 2551-2558; Wettability Alteration of Clay in Solid-Stabilized Emulsions).
[0020] Additionally, in order to increase the performance of wetting capacity modifiers, formulations with improved properties have been developed, such as the following:
[0021] US Patent 4,270,607 (Emulsion Oil Recovery Process Usable in High Temperature, High Salinity Formations) mentions the fact that many formations contain water with high levels of salinity and/or concentrations of divalent ions such as calcium or magnesium, and additionally, they have temperatures ranging from 21 °C to 149 °C. Furthermore, it indicates that most surfactants and polymers that are suitable for the generation of fluids or emulsions used in intensified recovery operations do not work properly at high levels of salinity and water hardness, or do not tolerate the high temperatures found in many formations. Furthermore, it mentions that a viscous emulsion containing a water-soluble and/or water-dispersible alkyl aryl polyalkoxyalkylene sulfonate and a phase stabilization additive such as a water-soluble and/or water-dispersible petroleum sulfonate is an effective fluid to be injected into oil formations containing brines whose salinity is within the range of 70000 to 220000 ppm total dissolved solids and where temperatures are as high as 149 °C. The emulsion is a stable phase over a wide range of temperatures, formations, and salinity and hardness values that can be found in water.
[0022] US Patent 6,828,281 (Surfactant Blends for Aqueous Solutions Useful for Improving Oil Recovery) mentions an aqueous fluid useful for the recovery of liquid hydrocarbon in underground reservoirs and where the aqueous fluid comprises an aqueous medium and a mixture of surfactants. The surfactant blend contains at least one polyisobutylene-based synthetic surfactant and a secondary surfactant selected from the group comprising sulfonated surfactants, alcohols and ionic surfactants. The surfactant blend reduces the interfacial tension between the hydrocarbon and the aqueous fluid.
US patent application 2009/0111717 (Enhanced Oil Recovery Surfactant Formulation and Method of Making the Same) mentions improved hydrocarbon recovery formulations comprising: a) an alkyl aryl sulfonate, b) an isomerized olefin sulfonate, c) a solvent, d) a passivator and e) a polymer.
[0024] On the other hand, and due to the impact of the phenomenon of wetting capacity on intensified recovery processes, different institutions and companies have been working internationally on the development of new chemical structures with improved properties, and as examples, we can cite the US patent 7,629,299 (Process for Recovering Residual Oil Employing Alcohol Ether Sulfonates) and patent application MX/a/2010/012348 (Base Composition GemInal Zwitterionic Liquids as Mobility Modifiers in Processes for Improved Oil Recovery).
[0025] With regard to their use as corrosion inhibitors with application in hydrocarbon exploration and transport processes, the specialized literature mentions that the main families of chemical products that were used are the following: 1) 1-heteroalkyl-2- alkyl imidazolines (Patent MX 254565, Composition Inhibitory of Corrosion for Ferrous Metals in Medium Acids; Patent MX 260049, Composition Inhibitory of Corrosion and Boosting by Hydrogen for Ferrous Metals in Basic Mediums), 2) Alkyl Starch Amines (Revista de la Sociedad Química de México 2002, 46, 4, 335-340, Control of the Corrosion of Acero al Carbon in Sulfhydric Acid Environments by 1-(2-Hydroxyethyl)-2-Alkyl-Imidazolines and their corresponding Amidic Precursors; Science 2006, 252, 6, 2139-2152, Surface Analysis of Inhibitor Films Formed by Imidazoles and Amides on Mild Steel in an Acidic Environment), 3) Polyalkylene Polyamines (US Patent 4,900,458, Po lyalkylenepolyamines as Corrosion Inhibitors; US Patent 4,275,744, Derivatives of Polyalkylenepolyamines as Corrosion Inhibitors), 4) acetylenic alcohols (US Patent 5084210, Corrosion inhibitors), 5) diacetyl alcohols (US Patent 4,039,336, Diacetylenic Alcohol Corrosion inhibitors), 6) Ammonium Salts, 028 US Quaternary Patent , Low Hazard Corrosion Inhibitors and Cleaning Solutions Using Quaternary Ammonium Salts), 7) Bis-imidazolines (Patent MX 246603, Multifunctional Corrosion Inhibitors, Biodegradables and Low Toxicity) and 8) Bis-Quaternary Ammonium Salts (Patent application US 2006 /0013798, Bis-Quaternary Ammonium Salt Corrosion Inhibitors).
[0026] Furthermore, and due to the impact that 1-heteroalkyl-2-alkyl imidazolines had on the oil industry, several companies were able to increase their solubility in water by: 1) Performing their quaternization, thus generating the quaternary salts ( Patent US 6,475,431, Corrosion Inhibitors with Low Environmental Toxicity), 2) Introduce ethoxy groups in its structure (Patent US 5,785,895, Biodegradable Corrosion Inhibitors of Low Toxicity) and 3) Generate zwitterion ions through quaternization processes (Patent US 6,303,079, Corrosion Inhibitor Compositions).
[0027] Additionally, and due to the impact that the corrosion phenomenon has on the oil industry, when there is a concentration of high salinity and bivalent ions, different institutions and companies have been working internationally on the development of new chemical structures with improved properties and as examples we can cite US patent 8,105,987 (Corrosion Inhibitors for an Aqueous Medium) and US patent application 2011/0138683 (Gemini Surfactants, Process of Manufacture and Use as Multifunctional Corrosion Inhibitors).
[0028] On the other hand, supramolecular chemistry is the part of chemistry that deals with the study of systems that involve molecules or aggregated ions that are bound through non-covalent interactions, such as electrostatic interactions, hydrogen bonds, II- II, dispersion interactions and hydrophobic effects. Supramolecular chemistry can be divided into two broad areas: 1) Host-Guest Chemistry and 2) Self-Preparation. The difference between these two major areas is a matter of size and shape; where there is no significant difference in size and neither species acts as a host for the other, the non-covalent bond between the two or more species is termed self-preparation.
[0029] From an energetic point of view, supramolecular interactions are much weaker than covalent interactions, which fall in the energetic range of 150 to 450 kJ/mol with respect to single bonds. The energetic range of non-covalent interactions is from 2 kj/mol for dispersion interactions to 300 kj/mol for ion-ion interactions (Table 1), and the sum of the various supramolecular interactions can produce highly stable supramolecular complexes. Table 1. Intensity of Supramolecular Interactions

[0030] Computational chemistry is a tool that is widely used around the world to predict the stability and structure of chemical systems with better potential properties and has found application at the industrial level in the development of quantitative studies of connection of structure activity. The computational calculation methods that have been used for this purpose include molecular mechanics methods, quantum methods, which comprise the semi-empirical and ab-initio methods, as well as the density functional theory methods. As examples in the literature demonstrating the use of computational chemistry to accurately predict supramolecular interactions in chemical systems and/or the thermodynamic and kinetic aspects of chemical processes, the following articles can be cited: 1) Cornucopian Cylindrical Aggregate Morphologies from Self-Assembly of Amphiphilic Triblock Copolymer in Selective Media (Journal of Physical Chemistry B, 2005, 109, 21549-21555), 2) Density Functional Calculations, Synthesis, and Characterization of Two Novel Quadruple Hydrogen-Bonded Supramolecular Complexes (Journal of Physical Chemistry A, 2004) , 108, 5258-5267), 3) Strong Decrease of the Benzene-Ammonium Ion Interaction upon Complexation with a Carboxylate Anion (Journal of the American Chemical Society, 1999, 121, 2303-2306).
[0031] It is important to note that none of the aforementioned references addresses the generation and use of foaming compositions with wetting capacity modification and corrosion inhibiting properties that control the channeling of fluids in naturally fractured carbonate reservoirs, change the capacity wetting the rock favorably in intensified crude oil recovery processes and controlling the problems of uniform corrosion occurring in production equipment under conditions of high temperature and ultra high salinity; through the synergistic effect resulting from the supramolecular interaction of alkyl amido propyl hydroxy sultains or alkyl amino hydroxy sultanas with sodium alkyl hydroxy sulphonates and sodium alpha olefin sulphonates; this is the first time that supramolecular complexes with the aforementioned properties have been developed worldwide. Additionally, the supramolecular complexes object of the present invention generate foams that have superior stabilities with respect to those generated by products currently used for this purpose throughout the world. BRIEF DESCRIPTION OF THE DRAWINGS THE INVENTION
[0032] The contents of the figures of the present invention are briefly described below.
[0033] Figure 1. 1H Nuclear Magnetic Resonance Spectrum of coco amido propyl hydrosultaine.
[0034] Figure 2. 13C Nuclear Magnetic Resonance Spectrum of coco amido propyl hydrosultaine.
[0035] Figure 3. 1H Nuclear Magnetic Resonance Spectrum of a mixture of sodium 3-hydroxydodecane-1-sulfonate and sodium dodec-2-en-1-sulfonate.
[0036] Figure 4. 13C Nuclear Magnetic Resonance Spectrum of a mixture of sodium 3-hydroxydodecane-1-sulfonate and sodium dodec-2-en-1-sulfonate.
[0037] Figure 5. 1H Nuclear Magnetic Resonance Spectrum of the supramolecular complex described in example 19.
[0038] Figure 6. 13C Nuclear Magnetic Resonance Spectrum of the supramolecular complex described in example 19.
[0039] Figure 7. Infrared spectrum of coco starch cpropyl hydrosultaine.
[0040] Figure 8. Infrared spectrum of the supramolecular complex described in example 19.
[0041] Figure 9. System used in foam generation tests comprising the following parts: gas cylinder (TG-1), foam metering tube (EPM-1), lance coupled to 0.5μ of the diffuser (DF- 1), flowmeter with a capacity of 0 to 150 cm3/min. (R-1), thermal bath with recirculation (BTR-1), set of valves to control the gas flow (VR-1, VP-1, VP-2, VR-2, VP-3, VP- 4) , temperature and pressure gauges (T-1, P-1 and P2).
[0042] Figure 10. Stability behavior of the foam at 1 kg/cm2 and 70 °C dependent on time, prepared with the brine described in example 23 at 0.2% by weight of supramolecular complexes described in examples 19, 20 and 21 .
[0043] Figure 11. Stability behaviors of foams at 1 kg/cm2 and 70 °C dependent on time, prepared with the brine described in example 23 in 0.2% by weight of coco amido propyl hydroxysultaine, from the mixture of 3- sodium hydroxydodecane-1-sulfonate and sodium dodec-2-en-1-sulfonate, of supramolecular complexes described in Mexican patent MX 297297 and of the supramolecular complex described in example 19.
[0044] Figure 12. Stability behavior of the foam at 1 kg/cm2 and 70 °C dependent on time, prepared with the brine described in example 23 at 0.2% by weight of the formulations of 1, 2, 3 and 4.
[0045] Figure 13. Stability behaviors of foams at 1 kg/cm2 and 70 °C dependent on time, prepared with brines 2, 3 and 4 described in example 27 and supramolecular complex described in example 19.
[0046] Figure 14. Stability behaviors of foams at 1 kg/cm2 and 70 °C dependent on time, prepared with brine 4 described in example 27 and using nitrogen, carbon dioxide and methane as gases.
[0047] Figure 15. Equipment for evaluating the stability of foam at high pressure and high temperature, where: 1) Temperature controller, 2) IPR (inverse pressure regulator), 3) Window, 4) Filter, 5) transfer, 6) Injection pumps and 7) Valves.
[0048] Figure 16. Sequence of images of the foam stability for the supramolecular complex described in example 19 using the brine 4 whose composition is described in example 27 under conditions of high pressure and high temperature, where: 1) At the beginning of the test, 2), 1 h, 3) 18 h, 4) 24 h, 5) 36 h, 6), 72 h, 7) 154 h and 8) 168 h.
[0049] Figure 17. Foam stability behavior of the supramolecular complex described in example 19 at 3500 psi and 150 °C dependent on time, prepared with the brine 4 described in example 27.
[0050] Figure 18. Graph of shear rate versus shear stress for the supramolecular complex described in example 19 at 3500 psi and 150 °C.
[0051] Figure 19. Graph of shear rate versus shear stress for the supramolecular complex described in example 19 at 3500 psi and 150 °C.
[0052] Figure 20. Contact angle when the first drop begins to form at different concentrations of supramolecular complex described in example 19.
[0053] Figure 21. Contact angle just before oil drop separation at different concentrations of supramolecular complexes described in example 19.
[0054] Figure 22. Photographic sequence of the separation of oil droplets at different concentrations of the supramolecular complex described in example 19.
[0055] Figure 23. Amott cell containing pieces of dolomite-like rock and the supramolecular complex derived from example 19.
[0056] Figure 24. a) Limestone core saturated with oil inside the amott cell at 80 °C and atmospheric pressure and b) oil recovery in the amott cell at 80 °C and atmospheric pressure.
[0057] Figure 25. Glass-lined reactor used for the soaking process at high temperatures, where: a) Recirculation heating device, b) Pressure gauge, c) Safety valve, d) Gas inlet, e) Container of glass and f) Reactor base.
[0058] Figure 26. High temperature soaking system with supramolecular complex derived from example 19, where: a) Limestone core saturated with crude oil, b) Limestone core saturated with crude oil at the beginning of the test and c) limestone saturated with crude oil and oil recovery.
[0059] Figure 27. Limestone core saturated with crude oil at elevated temperature with brine added with supramolecular complex derived from example 19, where: A) Formation of the first drop of oil and b) Separation of the first drop of oil at 150 °C .
[0060] Figure 28. Limestone cores, where: a) Limestone cores unsaturated with oil and b) Limestone cores saturated with crude oil.
[0061] Figure 29. High temperature soaking system with images of measured cores and saturated with crude oil with a brine added with supramolecular complex described in example 19, as well as an image sequence of oil recovery in the soaking system at high temperature for the supramolecular complex described in example 19.
[0062] Figure 30. Graph of the behavior of shear rate versus graph of viscosity for crude oil and crude oil additive with supramolecular complex derived from example 19 at a temperature of 25 °C.
[0063] Figure 31. Graph of the behavior of shear rate versus viscosity for crude oil and crude oil added with the supramolecular complex derived from example 19 at a temperature of 40 °C.
[0064] Figure 32. Appearance of metal test samples used in the dynamic wheel test, where: 1) Reference, 2) Supramolecular complex described in example 19 and 3) Formulation 3 described in example 23. DETAILED DESCRIPTION OF THE INVENTION
[0065] The present invention relates to the synergistic effect resulting from the supramolecular interaction of alkyl amido propyl hydroxy sultains or alkyl amino hydroxy sultanas with sodium alkyl hydroxy sulphonates and sodium alkenyl sulphonates and its application in the development of foam-forming compositions with improved stability that control the channeling of fluids in naturally fractured carbonate reservoirs with ultra-high salinity and high temperature conditions, change the wetting capacity of the rock favorably in intensified crude oil recovery processes, and control the uniform corrosion problems that occur in the production equipment.
[0066] The developed supramolecular complexes vastly outperform commercial surfactants in terms of performance as foaming and wetting capacity modifying agents. Supramolecular complexes based on sodium alkenyl sulphonates, alkyl amido propyl hydroxysultaines or alkyl hydroxysultaines are characterized by being tolerant to brines with high concentrations of divalent ions such as calcium, magnesium, strontium and barium, and by the fact that their application to the reservoir , sea water and/or congenital water characteristic of the reservoir can be used as a means of transport.
[0067] For the development of the present invention a procedure was followed which comprises the following stages: 1) Molecular design through computational chemistry, 2) Synthesis of supramolecular complexes, 3) Spectroscopic characterization of supramolecular complexes and 4) Experimental evaluation of the properties foaming, modifying the wetting capacity and inhibiting corrosion. The selection of the present methodology is based on the fact that the key to solving the set of problems associated with the development of foaming agents with wetting capacity modification and corrosion inhibiting properties that are tolerant to high salinity and concentrations of divalent ions and able to withstand the conditions of high temperature and pressure is the understanding at the molecular level of: 1) How to control the ion exchange reaction between the foaming agent and the divalent ions present in the injection water and/or formation water; 2) How to generate dipole-dipolar pairs between the agent with wetting capacity modifying properties and the polar compounds present in the hydrocarbon so that they are able to change the wetting capacity of carbonate rocks from oil-wettable to water-wettable 3 ) How to generate stable films resulting from the interaction between the corrosion inhibitor and the corroded surfaces that are present in typical production equipment in the oil industry.
[0068] 1) MOLECULAR PROJECT THROUGH COMPUTATIONAL CHEMISTRY. Before going into details, and for clarification purposes, it is worth mentioning that the current custom regarding the first stage of each process that involves the development of chemical products with industrial applications is the design, through computational chemistry, of molecules or supramolecular complexes that will have the potential capacity to solve the problems of interest. This molecular project is intended to systematically guide efforts directed towards the synthesis of new molecules or new supramolecular complexes with new improved properties.
[0069] Once this is established, the first thing to establish in molecular design is how to control the ion exchange reaction between the foaming agent and the divalent ions present in the injection water and/or forming water, and the The first premise to consider is based on the fact that in order for the foaming phenomenon to occur, it is necessary that the foaming agent contains at least one atom of sodium or potassium and that this monovalent atom is replaced in the forming agents of traditional foam by divalent ions, since the process is thermodynamic and kinetically favored when the temperature present in the system increases (Mexican patent MX 297297, Composición Espumante para Alta Temperature y Salinidad), and thus it would be necessary to find a way to encapsulate the atoms of sodium or potassium through supramolecular chemistry. Furthermore, it is documented in the specialized literature that the sulfonate group is tolerant to high salinity and dissolved divalent ion concentrations; therefore, it is present in a wide array of products with antifouling properties (US patent 5,092,404, Polyvinyl Sulfonate Scale Inhibitor; Industrial & Engineering Chemistry Research, 2011, 50, 5852-5861, Effect of Various Cations on the Formation of Calcium Carbonate and Barium Sulfate Scale with and without Scale Inhibitors), whereby, as the second premise, it can be considered that the presence of the sulfonate group in the foaming agents will confer tolerance to high salinity and concentrations of divalent ions. Additionally, it is documented that in supramolecular chemistry, self-preparation processes can produce molecular cavities that, depending on their structure, may be able to behave as receptors and generate inclusion complexes (Inorganic Chemistry, 2006, 45, 2553-2561, Boron Macrocycles Having a Calix-Like Shape. Synthesis, Characterization, X-ray Analysis, and Inclusion Properties; Chemical Communications. 2004, 24, 2834,2835, Boron-Nitrogen Macrocycles: A New Generation of calix[3]arenes), by means of which, as a third premise, it can be considered that the supramolecular interaction of alkyl amido propyl hydroxysultaines or alkyl amino hydroxysultaines with sodium alkyl hydroxysulphonates and sodium alkenyl sulphonates will produce nanocavities, which in an aqueous medium will behave as gas-capturing receptors and forms inclusion complexes characterized by the fact that, in their polar part, the sodium or potassium atoms of the alkyl hydroxysulfonate of only Indium and/or sodium alkenyl sulphonate are encapsulated and thus it will be possible to use them as high performance foaming agents under conditions of high salinity, high concentrations of divalent ions and high temperatures.
[0070] In order to demonstrate regarding the subjects already mentioned, theoretical calculations were performed, where the process of self-preparation between the various alkyl amido propyl hydroxysultaines or alkyl hydroxysultaines with sodium alkyl hydroxysulphonates and sodium alkenyl sulphonates is simulated and the results obtained are described in the following examples: Example 1
[0071] By means of computational chemistry, and using the semi-empirical method MNDO/d as the theoretical level, the geometries of the compounds trans-dodec-2-en-1- sodium sulfonate (sodium alkenyl sulfonate) 1, 3- sodium hydroxy-dodecyl-1-sulfonate (sodium alkyl hydroxy sulfonate) 2 and pentyl-amido-propyl-hydroxysultaine (alkyl amido propyl hydroxysultaine) 3, as well as the geometry of the supramolecular complex resulting from the interaction of three-dimensional compounds were optimized in gas phase in the molecular ratios 1:1:2 4 (6).

[0072] The energetic results, the most relevant binding distances and the most important Mulliken atomic charges for the mentioned complexes and the corresponding supramolecular complex are shown in tables 2, 3 and 4, respectively. Table 2. Energy of compounds 1, 2, 3 and supramolecular complex 4 obtained with the semi-empirical method MNDO/d

[0073] Where:
[0074] 1 = sodium trans-dodec-2-en-1-sulfonate
[0075] 2 = sodium 3-hydroxy-dodecyl-1-sulfonate
[0076] 3 = pentyl-amido-propyl-hydroxysultaine
[0077] 4 = Supramolecular complex that results from the interaction of sodium trans-dodec-2-en-1-sulfonate, sodium 3-hydroxy-dodecyl-1-sulfonate and pentyl-amido-propyl-hydroxysultaine in a molecular relationship of 1:1:2.
[0078] The analysis of the results in Table 2 shows that the formation of supramolecular complex 4 from the 1:1:2 molecular interaction of compounds 1, 2 and 3 should be strongly favored from the thermodynamic point of view. Additionally, the interaction energy -263.340 kJ/mol indicates that supramolecular ion-ion interactions and/or a combination of ion-bipolar interactions and hydrogen bonds must be present. Table 3. Main binding distances in compounds 1, 2, 3 y and supramolecular complex 4


[0079] The analysis of the results of Table 3 shows that the distances 2.520, 2.407, 3.672, 2.247, 2.244 and 2.270 A for the interactions O1-Na1, O2-Na1, O2-Na2, O3-Na2, O11-Na2 and O12 -Na1 are smaller than the sum of the Van der Waals Rays for oxygen (Van der Waals rays 1.52 A) and sodium atoms (Van der Waals rays 2.27 A) and are typical of structures containing bonds of coordination of Na-O and sulfonate groups (Crystal Growt & Design 2006, 6[2], 514-518). Additionally, a nanocavity is observed in the supramolecular complex 4, which can act as the gas receptor and generate the inclusion complexes that must act as foaming agents in aqueous media. Furthermore, this complex 4 shows that sodium atoms have been encapsulated and therefore new foaming agents must be tolerant to brines containing large amounts of divalent ions and at high temperatures.
[0080] The analysis of the results in Table 4 shows that the Mulliken atomic charge on the sodium atom Na1 of the supramolecular complex 4 is reduced by 0.136 units with respect to the charge that this atom has on the trans-dodec-2-en-1 -sodium sulphonate (sodium alkenyl sulphonate) 1, while the atomic charges of the oxygen atoms O1, O2 and O12 undergo a decrease of 0.104, 0.126 and 0.103 units, with respect to pentyl-amido-propyl-hydroxysultaine ( alkyl amido hydroxysultaine); this significant change in the Mullikens atomic charge confirms that in supramolecular complex 4, the sodium atom Na1 is coordinated with the oxygen atoms O1, O2 and O12 and encapsulated between the two molecules of pentyl-starch-propyl-hydroxysultaine (alkyl amido hydroxysultaine) 3 and the sodium trans-dodec-2-en-1-sulfonate molecule (sodium alkenyl sulfonate) 1. In addition, the results in Table 3 show that the Mulliken atomic charge on the sodium atom Na2 of the supramolecular complex 4 is reduced by 0.301 units with respect to the charge this atom has on sodium 3-hydroxy-dodecyl-1-sulfonate (sodium alkyl hydroxy sulfonate) compound 2, while the atomic charges of the oxygen atoms O2, O3 and O11 undergo a decrease of 0.126, 0.086 and 0.077 units, with respect to pentyl-amido-propyl-hydroxysultaine (alkyl amido propyl hydroxysultaine) 3; this significant change in Mulliken atomic charges confirms that in supramolecular complex 4, the sodium atom Na2 is coordinated with the oxygen atoms O2, O3 and O11 and encapsulated between the two molecules of pentyl amido propylhydroxysultaine (alkyl amido hydroxysultaine) 3 and the molecule of sodium hydroxydodecyl-1-sulfonate (sodium alkyl hydroxy sulfonate) 2. In addition, the results in Table 4 confirm that a nanocavity is present in supramolecular complex 4, which can act as the gas receptor and produce complexes of inclusion that should act as foaming agents in an aqueous medium. Example 2
[0081] By means of computational chemistry, and using the semi-empirical method MNDO/d as the theoretical level, the geometries of the compounds trans-tetraec-2-en-1-sodium sulfonate (sodium alkenyl sulfonate) 5, 3- sodium hydroxy-tetradecyl sulfonate 6 (sodium alkyl hydroxy sulfonate) and undecyl amido propyl hydroxysultaine (alkyl amido hydroxy sultaine) 7, as well as the geometry of the supramolecular complex resulting from the interaction of three-dimensional compounds were optimized in the gas phase in the molecular relationships 1:1:2 8 (7).
[0082] The energetic results, the most relevant binding distances and the most important Mulliken atomic charges for said complexes and the corresponding supramolecular complex are shown in tables 5, 6 and 7, respectively.
[0083] The analysis of the results in Table 5 shows that the formation of the supramolecular complex 8 from the 1:1:2 molecular interaction of compounds 5, 6 and 7 should be strongly favored from a thermodynamic point of view. Additionally, the interaction energy of -264.160 kJ/mol indicates that supramolecular ion-ion interactions and/or a combination of ion-bipolar interactions and hydrogen bonds must be present. Table 4. Mulliken atomic charges of compounds 1, 2, 3 and supramolecular complex 4

Table 5. Energy of compounds 5, 6, 7 and supramolecular complex 8 obtained with the semi-empirical method MNDO/d

[0084] Where:
[0085] 5 = sodium trans-tetradec-2-en-1-sulfonate
[0086] 6 = sodium 3-hydroxy-tetradecyl-1-sulfonate
[0087] 7 = undecyl-amido-propyl-hydroxysultaine
[0088] 8 = Supramolecular complex that results from the interaction of trans-tetradec-2-en-1-sulfonate sodium, 3-hydroxy-tetradecyl-1-sulfonate sodium and undecyl-amido-propyl-hydroxysultaine in a molecular ratio 1 :1:2. Table 6. Main binding distances in compounds 5, 6, 7 and supramolecular compound 8


[0089] The analysis of the results of the Table shows that the distances 2.519, 2.407, 3.681, 2.247, 2.243 and 2.273 A for the interactions O1-Na1, O2-Na1, O2-Na2, O3-Na2, O11-Na2 and O12- Na1 are smaller than the sum of the Van der Waals Rays for oxygen (Van der Waals rays 1.52 A) and sodium atoms (Van der Waals rays 2.27 A) and are typical of structures containing coordination bonds of Na-O and sulfonate groups (Crystal Growt & Design 2006, 6[2], 514-518). Additionally, as in the molecular model of complex 4, the supramolecular complex 8 shows the presence of a nanocavity and that the sodium atoms have been encapsulated; therefore, new foaming agents must be tolerant to brines containing high amounts of divalent ions and to high temperatures.
[0090] The analysis of the results in Table 4 shows that the Mulliken atomic charge on the sodium atom Na1 of the supramolecular complex 8 is reduced by 0.136 units with respect to the charge that this atom has on trans-tetradec-2-en-1 -sodium sulfonate (sodium olefin sulfonate) compound 5, while the atomic charges of oxygen atoms O1, O2 and O12 undergo a decrease of 0.104, 0.127 and 0.145 units, with respect to undecyl-starch-propyl- hydroxysultaine (alkyl amido hydroxysultaine); this significant change in Mullikens atomic charge confirms that in supramolecular complex 8, the sodium atom Na1 is coordinated with the oxygen atoms O1, O2 and O12 and encapsulated between the two molecules of undecyl-amido-propyl-hydroxysultaine (alkyl amido hydroxysultaine) 7 and the sodium trans-tetradec-2-en-1-sulfonate molecule (sodium alkenyl sulfonate) 5. In addition, the results in Table 7 show that the Mulliken atomic charge on the sodium atom Na2 of the supramolecular complex 8 is reduced by 0.301 units with respect to the charge this atom has on sodium 3-hydroxy-tetradecyl-1-sulfonate (sodium hydroxy alkyl sulfonate) compound 6, while the atomic charges of the oxygen atoms O2, O3 and O11 suffer a decrease of 0.127, 0.086 and 0.077 units, with respect to undecyl-amido-propyl-hydroxysultaine (alkyl amido propyl hydroxysultaine) 7; this significant change in Mulliken atomic charges confirms that in supramolecular complex 8, the sodium atom Na2 is coordinated with the oxygen atoms O2, O3 and O11 and encapsulated between the two molecules of undecyl-amido-propyl-hydroxysultaine (alkyl amido hydroxysultaine) 7 and the sodium hydroxy-tetradecyl-1-sulfonate molecule (sodium alkyl hydroxy sulfonate) 6. In addition, the results in Table 7 confirm that a nanocavity is present in the supramolecular complex 8, which can act as the gas receptor and generating the inclusion complexes which must act as foaming agents in an aqueous medium. Example 3
[0091] By means of computational chemistry, and using the semi-empirical method MNDO/d as the theoretical level, the geometries of the compounds trans-dodec-2-en-1- sodium sulfonate (sodium alkenyl sulfonate) 9, 3- sodium hydroxy-dodecyl sulfonate 10 (sodium alkyl hydroxy sulfonate) and pentyl amido propyl hydroxysultaine (alkyl amido hydroxysultaine) 11, as well as the geometry of the supramolecular complex resulting from the interaction of the three aforementioned compounds were optimized in the gas phase in the relationships molecular 1:1:1 12 (8).
[0092] The energetic results, the most relevant binding distances and the main Mulliken atomic charges for said complexes and the corresponding supramolecular complex are shown in tables 8, 9 and 10, respectively.
[0093] The analysis of the results in Table 8 shows that the formation of the supramolecular complex 12 from the 1:1:1 molecular interaction of compounds 9, 10 and 11 should be strongly favored from a thermodynamic point of view. Additionally, the -201.987 kJ/mol interaction energy indicates that supramolecular ion-ion interactions and/or a combination of ion-bipolar interactions and hydrogen bonds must be present. Table 7. Main Mulliken atomic charges in compounds 5, 6, 7 and supramolecular complex 8

Table 8. Energy of compounds 9, 10 and 11 and of supramolecular complex 12 obtained with the semi-empirical method MNDO/d

[0094] Where:
[0095] 9 = sodium trans-dodec-2-en-1-sulfonate
[0096] 10 = sodium 3-hydroxy-dodecyl-1-sulfonate
[0097] 11 = pentyl-amido-propyl-hydroxysultaine
[0098] 12 = Supramolecular complex resulting from the interaction of sodium trans-dodec-2-en-1-sulfonate, sodium 3-hydroxy-dodecyl-1-sulfonate and pentyl-amido-propyl-hydroxysultaine in a molecular relationship 1 :1:1. Table 9. Main binding distances in compounds 9, 10, 11 and supramolecular complex 12

[0099] The analysis of the results in Table 9 shows that the distances 2.414, 2.377 and 2.163 A for the interactions O1^Na2, O2-Na2 and O3-Na1 are smaller than the sum of the Van der Waals Rays for oxygen (Rays Van der Waals of 1.52 A) and sodium atoms (2.27 A Van der Waals rays) and are typical of structures containing Na-O coordination bonds and sulfonate groups (Crystal Growt & Design 2006, 6[ 2], 514-518). Additionally, the supramolecular complex 12 shows that sodium atoms have been encapsulated and therefore new foaming agents must be tolerant to brines containing high amounts of divalent ions and at high temperatures, in addition to the fact that in order to generate nanocavities, a dimerization process of the supramolecular complex 12 should be required.
[0100] The analysis of the results in Table 10 shows that the Mulliken atomic charge on the sodium atom Na1 of the supramolecular complex 12 is reduced by 0.019 units with respect to the charge that this atom has on trans-dodec-2-en- 1- sodium sulphonate (sodium alkenyl sulphonate) compound 9, while the atomic charge of the oxygen atom O3 undergoes a decrease of 0.073 units, with respect to pentyl-amido-propyl-hydroxysultaine (alkyl amido hydroxysultaine) 11; this significant change in Mulliken atomic charges confirms that in supramolecular complex 12, the sodium atom Na1 is coordinated with the oxygen atom O3. Additionally, the results in Table 10 show that the Mulliken atomic charge on the sodium atom Na2 of supramolecular complex 12 is reduced by 0.152 units with respect to the charge this atom has on sodium 3-hydroxy-dodecyl-1-sulfonate (sodium hydroxy alkyl sulfonate) compound 10, while the atomic charges of oxygen atoms O1 and O2 undergo a decrease of 0.092 and 0.144 units, with respect to pentyl-amido-propyl-hydroxysultaine (alkyl amido propyl hydroxysultaine) 11 ; this significant change in Mulliken atomic charges confirms that in supramolecular complex 8, the sodium atom Na2 is coordinated with the oxygen atoms O1 and O2. Furthermore, the supramolecular complex 12 confirms the fact that in order to generate nanocavities, a dimerization process of the same supramolecular complex 12 must be required. Table 10. Main Mulliken atomic charges in compounds 9, 10, 11 and supramolecular complex 12
Example 4
[0101] By means of computational chemistry, and using the semi-empirical method MNDO/d as the theoretical level, the geometries of the compounds trans-dodec-1-en-1-sodium sulfonate (sodium alkenyl sulfonate) 13, 3- sodium hydroxy-dodecyl-1-sulfonate (sodium alkyl hydroxy sulfonate) 14 and pentyl amido propyl hydroxysultaine (alkyl amido hydroxysultaine) 15, as well as the geometry of the supramolecular complex resulting from the interaction of the three aforementioned compounds were optimized in the gas phase in the 1:1:2 molecular ratios 16 (9).

[0102] The energetic results, the most relevant binding distances and the main Mulliken atomic charges for said complexes and the corresponding supramolecular complex are shown in tables 11, 12, and 13, respectively. Table 11. Energy of compounds 13, 14 and 15 and of supramolecular complex 16 obtained with the semi-empirical method MNDO/d


[0103] Where:
[0104] 13 = sodium trans-dodec-1-en-1-sulfonate
[0105] 14 = sodium 3-hydroxy-dodecyl-1-sulfonate
[0106] 15 = pentyl-amido-propyl-hydroxysultaine
[0107] 16 = Supramolecular complex resulting from the interaction of sodium trans-dodec-1-en-1-sulfonate, sodium 3-hydroxy-dodecyl-1-sulfonate and pentyl-amido-propyl-hydroxysultaine in a molecular relationship 1 :1:2.
[0108] The analysis of the results in Table 11 shows that the formation of the supramolecular complex 16 from the 1:1:2 molecular interaction of compounds 13, 14 and 15 should be strongly favored from a thermodynamic point of view. Additionally, the interaction energy -299,323 kJ/mol indicates that supramolecular ion-ion interactions and/or a combination of ion-bipolar interactions and hydrogen bonds must be present.
[0109] The analysis of the results in Table 12 shows that the distances 2.247, 2.235, 2.214 and 2.178 A for the interactions O1-Na1, O3-Na2, O11-Na2 and O12--Na1 are smaller than the sum of the Van Rays der Waals for oxygen (1.52 A Van der Waals rays) and sodium atoms (2.27 A Van der Waals rays) and are typical of structures containing Na-O coordination bonds and sulfonate groups (Crystal Growt & Design 2006, 6[2], 514-518). Table 12. Main binding distances in compounds 13, 14, 15 and supramolecular complex 16

[0110] Additionally, the supramolecular complex 16 reveals the presence of a nanocavity, which can act as the gas receptor and generate the inclusion complexes that should act as foaming agents in an aqueous medium. Additionally, said complex 16 shows that sodium atoms have been encapsulated, whereby new foaming agents must be tolerant to brines containing large amounts of divalent ions and at high temperatures. Analysis of the results in Table 4 shows that the Mulliken atomic charge on the sodium atom Na1 of the supramolecular complex 16 is reduced by 0.309 units with respect to the charge this atom has on the trans-dodec-1-en-1-sulfonate of sodium (sodium alkenyl sulfonate) compound 13, while the atomic charges of oxygen atoms O1 and O12 undergo a decrease of 0.067 and 0.100 units, with respect to pentyl amido propyl hydroxysultaine (alkyl amido hydroxysultaine) 15; this significant change in Mulliken atomic charges confirms that in supramolecular complex 16, the sodium atom Na1 is coordinated with the oxygen atoms O1 and O12 and encapsulated between the two molecules of pentyl amido propyl hydroxysultaine (alkyl amido hydroxysultaine) 15 and the molecule of trans-dodec-1-en-1-sodium sulfonate (sodium alkenyl sulfonate) 13. In addition, the results in Table 13 show that the Mulliken atomic charge on the sodium atom Na2 of the supramolecular complex 16 is reduced by 0.221 units with respect to the charge that this atom has on sodium 3-hydroxy-dodecyl-1-sulfonate (sodium alkyl hydroxy sulfonate) compound 14, while the atomic charges of oxygen atoms O3 and O11 undergo a decrease of 0.158 and 0.051 units, with respect to pentyl amido propyl hydroxysultaine (alkyl amido propyl hydroxysultaine) 15; this significant change in Mulliken atomic charges confirms that in supramolecular complex 16, the sodium atom Na2 is coordinated with oxygen atoms O3 and O11 and encapsulated between the two molecules of pentyl-starch-propyl-hydroxysultaine (alkyl amido hydroxysultaine) 15 and the sodium 3-hydroxy-dodecyl-1-sulfonate molecule (sodium alkyl hydroxy sulfonate) 14. In addition, the results in Table 13 confirm the presence of a nanocavity in the supramolecular complex 16, which can act as the gas receptor and generating the inclusion complexes which must act as foaming agents in an aqueous medium. Table 13. Mulliken atomic charges of compounds 13, 14, 15 and supramolecular complex 16
Example 5
[0111] By means of computational chemistry, and using the semi-empirical method MNDO/d as the theoretical level, the geometry of trans-dodec-1-en-1-sodium sulfonate (sodium alkenyl sulfonate) compounds 17, 2- sodium hydroxy-dodecyl-1-sulfonate (sodium alkyl hydroxy sulfonate) 18 and pentyl amido propyl hydroxysultaine (alkyl amido hydroxysultaine) 19, as well as the geometry of the supramolecular complex that results from the interaction of the three aforementioned compounds, were optimized in the phase gas at the molecular ratios 1:1:2 20 (10).

[0112] The energetic results, the most relevant binding distances and the main Mulliken atomic charges for said complexes and the corresponding supramolecular complex are shown in tables 14, 15 and 16, respectively.
[0113] The analysis of the results in Table 14 shows that the formation of the supramolecular complex 20 from the 1:1:2 molecular interaction of compounds 17, 18 and 19 should be strongly favored from a thermodynamic point of view. Additionally, the interaction energy -291.521 kJ/mol indicates that supramolecular ion-ion interactions and/or a combination of ion-bipolar interactions and hydrogen bonds must be present. Table 14. Energy of compounds 17, 18 and 19 and of the supramolecular complex 20 obtained with the semi-empirical method MNDO/d

[0114] Where:
[0115] 17 = sodium trans-dodec-1-en-1-sulfonate
[0116] 18 = sodium 2-hydroxy-dodecyl-1-sulfonate
[0117] 19 = pentyl-amido-propyl-hydroxysultaine
[0118] 20 = Supramolecular complex resulting from the interaction of sodium trans-dodec-1-en-1-sulfonate, sodium 2-hydroxy-dodecyl-1-sulfonate and pentyl-amido-propyl-hydroxysultaine in a molecular relationship 1 :1:2.
[0119] The analysis of the results of Tables 15 and 16 indicates that the supramolecular complex 20 has a nanocavity and that the sodium atoms were encapsulated and, therefore, can act as the gas receptor and generate the inclusion complexes that, in the medium aqueous, should act as foaming agents tolerant to brines containing large amounts of divalent ions and at high temperatures. Example 6
[0120] By means of computational chemistry, and using the semi-empirical method MNDO/d as the theoretical level, the geometries of trans-dodec-1-en-1-sodium sulfonate (sodium alkenyl sulfonate) compounds 21, 2- sodium hydroxy-dodecyl-1-sulfonate (sodium alkyl hydroxy sulfonate) 22 and decyl hydroxysulfaine (alkyl amido hydroxysulfaine) 23, as well as the geometry of the supramolecular complex that results from the interaction of the three aforementioned compounds were optimized in the gas phase in the relationships molecular 1:1:2 24 (11). Table 15. Main binding distances in compounds 17, 18, 19 and supramolecular complex 20
Table 16. Mulliken atomic charges of compounds 17, 18, 19 and supramolecular complex 20


[0121] The energetic results, the most relevant binding distances and the main Mulliken atomic charges for said complexes, as well as the corresponding supramolecular complex are shown in tables 17, 18 and 19, respectively. Table 17. Energy of compounds 21, 22, 23 and supramolecular complex 24 obtained with the semi-empirical method MNDO/d

[0122] Where:
[0123] 21 = trans-dodec-1-en-1-sodium sulfonate
[0124] 22 = sodium 2-hydroxy-dodecyl-1-sulfonate
[0125] 23 = decylhydroxysultaine
[0126] 24 = Supramolecular complex resulting from the interaction of trans-dodec-1-en-1-sulfonate sodium, 2-hydroxy-dodecyl-1-sulfonate sodium and decyl-hydroxysultaine in a 1:1:2 molecular ratio .
[0127] The analysis of the results in Table 17 shows that the formation of the supramolecular complex 24 from the 1:1:2 molecular interaction of compounds 21, 22 and 23 should be strongly favored from a thermodynamic point of view. Additionally, the -280.811 kJ/mol energy of interaction indicates that supramolecular ion-ion interactions and/or a combination of ion-bipolar interactions and hydrogen bonds must be present.
[0128] The analysis of the results of Tables 18 and 19 indicates that the supramolecular complex 24 has a nanocavity and that the sodium atoms were encapsulated and, therefore, can act as the gas receptor and generate the inclusion complexes that, in the medium aqueous, should act as foaming agents tolerant to brines containing large amounts of divalent ions and at high temperatures.
[0129] As demonstrated through computational chemistry that the process of self-preparation of alkyl starch propyl hydroxysultaines or alkyl hydroxysultaines with sodium alkyl hydroxy sulphonates and sodium alkenyl sulphonates is thermodynamically favored and generates supramolecular complexes that present nanocavities, through from molecular simulation, the ability of these nanocavities to act as receptors for gases that are used around the world to generate foams with application in improved recovery and/or mobility control processes was then determined, and the results obtained in the methane cases , propane, nitrogen and carbon dioxide are as follows: Example 7
[0130] By means of computational chemistry, and using the semi-empirical method MNDO/d as a theoretical level, the geometry of the molecular complex that results from the interaction of trans-non-2-en-1-sulfonate sodium (alkenyl sulfonate) sodium) 25, sodium 3-hydroxy-hexyl-1-sulfonate 26 (sodium alkyl hydroxy sulfonate) and ethyl starch propyl hydroxysulfaine (alkyl starch hydroxysulfaine) 27 was optimized in the gas phase at the molecular ratios 1:1:2 28, as were the geometry of methane 29 and the geometry of the inclusion complex 30 generated by the interaction of the complex 28 with methane 29 (12), and the energy results obtained from the inclusion process (13) are shown in table 20.
[0131] The analysis of the results in Table 20 shows that the formation of the supramolecular complex 30 through the interaction of nanocavity 28 with methane 29 should be favored from a thermodynamic point of view. Additionally, the interaction energy -5.814 kJ/mol indicates that supramolecular Van der Waals-type interactions must be present and therefore the supramolecular complex 28 can be used as a foaming agent to control fluid channeling problems in the reservoirs where methane is used as a gas to generate foam. Table 18. Main binding distances in compounds 21, 22, 23 and supramolecular complex 24

* Hydrogen atoms have been removed for better visualization Table 19. Mulliken atomic charges of compounds 21, 22, 23 and supramocular complex 24


Table 20. Energies of supramolecular complex 28, compound 29 and inclusion complex 30 obtained with the semi-empirical method MNDO/d

[0132] Where:
[0133] 28 = Supramolecular complex resulting from the interaction of sodium trans-non-2-en-1-sulfonate, sodium 3-hydroxy-hexyl-1-sulfonate and ethyl-amido-propyl-hydroxysultaine in a molecular relationship 1 :1:2.
[0134] 29 = methane
[0135] 30 = Inclusion complex that results from the interaction of the supramolecular complex 28 with methane 29. Example 8
[0136] By means of computational chemistry, and using the semi-empirical method MNDO/d as a theoretical level, the geometry of the molecular complex that results from the interaction of trans-non-2-en-1-sulfonate sodium (alkenyl sulfonate) sodium) 25, sodium 3-hydroxy-hexyl-1-sulfonate 26 (sodium alkyl hydroxy sulfonate) and ethyl starch propyl hydroxysulfaine (alkyl starch hydroxysulfaine) 27 was optimized in the gas phase at the molecular ratios 1:1:2 28, as were the geometry of carbon dioxide 31 and the geometry of the inclusion complex 32 generated by the interaction of the complex 28 with carbon dioxide 31 (14), and the energy results obtained for the inclusion process (15) are shown in table 21 .
[0137] The analysis of the results in Table 21 shows that the formation of inclusion complex 32 through the interaction of nanocavity 28 with carbon dioxide 31 should be favored from a thermodynamic point of view. Additionally, the interaction energy -4.952 kJ/mol indicates that supramolecular Van der Waals-type interactions must be present and therefore the supramolecular complex 28 can be used as the foaming agent to control fluid channeling problems in reservoirs where carbon dioxide is used as the gas to generate foam.
Table 21. Energies of supramolecular complex 28, compound 31 and inclusion complex 32 obtained with the semi-empirical method MNDO/d

[0138] Where:
[0139] 28 = Supramolecular complex resulting from the interaction of sodium trans-non-2-en-1-sulfonate, sodium 3-hydroxy-hexyl-1-sulfonate and ethyl-amido-propyl-hydroxysultaine in a molecular relationship 1 :1:2.
[0140] 31 = Carbon dioxide
[0141] 32 = Inclusion complex that results from the interaction of the supramolecular complex 28 with carbon dioxide 31. Example 9
[0142] By means of computational chemistry, and using the semi-empirical method MNDO/d as a theoretical level, the geometry of the molecular complex that results from the interaction of trans-non-2-en-1-sulfonate sodium (alkenyl sulfonate) sodium) 25, sodium 3-hydroxy-hexyl-1-sulfonate 26 (sodium alkyl hydroxy sulfonate) and ethyl starch propyl hydroxysulfaine (alkyl starch hydroxysulfaine) 27 was optimized in the gas phase at the molecular ratios 1:1:2 28, how were the geometry of nitrogen 33 and the geometry of the inclusion complex 34 generated by the interaction of the complex 28 with nitrogen 33 (16), and the energy results obtained for the inclusion process (17) are shown in table 22.
[0143] The analysis of the results of Table 22 shows that the formation of the inclusion complex 34 from the interaction of the nanocavity 28 with nitrogen 31 should be favored from a thermodynamic point of view. Additionally, the interaction energy -3.827 kJ/mol indicates that supramolecular Van der Waals-type interactions must be present and therefore the supramolecular complex 28 can be used as a foaming agent to control fluid channeling problems in the reservoirs where nitrogen is used as the gas to generate foam.
Table 22. Energies of supramolecular complex 28, compound 33 and inclusion complex 34 obtained with the semi-empirical method MNDO/d


[0144] Where:
[0145] 28 = Supramolecular complex resulting from the interaction of sodium trans-non-2-en-1-sulfonate, sodium 3-hydroxy-hexyl-1-sulfonate and ethyl-amido-propyl-hydroxysultaine in a molecular relationship 1 :1:2.
[0146] 33 = Nitrogen
[0147] 34 = Inclusion complex that results from the interaction of the supramolecular complex 28 with nitrogen 33. Example 10
[0148] By means of computational chemistry, and using the semi-empirical method MNDO/d as a theoretical level, the geometry of the molecular complex that results from the interaction of trans-non-2-en-1-sulfonate sodium (alkenyl sulfonate) sodium) 25, sodium 3-hydroxy-hexyl-1-sulfonate 26 (sodium alkyl hydroxy sulfonate) and ethyl-amido-propyl-hydroxysulfaine (alkyl starch hydroxysulfaine) 27 was optimized in the gas phase in the molecular ratios 1:1: 2 28, as were the n-propane 35 geometry and the inclusion complex 36 geometry generated by the interaction of the 28 complex with n-propane 35 (18), and the energy results obtained for the inclusion process (19) are shown in table 23.
[0149] The analysis of the results in Table 23 shows that the formation of the inclusion complex 36 through the interaction of nanocavity 28 with n-propane 35 should be favored from a thermodynamic point of view. Additionally, the interaction energy -12.172 kJ/mol indicates that supramolecular Van der Waals-type interactions must be present and that, therefore, the supramolecular complex 28 can be used as a foaming agent to control fluid channeling problems. in reservoirs where n-propane is used as the gas to generate foam.
Table 23. Energies of supramolecular complex 28, compound 35 and inclusion complex 36 obtained with the semi-empirical method MNDO/d

[0150] Where:
[0151] 28 = Supramolecular complex resulting from the interaction of sodium trans-non-2-en-1-sulfonate, sodium 3-hydroxy-hexyl-1-sulfonate and ethyl-amido-propyl-hydroxysultaine in a molecular relationship 1 :1:2.
[0152] 35 = n-propane
[0153] 36 = Inclusion complex that results from the interaction of the supramolecular complex 28 with n-propane 35.
[0154] As demonstrated through computational chemistry that the process of self-preparation of alkyl starch propyl hydroxysultaines or alkyl hydroxysultaines with sodium alkyl hydroxy sulphonate and sodium alkenyl sulphonate is thermodynamically favored and generates supramolecular complexes with nanocavities capable of acting as gas receptors that are used around the world to generate foams with application in accentuated recovery and/or mobility control processes, using molecular simulation, the ability of said supramolecular complexes to sequester divalent ions such as calcium, magnesium, strontium or barium was determined, with the following results obtained for calcium chloride: Example 11
[0155] Through computational chemistry, and using quantum methods that employ the Density Functional Theory and the functional LDA-VWN, in a medium subjected to solvate in water (dielectric constant 78.54), the geometry of the supramolecular complex that results from interaction of the compounds sodium trans-non-2-en-1-sulfonate (sodium alkenyl sulfonate) 25, sodium 3-hydroxy-hexyl-1-sulfonate 26 (sodium alkyl hydroxy sulfonate) and ethyl amido propyl hydroxysultaine (alkyl starch hydroxysultaine) 27 was optimized in 1:1:1 37 molecular ratios, as were the geometry of CaCl2 38 and the geometry of the supramolecular complex 39 generated by the interaction of 2 units of supramolecular complex 37 with CaCl2 38 (20) and the results energy sources obtained for the CaCl2 sequestration process 38 (21) are shown in table 24.
Table 24. Energies of supramolecular complex 37, compound 38 and compound derived from the CaCl2 sequestration process 39 obtained with Density Functional Theory and functional LDA-VWN in a medium subjected to water solvate

[0156] Where:
[0157] 37 = Supramolecular complex resulting from the interaction of sodium trans-non-2-en-1-sulfonate, sodium 3-hydroxy-hexyl-1-sulfonate and ethyl-amido-propyl-hydroxysultaine in a molecular relationship 1 :1:1.
[0158] 38 = Calcium chloride
[0159] 39 = Supramolecular complex generated by the interaction of 2 units of supramolecular complex 37 with CaCl2.
[0160] The analysis of the results in Table 24 shows that the formation of the supramolecular complex 39 by the interaction of two units of supramolecular complex 37 with calcium chloride 38 should be favored from a thermodynamic point of view. Additionally, the interaction energy -173.212 kJ/mol indicates that in the calcium ion sequestration process through the supramolecular complex 37, the supramolecular ion-dipolar interactions must be present and thus, in an aqueous medium, the molecular weight of supramolecular complex 37 should increase as a function of the concentration of divalent ions present in the solution. This aspect is relevant in accentuated recovery processes where the use of surfactants and brines with high contents of divalent ions is planned in order to increase the recovery factor, since with supramolecular complex 37 the brine viscosity can be significantly increased, reducing thus displacement fluid mobility and thus generate a greater volumetric hydrocarbon sweep. Example 12
[0161] Through computational chemistry, and using quantum methods that employ the Density Functional Theory and the functional GGA-PBE, in a medium subjected to solvate in water (dielectric constant 78.54), the geometry of the supramolecular complex that results from interaction of the compounds sodium trans-non-2-en-1-sulfonate (sodium alkenyl sulfonate) 25, sodium 3-hydroxy-hexyl-1-sulfonate 26 (sodium alkyl hydroxy sulfonate) and ethyl amido propyl hydroxysultaine (alkyl starch hydroxysultaine) 27 was optimized in molecular ratios 1:1:2 28, as were the geometry of CaCl2 38 and the geometry of the supramolecular complex 40 generated by the interaction of 2 units of supramolecular complex (nanocaviti) 28 with CaCl2 38 (22) and the energetic results obtained for the CaCl2 sequestration process 38 (23) are shown in table 25.
[0162] The analysis of the results in Table 25 shows that the formation of the supramolecular complex 40 through the interaction of two units of supramolecular complex 28 with calcium chloride 38 should be favored from a thermodynamic point of view. Additionally, the interaction energy -278,010 kJ/mol indicates that in the calcium ion sequestration process through the supramolecular complex 28, the supramolecular ion-dipolar interactions must be present and, therefore, in an aqueous medium, the molecular weight of the supramolecular complex 28 should increase as a function of the concentration of divalent ions present in the solution.
Table 25. Energies of supramolecular complex 28, compound 38 and complex derived from the CaCl2 sequestration process 40 obtained with Density Functional Theory and functional GGA-PBE in a medium subjected to water solvate

[0163] Where:
[0164] 28 = Supramolecular complex resulting from the interaction of sodium trans-non-2-en-1-sulfonate, sodium 3-hydroxy-hexyl-1-sulfonate and ethyl-amido-propyl-hydroxysultaine in a molecular relationship 1 :1:1.
[0165] 38 = Calcium chloride.
[0166] 40 = Supramolecular complex generated by the interaction of 2 units of supramolecular complex 28 with CaCl2.
[0167] As demonstrated through computational chemistry that the supramolecular complexes that result from the process of self-preparation of alkyl amido propyl hydroxysultaines or alkyl hydroxysultaines with sodium alkyl hydroxysulphonates and sodium alkenyl sulphonates have the ability to sequester divalent ions, such as calcium, and that this aspect affects through the increase of its molecular weight as a function of the concentration of divalent ions present in the solution, through molecular simulation, the capacity of said molecular complexes to change the wetting capacity of carbonate rocks such how limestone and dolomite was later determined. For this purpose, the fact that polar organic compounds present in heavy organic hydrocarbon fractions, such as asphaltenes and resins, are responsible for carbonate rocks being oil-wetting is considered (International-Mexican Congress on Chemical Reaction Engineering; Ixtapa- Zihuatanejo, Guerrero, Mexico, June 10-15, 2012, 162-163; Abstract: Theoretical and Experimental Study of Ion-Dipole Pair Formation and its Impact on Spontaneous Water Imbibition Processes in Fractured Carbonate Reservoirs) and that in order to that capacity The humectant of the rock is altered, it is necessary that, thermodynamically, the supramolecular complexes object to this invention by removing said fractions from the rock surface. Additionally, to represent asphaltenes or resins, average molecular structure models that globally represent their physicochemical properties are used (Energy & Fuels, 2000, 14, 6-10, Asphaltenes: Structural Characterization, Self-Association, and Stability Behavior; García-Martínez; J.; Maestry Thesis 2004; An Approximation to the Molecular Structure of Asphaltenes Separated from Mexican Crude Acceptances; Faculty of Superior Studies Cuautitlán de la Universidad Nacional Autónoma de Mexico; Mexico. Example 13
[0168] Through computational chemistry, and using quantum methods that employ the Density Functional Theory and the functional LDA-VWN, in a medium subjected to solvate in water (dielectric constant 78.54), the geometry of the supramolecular complex that results from interaction of trans-dodec-2-en-1-sulfonate sodium (sodium alkenyl sulfonate) 41, sodium 3-hydroxy-dodecyl-1-sulfonate 42 (sodium alkyl hydroxysulfonate) and undecyl amido propyl hydroxysultaine (alkyl starch) hydroxysultaine) 43 was optimized at 1:1:1 molecular ratios 44, as were the geometry of the calcite surface (CaCO3) 45 and the adsorption product 46 geometry generated by the interaction of the supramolecular complex 44 with the calcite surface (CaCO3 ) 45 (24) and the energetic results obtained for the adsorption process of the supramolecular complex 44 on the calcite surface (CaCO3) 45 (25) are shown in table 26.
[0169] The analysis of the results of Table 26 shows that the adsorption process of the supramolecular complex 44 on the surface of calcite (CaCO3) 45 is favored from the thermodynamic point of view.
Table 26. Energetic results obtained for the adsorption process of the supramolecular complex 44 on the calcite surface (CaCO3)45 obtained with Density Functional Theory and functional LDA-VWN in a medium subjected to water solvate

[0170] Where:
[0171] 44 = Supramolecular complex resulting from the interaction of sodium trans-dodec-2-en-1-sulfonate, sodium 3-hydroxy-dodecyl-1-sulfonate and undecyl-amido-propyl-hydroxysultaine in a molecular relationship 1 :1:1.
[0172] 45 = Surface of calcite (CaCO3).
[0173] 46 = Adsorption product generated by the interaction of the supramolecular complex 44 with the surface of calcite (CaCO3) 45. Example 14
[0174] Through computational chemistry, and using quantum methods that employ the Density Functional Theory and the functional LDA-VWN, the geometry of an asphaltene molecular structure model that represents the characteristics of a heavy oil from the Sea Region in Mexico ( García-Martínez; J.; Maestria Thesis 2004; An Approximation to the Molecular Structure of Asphaltenes Separated from Mexican Crude Acceptances; Faculty of Superior Studies Cuautitlán de la Universidad Nacional Autónoma de Mexico; Mexico 47, the geometry of the calcite surface (CaCO3) 45 and the geometry of the adsorption product 48 generated by the interaction of the molecular structure model of asphaltene 47 with the surface of calcite (CaCO3) 45 (26) were optimized in a medium subjected to water solvation (dielectric constant 78 .54), and the energetic results obtained for the adsorption process of the molecular structure model of asphaltene 47 on the calcite structure (CaCO3) 45 (27) are shown in table 27
Table 27. Energetic results for the adsorption process of an asphaltene 47 molecular surface model on the calcite surface (CaCO3)45 obtained with Density Functional Theory and functional LDA-VWN in a medium subjected to water solvate

[0175] Where:
[0176] 45 = Surface of calcite (CaCO3).
[0177] 47 = Molecular structure model of asphaltene representing the characteristics of a heavy oil from the Sea Region in Mexico.
[0178] 48 = Adsorption product generated by the interaction of the molecular structure model of asphaltene 47 with the surface of calcite (CaCO3)45.
[0179] The analysis of the results of Table 27 shows that the adsorption process of molecular structure model of asphaltene 47 on the surface of calcite (CaCO3) 45 is favored from the thermodynamic point of view. Example 15
[0180] Through computational chemistry, and using quantum methods that employ the Density Functional Theory and the functional LDA-VWN, the water geometry 49, the calcite surface geometry (CaCO3) 45 and the adsorption product geometry 50 generated by the interaction of water 49 with the surface of calcite (CaCO3) 45 (28) were optimized in a medium subjected to solvate in water (dielectric constant 78.54), and the energy results obtained for the water adsorption process 49 on the surface of calcite (CaCO3)45 (29) are shown in table 28.

Table 28. Energy results for the water adsorption process 49 on the calcite surface (CaCO3)45 obtained with Density Functional Theory and functional LDA-VWN in a medium subjected to water solvate

[0181] Where:
[0182] 45 = Surface of calcite (CaCO3).
[0183] 49 = Molecular structure of water
[0184] 50 = Adsorption product generated by the interaction of water 49 with the calcite surface (CaCO3)45.
[0185] The analysis of the results of Table 28 shows that the water adsorption process 49 on the surface of calcite (CaCO3) 45 is favored from the thermodynamic point of view.
[0186] A comparison of adsorption results obtained through molecular simulation in the cases of supramolecular complex 44, the molecular structure model of asphaltene that represents the characteristics of a heavy oil from Sea Region in Mexico 47 and water 49 on the surfaces of calcite (CaCO3) 45 indicates that, thermodynamically, the supramolecular complex 44 must remove asphaltene 47 from the surface of calcite (CaCO3) 45 and thus would have the ability to change the wetting capacity of the rock; additionally, observations also reveal that asphaltene 47 would have the ability to remove water 49 from the surface of calcite (CaCO3) 45 and this fact is consistent with the existing theory in the oil industry, which initially in the porous medium (carbonate rock ) there was water and that it was removed by hydrocarbon over the years due to thermodynamic processes.
[0187] As demonstrated through computational chemistry that the supramolecular complexes that result from the process of self-preparation of alkyl amido propyl hydroxysultaines or alkyl hydroxysultaines with sodium alkyl hydroxysulphonates and sodium alkenyl sulphonates have the ability to change the wetting power of rock from oil humectant to water humectant, through molecular simulation, the ability of said molecular complexes to reduce the viscosity of heavy hydrocarbons with high contents of asphaltenes was then determined. For this purpose, the fact is considered that in order to reduce the viscosity of these hydrocarbons, it is necessary to weaken the supramolecular interactions responsible for the aggregation of asphaltenes and for this it is required that the viscosity reducers form with them a guest-host complex, in that the guest is the viscosity reducer and the host is the asphaltenes. The results obtained in the case of supramolecular complex 44 are as follows: Example 16
[0188] Through computational chemistry, and using quantum methods that employ the Density Functional Theory and the functional LDA-VWN, the geometry of the supramolecular complex that results from the interaction of trans-dodec-2-en-1-sodium sulfonate compounds (sodium alkenyl sulfonate) 41, sodium 3-hydroxy-dodecyl-1-sulfonate 42 (sodium alkyl hydroxysulfonate) and undecyl starch propyl hydroxysulfaine (alkyl starch hydroxysulfaine) 43 was optimized in a medium subjected to solvate in water (dielectric constant 78,54) in molecular ratios 1:1:1 44, as were the geometry of a dimer that results from the interaction of two molecular structures of an asphaltene model that represents the characteristics of a heavy oil from Sea Region in Mexico 51 and the geometry of the host-guest complex 52 generated by the interaction of the supramolecular complex 44 with dimer of asphaltene 51 (30), and the energetic results obtained by the process of formation of the host-guest complex 52 (31) are shown in table 29.
[0189] The analysis of the results in Table 29 shows that the process of formation of the host-guest complex 52 is favored from the thermodynamic point of view and, therefore, it is possible that the supramolecular complex 44 can be used as a viscosity reducer in heavy crude oils.

Table 29. Energetic results obtained with Density Functional Theory and functional LDA-VWN in a medium subjected to water solvation for the process of formation of the host-guest complex 52 through the interaction of the supramolecular complex 44 with the dimer of asphaltene 51

[0190] Where:
[0191] 44 = Supramolecular complex resulting from the interaction of sodium trans-dodec-2-en-1-sulfonate, sodium 3-hydroxy-dodecyl-1-sulfonate and undecyl-amido-propyl-hydroxysultaine in a molecular relationship 1 :1:1.
[0192] 51 = Interaction dimer of two molecular structure models of asphaltene representing the characteristics of a heavy oil from Sea Region in Mexico
[0193] 52 = Host-guest complex generated by the interaction of the supramolecular 44 complex with the asphaltene dimer51.
[0194] As demonstrated, through computational chemistry, that the supramolecular complexes that result from the process of self-preparation of alkyl amido propyl hydroxysultaines or alkyl hydroxysultaines with sodium alkyl hydroxysulphonates and sodium alkenyl sulphonates have the ability to generate foams, to alter the wetting capacity of the rock, and to reduce the viscosity of heavy crude oils, through molecular simulation, the capacity of said molecular complexes to act as corrosion inhibitors in typical environments that occur in the oil industry was then determined. For this purpose, the fact is considered that for a product to act as a corrosion inhibitor, it has to form a protective film on the metal surface that must be protected and that under the operating conditions present in the oil industry, the surfaces generated due to electrochemical processes and which must be protected against corrosion mainly consist of hematite and/or pyrite (Revista de la Sociedad Química de México 2002, 46[4], 335-340; Langmuir 1996, 12, 6419-6428) . The results obtained as a corrosion inhibitor for the supramolecular complex 56 which results from the interaction of trans-non-2-en-1-sulfonate sodium (sodium alkenyl sulfonate) 53, 3-hydroxy-hexyl-1-sulfonate sodium 54 (sodium alkyl hydroxysulfonate) and ethyl amido propyl hydroxysultaine (alkyl amido hydroxysultaine) 55 at 1:1:1 molecular ratios are as follows: Example 17
[0195] Through computational chemistry, and using quantum methods that employ the Density Functional Theory and the functional LDA-VWN, the geometry of the supramolecular complex that results from the interaction of trans-non-2-en-1-sodium sulfonate compounds (sodium alkenyl sulfonate) 53, sodium 3-hydroxy-hexyl-1-sulfonate 54 (sodium alkyl hydroxysulfonate) and ethyl starch propyl hydroxysulfaine (alkyl starch hydroxysulfaine) 55 was optimized in a medium subjected to solvate in water (dielectric constant 78.54) in molecular ratios 1:1:1 56, as was the hematite surface geometry (α-Fe2O3) 57 and the adsorption product 58 geometry generated by the interaction of the supramolecular complex 56 with the hematite surface ( α-Fe2O3) 57 (32), and the energetic results obtained for the adsorption process of the supramolecular complex 56 on the hematite surface (α-Fe2O3) 57 (33) are shown in table 30.
Table 30. Energetic results for the adsorption process of the supramolecular complex 56 on the surface of hematite (α-Fe2O3)57 obtained with Density Functional Theory and functional LDA-VWN in a medium subjected to water solvate

[0196] Where:
[0197] 56 = Supramolecular complex that results from the interaction of sodium trans-non-2-en-1-sulfonate, sodium 3-hydroxy-hexyl-1-sulfonate and ethyl amido propyl hydroxysultaine (alkyl amido hydroxysultaine) in the molecular relationships 1:1:1.
[0198] 57 = Surface of hematite (α-Fe2O3)
[0199] 58 = Adsorption product generated by the interaction of the supramolecular complex 56 with the surface of hematite (α-Fe2O3)57.
[0200] The analysis of the results in Table 30 shows that the adsorption process of the supramolecular complex 56 on the hematite surface (α-Fe2O3) 57 is favored from the thermodynamic point of view and, therefore, the formation of the protective film is spontaneous and supramolecular 56 can be used as the corrosion inhibitor in environments that are characteristic of the oil industry. Example 18
[0201] Through computational chemistry, and using quantum methods that employ the Density Functional Theory and the functional LDA-VWN, the geometry of the supramolecular complex that results from the interaction of trans-non-2-en-1-sodium sulfonate compounds (sodium alkenyl sulfonate) 53, sodium 3-hydroxy-hexyl-1-sulfonate 54 (sodium alkyl hydroxy sulfonate) and ethyl-amido-propyl-hydroxysultaine (alkyl amido-hydroxysultaine) 55 was optimized in a solvated medium in water (dielectric constant 78.54) at molecular ratios 1:1:1 56, as were the geometry of the pyrite surface (Fe2S) 59 and the geometry of the adsorption product 60 generated by the interaction of the supramolecular complex 56 with the surface of pyrite (Fe2S) 59 (34), and the energetic results obtained for the adsorption process of the supramolecular complex 56 on the surface of pyrite (Fe2S) 59 (35) are shown in table 31.

[0202] Table 31. Energetic results for the adsorption process of the supramolecular complex 56 on the surface of pyrite (Fe2S) 59 obtained with the Density Functional Theory and the functional LDA-VWN in a medium subjected to solvate in water

[0203] Where:
[0204] 56 = Supramolecular that results from the interaction of trans-non-2-en-1-sodium sulfonate, sodium 3-hydroxy-hexyl-1-sulfonate and ethyl amido propyl hydroxysultaine (alkyl amido hydroxysultaine) in the molecular relationships 1 :1:1.
[0205] 59 = Pyrite surface (Fe2S).
[0206] 60 = Adsorption product generated by the interaction of the supramolecular complex 56 with the pyrite surface (Fe2S) 59.
[0207] The analysis of the results of Table 31 shows that the adsorption process of the supramolecular complex 56 on the surface of pyrite (Fe2S) 59 is favored from the thermodynamic point of view and thus the formation of the protective film is spontaneous and the supramolecular complex 56 can be used as a corrosion inhibitor in environments that are characteristic of the oil industry.
[0208] A comparison of the adsorption results obtained by molecular simulation for the supramolecular complex 56 on the surfaces of hematite (α-Fe2O3) 57 and pyrite (Fe2S) 59 indicates that the protective film that the supramolecular complex 56 would form on the surface of hematite (α-Fe2O3) would be more stable than the film that must form on the surface of pyrite (Fe2S) 59 and that on both types of surfaces, the supramolecular complex 56 can be used as a corrosion inhibitor.
[0209] 2) SYNTHESIS OF SUPRAMOLECULAR COMPLEXES. The supramolecular complexes derived from the present invention are obtained according to the synthesis procedure (36) which consists of mixing sodium alkyl hydroxysulphonates, sodium alkenyl sulphonates with alkyl amido propyl hydroxysultaines or alkyl hydroxysultaines at room temperature and atmospheric pressure.
[0210] The molar ratio at which supramolecular complexes are formed is within the ranges of 1:1:7 to 7:7:1, respectively, with molar ratios within the range of 1:1:2 to 1:2:4 being preferred.
[0211] The formation of supramolecular complexes from sodium alkyl hydroxysulphonates, sodium alkenyl sulphonates with alkyl amido propyl hydroxysultaines or alkyl hydroxysultaines can be carried out with water, brine, alcohols or a mixture of water-alcohols, with the aqueous medium being preferable. The final concentration by weight of supramolecular complexes in the mixture may range from 0.1% to 50%, preferably within the range of 20% to 50%.

[0212] Sodium alkenyl sulfonates useful in the present invention include sodium but-2-en-1-sulfonate, sodium pent-2-en-1-sulfonate, sodium hex-2-en-1-sulfonate, sodium hept-2-en-1-sulfonate, sodium oct-2-en-1-sulfonate, sodium non-2-en-1-sulfonate, sodium dec-2-en-1-sulfonate, undec- sodium 2-en-1-sulfonate, sodium dodec-2-en-1-sulfonate, sodium tetradec-2-en-1-sulfonate, sodium hexadec-2-en-1-sulfonate and the mixture of two or more of these sodium alkenyl sulfonates. Sodium alkyl hydroxysulfonates useful in the present invention include sodium 3-hydroxybutane-1-sulfonate, sodium 3-hydroxypentane-1-sulfonate, sodium 3-hydroxyhexane-1-sulfonate, sodium 3-hydroxyheptane-1-sulfonate , sodium 3-hydroxyoctane-1-sulfonate, sodium 3-hydroxynonane-1-sulfonate, sodium 3-hydroxydecane-1-sulfonate, sodium 3-hydroxyundecane-1-sulfonate, sodium 3-hydroxydodecane-1-sulfonate , sodium 3-hydroxytetradecane-1-sulfonate, sodium 3-hydroxyexadecan-1-sulfonate, sodium 2-hydroxybutane-1-sulfonate, sodium 2-hydroxypentane-1-sulfonate, sodium 2-hydroxyhexane-1-sulfonate , sodium 2-hydroxyheptane-1-sulfonate, sodium 2-hydroxyoctane-1-sulfonate, sodium 2-hydroxynonane-1-sulfonate, sodium 2-hydroxydecane-1-sulfonate, sodium 2-hydroxyundecane-1-sulfonate , sodium 2-hydroxydodecane-1-sulfonate, sodium 2-hydroxytetradecane-1-sulfonate and sodium 2-hydroxyhexadecane-1-sulfonate and a mixture of two or more of these alkyl hydroxys sodium ulphonates. Alkyl amidopropylhydroxysultains useful in the present invention include ethylamidopropylhydroxysultaine, hydroxysultain, hydroxysultaine, hydroxysultaine, hydroxysultaine, hydroxysultaine, hydroxysultaine, hydroxysultaine hydroxysultaine, hydroxysultaine, nonhydroxysultaine, nonhydroxysultaine decylhydroxysultaine, undecylhydroxysultaine, dodecylhydroxysultaine, tetradecylhydroxysultaine, hexadecylhydroxysultaine, cocohydroxysultaine and mixtures of two or more of these alkylhydroxysultaines.
[0213] The following examples will serve to illustrate the synthesis of the molecular complexes object of the present invention. Example 19
[0214] In a 1000 ml two-necked round bottom flask provided with a magnetic stirrer and a thermometer, 160.6 g of distilled water, 250.0 g of an aqueous solution containing 43.5% by weight (0.278 mol ) of coco-amido-propyl-hydroxysultaine were mixed at room temperature and atmospheric pressure under vigorous stirring with 81.0 g of an aqueous solution containing 47.8% by weight of a mixture of sodium 3-hydroxydodecane-1-sulfonate and sodium dodec-2-en-1-sulfonate, and which is characterized by having 47.4% by weight (0.0636 mol) of sodium 3-hydroxydodecane-1-sulfonate and 52.6% by weight (0. 0753 mol) of sodium dodec-2-en-1-sulfonate. The mixture is vigorously stirred for 8 hours to produce 490.7 g of an amber colored viscous liquid containing 30% by weight of the supramolecular complexes which are characterized by having as the basic structural formula that indicated in (36) and where the R1 corresponds to the 2-hydroxyundecyl radical, R2 corresponds to the coco-amido-propyl radical and R3 corresponds to the dodec-2-enyl radical. Example 20
[0215] In a 1000 ml two-necked round bottom flask provided with a magnetic stirrer and a thermometer, 165.3 g of distilled water, 198 g of an aqueous solution containing 43.5% by weight (0.220 mol) of coco-amido-propyl-hydroxysultaine were mixed at room temperature and atmospheric pressure under vigorous stirring with 128.5 g of an aqueous solution containing 47.8% by weight of a mixture of sodium 3-hydroxydodecane-1-sulfonate and dodec- sodium 2-en-1-sulfonate, and which is characterized in that it contains 47.4% by weight (0.100 mol) of sodium 3-hydroxydodecane-1-sulfonate and 52.6% by weight (0.120 mol) of dodec- sodium 2-en-1-sulfonate. The mixture is vigorously stirred for 8 hours to produce 490.4 g of an amber colored viscous liquid containing 30% by weight of supramolecular complexes which are characterized by having as the basic structural formula that indicated in (36) and wherein R1 corresponds to the 2-hydroxyundecyl radical, R2 corresponds to the coco-amido-propyl radical and R3 corresponds to the dodec-2-enyl radical. Example 21
[0216] In a 1000 ml two-necked round bottom flask provided with a magnetic stirrer and a thermometer, 224.1 g of distilled water, 250 g of an aqueous solution containing 49% by weight (0.380 mol) of dodecyl- hydroxysultaine were mixed at room temperature and atmospheric pressure under vigorous stirring with 110.9 g of an aqueous solution containing 47.8% by weight of a mixture of sodium 3-hydroxydodecane-1-sulfonate and dodec-2-en-1- sodium sulfonate, and which is characterized in that it contains 47.4% by weight (0.087 mol) of sodium 3-hydroxydodecane-1-sulfonate and 52.6% by weight (0.100 mol) of dodec-2-en-1- sodium sulphonate. The mixture is vigorously stirred for 8 hours to produce 584.8 g of an amber colored viscous liquid containing 30% by weight of the supramolecular complexes which are characterized by having as the basic structural formula that indicated in (36) and wherein R1 corresponds to the 2-hydroxyundecyl radical, R2 corresponds to the dodecyl radical and R3 corresponds to the dodec-2-enyl radical. 3) SPECTROSCOPIC CHARACTERIZATION OF SUPRAMOLECULAR COMPLEXES. Example 22
[0217] Spectroscopic characterization through 1H and 13C Nuclear Magnetic Resonance and infrared of the supramolecular complex resulting from the interaction of coco-amido-propyl hydroxysultaine, sodium 3-hydroxydodecane-1-sulphonate and dodec-2-en-1-sulphonate of sodium, whose synthesis process was described in example 19, and which is characterized by having as the basic structural formula the one indicated in (36) and in which R1 corresponds to the 2-hydroxyundecyl radical, R2 corresponds to the coco-amido-propyl radical and R3 corresponds to the dodec-2-enyl radical.
[0218] In the 1H nuclear magnetic resonance spectrum obtained in deuterated water of supramolecular complexes described in example 19, the following characteristic signals are observed: 1) multiple signals in the range of 3.14 to 3.29 for the methyl protons H5 and H6, and 2) multiple signals in the range of 3.48 to 3.77 ppm for methylene protons H2 and H4 and methine proton H3; whereas in the 1H nuclear magnetic resonance spectrum of coco-amido-propyl hydroxysultaine used as raw material, the following characteristic signals are observed: 1) multiple signals in the range of single signals for methyl protons H5 and H6 in the range 3.13 a 3.30 ppm, 2) multiple signals in the range 3.51 to 3.67 for methylene protons H2 and H4 and methine proton H3. The lack of protection suffered by methylene protons H2 and H4 and by the methine proton H3 in supramolecular complexes with respect to those present in coco-amido-propyl hydroxysultaine, indicates the existence of interactions that give rise to the supramolecular complex object of the present invention ( 36).
[0219] In the 13C nuclear magnetic resonance spectrum of supramolecular complexes, the following characteristic signals are observed: 1) a single signal for the methine carbon C3 that contains the hydroxyl group at 72.2 ppm, 2) isolated signals in the range of 62.6 to 67.4 ppm for the C2 and C4 methylene carbons, 3) isolated signals in the range of 51.7 to 52.1 ppm for the C5 and C6 methyl carbons, while in the 13C nuclear magnetic resonance spectrum of the coco-amido-propyl hydroxysultaine used as raw material, the following characteristic signals are observed: 1) a single signal for the methine carbon C3 which contains the hydroxyl group in 74.8 ppm, 2) isolated signals in the range of 62, 6 to 67.4 ppm for C2 and C4 methylene carbons, 3) isolated signals in the range of 54.7 to 54.9 ppm for C5 and C6 methyl carbons. The protection experienced by C3 methic carbon, which contains the hydroxyl group in supramolecular complexes in relation to those in coco-amido-propyl hydroxysultaine, indicates the existence of interactions that give rise to the supramolecular complex object of the present invention (36).
[0220] The infrared (IR) spectrum of the supramolecular complexes of example 19 was obtained by means of the ATR and presents the following main vibration bands: 1) A symmetrical, intense, wide band in 1648 cm-1 attributed to the vibration of the carbonyl amide group, 2) An intense, wide, asymmetric tension range at 1550 cm-1 attributed to the vibration of the carbonyl amide group, 3) An intense, wide, asymmetric tension range at 1175 cm-1 attributed to the vibration of the amide group sulfonate and 4) A symmetrical voltage range of medium intensity in 1037 cm-1 attributed to the vibration of the sulfonate group. Additionally, in the IR spectrum of coco-amido-propyl hydroxysultaine used as raw material, the following characteristic signals are observed: 1) A symmetrical, intense, wide range of tension at 1641 cm-1 attributed to the vibration of the amide carbonyl group, 2 ) An intense, asymmetrical stress range, wide at 1549 cm-1 attributed to the vibration of the carbonyl amide group, 3) An intense, asymmetrical stress range, wide at 1189 cm-1 attributed to the vibration of the sulfonate group, and 4) A range of medium intensity symmetric tension in 1039 cm-1 attributed to the vibration of the sulfonate group.
[0221] The variations observed in the vibration frequencies of the amide and sulfonate groups in the supramolecular complexes compared to those obtained in the coco-amido-propyl hydroxysultaine used as a raw material, confirms the existence of interactions that give rise to the supramolecular complexes (36) objects of the present invention.
[0222] Figures Nos. 1, 2, 3 and 4 show typical 1H and 13C NMR spectra of coco-amido-propyl hydroxysultaine and sodium 3-hydroxydodecane-1-sulphonate and sodium dodec-2-en-1-sulphonate blended raw materials. sodium, respectively, Figures No. 5 and 6 show the 1 H and 13 C NMR spectrum of the supramolecular complexes (36) described in Example 19, and Figures 7 and 8 show the infrared spectra of coco-amido-propyl hydroxysultaine and complexes supramoleculars (36) described in Example 19, respectively.
[0223] 4) EVALUATION OF THE EXPERIMENTAL PERFORMANCE OF SUPRAMOLECULAR COMPLEXES. The performance as foaming modifiers, wetting capacity and corrosion inhibitors in ultra-high salinity and high temperature environments of supramolecular complexes that result from the interaction of sodium alkyl hydroxy sulfonates with sodium alkenyl sulfonates with alkyl starch propyl hydroxysultains or alkyl hydroxysultaines (36) was determined using several experimental tests, which are described below.
[0224] Evaluation of phase stability in brines with ultra-high salinity and high contents of divalent ions. Example 23
[0225] A phase stability study was carried out by the supramolecular complexes object of the present invention, described in Examples 19, 20 and 21 and whose basic structural formula is indicated in (36).
[0226] All products were evaluated at a concentration of 0.2% by weight, dissolved in different waters with high salinity and concentrations of divalent ions, by measuring the turbidity in NTU (Nephelometric Turbidity Units). This value indicates how turbid or clear a solution/chemical is and the higher the value, the more turbid the solution is.
[0227] The measurement is based on the application of the nephelometric technique through the use of a photometer. The standard method is based on comparing the amount of light scattered by colloidal particles present in a water sample with the intensity of light emerging through the same sample.
[0228] Table 32 shows the compositions of the brines that were used in the evaluation of phase stability of the supramolecular complexes described in Examples 19, 20 and 21 and Table 33 shows the results obtained in the corresponding evaluation at room temperature. It is worth mentioning that, in order to pass this test, a value of 30 NTU must not be exceeded.
[0229] The analysis of Table 33 indicates that the supramolecular complexes described in Examples 19, 20 and 21 are soluble and tolerant to salinity and hardness levels ranging from 32803 to 253859 ppm and 6420 to 87700 ppm, respectively.
[0230] In order to demonstrate the technological advantage of using the supramolecular complexes object of the present invention (36) in brines with ultra-high salinities, comparative phase stability tests were conducted with respect to the raw materials used for its synthesis and with the supramolecular complexes described in the Mexican patent MX 297297. The results are shown in Table 34. Table 32
Table 33
Table 34

[0231] The analysis of Table 34 indicates that the mixture of sodium 3-hydroxydodecane-1-sulfonate and sodium dodec-2-en-1-sulfonate and the supramolecular complexes of the Mexican patent MX 297297 present phase stability problems in salinities of 253859 ppm and hardness levels of 87700 ppm (see Table 32). Additionally, a comparison of the results of Tables No. 33 and 34 demonstrates the advantage of using the supramolecular complexes (36) object of the present invention in brines with ultra-high salinities and high levels of hardness.
[0232] On the other hand, in order to determine the effect on the phase stability of supramolecular complexes (36) of the addition of corrosion inhibitors based on zwitterionic geminal liquids described in patent application US 2011/0138683 A1, viscosifying agents of the sodium poly-(acrylamide-co-2-acrylamido-2-methyl-1-propanesulfonate type), viscosifying agents such as terpolymers based on acrylamide/N-vinyl pyrrolidone/2-acrylamido-2-methyl-1-propane sodium sulphonate and foam stabilizers based on copolymers derived from itaconic acid and sodium vinyl sulphonate (Hernández-Altamirano, Raúl; Tesis de Doctorado 2010; Development of multifunctional chemical products with potential application in the solution of corrosion, incrustation problems, asphaltenes and improved recovery of hydrocarbons present in the oil industry; Instituto Mexicano del Petróleo; Mexico), the formulations presented in Table 35 were then prepared and its phase stability was evaluated, with the results shown in Table 36.
[0233] The analysis of Table 36 indicates that the addition of supramolecular complexes (36) of the corrosion inhibitors based on zwitterionic geminal liquids described in patent application US 2011/0138683 A1, viscosifying agents of the type poly-(acrylamide-co- sodium 2-acrylamido-2-methyl-1-propane sulfonate), viscosifying agents such as terpolymers based on acrylamide/N-vinyl pyrrolidone/2-acrylamido-2-methyl-1-propane sulfonate and foam stabilizers with based on copolymers derived from itaconium acid and sodium vinyl sulfonate does not generate any phase stability problems. Table 35
Table 36

[0234] II) Experimental evaluation of the foaming properties of supramolecular complexes.
[0235] The evaluation of the foaming capacity of supramolecular complexes that result from the interaction of sodium alkyl hydroxysulphonates, sodium alkenyl sulphonates and alkyl amido propyl hydroxysultaines or alkyl hydroxysultaines object of the present invention (36) was performed using two different tests: a) Measurement of foam stability in atmospheric conditions (atmospheric pressure foaming test), b) Measurement of foam stability in high pressure, high temperature and ultra high salinity conditions (high pressure foaming test ) and c) Determination of rheological properties.
[0236] a) Atmospheric pressure foaming test. The system used to generate foam at high pressure is a modification of the system described in Mexican patent MX 297297 and is designed to assess the stability of foams generated by surfactants at temperatures up to 75 °C, and is shown in Figure 9.
[0237] The foaming system consists of three sub-systems, with the first being the foam meter body, which comprises two concentric glass tubes. The outer tube is 1.35 m high with a diameter of 0.0762 m and the inner tube is 1.15 m high with a diameter of 0.0508 m. The solution to be evaluated (brine plus chemical) is loaded into the inner tube and the generation and confinement of the foam are carried out, while the function of the outer tube is to maintain the heating fluid through which the test temperature is controlled . The second subsystem is the one that controls the gas flow and comprises a storage tank through which the gas discharge pressure is regulated and a second smaller stabilizing tank is intended to contribute to the regulation of the gas flow. gas and prevent condensate carryover. The gas line has a set of three valves designed to control the direction and magnitude of gas flow: the first is a vent valve connected to the stabilization tank; then there is a flow valve, which contacts the gas to be fed into a calibrated flow meter (maximum flow, 100 cm3/min) and finally there is a three-way valve designed to control the admission of gas to the foam meter body as well as to open the system to the atmosphere. At the end of this subsystem, there is a section of stainless steel piping or a lance with a diffuser or disperser (which can be comprised of glass or steel), coupled to its lower end, through which the gas is injected into the phase. liquid in order to distribute the gas flow evenly and achieve a monodisperse foam texture.
[0238] Finally, the third subsystem is the one that controls the temperature in the ring-shaped space through the heating oil flow controlled by a digital recirculating thermal bath.
[0239] In order to measure the stability of the foam and its foaming capacity, a process was developed that comprises the following 18 stages: 1) Preparation of the study solution in the concentration required for the analysis, 2) Verification of the cleaning the inner glass tube, 3) Turn on the thermal bath and set a temperature of 70 °C (this process takes approximately 1 hour), 4) Open the gas tank valves, 5) Bleeding the valves of both the gas tank how much from the foam gauge, 6) Ensure that the pressure is at 50 psi, 7) Inject 60 ml of the solution to be studied using a syringe and hose, 8) Introduce and center the steel lance and leave it for 10 minutes so that its temperature is homogeneous, 9) Connect the gas line to the lance, 10) Place a heating band on the top of the foam meter, in order to avoid vapor condensation, 11) Record the initial height of liquid, 12) Open the gas inlet valve, 13) Open the rotameter and control the flow until reaching 50 and keep it, 14) Start the stopwatch as soon as the first gas bubble appears in the liquid, 15) After 45 seconds, close the gas inlet valve and measure the height of the foam (maximum height) and fluid, as well as resetting the timer, 16) Perform foam and fluid height measurements every minute for 10 minutes, in order to determine the drainage rate and foam quality, 17) Record the foam and fluid heights every 10 minutes until the foam height reaches 30% of its maximum height and, 18) Determine the percentage of foam stability at each moment and based on this, build a diagram of foam stability over time.
[0240] Foam stability is defined as the change in the initial height of the foam with respect to time and is determined according to equations 1 and 2.

[0241] Where:
[0242] = foam height
[0243] = height of the solution
[0244] = total height of experience
[0245] The experiment ends when 30% foam stability is achieved. The calculation to obtain foam stability is as follows:

[0246] Where:
[0247] = foam height
[0248] = maximum foam height
[0249] E= Foam stability
[0250] Where is calculated in 45 seconds of experience.
[0251] A study was carried out on the phase stability of supramolecular complexes object of the present invention, described in examples 19, 20 and 21 and whose basic structural formula is indicated in (36).
[0252] Based on the described methodology, the determination of the stability of the foam generated by the supramolecular complexes object of the present invention, described in Examples 19, 20 and 21 and whose basic structural formula is indicated in (36) was performed and the results obtained are shown in the following examples: Example 24
[0253] The stability of the foams generated by the supramolecular complexes described in examples 19, 20 and 21 and whose basic structural formula is described in (36), were evaluated by means of the foam formation test at atmospheric pressure, at a temperature of 70 °C, using a brine containing 32804 ppm of total dissolved solids, of which 1736 ppm corresponded to divalent ions (calcium and magnesium), total hardness as CaCO3 of 6420 ppm and a concentration of supramolecular complexes of 0.2% by weight and using nitrogen gas (N2) to generate the foam.
[0254] The composition of the brine used to dilute the supramolecular complex is shown in Table 37. Table 37

[0255] The established time to reach each parameter (height of foam and liquid) was 45 seconds and the minimum percentage of stability of the foam recorded was 30%.
[0256] Figure 10 shows the graph of time versus stability of the foam obtained with supramolecular complexes described in Examples 19, 20 and 21, and whose basic structural formula is indicated in (36), which reveals that the minimum stability of 30% is achieved in a time of 385, 360 and 345 minutes, respectively.
[0257] In order to demonstrate that supramolecular complexes offer technological advantages when used as foaming agents with regard to the raw materials used for their synthesis and with the supramolecular complexes described in the Mexican patent MX 297297, whose stabilities of the foams generated under the same conditions mentioned in Example 24 were determined. Example 25
[0258] A study was carried out on the stability of cocoamido propyl hydroxysultaine foam, mixture of sodium 3-hydroxydodecane-1-sulfonate and sodium dodec-2-en-1-sulfonate and supramolecular complexes of the Mexican patent MX297297.
[0259] The results obtained for the foam stability in the foaming test at atmospheric pressure and a concentration of 0.2% by weight of cocoamido propyl hydroxysultaine, the mixture of sodium 3-hydroxydodecane-1-sulfonate and dodec- Sodium 2-en-1-sulfonate and the supramolecular complexes of the Mexican patent MX 297297 are shown in Figure 11, which reveals that the minimum stability of 30% is reached in a time of 60, 30, 170 and 330 minutes, respectively.
[0260] The results indicate that the foam generated by the supramolecular complexes described in examples 19, 20 and 21 and whose basic structural formula is indicated in (36) is at least 10 times more stable than the foams generated by the mixture of 3-hydroxydodecane -1-sodium sulfonate and sodium dodec-2-en-1-sulfonate, 7 times more stable than those generated by coco amido propyl hydroxysultaine and 2 times more stable than those generated by coco amido propyl betaine, alpha olefin sulfonate sodium and dodecyl trimethyl ammonium chloride supramolecular complex. On the other hand, the stability of the foam generated by the supramolecular complex described in example 19 is 17% more stable than that generated by the complex derived from coconut amido propyl betaine, sodium alpha olefin sulfonate, dodecyl trimethyl ammonium chloride and poly(itaconic acid ).
[0261] These results demonstrate the technological advantage of using supramolecular complexes based on the interaction of sodium alkyl hydroxysulphonates, sodium alkenyl sulphonates with alkyl amido propyl hydroxysultaines or alkyl hydroxysultaines whose basic structural formula is indicated in (36) as builder agents of foam at atmospheric pressure, temperature of 70 °C and high concentration of total solids and divalent ions.
[0262] On the other hand, in order to determine the effect on the foam stability of supramolecular complexes (36) of the addition of corrosion inhibitors based on zwitterionic geminal liquids, viscosifying agents and foam stabilizers, the formulations 1, 2 , 3 and 4 described in Example 23 were then evaluated under the same conditions as in Example 24. Example 26
[0263] A foam stability study was conducted for formulations 1, 2, 3 and 4 described in Example 23, under the same conditions as in Example 24.
[0264] Figure 12 shows the graph of time versus foam stability obtained with formulations 1, 2, 3 and 4, which reveals that the minimum stability of 30% is achieved in a time of 240, 250, 375 and 440 minutes, respectively.
[0265] The results indicate that the stability of the foam generated by formulations 1 and 2, which contain polymeric viscosifying agents is about 38 and 35%, respectively, less stable than that with the supramolecular complex described in Example 19, therefore, the addition of this type of compounds in the supramolecular complex induces an antagonistic effect on the foaming properties. The stability of the foam generated by formulation 3, which contains a corrosion inhibitor based on zwitterionic geminal liquid, does not affect the performance of the foaming additive derived from the supramolecular complex described in Example 19. On the other hand, the stability of formulation 4, which contains a foam stabilizer, increases the foam stability of the supramolecular complex described in Example 19 by 14% and therefore a synergistic effect is observed.
[0266] In order to determine the effect of salinity and divalent ion content on the stability of the foam generated by the supramolecular complex described in Example 19 and whose basic structural formula is indicated in (36), a stability study was conducted in three different waters of formation characteristic of a reservoir with high levels of divalent ions (calcium, magnesium, barium and strontium) and salinity such as NaCl. Example 27
[0267] An evaluation was conducted of the stability of the foam generated by the supramolecular complex described in Example 19 and whose basic structural formula is indicated in (36), in three different brines whose characteristics are shown in Table 38. Table 38

[0268] A comparison of the stability results obtained for the foam generated by the supramolecular complex described in example 19 and whose basic structural formula is indicated in (36) in three different brines is shown in figure 13. A minimum stability of 30% is achieved in a time of 50, 30, 170 and 330 minutes. The results indicate that the foam generated by the complex shows a minimum stability of 30% over periods of 360, 400 and 600 minutes in brines with salinity such as sodium chloride of 152974, 253859 and 313203 ppm, respectively. These results show that very stable complexes are formed when salinity increases.
[0269] This demonstrates the advantage of using the supramolecular complexes (36) object of the present invention in brines with ultra-high salinity and high levels of hardness.
[0270] In order to determine what would be the effect of the gas type on the foam stability in the generation of foam with the supramolecular complex described in Example 19 and whose basic structure formula is indicated in (36) a foam stability study was carried out with nitrogen, carbon dioxide and methane. Example 28
[0271] The evaluation of the stability of the foam generated by the supramolecular complex described in Example 19 and whose basic structural formula is indicated in (36) was carried out by means of the foaming test at atmospheric pressure, at a temperature of 70 °C, using a brine containing 313203 ppm of salinity as NaCl, of which 154000 ppm corresponded to divalent ions (calcium and magnesium), a supramolecular complex concentration of 0.2% by weight, and methane (CH4), carbon dioxide (CO2) and nitrogen (N2) as gases.
[0272] The foam stability results obtained in the foaming test at atmospheric pressure and at a weight concentration of 0.2% of the supramolecular complex described in Example 19 and whose basic structural formula is given in (36) with methane , carbon dioxide and nitrogen gas are shown in figure 14. Analysis of the results indicates that a minimum stability of 30% is achieved in a time of 750 minutes for nitrogen, 760 minutes for carbon dioxide and more than 800 minutes for methane.
[0273] This demonstrates the technological advantage of using supramolecular complexes (36) objects of the present invention in brines with ultra-high salinity and high levels of hardness and the versatility of using different gases to produce the foam.
[0274] II) High pressure foaming test. The high-pressure, high-temperature foam generation system that was used was developed in the hydrocarbon recovery laboratory of the Instituto Mexicano del Petróleo and is designed to assess the stability of foams generated by surfactants at temperatures up to 170 °C and such pressures. high at 6000 psi and is shown in Figure 15. It comprises injection pumps, transfer cylinders, reverse pressure regulator (IPR), temperature control system, pressure monitoring system, digital camera, filter (foam generator) and experimental cell.
[0275] 1) TEST CONDITIONS • Temperature: 150 °C • Pressure: 3500 psi • Gas: Methane • Brine • Test time: 7 days • Liquid flow: 0.6 ml/min • Gas flow: 2, 4 ml/min
[0276] METHODOLOGY:
[0277] 1) Conditioning the system:
[0278] - Window
[0279] - IPR
[0280] - Transfer Cylinders
[0281] 2) The pressure transducer and thermocouples are calibrated.
[0282] 3) The temperature is raised to the desired level for the experiment and the pressure is maintained through the IPR.
[0283] 4) The liquid additivated with the chemical and the gas are injected to generate the foam in a ratio of 1 to 4, respectively, under reservoir conditions.
[0284] 5) Once the foam is formed and the cell is saturated, the system is isolated while maintaining temperature and pressure monitoring.
[0285] 6) Photographic images are taken at different times during the test to observe the stability of the foam.
[0286] Determination of foam stability. The methodology developed for the determination of foam stability is as follows: 1. A gray-graded color scale is designed for the photographic images. 2. Window area is calculated in pixels. 3. Coverslip free area is calculated. 4. The percentage of coverslip free area is calculated. % Coverslip Free Area = Coverslip Free Area / Window Area (Equation 3) 5. The percentage of coverslipped area is calculated. 6. Coverslip Area = 1 - % Coverslip Free Area (Equation 4) Example 29
[0287] The evaluation of the stability of the foam generated by the supramolecular complex described in Example 19 and whose basic structural formula is indicated in (36), was carried out by means of the high pressure foaming test, whose conditions are 3500 psi pressure and a temperature of 150 °C, using a brine containing 313203 ppm of salinity as NaCl, of which 154000 ppm corresponded to the divalent ions (calcium and magnesium), a supramolecular complex concentration of 0.2% by weight and of methane (CH4) like gas.
[0288] Figure 16 shows the sequence of photographic images of the foam formed by brine added to the supramolecular complex at a concentration of 0.2% by weight, whereby the behavior of the foam is observed during the test. Its duration was around 168 h, during which the system conditions were kept constant at a temperature of 150 °C and 3500 psi of pressure.
[0289] The test results are shown in Table 39 and indicate that the foam is stable under high pressure, ultra-high salinity and high temperature conditions and cannot completely agglutinate during 168 h. Table 39

[0290] Figure 17 shows the behavior of time against foam stability under the formation conditions.
[0291] This demonstrates the technological advantage of using supramolecular complexes (36) objects of the present invention, under conditions of high pressure (3500 psi), high temperature (150 °C) and brines with ultra-high salinity and high levels of hardness and the versatility of using different gases to produce the foam.
[0292] Determination of rheological behavior in a capillary rheometer under reservoir conditions. The test method consists of determining the rheological behavior of foams generated by the supramolecular complexes object of the present invention, with ultra-high salinity and high water hardness under reservoir conditions using a capillary rheometer for high pressures and high temperatures through a method experimental developed in the reservoir productivity laboratory of the Instituto Mexicano del Petróleo, which determines the pressure drop between two points of the capillary tube as a function of the foam flow.
[0293] Elements required for testing: • capillary rheometer for high pressures and temperatures. • nitrogen tank. • 1 L of foaming agent solution in characteristic brine.
[0294] Testing Procedures:
[0295] 1) Bring the capillary rheometer system to the test temperature and pressure.
[0296] 2) Establish the total flow or foam flow according to the dimensions of the capillary in order to obtain the maximum desired shear rate; the nitrogen gas flow and foaming solution will be set to obtain the required quality. This relationship must be adjusted with the following equation:

[0297] where the total flow is given by the sum of the gas and liquid flows.
[0298] 3) At a fixed full flow, record the corresponding pressure drop values at a time interval of 10 minutes.
[0299] 4) Change the total flow to a lower value and re-record the pressure drop values for the same period of time as in the previous point.
[0300] 5) repeat the procedure until at least 7 points or 7 different flows are obtained.
[0301] 6) Based on the experimental data on the total volumetric flow and the pressure drop, calculate the shear stress and the corresponding shear rate, in order to obtain the graph of shear stress versus shear rate, where the rheological behavior of the foam can be observed and determined.
[0302] 7) Perform a mathematical adjustment according to the observed curve to obtain the equation for the rheological model of the foam where the apparent viscosity can be calculated as a function of the shear rate. Example 30
[0303] The determination of the rheological behavior of a foam generated by the supramolecular complex described in example 19 and whose basic structure formula is indicated in (36), was carried out at a temperature of 150 °C and a pressure of 3500 psi, at a concentration of 0.2% by weight with brine 4 described in example 27 and employing as nitrogen gas to achieve a quality of 80% and in a range of high shear rates. Table 40 summarizes the most relevant conditions of the experiment and the capillary dimensions. Table 41 and Figure 18 show the results obtained. Table 40
Table 41


[0304] From the results obtained and when performing the mathematical adjustment of the rheological behavior for this foam with a correlation ratio R2 = 0.9706, the following equation was found, which is a characteristic of a pseudoplastic fluid:

[0305] Based on the above equation, viscosity can be calculated as a function of shear rate, and the results are shown in Table 42. Table 42


[0306] The results obtained in this evaluation for the foam generated by the supramolecular compound described in example 19, reveal that even at high shear rates of 1175 s-1 under pressure and temperature reservoir conditions, it is possible to reach viscosity values of 11 cP, that is, 60 times higher than water and 500 times the viscosity of nitrogen. Example 31
[0307] The determination of the rheological behavior of a foam generated by the supramolecular complex described in Example 19 and whose basic structural formula is indicated in (36), was carried out at a temperature of 150 °C and a pressure of 3500 psi at a concentration of 0.2% by weight with brine 4, the composition of which is described in Example 27, employing as nitrogen gas in order to achieve a quality of 80% and within a range of low shear rates. Table 43 summarizes the most relevant conditions of the experiment and the capillary dimensions. Table 44 below and Figure 19 show the results obtained. Table 43
Table 44

[0308] Based on the results obtained and the application of the mathematical adjustment of the rheological behavior for this foam with a correlation ratio R2 = 0.9581, the following equation was found, which is the characteristic of a pseudoplastic fluid:

[0309] Based on the above equation, viscosity can be calculated as a function of shear rate and the results are shown in Table 45. Table 45

[0310] The results obtained in this evaluation for the foam generated with the supramolecular complex 37 show that at low shear rates close to those found in the reservoir around 12 s-1 under reservoir conditions of pressure and temperature, it is possible to reach values of viscosity of 64 cP, ie 300 times more than water and 2700 times the viscosity of nitrogen.
[0311] This demonstrates the technological advantage of using the supramolecular complexes (36) objects of the present invention as foaming additives under conditions of high pressure (3500 psi), high temperature (150 °C) and with brines with ultra-salinities. high and high levels of hardness. 111) EVALUATION OF MODIFICATION PROPERTIES OF THE WEIGHTING CAPACITY. The following examples will help to demonstrate the use of the supramolecular complexes (36) object of the present invention as wetting capacity modifiers.
[0312] This evaluation was performed in 4 ways: a) Determination of contact angle changes under atmospheric conditions, b) Determination of spontaneous imbibition in small fragments of dolostone and limestone in Amott cells, c) Determination of spontaneous imbibition in nuclei of limestone in Amott cells and d) Determination of spontaneous imbibition in limestone nuclei in a high-temperature glass-lined reactor.
[0313] a) Determination of contact angle changes under atmospheric conditions. The test method comprises a procedure to observe how the contact angle of a rock/oil system immersed in brine with high contents of total dissolved solids and divalent ions such as calcium and magnesium with or without the presence of chemical is modified in environmental conditions in order to determine the time it takes for small proportions of oil to separate in the system.
[0314] Elements required for testing: • 50 milliliter glass beakers. • Small fragments of dolomite, limestone or sandstone. • Photographic camera. • Crude oil, typical of carbonate reservoirs. • Brine. test procedure
[0315] 1 - Prepare 100 ml of the aqueous solution (brine) to be evaluated at the concentration of chemical required in the test.
[0316] 2 - Place a small fragment of rock (dolostone, limestone or sandstone) with dimensions of 2 x 2 x 1 cm in a 50 ml glass beaker.
[0317] 3 - Carefully place two drops of crude oil on the surface of the small rock fragment.
[0318] 4 - Take into account the rock-oil system to balance, letting it rest for 30 minutes.
[0319] 5 - Check if the rock surface is moisturizing to oil.
[0320] 6 - Carefully add 25 ml of the aqueous solution to be evaluated at the concentration of the chemical required in the test. Check that the rock-oil system is completely submerged in the aqueous solution to be evaluated.
[0321] 7 - Observe the changes that occur with the contact angle in the rock-oil aqueous solution system and document them with photographs.
[0322] 8 - Determine the time when the oil separation in the system starts due to the effect of the chemical.
[0323] 9 - The test time duration is one hour. Example 32
[0324] The determination of the change in the contact angle was performed for the supramolecular complex described in Example 19 and whose basic structure formula is indicated in (36) at different concentrations.
[0325] The brine 1 whose composition is described in Example 24 was used, as well as the rock slabs composed of 99% dolomite and 1% limestone and the oil whose composition is shown in Table 46. Table 46

[0326] Tables 47, 48 and 49 show the results of the contact angle change experiment using the supramolecular complex described in Example 19 at different concentrations.
[0327] The results show that the supramolecular complex described in example 19 favorably modifies the contact angle and separates the oil in less than 1 hour from contact with the oil adsorbed on the rock under environmental conditions and using high salinity brines, as well as oils with high contents of asphaltenes.
[0328] This demonstrates the technological advantage of using supramolecular complexes (36) objects of the present invention as modifiers of the wetting capacity under environmental conditions of temperature and pressure and use of brines with ultra-high salinity and high levels of hardness.
[0329] b) Determination of the recovery factor in small fragments of dolostone and limestone in Amott cells. The test method consists of determining the oil recovery factor at different temperatures, due to spontaneous water imbibition processes in small fragments of carbonate rock and/or cores with known permeabilities and porosities.
[0330] Elements required for testing: • Amott cells. • Temperature controlled recirculation device. • Small fragments of dolostone, limestone or sandstone. • Photographic camera. • Typical crude oil from carbonate reservoirs. • Typical brine from reservoirs with high salinities. • Supramolecular complex or chemical to be evaluated. • Analytical Balance. • Glass equipment for the extraction of SOXHLET. • Volumetric glass materials. • Convection oven.
[0331] Test procedures: 1) Submit small rock fragments (dolomite, limestone or sandstone) from the reservoir to which the study is intended for hydrocarbon extraction processes with different organic solvents in a SOXHLET system. The extraction processes are carried out continuously, sequentially or by reflux, using as solvents: a) hexane b) xylene, c) chloroform, d) methanol, e) hexane, f) xylene and g) chloroform. The duration of each extraction stage is one day and the time for the entire process is 7 days. 2) Dry the small rock fragments in an oven at a temperature of 100 °C and record the weight as soon as a constant weight is reached. 3) Place the small rock fragments in contact with the permanent oil that originates from the reservoir of interest for 24 hours at the required temperature and at a pressure of 140 ± 5 psi, with an aging cell. 4) Filter the small rock fragments saturated with permanent oil at atmospheric temperature and pressure until no dripping is observed. The filtering process takes about 12 hours and a number 200 wire mesh is used for this purpose. 5) Weigh the small rock fragments soaked with permanent oil and, through the difference in weight, obtain the amount of oil absorbed by the porous medium. 6) Prepare 400 ml of the aqueous solution (brine) to be evaluated at the chemical concentration required in the test. 7) Place 60 grams of small rock fragments in the Amott cell and carefully add 350 ml of the chemical to be evaluated at the required concentration. 8) Raise the system temperature to the desired temperature for evaluating the performance of the chemical or sample under study and maintain it for the period of time that the recovery factor is planned to be determined under the temperature conditions and salinity. 9) Quantify the amount of oil produced due to spontaneous water soaking processes under study conditions and determine the recovery factor according to the following equation:
[0332] Rf = (Ro x 100)/Oopm (Equation 8)
[0333] Where:
[0334] Rf = recovery factor
[0335] Ro = recovered oil
[0336] Oopm = original oil adsorbed on the porous medium. Example 33
[0337] The evaluation of the total recovery factor was carried out for the supramolecular complexes described in Examples 19 and 20 and whose basic structure formula is indicated in (36) at a concentration of 0.2% by weight, using as a test medium the brine described in Example 24, limestone and oil fragments whose characteristics are shown in Table 50, for a temperature range of 80, 90 and 100 °C and at atmospheric pressure. Table 50

[0338] Table 51 shows the cumulative results of the recovery factor over the temperature range. Table 51

[0339] The results show that the supramolecular complexes described in Examples 19 and 20 recover 77 and 38% more oil with respect to the recovery obtained exclusively through brine. Example 34
[0340] The evaluation of the total recovery factor was carried out for the supramolecular complexes described in Examples 19 and 20, at a concentration of 0.2% by weight, using as a test medium the brine 1 whose composition is described in Example 24, rock fragments composed of 99% dolostone and 1% limestone, the oil whose composition is shown in Table 52 and in a temperature range of 80, 90 and 100 °C. Table 52

[0341] Table 53 shows the result of the cumulative recovery factor within the temperature range for the supramolecular complexes described in Examples 19 and 20. Table 53

[0342] Figure 23 shows the Amott cell containing the supramolecular complex derived from Example 19.
[0343] The results show that the supramolecular complexes of Examples 19 and 20 recover 87 and 65% more oil with respect to the recovery obtained using exclusively brine.
[0344] On the other hand, in order to determine what would be the effect of adding corrosion inhibitors based on zwitterionic geminal liquids on the supramolecular complex recovery factor described in example 19, formulation 3 described in example 23 was then evaluated under the same conditions described in this example.
[0345] Table 54 shows the result of the cumulative recovery factor within the temperature range for formulation 3 whose composition is described in Example 23. Table 54


[0346] With regard to the formulation of 3, a synergistic effect can be observed between the supramolecular complex described in Example 19 and the zwitterionic geminal liquid, which reflects in a 62% increase in the oil recovery factor, in relation to when only the supramolecular complex is used.
[0347] This demonstrates the technological advantage of using supramolecular complexes whose structural formula is shown in (36) object of the present invention as wetting capacity modifiers under ambient pressure conditions, temperature range of 80 and 100 °C, with brine of high salinity and high hardness levels, as well as oils and rock fragments with different compositions.
[0348] c) Determination of spontaneous imbibition in limestone nuclei with Amott cells. The test method consists of determining the oil recovery factor at different temperatures, due to spontaneous water imbibition processes in small carbonate rock cores with known permeabilities and porosities.
[0349] Elements required for testing: • Amott cells. • Temperature controlled recirculation device. • Limestone cores measuring 3.81 cm in diameter x 7 cm in length with known permeabilities and porosities. • Photographic camera. • Typical crude oil from carbonate reservoirs. • Typical brine from reservoirs with high salinities. • Supramolecular complex or chemical to be evaluated. • Analytical Balance. • Glass equipment for the extraction of SOXHLET. • Volumetric glass materials. • Convection oven.
[0350] Test procedures: 1) Submit carbonate rock cores (dolostone or limestone) or sandstone that originates from the reservoir for which the study is intended for hydrocarbon extraction processes with different organic solvents in a SOXHLET system . The extraction processes are carried out continuously, sequentially or by reflux, using as solvents: a) xylene, b) chloroform, c) methanol, d) xylene, e) chloroform, f) methanol and g) xylene. The duration of each extraction stage is one day and the time for the entire process is 7 days. 2) Determine the absolute permeability of helium nuclei, as well as their effective porosity. 3) Dry the core in an oven at a temperature of 100 °C and record the weight as soon as a constant weight is reached. 4) Put the cores in contact with the permanent oil that originates from the reservoir of interest for 5 days at the temperature of interest and at a pressure of 140 ± 5 lb, with an aging cell. 5) Filter the saturated core with permanent oil at atmospheric temperature and pressure until no dripping is observed. The filtering process takes about 12 hours and a number 200 wire mesh is used for this purpose. 6) Weigh the small fragments of rock saturated with permanent oil and, through the difference in weight, obtain the amount of oil absorbed by the porous medium. 7) Prepare 500 milliliters of the aqueous solution (brine) to be evaluated at the concentration of chemical required in the test. 8) Place the nuclei soaked with permanent oil in the Amott cell and carefully add 350 milliliters of the chemical to be evaluated at the required concentration. 9) Raise the system temperature to the desired temperature for evaluating the performance of the chemical or sample under study and maintain it for the period of time that the recovery factor is planned to be determined under the temperature conditions and salinity. 10) Quantify the amount of oil produced due to spontaneous water soaking processes under study conditions and determine the recovery factor according to the following equation:
[0351] Rf = (Ro x 100)/Oopm (Equation 9)
[0352] Where:
[0353] Rf = recovery factor
[0354] Ro = recovered oil
[0355] Oopm = original oil adsorbed on the porous medium. Example 35
[0356] The evaluation of the total recovery factor was carried out for the supramolecular complex described in Example 19 and whose basic structure formula is indicated in (36) at a concentration of 0.2% by weight, using as a test medium the brine 4 whose composition is shown in Example 27, crude oil and a limestone core for a temperature range of 80, 90 and 100°C.
[0357] Tables 55 and 56 show the characteristics of the oil and limestone cores used. Table 55
Table 56


[0358] Table 57 shows the result of the total recovery factor for the supramolecular complex described in example 19 at a concentration of 0.2% by weight. Table 57

[0359] Figure 24 shows the saturated core and oil separation.
[0360] The results presented in Table 57 indicate that the supramolecular complex described in Example 19 recovers 2.8 times more oil in relation to the recovery obtained using exclusively brine.
[0361] This demonstrates the technological advantage of using the supramolecular complexes object of the present invention and whose structural formula is presented in (36) as wetting capacity modifiers under ambient pressure conditions, the temperature range from 80 to 100 °C, brines with ultra-high salinity and high levels of hardness, oil and carbonate-type rock cores (limestone).
[0362] d) Determination of the recovery factor in a high temperature glass coated reactor. The equipment comprises a glass-lined reactor where a core, previously soaked with oil, is introduced and comes into contact with an aqueous medium containing a chemical product. The experimental conditions are as follows: • Experiment pressure: 140 psi • Experiment temperature: 150 °C • Injection gas: Nitrogen
[0363] Procedure:
[0364] Elements required for testing: • Glass-lined reactor. • Temperature controlled recirculation device. • Limestone cores with known permeabilities and porosities. • Photographic camera. • Typical crude oil from carbonate reservoirs. • Typical brine from reservoirs with ultra high salinities. • Supramolecular complex or chemical to be evaluated. • Analytical Balance. • Glass equipment for the extraction of SOXHLET. • Volumetric glass materials. • Convection oven.
[0365] Test procedures: 1) Submit the carbonate rock core (dolostone or limestone) or sandstone that originates from the reservoir for which the study is intended for hydrocarbon extraction processes with different organic solvents in a SOXHLET system . The extraction processes are carried out continuously, sequentially or by reflux, using as solvents: a) xylene, b) chloroform, c) methanol, d) xylene, e) chloroform, f) methanol and g) xylene. The duration of each extraction stage is one day and the time for the entire process is 7 days. 2) Determine the absolute permeability of the helium core, as well as its effective porosity. 3) Dry the core in an oven at a temperature of 100 °C and record the weight as soon as a constant weight is reached. 4) Put the core in contact with the permanent oil that originates from the reservoir of interest for 5 days at the temperature of interest and at a pressure of 140 ± 5 lb, with an aging cell. 5) Filter the saturated core with permanent oil at atmospheric temperature and pressure until no dripping is observed. The filtering process takes around 12 hours and a number 200 wire mesh is used for this purpose. 6) Weigh the core saturated with permanent oil and, through the difference in weight, obtain the amount of oil absorbed by the porous medium. 7) Prepare 500 milliliters of the aqueous solution (brine) to be evaluated at the concentration of chemical required in the test. 8) Place the permanent oil-saturated core in the glass-lined reactor and carefully add 500 ml of the chemical to be evaluated at the required concentration. 9) Pressurize with nitrogen until 140 psi is reached. 10) Raise the system temperature to the desired temperature for evaluating the performance of the chemical or sample under study and maintain it for the period of time in which the recovery factor is planned to be determined under the temperature conditions and salinity. 11) Quantify the amount of oil produced due to spontaneous water soaking processes under study conditions and determine the recovery factor according to the following equation:
[0366] Rf = (Ro x 100)/Oopm (Equation 10)
[0367] Where:
[0368] Rf = recovery factor
[0369] Ro = recovered oil
[0370] Oopm = original oil adsorbed on the porous medium.
[0371] Figure 25 shows the equipment used. Example 36
[0372] The recovery factor evaluation was performed at a temperature of 150 oC and a pressure of 140 psi for the supramolecular complex described in Example 19 and whose structural formula is shown in (36) at a concentration of 0.2% in weight, using as a test medium brine 4 and crude oil whose compositions are described in Examples 27 and 35, respectively, and a limestone core whose characteristic is shown in Table 58. Table 58

[0373] Table 59 shows the result of the recovery factor at a temperature of 150 °C and pressure of 140 psi for the supramolecular complex described in Example 19. Table 59

[0374] These results show that the supramolecular complex described in Example 19 increased almost three times the recovery factor compared to the system that uses only brine, under conditions of high temperature (150 °C).
[0375] Figures 26 and 27 show the rock core used inside the reactor, as well as the separation of oil due to the effect of the supramolecular complex, respectively. Example 37
[0376] The recovery factor evaluation was performed at a temperature of 150 °C and a pressure of 140 psi for the supramolecular complex described in Example 19 and whose structural formula is shown in (36) at a concentration of 0.2% in weight, using as a test medium brine 4 and crude oil whose compositions are described in Examples 27 and 35, respectively, and a limestone core whose characteristics are shown in Table 60, used to evaluate the supramolecular complex of Example 19. Table 60

[0377] Table 61 shows the result of the recovery factor at a temperature of 150 °C and a pressure of 140 psi for the supramolecular complex described in Example 19. Table 61

[0378] The above results show that the supramolecular complex described in Example 19 increased the recovery factor more than twice compared to the system that uses only brine, under conditions of high temperature (150 °C).
[0379] Figure 28 shows the rock core used inside the reactor and figure 29 shows the separation of crude oil due to the effect of the supramolecular complex described in Example 19.
[0380] This demonstrates the technological advantage of using the supramolecular complexes object of the present invention and whose structural formula is presented in (36) as wetting capacity modifiers under conditions of high pressure, high temperature (150 °C), brines with ultra salinities -high and high levels of hardness, as well as oils and carbonate rock cores of different characteristics.
[0381] On the other hand, in order to determine what would be the effect of adding corrosion inhibitors based on zwitterionic geminal liquids on the supramolecular complex recovery factor described in example 19, formulation 3 described in example 23 was then evaluated under the same conditions described in this example and a limestone core whose characteristics are shown in Table 62, used to evaluate formulation 3. Table 62

[0382] Table 63 shows the recovery factor results at a temperature of 150 °C and a pressure of 140 psi for formulation 3. Table 63

[0383] The above results show that the formulation 3 described in Example 23 increased about 3% more the recovery factor obtained with the supramolecular complex described in example 19, under conditions of high temperature (150 °C).
[0384] Determination of adsorption on the carbonate type mineral. The methodology consists of the quantitative determination of adsorption through high performance liquid chromatography of a chemical in contact with the carbonate mineral type.
[0385] Procedure: a) The rock (limestone) is fragmented into 1 m2/g. b) Small rock fragments are washed sequentially and at the reflux temperature of the following solvents: a) Hexane b) Toluene c) chloroform and d) methanol. c) The rock fragments are dried in an oven at a temperature of 100 °C until a constant weight is reached. d) A 5000 ppm solution of the chemical is prepared in the desired brine which produces dilutions with the same solvent for concentrations of 4000, 3000, 2000, 1000, 500, 200 and 100 ppm. e) 4 g of rock are weighed by adding 20 ml of the different prepared concentrations of the chemical. f) The rock/chemical solution is stirred for 12 h at room temperature. g) Once the stirring time is complete, the sample is filtered in a glass funnel with #2 filters, followed by 0.5 µm filters. h) Subsequently, an injection of 15 μl was performed on the HPLC for each concentration prepared. Example 38
[0386] The determination of the adsorption of the supramolecular complex described in Example 19 was carried out on limestone at a concentration of 0.2% by weight (2000 ppm) using brine 4, whose characteristics are shown in Example 27.
[0387] The adsorption result for the supramolecular complex derived from example 19 at a concentration of 2000 ppm was 5.0 mg of the supramolecular complex/g of rock.
[0388] Additionally, in order to determine the effect on corrosion when using supramolecular complexes whose structural formula is described in (36) together with ultra-high salinity brines, the determination of the inhibition efficiency was performed according to the description below.
[0389] Determination of apparent viscosity at different temperatures and atmospheric pressure. Tests for the determination of viscosity according to shear rate at 25 and 40 °C were performed in a rheometer using concentric cylinder geometry.
[0390] Test System: • An Anton Parr model Physica MCR 301 rheometer. • Concentric cylinders • Camera. • Typical brine from reservoirs with high salinities. • Supramolecular product or chemical to be evaluated.
[0391] Test Procedures
[0392] 1 - Prepare 25 ml of the sample to be evaluated at the required concentration of the chemical.
[0393] 2 - Pour 7 ml into the concentric cylinders.
[0394] 3 - Adjust the rheometer to the desired temperature for the evaluation.
[0395] 4 - Determine the apparent viscosity within shear rates ranging from 1 to 20 s-1.
[0396] 5 - Save the results obtained for the determinations on the hard disk of the workstation assigned to the rheometer.
[0397] Under the described procedure, the determination of viscosity according to the shear rate of supramolecular complex described in Example 19 was carried out at different temperatures. Example 39
[0398] The determination of viscosities according to the shear rate of the crude oil described in Example 32 added with 2000 ppm of supramolecular complex described in Example 19 was carried out at temperatures of 25 and 40 °C and at atmospheric pressure.
[0399] Table 64 shows the results of viscosity and shear rate at two different temperatures. Table 64

[0400] The above results show that the supramolecular complex of Example 19 reduces the viscosity of the crude oil by approximately 20 and 4% at 25 and 40 °C, respectively.
[0401] Figures 30 and 31 show the graphs of shear rate versus viscosity for the unadditivated oil and for the oil added with the supramolecular complex of example 19 at 25 and 40 °C.
[0402] Determination of corrosion inhibition effectiveness. It is a gravimetric test commonly known as the Wheel Test, which simulates the corrosive medium characteristic of oil production; is a dynamic process designed for fluids (oil, water and inhibitor).
[0403] Test equipment and reagents a) Corrosion inhibitor dynamic evaluation system with a temperature controller, 30 rpm agitation speed and capacity for 52 180 ml bottles. b) Bottles with a capacity of 200 ml. c) SAE 1010 carbon steel test samples, with dimensions of 1" x 0.5" x 0.010". d) Glass equipment for the preparation of corrosive media. This comprises a glass reactor with a capacity of 2 L provided with a cooling bath, a mechanical stirrer, a gas sprayer (for nitrogen and hydrogen sulfide), has a discharge valve connected to two charged collectors (the first with hydroxide of sodium in lentils and the second with a 20% sodium hydroxide solution) connected in series so that the hydrogen sulfide does not contaminate the environment. e) Potentiometer for measuring pH. Example 40
[0404] The evaluation of the efficiency as a corrosion inhibitor was carried out for the supramolecular complex described in Example 19 at a concentration of 0.2% by weight (2000 ppm), using as a test medium the brine 4 and crude oil whose compositions are described in Examples 27 and 35, respectively.
[0405] The test conditions are shown in Table 65. Table 65


[0406] The brine and crude oil compositions are described in Examples 27 and 35.
[0407] Generation of results. The difference in weight of test samples before and after being exposed to corrosive media for 46 hours is a direct indication of metal lost due to corrosion.
[0408] Effectiveness as a corrosion inhibitor is established by comparing the evidence or blank corrosion rates to the evidence rates with a given concentration of inhibitor product as shown in the following formula:

[0409] Where: Ro = Corrosion rate of the test sample in evidence (Reference).
[0410] R = Corrosion rate of test sample with corrosion inhibitor.
[0411] Table 66 shows the results for supramolecular complex 37 and formulation 40, at a concentration of 2000 ppm.
[0412] Figure 32 shows the metal test samples used in the test. Table 66

[0413] The results show that the supramolecular complex described in Example 19 of the present invention has anti-corrosive properties in acidic environments and with high salinity, characteristic of crude oil production pipelines.
[0414] On the other hand, in order to determine what would be the effect of adding corrosion inhibitors based on zwitterionic geminal liquids on the supramolecular complex recovery factor described in Example 19, formulation 3 described in Example 23 was then evaluated under the same conditions described in this example.
[0415] Table 67 shows the corrosion inhibition efficiency results for formulation 3. Table 67

[0416] The above results show that formulation 3 described in Example 23 increased by 3.3% the efficiency as an inhibitor of corrosion of the supramolecular complex described in Example 19 in acidic and high salinity environments, characteristic of crude oil production pipelines .
[0417] This demonstrates the technological advantage of using the supramolecular complexes object of the present invention and whose structural formula is shown in (36), because they have anti-corrosive properties when supplied in ultra-high salinity brines and in acidic environments that are characteristic of crude oil production pipelines.
[0418] Determination of acute toxicity. The determination of acute toxicity was carried out using two methods widely used around the world to measure the level of a pure substance or mixtures: I) Determination of acute toxicity using the Microtox® method, II) Assessment of acute toxicity with Daphnia Magna. Determination of acute toxicity using the Microtox® method
[0419] The Microtox® bacterial bioassay, designed by Strategic Diagnostic Inc. (Azur Environmental) is based on monitoring changes in natural light emissions by a luminescent bacterium, Vibrio fischeri (Photobacterium phosphoreum).
[0420] The Microtox assay measures the acute toxicity of the test substance present in the aqueous solution using a suspension of approximately one million luminescent bacteria (Photobacterium phosphoreum) as the test organism. The suspension of microorganisms is added to a series of temperature-controlled dilution tubes with different concentrations of the test substance, to subsequently read, in a photometric device, the light intensity emitted by each dilution, considering an arm space of reference where the test substance is not present.
[0421] With the data obtained, a dose-response graph can be drawn, through which the EC50 value is calculated. The EC50 is a measure of the decrease in light emitted by bioluminescent bacteria through the analysis equipment, and specifically represents the concentration at which a 50 percent reduction in light was obtained, relative to a reference blank. Concretely, the EC50 value indicates the relative toxicity of the test substance. Example 41
[0422] The determination of acute toxicity was performed with Vibrio fischeri (Photobacterium phosphoreum) with respect to the supramolecular complex derived from example 19 using the established test procedure and described in the NMX-AA-112-1995-SCFI Mexican standard, used for the evaluation of the toxicity of natural and waste waters, as well as pure or combined substances, by means of the bioluminescent bacteria photobacterium phosphoreum.
[0423] Table 68 shows the average toxicity results of a total of three replicates.
[0424] The toxicity results shown in table 68 indicate that the supramolecular complex derived from example 19 is slightly toxic to luminescent bacteria photobacterium phosphoreum. II) Assessment of acute toxicity with Daphnia Magna.
[0425] This method is applicable for the assessment of acute toxicity in water and water soluble substances. In freshwater bodies, industrial and urban wastewater, agricultural runoff and pure or combined substances or leachate, and the solubilisable fraction in soils and sediments.
[0426] Within the Cladocera group, species of the genus Daphnia are the most widely used as bioindicators in toxicity tests, due to their wide geographic distribution, the important role they play within the zooplankton community, and because they are they are easy to grow in the laboratory and they are sensitive to a wide range of toxics.
[0427] The determination of acute toxicity was performed using the Mexican standard NMX-AA-087-SCFI-2010, which establishes the method for measuring acute toxicity, using the freshwater organism Daphnia magna (Crustacea - Cladocera). Table 68
Example 42
[0428] The determination of acute toxicity was performed with Daphnia magna for the supramolecular complex derived from example 19, using the established test procedure and described in standard NMX-AA-087-2010.
[0429] Table 69 shows the mean toxicity results of a total of three replicates, of which a standard deviation of 0.15 and a coefficient of variation of 1.92% were obtained. Table 69

[0430] Acute toxicity results indicate that the supramolecular complex derived from Example 19 is moderately toxic to the freshwater organism Daphnia magna.

权利要求:
Claims (35)
[0001]
1. Foaming composition with wetting capacity modification and corrosion inhibiting properties at high temperatures and ultra-high salinity conditions, characterized by the fact that, as an active component, it contains supramolecular complexes that result from the interaction of alkyl starch propyl or hydroxysultaines alkyl hydroxysulfaines with sodium alkyl hydroxysulfonates and sodium alkenyl sulfonates, wherein the active component can be obtained from a weight ratio of sodium alkyl hydroxysulfonates, sodium alkenyl sulfonates with alkyl starch propyl hydroxysulfaines or alkyl hydroxysulfaines within from the range of 1:1:7 to 7:7:1.
[0002]
2. A foaming composition with wetting capacity modification and corrosion inhibiting properties at high temperatures and ultra-high salinity conditions according to claim 1, wherein the supramolecular complex is characterized by the following structural formula:
[0003]
A foaming composition with wetting capacity modifying and corrosion inhibiting properties according to claim 2, characterized in that useful sodium alkenyl sulfonates include sodium but-2-en-1-sulfonate, pent-2- sodium en-1-sulfonate, sodium hex-2-en-1-sulfonate, sodium hept-2-en-1-sulfonate, sodium oct-2-en-1-sulfonate, non-2-en- sodium 1-sulfonate, sodium dec-2-en-1-sulfonate, sodium undec-2-en-1-sulfonate, sodium dodec-2-en-1-sulfonate, tetradec-2-en-1- sodium sulfonate, sodium hexadec-2-en-1-sulfonate, sodium octadec-2-en-1-sulfonate, sodium eicos-2-en-1-sulfonate, sodium docos-2-en-1-sulfonate sodium, sodium tetracos-2-en-1-sulfonate, sodium hexacos-2-en-1-sulfonate, sodium octacos-2-en-1-sulfonate and mixtures thereof.
[0004]
4. A foaming composition with wetting capacity modification and corrosion inhibiting properties according to claim 2, characterized in that the sodium alkyl hydroxysulfonates are selected from the group consisting of sodium 3-hydroxybutane-1-sulfonate, sodium 3-hydroxypentane-1-sulfonate, sodium 3-hydroxyhexane-1-sulfonate, sodium 3-hydroxyheptane-1-sulfonate, sodium 3-hydroxyoctane-1-sulfonate, sodium 3-hydroxynonane-1-sulfonate, sodium 3-hydroxydecane-1-sulfonate, sodium 3-hydroxyundecane-1-sulfonate, sodium 3-hydroxydodecane-1-sulfonate, sodium 3-hydroxytetradecane-1-sulfonate, sodium 3-hydroxyexadecan-1-sulfonate, sodium 2-hydroxybutane-1-sulfonate, sodium 2-hydroxypentane-1-sulfonate, sodium 2-hydroxyhexane-1-sulfonate, sodium 2-hydroxyeptan-1-sulfonate, sodium 2-hydroxyoctane-1-sulfonate, sodium 2-hydroxynonane-1-sulfonate, sodium 2-hydroxydecane-1-sulfonate, sodium 2-hydroxyundecane-1-sulfonate , sodium 2-hydroxydodecane-1-sulfonate, sodium 2-hydroxytetradecane-1-sulfonate, sodium 2-hydroxyexadecane-1-sulfonate, sodium 2-hydroxyoctadecane-1-sulfonate, sodium 2-hydroxyeicosane-1-sulfonate , sodium 2-hydroxydocosane-1-sulfonate, sodium 2-hydroxytetracosane-1-sulfonate, sodium 2-hydroxyexacosane-1-sulfonate, sodium 2-hydroxyoctacosane-1-sulfonate and mixture thereof.
[0005]
5. A foaming composition with wetting capacity modification and corrosion inhibiting properties according to claim 2, characterized in that the alkyl starch propyl hydroxysultaines are selected from the group consisting of ethyl starch-propyl hydroxysultaine, propyl -amido-propyl-hydroxysultaine, butyl-amido-propyl-hydroxysultaine, pentyl-amidopropyl-hydroxysultaine, hexyl-amido-propyl-hydroxysultaine, heptyl-amido-propylhydroxysultaine, octyl-amido-propyl-hydroxysultaine, nonyl-amido-propylhydroxysultaine -amido-propyl-hydroxysultaine, undecyl-amido-propylhydroxysultaine, dodecyl-amido-propyl-hydroxysultaine, tetradecyl-amido-propylhydroxysultaine, hexadecyl-amido-propyl-hydroxysultaine, octadecyl-amido-propylhydroxysultaine, coco-amido-propyl hydroxysultaine starch-propyl hydroxysulfaine, docosyl-amido-propyl hydroxysulfaine, tetracosyl-amido-propyl hydroxysulfaine, hexacosyl-amido-propyl hydroxysulfaine, octacosyl 1-starch-propyl hydroxysultaine and mixtures thereof.
[0006]
6. Foaming composition with wetting capacity modification and corrosion inhibiting properties according to claim 2, characterized in that the alkyl hydroxysultaines are selected from the group consisting of ethylhydroxysultaine, propylhydroxysultaine, butylhydroxysultaine, pentyl -hydroxysultaine, hexylhydroxysultaine, heptylhydroxysultaine, octylhydroxysultaine, nonylhydroxysultaine, decylhydroxysultaine, undecylhydroxysultaine, dodecylhydroxysultaine, tetradecylhydroxysultaine, hexadecylhydroxysultaine, hexadecylhydroxysultaine, cocohydroxysultaine -hydroxysultaine, hexacosylhydroxysultaine, octacosylhydroxysultaine and mixtures thereof.
[0007]
7. Foaming composition with wetting capacity modification and corrosion inhibiting properties according to claim 2, characterized in that the active component can be obtained from a mixture of sodium alkyl hydroxysulphonates, sodium alkenyl sulphonates with hydroxysultaines of alkyl amido propyl or alkyl hydroxysultaines.
[0008]
8. Foaming composition with wetting capacity modification and corrosion inhibiting properties according to claim 2, characterized in that the sodium alkenyl sulfonate is sodium dodec-2-en-1-sulfonate.
[0009]
9. Foaming composition with wetting capacity modification and corrosion inhibiting properties according to claim 2, characterized in that the sodium alkyl hydroxysulfonate is sodium 3-hydroxydecyl-sulfonate.
[0010]
10. Foaming composition with wetting capacity modification and corrosion inhibiting properties according to claim 2, characterized in that the alkyl starch hydroxysultaine is coco amido propyl hydroxysultaine.
[0011]
11. Foaming composition with wetting capacity modification and corrosion inhibiting properties according to claim 2, characterized in that the alkyl hydroxysultaine is dodecyl hydroxysultaine.
[0012]
12. Foaming composition with wetting capacity modification and corrosion inhibiting properties according to claim 2, characterized in that it further comprises an aqueous solvent, alcohol or mixture of aqueous solvent and alcohol.
[0013]
13. A foaming composition with wetting capacity modification and corrosion inhibiting properties according to claim 12, characterized in that the aqueous solvents are selected from the group consisting of fresh water, sea water, formation water and their mixtures.
[0014]
14. Foaming composition with wetting capacity modification and corrosion inhibiting properties according to claim 12, characterized in that the alcohol is selected from the group consisting of methanol, ethanol and isopropanol and their mixtures.
[0015]
15. Foaming composition with wetting capacity modification and corrosion inhibiting properties according to claim 12, characterized in that the percentage by weight of supramolecular complexes in aqueous solvent, alcohol or mixture thereof is in the range of 0.1 at 50.0% by weight.
[0016]
16. Foaming composition with wetting capacity modification and corrosion inhibiting properties according to claim 1, characterized in that a gas used to generate the foam is selected from the group consisting of nitrogen, oxygen, carbon dioxide, natural gas , methane, propane, butane and mixtures thereof.
[0017]
A foaming composition with wetting capacity modification and corrosion inhibiting properties according to claim 2, characterized in that it further comprises foam stabilizers.
[0018]
18. A foaming composition with wetting capacity modification and corrosion inhibiting properties according to claim 17, characterized in that the foam stabilizers are selected from the group consisting of copolymers derived from itaconic acid and sodium vinyl sulfonate having a weight average molecular ranges from 200 to 20,000 Daltons.
[0019]
19. Foaming composition with wetting capacity modification and corrosion inhibiting properties according to claim 17, characterized in that the foam stabilizer is present in an amount based on the weight of the supramolecular complex.
[0020]
20. Foaming composition with wetting capacity modification and corrosion inhibiting properties according to claim 2, characterized in that it additionally comprises zwitterionic geminal liquids selected from the group consisting of bis-N-alkylpolyether or bis-Nalkenylpolyether or bis-beta amino acids of bis-N-arylpolyether or salts thereof.
[0021]
21. Foaming composition according to claim 2, characterized in that the zwitterionic geminal liquid is present in an amount of 0.5 to 10% by weight based on the supramolecular complex.
[0022]
22. Use of foaming compositions with wetting capacity modification and corrosion inhibiting properties as defined in claim 2, characterized in that it is to generate stable foams to modify wetting capacity and inhibit corrosion at high temperature, high pressure, ultra salinity -High and high concentration of divalent ions in an oil well or reservoir.
[0023]
23. Use of foaming compositions with wetting capacity modification and corrosion inhibiting properties, according to claim 22, characterized in that it is to change the wetting capacity of the carbonate or sandy clay reservoir or well.
[0024]
24. Use of foaming compositions with wetting capacity modification and corrosion inhibiting properties, according to claim 23, characterized in that said foaming composition is injected in an amount to prevent and control pitting and widespread corrosion of ferrous metals in crude oil production wells or reservoirs.
[0025]
25. Use of foaming compositions with properties for modifying the wetting capacity and inhibiting corrosion, according to claim 23, characterized in that the temperature is up to 200 °C.
[0026]
26. Use of foaming compositions with properties for modifying the wetting capacity and inhibiting corrosion, according to claim 23, characterized in that the pressure is up to 37921165,112 Pa.
[0027]
27. Use of foaming compositions with wetting capacity modification and corrosion inhibiting properties according to claim 23, characterized in that said well has a salt concentration of up to 400,000 ppm as sodium chloride.
[0028]
28. Use of foaming compositions with properties for modifying the wetting capacity and inhibiting corrosion, according to claim 23, characterized in that said well has a concentration of bivalent ions of up to 250,000 ppm.
[0029]
29. Use of foaming compositions with wetting capacity modification and corrosion inhibiting properties, according to claim 23, characterized in that the foaming composition is injected into said well at a concentration of 25 to 40,000 ppm based on the amount of crude oil.
[0030]
30. Use of foaming compositions with wetting capacity modification and corrosion inhibiting properties, according to claim 23, characterized in that said foaming composition is injected into said well at a concentration of 500 to 10,000 ppm.
[0031]
31. Use of foaming compositions with wetting capacity modification and corrosion inhibiting properties, according to claim 23, characterized in that it additionally comprises the step of generating a foam and injecting a gas as a displacement fluid in said well or reservoir.
[0032]
32. Use of a foaming composition as defined in claim 2, characterized in that it injects the foam through an injection well and oil recovery from the production well.
[0033]
33. Use according to claim 32, characterized in that the process is performed through the same well that acts as an injection and production well.
[0034]
34. Use according to claim 32, characterized in that the process is carried out in naturally fractured reservoirs that simultaneously act as an injection and production well and that comprises the following steps: a) placing the foam composition with modification properties the wetting and corrosion inhibiting capacity in the high conductivity zones of said reservoir; b) stop said production well for a period of 6 to 9 days; and c) opening the well and reactivating the production, in which said foaming composition includes a supramolecular complex having the formula:
[0035]
35. Use according to claim 32, characterized in that the process is carried out in naturally fractured reservoirs through an injection well and production wells and comprises the following steps: a) continuously supplying a foaming composition with modifying properties the wetting and corrosion inhibiting capacity through the injection well; 2) forcefully displace the foam composition with wetting capacity modification and corrosion inhibiting properties through high conductivity zones of the reservoir; and 3) recover crude oil and hydrocarbon through the production well, wherein said foaming composition includes a supramolecular complex having the formula: wherein R 1 , R 2 and R 3 are linear alkyl, alkenyl or branched chains having 1 to 30 carbon atoms, and wherein said supramolecular molecular complex is obtained by interaction of alkyl amido propyl hydroxysulphates or alkyl hydroxysulphates with sodium and alkyl hydroxysulphonates sodium alkenyl sulfonates.

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同族专利:

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公开号 | 公开日

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CO7240101A1|2015-04-17|

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CN103849366B|2017-09-29|

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PH12013000298B1|2015-04-20|

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US9469804B2|2016-10-18|

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CN103849366A|2014-06-11|

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PH12013000298A1|2015-04-20|

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MX338862B|2016-04-28|

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EP2740781A1|2014-06-11|

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US20140151041A1|2014-06-05|

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CA2828519C|2016-10-18|

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CA2828519A1|2014-06-05|

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EP2740781B1|2015-12-30|

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MX2012014187A|2014-06-24|

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法律状态:
2017-06-27| B03A| Publication of a patent application or of a certificate of addition of invention [chapter 3.1 patent gazette]|

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2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |

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2019-09-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-10-06| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2021-03-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-05-25| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 26/09/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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MXMX/A/2012/014187|2012-12-05|

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MX2012014187A|MX338862B|2012-12-05|2012-12-05|Foaming composition with wettability modifying and corrosion inhibitory properties for high temperature and ultra-high salinity.|

---