WO2016159834A1

WO2016159834A1 - Liquid for extracting low-pressure gas and oil

Info

Publication number: WO2016159834A1
Application number: PCT/RU2016/000173
Authority: WO
Inventors: Абдурашид Содикович ВОХИДОВ
Original assignee: Общество С Ограниченной Ответственностью "Автостанкопром"
Priority date: 2014-12-25
Filing date: 2016-03-28
Publication date: 2016-10-06
Also published as: EA201500308A1

Abstract

The invention relates to the oil and gas extraction industry and chemical industry, and specifically to compositions which can be used in the oil and gas industry for extracting gas and oil, in particular for solving problems relating to an increase in the extraction of oil and gas, to the separation of water and impurities from gas and oil products, to uniform movement of the gas-water and oil-water contact, to an increase in the gas and oil output of a formation, to an increase in the pumping intensity, to a reduction in the danger of the formation of fire-hazardous emissions of gas and oil, and to bactericidal activity and desulphurization. A composition for increasing the oil output from flooded formations and the extraction of low-condensate gas, which is in the form of a liquid with internal particle interaction, contains a surfactant with a di-monophilic molecule structure and dispersing properties, a chemical initiator in the form of particles or nanoparticles of an activating mineral (salts) of inorganic substances or organic esters, a branched fluorocarbon polymer and a liquid solvent which transitions into a gas-vapour phase according to the type of fractalizing structure, in which the polymer macro-molecules are dissolved according to the fractal principle, in the following ratio: chemical initiator - 1.0-10.8 % by mass; surfactant - 0.1-6.2 % by mass; branched fluorocarbon polymer - 0.03-8.5 % by mass; solvent - the remainder.

Description

LIQUID GAS AND OIL PRODUCTION LIQUID TECHNICAL FIELD

The invention relates to the oil and gas production and chemical industry 5, and in particular to technological compositions used in the oil and gas industry for gas and oil production, in particular, to solving problems of increasing oil and gas production, the allocation of water and impurities from gas and oil products, the uniformity of the contour advancement gas and oil content, increase gas and oil recovery, increase pumping intensity, reduce the risk of fire hazardous gas and oil emissions.

BACKGROUND

From the patent of the Russian Federation N22524227, IPC С09К8 / 68, publ. 07.27.2014, Schlumberger Technology B.V. (NL), a subterranean fluid treatment additive and a subterranean treatment method are known. Manufacturing Additive

15 liquids to increase the permeability of the proppant package contains an agent for adjusting the pH and an agent that controls the precipitation, when their mass ratio is from 1: 1 to 200: 1, and the additive itself is selected in granular form. A method of increasing the proppant packaging permeability involves preparing a processing fluid containing a viscoelastic

20, a surfactant having at least one degradable bond, or a thickening polymer, a hydrolyzable material, the aforementioned additive, followed by the introduction of the prepared treatment fluid into the formation.

The known composition has a number of disadvantages associated with 25 different viscosity values of additives due to the lack of components that provide a complex structured polymer structure, lack of the ability to transition to intermolecular effects and is limited by the application technology in the absence of a unified method of formation treatment,

zo In another patent of the Russian Federation Ns2506299 "Adding nonionic surfactants to water-soluble block copolymers to increase the stability of copolymers in aqueous solutions containing salt and / or surfactants", IPC C09K8 / 68, publ. 02/10/2014, RODIA INC. (US), disclosed invention for extracts hydrocarbons from underground reservoirs by introducing into the reservoir an aqueous fluid with a certain concentration of nonionic surfactant, which is selected from the group including condensation products of polyethylene oxide and alkyl phenols, condensation products of ethylene oxide with a product formed by the reaction of propylene oxide and ethylene diamine products, condensation products of aliphatic alcohols with hydrophobic alcohols styrene monomers. Condensation, hydrophobization and sedimentation can create cracks in the subterranean formation surrounding the wellbore due to the hydraulic fracturing that does not solve the problems posed by the invention.

Closest to the proposed technical solution (prototype) is a composition for enhancing oil recovery disclosed in RF patent N22266398, IPC E21 B43 / 22, publ. 12.20.2005, Pozdnyshev Gennady Nikolaevich (RU), in which the enhanced oil recovery of flooded reservoirs is achieved by pumping into the reservoir the estimated volume of the water-dispersed system (GVA), which spontaneously forms when dosing in fresh water 0.5 ... 1.0% reagent a solution of the surfactant RDN-0, followed by injection into the formation of an equal volume of an aqueous solution of sodium silicate.

Reagent RDN-0 is a concentrated (25 wt.%) Solution of a nonionic surfactant, for example, OP-10 or neonol (ethoxylated isononylphenol) Af 9-12, in an aromatic solvent, for example, toluene.

The prototype indicates that the injected solution has high oil laundering properties. It not only prevents unwanted contact of an aqueous solution of sodium silicate with produced water, but also as a result of washing the oil film from the surface of rock-containing clay particles, it favors more effective interaction with sodium silicate, that is, it promotes the formation of strong silicate gels in the washed water-saturated channels of the formation or poroplasts.

However, the prototype composition with surface-active substances (surfactants) with a diphilic structure of the molecule’s structure, which is injected, has a main disadvantage that impedes the achievement of the result indicated in the previous paragraph, although the prototype composition, in comparison with other known formulations, makes it possible to refuse expensive water-soluble polymers, special technological equipment or other chemical reagents. This drawback is that oil wettability of reservoir rocks remains.

SUMMARY OF THE INVENTION

The objective and technical result to which the invention is directed is to increase the efficiency of gas and oil production and the effectiveness of controlling the reduction of viscosity, as well as increasing the level of intensification of the production of natural gas, gas condensate and oil with an increase in the flow rate of the well, as well as for resuscitation of idle and low-production oil and gas wells, low-pressure gas or gas condensate wells with an increase in the gas recovery coefficient (including natural and low condensate), oil including by reducing the water content of the pumped oil or gas-liquid condensed mixture, as well as gas and gas condensate by homogenizing and creating excess or additional pressure to displace the extracted volumes of gas and oil. The task and the required technical result are achieved due to the new composition for increasing oil recovery in flooded formations and producing low condensate gas in the form of a liquid with internal interaction of particles containing a surfactant with a dimonophilic molecular structure and dispersing properties, a chemical initiator in the form of particles or nanoparticles of an activating mineral (salts) of inorganic substances or organic esters, a branched fluorocarbon polymer and a liquid solvent, th into the vapor-gas phase according to the type of fractal structure, in which the polymer macromolecules dissolve according to the fractal principle, in the following mass% ratio: chemical initiator - 1.0-10.8; Surfactant - 0.1-6.2; branched fluorocarbon polymer - 0.03-8.5; the solvent is the rest, while surfactants with a dimonophilic structure of a molecule of the type anionic, fluorinated or cationic surfactants are used as a surfactant, and organic and inorganic solvents of the polymer group of solvents that transform into the vapor-gas phase according to the fractal principle when exposed to temperature are used as a surfactant and / or chemical initiation having injection properties, in addition, as a chemical initiator having the chemical structure of a mineral, the method which injects a liquid molecule to separate hydrocarbons, oil products from water and impurities, and increasing particle motion by ordering the diphilic polarity, which creates a forward force field with respect to the direction of motion, thereby increasing the homogenization of substances, use serpentine and / or schungite and / or ethers, and an organic polymer of the group including the branched fluorocarbon or fluorocarbon polymer soluble groups of perfluoropolyesters of the synthesized structure containing fluorine atoms F or radicals with fluorine atoms F according to the structure of a branched fluorocarbon polymer, in which m backbone of the macromolecule is different in chemical composition from side chains - copolymers of a fluorine type n hydrides ftoramidov and / or carboxyl groups. A significant difference of the invention is a new liquid composition for the production of low-pressure gas and / or oil, containing a surfactant with a dimonophilic molecule structure and dispersing properties (0.1 -6.2 mass%), the chemical initiator is particles or nanoparticles of an activating mineral (salts) of inorganic substances or organic esters (1, 0-10.8 mass%), branched fluorocarbon polymer (0.03-8.5 mass%), in the form of a liquid of a colloidal solution with internal interaction of particles bound by van der forces -Vaal and (in some cases, ion-covalent bond) and an induction field and a liquid solvent (balance), rolling in the vapor phase fractalized type structure, wherein when pumping the proposed compound into the formation of soluble macromolecule polymers fractal principle; in this case, during depressurization, distribution or other movement, the interaction of liquid molecules with gas and oil products occurs due to the internal electric pulse moment, pressure is created and the process of separation and homogenization of gas oil products is activated according to the fractal (additive) scheme, the pressure changes according to the Boyle-Mariotte law and after introducing (pumping) fluid into the well increases the yield of produced volumes of gas and oil. In this case, the solvent macromolecules after injection into the well in the reservoir zone begin to separate according to the multifractal principle, their diffusion and concentration gradually increase as they interact with particles, creating clusters of homogeneous substances.

Micellar-polymer reduction in water cut is aimed both at increasing the coverage of productive formations by impact, and at eliminating capillary forces in water-filled formations. Due to the fact that interfacial tension between the micellar solution and formation fluids (oil and water or gas and condensates) is very low, the action of capillary forces is eliminated, oil or gas and water are displaced. The mechanism of the process of displacement by micellar solutions is determined by their physicochemical properties, as well as by the property of homogenization and the creation of excess pressure (Table 1).

Table 1

During the transition of the solution to the vapor-gas phase, fractalization and pressure build up during the interaction of the magnetic field with substances (hydrocarbons). Wettability affects some types of resistance logging. Nuclear magnetic resonance (NMR) measurements depend on the position of the molecules and the ability to interact with fluids with respect to the pore surface.

In real molecules, there are magnetic interactions of the nuclei that make up the molecule with each other and with the electron shells of the atoms in the molecule. These interactions affect the resonance parameters, since the bonds between the atoms and the electrons inside the atom have different energy levels. The principal conclusion follows from this that using the NMR method one can obtain various information about the properties of molecules: their fractal orientation and progressions in the spatial structure (conformation) during intermolecular interactions, chemical exchange, coagulation, homogenization.

An analysis of the properties of fractalizing atoms possessing NMR shows that for using the NMR phenomenon to study the behavior of solution molecules during film formation and applying the proposed composition, the role of NMR is the most suitable tool. This conclusion is based on the fact that it is the protons of the nuclei of hydrogen atoms ¹ H and the nuclei of fluorine atoms ⁹ F that have the strongest and most pronounced effect of MP. This can be illustrated in table. 2.

table 2

where μ _Β is the nuclear magneton equal to e p / 4ttm _pr , where e is the electron charge, n is the Planck constant, m _pr is the mass of the proton. The value μ _Β = 5.0505 · 10 ^"27 J / T.

Excess pressure (Table 3) is created as physical properties change with increasing temperature and / or chemical initiation.

The use of surfactants is based on increasing the oil washing properties of water and the activation of polymer and diffuse displacement processes with a decrease in interfacial tension at the oil-water interface. Adsorbed on the surface of oil and rock droplets, surfactants prevent the coalescence of droplets and their attachment to the rock. With a low surface tension, the oil droplets are easily deformed, thereby reducing the work required to push them through the narrowing of the pores. An additional effect is bactericidal and desulfurization. Fractalization reduces the development of bacteria in that it allows the transition of bacterial and sulfur cells from gas and oil to the hydrophobic phase by denitrification of hydrocarbons and by electron transfer. Bactericidal properties are explained by the chemical action of fractalizing liquid capillaries on colloids of bacterial cells, causing a change in their structure, dispersion and coagulation, as a result of which the cells die. Table 3. Vapor pressure, viscosity, density and surface tension on the liquid-vapor equilibrium line

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be more clear from the description, which is not restrictive and given with reference to the accompanying figure, in which:

FIG. 1 - schematically shows micelles with fractalized structures, namely the behavior of various types of surfactants in water, gas or oil.

DETAILED DESCRIPTION OF THE INVENTION

In the proposed composition to increase oil recovery and gas production, including in flooded formations, an increase in the recovery coefficient is achieved by using surfactants with a dimonophilic structure of the molecule. The structure of such a surfactant molecule is conventionally shown in FIG. 1. It can be seen from the figure that a molecule with a dimonophilic structure has two active heads at the ends of the molecule. It should be noted that the active heads of the molecule can be different in strength. It depends on the chemical formula of the surfactant. The molecule is oriented and penetrates at one end of the wetting angle (Q) - the hydrophilic side - sharp (advancing) into the structure of substances. The other end of the molecule is oriented and penetrates the hydrophobic dull (retreating) side into the structure of other substances. At a constant level of fractalization and the diffusion process, transitional surfaces (i.e., amphoteric) can be found that are well wetted and penetrate by both polar and nonpolar systems. The use of the anionic, fluorinated or cationic surfactants as a surfactant in the present invention provides a polarization of the wettability angle.

As a molecule with a dimonophilic structure, 5 molecules of anionic, fluorinated or cationic surfactants can be used. Such molecules are selected based on the characteristics of surfactants, activated by mixing and adding activating particles (nanoparticles). Upon contact with the surface, activated branched molecules lower the surface energy by a factor of 2–3 or more, that is, they are the strongest surfactants among the known ones. Therefore, when in contact with an oil film or natural or low condensate gas, such a molecule will easily break through the oil film and adsorb on the surface of the rock material of the reservoir, flushing (rolling) oil and creating a microemulsion with water. Thus, the dimonophilic surfactant molecule has powerful washing properties and 15 film-forming properties. Even more actively, the process of washing off oil and gas particles from the surface will occur upon contact with micelles (Fig. 1).

Since the lyophilic properties of such a surfactant molecule with respect to oil are completely absent, the rock surface will become absolutely non-wettable oil. This means that when the oil moves along such a surface 20 there will be no adhesive forces, friction will decrease, which will inevitably lead to a decrease in capillary resistance. The latter is a very important factor for oil and gas production.

At the same time, particles of oil and gas washed off the surface, which are gaseous or liquid globules, will inevitably 25 merge into the oil or gas phase, since the surface of the globules has a natural nature without surfactant. As a result of the active formation of the oil or gas phase, a process is formed, which in oil production is called the “oil shaft”. This means that the water-oil-surfactant system will go into the oil-water-surfactant state, which will naturally increase the influx of oil into the bottomhole zone of the well and increase oil recovery. As a consequence of the formation of the oil shaft, formation pressure will increase in the zone of high water saturation, just as if chemicals were used to thicken the water. As a result, conditions will be created for the penetration of water with surfactants into the zones of shunted volumes of oil, that is, there, where previously displacing water did not fall. Thus, the processes of oil unloading will occur in previously unreached areas of the oil reservoir, which injected water flowed around.

In the case of gas production, the level of particle motion and fractalization increases by ordering the polarity (creating an induction field) created by the force field, in which the molecules, passing into the vapor-gas medium, acquire the desired specified optimal orientation, that is, the active head of the molecule is positioned forward relative to the direction movements based on the use of an organofluorine polymer as a branched fluorocarbon polymer, including soluble perfluoropolyether polymers Synthesize structure containing fluorine F radicals or F fluorines structure or branched fluorocarboxylic fluorocarbon polymer wherein the main chain of the macromolecule is different in chemical composition from side chains - copolymers of fluorides type ftoramidov and / or carboxyl groups.

For example, derivatives of perfluoropolyesters with a molecular weight of more than 1500 may be present as a fluorine-containing polymer.

Perfluoropolyesters and their derivatives form a stable mixture with a weak chemical reaction between the components in a liquid with other components. When pumped into a well (layer) by technological methods, solvent fractions and other reagents, the liquids are fractalized, facilitating the interaction and intermolecular diffusion between the components of the heavy gas or oil fractions (condensate) and water (reservoir), where diphilic separation occurs, with subsequent creation of a separating nanoscale film thickness .

An increase in manufacturability, in particular, an increase in the level of intensification of production of natural gas, gas condensate, and oil with an increase in well production, occurs due to fractalization and decomposition of polymer macromolecules into smaller values. The expansion of the scope is due to the injection of fluid into hard-to-reach and mothballed wells, as well as in harsh climates (including the Arctic) based on the high temperature stability of the fluid. This is due to the properties of neutral perfluoropolyesters, which do not have reactive groups, by the end groups of the polymer chain may be —CF ₂ , —CF ₃ , —C2F5, —C3F6, —C3F7, and others.

The chemical nature of perfluoropolyethers (high strength of С-0 and C-F bonds, spatial protection provided by fluorine atoms) determines the high stability of compounds, making them suitable for use in 5 aggressive environments and in harsh climates.

In the present invention, organic and inorganic solvents of the group that create separating particles of oil or gas from impurities are used as a fractalizing agent in the liquid composition.

In the present invention, as an additional reinforcing reagent (soluble compound) in the composition of the liquid, crushed particles or nanoparticles of the type serpentine and / or shungite or ethers are used, which helps to inject a liquid molecule to separate hydrocarbons, oil products from water and impurities (for example, hydrogen sulfide, ethane , dodecane, particles of sand, clay, limestone) and increases the movement of particles 15 by ordering the diphilic polarity, which creates a forward force field with respect to the direction of motion oia, thereby increasing the homogenization of substances. This contributes to the injection of a liquid molecule in the separation and increases the movement of particles by ordering, which creates a force field. The effect is described in such a way that the molecules, acquiring the required desired optimal normal orientation when interacting with particles of oil or gas, enhance this effect with respect to the direction of motion.

The proposed composition is used as follows.

A fluid is injected into the formation — a colloidal solution with an internal interaction of 25 particles bound by van der Waals forces (in some cases, ion-covalent bonds) and an induction field, during depressurization, distribution or other movement, the interaction of the liquid molecules with gas and oil products occurs internal electric pulse moment at which pressure is created and the process of separation and homogenization of gas and oil products is activated according to the fractal (additive) circuit of the PS, pressure changes according to the Boyle-Mariotte law after administration (injection) of fluid in the wellbore is increased yield of harvested volume / particle and gas oil. In this case, the scattered flows of molecules will be practically minimized, which will correspond to the maximum minimization of flow solution and environmental impact.

Thus, the use of the proposed composition to increase oil recovery in flooded formations and the production of natural and low condensate gas allows increasing the coverage coefficient by watering the productive reservoir 5 of an oil and gas field both for fields with a heterogeneous reservoir structure and for fields with highly viscous parameters.

In addition, the water content in the produced products of the wells is reduced with a simpler separation of water and oil or condensates and gas. Due to the achieved higher coefficient of oil displacement and gas production and effective washing of the rock from oil and gas products, the volume of extracted products will directly increase. In the inventive method, as a surfactant for separation, surfactants of different groups (anionic, fluorinated, cationic, etc.) are used, depending on the nature

15 natural gas, gas condensate, oil and fields. When liquid is injected into the formation, the activated polymer molecules, which are capable of reacting with low-condensate gas or oil particles and attached to them, do not lose their reactivity. This process is associated with the breaking of the double bond or the destruction of the cycle, where the ability to further

20 addition of impurities. Chain growth occurs very quickly with the homogenization of substances and the release (creation) of pressure. Moreover, the method is not explosive or fire hazardous in its application.

The development can be used in various fields of industry both for intensification of oil, natural gas and gas condensate production with

25 by increasing the flow rate of the well, and for resuscitation of idle and low-flowing oil - gas wells, low-pressure gas or gas condensate wells with an increase in the gas recovery coefficient (including natural and low condensate) and oil with a decrease in the water cut of the pumped oil or gas-liquid condensed mixture, as well as gas and gas condensate by homogenizing and creating excess or additional pressure to displace the extracted volumes of gas and oil.

Although the present invention has been described in detail with examples of options that appear to be preferred, it must be remembered that these embodiments are for purposes only. illustration of the invention. This description should not be construed as limiting the scope of the invention, since variations in the described compositions and steps of the described methods by specialists in the field of chemistry, petrochemistry, the oil and gas industry, and others can be made to adapt them to specific compositions or situations, and not beyond the scope of the attached claims. Specialist in this field it is clear that within the scope of the invention, which is defined by the claims, various options and modifications are possible, including equivalent solutions.

Claims

FORMULA

1. Composition for improving oil recovery in flooded formations and production of low condensate gas in the form of a liquid with internal interaction

5 particles, containing a surfactant with a dimonophilic molecular structure and dispersing properties, a chemical initiator in the form of particles or nanoparticles of an activating mineral (salts) of inorganic substances or organic esters, a branched fluorocarbon polymer and a liquid solvent, which passes into the vapor-gas phase by the type of fractalizing structure in which the polymer macromolecules dissolve according to the fractal principle, in the following mass% ratio:

chemical initiator - 1, 0-10.8

Surfactant - 0.1-6.2

15 branched fluorocarbon polymer - 0.03-8.5

solvent is the rest.

2. The composition according to claim 1, in which a surfactant with a dimonophilic molecular structure of the type anionic, fluorinated or cationic surfactant is used as a surfactant.

20 3. The composition according to claim 1, in which organic and inorganic solvents of the polymer group of solvents are used as the solvent, which pass into the vapor-gas phase according to the fractal principle when exposed to temperature and / or chemical initiation, having injection properties.

25 4. The composition according to claim 1, in which, as a chemical initiator, having a chemical structure of a mineral that promotes the injection of a liquid molecule to separate hydrocarbons, oil products from water and impurities and increases the movement of particles by ordering the diphilic polarity, which creates a forward force field with respect to to the direction of motion, thereby increasing the homogenization of substances, use serpentine and / or shungite and / or esters.

5. The composition according to claim 1, in which as an branched fluorocarbon or fluorocarbon polymer using an organic polymer of a group comprising soluble groups of synthesized perfluoropolyesters structures containing fluorine atoms F or radicals with fluorine atoms F according to the structure of a branched fluorocarbon polymer in which the main chain of a macromolecule differs in chemical composition from side chains - copolymers of the type of fluorohydrides, fluoroamides and / or carboxyl groups.