CN108728066B - Composition with selective water plugging function and preparation method and application thereof - Google Patents
Composition with selective water plugging function and preparation method and application thereof Download PDFInfo
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- CN108728066B CN108728066B CN201710256345.7A CN201710256345A CN108728066B CN 108728066 B CN108728066 B CN 108728066B CN 201710256345 A CN201710256345 A CN 201710256345A CN 108728066 B CN108728066 B CN 108728066B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/5086—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/514—Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose
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- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/13—Methods or devices for cementing, for plugging holes, crevices, or the like
Abstract
The invention relates to the field of water plugging materials, and discloses a composition with a selective water plugging function, a preparation method thereof, a composition prepared by the method and application thereof. Specifically, the composition contains asphalt modified oil-soluble resin, a main emulsifier and a water-soluble polymer, wherein the main emulsifier is selected from a compound shown as a formula (I) and/or a compound shown as a formula (II), R1Is C12-C18 alkyl, M1Is an alkali metal or alkaline earth metal, R2Is C12-C18 alkyl or aralkyl, M2Is an alkali metal or an alkaline earth metal. The composition with the selective water plugging function provided by the invention has good effects of plugging water and not plugging oil, has temperature resistance and salt resistance and scouring resistance, and can be well adapted to high-temperature and high-salt oil reservoir conditions. R1O‑SO3‑M1(formula I) R2‑SO3‑M2(formula II).
Description
Technical Field
The invention relates to the field of water plugging materials, in particular to a composition with a selective water plugging function and a preparation method thereof, and the composition prepared by the method and application thereof.
Background
The polymer water shutoff material is a water shutoff agent which is applied in large scale at present and is mainly divided into a polymer phase permeation regulator and a polymer gel water shutoff agent. The main difference between the two is that the phase permeation regulator is mainly long-chain polymer molecules, and the polymer molecular chains stretch in the water phase and shrink in the oil phase to form a dragging effect on the water phase and reduce the water phase permeability, and the system cannot cause physical blocking of the pore volume, but the water blocking strength is not enough and the scouring resistance is poor. The polymer gel water shutoff agent enables the oil-water phase permeability to be reduced unevenly by means of the change of the effective movable volume under the action of oil and water, but the oil-water channel physical shutoff can be caused by the treatment mode, so that the seepage capability of a porous medium is reduced, the oil production capability is also reduced while the water production of an oil well is greatly reduced, the liquid production amount is too low due to improper treatment, and the yield of crude oil is reduced. Therefore, the system is mostly used for treating the water absorption profile of the water injection well with serious heterogeneous condition, and when the system is used for plugging water in a production well, a more complex auxiliary method such as a temporary plugging method, an annular space extreme pressure method, an over-displacement method and the like is needed. Although the polymer water plugging material has a good practical effect, a corresponding injection process must be formulated according to the actual conditions of each oil field in the using process, otherwise, the injection of the water plugging agent cannot achieve the water plugging effect, the water yield is increased, and the crude oil yield is reduced.
Although the existing oil-based and water-based water plugging systems have certain selectivity, the water plugging and oil plugging systems can block water and oil, and indoor physical and model experiments show that the oil plugging rate of the existing plugging agent is more than 35%, the temperature resistance and salt resistance of the systems are poor, and the popularization and application range is small. The research of the solution type selective plugging agent is the development direction of the polymer material technology, and the material microstructure recognition and synthesis modification technology based on the molecular level is the key of the research of the selective plugging agent; the interaction mechanism of the plugging agent and the rock is researched under the real oil reservoir condition, the essence of the plugging agent is deduced from the molecular level, and the method is the basis of the research and evaluation of the selective plugging agent. However, the water plugging material has low flushing resistance and short service cycle. Therefore, aiming at harsh oil reservoir conditions, the improvement of the temperature resistance and salt tolerance of the water plugging material and the scouring resistance thereof have important significance.
At present, selective water shutoff agents and deep profile control technologies at home and abroad are improved day by day, and the selective water shutoff materials are developed greatly on the technologies of research development, construction process and the like, but along with the development of oil fields, the characteristics of oil layers and the environment are changed constantly, particularly, the water shutoff materials are adopted for a long time to make the contradiction of oil reservoir development more prominent in the later development period, the practical development experience of the oil fields is summarized according to the characteristics of the selective water shutoff materials, and the technical problem which must be overcome at present by the selective water shutoff agents is provided so as to develop new technologies in a targeted manner to adapt to the special oil fields and improve the water shutoff effect of a selective system.
In summary, most of the selective plugging agents used for water plugging of oil wells at present are gels or jelly generated by water-soluble polymers such as polyacrylamide and derivatives thereof in the stratum to plug the stratum water, or oil-based plugging agents are used for gelling or curing when meeting water to plug water channeling passages, but due to poor selectivity, the oil phase permeability can be greatly reduced while water plugging is carried out, so that low liquid after plugging is caused, and the application of the water plugging technology of the oil wells is restricted. Therefore, a novel high-selectivity water plugging material is developed, the water plugging and oil plugging of an oil layer are realized, and the method has important significance for improving the productivity of an oil well in an ultrahigh water cut period.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a composition with a selective water plugging function, a preparation method and application thereof. The composition with the selective water plugging function provided by the invention has good effects of plugging water and not plugging oil, has temperature resistance and salt resistance and scouring resistance, and can be well adapted to high-temperature and high-salt oil reservoir conditions.
The inventor of the invention discovers in research that a novel emulsion suspension type water plugging material can be obtained by matching specific asphalt modified oil-soluble resin, a main emulsifier and a surface active polymer, has stronger affinity with oil reservoir stratum rock, and can generate powerful plugging to stratum pore canal water phase after being injected into stratum oil reservoir pores at an oil production well through an injection pump, and has strong scouring resistance, thereby greatly reducing the water phase permeability; and when the water plugging material meets the oil phase of a stratum pore channel, the water plugging material can act with crude oil to automatically plug, so that the influence on the oil phase permeability is reduced, and the effect of plugging water and not plugging oil is achieved. In addition, the water plugging material has insensitivity to the salinity of formation water and a higher softening point (above 90 ℃), so that the temperature resistance and salt resistance of the water plugging material are enhanced, and the water plugging material is suitable for the conditions of high-temperature and high-salinity oil reservoirs.
Further, the inventors of the present invention have found, through further studies, that a novel emulsion suspension type water shutoff material is prepared by adding a specific primary emulsifier to an aqueous solution of a water-soluble polymer to form a stable emulsion and then adding an asphalt-modified oil-soluble resin to the emulsion. The addition of the water-soluble polymer improves the viscosity of the emulsion, can further activate the asphalt modified oil-soluble resin particles, prevents agglomeration and adhesion among the resin particles, is more convenient for suspension, injection and sand carrying of the resin particles, and is beneficial to enhancing the scouring resistance of the water plugging material.
Accordingly, in order to achieve the above objects, in a first aspect, the present invention provides a composition having a selective water shutoff function, comprising an asphalt-modified oil-soluble resin, a primary emulsifier and a water-soluble polymer, wherein the primary emulsifier is selected from a compound represented by formula (I) and/or a compound represented by formula (II),
R1O-SO3-M1(formula I) is shown in the specification,
R2-SO3-M2(formula II) in the formula (III),
wherein R is1Is C12-C18 alkyl, M1Is an alkali metal or alkaline earth metal, R2Is aralkyl or C12-C18 alkyl, M2Is an alkali metal or an alkaline earth metal.
In a second aspect, the present invention also provides a preparation method of a composition with a selective water shutoff function, comprising the following steps:
(1) mixing a water-soluble polymer with water to form an aqueous solution;
(2) mixing a primary emulsifier with the aqueous solution to form an emulsion;
(3) mixing an asphalt-modified oil-soluble resin with the emulsion;
wherein the main emulsifier is selected from a compound shown in a formula (I) and/or a compound shown in a formula (II),
R1O-SO3-M1(formula I) is shown in the specification,
R2-SO3-M2(formula II) in the formula (III),
wherein R is1Is C12-C18 alkyl, M1Is an alkali metal or alkaline earth metal, R2Is aralkyl or C12-C18 alkyl, M2Is an alkali metal or an alkaline earth metal.
In a third aspect, the invention also provides a composition with the selective water plugging function, which is prepared by the preparation method.
In a fourth aspect, the invention also provides the application of the composition in a water plugging material, in particular to the application in an oil field water plugging material.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the invention provides a composition with selective water plugging function, which comprises asphalt modified oil-soluble resin, a main emulsifier and a water-soluble polymer, wherein the main emulsifier is selected from a compound shown in a formula (I) and/or a compound shown in a formula (II),
R1O-SO3-M1(formula I) is shown in the specification,
R2-SO3-M2(formula II) in the formula (III),
wherein R is1Is C12-C18 alkyl (or straight chain alkyl), M1Is an alkali metal or alkaline earth metal, R2Is aralkyl or C12-C18 alkyl (or linear alkyl), M2Is an alkali metal or an alkaline earth metal.
According to the composition, relative to 100 parts by weight of the asphalt modified oil-soluble resin, the content of the main emulsifier is 10-400 parts by weight, and the content of the surface active polymer is 0.05-100 parts by weight; preferably, the content of the primary emulsifier is 40 to 100 parts by weight and the content of the water-soluble polymer is 0.1 to 20 parts by weight with respect to 100 parts by weight of the asphalt-modified oil-soluble resin.
According to the composition of the present invention, in the asphalt-modified oil-soluble resin, the weight ratio of the asphalt to the oil-soluble resin is 1: 0.01 to 100, preferably 1: 0.1-20. The source of the asphalt-modified oil-soluble resin is not particularly limited in the present invention, and can be obtained by a conventional laboratory means, for example, by melt blending asphalt with an oil-soluble resin. Preferably, the particle size of the asphalt-modified oil-soluble resin is 3 to 100 μm, preferably 3 to 50 μm, for better selective water shutoff.
In the composition of the present invention, the asphalt-modified oil-soluble resin is selected from one or more of asphalt-modified rosin resin, asphalt-modified dammar resin, asphalt-modified oil-soluble phenol resin, asphalt-modified petroleum resin, asphalt-modified terpene resin, and asphalt-modified coumarone resin. The source of the oil-soluble resin in the present invention is not particularly limited, and for example, it can be obtained by a conventional commercially available means.
In the composition of the present invention, in the primary emulsifier, R1Is C12-C14 alkyl, M1Is an alkali metal, R2Is aralkyl or C12-C14 alkyl, M2Is an alkali metal. Preferably, the primary emulsifier is selected from one or more of sodium dodecyl sulfate, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
The composition of the present invention is not particularly limited in the kind of the water-soluble polymer, and may be any conventional water-soluble polymer. In a preferred case, the water-soluble polymer is at least one of an anionic polymer, a cationic polymer, and a surface-active polymer.
More preferably, the anionic polymer is one having an ionicity of 5 to 30%, preferably 15 to 25%; the viscosity-average molecular weight is 1000-3500 ten thousand, preferably 2000-3000 ten thousand; further preferably, the anionic polymer is a partially hydrolyzed polyacrylamide and/or a sulfonic acid polyacrylamide. In the present invention, "the ionic degree of an anionic polymer" means the mass percentage content of anionic structural units in the anionic polymer, and is measured according to GB 12005.6-89.
More preferably, the cationic polymer has an ionicity of from 5 to 30%, preferably from 15 to 25%; the viscosity-average molecular weight is 1000-3500 ten thousand, preferably 2000-3000 ten thousand; further preferably, the cationic polymer is a cationic polyacrylamide and/or a cationic acrylamide copolymer. In the present invention, "the ionic degree of the cationic polymer" means the mass percentage content of the cationic structural unit in the cationic polymer, and is measured by a titration method.
More preferably, the surface active polymer has a surface tension of 25 to 50mN/m, preferably 30 to 40 mN/m; the viscosity average molecular weight is 500-3000 ten thousand, preferably 1000-2500 ten thousand; further preferably, the surface active polymer is a copolymer of an acrylamide-based monomer and a surface active monomer. The surface active monomer is a non-ionic monomer. In the present invention, the "surface tension of the surface-active polymer" was measured by using a surface tension meter model DCAT-21 from Datophysics, Germany.
In the composition of the present invention, the source of the water-soluble polymer is not particularly limited in the present invention, and for example, it can be obtained by a conventional commercial method or can be prepared in a laboratory.
The compositions according to the invention may also contain a co-emulsifier. The kind of the co-emulsifier is not particularly limited in the present invention, for example, the co-emulsifier may be selected from one or more of span 20, span 40, span 60, span 80, tween 20, tween 40, tween 60 and tween 80. Preferably, the co-emulsifier is contained in an amount of 0 to 500 parts by weight, preferably 10 to 50 parts by weight, relative to 100 parts by weight of the asphalt-modified oil-soluble resin.
In the composition of the present invention, the components of the composition may be stored in a mixed state before use or may be stored independently of each other. Preferably, each component of the composition is stored separately prior to use.
According to the composition of the present invention, the composition may further contain water. In particular, the composition may be mixed with water at the time of use. In a preferred case, the water content is 5 to 1000mL, preferably 8 to 120mL, more preferably 10 to 100mL, per gram of the asphalt-modified oil-soluble resin. In a second aspect, the present invention also provides a method for preparing a composition with selective water shutoff function, comprising: mixing the asphalt modified oil-soluble resin, the main emulsifier and the water-soluble polymer with water.
In the present invention, a material having a selective water shutoff function can be obtained by mixing the above-mentioned components, however, mixing the components in a certain order can further improve the water shutoff performance thereof, and therefore, in a preferred embodiment of the present invention, the present invention also provides a method for preparing a composition having a selective water shutoff function, the method comprising the steps of:
(1) mixing a water-soluble polymer with water to form an aqueous solution;
(2) mixing a primary emulsifier with the aqueous solution to form an emulsion;
(3) mixing an asphalt-modified oil-soluble resin with the emulsion;
wherein the main emulsifier is selected from a compound shown in a formula (I) and/or a compound shown in a formula (II),
R1O-SO3-M1(formula I) is shown in the specification,
R2-SO3-M2(formula II) in the formula (III),
wherein R is1Is C12-C18 alkyl (or straight chain alkyl), M1Is an alkali metal or alkaline earth metal, R2Is aralkyl or C12-C18 alkyl (or linear alkyl), M2Is an alkali metal or an alkaline earth metal.
According to the preparation method, relative to 100 parts by weight of the asphalt modified oil-soluble resin, the amount of the main emulsifier is 10-400 parts by weight, and the amount of the surface active polymer is 0.05-100 parts by weight; preferably, the primary emulsifier is used in an amount of 4 to 100 parts by weight and the water-soluble polymer is used in an amount of 0.1 to 30 parts by weight, relative to 100 parts by weight of the asphalt-modified oil-soluble resin. In the invention, the weight of each raw material is calculated according to the charging ratio.
According to the preparation method of the present invention, in the asphalt-modified oil-soluble resin, the weight ratio of the asphalt to the oil-soluble resin is 1: 0.01 to 100, preferably 1: 0.1-20. The source of the asphalt-modified oil-soluble resin is not particularly limited in the present invention, and can be obtained by a conventional laboratory means, for example, by melt blending asphalt with an oil-soluble resin. Preferably, the particle size of the asphalt-modified oil-soluble resin is 3 to 100 μm, preferably 3 to 50 μm, for better selective water shutoff.
In the preparation method of the present invention, the asphalt-modified oil-soluble resin may be selected from one or more of asphalt-modified rosin resin, asphalt-modified dammar resin, asphalt-modified oil-soluble phenol resin, asphalt-modified petroleum resin, asphalt-modified terpene resin, and asphalt-modified coumarone resin. The source of the oil-soluble resin in the present invention is not particularly limited, and for example, it can be obtained by a conventional commercially available means.
In the preparation method of the present invention, in the primary emulsifier, R is1Is C12-C14 alkyl, M1Is an alkali metal, R2Is aralkyl or C12-C14 alkyl, M2Is an alkali metal. Preferably, the primary emulsifier is selected from one or more of sodium dodecyl sulfate, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
The kind of the water-soluble polymer is not particularly limited in the present invention according to the production method of the present invention, and may be conventionally selected in the art. In a preferred case, the water-soluble polymer is at least one of an anionic polymer, a cationic polymer, and a surface-active polymer.
More preferably, the anionic polymer is one having an ionicity of 5 to 30%, preferably 15 to 25%; the viscosity-average molecular weight is 1000-3500 ten thousand, preferably 2000-3000 ten thousand; further preferably, the anionic polymer is a partially hydrolyzed polyacrylamide and/or a sulfonic acid polyacrylamide.
More preferably, the cationic polymer has an ionicity of from 5 to 30%, preferably from 15 to 25%; the viscosity-average molecular weight is 1000-3500 ten thousand, preferably 2000-3000 ten thousand; further preferably, the cationic polymer is a cationic polyacrylamide and/or a cationic acrylamide copolymer.
More preferably, the surface active polymer has a surface tension of 25 to 50mN/m, preferably 30 to 40 mN/m; the viscosity average molecular weight is 500-3000 ten thousand, preferably 1000-2500 ten thousand; further preferably, the surface active polymer is a copolymer of an acrylamide-based monomer and a surface active monomer. Further preferably, the surface active monomer is a non-ionic monomer.
In the production method of the present invention, the source of the water-soluble polymer is not particularly limited, and for example, the water-soluble polymer can be obtained by a conventional commercially available method or can be produced in a laboratory.
According to the preparation method of the present invention, the composition may further contain a co-emulsifier. The kind of the co-emulsifier is not particularly limited in the present invention, for example, the co-emulsifier may be selected from one or more of span 20, span 40, span 60, span 80, tween 20, tween 40, tween 60 and tween 80. Preferably, the co-emulsifier is used in an amount of 0 to 500 parts by weight, preferably 10 to 50 parts by weight, relative to 100 parts by weight of the asphalt-modified oil-soluble resin.
In the production method of the present invention, the components in the composition may be stored in a mixed state before use or may be stored independently of each other. Preferably, each component of the composition is stored separately prior to use.
According to the preparation method of the present invention, the amount of the water used in the present invention is not particularly limited as long as a stable emulsion-suspended water shutoff material can be finally formed. For example, the water content is 5 to 1000mL, preferably 8 to 120mL, and more preferably 10 to 100mL per gram of the asphalt-modified oil-soluble resin.
According to the preparation method of the present invention, in the step (1), the mixing manner is not particularly limited in the present invention as long as the components in the system can be uniformly mixed, and for example, the mixing can be performed under stirring. In a preferred aspect, the mixing conditions include: the mixing temperature is 20-50 ℃, the mixing time is 1-6h, and the stirring speed is 500-700 r/min.
According to the preparation method of the present invention, in the step (2), the mixing manner is not particularly limited in the present invention as long as the components in the system can be uniformly mixed, and for example, the mixing can be performed under stirring. In a preferred aspect, the mixing conditions include: the mixing temperature is 20-50 ℃, the mixing time is 1-3h, and the stirring speed is 500-700 r/min.
According to the preparation method of the present invention, in the step (3), the mixing manner is not particularly limited in the present invention as long as the components in the system can be uniformly mixed, and for example, the mixing can be performed under stirring. In a preferred aspect, the mixing conditions include: the mixing temperature is 20-50 ℃, the mixing time is 0.5-2h, and the stirring speed is 500-700 r/min.
In a third aspect, the invention also provides a composition (material) with a selective water plugging function, which is prepared by the preparation method.
In a fourth aspect, the invention also provides the application of the composition in a water plugging material, in particular to the application in an oil field water plugging material.
In the present invention, the environmental conditions of the oil field may include: the temperature is 40-130 ℃, preferably 70-110 ℃, and more preferably 90-110 ℃; the degree of mineralization is 100-200,000mg/L, preferably 10,000-100,000mg/L, more preferably 50,000-100,000 mg/L.
The present invention will be described in detail below by way of examples.
Unless otherwise specified, the reagents used in the following examples and comparative examples are commercially available.
In the following examples and comparative examples,
the oil-soluble phenolic resin is purchased from Jining HuaKai resin Co., Ltd, and has the brand number of 2402;
the petroleum resin is purchased from Jitian chemical industry Co., Ltd, Shenzhen, and the brand is C5C 9;
coumarone resin was purchased from Shandong Xiang Showa New materials Co., Ltd, and was designated 18 #;
the rosin resin is purchased from Shanghai Sanlian industry Co Ltd, and the brand is TF-100;
the anionic polymer (partially hydrolyzed polyacrylamide) is purchased from Beijing Hokkolyme chemical industry group, Inc., and has a trade name of KYPAM, a viscosity-average molecular weight of 2500 ten thousand and an ionic degree of 24 percent;
the cationic polyacrylamide is purchased from Beijing Homex chemical industry group, Limited liability company, and has the brand number of CPAM, the viscosity-average molecular weight of 2300 ten thousand and the ionic degree of 26 percent;
the surface active polymer is purchased from China petrochemical Beijing chemical research institute, and has the brand number of BHJ-1, the viscosity average molecular weight of 2000 ten thousand and the surface tension of 32 mN/m.
In the following examples and comparative examples, the test methods involved are as follows:
the plugging rate is carried out on a rock core flow test device according to the plugging rate test procedure in SY/T5840-2007 bridge plugging material indoor test method for drilling fluid. Specifically, the method comprises the following steps:
and (3) measuring the water plugging rate: loading the artificial core into core holder, saturating with water, and measuring water phase permeability (K)w1) Then 10mL of water plugging agent is extruded, and after curing for 24h at 90 ℃, the permeability (K) of the mixture after adding the water plugging agent is measured by waterw2)，Kw2And Kw1Ratio (K)w2/Kw1) Namely the water plugging rate.
And (3) measuring the oil plugging rate: loading the artificial core into core holder, saturating with oil, and measuring oil phase permeability (K)o1) Then 10mL of water shutoff agent is extruded, and after curing for 24h at 90 ℃, the permeability (K) of the water shutoff agent added is measured by oilo2)，Ko2And Ko1Of (K)o2/Ko1) Namely the oil plugging rate.
And (3) measuring the scouring resistance multiple: after the water plugging rate is measured, water with 50 times of pore volume multiple (PV) is continuously injected into the rock core, the permeability under different PV numbers is recorded, the water plugging rate under different PV numbers is calculated according to the measuring method of the water plugging rate, and the scouring resistance multiple is the maximum PV number of the injected water when the water plugging rate is more than or equal to 80%. Normally, the water blocking rate at 50PV number is measured, and the value is more than or equal to 80 percent, which indicates that the material has excellent flushing resistance.
Wherein the artificial core is obtained by filling quartz sand of 40-60 meshes in a mould.
Preparation example 1
The preparation example is used for illustrating the asphalt modified oil-soluble resin provided by the invention.
1g of asphalt and 10g of oil-soluble phenolic resin are melted and blended at the temperature of 130 ℃, and are crushed and sieved after being cooled to prepare the asphalt modified oil-soluble phenolic resin S1.
Preparation example 2
The preparation example is used for illustrating the asphalt modified oil-soluble resin provided by the invention.
The procedure of production example 1 was conducted, except that 10g of rosin resin was used in place of the oil-soluble phenol resin used in production example 1, to obtain an asphalt-modified rosin resin S2.
Preparation example 3
The preparation example is used for illustrating the asphalt modified oil-soluble resin provided by the invention.
The procedure of preparation example 1 was followed, except that 10g of a petroleum resin was used in place of the oil-soluble phenol resin used in preparation example 1, to obtain an asphalt-modified rosin resin S3.
Preparation example 4
The preparation example is used for illustrating the asphalt modified oil-soluble resin provided by the invention.
The procedure of preparation example 1 was followed, except that 10g of coumarone resin was used in place of the oil-soluble phenol resin used in preparation example 1, to obtain an asphalt-modified rosin resin S4.
Example 1
This example illustrates the composition with selective water shutoff function provided by the present invention.
1. 0.03g of anionic polymer is weighed and added into 100mL of water, and after the mixture is fully stirred (600r/min) for 1h at the temperature of 20 ℃, an aqueous solution is formed;
2. respectively weighing 1g of sodium dodecyl benzene sulfonate and 0.5g of span 60, sequentially adding into the aqueous solution, and fully stirring (600r/min) for 3h at 20 ℃ to form stable emulsion;
3.1 g of asphalt modified oil soluble phenolic resin S1 (with the grain diameter of 3-50 mu m) is weighed and added into the emulsion, and after the mixture is fully stirred (600r/min) for 1h at the temperature of 20 ℃, the stable emulsion suspension-shaped water plugging material A1 is formed.
Tests show that under the conditions of high temperature (90 ℃) and high salt (the mineralization degree is 50,000mg/L), the water blocking rate of the water blocking material A1 is 95.74%, the oil blocking rate is 3.25%, and the scouring resistance multiple is more than 50 PV. This shows that the water plugging material prepared in this example has excellent selective plugging rate and flushing resistance to oil/water, and particularly still has good selective plugging rate to oil/water under high temperature and high salt conditions.
Example 2
This example illustrates the composition with selective water shutoff function provided by the present invention.
1. Weighing 0.01g of cationic polymer, adding the cationic polymer into 100mL of water, and fully stirring (600r/min) for 6h at 20 ℃ to form an aqueous solution;
2. respectively weighing 5g of sodium dodecyl sulfate and 1g of Tween 60, sequentially adding into the aqueous solution, and fully stirring (600r/min) at 30 ℃ for 1h to form stable emulsion;
3. 10g of asphalt modified petroleum resin S3 (with the particle size of 3-50 mu m) is weighed and added into the emulsion, and after the mixture is fully stirred (600r/min) for 2h at the temperature of 50 ℃, the stable emulsion suspension-shaped water plugging material A2 is formed.
Tests show that under the conditions of high temperature (90 ℃) and high salt (the mineralization is 80,000mg/L), the water blocking rate of the water blocking material A2 is 94.42%, the oil blocking rate is 4.62%, and the scouring resistance multiple is more than 50 PV. This shows that the water plugging material prepared in this example has excellent selective plugging rate and flushing resistance to oil/water, and particularly still has good selective plugging rate to oil/water under high temperature and high salt conditions.
Example 3
This example illustrates the composition with selective water shutoff function provided by the present invention.
1. Weighing 1g of surface active polymer, adding the surface active polymer into 100mL of water, and fully stirring (600r/min) for 3h at 20 ℃ to form an aqueous solution;
2. respectively weighing 2g of sodium dodecyl sulfate and 1g of Tween 60, sequentially adding into the aqueous solution, and fully stirring (600r/min) at 30 ℃ for 2h to form stable emulsion;
3. 5g of asphalt modified rosin resin S2 (with the particle size of 3-50 mu m) is weighed and added into the emulsion, and after the mixture is fully stirred (600r/min) for 1.5h at the temperature of 30 ℃, a stable emulsion suspension-shaped water plugging material A3 is formed.
Tests show that under the conditions of high temperature (90 ℃) and high salt (the mineralization degree is 100,000mg/L), the water plugging rate of the water plugging material A3 is 99.21%, the oil plugging rate is 4.02%, and the scouring resistance multiple is more than 50 PV. This shows that the water plugging material prepared in this example has excellent selective plugging rate and flushing resistance to oil/water, and particularly still has good selective plugging rate to oil/water under high temperature and high salt conditions.
Example 4
This example illustrates the composition with selective water shutoff function provided by the present invention.
1. 0.3g of surface active polymer is weighed and added into 100mL of water, and the mixture is fully stirred (600r/min) for 3 hours at the temperature of 20 ℃ to form aqueous solution;
2. respectively weighing 1.5g of sodium dodecyl benzene sulfonate and 0.5g of span 40, sequentially adding into the aqueous solution, and fully stirring (600r/min) for 1h at 30 ℃ to form stable emulsion;
3. 1.5g of asphalt modified coumarone resin S4 (particle size 3-50 μm) was weighed out and added to the above emulsion, and after stirring thoroughly (600r/min) at 40 ℃ for 0.5h, a stable emulsion suspended water shutoff material A4 was formed.
Tests show that under the conditions of high temperature (90 ℃) and high salt (the mineralization is 80,000mg/L), the water plugging rate of the water plugging material A4 is 99.56%, the oil plugging rate is 3.18%, and the scouring resistance multiple is more than 50 PV. This shows that the water plugging material prepared in this example has excellent selective plugging rate and flushing resistance to oil/water, and particularly still has good selective plugging rate to oil/water under high temperature and high salt conditions.
Example 5
This example illustrates the composition with selective water shutoff function provided by the present invention.
The procedure was followed as in example 4, except that span 40, water-blocking material A5, was not added in step (2).
Tests show that under the conditions of high temperature (90 ℃) and high salt (the mineralization is 80,000mg/L), the water plugging rate of the water plugging material A5 is 96.72%, the oil plugging rate is 3.89%, and the scouring resistance multiple is more than 50 PV. This shows that the water plugging material prepared in this example has excellent selective plugging rate and flushing resistance to oil/water, and particularly still has good selective plugging rate to oil/water under high temperature and high salt conditions.
Example 6
This example illustrates the composition with selective water shutoff function provided by the present invention.
The procedure was followed as in example 4, except that, in step (1), the surface-active polymer was added in an amount of 1.5g, to obtain a water-blocking material A6.
Tests show that under the conditions of high temperature (90 ℃) and high salt (the mineralization is 80,000mg/L), the water plugging rate of the water plugging material A6 is 99.56%, the oil plugging rate is 7.35%, and the scouring resistance multiple is more than 50 PV. This shows that the water plugging material prepared in this example has better selective plugging rate and flushing resistance to oil/water.
Example 7
This example illustrates the composition with selective water shutoff function provided by the present invention.
The procedure was followed as in example 4, except that, in the step (1), the surface-active polymer was added in an amount of 0.75mg to obtain a water-plugging material A7.
Tests show that under the conditions of high temperature (90 ℃) and high salt (the mineralization is 80,000mg/L), the water blocking rate of the water blocking material A6 is 86.75%, the oil blocking rate is 13.25%, and the scouring resistance multiple is 50 PV. This shows that the water plugging material prepared in this example has better selective plugging rate and flushing resistance to oil/water.
Example 8
This example illustrates the composition with selective water shutoff function provided by the present invention.
The procedure was carried out in accordance with example 4 except that, in step (2), sodium dodecylbenzenesulfonate was added in an amount of 6g, to obtain a water-plugging material A8.
Tests show that under the conditions of high temperature (90 ℃) and high salt (the mineralization is 80,000mg/L), the water blocking rate of the water blocking material A8 is 92.15%, the oil blocking rate is 12.54%, and the scouring resistance multiple is more than 50 PV. This shows that the water plugging material prepared in this example has better selective plugging rate and flushing resistance to oil/water.
Example 9
This example illustrates the composition with selective water shutoff function provided by the present invention.
The procedure was carried out in accordance with example 4 except that, in step (1), sodium dodecylbenzenesulfonate was added in an amount of 0.15g, to obtain a water-plugging material A9.
Tests show that under the conditions of high temperature (90 ℃) and high salt (the mineralization is 80,000mg/L), the water plugging rate of the water plugging material A6 is 89.25%, the oil plugging rate is 13.63%, and the scouring resistance multiple is more than 50 PV. This shows that the water plugging material prepared in this example has better selective plugging rate and flushing resistance to oil/water.
Example 10
This example illustrates the composition with selective water shutoff function provided by the present invention.
The procedure of example 4 was followed, except that in step (1), the same weight of the skin-forming agent (available from Shanghai Haibo Co., Ltd., brand Haibo I, viscosity average molecular weight 350 ten thousand, surface tension 36mN/m) was used in place of the surface-active polymer, to obtain a water-blocking material A11.
Tests show that under the conditions of high temperature (90 ℃) and high salt (the mineralization is 80000mg/L), the water blocking rate of the water blocking material A11 is 82.15%, the oil blocking rate is 17.62%, and the scouring resistance multiple is less than 50 PV. This shows that the water plugging material prepared in this example has better selective plugging rate and flushing resistance to oil/water.
Example 11
This example illustrates the composition with selective water shutoff function provided by the present invention.
0.03g of surface active polymer, 1g of sodium dodecyl benzene sulfonate, 0.5g of span 60 and 1g of asphalt modified oil-soluble phenolic resin S1 (with the particle size of 3-50 mu m) are weighed and added into 100mL of water, and after the mixture is fully stirred for 5 hours at the temperature of 20 ℃, the stable emulsion suspension-shaped water plugging material A11 is formed.
Tests show that under the conditions of high temperature (90 ℃) and high salt (the mineralization is 80,000mg/L), the water blocking rate of the water blocking material A11 is 82.12%, the oil blocking rate is 17.58%, and the scouring resistance multiple is less than 50 PV. This shows that the water plugging material prepared in this example has better selective plugging rate and flushing resistance to oil/water.
Comparative example 1
The procedure of example 4 was followed, except that sodium laurylsulfate was not added, to obtain a water blocking material D1.
Tests show that under the conditions of high temperature (90 ℃) and high salt (the mineralization is 80,000mg/L), the water blocking rate of the water blocking material D1 is 92.16%, the oil blocking rate is 23.45%, and the scouring resistance multiple is less than 50 PV.
Comparative example 2
The procedure of example 4 was followed, except that no surface active polymer was added, to obtain a water-plugging material D2.
Tests show that under the conditions of high temperature (90 ℃) and high salt (the mineralization is 80,000mg/L), the water blocking rate of the water blocking material D2 is 82.69%, the oil blocking rate is 21.58%, and the scouring resistance multiple is less than 50 PV.
Comparative example 3
The procedure of example 4 was followed, except that 1.5g of coumarone resin was used in place of the asphalt-modified coumarone resin S4 in step (3), to obtain a water-blocking material D3.
Tests show that under the conditions of high temperature (90 ℃) and high salt (the mineralization is 80,000mg/L), the water plugging rate of the water plugging material D3 is 97.22%, the oil plugging rate is 3.78%, and the scouring resistance multiple is more than 50 PV.
Comparative example 4
The procedure was carried out as in example 4, except that in step (1), 1.5g of nonylphenol polyoxyethylene ether was used in place of sodium dodecylbenzenesulfonate, to obtain a water-plugging material D4.
Tests show that under the conditions of high temperature (90 ℃) and high salt (the mineralization is 80,000mg/L), the water blocking rate of the water blocking material D4 is 75.86%, the oil blocking rate is 21.58%, and the scouring resistance multiple is less than 50 PV.
Comparing the results of the above examples 1-11 and comparative examples 1-4, it can be seen that the composition with selective water shutoff function provided by the invention has good water shutoff and oil non-shutoff effects, and has temperature resistance, salt resistance and flushing resistance, and can be well adapted to high-temperature and high-salt reservoir conditions. Particularly, by comparing example 4 with comparative examples 3 to 4, it can be seen that the present invention can further improve the water-blocking and oil-blocking effect of the water-blocking material by using the asphalt-modified oil-soluble resin in combination with the primary emulsifier.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (33)
1. The composition with the selective water plugging function is characterized by comprising asphalt modified oil-soluble resin, a main emulsifier and a water-soluble polymer, wherein the main emulsifier is selected from one or more of sodium dodecyl sulfate, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate;
the composition also contains a co-emulsifier, wherein the co-emulsifier is selected from one or more of span 20, span 40, span 60, span 80, tween 20, tween 40, tween 60 and tween 80;
relative to 100 parts by weight of the asphalt modified oil-soluble resin, the content of the main emulsifier is 40-100 parts by weight, the content of the water-soluble polymer is 0.1-20 parts by weight, and the content of the co-emulsifier is 10-50 parts by weight;
the particle size of the asphalt modified oil-soluble resin is 3-50 mu m;
the water-soluble polymer is at least one of an anionic polymer, a cationic polymer and a surface active polymer; the anionic polymer is partially hydrolyzed polyacrylamide and/or sulfonic acid polyacrylamide; the cationic polymer is cationic polyacrylamide and/or cationic acrylamide copolymer;
the composition further comprises water;
the surface active polymer is a copolymer of an acrylamide monomer and a surface active monomer;
the asphalt modified oil-soluble resin is selected from one or more of asphalt modified rosin resin, asphalt modified dammar resin, asphalt modified oil-soluble phenolic resin, asphalt modified terpene resin and asphalt modified coumarone resin.
2. The composition according to claim 1, wherein, in the asphalt-modified oil-soluble resin, the weight ratio of the asphalt to the oil-soluble resin is 1: 0.01-100.
3. The composition according to claim 2, wherein, in the asphalt-modified oil-soluble resin, the weight ratio of the asphalt to the oil-soluble resin is 1: 0.1-20.
4. The composition of claim 1, wherein the anionic polymer has an ionic degree of 5 to 30% and a viscosity average molecular weight of 1000 to 3500 ten thousand.
5. The composition of claim 4, wherein the anionic polymer has an ionic degree of 15 to 25% and a viscosity average molecular weight of 2000 to 3000 ten thousand.
6. The composition of claim 1, wherein the cationic polymer has an ionic degree of 5 to 30% and a viscosity average molecular weight of 1000 to 3500 ten thousand.
7. The composition of claim 6, wherein the cationic polymer has an ionicity of 15-25%; the viscosity average molecular weight is 2000-3000 ten thousand.
8. The composition as claimed in claim 1, wherein the surface active polymer has a surface tension of 25-50mN/m and a viscosity average molecular weight of 500-3000 ten thousand.
9. The composition of claim 8, wherein the surface active polymer has a surface tension of 30-40 mN/m; the viscosity-average molecular weight is 1000-2500 ten thousand.
10. The composition of claim 1, wherein the water is present in an amount of 5-1000mL per gram of the asphalt-modified, oil-soluble resin.
11. The composition of claim 10, wherein the water is present in an amount of 8-120mL per gram of the asphalt-modified, oil-soluble resin.
12. The composition of claim 11, wherein the water is present in an amount of 10-100mL per gram of the asphalt-modified, oil-soluble resin.
13. The preparation method of the composition with the selective water shutoff function is characterized by comprising the following steps:
(1) mixing a water-soluble polymer with water to form an aqueous solution;
(2) sequentially mixing a main emulsifier and a co-emulsifier with the aqueous solution to form an emulsion;
(3) mixing an asphalt-modified oil-soluble resin with the emulsion;
the main emulsifier is selected from one or more of sodium dodecyl sulfate, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate, and the auxiliary emulsifier is selected from one or more of span 20, span 40, span 60, span 80, tween 20, tween 40, tween 60 and tween 80; the water-soluble polymer is at least one of an anionic polymer, a cationic polymer and a surface active polymer; the anionic polymer is partially hydrolyzed polyacrylamide and/or sulfonic acid polyacrylamide; the cationic polymer is cationic polyacrylamide and/or cationic acrylamide copolymer;
relative to 100 parts by weight of the asphalt modified oil-soluble resin, the content of the main emulsifier is 40-100 parts by weight, the content of the water-soluble polymer is 0.1-20 parts by weight, and the content of the co-emulsifier is 10-50 parts by weight;
the particle size of the asphalt modified oil-soluble resin is 3-50 mu m;
the surface active polymer is a copolymer of an acrylamide monomer and a surface active monomer;
the asphalt modified oil-soluble resin is selected from one or more of asphalt modified rosin resin, asphalt modified dammar resin, asphalt modified oil-soluble phenolic resin, asphalt modified terpene resin and asphalt modified coumarone resin.
14. The production method according to claim 13, wherein, in the asphalt-modified oil-soluble resin, a weight ratio of the asphalt to the oil-soluble resin is 1: 0.01-100.
15. The production method according to claim 14, wherein, in the asphalt-modified oil-soluble resin, a weight ratio of the asphalt to the oil-soluble resin is 1: 0.1-20.
16. The production process according to claim 13, wherein the anionic polymer has an ionic degree of 5 to 30% and a viscosity average molecular weight of 1000 to 3500 n.
17. The method of claim 16, wherein the anionic polymer has an ionic degree of 15 to 25%; the viscosity average molecular weight is 2000-3000 ten thousand.
18. The production method according to claim 13, wherein the cationic polymer has an ionic degree of 5 to 30% and a viscosity average molecular weight of 1000 to 3500 ten thousand.
19. The method of claim 18, wherein the cationic polymer has an ionicity of 15-25%; the viscosity average molecular weight is 2000-3000 ten thousand.
20. The production method as claimed in claim 13, wherein the surface active polymer has a surface tension of 25 to 50mN/m and a viscosity average molecular weight of 500-3000 ten thousand.
21. The production method according to claim 20, wherein the surface active polymer has a surface tension of 30 to 40 mN/m; the viscosity-average molecular weight is 1000-2500 ten thousand.
22. The production method according to any one of claims 13 to 15, wherein the amount of water used is 5 to 1000mL per gram of the asphalt-modified oil-soluble resin.
23. The production method according to claim 22, wherein the amount of water used is 8 to 120mL per gram of the asphalt-modified oil-soluble resin.
24. The production method according to claim 23, wherein the amount of water used is 10 to 100mL per gram of the asphalt-modified oil-soluble resin.
25. The production method according to claim 13, wherein, in the step (1), the mixing is performed in a stirring manner, and the conditions of the mixing include: the mixing temperature is 20-50 ℃, the mixing time is 1-6h, and the stirring speed is 500-700 r/min.
26. The production method according to claim 13, wherein, in the step (2), the mixing is performed in a stirring manner, and the conditions of the mixing include: the mixing temperature is 20-50 ℃, the mixing time is 1-3h, and the stirring speed is 500-700 r/min.
27. The production method according to claim 13, wherein, in step (3), the mixing is performed in a stirring manner, and the conditions of the mixing include: the mixing temperature is 20-50 ℃, the mixing time is 0.5-2h, and the stirring speed is 500-700 r/min.
28. The composition with selective water shutoff function prepared by the preparation method of any one of claims 13 to 27.
29. Use of a composition according to any one of claims 1 to 12 and 28 in a water-blocking material.
30. Use of a composition according to any one of claims 1 to 12 and 28 in an oilfield water shutoff material.
31. The use of claim 29 or 30, wherein the environmental conditions of the oilfield comprise: the temperature is 40-130 ℃, and the degree of mineralization is 100-200,000 mg/L.
32. The use of claim 31, wherein the environmental conditions of the oilfield comprise: the temperature is 70-110 ℃, and the degree of mineralization is 10,000-100,000 mg/L.
33. The use of claim 32, wherein the environmental conditions of the oilfield comprise: the temperature is 90-110 ℃; the degree of mineralization was 50,000-100,000 mg/L.
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