CN113337267A - Application of biological enzyme gel breaker in high-salinity water-based fracturing fluid product and fracturing fluid product - Google Patents

Application of biological enzyme gel breaker in high-salinity water-based fracturing fluid product and fracturing fluid product Download PDF

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CN113337267A
CN113337267A CN202110604038.XA CN202110604038A CN113337267A CN 113337267 A CN113337267 A CN 113337267A CN 202110604038 A CN202110604038 A CN 202110604038A CN 113337267 A CN113337267 A CN 113337267A
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fracturing fluid
fluid product
gel breaking
fracturing
water
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赵静
孙秀鹏
刘雨
孙钰钧
韩俊杰
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Dalian Zhiwei Biotechnology Co ltd
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Dalian Zhiwei Biotechnology Co ltd
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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
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/66—Compositions based on water or polar solvents
    • C09K8/68—Compositions based on water or polar solvents containing organic compounds
    • 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
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/66—Compositions based on water or polar solvents
    • C09K8/68—Compositions based on water or polar solvents containing organic compounds
    • C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
    • 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
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/86—Compositions based on water or polar solvents containing organic compounds
    • C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/887—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
    • 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
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/86—Compositions based on water or polar solvents containing organic compounds
    • C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/90—Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose
    • 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
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/25—Methods for stimulating production
    • E21B43/26—Methods for stimulating production by forming crevices or fractures
    • 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
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/24—Bacteria or enzyme containing gel breakers
    • 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
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/32—Anticorrosion additives

Abstract

The invention provides a fracturing fluid product which comprises base fluid, gel breaking enzyme and a cross-linking agent, wherein the base fluid, the gel breaking enzyme and the cross-linking agent are mixed when the fracturing fluid product is used for hydraulic fracturing, and the gel breaking enzyme comprises beta-mannanase produced by bacillus amyloliquefaciens CB-019 with the preservation number of CGMCC No. 11950. The fracturing fluid product can meet the low-temperature construction requirement of high-salinity water, can be directly prepared by using the high-salinity water, overcomes the problems of guar gum in chemical tackifying under high salinity, difficult pH value control, incapability of carrying sand and the like, and achieves the requirements of stably increasing yield and improving the exploitation amount. The gel breaking enzyme has obvious improvement effect on the problems of difficult low-temperature gel breaking, poor gel breaking timeliness, high residue content and the like of a high-salinity hydraulic fracturing fluid system.

Description

Application of biological enzyme gel breaker in high-salinity water-based fracturing fluid product and fracturing fluid product
Technical Field
The invention belongs to the field of research on offshore oil and gas resource development technology, and particularly relates to application of a biological enzyme gel breaker in a high-salinity water-based fracturing fluid product and the fracturing fluid product.
Background
With the development strategy of oil and gas resources, the ocean has become one of the important trends of oil and gas resource development. Ocean oil and gas resources are quite rich, but the development degree of ocean oil and gas fields is generally lower, so that more and more attention is paid to the development of the ocean oil and gas fields to improve the oil and gas yield.
The fracturing fluid is widely applied to onshore oil fields, and the main component of the fracturing fluid is fresh water except for the thickening agent. If the land fresh water fracturing fluid is used for offshore construction, the scale of the fracturing construction is greatly limited due to the limitation of an operation carrier, a liquid storage space and fresh water delivery, the operation period can be seriously influenced, and the cost is increased. Therefore, the seawater-based fracturing fluid system which meets the requirement of offshore platform construction and realizes continuous mixing has the advantages of reducing cost, improving construction efficiency, saving fresh water resources and the like, thereby realizing the efficient development of offshore oil and gas fields.
The thickening agent is widely applied to hydraulic fracturing, because the thickening agent contains a small amount of protein, crude fiber and other insoluble substances, if seawater is used for replacing fresh water for fracturing, gel breaking is incomplete, and a large amount of water-insoluble substances are generated in the gel breaking process, so that channels are blocked, and the fracturing effect is influenced. Currently, oxidizers and enzymes are mainly used as breakers. However, since the reactivity of the oxidant is proportional to the temperature, the higher the temperature, the stronger the reactivity, the faster the gel breaking, and the more thorough the gel breaking. The gel breaking performance is obviously reduced at low temperature. And the general gel breaking enzyme can only break gel at 40-70 ℃ and pH value of 3.5-7.5, and has small temperature range and large limitation. Therefore, the purpose of gel breaking is difficult to achieve in the fracturing process of the low-temperature oil and gas reservoir, and therefore offshore low-temperature gel breaking becomes a technical difficulty. The novel gel breaking method can realize gel breaking of the offshore fracturing fluid at low temperature, has less gel breaking residues, and is a research hotspot and improvement direction of the existing seawater fracturing technology and fracturing fluid performance evaluation.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a fracturing fluid product and application thereof.
Specifically, the present invention relates to the following aspects:
1. a fracturing fluid product, which is characterized by comprising a base fluid, a gel breaking enzyme and a cross-linking agent, wherein the base fluid, the gel breaking enzyme and the cross-linking agent are mixed when used for hydraulic fracturing, wherein the gel breaking enzyme comprises beta-mannanase produced by Bacillus amyloliquefaciens CB-019 with the preservation number of CGMCC No. 11950.
2. The fracturing fluid product of item 1, wherein the base fluid comprises a thickener, a cleanup additive, a bactericide, a clay stabilizer, a pH regulator and hypersalinity water, wherein the hypersalinity water has a mineralization degree of not less than 1 x 104mg/L。
3. The fracturing fluid product of claim 2, wherein the base fluid is comprised of a thickener, a cleanup additive, a biocide, a clay stabilizer, a pH adjuster, and hypersalinity water.
4. The fracturing fluid product of claim 2, wherein the base fluid contains 0.25 to 0.45 mass% of the thickener, 0.1 to 0.5 mass% of the cleanup additive, 0.01 to 0.05 mass% of the bactericide, 0.2 to 1 mass% of the clay stabilizer, and 0.05 to 0.1 mass% of the pH regulator.
5. The fracturing fluid product of claim 2, wherein the thickener is selected from one or more of guar gum raw powder, guar gum or hydroxypropyl guar gum powder.
6. The fracturing fluid product of claim 2, wherein the cleanup additive is one or more selected from the group consisting of sodium dodecylbenzene sulfonate, sodium fatty alcohol ether sulfate, quaternary dodecyl ammonium salt, sodium perfluorononenoxybenzene sulfonate, and octylphenol polyoxyethylene ether-10.
7. The fracturing fluid product of claim 2, wherein the biocide is selected from one or more of a bimolecular surfactant type biocide, dodecyl dimethyl benzyl chloride, and a quaternary phosphonium salt biocide.
8. The fracturing fluid product of claim 2, wherein the clay stabilizer is selected from one or more of inorganic salts, inorganic cationic polymers, and cationic surfactants.
9. The fracturing fluid product of claim 2, wherein the pH regulator is selected from one or more of sodium carbonate, sodium bicarbonate and sodium hydroxide.
10. The fracturing fluid product of claim 2, wherein the base fluid has a pH of 6.7 to 7.0.
11. The fracturing fluid product of claim 1, wherein the cross-linking agent comprises one or more of a polyepoxy compound pEPC, a water-soluble phenolic resin, an organoboron and a methylene bisacrylamide, and preferably the cross-linking agent comprises the polyepoxy compound pEPC, the water-soluble phenolic resin and the organoboron.
12. The fracturing fluid product according to item 1, wherein in the fracturing fluid product, the ratio of the enzyme activity of the gel breaker to the volume of the base fluid is 100-900 IU/ml, preferably 200-500 IU/ml, and the volume ratio of the crosslinking agent to the base fluid is 0.1-0.8: 100, preferably 0.2-0.5: 100.
13. Use of a fracturing fluid product in hydraulic fracturing, wherein the fracturing fluid product is a fracturing fluid product according to any one of items 1 to 12.
14. Use according to claim 13, comprising the step of mixing the base fluid, the gel breaker and the cross-linking agent to form a gel.
15. Use according to item 13, characterized in that it comprises use in offshore low-permeability oil fields.
16. The use according to item 13, wherein the temperature during hydraulic fracturing is 0-85 ℃ which is adaptable during hydraulic fracturing.
17. A method of gel breaking under hypersalinity water-based conditions, comprising:
mixing the base solution, the gel breaking enzyme and the cross-linking agent to form jelly;
performing gel breaking on the jelly;
wherein the water-based condition of high mineralization degree refers to that the mineralization degree is more than or equal to 1 multiplied by 104Conditions of mg/L;
the gel breaking enzyme comprises beta-mannanase produced by bacillus amyloliquefaciens CB-019 with the preservation number of CGMCC No. 11950.
18. The method of claim 17, wherein the base fluid is the base fluid of any one of items 2-10.
19. The method according to item 17, wherein the crosslinking agent comprises one or more of a polyepoxy compound pEPC, a water-soluble phenol resin, an organoboron, and methylenebisacrylamide, and preferably the crosslinking agent comprises the polyepoxy compound pEPC, a water-soluble phenol resin, and an organoboron.
20. The method according to item 17, wherein the ratio of the enzyme activity of the gel breaker to the volume of the base solution is 100 to 900IU/ml, preferably 200 to 500IU/ml, and the volume ratio of the crosslinking agent to the base solution is 0.1 to 0.8:100, preferably 0.2 to 0.5: 100.
21. The application of the biological enzyme gel breaker in the high-salinity water-based fracturing fluid product is characterized in that the gel breaker comprises beta-mannanase produced by bacillus amyloliquefaciens CB-019 with the preservation number of CGMCC No.11950, and the high-salinity water has the salinity of more than or equal to 1 x 104mg/L of water.
The fracturing fluid product can meet the requirements of offshore low-temperature construction, can be prepared directly by using seawater, overcomes the problems of guar gum in high salinity, difficult pH value control, incapability of carrying sand and the like, and achieves the requirements of increasing yield stably and improving the production yield.
The gel breaking enzyme has obvious improvement effect on the problems of difficult low-temperature gel breaking, poor gel breaking timeliness, high residue content and the like of an offshore fracturing fluid system. The addition of the gel breaking enzyme does not affect the sand carrying capacity of a system in the offshore fracturing process, the gel breaking time, residue amount and surface interfacial tension of the gel breaking liquid of the system can meet or exceed the requirements of national and industrial standards, and the innovative application of the gel breaking enzyme in the weight of the seawater fracturing liquid is an important research and development direction of the low-temperature seawater-based fracturing liquid.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be purely exemplary of the invention and are not intended to be limiting.
Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Although methods and materials similar or equivalent to those described herein can be used in experimental or practical applications, the materials and methods are described below. In case of conflict, the present specification, including definitions, will control, and the materials, methods, and examples are illustrative only and not intended to be limiting. The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
The invention provides a fracturing fluid product which comprises base fluid, gel breaking enzyme and a cross-linking agent, wherein the base fluid, the gel breaking enzyme and the cross-linking agent are mixed when the fracturing fluid product is used for hydraulic fracturing, wherein the gel breaking enzyme comprises beta-mannanase (mainly crude enzyme) produced by bacillus amyloliquefaciens CB-019 with the preservation number of CGMCC No. 11950. The base fluid, gel breaker and cross-linking agent in the fracturing fluid product are separate, i.e., not mixed together, prior to use in hydraulic fracturing. When the fracturing fluid product is used for hydraulic fracturing, the fracturing fluid product is mixed, namely base fluid, gel breaking enzyme and a cross-linking agent are mixed.
Beta-mannase (beta-mannase) is a hemicellulose hydrolase with wide source, wherein guar gum is a polymer which is galactomannan and is formed by connecting beta-1, 4-glycosidic bond as a main chain and alpha-1, 6-glycosidic bond as a branched chain; the beta-mannase can hydrolyze guar gum (mannan) into mannan-oligosaccharide by decomposing beta-1, 4-glycosidic bond, and then the mannan-oligosaccharide is changed into monosaccharide or oligosaccharide, thereby achieving the purpose of breaking gum. . The gel breaking enzyme is beta-mannase produced by bacillus amyloliquefaciens CB-019 with the preservation number of CGMCC No. 11950.
Wherein, Bacillus amyloliquefaciens (Bacillus amyloliquefaciens) is gram-positive Bacillus, aerobic bacteria and Bacillus subtilis, has high affinity, can generate a series of low molecular weight antibiotics, antibacterial proteins or polypeptides and other active metabolites during the growth process, and has surface activity, broad-spectrum antibacterial activity and anti-adversity, high growth speed and good stability. The related information of the Bacillus amyloliquefaciens CB-019 with the preservation number of CGMCC No.11950 can be seen in CN 201610632519.0.
In a specific embodiment, the method for producing the beta-mannanase by using the bacillus amyloliquefaciens CB-019 with the preservation number of CGMCC No.11950 comprises the following steps: sterilizing and cooling the liquid culture medium, inoculating the enzyme-producing microorganism bacillus amyloliquefaciens CB-019, culturing and fermenting, and extracting the beta-mannase.
In a specific embodiment, the gel breaker is a FANTA-05 low temperature bio-enzyme gel breaker (Dalian know Microbiol technologies, Inc.).
The base fluid comprises a thickening agent, a discharge assistant, a bactericide, a clay stabilizer, a pH regulator and hypersalinity water, wherein the mineralization degree of the hypersalinity water is more than or equal to 1 x 104mg/L。
Wherein, the thickening agent can increase the viscosity of the system, and the system can keep a uniform and stable suspension state or an emulsion state or form gel. In a specific embodiment, the thickener is selected from one or more of galactomannan gum, guar raw powder, guar gum or hydroxypropyl guar powder. Wherein the guar gum is a macromolecular natural hydrophilic colloid, belongs to natural galactomannan, is one of quality modifiers, and is a natural thickener. The guar collagen powder contains protein and crude fiber, has high content of water insoluble substances, has the disadvantages of slow dissolving speed, easy generation of caking, fish eyes and the like, and seriously influences the applicability of the guar collagen powder; the modified guar gum is prepared by chemically modifying guar gum raw powder mainly by utilizing unique structural characteristics and performance of guar gum, namely introducing cationic groups on a molecular chain to produce cationic guar gum, overcomes the defects of the raw gum in the aspect of physical and chemical performance, and is widely applied, including that propylene oxide is used for preparing hydroxypropyl guar gum under the action of an alkaline catalyst.
The cleanup additive has high surface activity, low surface tension and interfacial tension, can improve the wettability of the rock surface of an oil layer, and accelerates the reverse drainage of fracturing fluid; meanwhile, the emulsion breaking agent has good emulsion preventing and breaking performances, and can reduce formation damage. In a specific embodiment, the cleanup additive is one or more selected from sodium dodecyl benzene sulfonate, sodium fatty alcohol ether sulfate, quaternary dodecyl ammonium salt, sodium perfluorononenoxybenzene sulfonate, and octyl phenol polyoxyethylene ether-10.
Biocides, also known as biocides, bactericidal algicides, microbicides, and the like, generally refer to chemical agents that are effective in controlling or killing microorganisms, bacteria, fungi, and algae, in aqueous systems. Generally speaking, the traditional Chinese medicine is a general term of the medicine for preventing and treating various pathogenic microorganisms. In a specific embodiment, the bactericide is one or more selected from a bimolecular film surfactant type bactericide, dodecyl dimethyl benzyl chloride and a quaternary phosphonium salt type bactericide.
The clay stabilizer can be effectively adsorbed on the surface of clay, and the damage to an oil-gas layer caused by hydration expansion and dispersion migration of water-sensitive minerals is prevented. In one embodiment, the clay stabilizer is one or more selected from inorganic salts, inorganic cationic polymers, and cationic surfactants. The pH regulator is used for regulating the pH of the base fluid. In a specific embodiment, the pH adjusting agent is selected from one or more of sodium carbonate, sodium bicarbonate, and sodium hydroxide. In a specific embodiment, the pH of the base fluid is adjusted to 6.7 to 7.0 using a pH adjuster.
In a specific embodiment, the degree of mineralization of said hypersaline water is ≧ 1X 104mg/L, for example, may be 1X 104mg/L、2×104mg/L、3×104mg/L、4×104mg/L、5×104mg/L, etc. Wherein, the Mineralization (Mineralization of water) refers to the sum of carbonate, bicarbonate, chloride, sulfate, nitrate and various sodium salts of metals such as calcium, magnesium, aluminum, manganese and the like contained in water. Generally expressed in terms of the total amount of various salts contained in 1L of water, in mg/L or g/L, and also approximately expressed in parts per thousand (thousandth). The degree of mineralization is an important index for measuring the chemical components of water, is used for evaluating the total salt content in water, and can divide underground water into five types according to the degree of mineralization: (1) fresh water with the mineralization degree less than 1 g/L; (2) brackish water (weakly mineralized water) with a degree of mineralization of 1-3 g/L; (3) the salinity of the salt water (moderate mineralized water) is 3-10 g/L; (4) the salinity of the saline water (strongly mineralized water) is 10-50 g/L; (5) the mineralization degree of the brine is more than 50 g/L.
In a particular embodiment, the hypersaline water is seawater. Because the thickening agent in the base fluid contains a small amount of protein, crude fiber and other insoluble substances, when seawater is used for replacing fresh water for fracturing, the fracturing is usually incomplete, and a large amount of water-insoluble substances are generated in the fracturing process, so that channels are blocked, and the fracturing effect is influenced. In the invention, the beta-mannase produced by using the bacillus amyloliquefaciens CB-019 with the preservation number of CGMCC No.11950 ensures that the fracturing fluid product is also applicable to seawater with high salinity. The enzyme can ensure high enzyme activity and good functionality under the condition of high mineralization degree, and can meet the characteristics of continuous gel breaking and thorough gel breaking.
In a specific embodiment, the mass content of the thickener is 0.25 to 0.45%, and may be, for example, 0.25%, 0.26%, 0.27%, 0.28%, 0.29%, 0.30%, 0.31%, 0.32%, 0.33%, 0.34%, 0.35%, 0.36%, 0.37%, 0.38%, 0.39%, 0.40%, 0.41%, 0.42%, 0.43%, 0.44%, 0.45%; the mass content of the cleanup additive is 0.1-0.5%, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%; (ii) a The mass content of the bactericide is 0.01-0.5%, for example, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%; the clay stabilizer may be contained in an amount of 0.2 to 1% by mass, for example, 0.2%, 0.21%, 0.22%, 0.23%, 0.24%, 0.25%, 0.26%, 0.27%, 0.28%, 0.29%, 0.30%, 0.31%, 0.32%, 0.33%, 0.34%, 0.35%, 0.36%, 0.37%, 0.38%, 0.39%, 0.40%, 0.41%, 0.42%, 0.43%, 0.44%, 0.45%, 0.46%, 0.47%, 0.48%, 0.49%, 0.50%, 0.51%, 0.52%, 0.53%, 0.54%, 0.55%, 0.56%, 0.57%, 0.58%, 0.59%, 0.60%, 0.61%, 0.62%, 0.63%, 0.64%, 0.65%, 0.66%, 0.67%, 0.68%, 0.70%, 0.76%, 0.80%, 0.90%, 0.80%, 0., 0.98%, 0.99% and 1.00%. The content of the pH adjuster is 0.05 to 0.1% by mass, and may be, for example, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%.
In a particular embodiment, the base fluid is comprised of a thickener, a drainage aid, a biocide, a pH adjuster, and hypersaline water. Wherein the thickener, cleanup additive, biocide, clay stabilizer, pH adjuster, and hypersaline water are defined as above.
In one specific embodiment, the base fluid is prepared by the following method: accurately taking the components of the thickening agent, the cleanup additive, the bactericide, the pH regulator and the like according to the mixture ratio, adding the thickening agent, the bactericide and the clay stabilizer into seawater, uniformly mixing, then adding the cleanup additive and the pH regulator, uniformly mixing, standing and swelling, and regulating the pH of the base solution to be 7; wherein the standing and swelling time is 0.5-4 h, preferably 4h, and the temperature is room temperature; the mixing method can adopt a stirring mode, for example, stirring for 5-20 min at a rotating speed of 150-300 r/min to obtain a uniform solution, namely the base solution.
In a specific embodiment, the cross-linking agent comprises one or more than two of polyepoxy compound pEPC, water-soluble phenolic resin, organoboron and methylene bisacrylamide. For example, the crosslinking agent may include only the polyepoxide pEPC, a water-soluble phenolic resin, an organoboron, or methylenebisacrylamide. Any two, any three, or four of the four substances described above may also be included. Preferably, the cross-linking agent comprises three substances of a polyepoxy compound pEPC, a water-soluble phenolic resin and an organic boron.
In a preferred embodiment, the crosslinking agent is a super-strong delayed crosslinking agent of SITAR-II type (Dalianzhi microbial science and technology Co., Ltd.), and the components of the crosslinking agent comprise 0.1-2% by mass of a polyepoxy compound pEPC, 0.2-3% by mass of a water-soluble phenolic resin, 5-35% by mass of an organoboron, and the balance of water.
In the fracturing fluid product, the ratio of the enzyme activity of the gel breaker to the volume of the base fluid is 100-900 IU/ml, and the volume ratio of the cross-linking agent to the base fluid is 0.1-0.8: 100. Wherein, the enzyme activity unit IU of the gel breaking enzyme refers to the enzyme quantity which can convert 1 micromole of substrate in 1 minute under specific conditions (25 ℃, and the other conditions are optimal conditions), or the enzyme quantity which can convert 1 micromole of related groups in the substrate. Specifically, the enzyme activity unit IU of the beta-mannanase refers to the amount of enzyme capable of converting 1 micromole of mannan at 25 ℃ in 1 minute. The ratio of the enzyme activity of the gel breaking enzyme to the volume of the base solution is 100-900 IU/ml, and can be 100IU/ml, 200IU/ml, 300IU/ml, 400IU/ml, 500IU/ml, 600IU/ml, 700IU/ml, 800IU/ml and 900IU/ml, and the preferable range is 200-500 IU/ml. The volume ratio of the crosslinking agent to the base fluid is 0.1-0.8: 100, and for example, may be 0.1:100, 0.2: 100. 0.3:100, 0.4:100, 0.5:100, 0.6:100, 0.7:100, 0.8:100, preferably in the range of 0.2-0.5: 100.
The invention also provides application of the fracturing fluid product in hydraulic fracturing.
Further, the application comprises the steps of adding a cross-linking agent and gel breaking enzyme into the base fluid to form stable gel, breaking the gel at low temperature, fracturing and discharging the gel-breaking fluid carrying crude oil to the ground, and improving the crude oil recovery rate of the oil well.
In a particular embodiment, the application comprises an application in an offshore low-permeability oil field.
In a specific embodiment, the hydraulic fracturing may be applied at 0-85 ℃, for example, at 0 ℃,4 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 85 ℃.
The invention also provides a method for breaking gel under the condition of high salinity water base, which comprises the following steps: mixing the base solution, the gel breaking enzyme and the cross-linking agent to form jelly; performing gel breaking on the jelly; wherein the water-based condition of high mineralization degree refers to that the mineralization degree is more than or equal to 1 multiplied by 104Conditions of mg/L; the gel breaking enzyme comprises beta-mannanase produced by bacillus amyloliquefaciens CB-019 with the preservation number of CGMCC No. 11950.
Wherein, the ratio of the enzyme activity of the base fluid, the cross-linking agent and the gel breaking enzyme to the volume of the base fluid and the volume ratio of the cross-linking agent to the base fluid are as described above.
The invention also provides application of the biological enzyme gel breaker in a high-salinity water-based fracturing fluid product, wherein the gel breaker comprises beta-mannanase produced by bacillus amyloliquefaciens CB-019 with the preservation number of CGMCC No.11950, and the high-salinity water has the salinity of more than or equal to 1 x 104mg/L of water.
When the gel breaking enzyme and the cross-linking agent are used, particularly the ratio of the enzyme activity of the gel breaking enzyme to the volume of the base fluid is 100-900 IU/ml, and the volume ratio of the cross-linking agent to the base fluid is 0.1-0.8: 100, the fracturing fluid product has good gel breaking performance at low temperature such as 4 ℃ and 10 ℃, and particularly can be used for the condition that the mineralization degree is more than or equal to 1 x 104The base fluid of mg/L hypersalinity water can meet the requirement of offshore low-temperature construction, can directly prepare fracturing fluid by using seawater, and achieves the requirements of increasing yield stably and improving the production yield.
Example 1
The seawater-based fracturing fluid system consists of seawater-based base fluid (referred to as base fluid in the following description), a gel breaker and a cross-linking agent, wherein the base fluid consists of the following components in percentage by mass: 0.28% of thickening agent (hydroxypropyl guar gum), 0.3% of discharge assistant (ZITHE-34, a type efficient discharge assistant, Dalianzhi microbial technology limited company, which takes sodium dodecyl benzene sulfonate, sodium fatty alcohol ether sulfate and dodecyl quaternary ammonium salt as main components), 0.05% of bactericide (DMTPC, the Dalianzhi microbial technology limited company, which takes a bi-molecular film surfactant type bactericide and a quaternary phosphonium salt bactericide as main components), 0.05% of pH regulator (sodium bicarbonate) and the balance of seawater, wherein the mineralization degree of the seawater is 26030 mg/L. The cross-linking agent is SITAR-II type super strong delayed cross-linking agent (Dalianzhi microbial technology Co., Ltd.), and the volume ratio of the base liquid to the cross-linking agent is 100: 0.3; the gel breaking enzyme is FANTA-05 low-temperature gel breaking enzyme (Dalianzhi microbial technology Co., Ltd.) 300 IU/ml.
Accurately taking the components according to the given mass percentages of the components, and preparing the jelly of the seawater-based fracturing pad fluid system according to the following method: sequentially adding a thickening agent and a bactericide into seawater at a rotation speed of 300r/min while stirring according to a ratio, sequentially adding a cleanup additive and a pH regulator after stirring for l0min, continuously stirring for 5min, uniformly mixing, standing and swelling for 4h to obtain a base solution; and (3) taking 100mL of the base solution, adding the SITAR-II type super strong delayed crosslinking agent and the gel breaking enzyme while stirring at the rotating speed of 300r/min, and continuously stirring for 1min to form the gel. The gel is broken at constant temperature of 10 ℃ and 4 ℃ respectively.
The residue content, viscosity and surface tension of the gel breaking solution were measured according to the specification of SY/T5107-2016 Water-based fracturing fluid Performance evaluation method.
Examples 2 to 3
Examples 2-3 differ from example 1 only in the amount of the gel breaker used, namely FANTA-05 low temperature gel breaker. Wherein, the volume ratio of the gel breaking enzyme to the base liquid used in the embodiment 2 is 100IU/ml, and the volume ratio of the gel breaking enzyme to the base liquid used in the embodiment 3 is 900 IU/ml. Other reaction conditions were the same. Specifically, the results are shown in Table 1.
Examples 4 to 7
Examples 4-7 differ from example 1 only in the amount of the superstrong retardation crosslinking agent of type SITAR-ii. Wherein, the volume ratio of the SITAR-II type super strong delayed crosslinking agent used in the example 4 to the base liquid is 8:100, the volume ratio of the SITAR-II type super strong delayed crosslinking agent used in the example 5 to the base liquid is 0.1:100, the volume ratio of the SITAR-II type super strong delayed crosslinking agent used in the example 6 to the base liquid is 0.01:100, and the volume ratio of the SITAR-II type super strong delayed crosslinking agent used in the example 7 to the base liquid is 10: 100. Other reaction conditions were the same. Specifically, the results are shown in Table 1.
Example 8
Example 8 differs from example 1 in that the crosslinker used is not a superstrong retardation crosslinker of the type SITAR-ii but borax. Other reaction conditions were the same. Specifically, the results are shown in Table 1.
Example 9
The difference between example 9 and example 1 is that the crosslinking agent used is not a SITAR-II type ultra-strong delayed crosslinking agent, but JL-011 ultra-strong delayed crosslinking agent (Dalian Mikroorganscience, Inc.), which comprises polyepoxy compound pEPC 0.05-0.1 wt%, methylenebisacrylamide 0.2-2 wt%, organoboron 7-15 wt%, and water in balance. Other reaction conditions were the same. Specifically, the results are shown in Table 1.
Comparative example 1
Comparative example 1 differs from example 1 in that the gel breaker used is not FANTA-05 low temperature gel breaker, but Ammonium Persulfate (APS). Other reaction conditions were the same. Specifically, the results are shown in Table 1.
The reaction conditions of the specific examples and comparative examples are shown in table 1.
TABLE 1 specific conditions for the examples and comparative examples
Figure BDA0003093600810000101
Figure BDA0003093600810000111
The gel breaking effect at 10 ℃ measured in the above examples and comparative examples is shown in Table 2.
TABLE 2 gel breaking Performance at 10 ℃ for each of the examples and comparative examples
Figure BDA0003093600810000112
The gel breaking effect at 4 ℃ measured in the above examples and comparative examples is shown in Table 3.
TABLE 3 gel breaking Properties at 4 ℃ of the examples and comparative examples
Figure BDA0003093600810000113
Figure BDA0003093600810000121
Gel breaking time, viscosity, surface tension and residue amount can represent the gel breaking capacity of the fracturing fluid product, wherein the gel breaking time is too long to meet the requirements of site fracturing construction; the viscosity of the gel breaking liquid is high, and the sand carrying capacity is poor; the surface tension is low, the wettability of rock can be changed, the sweep effect is increased, and the oil extraction efficiency is improved; the low residue can reduce the damage of the flowback liquid to the reservoir, reduce the economic loss of the abrasion of the pipeline and simultaneously improve the recovery rate of crude oil.

Claims (10)

1. A fracturing fluid product, which is characterized by comprising a base fluid, a gel breaking enzyme and a cross-linking agent, wherein the base fluid, the gel breaking enzyme and the cross-linking agent are mixed when used for hydraulic fracturing, wherein the gel breaking enzyme comprises beta-mannanase produced by Bacillus amyloliquefaciens CB-019 with the preservation number of CGMCC No. 11950.
2. The fracturing fluid product of claim 1, wherein the base fluid comprises a thickener, a cleanup additive, a biocide, a clay stabilizer, a pH adjusterAgent and high salinity water, wherein the salinity of the high salinity water is more than or equal to 1 x 104mg/L。
3. The fracturing fluid product of claim 2, wherein the base fluid is comprised of a thickener, a cleanup additive, a biocide, a clay stabilizer, a pH adjuster, and hypersaline water.
4. The fracturing fluid product of claim 2, wherein the base fluid comprises 0.25 to 0.45% by mass of the thickener, 0.1 to 0.5% by mass of the cleanup additive, 0.01 to 0.05% by mass of the bactericide, 0.2 to 1% by mass of the clay stabilizer, and 0.05 to 0.1% by mass of the pH regulator.
5. The fracturing fluid product of claim 2, wherein the thickener is selected from one or more of guar gum raw powder, guar gum, or hydroxypropyl guar powder.
6. The fracturing fluid product of claim 2, wherein the cleanup additive is one or more selected from the group consisting of sodium dodecylbenzene sulfonate, sodium fatty alcohol ether sulfate, quaternary dodecyl ammonium salt, sodium perfluorononenoxybenzene sulfonate, and octyl phenol polyoxyethylene ether-10.
7. The fracturing fluid product of claim 2, wherein the biocide is selected from one or more of a bi-molecular membrane surfactant type biocide, dodecyl dimethyl benzyl chloride, and a quaternary phosphonium salt biocide.
8. The fracturing fluid product of claim 2, wherein the clay stabilizer is selected from one or more of inorganic salts, inorganic cationic polymers, and cationic surfactants.
9. The fracturing fluid product of claim 2, wherein the pH modifier is selected from one or more of sodium carbonate, sodium bicarbonate, and sodium hydroxide.
10. The fracturing fluid product of claim 2, wherein the base fluid has a pH of 6.7 to 7.0.
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