CN112480899A - Demulsification cleanup additive for fracturing and preparation method thereof - Google Patents
Demulsification cleanup additive for fracturing and preparation method thereof Download PDFInfo
- Publication number
- CN112480899A CN112480899A CN202011452974.5A CN202011452974A CN112480899A CN 112480899 A CN112480899 A CN 112480899A CN 202011452974 A CN202011452974 A CN 202011452974A CN 112480899 A CN112480899 A CN 112480899A
- Authority
- CN
- China
- Prior art keywords
- alkyl
- fracturing
- fatty acid
- polyoxyethylene ether
- cleanup additive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
-
- 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
- C09K8/885—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Detergent Compositions (AREA)
Abstract
The application discloses a demulsification cleanup additive for fracturing and a preparation method thereof, wherein the demulsification cleanup additive comprises the following components in parts by weight: 1-30 parts of alkanolamine compound, 1-30 parts of fatty acid polyoxyethylene ether sulfonate, 1-20 parts of alkyl glycoside and 1-15 parts of low molecular alcohol; wherein the alkanolamine compound is at least one selected from compounds with a structural formula shown in a formula I. The alkanolamine compound not only has the functions of demulsification and drainage assistance, but also can effectively fuse and enhance the effects of fatty acid polyoxyethylene ether sulfonate, alkyl glycoside and low molecular alcohol, so that the demulsification drainage assistance agent has lower surface tension and interfacial tension and higher demulsification rate and drainage assistance rate, and can be used for fracturing treatment of oil field reservoirs, effectively reduce capillary resistance and resistance generated by emulsion blockage, further effectively improve the flowback rate of waste liquid after fracturing, and improve the fracturing treatment effect.
Description
Technical Field
The application relates to a demulsification cleanup additive for fracturing and a preparation method thereof, belonging to the technical field of oilfield chemicals.
Background
The oil field fracturing operation is the main process for increasing the yield of new oil fields and old oil fields. The fracturing fluid is a key factor of fracturing construction, and the performance of the fracturing fluid not only directly influences the success rate of hydraulic fracturing construction, but also has great influence on the transformation effect of a fractured hydrocarbon reservoir.
The fracturing fluid is an aqueous fluid, and after the fracturing fluid invades into a pore canal of an oil-gas layer, a meniscus which is concave to an oil phase can be formed due to the existence of an oil-water interface in a tiny pore, so that capillary resistance is generated; meanwhile, when oil and water flow in the stratum, a large amount of emulsified liquid drops appear, and when the emulsified liquid drops pass through the pore throat of the oil-gas reservoir, additional pressure is generated due to the Jamin effect. When a well fluid invades the formation, the crude oil is driven into the wellbore, and the resistance caused by capillary resistance and emulsion blockage needs to be overcome. If the formation does not provide sufficient pressure, the resistance cannot be overcome to create a flow of liquid phase in the formation, which can produce water damage (capillary resistance and emulsion plugging). For a low-permeability oilfield reservoir, because the diameter of a pore throat is small, water damage is easy to occur, and the influence degree on the productivity of an oil-water well is even more serious than that of stratum damage caused by solid-phase particle blockage. All the well entering fluids can cause damage to the permeability of a reservoir stratum, and the flowback of the fracturing fluid needs to be enhanced to achieve a good fracturing effect. At present, the demulsification cleanup additive for fracturing has single performance, can not effectively reduce surface tension and interfacial tension, and has poor flowback effect of waste liquid after fracturing.
Disclosure of Invention
In order to solve the problems, the demulsification cleanup additive for fracturing and the preparation method thereof are provided, and the demulsification cleanup additive can obviously reduce surface tension and interfacial tension and improve the flowback rate of waste liquid after fracturing.
According to one aspect of the application, a demulsification cleanup additive for fracturing is provided, which comprises the following components in parts by weight: 1-30 parts of alkanolamine compound, 1-30 parts of fatty acid polyoxyethylene ether sulfonate, 1-20 parts of alkyl glycoside and 1-15 parts of low molecular alcohol; wherein the alkanolamine compound is at least one selected from compounds with a structural formula shown in a formula I;
in the formula I, R1 is selected from one of C8-C24 alkyl; r2 is selected from one of C1-C8 alkyl; r3 is selected from H and one of alkyl of C1-C8; m and n are each independently selected from 1 or 2, but m and n cannot both be 1 or 2; x is selected from halogen.
Further, the demulsification cleanup additive comprises the following components in percentage by weight: 1-30 wt% of alkanolamine compound, 1-30 wt% of fatty acid polyoxyethylene ether sulfonate, 1-20 wt% of alkyl glycoside, 1-15 wt% of low molecular alcohol and the balance of water;
preferably, the demulsification cleanup additive comprises the following components in percentage by weight: 10 to 20 weight percent of alkanolamine compound, 10 to 20 weight percent of fatty acid polyoxyethylene ether sulfonate, 5 to 15 weight percent of alkyl glycoside, 5 to 10 weight percent of low molecular alcohol and the balance of water;
more preferably, the demulsification cleanup additive comprises the following components in percentage by weight: 18 wt% of alkanolamine compound, 16 wt% of fatty acid polyoxyethylene ether sulfonate, 12 wt% of alkyl glycoside, 8 wt% of low molecular alcohol and 46% of water.
Further, R1 is selected from one of C10-C22 alkyl, R2 is selected from one of C2-C6 alkyl, R3 is selected from one of H and C2-C6 alkyl, and X is selected from one of F, Cl and Br; preferably, R1 is selected from one of C12-C18 alkyl, R2 is selected from one of C2-C4 alkyl, R3 is H, and X is Cl.
Further, R1 is selected from at least one of alkyl groups comprising linear, branched and cyclic structures; preferably, the alkyl group in R1 is substituted with one or more substituents, which are halogen, alkyl or alkoxy; preferably, the alkyl group in R2 is substituted with one or more substituents, which are hydroxy or alkoxy.
Further, the polymerization degree of a polyoxyethylene ether chain in the fatty acid polyoxyethylene ether sulfonate is selected from one of 4-12, and the fatty acid in the fatty acid polyoxyethylene ether sulfonate is selected from one of C6-C26; preferably, the polymerization degree of polyoxyethylene ether in the fatty acid polyoxyethylene ether sulfonate is selected from one of 5-9, and the fatty acid in the fatty acid polyoxyethylene ether sulfonate is selected from one of C8-C24 fatty acids; preferably, the fatty acid polyoxyethylene ether sulfonate is synthesized by adopting a hydroxyethyl sodium sulfonate method.
Further, the alkyl in the alkyl glycoside is selected from one of C8-C24 alkyl; preferably, the alkyl group in the alkyl glycoside is selected from one of C12-C18 alkyl groups; preferably, the alkyl glycoside is synthesized from fatty alcohol and glucose.
Further, the low molecular alcohol is selected from at least one of ethanol, isopropanol and n-butanol; preferably, the low molecular alcohol is isopropanol.
According to another aspect of the application, a preparation method of the demulsifying and cleanup additive for fracturing is provided, which comprises the following steps:
(1) carrying out ring-opening reaction on fatty alcohol, epoxy chloropropane and fatty alcohol amine in a lower alcohol solution to obtain a product, mixing the product with halogen acid, and filtering to obtain an alkanolamine compound;
(2) and mixing the alkanolamine compound with fatty acid polyoxyethylene ether sulfonate, alkyl glycoside and low molecular alcohol to obtain the demulsification cleanup additive.
Further, in the step (1), the ring-opening reaction specifically includes the following steps:
dripping epoxy chloropropane into fatty alcohol for reaction to obtain alkyl glycidyl ether;
dropping the alkyl glycidyl ether into the fatty alcohol amine to react to obtain the product.
Preferably, in the step I, epoxy chloropropane is dripped into fatty alcohol, the reaction is carried out for 1-2 h at the temperature of 50-80 ℃, then the temperature is reduced to 30-50 ℃, alkali liquor is dripped, and the reaction is continued for 0.2-1 h, so as to obtain the alkyl glycidyl ether;
preferably, in the step II, the alkyl glycidyl ether is dripped into the fatty alcohol amine, and the reaction is carried out for 2-4 hours at the temperature of 50-80 ℃ to obtain the product.
Further, in step (2), the mixing includes: mixing an alkanolamine compound and fatty acid polyoxyethylene ether sulfonate, and stirring for at least 10min to obtain a first mixture;
secondly, mixing the alkyl glycoside and the low molecular alcohol, and stirring for at least 5min to obtain a second mixture;
mixing the first mixture and the second mixture, and performing ultrasonic oscillation at the constant temperature of 30-40 ℃ for at least 20min to obtain the demulsification cleanup additive.
Benefits of the present application include, but are not limited to:
(1) according to the demulsification cleanup additive for fracturing, the demulsifier comprises an alkanolamine compound shown in the formula I, fatty acid polyoxyethylene ether sulfonate, alkyl glycoside and low molecular alcohol, the alkanolamine compound has the functions of demulsification and cleanup, and can effectively fuse and synergize the fatty acid polyoxyethylene ether sulfonate, the alkyl glycoside and the low molecular alcohol, so that the demulsification cleanup additive has lower surface tension and interfacial tension and higher demulsification rate and cleanup rate, and the demulsification cleanup additive is used for fracturing treatment of oil field reservoirs, can effectively reduce capillary resistance and resistance generated by emulsion blockage, further effectively improve the flowback rate of waste liquid after fracturing, and improve the effect of fracturing treatment.
(2) According to the demulsification cleanup additive for fracturing, the compatibility of each component is good, a synergistic effect can be generated, the surface tension and the interfacial tension are obviously reduced, and the flowback effect of the waste liquid after fracturing is effectively improved.
(3) According to the preparation method of the demulsification cleanup additive for fracturing, the preparation method is mild in reaction conditions, beneficial to operation, low in production cost and easy for industrial production.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and reagents in the examples of the present application were all purchased commercially.
Example 1 demulsifying cleanup additive No. 1#
The demulsification cleanup additive 1# for fracturing comprises the following components in percentage by weight: alkanolamine compound (R) shown as formula I1Is C18, R2Is C2, R3H, m is 1, n is 2, X is CI), 18 wt%, C18 fatty acid polyoxyethylene ether sulfonate (the polymerization degree of polyoxyethylene ether is 5)16 wt%, C12 alkyl glycoside 12 wt%, isopropanol 8 wt% and 46 wt% of water.
The preparation method of the demulsification cleanup additive 1# for fracturing comprises the following steps:
(1) preparation of alkanolamine compound shown in formula I:
adding 270.5g of octadecanol and cyclohexane into a four-mouth bottle, heating the four-mouth bottle in a constant-temperature water bath to 60 ℃, starting to dropwise add epichlorohydrin, and continuing to react for 1h after dropwise adding; then reducing the temperature to 40 ℃, dropwise adding a sodium hydroxide aqueous solution, and reacting for 0.5h after dropwise adding to obtain octadecyl glycidyl ether;
adding 105g of diethanolamine into a four-mouth bottle, adding a certain amount of absolute ethanol, stirring and heating to 60 ℃, slowly dropwise adding the octadecyl glycidyl ether, continuing to react for 2 hours after dropwise adding, cooling after the reaction is finished, distilling under reduced pressure to remove the solvent, dissolving the obtained product into diethyl ether, slowly adding a certain amount of hydrochloric acid, generating a precipitate, performing suction filtration, and performing vacuum drying on the solid at 30 ℃ for 12 hours to obtain the alkanolamine compound; the alkanolamine compound is obtained by detection and analysis, wherein R in the alkanolamine compound1Is C18, R2Is C2, R3Is H, m is 1, n is 2, X is CI;
(2) weighing the alkanolamine compound, the fatty acid polyoxyethylene ether sulfonate, the alkyl glycoside and the isopropanol according to the proportion; firstly, mixing an alkanolamine compound and fatty acid polyoxyethylene ether sulfonate, and stirring for 15min to obtain a first mixture; mixing alkyl glycoside, isopropanol and water, and stirring for 10min to obtain a second mixture; and mixing the first mixture and the second mixture, and performing ultrasonic oscillation at the constant temperature of 35 ℃ for 25min to obtain the demulsification cleanup additive.
Example 2 demulsifying cleanup additive No. 2#
The demulsification cleanup additive 2# for fracturing comprises the following components in percentage by weight: alkanolamine compound (R) shown as formula I1Is C16, R2Is C2, R3C2, m is 2, n is 1, X is Br)20 wt%, C12 fatty acid polyoxyethylene ether sulfonate (polymerization degree of polyoxyethylene ether is 10)10 wt%, C18 alkyl glucoside 15 wt%, ethanol 5 wt% and 50 wt% of water.
The preparation method of the demulsification cleanup additive 2# for fracturing comprises the following steps:
(1) preparation of alkanolamine compound shown in formula I:
adding 242.5g of hexadecanol and cyclohexane into a four-mouth bottle, heating the four-mouth bottle in a constant-temperature water bath to 55 ℃, starting to dropwise add epichlorohydrin, and continuing to react for 1.5h after dropwise addition; then reducing the temperature to 35 ℃, dropwise adding a sodium hydroxide aqueous solution, and reacting for 1h after dropwise adding to obtain hexadecyl glycidyl ether;
② adding 61.1g of monoethanolamine into a four-mouth bottle, adding a certain amount of absolute ethanol, stirring and heating to 55 ℃, slowly dripping the hexadecyl glycidyl ether, and continuing to react for 2.5 hours after the dripping is finished. Cooling after the reaction is finished, slowly adding a certain amount of hydrobromic acid, generating a precipitate, performing suction filtration, and performing vacuum drying on the solid at the temperature of 30 ℃ for 12 hours to obtain the alkanolamine compound; the alkanolamine compound is obtained by detection and analysis, wherein R in the alkanolamine compound1Is C16, R2Is C2, R3Is C2, m is 2, n is 1, X is Br;
(2) weighing the alkanolamine compound, the fatty acid polyoxyethylene ether sulfonate, the alkyl glycoside and the ethanol according to the proportion; firstly, mixing an alkanolamine compound and fatty acid polyoxyethylene ether sulfonate, and stirring for 10min to obtain a first mixture; mixing alkyl glycoside, ethanol and water, and stirring for 5min to obtain a second mixture; and mixing the first mixture and the second mixture, and performing ultrasonic oscillation at the constant temperature of 40 ℃ for 30min to obtain the demulsification cleanup additive.
Example 3 demulsifying cleanup additive No. 3#
The demulsifying and cleanup additive 3# for fracturing comprises the following components in percentage by weight: alkanolamine compound (R) shown as formula I1Is C12, R2Is C3, R3C3, m is 2, n is 1, X is Br)10 wt%, C16 fatty acid polyoxyethylene ether sulfonate (the polymerization degree of polyoxyethylene ether is 9)20 wt%, C14 alkyl glucoside 5 wt%, isopropanol 10 wt% and 55 wt% of water.
The preparation method of the demulsifying and cleanup additive 3# for fracturing comprises the following steps:
(1) preparation of alkanolamine compound shown in formula I:
adding 186.4g of dodecanol and cyclohexane into a four-mouth bottle, heating the four-mouth bottle in a constant-temperature water bath to 80 ℃, starting to dropwise add epichlorohydrin, and continuing to react for 1h after dropwise addition; then reducing the temperature to 50 ℃, dropwise adding a sodium hydroxide aqueous solution, and reacting for 0.2h after dropwise adding to obtain dodecyl glycidyl ether;
adding 75.1g of propanolamine into a four-mouth bottle, adding a certain amount of isopropanol solution, stirring and heating to 80 ℃, slowly dropwise adding the dodecyl glycidyl ether, continuing to react for 2 hours after dropwise adding, cooling after the reaction is finished, distilling under reduced pressure to remove the solvent, dissolving the obtained product into diethyl ether, slowly adding a certain amount of hydrobromic acid, generating a precipitate, performing suction filtration, and performing vacuum drying on the solid at 30 ℃ for 12 hours to obtain the alkanolamine compound; the alkanolamine compound is obtained by detection and analysis, wherein R in the alkanolamine compound1Is C12, R2Is C3, R3Is C3, m is 2, n is 1, X is Br;
(2) weighing the alkanolamine compound, the fatty acid polyoxyethylene ether sulfonate, the alkyl glycoside and the isopropanol according to the proportion; firstly, mixing an alkanolamine compound and fatty acid polyoxyethylene ether sulfonate, and stirring for 15min to obtain a first mixture; mixing alkyl glycoside, isopropanol and water, and stirring for 10min to obtain a second mixture; and mixing the first mixture and the second mixture, and performing ultrasonic oscillation at the constant temperature of 30 ℃ for 30min to obtain the demulsification cleanup additive.
Example 4 demulsifying cleanup additive No. 4#
The demulsifying and cleanup additive 4# for fracturing comprises the following components in percentage by weight: alkanolamine compound (R) shown as formula I1Is C20, R2Is C4, R3H, m is 1, n is 2, X is F)30 wt%, C22 fatty acid polyoxyethylene ether sulfonate (the polymerization degree of polyoxyethylene ether is 8)30 wt%, C8 alkyl glycoside 8 wt%, ethanol 4 wt% and 28 wt% of water.
The preparation method of the demulsifying and cleanup additive 4# for fracturing comprises the following steps:
(1) preparation of alkanolamine compound shown in formula I:
adding 298.5g of eicosanol and cyclohexane into a four-mouth bottle, heating the four-mouth bottle in a constant-temperature water bath to 50 ℃, starting to dropwise add epichlorohydrin, and continuing to react for 2 hours after dropwise adding; then reducing the temperature to 30 ℃, dropwise adding a sodium hydroxide aqueous solution, and reacting for 1h after dropwise adding to obtain eicosyl glycidyl ether;
adding 89.1g of butanol amine into a four-mouth bottle, adding a certain amount of absolute ethyl alcohol, stirring and heating to 50 ℃, slowly dropwise adding the eicosyl glycidyl ether, continuing to react for 4 hours after dropwise adding, cooling after the reaction is finished, distilling under reduced pressure to remove the solvent, dissolving the obtained product into ether, slowly adding a certain amount of hydrofluoric acid, generating a precipitate, performing suction filtration, and performing vacuum drying on the solid at 30 ℃ for 12 hours to obtain the alkanolamine compound; the alkanolamine compound is obtained by detection and analysis, wherein R in the alkanolamine compound1Is C20, R2Is C4, R3Is H, m is 1, n is 2, X is F;
(2) weighing the alkanolamine compound, the fatty acid polyoxyethylene ether sulfonate, the alkyl glycoside and the ethanol according to the proportion; firstly, mixing an alkanolamine compound and fatty acid polyoxyethylene ether sulfonate, and stirring for 10min to obtain a first mixture; mixing alkyl glycoside, ethanol and water, and stirring for 5min to obtain a second mixture; and mixing the first mixture and the second mixture, and performing ultrasonic oscillation at the constant temperature of 35 ℃ for 40min to obtain the demulsification cleanup additive.
Example 5 demulsifying cleanup additive No. 5#
The demulsifying and cleanup additive 5# for fracturing comprises the following components in percentage by weight: alkanolamine compound (R) shown as formula I1Is C22, R2Is C2, R3C3, m is 1, n is 2, X is CI)5 wt%, C8 fatty acid polyoxyethylene ether sulfonate (the polymerization degree of polyoxyethylene ether is 7)15 wt%, C22 alkyl glucoside 10 wt%, n-butanol 10 wt% and water 60 wt%.
The preparation method of the demulsifying and cleanup additive 5# for fracturing comprises the following steps:
(1) preparation of alkanolamine compound shown in formula I:
adding 326.6g of docosanol and cyclohexane into a four-mouth bottle, heating the four-mouth bottle in a constant-temperature water bath to 55 ℃, starting to dropwise add epichlorohydrin, and continuing to react for 1h after dropwise addition; then reducing the temperature to 40 ℃, dropwise adding a sodium hydroxide aqueous solution, and reacting for 0.5h after dropwise adding to obtain docosyl glycidyl ether;
adding 105g of diethanolamine into a four-mouth bottle, adding a certain amount of isopropanol solution, stirring and heating to 55 ℃, slowly dropwise adding the docosyl glycidyl ether, continuing to react for 2 hours after dropwise adding, cooling after the reaction is finished, distilling under reduced pressure to remove the solvent, dissolving the obtained product in diethyl ether, slowly adding a certain amount of hydrochloric acid, generating a precipitate, performing suction filtration, and performing vacuum drying on the solid at 30 ℃ for 12 hours to obtain the alkanolamine compound; the alkanolamine compound is obtained by detection and analysis, wherein R in the alkanolamine compound1Is C22, R2Is C2, R3Is C3, m is 1, n is 2, X is CI;
(2) weighing the alkanolamine compound, the fatty acid polyoxyethylene ether sulfonate, the alkyl glycoside and the n-butyl alcohol according to the proportion; firstly, mixing an alkanolamine compound and fatty acid polyoxyethylene ether sulfonate, and stirring for 15min to obtain a first mixture; mixing alkyl glycoside, n-butanol and water, and stirring for 10min to obtain a second mixture; and mixing the first mixture and the second mixture, and performing ultrasonic oscillation at the constant temperature of 40 ℃ for 20min to obtain the demulsification cleanup additive.
Example 6 demulsifying cleanup additive 6#
The demulsification cleanup additive 6# for fracturing comprises the following components in percentage by weight: alkanolamine compound (R) shown as formula I1Is C15, R2Is C6, R3C2, m is 1, n is 2, X is CI)15 wt%, C20 fatty acid polyoxyethylene ether sulfonate (the polymerization degree of polyoxyethylene ether is 6)5 wt%, C12 alkyl glucoside 8 wt%, isopropanol 8 wt% and 64 wt% of water.
The preparation method of the demulsification cleanup additive 6# for fracturing comprises the following steps:
(1) preparation of alkanolamine compound shown in formula I:
adding 228.4g of pentadecanol and cyclohexane into a four-mouth bottle, heating the four-mouth bottle in a constant-temperature water bath to 65 ℃, starting to dropwise add epichlorohydrin, and continuing to react for 1h after dropwise adding; then reducing the temperature to 40 ℃, dropwise adding a sodium hydroxide aqueous solution, and reacting for 0.5h after dropwise adding to obtain pentadecyl glycidyl ether;
② adding 185g of dihexanolamine into a four-mouth bottle, adding a certain quantityAnhydrous ethanol, stirring and heating to 65 ℃, slowly dripping the pentadecyl glycidyl ether, continuing to react for 2 hours after dripping is finished, cooling after the reaction is finished, distilling under reduced pressure to remove the solvent, dissolving the obtained product in diethyl ether, slowly adding a certain amount of hydrochloric acid, generating a precipitate, performing suction filtration, and performing vacuum drying on the solid at 30 ℃ for 12 hours to obtain the alkanolamine compound; the alkanolamine compound is obtained by detection and analysis, wherein R in the alkanolamine compound1Is C15, R2Is C6, R3Is C2, m is 1, n is 2, X is CI;
(2) weighing the alkanolamine compound, the fatty acid polyoxyethylene ether sulfonate, the alkyl glycoside and the isopropanol according to the proportion; firstly, mixing an alkanolamine compound and fatty acid polyoxyethylene ether sulfonate, and stirring for 15min to obtain a first mixture; mixing alkyl glycoside, isopropanol and water, and stirring for 10min to obtain a second mixture; and mixing the first mixture and the second mixture, and performing ultrasonic oscillation at the constant temperature of 35 ℃ for 25min to obtain the demulsification cleanup additive.
Comparative example 1 demulsifying cleanup additive D1#
The demulsification cleanup additive D1# comprises the following components in percentage by weight: 22 wt% of C18 fatty acid polyoxyethylene ether sulfonate (the polymerization degree of polyoxyethylene ether is 5), 18 wt% of C12 alkyl glycoside, 14 wt% of isopropanol and 46 wt% of water.
The preparation method of the demulsification cleanup additive D1# comprises the following steps:
weighing the fatty acid polyoxyethylene ether sulfonate, alkyl glycoside and isopropanol according to the proportion; mixing alkyl glycoside, ethanol and water, and stirring for 10min to obtain mixture; and mixing the mixture with fatty acid polyoxyethylene ether sulfonate, and performing ultrasonic oscillation for 25min at the constant temperature of 35 ℃ to obtain the demulsification cleanup additive.
Comparative example 2 demulsifying cleanup additive D2#
The demulsification cleanup additive D2# comprises the following components in percentage by weight: 18 wt% of octadecyl trimethyl ammonium chloride, 16 wt% of C18 fatty acid polyoxyethylene ether sulfonate (the polymerization degree of polyoxyethylene ether is 5), 12 wt% of C12 alkyl glycoside, 8 wt% of isopropanol and 46 wt% of water.
The preparation method of the demulsification cleanup additive D2# comprises the following steps:
weighing the following components in proportion: octadecyl trimethyl ammonium chloride, fatty acid polyoxyethylene ether sulfonate, alkyl glycoside and isopropanol; firstly, the following steps: mixing octadecyl trimethyl ammonium chloride and fatty acid polyoxyethylene ether sulfonate, and stirring for 15min to obtain a first mixture; mixing alkyl glycoside, isopropanol and water, and stirring for 10min to obtain a second mixture; and mixing the first mixture and the second mixture, and performing ultrasonic oscillation at the constant temperature of 35 ℃ for 25min to obtain the demulsification cleanup additive.
Comparative example 3 demulsifying cleanup additive D3#
The demulsification cleanup additive D3# comprises the following components in percentage by weight: alkanolamine compound (R) shown as formula I1Is C18, R2Is C2, R3Is H, m is 1, n is 2, X is CI)23 wt%, C12 alkyl glycoside 17 wt%, isopropanol 14 wt% and 46 wt% water.
The preparation method of the demulsification cleanup additive D3# comprises the following steps:
(1) the preparation method of the alkanolamine compound shown in the formula I is the same as that of the example 1.
(2) Weighing the alkanolamine compound, the alkyl glycoside and the isopropanol according to the proportion; mixing alkyl glycoside, isopropanol and water, and stirring for 10min to obtain a mixture; and mixing the mixture with an alkanolamine compound, and performing ultrasonic oscillation for 25min at the constant temperature of 35 ℃ to obtain the demulsification cleanup additive.
The demulsifying and cleanup additive prepared in the above examples and the demulsifying and cleanup additive prepared in the comparative examples, D1# to D3# have the following performances:
(1) testing the surface tension and the interfacial tension of the demulsifying and cleanup additive by using a JYW-200B full-automatic surface tensiometer;
(2) testing the demulsification rate of the demulsification cleanup additive by using an IPOA-2001 infrared spectroscopic oil analyzer and a TDL-40B type desk centrifuge;
(3) the measurement of the cleanup rate was performed using the specification of SYT 5755-2016 "cleanup additive performance evaluation method for fracture acidizing".
The test results are shown in table 1.
TABLE 1
The results in table 1 show that the demulsification cleanup additive 1-6# obtained in the example of the present invention has a surface tension of 22.9-23.6 mN/m, an interfacial tension of 0.22-0.28 mN/m, a demulsification rate of 90% or more and a cleanup rate of 90% or more, and particularly that the demulsification cleanup additive 1 obtained in the example 1 has a demulsification rate of 92.4% and a cleanup rate of 96.5%. Compared with the component of the example 1, the component of the comparative example 1 does not contain the alkanolamine compound, the component of the comparative example 2 uses the quaternary ammonium salt compound to replace the alkanolamine compound, the component of the comparative example 3 does not contain the fatty acid polyoxyethylene ether sulfonate, the demulsification and cleanup additive D3# obtained has the demulsification rate and the cleanup additive rate which are far lower than those of the application, and the surface tension and the interfacial tension are far higher than those of the application. The results show that the components of the demulsification cleanup additive are optimized, and the alkanolamine compound and the fatty acid polyoxyethylene ether sulfonate are selectively used, so that the surface tension and the interfacial tension can be obviously reduced, and the flowback effect of the waste liquid after fracturing can be effectively improved.
The above description is only an example of the present application, and the protection scope of the present application is not limited by these specific examples, but is defined by the claims of the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The demulsification cleanup additive for fracturing is characterized by comprising the following components in parts by weight: 1-30 parts of alkanolamine compound, 1-30 parts of fatty acid polyoxyethylene ether sulfonate, 1-20 parts of alkyl glycoside and 1-15 parts of low molecular alcohol; wherein the alkanolamine compound is at least one selected from compounds with a structural formula shown in a formula I;
in the formula I, R1One selected from C8-C24 alkyl; r2One selected from C1-C8 alkyl; r3One selected from H and C1-C8 alkyl; m and n are each independently selected from 1 or 2, but m and n cannot both be 1 or 2; x is selected from halogen.
2. The demulsification cleanup additive for fracturing as claimed in claim 1, which comprises the following components in percentage by weight: 1-30 wt% of alkanolamine compound, 1-30 wt% of fatty acid polyoxyethylene ether sulfonate, 1-20 wt% of alkyl glycoside, 1-15 wt% of low molecular alcohol and the balance of water;
preferably, the composition comprises the following components in percentage by weight: 10 to 20 weight percent of alkanolamine compound, 10 to 20 weight percent of fatty acid polyoxyethylene ether sulfonate, 5 to 15 weight percent of alkyl glycoside, 5 to 10 weight percent of low molecular alcohol and the balance of water;
more preferably, the composition comprises the following components in percentage by weight: 18 wt% of alkanolamine compound, 16 wt% of fatty acid polyoxyethylene ether sulfonate, 12 wt% of alkyl glycoside, 8 wt% of low molecular alcohol and 46% of water.
3. The demulsification cleanup additive for fracturing of claim 1 or 2, wherein R is R1One selected from C10-C22 alkyl, R2One selected from C2-C6 alkyl, R3One selected from H and C2-C6 alkyl, and X is one selected from F, Cl and Br;
preferably, R1One selected from C12-C18 alkyl, R2One selected from C2-C4 alkyl, R3Is H, X is Cl。
4. The demulsification cleanup additive for fracturing as claimed in claim 1 or 2, wherein R1 is selected from at least one of alkyl groups comprising linear, branched and cyclic structures;
preferably, the alkyl group in R1 is substituted with one or more substituents, which are halogen, alkyl or alkoxy;
preferably, the alkyl group in R2 is substituted with one or more substituents, which are hydroxy or alkoxy.
5. The demulsification cleanup additive for fracturing as claimed in claim 1 or 2, wherein the polymerization degree of polyoxyethylene ether chains in the fatty acid polyoxyethylene ether sulfonate is selected from one of 4-12, and the fatty acid in the fatty acid polyoxyethylene ether sulfonate is selected from one of C6-C26;
preferably, the polymerization degree of polyoxyethylene ether in the fatty acid polyoxyethylene ether sulfonate is selected from one of 5-9, and the fatty acid in the fatty acid polyoxyethylene ether sulfonate is selected from one of C8-C24 fatty acids;
preferably, the fatty acid polyoxyethylene ether sulfonate is synthesized by adopting a hydroxyethyl sodium sulfonate method.
6. The demulsification cleanup additive for fracturing as claimed in claim 1 or 2, wherein the alkyl group in the alkyl glycoside is selected from one of C8-C24 alkyl groups;
preferably, the alkyl group in the alkyl glycoside is selected from one of C12-C18 alkyl groups;
preferably, the alkyl glycoside is synthesized from fatty alcohol and glucose.
7. The demulsification cleanup additive for fracturing as claimed in claim 1 or 2, wherein the low molecular alcohol is selected from at least one of ethanol, isopropanol and n-butanol;
preferably, the low molecular alcohol is isopropanol.
8. The preparation method of the demulsification cleanup additive for fracturing, which is characterized by comprising the following steps of:
(1) fatty alcohol, epoxy chloropropane and fatty alcohol amine are subjected to ring opening reaction in a lower alcohol solution, and the obtained product is mixed with halogen acid, filtered and dried to prepare an alkanolamine compound;
(2) and mixing the alkanolamine compound with fatty acid polyoxyethylene ether sulfonate, alkyl glycoside and low molecular alcohol to obtain the demulsification cleanup additive.
9. The method for preparing the demulsification cleanup additive for fracturing as recited in claim 8, wherein in the step (1), the ring-opening reaction comprises the following steps:
dripping epoxy chloropropane into fatty alcohol for reaction to obtain alkyl glycidyl ether;
dropping the alkyl glycidyl ether into the fatty alcohol amine to react to obtain a product;
preferably, in the step I, epoxy chloropropane is dripped into fatty alcohol, the reaction is carried out for 1-2 h at the temperature of 50-80 ℃, then the temperature is reduced to 30-50 ℃, alkali liquor is dripped, and the reaction is continued for 0.2-1 h, so as to obtain the alkyl glycidyl ether;
preferably, in the step II, the alkyl glycidyl ether is dripped into the fatty alcohol amine, and the reaction is carried out for 2-4 hours at the temperature of 50-80 ℃ to obtain the product.
10. The method for preparing the demulsification cleanup additive for fracturing as recited in claim 8, wherein in the step (2), the mixing comprises: mixing an alkanolamine compound and fatty acid polyoxyethylene ether sulfonate, and stirring for at least 10min to obtain a first mixture;
secondly, mixing the alkyl glycoside and the low molecular alcohol, and stirring for at least 5min to obtain a second mixture;
mixing the first mixture and the second mixture, and performing ultrasonic oscillation at the constant temperature of 30-40 ℃ for at least 20min to obtain the demulsification cleanup additive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011452974.5A CN112480899B (en) | 2020-12-11 | 2020-12-11 | Demulsification and cleanup additive for fracturing and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011452974.5A CN112480899B (en) | 2020-12-11 | 2020-12-11 | Demulsification and cleanup additive for fracturing and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112480899A true CN112480899A (en) | 2021-03-12 |
| CN112480899B CN112480899B (en) | 2022-05-24 |
Family
ID=74916693
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011452974.5A Active CN112480899B (en) | 2020-12-11 | 2020-12-11 | Demulsification and cleanup additive for fracturing and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112480899B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114773589A (en) * | 2022-05-06 | 2022-07-22 | 麦加芯彩新材料科技(上海)股份有限公司 | Low-temperature demulsifier and preparation method and application thereof |
| CN115785940A (en) * | 2022-12-01 | 2023-03-14 | 克拉玛依中科恒信科技有限责任公司 | Demulsification cleanup additive for fracture acidizing and preparation method and use method thereof |
| CN116218507A (en) * | 2023-05-08 | 2023-06-06 | 东营江源化工有限公司 | Demulsification and drainage-assisting composite additive for fracturing and acidizing and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618250A (en) * | 2012-03-02 | 2012-08-01 | 陕西延长石油(集团)有限责任公司研究院 | Preparation method of environmental-friendly demulsify-cleanup additive for fracture acidizing |
| CN104059168A (en) * | 2014-05-07 | 2014-09-24 | 盐城工学院 | Allyldimethyl dehydrogenated abietyl ammonium chloride grafted chitooligosaccharide and preparation method thereof |
| CN105062452A (en) * | 2015-07-15 | 2015-11-18 | 国勘石油技术有限公司 | Demulsification and discharge aiding agent and preparation method thereof as well as treatment method of oil field reservoir |
| CN106256882A (en) * | 2016-07-11 | 2016-12-28 | 威海晨源分子新材料有限公司 | A kind of star-like crude oil demulsifier of oil-in-water type and preparation method thereof |
| CN109233897A (en) * | 2018-10-08 | 2019-01-18 | 天津正达科技有限责任公司 | A kind of preparation method for oil-in-water emulsion crude oil reverse-phase emulsifier |
| CN111961457A (en) * | 2020-08-05 | 2020-11-20 | 德仕能源科技集团股份有限公司 | Oil displacement complexing agent for heavy oil reservoir and preparation method and application thereof |
-
2020
- 2020-12-11 CN CN202011452974.5A patent/CN112480899B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618250A (en) * | 2012-03-02 | 2012-08-01 | 陕西延长石油(集团)有限责任公司研究院 | Preparation method of environmental-friendly demulsify-cleanup additive for fracture acidizing |
| CN104059168A (en) * | 2014-05-07 | 2014-09-24 | 盐城工学院 | Allyldimethyl dehydrogenated abietyl ammonium chloride grafted chitooligosaccharide and preparation method thereof |
| CN105062452A (en) * | 2015-07-15 | 2015-11-18 | 国勘石油技术有限公司 | Demulsification and discharge aiding agent and preparation method thereof as well as treatment method of oil field reservoir |
| CN106256882A (en) * | 2016-07-11 | 2016-12-28 | 威海晨源分子新材料有限公司 | A kind of star-like crude oil demulsifier of oil-in-water type and preparation method thereof |
| CN109233897A (en) * | 2018-10-08 | 2019-01-18 | 天津正达科技有限责任公司 | A kind of preparation method for oil-in-water emulsion crude oil reverse-phase emulsifier |
| CN111961457A (en) * | 2020-08-05 | 2020-11-20 | 德仕能源科技集团股份有限公司 | Oil displacement complexing agent for heavy oil reservoir and preparation method and application thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114773589A (en) * | 2022-05-06 | 2022-07-22 | 麦加芯彩新材料科技(上海)股份有限公司 | Low-temperature demulsifier and preparation method and application thereof |
| CN114773589B (en) * | 2022-05-06 | 2024-02-23 | 麦加芯彩新材料科技(上海)股份有限公司 | Low-temperature demulsifier and preparation method and application thereof |
| CN115785940A (en) * | 2022-12-01 | 2023-03-14 | 克拉玛依中科恒信科技有限责任公司 | Demulsification cleanup additive for fracture acidizing and preparation method and use method thereof |
| CN116218507A (en) * | 2023-05-08 | 2023-06-06 | 东营江源化工有限公司 | Demulsification and drainage-assisting composite additive for fracturing and acidizing and preparation method thereof |
| CN116218507B (en) * | 2023-05-08 | 2023-08-15 | 东营江源化工有限公司 | Demulsification and drainage-assisting composite additive for fracturing and acidizing and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112480899B (en) | 2022-05-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112480899B (en) | Demulsification and cleanup additive for fracturing and preparation method thereof | |
| US6306800B1 (en) | Methods of fracturing subterranean formations | |
| RU2417243C2 (en) | Cleaning additive for liquids based on viscoelastic surfactants | |
| US10066149B2 (en) | Delayed breaker for viscoelastic surfactant-based fluids | |
| US6637517B2 (en) | Compositions containing aqueous viscosifying surfactants and methods for applying such compositions in subterranean formations | |
| RU2424270C2 (en) | Zirconium cross-linking compositions and procedures of their utilisation | |
| EA006867B1 (en) | Agueous viscoelastic fluid | |
| WO2000073620A1 (en) | Removal of wellbore residues | |
| CN104946230A (en) | Clean fracturing fluid suitable for oil field water and preparing method thereof | |
| CN102952531A (en) | Surfactant for displacing oil of offshore oilfield and preparation method thereof | |
| CA3071691A1 (en) | Injection fluids comprising an anionic surfactant for treating unconventional formations | |
| RU2543224C2 (en) | Acid composition for treatment of wells in carbonate and terrigenous reservoirs, and acid treatment method of bottom-hole zone of formation with its application | |
| CN110665431A (en) | Preparation of sulfonic acid amphoteric gemini viscoelastic surfactant and application of surfactant in fracturing fluid | |
| CN113004881A (en) | Nano-emulsion composition, nano-emulsion and preparation method thereof, and coagulation-resisting viscosity-reducing agent for fracturing fluid and preparation method thereof | |
| US20050087341A1 (en) | Liquid gelling agent concentrates and methods of treating wells therewith | |
| CN102643637A (en) | clean fracturing fluid | |
| CN115785940A (en) | Demulsification cleanup additive for fracture acidizing and preparation method and use method thereof | |
| CN117185940B (en) | Asymmetric amphoteric Gemini surfactant, preparation method thereof, preparation method of fracturing oil displacement agent and application of fracturing oil displacement agent | |
| CN104403655A (en) | Novel fracturing fluid for oil field and preparation method thereof | |
| CN114181689B (en) | High-temperature-resistant composite emulsion viscosity-reducing system and preparation method thereof | |
| RU2208147C1 (en) | Method of interval acid treatment of bottomhole zone, mainly, of horizontal wells | |
| RU2365611C1 (en) | Composition of polysaccharide gel for damping and washing of wells and method of its preparing | |
| RU2242604C1 (en) | Acid composition for treating low-permeable terrigenous oil reservoirs and a method for treating bottom zone of formation using indicated composition | |
| CN107868043A (en) | A kind of quinoline quatemay ammonium inner salt type corrosion inhibiter and preparation method thereof | |
| RU2297436C2 (en) | Composition of well-killing emulsion polysaccharide fluid and a method for preparation thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210429 Address after: 257000 building 18, college student Pioneer Park, Zoucheng Road, Dongying District, Dongying City, Shandong Province Applicant after: Deshi Energy Technology Group Co.,Ltd. Applicant after: SHANDONG DESHI CHEMICAL Co.,Ltd. Address before: 257000 building 18, college student Pioneer Park, Zoucheng Road, Dongying District, Dongying City, Shandong Province Applicant before: Deshi Energy Technology Group Co.,Ltd. Applicant before: SHANDONG DESHI CHEMICAL Co.,Ltd. Applicant before: Shandong anengtai oil and gas stimulation Technology Research Institute Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |