CN111607380B - Surfactant for reservoir transformation and preparation method thereof - Google Patents
Surfactant for reservoir transformation and preparation method thereof Download PDFInfo
- Publication number
- CN111607380B CN111607380B CN201910137342.0A CN201910137342A CN111607380B CN 111607380 B CN111607380 B CN 111607380B CN 201910137342 A CN201910137342 A CN 201910137342A CN 111607380 B CN111607380 B CN 111607380B
- Authority
- CN
- China
- Prior art keywords
- reaction
- surfactant
- carrying
- acid
- solvent
- 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.)
- Active
Links
Images
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
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/13—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
- C07C309/14—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton
-
- 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
- C09K2208/30—Viscoelastic surfactants [VES]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a surfactant for reservoir transformation and a preparation method thereof. The structural formula of the surfactant is as follows:
wherein m is any integer from 2 to 20, and n is any integer from 2 to 25. The surfactant disclosed by the invention has a special structure and group, has good temperature resistance, can be used for preparing a high-temperature diverting acid system with the plugging pressure of more than 6MPa, the viscosity of a viscosity-changing peak value of more than 30mPa.s at 160 ℃, the viscosity of a gel breaking solution of less than 5mPa.s and the core acidification effect of more than 1.3 times, can be used for better solving the problem of uniform acid distribution of a 160-180 ℃ high-temperature heterogeneous reservoir and greatly improving the acidification effect of the high-temperature heterogeneous reservoir.
Description
Technical Field
The invention belongs to the field of acidizing and fracturing reservoir transformation in the oil and gas development process. More particularly, relates to a surfactant for reservoir transformation and a preparation method thereof.
Background
Reservoir transformation is an effective technology for increasing the yield of oil and gas wells and increasing the injection of injection wells. The reservoir heterogeneity of an actual oil and gas reservoir is serious, conventional acidizing fracturing liquid enters along a high-permeability layer, the low-permeability reservoir is difficult to effectively transform, and the acidizing operation effect is seriously influenced. In order to transform a heterogeneous oil and gas reservoir, an acid liquid system capable of blocking and steering is generally adopted at home and abroad, namely, the steering acid is used for acidizing. The diverting acid is prepared by adding a special surfactant into a conventional acidizing fluid to enable the acidizing fluid to have special diverting performance. In the acidification process, acid liquor enters a reservoir to react with rock, the concentration of the acid liquor is reduced, the pH of the acid liquor is gradually increased, the concentration of calcium and magnesium ions is gradually increased, the viscoelastic surfactant in the acid liquor is changed from a spherical shape to a winding micelle, the viscosity is rapidly increased, fresh acid with low viscosity is forced to enter the reservoir with low permeability, the low permeability reservoir is reformed, and the purpose of diversion is achieved.
A large amount of research on the diverting agent is carried out at home and abroad, but most diverting agent prepared diverting acid systems resist the temperature within 150 ℃, and the requirements of site construction are difficult to meet. CN 201110385338.X provides a composition of an acidification diversion agent, wherein the main agent of the diversion agent is: the mixture of erucic acid amide propyl dimethylamine, arachidic acid amide propyl dimethylamine and oleic acid amide propyl dimethylamine is used as the main agent of the diverter, the system is suitable for the acidification construction of oil and gas wells with the temperature not exceeding 100 ℃, and the maximum viscosity change value of the diverting acid can reach 470mPa & s when the concentration of the acid solution is 12-16% at 90 ℃.
CN 20110247626.9 discloses a diverting acid system consisting of two carboxylic acid chelating agents, which not only has a diverting function, but also has an effect of stabilizing iron ions, sodium salts of EDTA, HEDTA, DTPA or GLDA are selected as the carboxylic acid chelating agents, and the diverting is realized by crystallization of solids.
CN 200910018905.0 discloses a viscosity-variable diverting acid system for improving a formation acidizing profile, wherein the optimal combination is dilute hydrochloric acid with the mass concentration of 15-18%, the optimal combination is erucic acid amide propyl betaine 3.5-3.8 parts, the initial viscosity of acid liquor is 11-13mPa & s, the viscosity-variable viscosity at normal temperature is up to 500mPa & s, and related parameters such as the temperature resistance of the system are not given by authors, in 100 parts of the total composition, oleic acid amide propyl betaine, erucic acid amide propyl betaine and lauric acid amide propyl betaine are adopted.
The technical scheme disclosed by CN 201410213649.1 synthesizes a high-temperature-resistant Gemini cationic viscoelastic surfactant, the structure is shown as follows, the prepared diverting acid system reacts with rock at 160 ℃, obvious diverting characteristic appears, and 170s-1Under the condition of shearing for 60min, the viscosity is 49 mPas, and the gel is automatically broken under the concentration of 5 percent hydrochloric acid, but the gel is not applied on site.
Wherein RCO is oleic acid acyl or erucic acid acyl.
The technical scheme disclosed in CN 201310101432.7 is that 0.0-10% of amide amphoteric surfactant with two or three hydrophilic groups and two or three hydrophobic groups is adopted, the structural formula is shown as follows, 0.1-2% of anionic surfactant is sodium benzenesulfonate or oleic acid acyl methyl taurate containing straight-chain alkyl or branched-chain alkyl with 8-18 carbons, and the maximum viscosity value of the prepared diverting acid system at 80 ℃ is 180mPa & s.
In the formula: x is 2 or 3; r1Acyl containing x-CO-groups, the total number of carbons being between 24 and 54; r2Is alkylene containing 2 to 5 carbons; r3、R4Each independently is alkyl containing 1-4 carbon atoms, -CH2CH2COO-or-CH2CH2OH；R5is-CH2-or-CH2CH2-。
CN 201210219382.8 discloses a diverting agent which is prepared by mixing butanol, bromoethane and N-alkyl-N-dioctadecane and reacting for 6-6.5h at 70-75 ℃, and the diverting acid prepared by the diverting agent can resist the temperature of 150 ℃, but no test data of temperature resistance is given.
A diverting acid system prepared by the existing surfactant can realize good diverting of a heterogeneous reservoir, but the temperature resistance is within 160 ℃, an acid liquid system used for field use is within 150 ℃, and the temperature resistance of a 160-DEG C diverting agent is not involved. With the development of exploration and development towards deep reservoirs, reservoirs with formation temperature of 160-180 ℃ are more and more, and a novel surfactant is required to be researched and developed to meet the exploration and development requirements of high-temperature reservoirs.
Disclosure of Invention
Based on the background technology, the invention provides a surfactant for reservoir transformation and a preparation method thereof. After a high-temperature diverting acid system prepared by the surfactant reacts with acid rocks, the viscosity is increased sharply, larger cracks and pores are blocked, fresh acid liquid with lower viscosity is prevented from entering a high-permeability area, the flowing direction of the acid liquid is forced to change, the aim of uniform acid distribution is fulfilled, and residual acid with low viscosity is obtained after the acid liquid breaks the gel, so that the pollution to the stratum is avoided.
In order to realize the purpose, the invention adopts the following technical scheme:
the invention provides a surfactant for reservoir transformation, which has the following structural formula:
wherein m is any integer from 2 to 20, and n is any integer from 2 to 25.
The surfactant has a special structure and groups, has good temperature resistance, and can generate a large amount of calcium and magnesium ions due to acid-rock reaction after a diverting acid liquid system prepared by the surfactant enters a stratum according to the requirement of uniform acidification of a long well section heterogeneous reservoir in the acidification process, the concentration of the acid liquid is reduced, the acid liquid is gradually changed into a mutually-wound worm shape from a single micelle shape, the viscosity is rapidly increased, the acid liquid is changed into a strong viscoelasticity system capable of plugging a high-permeability reservoir, fresh acid with lower viscosity is forced to enter a low-permeability reservoir, the reservoir pollution is removed, and the purpose of uniform acid distribution in the whole well section is realized. And (3) with the further proceeding of the acid rock reaction, the concentration of the acid liquor is continuously reduced and is gradually reduced to residual acid, the gel breaking of the acid liquor system is realized, the worm-shaped structure is changed into a spherical low-viscosity acid liquor system, and after the construction is finished, the acid liquor is discharged back to the ground. The acidification effect of the heterogeneous reservoir can be effectively improved through the uniform modification of the reservoir.
The invention also provides a preparation method of the surfactant, and the synthetic route of the method is as follows:
specifically, the method comprises the following steps:
fatty acyl chloride
Carrying out bromination reaction with elemental bromine to obtain an intermediate 1;
carrying out methyl esterification reaction on the intermediate 1 and methanol to obtain an intermediate 2;
intermediate 2 and diol
Carrying out condensation reaction to obtain an intermediate 3;
carrying out ammonolysis reaction on the intermediate 3 and N, N-dimethyl-1, 3-propane diamine to obtain an intermediate 4;
and reacting the intermediate 4 with 3-chloro-2-hydroxypropyl sodium sulfonate to obtain the surfactant 5.
Preferably, the catalyst of the bromination reaction is elemental iodine.
More preferably, the feeding molar ratio of the fatty acyl chloride to the elemental bromine is 2: 1.05-2: 1.10, and the feeding molar ratio of the elemental iodine to the fatty acyl chloride is 1: 100-1: 105, preferably 1: 100.
Preferably, the feeding molar ratio of the intermediate 1 to the methanol in the methyl esterification reaction is 1: 1.15-1: 1.25.
Preferably, the step of condensation reaction comprises: mixing carbonate, a solvent and glycol under the atmosphere of protective gas, and heating to a first preset temperature; dropwise adding the intermediate 2 into the reaction system for reaction; after the reaction is finished, the intermediate 3 is obtained by post-treatment and purification. Preferably, the first preset temperature is 60 ℃.
More preferably, the molar ratio of the carbonate to the solvent to the glycol is 1 (10-15) to (97-100), preferably 1:10 (97-100); the feeding molar ratio of the intermediate 2 to the diol is 2: 1.15-2: 1.25.
Preferably, the carbonate is preferably one or a combination of potassium carbonate and sodium carbonate.
Preferably, the solvent is one or more of acetone, ethanol and chloroform. More preferably, the step of post-treatment purification comprises: and after the reaction is finished, carrying out suction filtration on a reaction system, carrying out rotary evaporation on the filtrate to remove the solvent, dissolving the filtrate by using dichloromethane, washing the filtrate by using a sodium hydroxide aqueous solution and water respectively, then carrying out rotary evaporation to remove the solvent, and recrystallizing the obtained solid by using petroleum ether to obtain an intermediate 3.
Preferably, the step of ammonolysis reaction comprises: heating and melting the intermediate 3, heating to a second preset temperature, dropwise adding N, N-dimethyl-1, 3-propanediamine in a protective gas atmosphere, and carrying out condensation reflux to carry out reaction; after the reaction is finished, the intermediate 4 is obtained by post-treatment and purification. Preferably, the second preset temperature is 120 ℃.
More preferably, the feeding molar ratio of the intermediate 3 to the N, N-dimethyl-1, 3-propane diamine is 1: 2.15-1: 2.25.
More preferably, the step of post-treatment purification comprises: after the reaction is finished, recrystallizing the obtained solid by using petroleum ether; dissolving the crystal in carbon tetrachloride, then adding a hydrochloric acid solution, shaking for layering, and then adding a sodium hydroxide solution into the upper layer liquid to adjust the pH value to 12; and filtering the system, drying a filter cake, and recrystallizing with petroleum ether to obtain an intermediate 4.
Preferably, the step of reacting said intermediate 4 with sodium 3-chloro-2-hydroxypropyl sulfonate to obtain said surfactant comprises: and adding the intermediate 4 and the 3-chloro-2-hydroxypropanesulfonic acid sodium salt into a mixed solvent of ethanol/water, heating to a third preset temperature for reaction, and performing post-treatment and purification after the reaction is finished to obtain the surfactant. Preferably, the third preset temperature is 60 ℃; the volume content of ethanol in the ethanol/water mixed solvent is 40-45%.
More preferably, the feeding molar ratio of the intermediate 4 to the sodium 3-chloro-2-hydroxypropanesulfonate is 1: 2.05-1: 2.15.
More preferably, the step of post-treatment purification comprises: after the reaction is finished, removing the solvent to obtain a crude product, and dissolving the crude product in isopropanol for filtering; and (3) dropwise adding the filtrate into boiling petroleum ether for crystallization, and carrying out hot filtration to obtain the surfactant.
Preferably, the protective gas is one or a combination of several of nitrogen, argon and helium.
The plugging pressure of a high-temperature diverting acid system prepared by the surfactant is more than 6MPa, the viscosity of a viscosity-changing peak value at 160 ℃ is more than 30mPa & s, the viscosity of a gel breaking solution is less than 5mPa & s, and the core acidizing effect is more than 1.3 times. The method can better solve the problem of uniform acid distribution of the high-temperature heterogeneous reservoir at 160-180 ℃, and meanwhile, the plugging pressure of an acid system is up to more than 6MPa, the viscosity of residual acid is low, and the acidification effect of the high-temperature heterogeneous reservoir is greatly improved.
Drawings
FIG. 1 is a peak viscosity-temperature curve for a diverting acid system configured in example 1 of the present invention.
FIG. 2 is a construction curve of a GS-xx well in example 2 of the present invention.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention should not be construed as limiting the implementable scope of the present invention.
The raw materials and additives used in the examples of the present invention were commercially available unless otherwise specified.
Example 1
Adding 218.5g of dodecanoyl chloride and 2.54g of elemental iodine as catalysts into a three-neck flask, standing for 30min, slowly dropwise adding 84g of elemental bromine at a constant speed, controlling the dropwise adding time to be 45-50 min, heating to 60 ℃, reacting for 360min, reducing the temperature to 50 ℃, and cooling at a speed of 1 ℃/min to obtain an intermediate 1 a.
After obtaining the intermediate 1a, 37g of methanol was added and cooled to 20 ℃ at a cooling rate of 1.5 ℃/min. And washing the cooled liquid with saturated sodium bisulfite aqueous solution for 4-6 times, and then washing with pure water for 3-5 times. The liquid obtained after washing was dried at 95 ℃ for 12 hours and then filtered to obtain intermediate 2 a.
After intermediate 2a was obtained, anhydrous potassium carbonate 0.8g and acetone 3.4g were added at 99.99% N2The mixture was stirred at a speed of 120r/min in a three-necked flask with a protection, and 100g of 1, 10-decanediol was added thereto. And (3) dropwise adding the intermediate 2a when the temperature is raised to 60 ℃ at the temperature raising speed of 1 ℃/min, wherein the dropwise adding speed is about 1 drop/second, and reacting for 48 hours after the dropwise adding is finished. And (3) performing rotary evaporation on the liquid obtained after suction filtration to remove the solvent, dissolving the liquid by using dichloromethane, washing the liquid for 3 times by using 5% sodium hydroxide aqueous solution and pure water respectively, performing rotary evaporation to remove the solvent, and recrystallizing the obtained solid for 3 times by using petroleum ether to obtain an intermediate 3 a.
After the intermediate 3a is obtained, adding the intermediate 3a into a three-neck flask, heating to 120 ℃ at a heating rate of 1 ℃/min after the intermediate 3a is completely dissolved, introducing 99.99% nitrogen at 120 ℃ for 20min to discharge oxygen, dropwise adding 110g of N, N-dimethyl-1, 3-propane diamine at a dropping rate of about 1 drop/sec, and then carrying out condensation reflux for 24 h. And (3) reducing the temperature to 20 ℃ at the cooling speed of 2 ℃/min, recrystallizing the obtained solid with petroleum ether for 3 times, dissolving the solid in carbon tetrachloride, then adding hydrochloric acid with the mass concentration of 10%, oscillating, adding a sodium hydroxide solution with the concentration of 5% into the upper-layer liquid, adjusting the pH value to 12, and filtering. And drying the filter cake, recrystallizing for 2 times by using petroleum ether, and drying at 95 ℃ to obtain the intermediate 4 a.
After the intermediate 4a is obtained, adding the intermediate 4a into 500mL of ethanol/water mixed solvent, wherein the volume content of ethanol is 45%, adding 201g of 3-chloro-2-hydroxypropanesulfonic acid sodium salt, heating to 60 ℃, stirring at the speed of 120r/min for 6 hours, then performing rotary evaporation, and putting the residual liquid into an oven for drying. Dissolving the dried crude product with isopropanol, and filtering to remove salt. And slowly dripping the filtrate into boiling petroleum ether at the speed of 1 drop/2 seconds to crystallize the target product, filtering while the filtrate is hot, and repeating for 2 times to obtain the target product 5 a.
40g of the target product 5a is dissolved in water to prepare a diverting acid system with 20% hydrochloric acid concentration, the addition amount of the additive is shown in the table 1, the balance is water, and the diverting acid system with the total amount of 500mL is prepared.
Example 2
Adding 120g of valeryl chloride and 2.54g of elemental iodine serving as catalysts into a three-neck flask, standing for 30min, slowly dropwise adding 84g of elemental bromine at a constant speed, controlling the dropwise adding time to be 45-50 min, heating to 60 ℃, reacting for 360min, reducing the temperature to 50 ℃, and cooling at a speed of 1 ℃/min to obtain an intermediate 1 b.
After obtaining the intermediate 1b, 37g of methanol was added and cooled to 20 ℃ at a cooling rate of 1.5 ℃/min. And washing the cooled liquid with saturated sodium bisulfite aqueous solution for 4-6 times, and then washing with pure water for 3-5 times. The liquid obtained after washing was dried at 95 ℃ for 12 hours and then filtered to obtain intermediate 2 b.
After intermediate 2b was obtained, anhydrous potassium carbonate 0.8g and ethanol 4.1g were added at 99.99% N2The mixture was stirred at 120r/min in a three-necked flask with protection, and 36g of ethylene glycol was added thereto. And (3) dropwise adding the intermediate 2b when the temperature is raised to 60 ℃ at the temperature raising speed of 1 ℃/min, wherein the dropwise adding speed is about 1 drop/second, and reacting for 48 hours after the dropwise adding is finished. And (3) removing the solvent from the liquid obtained after suction filtration by rotary evaporation, dissolving the liquid by using dichloromethane, washing the liquid for 3 times by using 5% sodium hydroxide aqueous solution and pure water respectively, then removing the solvent by rotary evaporation, and recrystallizing the obtained solid for 3 times by using petroleum ether to obtain an intermediate 3 b.
After an intermediate 3b is obtained, adding the intermediate 3b into a three-neck flask, heating up to 120 ℃ at a heating rate of 1 ℃/min after the intermediate 3b is completely dissolved, introducing 99.99% nitrogen at 120 ℃ for 20min to discharge oxygen, dropwise adding 110g of N, N-dimethyl-1, 3-propane diamine at a dropping rate of about 1 drop/sec, and then carrying out condensation reflux for 24 h. And (3) reducing the temperature to 20 ℃ at the cooling speed of 2 ℃/min, recrystallizing the obtained solid with petroleum ether for 3 times, dissolving the solid in carbon tetrachloride, then adding hydrochloric acid with the mass concentration of 10%, oscillating, adding a sodium hydroxide solution with the concentration of 5% into the upper-layer liquid, adjusting the pH value to 12, and filtering. And drying the filter cake, recrystallizing the filter cake for 2 times by using petroleum ether, and drying the filter cake at 95 ℃ to obtain an intermediate 4 b.
After the intermediate 4b is obtained, the intermediate 4b is added into 500mL of mixed solvent of ethanol/water, wherein the volume content of ethanol is 45%, 201g of 3-chloro-2-hydroxypropanesulfonic acid sodium salt is added, the temperature is raised to 60 ℃, stirring is carried out at the speed of 120r/min for 6 hours, then rotary evaporation is carried out, and the residual liquid is put into an oven for drying. Dissolving the dried crude product with isopropanol, and filtering to remove salt. And slowly dripping the filtrate into boiling petroleum ether at the speed of 1 drop/2 seconds to crystallize the target product, filtering while the filtrate is hot, and repeating for 2 times to obtain a target product 5 b.
40g of the target product 5b is dissolved in water to prepare a diverting acid system with 20% hydrochloric acid concentration, the addition amount of the additive is shown in the table 1, the balance is water, and the diverting acid system with the total amount of 500mL is prepared.
Example 3
Adding 373g of tricosanoyl chloride and 2.54g of elemental iodine into a three-neck flask as catalysts, standing for 30min, slowly dropwise adding 84g of elemental bromine at a constant speed, controlling the dropwise adding time to be 45-50 min, heating to 60 ℃, reacting for 360min, reducing the temperature to 50 ℃, and cooling at a speed of 1 ℃/min to obtain an intermediate 1 c.
After obtaining the intermediate 1c, 37g of methanol was added and cooled to 20 ℃ at a cooling rate of 1.5 ℃/min. And washing the cooled liquid with saturated sodium bisulfite aqueous solution for 4-6 times, and then washing with pure water for 3-5 times. The liquid obtained after washing was dried at 95 ℃ for 12 hours and then filtered to obtain intermediate 2 c.
After obtaining intermediate 2c, 0.6g of anhydrous sodium carbonate and 7.1g of chloroform were added to 99.99% N2The mixture was charged into a three-necked flask with a protection, and 148g of 1, 16-hexadecanediol was added thereto with stirring at a rate of 120 r/min. Heating to 60 deg.C at a rate of 1 deg.C/min, and adding dropwise the intermediate 2c at a rate of 1 drop/secondAnd reacting for 48 hours after the addition is finished. And (3) removing the solvent from the liquid obtained after suction filtration by rotary evaporation, dissolving the liquid by using dichloromethane, washing the liquid for 3 times by using 5% sodium hydroxide aqueous solution and pure water respectively, then removing the solvent by rotary evaporation, and recrystallizing the obtained solid for 3 times by using petroleum ether to obtain an intermediate 3 a.
After an intermediate 3c is obtained, the intermediate 3c is added into a three-neck flask, the temperature is raised to 120 ℃ finally after the intermediate 3c is completely dissolved at the heating rate of 1 ℃/min, 99.99% nitrogen is introduced at the temperature of 120 ℃ for 20min to discharge oxygen, 110g of N, N-dimethyl-1, 3-propane diamine is added dropwise at the dropping rate of about 1 drop/second, and then the mixture is condensed and refluxed for 24 h. And (3) reducing the temperature to 20 ℃ at the cooling speed of 2 ℃/min, recrystallizing the obtained solid with petroleum ether for 3 times, dissolving the solid in carbon tetrachloride, then adding hydrochloric acid with the mass concentration of 10%, oscillating, adding a sodium hydroxide solution with the concentration of 5% into the upper-layer liquid, adjusting the pH value to 12, and filtering. And drying the filter cake, recrystallizing for 2 times by using petroleum ether, and drying at 95 ℃ to obtain an intermediate 4 c.
After an intermediate 4c is obtained, the intermediate 4c is added into 500mL of mixed solvent of ethanol/water, wherein the volume content of ethanol is 45%, 201g of 3-chloro-2-hydroxypropanesulfonic acid sodium salt is added, the temperature is raised to 60 ℃, the mixture is stirred for 6 hours at the speed of 120r/min and then is subjected to rotary evaporation, and the residual liquid is put into an oven for drying. Dissolving the dried crude product with isopropanol, and filtering to remove salt. And slowly dripping the filtrate into boiling petroleum ether at the speed of 1 drop/2 seconds to crystallize the target product, filtering while the filtrate is hot, and repeating for 2 times to obtain the target product 5 a.
40g of the target product 5c is dissolved in water to prepare a diverting acid system with 20% hydrochloric acid concentration, the addition amount of the additive is shown in the table 1, the balance is water, and the diverting acid system with the total amount of 500mL is prepared.
TABLE 1 ingredient Table of diverting acid System
The properties of the diverting acid system at 160 ℃ are shown in Table 2 and FIG. 1 (where the initial viscosity, residual acid viscosity and drag reduction were measured at 20 ℃).
TABLE 2 turning to the acid system Performance Table
As can be seen from the data in Table 2, the plugging pressure of a high-temperature diverting acid system prepared by using the surfactant designed and synthesized by the invention is more than 6MPa, the viscosity of the viscosity-changing peak value at 160 ℃ is more than 30mPa & s, the viscosity of the gel breaking liquid is less than 5mPa & s, and the core acidification effect is more than 1.3 times.
Example 4
The diverting acid system prepared by the surfactant is applied to a GS-xx well in a Sichuan basin, the well is an evaluation well in the northwest of the ancient elevated high-grade ladder structure of the Sichuan basin, the Leshan mountain and the Longnu temple, and the well is a horizontal well. The well completion depth is 6586m, the porosity of the reservoir is 2.0-9.5%, the average porosity is 3.9%, and the length of the reservoir section is 550 m. Is a grey matter dolomite reservoir and has the temperature as high as 163 ℃. The well has high temperature, deep construction reservoir section, long construction well section and strong heterogeneity, and in order to realize uniform reconstruction, 800m is recommended3High temperature diverting acid +500m3After the high-temperature gelled acid system is acidified, the high-temperature diverting acid is the system synthesized in the embodiment 1, the high-temperature gelled acid is the system provided by the Duchen Technological development Limited company, the test yield is 65 ten thousand cubic meters per day, the construction curve is shown in figure 2, when the discharge capacity is stable at the ratio of 9:26, the oil pressure is increased from 95MPa to 107.5MPa, when the discharge capacity is stable at the ratio of 10:47, the oil pressure is increased from 77.7MPa to 93.1MPa, multiple pressure fluctuations obviously occur in the construction process of the latter two sections of diverting acids, the diverting acid is indicated to be continuously blocked and diverted, the diverting effect in the whole construction is obvious, the directly calculated diverting pressure reaches about 16MPa, the residual acid analysis indicates that the viscosity is less than 3 mPa.s, and the bottom hole pressure data and the construction data analysis indicate that the resistance reduction rate reaches 60%.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (17)
1. A surfactant for reservoir modification, characterized in that the surfactant has the following structural formula:
wherein m is any integer from 2 to 20, and n is any integer from 2 to 25.
2. A method of preparing the surfactant of claim 1, comprising the steps of:
fatty acyl chloride
Carrying out bromination reaction with elemental bromine to obtain an intermediate 1;
carrying out methyl esterification reaction on the intermediate 1 and methanol to obtain an intermediate 2;
intermediate 2 and diol
Carrying out condensation reaction to obtain an intermediate 3;
carrying out ammonolysis reaction on the intermediate 3 and N, N-dimethyl-1, 3-propane diamine to obtain an intermediate 4;
the intermediate 4 reacts with 3-chloro-2-hydroxypropyl sodium sulfonate to obtain the surfactant;
wherein, the structural formula of the intermediate is as follows:
3. the method of claim 2, wherein the catalyst of the bromination reaction is elemental iodine.
4. The preparation method according to claim 3, wherein the feeding molar ratio of the fatty acyl chloride to the elemental bromine is 2: 1.05-2: 1.10, and the feeding molar ratio of the elemental iodine to the fatty acyl chloride is 1: 100-1: 105.
5. The preparation method according to claim 2, wherein the feeding molar ratio of the intermediate 1 to the methanol in the methyl esterification reaction is 1: 1.15-1: 1.25.
6. The method of claim 2, wherein the step of condensing comprises: mixing carbonate, a solvent and glycol under the condition of protective gas atmosphere, and heating to a first preset temperature; dropwise adding the intermediate 2 into the reaction system for reaction; after the reaction is finished, the intermediate 3 is obtained by post-treatment and purification.
7. The preparation method of claim 6, wherein the molar ratio of the carbonate, the solvent and the glycol is 1 (10-15) to (97-100);
the feeding molar ratio of the intermediate 2 to the diol is 2: 1.15-2: 1.25.
8. The method according to claim 6, wherein the carbonate is one or a combination of potassium carbonate and sodium carbonate.
9. The method according to claim 6, wherein the solvent is a combination of one or more of acetone, ethanol and chloroform.
10. The method of claim 6, wherein the step of post-treating purification comprises:
and after the reaction is finished, carrying out suction filtration on a reaction system, carrying out rotary evaporation on the filtrate to remove the solvent, dissolving the filtrate by using dichloromethane, washing the filtrate by using a sodium hydroxide aqueous solution and water respectively, then carrying out rotary evaporation to remove the solvent, and recrystallizing the obtained solid by using petroleum ether to obtain an intermediate 3.
11. The method of claim 2, wherein the step of ammonolysis comprises:
heating and melting the intermediate 3, heating to a second preset temperature, dropwise adding N, N-dimethyl-1, 3-propanediamine in a protective gas atmosphere, and carrying out condensation reflux to carry out reaction; after the reaction is finished, the intermediate 4 is obtained through post-treatment and purification.
12. The preparation method according to claim 11, wherein the feeding molar ratio of the intermediate 3 to the N, N-dimethyl-1, 3-propanediamine is 1:2.15 to 1: 2.25.
13. The method of claim 11, wherein the step of post-treating purification comprises:
after the reaction is finished, recrystallizing the obtained solid by using petroleum ether; dissolving the crystal in carbon tetrachloride, then adding a hydrochloric acid solution, shaking for layering, and adding a sodium hydroxide solution into the upper layer liquid to adjust the pH value to 12; and filtering the system, drying a filter cake, and recrystallizing with petroleum ether to obtain an intermediate 4.
14. The method of claim 2, wherein the step of reacting intermediate 4 with sodium 3-chloro-2-hydroxypropylsulfonate to obtain the surfactant comprises:
and adding the intermediate 4 and the 3-chloro-2-hydroxypropanesulfonic acid sodium salt into a mixed solvent of ethanol/water, heating to a third preset temperature for reaction, and performing post-treatment and purification after the reaction is finished to obtain the surfactant.
15. The preparation method of claim 14, wherein the feeding molar ratio of the intermediate 4 to the sodium 3-chloro-2-hydroxypropanesulfonate is 1: 2.05-1: 2.15.
16. The method of claim 14, wherein the step of post-treating purification comprises:
after the reaction is finished, removing the solvent to obtain a crude product, and dissolving the crude product in isopropanol to filter; and (3) dropwise adding the filtrate into boiling petroleum ether for crystallization, and carrying out hot filtration to obtain the surfactant.
17. The method according to claim 7 or 11, wherein the shielding gas is one or a combination of nitrogen, argon and helium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910137342.0A CN111607380B (en) | 2019-02-25 | 2019-02-25 | Surfactant for reservoir transformation and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910137342.0A CN111607380B (en) | 2019-02-25 | 2019-02-25 | Surfactant for reservoir transformation and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111607380A CN111607380A (en) | 2020-09-01 |
| CN111607380B true CN111607380B (en) | 2022-07-05 |
Family
ID=72202062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910137342.0A Active CN111607380B (en) | 2019-02-25 | 2019-02-25 | Surfactant for reservoir transformation and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111607380B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115477597B (en) * | 2022-09-23 | 2023-10-27 | 山东科洗新材料有限公司 | Preparation method and application of surfactant |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1760316A (en) * | 2005-10-18 | 2006-04-19 | 中国石油大学(华东) | New type high temperature acidified diverting agent and preparation method |
| CN102863948A (en) * | 2012-10-14 | 2013-01-09 | 东北石油大学 | Hydroxysulfobetaine amphoteric surfactant for flooding and preparation method of hydroxysulfobetaine amphoteric surfactant |
| US20140166291A1 (en) * | 2012-12-14 | 2014-06-19 | Sanjel Canada Ltd. | Surfactant system as a self-diverted acid for well stimulation |
| CN106631912A (en) * | 2015-10-29 | 2017-05-10 | 中国石油天然气股份有限公司 | Hydroxysulfobetaine surfactant and preparation method and application thereof |
-
2019
- 2019-02-25 CN CN201910137342.0A patent/CN111607380B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1760316A (en) * | 2005-10-18 | 2006-04-19 | 中国石油大学(华东) | New type high temperature acidified diverting agent and preparation method |
| CN102863948A (en) * | 2012-10-14 | 2013-01-09 | 东北石油大学 | Hydroxysulfobetaine amphoteric surfactant for flooding and preparation method of hydroxysulfobetaine amphoteric surfactant |
| US20140166291A1 (en) * | 2012-12-14 | 2014-06-19 | Sanjel Canada Ltd. | Surfactant system as a self-diverted acid for well stimulation |
| CN106631912A (en) * | 2015-10-29 | 2017-05-10 | 中国石油天然气股份有限公司 | Hydroxysulfobetaine surfactant and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111607380A (en) | 2020-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101081976B (en) | Fire-resistant non-injury fracturing fluid thickening agent and preparation method and usage thereof | |
| CN102277146B (en) | Composition for improving recovery ratio substantially and preparation method thereof | |
| CN102464598B (en) | Fatty acid amide polyoxylethylene ether benzene sulfonate and preparation method thereof | |
| CN104877654A (en) | Compound oil-displacing agent containing asymmetric di-long chain alkylmethyl carboxyl betaine and application thereof | |
| US20190016683A1 (en) | Imidazoline compound, mobility control system, plugging agent for gas channeling, and method for carbon dioxide flooding | |
| CN102093874A (en) | Anion type nano compound clean fracturing fluid and preparation method thereof | |
| CN102690641B (en) | Sulfonate surfactant and preparation method thereof | |
| CN104694103A (en) | Surfactant compounded system with oil reservoir adaptability | |
| CN111607380B (en) | Surfactant for reservoir transformation and preparation method thereof | |
| CN105086960B (en) | A kind of drilling fluid and preparation method and application | |
| CN102585797B (en) | Diverting acid for carrying out acidification and transformation on high-temperature oil and gas well with long well segment | |
| CN105086959B (en) | A kind of high inhibition water-base drilling fluid and its preparation method and application | |
| CN111218268B (en) | Slickwater for compact sandstone reservoir and preparation method thereof | |
| CN102277148B (en) | Composition for improving recovery ratio of crude oil and preparation method thereof | |
| CN105086961B (en) | A kind of high-efficiency water-base drilling fluid and its synthetic method and application | |
| CN111607381B (en) | High-temperature diverting acid composition and preparation method thereof | |
| CN113896881A (en) | Alkyl naphthylamine polyether naphthalene sulfonate surfactant and preparation method and application thereof | |
| CN111154473B (en) | Blockage removal oil displacement agent and preparation method and application thereof | |
| CN112280547A (en) | Viscosity-reducing oil displacement agent for super-thick crude oil and preparation method and application thereof | |
| CN104531108A (en) | Solid phase-free foam workover fluid, preparation method and uses thereof | |
| CN105086962B (en) | A kind of drilling fluid of strong inhibition capability and preparation method and application | |
| CN111087608A (en) | Oil-displacing surfactant and composition of alkyl phenol polyether bisbenzenesulfonate, and preparation method and application thereof | |
| CN112694884B (en) | Foaming agent composition for low-permeability reservoir enhanced oil recovery and preparation method thereof | |
| CN105647493B (en) | A kind of high inhibition blocks by force drilling fluid and preparation method thereof | |
| CN111087601B (en) | Surfactant and composition for oil extraction and preparation method 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |