CN118978649A - A clay stabilizer for oil well fracturing and preparation method thereof - Google Patents
A clay stabilizer for oil well fracturing and preparation method thereof Download PDFInfo
- Publication number
- CN118978649A CN118978649A CN202411475484.5A CN202411475484A CN118978649A CN 118978649 A CN118978649 A CN 118978649A CN 202411475484 A CN202411475484 A CN 202411475484A CN 118978649 A CN118978649 A CN 118978649A
- Authority
- CN
- China
- Prior art keywords
- clay
- cyclodextrin
- clay stabilizer
- oil well
- well fracturing
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/10—Polymers provided for in subclass C08B
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明涉及石油开采技术领域，且公开了一种用于油井压裂的粘土稳定剂及其制备方法，以1,3‑二氨基丙烷、1,3‑丙烷磺内酯和烯丙基环糊精为原料，经过化学接枝反应，得到环糊精基两性离子单体，接着与丙烯酸、甲氧基聚乙二醇丙烯酸酯引发聚合，得到油井压裂的粘土稳定剂；该粘土稳定剂中含有季铵盐阳离子，可以插入粘土晶层之间，中和粘土表面的负电性；磺酸钠水化基团可以吸附在粘土颗粒表面形成致密的水化层，阻止和延缓水分子与粘土表面接触；环糊精侧链的引入，增大了空间位阻作用，抗盐水解能力较强；本发明制备的粘土稳定剂防膨性能良好，同时具有良好的耐洗刷、抗温抗盐性能，适用于油井压裂开采工程。The invention relates to the technical field of oil production, and discloses a clay stabilizer for oil well fracturing and a preparation method thereof. 1,3-diaminopropane, 1,3-propane sultone and allyl cyclodextrin are used as raw materials, and a cyclodextrin-based zwitterionic monomer is obtained through a chemical grafting reaction, and then polymerization is initiated with acrylic acid and methoxy polyethylene glycol acrylate to obtain the clay stabilizer for oil well fracturing. The clay stabilizer contains quaternary ammonium salt cations, which can be inserted between clay crystal layers to neutralize the negative charge on the clay surface. The sodium sulfonate hydration group can be adsorbed on the surface of clay particles to form a dense hydration layer, thereby preventing and delaying the contact between water molecules and the clay surface. The introduction of cyclodextrin side chains increases the steric hindrance and has a strong ability to resist salt hydrolysis. The clay stabilizer prepared by the invention has good anti-swelling performance, good washing resistance, temperature resistance and salt resistance, and is suitable for oil well fracturing and production engineering.
Description
Technical Field
The invention relates to the technical field of oil exploitation, in particular to a clay stabilizer for oil well fracturing and a preparation method thereof.
Background
With the continuous development of oil fields, the protection technology of reservoirs is receiving more and more attention; in the development processes of oilfield water injection, acidification, fracturing and the like, clay minerals such as kaolinite, montmorillonite, illite, chlorite and the like contained in an oil reservoir layer are hydrated, expanded and dispersed and moved when encountering external water or water-based substances, so that pore canal blockage is caused, the stratum permeability is reduced, and the reservoir layer is damaged, thereby influencing the final recovery ratio; the clay stabilizer has the effect of protecting the oil layer and is used for preventing hydration expansion and dispersion migration of clay minerals in the reservoir to block seepage channels, so that the clay stabilizer is indispensable to use.
The clay stabilizer commonly adopted at present is mainly composed of small molecular quaternary ammonium salt or polyquaternary ammonium salt surfactants and polymers compounded by the small molecular quaternary ammonium salt or polyquaternary ammonium salt surfactants and inorganic salts, and has certain anti-swelling performance, but has limited temperature resistance, salt resistance and scouring resistance and larger damage to stratum; inorganic salt clay stabilizers are wide in goods source, low in price and simple to use and maintain, but only temporarily stabilize clay particles, cannot resist scouring, and cannot produce multi-point adsorption; the anionic polymer has low flocculation capability, is easy to generate precipitation when meeting high-valence inorganic cations such as magnesium, calcium and the like, and has poor anti-swelling effect; the cationic polymer has the advantages of strong adsorption capacity, small influence of pH value, strong adaptability to stratum and the like, but has limited temperature resistance and scouring resistance.
The zwitterionic polymer has positive and negative charges, and has great advantages in the aspects of inhibiting performance, keeping stability of drilling fluid, reducing filtration performance and the like; patent number CN114805682B discloses an amphoteric clay stabilizer and a preparation method thereof, wherein the amphoteric clay stabilizer is prepared by polymerizing prepared dimethyl dodecyl allyl ammonium chloride, sodium styrene sulfonate and diallyl amine, and is compounded with potassium chloride, ammonium sulfate, dodecyl trimethyl ammonium chloride and water, and has the advantage of high anti-swelling rate, however, under the condition of high temperature and high mineralization, the zwitterionic polymer has poor temperature resistance and salt resistance due to the fact that molecules lack of rigid structures, a large number of molecular chains curl, and the inhibition capacity is obviously reduced. To further increase the temperature and salt resistance of the zwitterionic polymer; the invention aims to synthesize a zwitterionic monomer containing cyclodextrin groups, and the zwitterionic monomer is polymerized with methoxy polyethylene glycol acrylic ester, acrylic acid and the like to obtain the clay stabilizer containing zwitterionic and rigid structures, and the clay stabilizer has the characteristics of multipoint adsorption, good temperature and salt resistance and high expansion resistance, and is suitable for industrial oil well fracturing exploitation engineering.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides a clay stabilizer for oil well fracturing and a preparation method thereof, which are used for preventing hydration expansion and dispersion migration of clay minerals, reducing damage to low-permeability oil layer permeability and having good temperature resistance and salt resistance.
The invention is realized by the following technical scheme:
the preparation method of the clay stabilizer for oil well fracturing comprises the following steps:
And (2) adding the cyclodextrin sodium sulfonate tertiary amine monomer and N, N-dimethylformamide into the reaction flask under the nitrogen atmosphere, uniformly stirring, adding 3-bromopropene, stirring for reaction, cooling to room temperature after the reaction is finished, and concentrating under reduced pressure to obtain the cyclodextrin amphoteric ion monomer.
And (2) adding acrylic acid, cyclodextrin-based zwitterionic monomer, methoxy polyethylene glycol acrylic ester and deionized water into a reaction flask under the nitrogen atmosphere, uniformly stirring, then dropwise adding ammonium persulfate at the speed of 0.8-1.2mL/min, reacting for 1-3h at 75-90 ℃ after the dropwise adding is finished, cooling to 40-50 ℃, adding triethylamine, regulating the pH value to be neutral, and obtaining the clay stabilizer for oil well fracturing.
Further, in the step (1), the molar ratio relationship of the cyclodextrin sodium sulfonate tertiary amine monomer to the 3-bromopropene is 1:2.5-4.
Further, the reaction temperature in the step (1) is 90-110 ℃ and the reaction time is 24-48h.
Further, in the step (2), the molar ratio relationship of the acrylic acid, the cyclodextrin radical zwitterionic monomer, the methoxy polyethylene glycol acrylate and the ammonium persulfate is 1:0.03-0.15:0.25-0.4:0.005-0.012.
Further, the preparation method of the cyclodextrin sodium sulfonate tertiary amine monomer in the step (1) is carried out according to the following steps:
And S1, under the nitrogen atmosphere, adding 1, 3-diaminopropane and tetrahydrofuran into a reaction flask, uniformly stirring, adding 1, 3-propane sultone and sodium hydride, stirring for reaction, extracting ethyl acetate and deionized water after the reaction is finished, concentrating an organic phase, recrystallizing with ethanol, and filtering to obtain a sodium diamido sulfonate monomer.
And S2, adding sodium diamido sulfonate monomer and methanol into a reaction flask under the nitrogen atmosphere, uniformly stirring, adding allyl cyclodextrin, stirring for reaction, cooling to room temperature after the reaction is finished, concentrating under reduced pressure, and washing with deionized water to obtain the cyclodextrin sodium sulfonate tertiary amine monomer.
Further, in the step S1, the molar ratio of the 1, 3-diaminopropane, the 1, 3-propane sultone and the sodium hydride is 1:2.05-2.2:2.3-2.8.
Further, the reaction temperature in the step S1 is 55-70 ℃ and the reaction time is 8-16h.
Further, in the step S2, the molar ratio relationship of the sodium diamido sulfonate monomer and the allyl cyclodextrin is 1:2.02-2.1.
Further, the reaction temperature in the step S2 is 40-55 ℃ and the reaction time is 12-24h.
Compared with the prior art, the invention has the following beneficial effects:
The invention takes 1, 3-diaminopropane, 1, 3-propane sultone, allyl cyclodextrin and 3-bromopropene as raw materials, and obtains cyclodextrin-based zwitterionic monomers through chemical grafting reaction, and then initiates polymerization with acrylic acid and methoxy polyethylene glycol acrylate to obtain the clay stabilizer for oil well fracturing; the clay stabilizer contains quaternary ammonium salt cations, can be inserted between clay crystal layers, neutralizes electronegativity of clay surfaces, can generate stronger chemical adsorption action with the clay particle surfaces than nonionic polar adsorption groups, is easy to associate to form a reticular structure in chain bundles, realizes complete coating action on clay particles through adsorption, and weakens repulsive force among clay particles; the sodium sulfonate hydration group in the structure can be adsorbed on the surface of clay particles to form a compact hydration layer, so that the contact between water molecules and the clay surface is prevented and delayed, and the purpose of preventing hydration expansion is achieved.
The introduction of cyclodextrin side groups in the molecular chain of the clay stabilizer provides a large number of hydroxyl groups with stronger polarity, and the hydroxyl groups can be closely adsorbed on the surface of clay through the action of hydrogen bonds, so that water molecules are prevented from continuously entering the area between clay crystal layers, the clay crystal layers are bridged, and the clay expansion is inhibited; meanwhile, the existence of the hydrophobic cavity of the cyclodextrin provides a natural barrier for preventing water molecules from entering the clay crystal layer, so that the ability of inhibiting the hydration expansion of the clay is enhanced; the clay stabilizer belongs to a polymer macromolecular structure, and long-chain molecules in the structure can be adsorbed to a plurality of crystal layers and clay particles at the same time, so that hydration expansion and osmotic hydration expansion of the clay surface are effectively reduced, dispersion of the clay and migration of particles are inhibited, and low-valence cations in the clay are difficult to replace from the clay particle surface or wash away by other acid flow, oil flow and water flow through ion exchange; the clay stabilizer contains a huge cyclodextrin side chain, increases the steric hindrance effect, has strong salt hydrolysis resistance, and can achieve the effect of stabilizing clay for a long time.
The clay stabilizer has wide sources of raw materials, simple synthesis and preparation processes, no byproducts, safety and environmental protection; the clay stabilizer has the advantages of high anti-swelling rate, the anti-swelling rate reaches more than 99% under the condition of using the concentration of 0.2wt%, and the clay stabilizer prepared by the invention has good anti-swelling performance, and simultaneously has the properties of washing resistance, temperature resistance and salt resistance, and can be used for development of oil and gas fields.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless otherwise indicated, all starting materials and reagents used in the present application are commercially available or may be prepared by known methods.
Preparation of allyl cyclodextrin is carried out by referring to China adhesive, 12 th month of 2010, 19 th volume, 12 th period, synthesis and structural characterization of 6-O-allyl-beta-cyclodextrin: dissolving 1.135g of beta-cyclodextrin in 60mL of anhydrous N, N-dimethylformamide and anhydrous dimethyl sulfoxide with the same volume, adding 3.54g of sodium hydroxide while stirring, stirring at room temperature for 1h, naturally cooling to 5-10 ℃, adding 8mL of allyl bromide while stirring, continuing to react for 48h, standing for 2h after the reaction is finished, concentrating under reduced pressure, washing residues with acetone for multiple times, and performing suction filtration and drying to obtain the allyl cyclodextrin.
Polyethylene glycol methyl ether acrylate with CAS number 32171-39-4 and structural formulaThe molecular weight is 1000.
1, 3-Diaminopropane, CAS number 109-76-2.
1, 3-Propane sultone, CAS number 1120-71-4.
3-Bromopropene with CAS number 106-95-6.
Example 1:
(1) 85mmol of 1, 3-diaminopropane and 340mL of tetrahydrofuran are added into a reaction flask under the nitrogen atmosphere, 180.2mmol of 1, 3-propane sultone and 205mmol of sodium hydride are added after uniform stirring, the reaction is carried out for 12 hours at 65 ℃, ethyl acetate and deionized water are used for extraction, an organic phase is concentrated, ethanol is used for recrystallization, and a sodium diamido sulfonate monomer is obtained after filtration.
(2) Under the nitrogen atmosphere, 75mmol of sodium diamido sulfonate monomer and 750mL of methanol are added into a reaction flask, after being stirred uniformly, 154.5mmol of allyl cyclodextrin is added, the mixture is reacted for 16 hours at 45 ℃, cooled to room temperature, concentrated under reduced pressure, and washed by deionized water, so that the cyclodextrin sodium sulfonate tertiary amine monomer is obtained.
(3) Under the nitrogen atmosphere, 60mmol of cyclodextrin sodium sulfonate tertiary amine monomer and 1080mL of N, N-dimethylformamide are added into a reaction flask, after uniform stirring, 210mmol of 3-bromopropene is added, the reaction is carried out at 100 ℃ for 32h, the reaction is cooled to room temperature, and the cyclodextrin zwitterionic monomer is obtained after decompression concentration. The preparation reaction process is as follows:
(4) Under nitrogen atmosphere, 100mmol of acrylic acid, 3mmol of cyclodextrin-based zwitterionic monomer, 35mmol of methoxypolyethylene glycol acrylate and 75mL of deionized water are added into a reaction flask, after uniform stirring, 0.8mmol of ammonium persulfate is added dropwise at the speed of 1mL/min, after the dropwise addition is finished, the reaction is carried out for 2 hours at 80 ℃, the temperature is reduced to 45 ℃, and triethylamine is added to adjust the pH value to be neutral, so that the clay stabilizer for oil well fracturing is obtained.
Example 2:
(1) 150mmol of1, 3-diaminopropane and 300mL of tetrahydrofuran are added into a reaction flask under the nitrogen atmosphere, after being stirred uniformly, 307.5mmol of1, 3-propane sultone and 345mmol of sodium hydride are added, the mixture is reacted for 8 hours at 70 ℃, the mixture is extracted by ethyl acetate and deionized water, an organic phase is concentrated, ethanol is recrystallized, and the mixture is filtered to obtain a sodium diamido sulfonate monomer.
(2) 120Mmol of sodium diamido sulfonate monomer and 960mL of methanol are added into a reaction flask under the nitrogen atmosphere, after being stirred uniformly, 242.4mmol of allyl cyclodextrin is added, the mixture is reacted for 12 hours at 55 ℃, cooled to room temperature, concentrated under reduced pressure and washed by deionized water, and the cyclodextrin sodium sulfonate tertiary amine monomer is obtained.
(3) 96Mmol of cyclodextrin sodium sulfonate tertiary amine monomer and 1440mL of N, N-dimethylformamide are added into a reaction flask under nitrogen atmosphere, after uniform stirring, 240mmol of 3-bromopropene is added, the reaction is carried out at 110 ℃ for 24 hours, the reaction is cooled to room temperature, and the cyclodextrin zwitterionic monomer is obtained after decompression concentration.
(4) 100Mmol of acrylic acid, 6mmol of cyclodextrin-based zwitterionic monomer, 25mmol of methoxypolyethylene glycol acrylate and 60mL of deionized water are added into a reaction flask under the nitrogen atmosphere, after the mixture is stirred uniformly, 0.5mmol of ammonium persulfate is added dropwise at the speed of 0.8mL/min, after the dropwise addition is finished, the mixture is reacted for 1h at 90 ℃, the temperature is reduced to 50 ℃, and triethylamine is added to adjust the pH value to be neutral, so that the clay stabilizer for oil well fracturing is obtained.
Example 3:
(1) Under nitrogen atmosphere, 32mmol of 1, 3-diaminopropane and 160mL of tetrahydrofuran are added into a reaction flask, after stirring uniformly, 70.4mmol of 1, 3-propane sultone and 89.6mmol of sodium hydride are added, the mixture is reacted for 16 hours at 55 ℃, ethyl acetate and deionized water are used for extraction, an organic phase is concentrated, ethanol is recrystallized, and a sodium diamido sulfonate monomer is obtained by filtration.
(2) Under the nitrogen atmosphere, 25mmol of sodium diamido sulfonate monomer and 300mL of methanol are added into a reaction flask, after being stirred uniformly, 52.5mmol of allyl cyclodextrin is added, the mixture is reacted for 24 hours at 40 ℃, cooled to room temperature, concentrated under reduced pressure, and washed by deionized water, so that the cyclodextrin sodium sulfonate tertiary amine monomer is obtained.
(3) Under the nitrogen atmosphere, 18mmol of cyclodextrin sodium sulfonate tertiary amine monomer and 360mL of N, N-dimethylformamide are added into a reaction flask, after uniform stirring, 72mmol of 3-bromopropene is added, the reaction is carried out at 90 ℃ for 48 hours, the reaction is cooled to room temperature, and the cyclodextrin zwitterionic monomer is obtained after decompression concentration.
(4) 100Mmol of acrylic acid, 9mmol of cyclodextrin-based zwitterionic monomer, 40mmol of methoxypolyethylene glycol acrylate and 80mL of deionized water are added into a reaction flask under a nitrogen atmosphere, after uniform stirring, 1.2mmol of ammonium persulfate is dropwise added at a speed of 1.2mL/min, after the dropwise addition is finished, the reaction is carried out for 3 hours at 75 ℃, the temperature is reduced to 40 ℃, and triethylamine is added to adjust the pH to be neutral, so that the clay stabilizer for oil well fracturing is obtained.
Example 4:
(1) 70mmol of 1, 3-diaminopropane and 245mL of tetrahydrofuran are added into a reaction flask under the nitrogen atmosphere, after being stirred uniformly, 147mmol of 1, 3-propane sultone and 175mmol of sodium hydride are added, the mixture is reacted for 15 hours at 65 ℃, the mixture is extracted by ethyl acetate and deionized water, an organic phase is concentrated, ethanol is recrystallized, and the mixture is filtered to obtain a sodium diamido sulfonate monomer.
(2) Under the nitrogen atmosphere, 65mmol of sodium diamido sulfonate monomer and 685mL of methanol are added into a reaction flask, after being stirred uniformly, 135mmol of allyl cyclodextrin is added, the mixture is reacted for 18 hours at 45 ℃, cooled to room temperature, concentrated under reduced pressure and washed by deionized water, and the cyclodextrin sodium sulfonate tertiary amine monomer is obtained.
(3) 50Mmol of cyclodextrin sodium sulfonate tertiary amine monomer and 900mL of N, N-dimethylformamide are added into a reaction flask under the nitrogen atmosphere, after uniform stirring, 175mmol of 3-bromopropene is added, the reaction is carried out for 32 hours at 105 ℃, the reaction flask is cooled to room temperature, and the cyclodextrin zwitterionic monomer is obtained after decompression concentration.
(4) 100Mmol of acrylic acid, 12mmol of cyclodextrin-based zwitterionic monomer, 30mmol of methoxypolyethylene glycol acrylate and 75mL of deionized water are added into a reaction flask under a nitrogen atmosphere, after uniform stirring, 0.8mmol of ammonium persulfate is added dropwise at a speed of 0.9mL/min, after the dropwise addition is finished, the reaction is carried out for 3 hours at 85 ℃, the temperature is reduced to 50 ℃, and triethylamine is added to adjust the pH value to be neutral, so that the clay stabilizer for oil well fracturing is obtained.
Example 5:
(1) 48mmol of 1, 3-diaminopropane and 168mL of tetrahydrofuran are added into a reaction flask under the nitrogen atmosphere, after being stirred uniformly, 103.2mmol of 1, 3-propane sultone and 120mmol of sodium hydride are added, the mixture is reacted for 10 hours at 65 ℃, the mixture is extracted by ethyl acetate and deionized water, an organic phase is concentrated, ethanol is recrystallized, and the mixture is filtered to obtain a sodium diamido sulfonate monomer.
(2) Under the nitrogen atmosphere, 35mmol of sodium diamido sulfonate monomer and 310mL of methanol are added into a reaction flask, after being stirred uniformly, 72.8mmol of allyl cyclodextrin is added, the mixture is reacted for 24 hours at 50 ℃, cooled to room temperature, concentrated under reduced pressure and washed by deionized water, and the cyclodextrin sodium sulfonate tertiary amine monomer is obtained.
(3) Under the nitrogen atmosphere, 30mmol of cyclodextrin sodium sulfonate tertiary amine monomer and 550mL of N, N-dimethylformamide are added into a reaction flask, after uniform stirring, 108mmol of 3-bromopropene is added, the reaction is carried out at 110 ℃ for 48 hours, the reaction is cooled to room temperature, and the cyclodextrin zwitterionic monomer is obtained after decompression concentration.
(4) Under nitrogen atmosphere, adding 100mmol of acrylic acid, 15mmol of cyclodextrin-based zwitterionic monomer, 35mmol of methoxypolyethylene glycol acrylate and 75mL of deionized water into a reaction flask, uniformly stirring, dropwise adding 1mmol of ammonium persulfate at a speed of 1.1mL/min, reacting at 90 ℃ for 3h after the dropwise addition is finished, cooling to 45 ℃, adding triethylamine, and regulating the pH to be neutral to obtain the clay stabilizer for oil well fracturing.
Comparative example 1
100Mmol of acrylic acid, 3mmol of allyl cyclodextrin, 35mmol of methoxypolyethylene glycol acrylate and 75mL of deionized water are added into a reaction flask under a nitrogen atmosphere, after uniform stirring, 0.8mmol of ammonium persulfate is added dropwise at a speed of 1mL/min, after the dropwise addition is finished, the reaction is carried out for 2 hours at 80 ℃, the temperature is reduced to 45 ℃, and triethylamine is added to adjust the pH to be neutral, so that the clay stabilizer for oil well fracturing is obtained.
Comparative example 2
Into a reaction flask were charged 100mmol of acrylic acid, 3mmol of dimethyldiallylammonium chloride (structural formulaCAS number 7398-69-8), 3mmol of sodium 4-vinylbenzenesulfonate (structural formula2695-37-6) Of CAS number, 35mmol of methoxypolyethylene glycol acrylate and 75mL of deionized water, dropwise adding 0.8mmol of ammonium persulfate at a speed of 1mL/min after uniformly stirring, reacting at 80 ℃ for 2 hours after the dropwise adding is finished, cooling to 45 ℃, adding triethylamine to adjust the pH to be neutral, and obtaining the clay stabilizer for oil well fracturing.
Static clay anti-swelling performance test: the anti-swelling rate of the clay stabilizer is tested by referring to a centrifugation method in SY/T5971-2016 method for evaluating the performance of clay stabilizer for oil and gas field fracturing acidification and water injection. Weighing 0.2g of clay stabilizer prepared in the examples and the comparative examples, adding 100mL of distilled water, and shaking uniformly to obtain clay stabilizer solution; weighing 0.50g of sodium bentonite, loading into a 10mL centrifuge tube, adding 10mL of clay stabilizer solution, shaking fully, standing for 2h at room temperature, loading into a centrifuge, centrifuging at a rotating speed of 1500r/min for 15min, reading the volume V 1 of the sodium bentonite after expansion, respectively replacing the clay stabilizer solution with 10mL of distilled water and kerosene, and measuring the expansion volumes V 2 and V 1 of the bentonite in water and kerosene; the calculation formula of the anti-swelling rate is as follows: b= (V 2-V1）/（V2-V0) ×100%. Wherein B: anti-swelling rate (%); v 0: swelling volume (mL) of bentonite in kerosene; v 1: swelling volume (mL) of bentonite in clay stabilizer; v 2: swelling volume (mL) of bentonite in distilled water.
Table 1 static anti-swelling Performance test
As shown by the test results of the table, with the increase of the content of cyclodextrin-based zwitterionic monomers, the static anti-swelling rate of the clay stabilizer is gradually increased, and the example 5 reaches 99.6%, because on one hand, the clay stabilizer contains quaternary ammonium salt cations inserted between clay crystal layers, and neutralizes electronegativity of the clay surface, so that stronger chemical adsorption effect can be generated with the clay particle surface than nonionic polar adsorption groups, association is easy to generate to form a network structure in chain bundles, complete coating effect on clay particles is realized through adsorption, and repulsive force among clay particles is weakened; the sodium sulfonate hydration groups in the structure can be adsorbed on the surface of clay particles to form a compact hydration layer, so that water molecules are prevented and delayed from contacting the surface of clay, and the purpose of preventing hydration expansion is achieved; on the other hand, the introduction of the cyclodextrin side group in the clay stabilizer provides a large number of hydroxyl groups with stronger polarity, and the hydroxyl groups can be closely adsorbed on the surface of the clay through the action of hydrogen bonds, so that water molecules are prevented from continuously entering the area between the clay crystal layers, the clay crystal layers are bridged, and the clay expansion is inhibited; meanwhile, the existence of the hydrophobic cavity of the cyclodextrin provides a natural barrier for preventing water molecules from entering the clay crystal layer, and enhances the capability of inhibiting the hydration expansion of the clay. The comparative example 1 contains no zwitterionic and the comparative example 2 contains no cyclodextrin, and the rate of expansion is lower than that of the examples.
Washing resistance test: the water-washing resistance of the clay stabilizer was measured by referring to the method specified in SY/T5971-2016 method for evaluating the properties of clay stabilizers for oil and gas field fracture acidizing and water injection. Weighing 0.2g of the clay stabilizer prepared in the examples and the comparative examples, adding 100mL of distilled water, shaking uniformly to obtain a clay stabilizer solution, mixing and centrifuging with 0.50g of bentonite, recording an expansion volume V 1, removing supernatant, adding 10mL of distilled water, shaking uniformly sufficiently, standing for 2h, loading into a centrifuge, centrifuging at 1500r/min for 15min, recording an expansion volume V 2, repeating the steps for 3-8 times, reading the volume after each expansion of bentonite, and judging the washing resistance of the clay stabilizer according to the change condition of the anti-expansion rate.
Table 2 wash resistance test
As shown by the test results of the table, the clay stabilizer solution prepared by the invention has good initial anti-swelling rate, and the anti-swelling rate is over 85 percent after 8 times of water washing and is kept at a higher level, because the clay stabilizer belongs to a polymer macromolecular structure, long-chain molecules in the structure can be adsorbed on a plurality of crystal layers and clay particles at the same time, thereby effectively reducing hydration swelling and osmotic hydration swelling of the clay surface, inhibiting the dispersion of the clay and the migration of particles, so that low-valence cations in the clay are difficult to replace the clay from the clay particle surface or wash the clay particles by other acid flow, oil flow and water flow through ion exchange; therefore, the clay stabilizer prepared by the invention has both economic and scouring-resistant effects, and can achieve the effect of stabilizing clay for a long time.
Temperature resistance test: 0.2g of the clay stabilizer prepared in the examples and the comparative examples is weighed, 100mL of distilled water is added for shaking to obtain a clay stabilizer solution, the clay stabilizer solution is placed in a high-pressure container, the clay stabilizer solution is placed for 30 days at a temperature rising speed of 1 ℃/min to 150 ℃, and a swelling experiment is carried out by using the clay stabilizer after high-temperature treatment according to SY/T5971-2016 'method for evaluating the performance of clay stabilizers for oil and gas field fracturing acidification and water injection'.
Salt resistance test: preparing standard saline with a certain mineralization degree according to the mass ratio (NaCl: caCl 2:MgCl2·6H2 O=7:0.6:0.4), adding a clay stabilizer solution with the mass fraction of 2%, and carrying out an expansion test on the clay stabilizer treated by the saline by using a centrifugal method with reference to SY/T5971-2016 (method for evaluating the performance of clay stabilizers for oil and gas field fracturing and water injection).
TABLE 3 test of temperature and salt resistance
As shown by the test results of the table, after the clay stabilizer is subjected to high-temperature and brine treatment, the anti-swelling rate of the clay stabilizer is more than 80%, and as the clay stabilizer contains a huge cyclodextrin side chain agent, the steric hindrance effect is increased, the anti-salt hydrolysis capability is strong, so that the clay stabilizer prepared by the invention has good anti-swelling performance, and has the washing and high-temperature resistance, and can be used for development of oil and gas fields.
The above examples merely represent a few embodiments of the present application, which are described in more detail and are not to be construed as limiting the scope of the claims. It should be noted that it is possible for those skilled in the art to make several variations and modifications without departing from the concept of the present application, all falling within the scope of protection of the present application; the methods used in the present application are conventional methods unless otherwise specified.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411475484.5A CN118978649B (en) | 2024-10-22 | 2024-10-22 | Clay stabilizer for oil well fracturing and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411475484.5A CN118978649B (en) | 2024-10-22 | 2024-10-22 | Clay stabilizer for oil well fracturing and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN118978649A true CN118978649A (en) | 2024-11-19 |
| CN118978649B CN118978649B (en) | 2024-12-31 |
Family
ID=93453456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202411475484.5A Active CN118978649B (en) | 2024-10-22 | 2024-10-22 | Clay stabilizer for oil well fracturing and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118978649B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119242281A (en) * | 2024-12-06 | 2025-01-03 | 山东德坤工贸有限公司 | A water-resistant clay stabilizer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140128295A1 (en) * | 2012-11-07 | 2014-05-08 | Halliburton Energy Services, Inc. | Water-based drilling fluid with cyclodextrin shale stabilizer |
| CN103897121A (en) * | 2014-04-08 | 2014-07-02 | 西南石油大学 | AM/AA/N-beta-CD polymer-ionic liquid [bquin]BF4 composite clay stabilizer and synthesis method thereof |
| CN112521316A (en) * | 2020-11-05 | 2021-03-19 | 中国石油集团渤海钻探工程有限公司 | Gemini surfactant type clay stabilizer and preparation method thereof |
-
2024
- 2024-10-22 CN CN202411475484.5A patent/CN118978649B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140128295A1 (en) * | 2012-11-07 | 2014-05-08 | Halliburton Energy Services, Inc. | Water-based drilling fluid with cyclodextrin shale stabilizer |
| CN103897121A (en) * | 2014-04-08 | 2014-07-02 | 西南石油大学 | AM/AA/N-beta-CD polymer-ionic liquid [bquin]BF4 composite clay stabilizer and synthesis method thereof |
| CN112521316A (en) * | 2020-11-05 | 2021-03-19 | 中国石油集团渤海钻探工程有限公司 | Gemini surfactant type clay stabilizer and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| YIBIE QIN: "Performance of cationic b-cyclodextrin as a clay stabilizer for use in enhanced oil recovery", 《STARCH》, 31 December 2014 (2014-12-31), pages 795 * |
| 秦一别: "带环糊精侧基丙烯酰胺低聚物的制备及粘土稳定性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, 15 April 2021 (2021-04-15), pages 016 - 152 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119242281A (en) * | 2024-12-06 | 2025-01-03 | 山东德坤工贸有限公司 | A water-resistant clay stabilizer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN118978649B (en) | 2024-12-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6277900B1 (en) | Well cementing aids | |
| CN118978649B (en) | Clay stabilizer for oil well fracturing and preparation method thereof | |
| CN108299592B (en) | 3-methacrylamide dopamine and acrylamide mixed polymer and preparation method and application thereof | |
| CN109294532B (en) | Environment-friendly high-performance coating inhibitor and preparation method and application thereof | |
| CN101104665A (en) | AM/NaAA/allyl cyclodextrin polymer with inclusion function and synthesis method | |
| CN108059950B (en) | A kind of preparation method of temperature-resistant and salt-resistant filtrate reducer for water-based drilling fluid | |
| CN108117621B (en) | Tackifying calcium salt resistant polymer filtrate reducer and preparation method thereof | |
| CA1148299A (en) | Copolymers of n,n-dimethylacrylamide and acrylamide | |
| CN111454401B (en) | A kind of graft-modified temperature-sensitive thickening polymer and its preparation method and application | |
| CN108676129A (en) | A kind of comb-type structure amphoteric ion polymer fluid loss additive and preparation method thereof | |
| CN113527601B (en) | Nanometer oil displacement agent for high-temperature high-salt oil-gas field and preparation method thereof | |
| CN113528113A (en) | Fracturing fluid comprising (co) polymer containing 2-acrylamido-2-methylpropanesulfonic acid as monomer | |
| CN117003940A (en) | Double-effect inhibitor suitable for well wall stabilization of natural gas hydrate reservoir, and preparation method and application thereof | |
| CN115947903B (en) | High-temperature-resistant high-salt-resistant hyperbranched organosilicon filtrate reducer and preparation method and application thereof | |
| CN106432632A (en) | Amido polymer filtrate loss reducer for water-based drilling fluid resistant to high temperature, salt and calcium and preparation method and application thereof | |
| CN111704695B (en) | Multifunctional drilling treatment agent and preparation and application thereof | |
| CN118685158A (en) | A high-temperature and high-density silicate water-based drilling fluid | |
| CN110790859B (en) | Acrylamide copolymer and preparation method and application thereof | |
| CN106967397B (en) | A thermal viscosification and settlement stabilizer suitable for oil well cement slurry, its preparation method and application | |
| CN110790862B (en) | Acrylamide copolymer and preparation method and application thereof | |
| CN115960304A (en) | High-temperature-resistant base bionic wall-fixing agent for water-based drilling fluid and preparation method and application thereof | |
| CN114105322B (en) | Scale inhibitor composition, scale inhibitor and preparation method thereof | |
| CN116075573A (en) | Sulfonated polymers | |
| CN118496433B (en) | Oilfield flooding stabilizer and preparation method thereof | |
| CN105154054A (en) | Cross-linked polymer flooding agent adopting triamine participating in synthesis and preparation method of cross-linked polymer flooding agent |
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 |