CN116217839B - Temperature-resistant and salt-resistant surface modified propping agent and preparation method thereof - Google Patents
Temperature-resistant and salt-resistant surface modified propping agent and preparation method thereof Download PDFInfo
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- CN116217839B CN116217839B CN202310158926.2A CN202310158926A CN116217839B CN 116217839 B CN116217839 B CN 116217839B CN 202310158926 A CN202310158926 A CN 202310158926A CN 116217839 B CN116217839 B CN 116217839B
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- 150000003839 salts Chemical class 0.000 title abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 97
- 239000006004 Quartz sand Substances 0.000 claims abstract description 59
- 239000000178 monomer Substances 0.000 claims abstract description 53
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 230000004048 modification Effects 0.000 claims abstract description 27
- 238000012986 modification Methods 0.000 claims abstract description 27
- 230000033444 hydroxylation Effects 0.000 claims abstract description 22
- 238000005805 hydroxylation reaction Methods 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 20
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims abstract description 16
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 15
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004381 surface treatment Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000012530 fluid Substances 0.000 abstract description 10
- 239000000243 solution Substances 0.000 description 40
- 229920000642 polymer Polymers 0.000 description 19
- 239000004576 sand Substances 0.000 description 19
- 239000000017 hydrogel Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 239000000523 sample Substances 0.000 description 10
- 238000004062 sedimentation Methods 0.000 description 10
- 239000000725 suspension Substances 0.000 description 10
- 239000012295 chemical reaction liquid Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000015784 hyperosmotic salinity response Effects 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000013643 reference control Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- AVSXGQJYEFAQNK-UHFFFAOYSA-N prop-2-enamide;hydrate Chemical compound O.NC(=O)C=C AVSXGQJYEFAQNK-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
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
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
-
- 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
- C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
- C09K8/805—Coated proppants
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Dental Preparations (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention provides a temperature-resistant and salt-resistant surface modified propping agent and a preparation method thereof. The preparation method of the invention comprises the following steps: a) Carrying out surface treatment on quartz sand to obtain surface hydroxylation quartz sand; b) Carrying out grafting modification on the surface of the surface hydroxylation quartz sand by using a silane coupling agent to obtain modified quartz sand; c) Mixing the modified quartz sand with a monomer solution and an initiator for reaction to obtain a surface modified propping agent; wherein the monomer solution is a solution of a monomer dissolved in water; the monomers are acrylamide, 2-acrylamide-2-methylpropanesulfonic acid and dimethyl diallyl ammonium chloride. The surface modified propping agent solves the problem that the traditional propping agent is easy to settle in clean water and low-viscosity fracturing fluid, and has excellent temperature resistance and salt resistance.
Description
Technical Field
The invention relates to the technical field of oil and gas wells, in particular to a temperature-resistant and salt-resistant surface modified propping agent and a preparation method thereof.
Background
Hydraulic fracturing is a technique in which a high-pressure pump pumps fracturing fluid into a wellbore to fracture a formation, thereby increasing the permeability of the formation and promoting the high-flux flow of petroleum, natural gas or other unconventional energy sources from a reservoir to the wellbore. To prevent the fracture from closing after the pressure drop, a fracturing fluid is pumped while proppant is brought into the fracture, thereby maintaining the fracture's conductivity. The choice of proppants directly affects fracture conductivity and oil and gas production. The ideal proppants should include the following features: the density is low, so that the fracturing fluid can conveniently enter the ground; (2) high strength, preventing crushing at formation pressure; (3) The chemical inertness is good, and the corrosion of oil, acid and salt water can be resisted; (4) The sphericity is good, and good pores can be kept among proppants; (5) low cost.
The traditional proppants currently commercialized mainly comprise quartz sand, ceramsite or coated proppants. However, these proppants have a high density, are prone to sedimentation in the fracturing fluid, and are difficult to transport to the fracture ends by the fracturing fluid. The problem can be effectively solved by using the high-viscosity sand-carrying fluid, but the energy consumption can be increased by using too much tackifier, so that the reservoir is damaged. The low-density propping agent has low sedimentation rate in the fracturing fluid, so that the use of chemical agents in the fracturing fluid is reduced, the fracturing cost is reduced, the damage to a reservoir is reduced, and the environment-friendly sustainable production is facilitated. There are three types of low density proppants: hollow/porous proppants, low density material proppants and surface modifying proppants. The hollow/porous propping agent has low compressive strength due to the structural characteristics, high sintering temperature and excessive energy consumption. The low-density material propping agent is made of a large amount of high-cost low-density materials, has high cost and complex production process. The surface modified low-density proppant is prepared by coating low-density substances on the surface of the traditional proppant with low cost, and can comprehensively consider cost, energy and performance.
Patent application number 202110141400.4 discloses a method for preparing an ultralow-density propping agent. The preparation of the disclosed ultra-low density propping agent mainly comprises the following steps: uniformly mixing a dispersing agent, an antioxidant and water in a low-pressure reaction kettle to obtain a liquid phase; adding the core material and the monomer into the liquid phase in sequence under the stirring condition to obtain a reaction liquid; and heating the reaction liquid and keeping the temperature constant to carry out suspension polymerization reaction to obtain the propping agent. However, the reaction temperature of the above technology is as high as 135-155 ℃, and the reaction temperature is too high, so that a large amount of heat is consumed, and the technology is not suitable for industrial production.
Patent application number 201910831808.7 discloses a method for producing ultra-low density proppants based on supramolecular materials. The invention discloses a production method of an ultra-low density propping agent based on a supermolecular material, which comprises the following steps: mixing the reaction liquid A and the non-reaction liquid B according to the ratio of 0-0.75:0.25-1 mass ratio, and sequentially injecting into a reaction kettle; the reaction kettle is used for uniformly stirring the reaction liquid A and the non-reaction liquid B, heating and preserving heat until the reaction between the components of the reaction liquid A is completed, and then naturally cooling; separating bead particles generated by the reaction liquid A from the non-reaction liquid B in the reaction kettle; adding the bead-shaped particles into a ball mill for further grinding into balls; sieving with a sieving machine to obtain the ultra-low density propping agent. However, the low-density proppants in this invention are all composed of high-cost supramolecular materials, which are too costly to be suitable for industrial large-scale use.
Disclosure of Invention
In view of this, the present invention provides a surface-modified proppant and a method of making the same. The surface modified propping agent provided by the invention has excellent suspension performance and temperature and salt resistance.
The invention provides a preparation method of a surface modified propping agent, which comprises the following steps:
a) Carrying out surface treatment on quartz sand to obtain surface hydroxylation quartz sand;
b) Carrying out grafting modification on the surface of the surface hydroxylation quartz sand by using a silane coupling agent to obtain modified quartz sand;
c) Mixing the modified quartz sand with a monomer solution and an initiator for reaction to obtain a surface modified propping agent;
Wherein,
The monomer solution is a solution of monomer dissolved in water;
The monomers are acrylamide, 2-acrylamide-2-methylpropanesulfonic acid and dimethyl diallyl ammonium chloride.
Preferably, in the step c), the molar ratio of the acrylamide, the 2-acrylamide-2-methylpropanesulfonic acid and the dimethyldiallylammonium chloride is 8: (0.25-1): (0.25-1).
Preferably, in step c), the temperature of the reaction is 50 to 70 ℃.
Preferably, step c) specifically comprises:
c1 After mixing the modified quartz sand with the monomer solution, regulating the pH value to obtain a mixture;
c2 Mixing the mixture with an initiator, raising the reaction temperature, and reacting while stirring until the viscosity of the system is too high to stir, and stopping the reaction;
c3 Taking out the reaction product, drying, crushing and screening to obtain the surface modified propping agent.
Preferably, in step c 1), the pH is adjusted to a pH of 7 to 8.
Preferably, in the step b), the silane coupling agent is at least one of a151, a171, a172 and KH 570.
Preferably, step b) specifically comprises:
b1 Mixing a silane coupling agent with a solvent to obtain a silane coupling agent solution;
b2 Adjusting the pH of the silane coupling agent solution;
b3 And d), soaking the surface hydroxylation quartz sand in the solution obtained in the step b 2), and then carrying out solid-liquid separation and drying to obtain the modified quartz sand.
Preferably, in step b 2), the pH is adjusted such that the pH is < 7.
Preferably, in step b 1):
the solvent is at least one of petroleum ether, ethanol, methanol and water;
the volume percentage concentration of the silane coupling agent solution is preferably 1% -5%;
In the step b 3), the soaking conditions are as follows: the temperature is 30-40 ℃ and the time is 12-48 h;
In step a), the surface treatment is a washing treatment;
the washing treatment is to carry out washing treatment by deionized water and an organic solvent respectively.
The invention also provides the surface modified propping agent prepared by the preparation method in the technical scheme.
According to the preparation method provided by the invention, the surface of the quartz sand is treated firstly, so that more hydroxyl groups are exposed on the surface of the quartz sand; then, the surface of the surface hydroxylation quartz sand is subjected to grafting modification by using a silane coupling agent and reacts with a monomer to form a hydrogel polymer coating layer, the main component of the quartz sand is inorganic SiO 2, the coated hydrogel polymer belongs to an organic phase, the physical and chemical properties of the two are greatly different, and the compatibility is poor. According to the invention, the silane coupling agent is used for modification, and silanol Si-OH at one end of the silane coupling agent can be hydrolyzed and hydrogen-bonded with hydroxyl on the surface of SiO 2 on the surface of quartz sand, so that the silane coupling agent is connected with the quartz sand; and the hydrogel polymer monomer and the carbon-carbon double bond at the other end of the silane coupling agent undergo free radical polymerization reaction to realize the connection between the quartz sand and the hydrogel polymer. In the process, the selection and proportion collocation of the three monomer raw materials, the control of the reaction temperature in the steps and other conditions are important, and the expansion multiple and the temperature resistance and the salt tolerance of the surface modification propping agent are effectively improved through the control in multiple aspects.
The test result shows that the expansion multiple of the surface modified propping agent provided by the invention is more than 11 times, and the maximum expansion multiple is 15 times, and the surface modified propping agent has better expansibility; the suspension time is more than 48 hours, and the suspension capacity is good; when the sand concentration is above 20%, the volume rise of the sedimentation bed is above 17mL at 150 ℃, and the high-temperature resistance is excellent; under the condition of high concentration of salt, the volume of the surface modification propping agent sedimentation bed is still higher than that of quartz sand, and the surface modification propping agent sedimentation bed has excellent salt tolerance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the effect of the expansion coefficient measurement of the surface-modified proppant of example 1; wherein, fig. 1 (a) is the volume of the surface-modifying proppants placed in kerosene, and fig. 1 (b) is the volume of the surface-modifying proppants placed in water after expansion;
FIG. 2 is a graph of the suspendable time test effect of the surface modified proppant of example 1; wherein, fig. 2 (a) is a schematic diagram of an initial sand concentration system, fig. 2 (b) is a schematic diagram of a sand concentration system after standing for 24 hours, and fig. 2 (c) is a schematic diagram of a sand concentration system after standing for 48 hours;
FIG. 3 is a plot of settled bed volume of surface modified proppant at various sand concentrations as a function of temperature for example 1;
FIG. 4 is a plot of settled bed volume for surface modified proppants at different salt concentrations for example 1.
Detailed Description
The invention provides a preparation method of a surface modified propping agent, which comprises the following steps:
a) Carrying out surface treatment on quartz sand to obtain surface hydroxylation quartz sand;
b) Carrying out grafting modification on the surface of the surface hydroxylation quartz sand by using a silane coupling agent to obtain modified quartz sand;
c) Mixing the modified quartz sand with a monomer solution and an initiator for reaction to obtain a surface modified propping agent;
Wherein,
The monomer solution is a solution of monomer dissolved in water;
The monomers are acrylamide, 2-acrylamide-2-methylpropanesulfonic acid and dimethyl diallyl ammonium chloride.
According to the preparation method provided by the invention, the quartz sand is subjected to surface treatment, so that more hydroxyl groups are exposed out of quartz sand storm; and then, carrying out grafting modification on the surface of the surface hydroxylation quartz sand by using a silane coupling agent, and then forming a hydrogel polymer coating layer by using a specific monomer through a free radical polymerization reaction, thereby obtaining the surface modification propping agent for fracturing. The surface-modified proppants in the present invention are comprised of surface hydratable molecules and coated aggregates. When the surface-modified proppants are dispersed in water, the surface-hydratable coating swells spontaneously by water absorption, the volume of the proppants increases, and the particle density decreases. Can be conveyed to the end of a crack by clean water or low-viscosity fracturing fluid, and has excellent temperature resistance and salt resistance.
Regarding step a):
a) And (3) carrying out surface treatment on the quartz sand to obtain the surface hydroxylation quartz sand.
In the invention, quartz sand is used as aggregate of the propping agent, and the granularity of the quartz sand is preferably 20-40 meshes, and can be specifically 20-25 meshes, 30 meshes, 35 meshes and 40 meshes.
In the present invention, the surface treatment is preferably a washing treatment. The washing treatment method is preferably to wash quartz sand with deionized water and an organic solvent, respectively. Among them, the washing with an organic solvent is preferably performed with ethanol, acetone and petroleum ether, respectively. In the present invention, more preferably, the washing treatment is washing with deionized water, ethanol, acetone and petroleum ether in sequence, and the treatment according to the specific sequence is favorable for ensuring the product performance. In the invention, more specifically, deionized water is used for washing 3-4 times, ethanol is used for washing 3-4 times, acetone is used for washing 3-4 times, and petroleum ether is used for washing 3-4 times. According to the invention, through the washing treatment, impurities on the surface of the quartz sand are removed, and more hydroxyl groups are exposed on the surface of the quartz sand.
In the present invention, the sample is preferably dried after the surface treatment. In the present invention, the drying is preferably vacuum drying. In the present invention, the drying temperature is preferably 45 to 60℃and may specifically be 45℃50℃55℃60 ℃. And drying to constant weight to obtain the surface hydroxylation quartz sand.
Regarding step b):
b) And (3) performing grafting modification on the surface of the surface hydroxylation quartz sand by using a silane coupling agent to obtain modified quartz sand.
In the present invention, the silane coupling agent is preferably at least one of a151, a171, a172 and KH 570. In the prior art, various silane coupling agents, such as KH550, KH560, KH570, KH590, A151, A171, A172 and the like, are adopted to facilitate the subsequent polymerization reaction by the research of the applicant, and the invention adopts A151, A171, A172 and KH 570.
In the present invention, when a silane coupling agent is used, it is preferably used in the form of a solution, that is, the surface-hydroxylated quartz sand is surface-graft-modified with a silane coupling agent solution.
In the present invention, the step b) preferably specifically includes:
b1 Mixing a silane coupling agent with a solvent to obtain a silane coupling agent solution;
b2 Adjusting the pH of the silane coupling agent solution;
b3 And d), soaking the surface hydroxylation quartz sand in the solution obtained in the step b 2), and then carrying out solid-liquid separation and drying to obtain the modified quartz sand.
Regarding step b 1):
The solvent is preferably at least one of petroleum ether, ethanol, methanol and water. The mode of mixing the silane coupling agent with the solvent is not particularly limited, and the materials may be uniformly mixed for conventional mixing operations in the art, such as stirring and mixing. In the present invention, the volume percentage concentration of the silane coupling agent solution is preferably 1% to 5%, and may specifically be 1%, 2%, 3%, 4%, 5%.
Regarding step b 2):
The pH value is preferably adjusted to be less than 7, and if the pH value is too high, the silane is unstable after hydrolysis in the subsequent polymerization step, so that the combination property between the silane coupling agent and quartz sand and the combination property between the hydrogel polymer and the silane coupling agent are affected, the combination property between materials in the whole propping agent is deteriorated, and the service performance of the whole propping agent is affected. In the present invention, the pH value is more preferably 3.5.ltoreq.7, most preferably 3.5 to 5.5, and particularly 3.5, 4.0, 4.5, and 5.0, and in this range, the hydrolysis rate and thus the internal binding property of the whole proppant can be improved, and the usability can be improved. In the present invention, the pH adjustor used for adjusting the pH is preferably at least one of formic acid, acetic acid, formaldehyde and oxalic acid.
The step b 2) preferably comprises: and adding a pH regulator into the silane coupling agent solution while stirring, and regulating the pH value of the solution. Wherein the temperature conditions for the above operation are preferably 25 to 40 ℃, specifically 25 ℃, 30 ℃, 35 ℃,40 ℃, more preferably 30 ℃; if the ambient temperature has reached the above temperature, no additional heating is required; if the ambient temperature fails to reach the above temperature, additional heating is required to solve the above problem; the heating mode is preferably water bath heating.
Regarding step b 3):
When the surface hydroxylation quartz sand is soaked in the solution obtained in the step b 2), the mass ratio of the surface hydroxylation quartz sand to the solution obtained in the step b 2) is preferably controlled to be 1:2.0, 1:2.5, 1:3.0, 1:3.5, 1:4.0, 1:4.5 and 1:5.0. The soaking temperature is preferably 30 to 40 ℃, more preferably 30 to 35 ℃, and even more preferably 40 ℃. The soaking time is preferably 12-48 h, and can be specifically 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 32h, 34h, 36h, 38h, 40h, 42h, 44h, 46h and 48h. After the soaking treatment, solid-liquid separation is carried out. The solid-liquid separation mode is not particularly limited, and the solid-liquid separation mode is performed according to a conventional solid-liquid separation operation mode, for example, solid matters are fished out, filtration and the like. And (3) performing solid-liquid separation and drying. In the present invention, the drying temperature is preferably 25 to 60 ℃.
According to the invention, through the step b), the surface hydroxylation quartz sand is subjected to surface grafting modification, so that modified quartz sand, namely, the quartz sand grafted and modified by the silane coupling agent is obtained.
Regarding step c):
c) And mixing the modified quartz sand with a monomer solution and an initiator for reaction to obtain the surface modified propping agent.
In the invention, the monomer solution is a solution of a monomer dissolved in water. Wherein the monomers are Acrylamide (AM), 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) and dimethyldiallylammonium chloride (DMDAAC). The invention adopts the specific three monomer collocations, wherein, 2-acrylamide-2-methylpropanesulfonic acid can lead the polymer to have larger steric hindrance, lead the main chain to have larger rigidity and greatly improve the viscosity of the polymer, and can form a ring structure on a molecular chain after the polymerization of dimethyl diallyl ammonium chloride, thus greatly improving the temperature resistance of the polymer; in addition, the DMDAAC with positive charges and the AMPS with negative charges are simultaneously introduced into polymer molecular chains to enable the product to be an ampholyte, the viscosity of the polymer with the specific structure formed after the reaction with the AM in a salt solution can not be reduced along with the increase of the concentration of an additional salt under certain conditions, and excellent temperature resistance and salt resistance are provided, namely, the specific three monomers are interacted, so that the performance of the product is improved. If the above-mentioned combination is broken, for example, dimethyl diallyl ammonium chloride is replaced with other acrylic or acrylamide monomers, the above-mentioned effect cannot be obtained.
In the invention, the molar ratio of the acrylamide, the 2-acrylamide-2-methylpropanesulfonic acid and the dimethyldiallylammonium chloride is preferably 8:0.25-1:0.25-1, and the control of the molar ratio is favorable for improving the temperature resistance and the salt resistance of the product in the above-mentioned ratio range, and the molar ratio can be 8∶0.25∶0.25、8∶0.25∶0.50、8∶0.25∶0.75、8∶0.25∶1、8∶0.50∶0.25、8∶0.50∶0.50、8∶0.50∶0.75、8∶0.50∶1、8∶0.75∶0.25、8∶0.75∶0.50、8∶0.75∶0.75、8∶0.75∶1、8∶1∶0.25、8∶1∶0.50、8∶1∶0.75、8∶1∶1,, more preferably 8:0.75:1. In the present invention, the aqueous solvent in the monomer solution is preferably deionized water. In the invention, the mass ratio of the total mass of the monomers to the water in the monomer solution is preferably (3-7) to 20, and can be specifically 3.0 to 20, 3.5 to 20, 4.0 to 20, 4.5 to 20, 5.0 to 20, 5.5 to 20, 6.0 to 20, 6.5 to 20 and 7.0 to 20.
In the present invention, the monomer solution is preferably prepared by: mixing acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, dimethyl diallyl ammonium chloride and water under a protective atmosphere, and stirring to dissolve to obtain a monomer solution. The gas species for providing the protective atmosphere is not particularly limited, and may be any protective gas conventionally used in the art, such as nitrogen or argon.
In the invention, the mass ratio of the total mass of the monomers to the quartz sand in the step a) is preferably 1:1.0, 1:1.5, 1:2.0, 1:2.5, 1:2.6 and 1:3.0.
In the present invention, the initiator is preferably an azo-based initiator, more preferably at least one of azobisisobutyronitrile, azobisisoheptonitrile, azobis Ding Qingji formamide and azobisisobutyronitrile hydrochloride. In the present invention, the initiator is preferably used in an amount of 0.5 to 2% by mass of the monomer, and specifically may be 0.5%, 1.0%, 1.5% or 2.0%.
In the invention, the reaction temperature is preferably 50-70 ℃, if the reaction temperature is too high, the activity of the initiator is greatly increased, and a large amount of free radicals can be generated to participate in the polymerization reaction in a short time; as the number of free radicals is increased, the reaction rate is faster, the phenomenon of sudden aggregation is easy to occur, and the stability of the final product is poor and the molecular weight is low. If the reaction temperature is too low, sufficient radicals cannot be generated, and the reaction monomers in the solution cannot be completely polymerized, resulting in a decrease in the molecular weight of the synthesized polymer. Both cases are characterized by low expansion times and poor temperature and salt resistance of the surface modified proppants. The temperature may be specifically 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃,60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃, 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃, 70 ℃.
In the present invention, the step c) preferably specifically includes:
c1 After mixing the modified quartz sand with the monomer solution, regulating the pH value to obtain a mixture;
c2 Mixing the mixture with an initiator, raising the reaction temperature, and reacting while stirring until the viscosity of the system is too high to stir, and stopping the reaction;
c3 Taking out the reaction product, drying, crushing and screening to obtain the surface modified propping agent.
Regarding step c 1):
the pH is preferably adjusted to a pH of 7 to 8, and specifically may be 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0. The pH regulator for regulating the pH value is preferably anhydrous sodium carbonate and/or sodium hydroxide.
Regarding step c 2):
The types and the reaction temperatures of the initiator are the same as those in the technical scheme, and are not repeated here. In the present invention, the mode of controlling the reaction temperature may be water bath heating. The stirring speed is preferably 125-200 rpm, and specifically 125rpm, 130rpm, 135rpm, 138rpm, 140rpm, 150rpm, 160rpm, 170rpm, 180rpm, 190rpm, 200rpm. After the initiator is added to initiate polymerization under the reaction temperature condition, the system starts to become sticky until the system is too high in viscosity to stir, and the reaction is stopped to form a polymer. In the present invention, the reaction is preferably carried out under a protective atmosphere.
Regarding step c 3):
Before the reaction product is taken out, the reactants obtained in step c 2) are preferably polymerized by standing at room temperature and the polymer reaction product obtained is then taken out. Wherein the time of the stationary polymerization is preferably 6 hours. After that, drying is performed. The drying temperature is preferably 70-110 ℃, and the drying is carried out to constant weight. After the above-mentioned drying, pulverizing and sieving are performed. The pulverizing method is not particularly limited, and is a conventional method for pulverizing materials in the art. The screening is preferably to screen out 20-40 mesh powder, and can be specifically 20 mesh, 25 mesh, 30 mesh, 35 mesh and 40 mesh. After the treatment, the surface modified propping agent is obtained.
The invention is treated by the step c), the monomer generates hydrogel through free radical polymerization reaction, and the hydrogel is coated on the surface of quartz sand to form a hydrogel coating layer.
The invention also provides the surface modified propping agent prepared by the preparation method in the technical scheme.
According to the preparation method provided by the invention, the surface of the quartz sand is treated firstly, so that more hydroxyl groups are exposed on the surface of the quartz sand; then, the surface of the surface hydroxylation quartz sand is subjected to grafting modification by using a silane coupling agent and reacts with a monomer to form a hydrogel polymer coating layer, the main component of the quartz sand is inorganic SiO 2, the coated hydrogel polymer belongs to an organic phase, the physical and chemical properties of the two are greatly different, and the compatibility is poor. According to the invention, the silane coupling agent is used for modification, and silanol Si-OH at one end of the silane coupling agent can be hydrolyzed and hydrogen-bonded with hydroxyl on the surface of SiO 2 on the surface of quartz sand, so that the silane coupling agent is connected with the quartz sand; and the hydrogel polymer monomer and the carbon-carbon double bond at the other end of the silane coupling agent undergo free radical polymerization reaction to realize the connection between the quartz sand and the hydrogel polymer. In the process, the selection and proportion collocation of the three monomer raw materials, the control of the reaction temperature in the steps and other conditions are important, and the expansion multiple and the temperature resistance and the salt tolerance of the surface modification propping agent are effectively improved through the control in multiple aspects.
The test result shows that the expansion multiple of the surface modified propping agent provided by the invention is more than 11 times, and the maximum expansion multiple is 15 times, and the surface modified propping agent has better expansibility; the suspension time is more than 48 hours, and the suspension capacity is good; when the sand concentration is above 20%, the volume rise of the sedimentation bed is above 17mL at 150 ℃, and the high-temperature resistance is good; under the condition of high concentration of salt, the volume of the surface modification propping agent sedimentation bed is still higher than that of quartz sand, and the surface modification propping agent sedimentation bed has excellent salt tolerance.
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
Example 1
1. Preparation of surface modified proppants
A) And (3) taking quartz sand (20-40 meshes), washing the quartz sand by deionized water, ethanol, acetone and petroleum ether respectively, and then vacuum drying at 45 ℃ to constant weight to obtain the surface hydroxylation quartz sand.
B1 Uniformly mixing a silane coupling agent KH570 with a petroleum ether reaction solvent to obtain a silane coupling agent solution (volume concentration is 1%).
B2 Heating the silane coupling agent solution in a water bath at 30 ℃, adding acetic acid while stirring, and adjusting the pH value to 4.
B3 Soaking the surface hydroxylation quartz sand obtained in the step a) in the solution obtained in the step b 2) (the solid-liquid mass ratio is 1:4) at 40 ℃, carrying out solid-liquid separation after soaking for 24 hours, and drying at 45 ℃ to constant weight to obtain the modified quartz sand.
C1 Introducing nitrogen into the three-neck flask for 20min, adding acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, dimethyl diallyl ammonium chloride and water (the molar ratio of the three monomers is 8:0.75:1, and the mass ratio of the total mass of the monomers to the water is 5:20), and rapidly stirring until the monomers are completely dissolved to obtain a monomer solution. Then, adding the modified quartz sand obtained in the step b 3) (the mass ratio of the total mass of the monomers to the quartz sand is 5:13), and then adding anhydrous sodium carbonate to adjust the pH value to 7.5, thereby obtaining the mixture.
C2 Adding an azodiisobutyronitrile initiator (the use amount of the initiator is 1% of the total mass of the monomers) into the three-neck flask, controlling the water bath temperature to 70 ℃, adjusting the rotating speed of a magnetic stirrer to be about 148rpm, carrying out reaction under the conditions, and starting to become sticky after a polymerization system is initiated until the system viscosity is too high to stir (about 40 min), wherein the reaction is stopped.
C3 Standing and polymerizing for 6h at room temperature, taking out the polymer, cutting, drying at 105 ℃ to constant weight, crushing, and screening to 20-40 meshes to obtain the surface modified propping agent.
2. Performance testing
(1) Determination of surface modified proppant settling bed volume
3G of the surface-modified proppant was placed in kerosene, and the volume of the surface-modified proppant was measured to be 2mL (see FIG. 1 a). 3g of the surface-modified proppant was taken and placed in water, after which it had been fully swelled, and its volume was measured to be 30mL (see FIG. 1 b). It follows that the surface modifying proppants can expand 15 times.
(2) Static sand suspension experiment
The settling time of the surface modified proppants at different sand concentrations at room temperature was determined. The method comprises the following steps: and (3) placing different amounts of the surface modification proppants into deionized water to respectively obtain mixed systems with mass concentrations of 10%, 20%, 30% and 40%, manually stirring the mixed systems in the deionized water by using a glass rod for 1min (stirring speed is about 60 r/min), standing and observing the surface modification proppants after the surface modification proppants are completely suspended, and recording the suspendable time of the surface modification proppants. Referring to fig. 2, fig. 2 is a diagram showing the effect of the surface-modified proppant according to example 1 on the floatable time test, wherein fig. 2 (a) is a schematic diagram of the as-prepared sand concentration system, fig. 2 (b) is a schematic diagram of the sand concentration system after standing for 24 hours, and fig. 2 (c) is a schematic diagram of the sand concentration system after standing for 48 hours; wherein, 4 samples are in each figure, and the sand concentration systems with the concentrations of 10%, 20%, 30% and 40% are arranged from left to right. It can be seen that the surface modified proppants of the present invention can be suspended for more than 48 hours.
(3) Suspension Property at high temperature
Different amounts of the surface modification proppants were placed in deionized water to obtain mixed systems with mass concentrations of 10%, 20%, 30% and 40%, respectively, and the volume of the surface modification proppants settled bed was tested as a function of temperature (20 ℃ to 150 ℃), and the results are shown in fig. 3, and fig. 3 is a graph showing the volume of the surface modification proppants settled bed as a function of temperature for different sand concentrations in example 1. It can be seen that when the sand concentration is more than 20%, the suspending capability can be still maintained at the high temperature of 150 ℃, and the process requirement of actual oilfield fracturing can be met.
(4) Suspension Property at high salt
And taking quartz sand to be placed in water to obtain a sand water sample as a comparison sample. Meanwhile, the surface modifying proppants are respectively placed in different salt solutions (NaCl solution, KCl solution, caCl 2 solution and MgCl 2 solution) to obtain different surface modifying proppants systems, the settled bed volumes of the surface modifying proppants of the samples under different salt concentrations are observed at normal temperature, the results are shown in fig. 4, and fig. 4 is a settled bed volume test chart of the surface modifying proppants under different salt concentrations in example 1. It can be seen that the settled bed volume of the surface modifying proppant decreases with increasing salt content in the aqueous solution, and when 6g of salt is contained per 30mL of the surface modifying proppant system (i.e., at high salt concentrations), the volume of the surface modifying proppant settled bed is still higher than that of quartz sand, demonstrating that the surface modifying proppant has excellent salt resistance.
Example 2
The procedure is as in example 1, except that in step c 1) the molar ratio of the three monomers is adjusted to 8:0.25:0.25 and the pH is adjusted to 7.
Example 3
The procedure is as in example 1, except that in step c 1) the molar ratio of the three monomers is adjusted to 8:1:1 and the pH is adjusted to 8.
Comparative example 1
The procedure is as in example 1, except that in step c 1) the dimethyldiallylammonium chloride monomer is replaced by an equimolar amount of acrylic acid.
Comparative example 2
The procedure is as in example 1, except that in step c 2) the temperature is adjusted to 90 ℃.
Comparative example 3
The procedure is as in example 1, except that in step c 2) the temperature is adjusted to 40 ℃.
Example 4: performance testing
Performance tests were performed on examples 2 to 3 and comparative examples 1 to 3 according to performance test items (1) to (4) in example 1, respectively, wherein a 30% sand concentration was used in item (3) and a NaCl solution was used as a salt solution in item (4). The results are shown in Table 1.
Table 1: results of Performance test
Note that: the term "increase in settled bed volume at 150" in item 3 refers to "the settled bed volume of the test sample at 150 ℃ with a 20% sand ratio minus the settled bed volume of the reference control sample (20% sand ratio, 30mL system)". The term "high salt settled bed volume up-scaling" refers to "settled bed volume of test sample minus settled bed volume of reference control sample (20% sand ratio, 30mL system)", wherein the settled bed volume of test sample is that of high salt concentration (i.e., 30mL surface modified proppant system containing CaCl 2 at a mass concentration of 20%) with a sample of quartz sand in water as the reference control sample.
As can be seen from the test results in Table 1, the expansion times of the surface modified proppants obtained in examples 1-3 are more than 11 times, and can be up to 15 times, and the surface modified proppants have better expansibility; the suspension time is more than 48 hours, and the suspension capacity is good; the volume rise of the sedimentation bed is more than 17mL at 150 ℃, and the sedimentation bed has excellent high temperature resistance; the volume increase of the settled bed under high salt is more than 4mL, and the high salt-resistant settling bed shows excellent salt resistance. Compared with the examples, the comparative example 1 changes the types of monomers, and as a result, various properties of the obtained product are obviously deteriorated, and the invention proves that the good properties can be obtained only by adopting three specific monomer collocations of acrylamide, 2-acrylamide-2-methylpropanesulfonic acid and dimethyl diallyl ammonium chloride. Compared with the examples, the reaction temperature in the step c 2) of the comparative examples 2-3 is too high and too low, and as a result, various properties of the obtained product are obviously deteriorated, which proves that the control of the specific reaction temperature condition is beneficial to the improvement of the properties of the product.
The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to aid in understanding the method of the invention and its core concept, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (7)
1. A method of preparing a surface-modified proppant comprising the steps of:
a) Carrying out surface treatment on quartz sand to obtain surface hydroxylation quartz sand;
b) Carrying out grafting modification on the surface of the surface hydroxylation quartz sand by using a silane coupling agent to obtain modified quartz sand;
c1 After mixing the modified quartz sand with the monomer solution, regulating the pH value to obtain a mixture;
c2 Mixing the mixture with an initiator, raising the reaction temperature, and reacting while stirring until the viscosity of the system is too high to stir, and stopping the reaction; the temperature of the reaction is 50-70 ℃;
c3 Taking out the reaction product, drying, crushing and screening to obtain the surface modified propping agent;
Wherein,
The monomer solution is a solution of monomer dissolved in water;
The monomer is acrylamide, 2-acrylamide-2-methylpropanesulfonic acid and dimethyl diallyl ammonium chloride, and the molar ratio of the acrylamide to the 2-acrylamide-2-methylpropanesulfonic acid to the dimethyl diallyl ammonium chloride is 8:0.25-1:0.25-1.
2. The method according to claim 1, wherein in step c 1), the pH is adjusted to a pH of 7 to 8.
3. The method according to claim 1, wherein in the step b), the silane coupling agent is at least one of a151, a171, a172 and KH 570.
4. A method according to claim 1 or 3, wherein step b) comprises:
b1 Mixing a silane coupling agent with a solvent to obtain a silane coupling agent solution;
b2 Adjusting the pH of the silane coupling agent solution;
b3 And d), soaking the surface hydroxylation quartz sand in the solution obtained in the step b 2), and then carrying out solid-liquid separation and drying to obtain the modified quartz sand.
5. The method according to claim 4, wherein in step b 2), the pH is adjusted so that the pH is < 7.
6. The method according to claim 4, wherein in step b 1):
the solvent is at least one of petroleum ether, ethanol, methanol and water;
the volume percentage concentration of the silane coupling agent solution is 1% -5%;
in the step b 3), the soaking conditions are as follows: the temperature is 30-40 ℃ and the time is 12-48 h;
In step a), the surface treatment is a washing treatment;
the washing treatment is to carry out washing treatment by deionized water and an organic solvent respectively.
7. A surface-modified proppant made by the method of any one of claims 1-6.
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