CN116042198A - Temperature response type bio-based temporary plugging agent and preparation method thereof - Google Patents
Temperature response type bio-based temporary plugging agent and preparation method thereof Download PDFInfo
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- CN116042198A CN116042198A CN202310045887.5A CN202310045887A CN116042198A CN 116042198 A CN116042198 A CN 116042198A CN 202310045887 A CN202310045887 A CN 202310045887A CN 116042198 A CN116042198 A CN 116042198A
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- 230000004044 response Effects 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 69
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 32
- 239000008158 vegetable oil Substances 0.000 claims abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical group COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920001971 elastomer Polymers 0.000 claims abstract description 13
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- 238000010276 construction Methods 0.000 claims abstract description 9
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- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 238000005553 drilling Methods 0.000 claims abstract description 5
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- 239000010936 titanium Substances 0.000 claims description 8
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- 238000007711 solidification Methods 0.000 claims description 3
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- 235000020661 alpha-linolenic acid Nutrition 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000006735 epoxidation reaction Methods 0.000 description 3
- 229960004488 linolenic acid Drugs 0.000 description 3
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 3
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- 229910052760 oxygen Inorganic materials 0.000 description 3
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
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- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 235000020778 linoleic acid Nutrition 0.000 description 2
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
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- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000010773 plant oil Substances 0.000 description 2
- 230000007281 self degradation Effects 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- DSEKYWAQQVUQTP-XEWMWGOFSA-N (2r,4r,4as,6as,6as,6br,8ar,12ar,14as,14bs)-2-hydroxy-4,4a,6a,6b,8a,11,11,14a-octamethyl-2,4,5,6,6a,7,8,9,10,12,12a,13,14,14b-tetradecahydro-1h-picen-3-one Chemical compound C([C@H]1[C@]2(C)CC[C@@]34C)C(C)(C)CC[C@]1(C)CC[C@]2(C)[C@H]4CC[C@@]1(C)[C@H]3C[C@@H](O)C(=O)[C@@H]1C DSEKYWAQQVUQTP-XEWMWGOFSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-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
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008398 formation water Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical group CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229960004232 linoleic acid Drugs 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/5086—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
-
- 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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/5045—Compositions based on water or polar solvents containing inorganic compounds
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/13—Methods or devices for cementing, for plugging holes, crevices, or the like
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/13—Methods or devices for cementing, for plugging holes, crevices, or the like
- E21B33/138—Plastering the borehole wall; Injecting into the formation
Abstract
The invention relates to a temperature response type bio-based temporary plugging agent which comprises the following components in parts by weight: 39.2 to 53.7 parts of epoxidized vegetable oil, 15.7 to 24.3 parts of curing agent, 0.5 to 5.2 parts of initiator, 1.6 to 4.3 parts of reinforcing agent, 0.8 to 3.7 parts of toughening agent and 18.6 to 30.6 parts of temperature response agent, wherein the sum of the parts by weight is 100. The epoxidized vegetable oil is obtained by epoxidizing double bonds in vegetable oil molecules; the curing agent is m-phenylenediamine, diethylenetriamine or a mixture thereof; the initiator is tetrabutyl phthalate; the reinforcing agent is nano silicon dioxide; the toughening agent is polysulfide rubber; the temperature responsive agent is dimethyl phthalate. The preparation method of the temporary plugging agent is simple and convenient to operate, raw materials are easy to obtain, the process is controllable, and the problems of high cost, incomplete degradation, complex construction and the like of the conventional temporary plugging agent are solved. The invention has excellent plugging performance, wide applicable temperature range and strong deep penetration, and can effectively improve the drilling efficiency of the oil-gas field.
Description
Technical Field
The invention belongs to the field of plant oil resource utilization and oilfield yield increase, and particularly relates to a temperature response type bio-based temporary plugging agent and a preparation method thereof.
Background
Repeated fracturing and temporary plugging diversion fracturing technology is an important method for improving residual oil gas resources for conventional oil and gas reservoirs, and temporary plugging diversion fracturing is also an important method for increasing the transformation volume of unconventional oil and gas reservoirs. Through earthquake detection and tracer detection, more than 30% of oil and gas wells have the problems of perforation cluster stress difference, casing deformation and the like, so that the transformation is insufficient, and the productivity of a single well or an oil and gas field block is required to be improved through repeated fracturing. Temporary plugging and turning fracturing (repeated fracturing) technology is an important technology for improving oil and gas resource recovery efficiency and guaranteeing unconventional oil and gas reservoir development benefits, and is widely applied to various large oil fields at home and abroad.
The key link of the temporary plugging turning fracturing technology is that the temporary plugging agent is used for effectively plugging, so that the temporary plugging agent needs to have excellent plugging performance in a fracturing construction period, can be rapidly degraded after the fracturing construction is finished, has no residue, and cannot cause damage to the fracture conductivity. Temporary plugging agents widely applied to oil fields mainly comprise temporary plugging balls, conventional temporary plugging agents and fiber temporary plugging agents, and fracturing fluid is required to be carried and transported to a designed position, and degradation principles comprise acid solubility, oil solubility and water solubility. Temporary plugging balls are easily influenced by gravity sedimentation, the conventional temporary plugging agent is high in throwing requirement, the bridging position of the fiber temporary plugging agent is influenced by crack morphology, deviation of the temporary plugging position possibly occurs, the temporary plugging steering fracturing effect is influenced, and long-distance temporary plugging construction is difficult to realize (Wang Jiwei, kang Yuzhu, zhang Dianwei, and the like; the application progress of the unconventional reservoir fracturing temporary plugging agent [ J ]. Special oil and gas reservoirs, 2021,28 (05): 1-9).
Along with the increasing serious environmental pollution problem, green chemistry is widely focused, and the plant oil resources in China are rich and renewable, but the research of preparing the liquid rubber plug type temporary plugging agent by taking low-price oil as a raw material is less at present. The invention discloses an MCF fracturing temporary plugging agent, a preparation method and application thereof (CN 114369450A), which comprises oil-soluble resin, ceresin and calcium stearate, and is added with additives such as thermosetting resin, water-soluble resin, positive photoresist and the like.
Therefore, development of a bio-based temporary plugging agent with low cost, high strength, thorough degradation and wide applicable temperature range is needed, and a guarantee is provided for successful implementation of temporary plugging and steering fracturing technology.
Disclosure of Invention
The invention aims to provide a temperature response type bio-based temporary plugging agent, which is obtained by epoxidation modification of vegetable oil, has the advantages of excellent plugging performance, wide application temperature range, strong deep penetration and the like, and can effectively improve the drilling efficiency of oil and gas fields.
The invention also aims to provide a preparation method of the temperature response type bio-based temporary plugging agent, which has the advantages of reliable principle, simple and convenient operation, low-cost and easily obtained raw materials, controllable reaction process and solves the problems of high cost, narrow applicable temperature range, incomplete degradation, complex construction and the like of the conventional temporary plugging agent.
In order to achieve the technical purpose, the invention adopts the following technical scheme.
The temperature response type bio-based temporary plugging agent consists of the following components in parts by weight: 39.2 to 53.7 parts of epoxidized vegetable oil, 15.7 to 24.3 parts of curing agent, 0.5 to 5.2 parts of initiator, 1.6 to 4.3 parts of reinforcing agent, 0.8 to 3.7 parts of toughening agent and 18.6 to 30.6 parts of temperature response agent, wherein the sum of the weight parts of the components is 100.
The epoxidized vegetable oil is obtained by epoxidizing double bonds in vegetable oil molecules, and the preparation process is as follows: mixing vegetable oil, acetic acid and hydrogen peroxide together, adding a catalyst titanium silicalite TS-1, wherein the molar ratio of the vegetable oil to the acetic acid to the hydrogen peroxide is 1 (1.5-2.5) (8-10), the adding amount of the titanium silicalite TS-1 is 0.2-0.5% of the total mass of the vegetable oil, the acetic acid and the hydrogen peroxide, stirring and reacting for 0.5-4 h at 80-95 ℃ with the stirring speed of 300-500 r/min, and then performing alkaline washing, water washing and purification to obtain the epoxidized vegetable oil.
Further, the stirring speed is 200-400 r/min.
Further, the vegetable oil is soybean oil or corn oil, and the mass percentage of the soybean oil is as follows: 2 to 3 percent of palmitic acid, 51 to 57 percent of linoleic acid, 4 to 5 percent of stearic acid, 32 to 36 percent of oleic acid, 5 to 10 percent of linolenic acid and 0.1 to 1 percent of arachidic acid. The corn oil comprises the following components in percentage by mass: 10.3 to 14.5 percent of palmitic acid, 1.6 to 2.7 percent of stearic acid, 31.5 to 35.4 percent of oleic acid, 48.3 to 53.8 percent of linoleic acid and 0.9 to 1.6 percent of linolenic acid, and linoleic acid and linolenic acid with a large amount of unsaturated double bonds in the molecule are easy to be epoxidized.
The curing agent is m-phenylenediamine, diethylenetriamine or a mixture thereof; the initiator is tetrabutyl phthalate; the reinforcing agent is nano silicon dioxide; the toughening agent is polysulfide rubber; the temperature responsive agent is dimethyl phthalate.
The preparation method of the temperature response type bio-based temporary plugging agent comprises the following steps: and mixing the epoxidized oil and the curing agent, uniformly stirring, and then adding the initiator, the reinforcing agent, the toughening agent and the temperature responsive agent, and continuously uniformly stirring to obtain the temperature responsive bio-based temporary plugging agent.
The temperature response type bio-based temporary plugging agent is applied to temporary plugging shielding and temporary plugging turning fracturing plugging processes in drilling construction of low-temperature, medium-temperature and high-temperature oil reservoirs, can meet high-strength plugging performance after solidification, and is controllable in degradation time.
When the stratum temperature is 90-160 DEGThe degree of mineralization is 0-20 multiplied by 10 at the temperature 4 When in mg/L, the curing time of the temperature response type bio-based temporary plugging agent is 1-20 h, and the compressive strength is 13.25-42.31 MPa.
When the stratum temperature is 90-160 ℃, the temporary plugging agent can be completely self-degraded within 1-14 d.
In actual use, the system components can be properly adjusted according to different well conditions, well types, construction methods and reservoir conditions.
The invention mainly utilizes the polymerization reaction of epoxy vegetable oil, curing agent and temperature response agent, can form reversible ester bond exchange polyurethane resin with thermal degradation in a medium-high temperature oil reservoir at 90-160 ℃, and has the following reaction process:
the mechanism of the invention is as follows: titanium hydroxy (Ti-OH) and H in TS-1 catalyst 2 O 2 Combining to form a peroxo titanium-based complex. Subsequently, the c=c double bond in the vegetable oil molecule is adsorbed on two active oxygen in the peroxo titanium-based complex structure, and the active oxygen further combined with the c=c is transferred to the unsaturated carbon-carbon double bond c=c on the vegetable oil molecule to participate in forming an epoxy bond after being broken off from the peroxo titanium-based complex structure. Finally, the epoxidized oil molecules are desorbed from the catalyst to form a product, and the catalyst is regenerated.
The reactivity of the non-end group epoxy group of the epoxy vegetable oil is low, the tetrabutyl titanate has better reactivity with the non-end group epoxy group, and C free radicals are formed after the reaction, so that the reactivity of the epoxy vegetable oil is improved. Subsequently, amine groups (-NH) in the curing agent 2 ) Reacts with C radicals on the epoxy groups. Further, -NH-reacts with C free radical on epoxy group to link different epoxy vegetable oil molecules, and finally a network structure is formed.
Nano silicon dioxide (SiO) 2 ) Has excellent heat resistance, and the oxygen in the nano silicon dioxide and O free radical after epoxy ring opening are increased by hydrogen bond (Si-O- - -H-O) or covalent bond (Si-O-C)The thermal stability of the polymer network structure is enhanced, and the storage modulus of the resin in a glassy state is improved. In addition, the nano silicon dioxide can also enable cracks formed when the polymer network structure is subjected to external force to be transferred and blocked, so that the compression resistance of the resin is improved. The polysulfide rubber is of a long-chain structure, a molecular main chain is mainly carbon-carbon single bond and ether bond, a rigid group is not arranged in the molecular structure, a terminal mercapto group is arranged on the molecule, and the polysulfide rubber is easy to react with epoxy groups in epoxy vegetable oil materials, so that the toughness and the impact resistance of the resin material are improved.
Dimethyl phthalate is hydrolyzed at the temperature of 90-160 ℃ to generate hydroxyl and carboxyl, and then epoxy groups react with the hydroxyl groups to form reversible ester bonds in the polymer network structure. Under the condition of long-term high temperature, the reversible ester bonds and part of ester bonds in the epoxidized oil are broken, the resin temporary plugging agent is thermally degraded into an oligomer with fluidity, and the degradation time of the resin temporary plugging agent is controlled by the dosage of dimethyl phthalate in the formula.
Compared with the prior art, the invention has the following beneficial effects:
(1) The vegetable oil material selected by the invention is obtained after epoxidation modification, has the characteristics of wide source, low price, environmental protection, biodegradability and the like, and has important significance from the aspects of economy and environment;
(2) The temporary plugging agent is a liquid homogeneous system, has low initial viscosity and is convenient to operate; the temporary plugging agent is a bio-based material, has little damage to a reservoir and is easy to be mixed with an oil phase; construction of the zone remote from the wellbore fracture is possible by a slug process.
The invention prepares the epoxidized oil by utilizing the epoxidation of the waste oil, and prepares the temperature-responsive bio-based temporary plugging agent by utilizing the epoxidized oil, which belongs to green chemistry, has the advantages of high strength, excellent self-degradation, excellent plugging performance, wide applicable temperature range, strong deep penetration and the like, can effectively improve the drilling and production efficiency of oil fields, is particularly suitable for water-sensitive reservoirs, and has important significance for temporary plugging and steering fracturing processes in unconventional oil and gas exploitation.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the following examples, the epoxidized vegetable oil is obtained by the steps of:
according to soybean oil: acetic acid: the molar ratio of hydrogen peroxide is 1:2.2:9, soybean oil, acetic acid and hydrogen peroxide are weighed, titanium-silicon molecular sieve TS-1 accounting for 0.35 percent of the total mass of vegetable oil, formic acid and hydrogen peroxide is weighed, stirring reaction is carried out for 3 hours at 90 ℃, stirring speed is 300r/min, and then the epoxidized vegetable oil is obtained through alkaline washing, water washing and purification.
Example 1
Adding 53.7g of epoxidized oil into a 200mL beaker, slowly adding 24.3g of m-phenylenediamine and 18.6g of dimethyl phthalate into the beaker in sequence at the stirring speed of 450r/min, uniformly stirring, then slowly adding 1.6g of nano silicon dioxide, 0.8g of polysulfide rubber and 1.0g of tetrabutyl phthalate into the beaker in sequence, and continuously stirring for 1h at the stirring speed of 300r/min to obtain a reaction solution; 20g of the reaction solution is weighed into a pressure-resistant bottle, the pressure-resistant bottle is placed into a constant-temperature oil bath pot at 160 ℃, the reaction is carried out for 2 hours, the pressure-resistant strength of the formed solid resin is 26.7MPa, and after the solid resin is maintained for 1d at the temperature, the solid resin starts to degrade automatically and is completely degraded after 10 hours.
Example 2
Adding 39.2g of epoxidized oil into a 200mL beaker, slowly adding 18.7g of diethylenetriamine and 30.6g of dimethyl phthalate into the beaker in sequence at the stirring speed of 450r/min, uniformly stirring, then slowly adding 4.1g of nano silicon dioxide, 3.2g of polysulfide rubber and 4.2g of tetrabutyl phthalate into the beaker in sequence, and continuously stirring for 1h at the stirring speed of 300r/min to obtain a reaction solution; 20g of reaction solution is weighed into a pressure-resistant bottle, the pressure-resistant bottle is placed into a constant-temperature oil bath pot at 120 ℃, the reaction is carried out for 4 hours, the compression strength of the formed solid resin is 42.31MPa, and after the solid resin is maintained for 2 days at the temperature, the solid resin starts to degrade automatically and is completely degraded after 24 hours.
Example 3
Adding 42.7g of epoxidized oil into a 200mL beaker, slowly adding 21.3g of m-phenylenediamine and 28.7g of dimethyl phthalate into the beaker in sequence at the stirring speed of 450r/min, uniformly stirring, then slowly adding 2.6g of nano silicon dioxide, 2.9g of polysulfide rubber and 1.8g of tetrabutyl phthalate into the beaker in sequence, and continuously stirring for 1h at the stirring speed of 300r/min to obtain a reaction solution; 20g of the reaction solution is weighed into a pressure-resistant bottle, the pressure-resistant bottle is placed into a constant-temperature oil bath pot at 130 ℃, the reaction is carried out for 3.5 hours, the pressure-resistant strength of the formed solid resin is 37.21MPa, and after the pressure-resistant bottle is maintained at the temperature for 1.5 days, the solid resin starts to self-degrade and is completely degraded after 20 hours.
Example 4
Adding 45.1g of epoxidized oil into a 200mL beaker, slowly adding 23.6g of diethylenetriamine and 25.7g of dimethyl phthalate into the beaker in sequence at the stirring speed of 450r/min, uniformly stirring, then slowly adding 1.9g of nano silicon dioxide, 3.2g of polysulfide rubber and 0.5g of tetrabutyl phthalate into the beaker in sequence, and continuously stirring for 1h at the stirring speed of 300r/min to obtain a reaction solution; 20g of the reaction solution is weighed into a pressure-resistant bottle, the pressure-resistant bottle is placed into a constant-temperature oil bath pot at 140 ℃, the reaction is carried out for 6 hours, the compression strength of the formed solid resin is 22.37MPa, and after the solid resin is maintained for 1d at the temperature, the solid resin starts to degrade automatically and is completely degraded after 15 hours.
Example 5
Adding 47.3g of epoxidized oil into a 200mL beaker, slowly adding 15.7g of m-phenylenediamine and 29.6g of dimethyl phthalate into the beaker in sequence at the stirring speed of 450r/min, uniformly stirring, then slowly adding 4.3g of nano silicon dioxide, 1.6g of polysulfide rubber and 1.5g of tetrabutyl phthalate into the beaker in sequence, and continuously stirring for 1h at the stirring speed of 300r/min to obtain a reaction solution; 20g of the reaction solution is weighed into a pressure-resistant bottle, the pressure-resistant bottle is placed into a constant-temperature oil bath pot at 110 ℃, the reaction is carried out for 4.5 hours, the pressure-resistant strength of the formed solid resin is 13.25MPa, and after the solid resin is maintained for 3 days at the temperature, the solid resin starts to degrade automatically and is completely degraded after 120 hours.
Example 6
Adding 49.1g of epoxidized oil into a 200mL beaker, slowly adding 17.3g of diethylenetriamine and 25.2g of dimethyl phthalate into the beaker in sequence at the stirring speed of 450r/min, uniformly stirring, then slowly adding 2.2g of nano silicon dioxide, 1.0g of polysulfide rubber and 5.2g of tetrabutyl phthalate into the beaker in sequence, and continuously stirring for 1h at the stirring speed of 300r/min to obtain a reaction solution; 20g of the reaction solution is weighed into a pressure-resistant bottle, the pressure-resistant bottle is placed into a constant-temperature oil bath pot at 90 ℃, the reaction is carried out for 20 hours, the pressure-resistant strength of the formed solid resin is 26.31MPa, and after the solid resin is maintained for 5 days at the temperature, the solid resin starts to degrade automatically and is completely degraded after 330 hours.
Example 7
Adding 46.5g of epoxidized oil into a 200mL beaker, sequentially adding 10.2g of diethylenetriamine, 9.5g of m-phenylenediamine and 23.6g of dimethyl phthalate into the beaker at a stirring speed of 450r/min, uniformly stirring, sequentially adding 2.6g of nano silicon dioxide, 3.3g of polysulfide rubber and 4.3g of tetrabutyl phthalate into the beaker, and continuously stirring for 1h at a stirring speed of 300r/min to obtain a reaction solution; 20g of the reaction solution is weighed into a pressure-resistant bottle, the pressure-resistant bottle is placed into a constant-temperature oil bath pot at 100 ℃, the reaction is carried out for 20 hours, the pressure-resistant strength of the formed solid resin is 29.62MPa, and after the solid resin is maintained for 3 days at the temperature, the solid resin starts to degrade automatically and is completely degraded after 235 hours.
Comparative example 1
The curing agent of example 2 was replaced with maleic anhydride and the other components, amounts and reaction conditions were the same as in example 2. The curing time is 10h, the compressive strength of the cured glue block is 7.6MPa, and degradation cannot be realized after curing.
Comparative example 2
The epoxy vegetable oil in example 2 was replaced with bisphenol a epoxy resin and the other components, amounts and reaction conditions were the same as in example 2. The curing time is 2h, the compressive strength after curing is 32.3MPa, but degradation cannot be realized after curing.
Comparative example 3
The temperature responsive agent of example 2 was replaced with butyl acetate and the other components, amounts and reaction conditions were the same as in example 2. The curing time was 4 hours, the compressive strength after curing was 0.73MPa, and after maintaining at this temperature for 3 hours, the solid began to self-degrade and after 5 hours was completely degraded.
Comparative example 4
The epoxy vegetable oil in example 2 was replaced with soybean oil or linseed oil, and other components, amounts and reaction conditions were the same as in example 2, and the reaction solution was not cured.
Temporary plugging agents prepared in example 2 and example 3 are taken as study objects, and are respectively marked as No. 1 and No. 2, and the temporary plugging performance and the degradation capability of the temporary plugging agents are examined.
The temporary plugging experiment comprises the following steps: placing a fracture core which is slotted and placed into a propping agent into a core holder, performing water injection displacement at a displacement speed of 5mL/min, and measuring an initial permeability K after pressure stabilization 1 . Injecting diesel oil with the volume of 0.1PV at the speed of 5mL/min, then injecting temporary plugging liquid in the embodiment 2 and the embodiment 3 with the volume of 0.8PV respectively, injecting simulated formation water with the volume of 0.1PV, raising the temperature to the experimental temperature of 120-130 ℃, solidifying for 5 hours at constant temperature, and then using a constant-current constant-pressure pump of a core temporary plugging tester to displace temporary plugging liquid with different concentrations, wherein the displacement flow is 5mL/min, and the ring pressure is kept to be always more than the plugging pressure by more than 3 MPa. Recording pressure, stopping displacement if the pressure breaks through 30MPa, keeping 30MPa, and if the pressure is more than 2h, judging that the plugging is successful, and obtaining the permeability K after the plugging 2 . Continuing to perform water injection displacement at a speed of 5mL/min after keeping the constant temperature of 120-130 ℃ for 24 hours to obtain the degraded permeability K 3 。
The permeability change of the core before and after plugging is compared to obtain the plugging rate E of the temporary plugging agent 1 ＝(K 1 -K 2 )/K 1 100% of blocking removal E 2 ＝K 3 /K 1 100%. The experimental results are shown in table 1.
Table 1 blocking Properties of temporary blocking agent
The results show that: the temporary plugging agent can realize solidification plugging and self-degradation in cracks simulating the reservoir temperature environment. The temporary plugging rates E1 and E2 of the temporary plugging agents prepared in the examples 2 and 3 are higher than 94% and 97%, respectively, which indicates that the temperature response type bio-based temporary plugging agent provided by the invention has excellent temporary plugging and plugging removal performances.
While the invention has been described with respect to the preferred embodiments, the scope of the invention is not limited thereto, and any changes or substitutions that would be apparent to those skilled in the art are intended to be included within the scope of the invention.
Claims (10)
1. The temperature response type bio-based temporary plugging agent consists of the following components in parts by weight: 39.2 to 53.7 parts of epoxidized vegetable oil, 15.7 to 24.3 parts of curing agent, 0.5 to 5.2 parts of initiator, 1.6 to 4.3 parts of reinforcing agent, 0.8 to 3.7 parts of toughening agent and 18.6 to 30.6 parts of temperature response agent, wherein the sum of the parts by weight is 100.
2. The temperature-responsive bio-based temporary plugging agent according to claim 1, wherein the epoxidized vegetable oil is prepared by the following steps: mixing vegetable oil, acetic acid and hydrogen peroxide together, adding a catalyst titanium silicalite molecular sieve, wherein the molar ratio of the vegetable oil to the acetic acid to the hydrogen peroxide is 1 (1.5-2.5): (8-10), the adding amount of the titanium silicalite molecular sieve is 0.2-0.5% of the total mass of the vegetable oil, the acetic acid and the hydrogen peroxide, stirring and reacting for 0.5-4 hours at 80-95 ℃, and then performing alkaline washing, water washing and purification to obtain the epoxidized vegetable oil.
3. The temperature-responsive bio-based temporary plugging agent of claim 2, wherein said vegetable oil is soybean oil or corn oil.
4. The temperature-responsive bio-based temporary plugging agent according to claim 1, wherein the curing agent is m-phenylenediamine, diethylenetriamine or a mixture thereof.
5. The temperature-responsive bio-based temporary plugging agent according to claim 1, wherein the initiator is tetrabutyl phthalate.
6. The temperature-responsive bio-based temporary plugging agent according to claim 1, wherein said reinforcing agent is nano silica.
7. The temperature-responsive bio-based temporary plugging agent according to claim 1, wherein said toughening agent is polysulfide rubber.
8. The temperature-responsive bio-based temporary plugging agent according to claim 1, wherein said temperature-responsive agent is dimethyl phthalate.
9. The method for preparing the temperature-responsive bio-based temporary plugging agent according to claim 1,2, 3, 4, 5, 6, 7 or 8, comprising the following steps: and mixing the epoxidized oil and the curing agent, uniformly stirring, and then adding the initiator, the reinforcing agent, the toughening agent and the temperature responsive agent, and continuously uniformly stirring to obtain the temperature responsive bio-based temporary plugging agent.
10. The temperature-responsive bio-based temporary plugging agent according to claim 1,2, 3, 4, 5, 6, 7 or 8, which is applied to temporary plugging shielding and temporary plugging turning fracturing plugging processes in drilling construction of low-temperature, medium-temperature and high-temperature oil reservoirs, can meet high-strength plugging performance after solidification, and has controllable degradation time.
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