CN111808580B - Oil well plugging material based on in-situ curing reaction and preparation and application methods thereof - Google Patents
Oil well plugging material based on in-situ curing reaction and preparation and application methods thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 76
- 239000003129 oil well Substances 0.000 title claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 15
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 229920005989 resin Polymers 0.000 claims abstract description 69
- 239000011347 resin Substances 0.000 claims abstract description 69
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- 239000003112 inhibitor Substances 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 239000000945 filler Substances 0.000 claims abstract description 13
- 239000000375 suspending agent Substances 0.000 claims abstract description 7
- 239000000080 wetting agent Substances 0.000 claims abstract description 6
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 12
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 10
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 9
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000005086 pumping Methods 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 2
- 229910052601 baryte Inorganic materials 0.000 claims description 2
- 239000010428 baryte Substances 0.000 claims description 2
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 claims description 2
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002524 organometallic group Chemical group 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 claims 2
- 239000000843 powder Substances 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 8
- 239000003085 diluting agent Substances 0.000 abstract description 8
- 239000004568 cement Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 238000009472 formulation Methods 0.000 description 11
- 239000003822 epoxy resin Substances 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 230000003014 reinforcing effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- -1 peroxyesters Chemical class 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000013022 formulation composition Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- 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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- 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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/426—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells for plugging
-
- 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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/428—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells for squeeze cementing, e.g. for repairing
-
- 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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/44—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing organic binders only
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK 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
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mining & Mineral Resources (AREA)
- Geology (AREA)
- Fluid Mechanics (AREA)
- Environmental & Geological Engineering (AREA)
- Physics & Mathematics (AREA)
- Geochemistry & Mineralogy (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
An oil well plugging material based on in-situ curing reaction and a preparation and application method thereof. The oil well plugging material comprises: 100 parts of resin liquid, 0.5-5 parts of curing agent, 0-0.1 part of accelerator, 0-0.3 part of polymerization inhibitor, 0-500 parts of filler, 0-2 parts of wetting agent, 0-2 parts of defoaming agent and 0-1 part of suspending agent; the resin liquid comprises resin and a crosslinking diluent, and the weight ratio of the resin to the crosslinking diluent is 85-65. The preparation method comprises the step of uniformly mixing various components to obtain the oil well plugging material. The oil well plugging material has the advantages of low material cost, controllable and adjustable curing time and excellent plugging performance.
Description
Technical Field
The application relates to the technical field of oilfield chemistry, in particular to an oil well plugging material based on in-situ curing reaction and a preparation and application method thereof.
Background
In the process of oil field development and production, operations such as repairing cement sheath, abandoning well (P & A), solving leakage, reinforcing near-wellbore area and the like all relate to the application of plugging materials. The most commonly used plugging material is cement, but the cement is a particle material and has poor permeability, so the effect of repairing the micro-gaps of the cement sheath is poor. The crosslinked polymer can also be used as a plugging material, but the application range is limited due to the low gel strength. In recent years, studies on the use of resin-based polymer materials as oil well plugging materials have attracted attention in the oil field, and the types of resins used have been mainly focused on epoxy resins. Epoxy resin is cured through a condensation reaction between an epoxy group and a curing agent, and the curing is slow, so that the epoxy resin plugging material for the oil well needs long curing time under the condition of high temperature in the well. In order to shorten the curing time of epoxy resin plugging materials, expensive aromatic amine curing agents are required, but this increases the cost of epoxy resin plugging materials. In addition, the epoxy resin-based plugging materials currently used for oil wells are also low in plugging strength at high temperatures because of low heat distortion temperature of the cured resin.
Disclosure of Invention
Compared with the existing oil well plugging material, the oil well plugging material is improved or improved in material cost, curing reaction and controllability and effective plugging.
Specifically, the application provides an oil well plugging material based on in-situ curing reaction, which comprises:
the resin liquid comprises resin and a crosslinking diluent, and the weight ratio of the resin to the crosslinking diluent is 85-65.
In embodiments of the present application, the well plugging material may comprise:
the resin liquid comprises resin and a crosslinking diluent, and the weight ratio of the resin to the crosslinking diluent is 7:3.
In an embodiment of the present application, the resin is selected from any one or more of phthalic acid type unsaturated resin, isophthalic acid type unsaturated resin, dicyclopentadiene (DCPD) -modified unsaturated resin, and vinyl resin.
Preferably, the resin is a dicyclopentadiene (DCPD) modified unsaturated polyester resin, which is relatively inexpensive.
In embodiments herein, the crosslinking diluent may be selected from any one or both of methylstyrene and alpha-methylstyrene. Preferably, the methylstyrene is p-methylstyrene.
In the embodiment of the present application, when the resin is dicyclopentadiene modified unsaturated polyester resin and the crosslinking diluent is p-methylstyrene, the resin liquid of the present application can be prepared by referring to the preparation method of DC191 (composed of dicyclopentadiene modified unsaturated polyester resin and styrene) which is a mature product in the chemical industry, for example, the resin liquid of the present application can be synthesized by referring to the synthesis method of DC191 disclosed in the document "synthesis of dicyclopentadiene modified unsaturated polyester resin", zhao Zhishan, et al, proceedings of composite materials, 1995, vol.12, no.1, replacing styrene with p-methylstyrene and adjusting the weight ratio of the dicyclopentadiene modified unsaturated polyester resin to p-methylstyrene.
In embodiments herein, the curing agent may be selected from any one or more of organic peroxide-based initiators, optionally, from any one or more of diacyl peroxides, dialkyl peroxides, peroxyesters, and alkyl hydroperoxides.
In embodiments herein, the accelerator may be selected from any one or more of tertiary amine accelerators and organometallic cobalt accelerators, optionally selected from any one or more of cobalt naphthenate, cobalt isooctanoate, dimethylaniline and dimethyl-p-toluidine.
In an embodiment of the present application, the polymerization inhibitor may be selected from any one or more of polyhydric phenol and substituted phenol type polymerization inhibitors and quinone type polymerization inhibitors, optionally, from any one or two of p-tert-butyl catechol and p-benzoquinone;
in an embodiment of the present application, the filler may be a lightening agent or a weighting agent, optionally, the lightening agent may be hollow glass beads, and the weighting agent may be selected from any one or two of iron ore and barite.
The application can increase or reduce the density of the plugging material by using the filler and using a wetting agent, a defoaming agent and a suspending agent together, and thus, the using amount of resin in a certain volume of plugging material is reduced, so that the cost of the plugging material is reduced.
In embodiments herein, the wetting agent may be selected from any one or more of the polymeric wetting agents containing phosphoric acid groups.
In embodiments herein, the defoamer may be selected from any one or more of polysiloxanes;
in embodiments of the present application, the suspending agent may be a modified organic soil.
The application also provides a preparation method of the oil well plugging material, which comprises the following steps: and uniformly mixing the components to obtain the oil well plugging material.
The application also provides an application method of the oil well plugging material, which comprises the following steps: pumping the oil well plugging material to a site to be plugged, and carrying out in-situ curing reaction on the oil well plugging material at the site to be plugged so as to seal the site to be plugged.
Before use, uniformly mixing various components for forming the oil well plugging material to obtain the oil well plugging material; and pumping the oil well plugging material to a site to be plugged through pumping equipment, decomposing a curing agent in the oil well packing material to generate free radicals, and curing the free radicals through in-situ chain reaction so as to seal the site to be plugged. The in-situ curing reaction time can be adjusted by curing agents, accelerators, polymerization inhibitors, and different combinations thereof.
The time for pumping the plugging material of the oil well is controlled within the range of not more than 10h, and the temperature of the site to be plugged is within the range of 10-90 ℃.
The excellent performance of the oil well plugging material based on the in-situ curing reaction is shown in the following specific points:
(1) The viscosity at 25 ℃ is only 0.20Pa.s-0.30Pa.s, which belongs to low viscosity and can achieve higher permeability;
(2) Within the temperature range of 10-90 ℃, the curing time can be adjusted within the range of not more than 10 h;
(3) The density range of the cured body formed after curing can reach 0.8g/cm 3 ～2.3g/cm 3 ；
(4) The thermal deformation temperature of the solidified body formed after solidification is higher and can reach 100 ℃, so the plugging strength at high temperature is higher;
(5) When no filler is contained, the mechanical properties of the cured body formed after curing can reach: the tensile strength is more than 50MPa, the tensile modulus is more than 3100MPa, the bending strength is more than 90MPa, and the bending elastic modulus is 3200MPa.
The technical indexes show that the oil well plugging material has the characteristics of low viscosity, high permeability, high strength, high thermal deformation temperature, fast and controllable curing reaction and the like, and can be used for repairing cement sheath, repairing damaged casing, repairing abandoned well, recovering effective plugging between oil well layers, stopping leakage of oil well, reinforcing near-wellbore area and the like.
Additional features and advantages of the application will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the application. Other advantages of the present application may be realized and attained by the instrumentalities and combinations particularly pointed out in the specification and the drawings.
Drawings
The accompanying drawings are included to provide an understanding of the present disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the examples serve to explain the principles of the disclosure and not to limit the disclosure.
FIG. 1 is a graph of the exotherm at 10 ℃ for formulations numbered 1-4 of example 1 of the present application;
FIG. 2 is an exotherm at 55 ℃ for formulations numbered 25-28 of example 1 of the present application;
FIG. 3 is a graph of the exotherm at 75 ℃ for the formulations numbered 49-52 of example 1 of the present application;
FIG. 4 is a solid object formed by the oil well plugging material of example 2 of the present application after curing;
FIG. 5 is a flow chart of a sand bed infiltration simulation experiment according to example 3 of the present application;
fig. 6 is a schematic diagram of a simulation experiment of micro gap plugging in embodiment 4 of the present application.
Detailed Description
To make the objects, technical solutions and advantages of the present application more apparent, embodiments of the present application will be described in detail below with reference to the accompanying drawings. It should be noted that the embodiments and features of the embodiments in the present application may be arbitrarily combined with each other without conflict.
The resin solution (code: R101) used in the following examples was composed of 70 parts by weight of a dicyclopentadiene modified unsaturated polyester resin and 30 parts by weight of p-methylstyrene, and the synthesis method was described in "Synthesis of a dicyclopentadiene modified unsaturated polyester resin", zhao Zhishan et al, published by composite materials, 1995, vol.12, no.1, which discloses a DC191 synthesis method, in which styrene was replaced with p-methylstyrene and the weight ratio of the dicyclopentadiene modified unsaturated polyester resin to p-methylstyrene was adjusted.
Some of the main raw materials are shown in Table 1, and other raw materials are all common commercial products unless otherwise specified.
TABLE 1
Example 1
The curing reaction of unsaturated resins in this application is a free radical chain polymerization reaction, accompanied by the generation of a large amount of heat during the polymerization reaction. By monitoring the exotherm, the onset of cure of the resin was examined. Obtaining an exothermic curve of the resin curing reaction process by using a Tam AIR 8 channel cement hydration thermal analyzer (TA of America), wherein the peak starting time corresponds to the time when the resin curing reaction starts to occur; the time corresponding to the peak-to-peak point of the curve represents the time at which the resin cured body has been substantially formed.
The oil well plugging material provided by the application is divided into a low-temperature section (10-55 ℃), a medium-temperature section (55-75 ℃) and a high-temperature section (75-90 ℃) according to the use working conditions. In formulation numbers 1 to 72 in tables 2 to 11, the amounts of the curing agent, the polymerization inhibitor or the accelerator were in weight percent based on the weight of the resin liquid R101, based on 100% by weight of the resin liquid R101. The formulation composition and the resin curing condition of each temperature zone are shown in tables 2 to 11.
1. The plugging material at the low temperature (10-55 ℃) is composed of resin liquid, curing agent, accelerator and polymerization inhibitor, the specific composition is shown as a formula with the number of 1-24, and the curing condition is reflected by the peak starting time and peak reaching time of an exothermic curve, as shown in tables 2-4. The exothermic curves of the formulations numbered 1 to 4 are shown in FIG. 1.
TABLE 2 curing conditions of the resin at a temperature of 10 ℃
| |
1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| The amount of the resin liquid R101 is calculated | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Amount of curing agent LV used% | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| Amount of polymerization inhibitor ZJ used% | 0.014 | 0.015 | 0.016 | 0.018 | 0.019 | 0.020 | 0.021 | 0.023 |
| Amount of accelerator DMA% | 0.040 | 0.040 | 0.040 | 0.040 | 0.040 | 0.040 | 0.040 | 0.040 |
| Peak onset time, H: min | 2:12 | 3:18 | 4:20 | 4:58 | 4:04 | 4:33 | 5:00 | 5:18 |
| Peak-to-peak time, H: min | 3:42 | 5:09 | 6:27 | 7:24 | 5:52 | 6:36 | 7:07 | 7:39 |
TABLE 3 curing conditions of the resin at a temperature of 30 ℃
| Recipe number | 9 | 10 | 11 | 12 | 13 | 14 | 15 | 16 |
| Amount of resin solution R101 used% | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Amount of curing agent LV used% | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| Amount of polymerization inhibitor ZJ,% | 0.0135 | 0.0140 | 0.0150 | 0.0170 | 0.0180 | 0.0190 | 0.0200 | 0.0220 |
| Amount of accelerator DMA% | 0.0280 | 0.0280 | 0.0280 | 0.0280 | 0.0360 | 0.0360 | 0.0360 | 0.0360 |
| Peak onset time, H: min | 0:57 | 1:12 | 1:19 | 2:21 | 1:55 | 1:27 | 1:40 | 2:29 |
| Peak-to-peak time, H: min(s) | 1:50 | 2:12 | 2:34 | 4:22 | 2:14 | 2:40 | 3:05 | 4:39 |
TABLE 4 curing conditions of the resin at a temperature of 50 deg.C
| Recipe number | 17 | 18 | 19 | 20 | 21 | 22 | 23 | 24 |
| The amount of the resin liquid R101 is calculated | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Amount of curing agent LV used% | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| Amount of polymerization inhibitor ZJ,% | 0.0075 | 0.0100 | 0.0125 | 0.015 | 0.0050 | 0.0075 | 0.0100 | 0.0125 |
| Amount of accelerator DMA% | 0.0160 | 0.0160 | 0.0160 | 0.0160 | 0.0240 | 0.0240 | 0.0240 | 0.0240 |
| Time to peak, H: min | 0:30 | 1:00 | 2:08 | 3:16 | 0:32 | 0:45 | 2:07 | 4:33 |
| Peak-to-peak time, H: min | 1:20 | 2:15 | 3:46 | 5:08 | 1:01 | 1:38 | 3:40 | 6:43 |
2. The plugging material at the medium temperature (55-75 ℃) consists of resin liquid, curing agent and polymerization inhibitor, the specific composition is shown as a formula with the number of 25-48, and the curing condition is reflected by the peak starting time and peak reaching time of a heat release curve, as shown in tables 5-7. The exothermic curves of the formulations numbered 25 to 28 are shown in FIG. 2.
TABLE 5 curing conditions of the resin at a temperature of 55 ℃
| |
25 | 26 | 27 | 28 | 29 | 30 | 31 | 32 |
| The amount of the resin liquid R101 is calculated | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Amount of curing agent LV used% | 1 | 1 | 1 | 1 | 2 | 2 | 2 | 2 |
| Amount of polymerization inhibitor ZJ used% | 0.000 | 0.0025 | 0.0050 | 0.0075 | 0.0000 | 0.0050 | 0.0075 | 0.0100 |
| Time to peak, H: min | 2:01 | 4:07 | 6:15 | 8:45 | 1:37 | 2:16 | 3:24 | 5:00 |
| Time to peak, H: min | 3:55 | 6:26 | 8:36 | 11:10 | 3:06 | 4:08 | 5:15 | 6:47 |
TABLE 6 curing conditions of the resin at a temperature of 65 ℃
| Recipe number | 33 | 34 | 35 | 36 | 37 | 38 | 39 | 40 |
| The amount of the resin liquid R101 is calculated | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Amount of curing agent LV used% | 1 | 1 | 1 | 1 | 2 | 2 | 2 | 2 |
| Amount of polymerization inhibitor ZJ,% | 0.0050 | 0.0150 | 0.0200 | 0.0250 | 0.0100 | 0.0200 | 0.0250 | 0.0300 |
| Time to peak, H: min | 2:26 | 5:01 | 6:22 | 8:12 | 1:58 | 3:18 | 4:17 | 5:07 |
| Time to peak, H: min | 3:17 | 6:01 | 7:30 | 9:23 | 2:27 | 3:58 | 4:59 | 5:53 |
TABLE 7 curing conditions of the resin at a temperature of 70 ℃
| Recipe number | 41 | 42 | 43 | 44 | 45 | 46 | 47 | 48 |
| The amount of the resin liquid R101 is calculated | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Amount of curing agent LV used% | 1 | 1 | 1 | 1 | 2 | 2 | 2 | 2 |
| Amount of polymerization inhibitor ZJ used% | 0.0100 | 0.0200 | 0.0300 | 0.0400 | 0.0100 | 0.0200 | 0.0300 | 0.0400 |
| Time to peak, H: min | 1:28 | 2:08 | 3:02 | 3:27 | 1:02 | 1:42 | 2:30 | 3:18 |
| Time to peak, H: min | 1:45 | 2:26 | 3:23 | 4:25 | 1:23 | 2:03 | 2:51 | 3:42 |
3. The plugging material at the high temperature section (75-90 ℃) consists of resin liquid, curing agent and polymerization inhibitor, the specific composition is shown as a formula with the number of 49-72, and the curing condition reflected by the peak starting time and peak reaching time of an exothermic curve is shown as tables 8-11. The exothermic curves of the formulations numbered 49 to 52 are shown in FIG. 3.
TABLE 8 curing conditions of the resin at a temperature of 75 deg.C
| |
49 | 50 | 51 | 52 |
| The amount of the resin liquid R101 is calculated | 100 | 100 | 100 | 100 |
| Amount of curing agent SC used therein% | 1 | 1 | 1 | 1 |
| Amount of polymerization inhibitor ZJ,% | 0.0200 | 0.0300 | 0.0400 | 0.0500 |
| Time to peak, H: min | 2:53 | 4:04 | 5:05 | 6:15 |
| Time to peak, H: min | 3:26 | 4:39 | 5:48 | 7:01 |
TABLE 9 curing conditions of the resin at a temperature of 75 deg.C
| Recipe number | 53 | 54 | 55 | 56 |
| The amount of the resin liquid R101 is calculated | 100 | 100 | 100 | 100 |
| Amount of curing agent LV used% | 2 | 2 | 2 | 2 |
| Amount of polymerization inhibitor ZJ,% | 0.0300 | 0.0400 | 0.0500 | 0.0600 |
| Time to peak, H: min | 2:20 | 3:07 | 3:44 | 4:17 |
| Time to peak, H: min | 2:43 | 3:32 | 4:12 | 4:41 |
TABLE 10 curing conditions of the resin at a temperature of 85 deg.C
| Recipe number | 57 | 58 | 59 | 60 | 61 | 62 | 63 | 64 |
| Amount of resin solution R101 used% | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Initiator LV in an amount of% | 1 | 1 | 1 | 1 | 2 | 2 | 2 | 2 |
| Amount of polymerization inhibitor ZJ used% | 0.0800 | 0.1000 | 0.1200 | 0.1400 | 0.1000 | 0.1200 | 0.1400 | 0.1600 |
| Time to peak, H: min | 2:55 | 3:47 | 5:11 | 5:57 | 1:49 | 2:5 | 2:51 | 3:21 |
| Time to peak, H: min | 3:19 | 4:19 | 5:58 | 9:48 | 2:04 | 2:43 | 3:14 | 3:45 |
TABLE 11 curing conditions of the resin at a temperature of 90 deg.C
| Recipe number | 65 | 66 | 67 | 68 | 69 | 70 | 71 | 72 |
| Amount of resin solution R101 used% | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| The initiator SC is used in an amount of% | 1 | 1 | 1 | 1 | 2 | 2 | 2 | 2 |
| Amount of polymerization inhibitor ZJ,% | 0.0050 | 0.0100 | 0.0150 | 0.0200 | 0.0100 | 0.0150 | 0.0200 | 0.0250 |
| Time to peak, H: min | 2:38 | 3:46 | 4:50 | 6:09 | 2:38 | 3:39 | 4:29 | 5:13 |
| Time to peak, H: min | 3:40 | 4:52 | 6:02 | 7:23 | 3:41 | 4:36 | 5:26 | 6:13 |
As can be seen from tables 2 to 11, the curing time of the oil well plugging material of the embodiment of the application is adjustable within 10 hours at the temperature range of 10 ℃ to 90 ℃, and the controllability is good.
Example 2
The oil well plugging material of the embodiment uses the filler, and uses the wetting agent, the defoaming agent and the suspending agent together to increase or reduce the density of the plugging material, thereby reducing the dosage of the resin in the plugging material and reducing the cost of the plugging material. Table 12 shows formulations of plugging materials with different fillers selected, and the cured bodies are shown in fig. 4.
TABLE 12 formulation of plugging materials with different fillers
The introduction of the filler can affect the mechanical properties of the resin plugging material. In general, the heat distortion temperature of the mechanical properties of the resin sealing material is not affected by the filler or slightly changed. The amount of filler introduced is large, and the tensile strength and flexural strength of the resin are affected and become small. The more filler is introduced, the greater the effect.
As can be seen from table 12, the thermal deformation temperature of the cured body formed after the oil well plugging material of the embodiment of the present application is cured is high, which is close to 100 ℃, and the tensile strength and the full strength are both high, which indicates that the oil well plugging material of the embodiment of the present application can be used for repairing cement sheath, repairing damaged casing, repairing abandoned well, recovering effective plugging between oil well layers, plugging oil well, reinforcing near wellbore zone, and the like.
Example 3
The consolidation of the near wellbore zone by plugging material was simulated in a sand bed infiltration experiment, as shown in fig. 5. A glass bottle having an inner diameter of 1.5cm was filled with 80 mesh fine sand and tapped, and the height of the sand bed in the bottle was measured to be 10cm as shown in graph A of FIG. 5. 10ml of plugging material with the formulation "R101 parts by weight + LV 2 parts by weight" was poured in as shown in Panel B of FIG. 5. After 15 minutes, as shown in panel C of FIG. 5. After the resin was cured, the glass bottle casing was removed, and the remaining cured resin body was tested to have a strength of 50MPa as shown in graph D of FIG. 5.
As can be seen from fig. 5, the oil well plugging material of the embodiment of the present application has excellent permeability and reinforcement characteristics, and has permeability and reinforcement properties required for reinforcing a near wellbore region and repairing a micro-gap of a wellbore.
Example 4
Fig. 6 is a schematic diagram of a simulation experiment for plugging a micro gap. The simulation experiment is carried out to illustrate the effect of the oil well plugging material of the embodiment in the repair of the micro-gap of the cement sheath. And (3) curing cement paste by using a high-pressure water loss barrel, removing the cured cement paste, measuring the height of the cement paste to be 7cm, slightly polishing the outer surface of the cement paste, then filling the cement paste into the high-pressure water loss barrel again to form a micro gap between the outer wall of the cement sheath and the inner wall of the high-pressure water loss barrel, connecting a pressure supply pipeline of a high-pressure water loss instrument for supplying pressure, and generating an air bleeding phenomenon at the bottom as shown in a diagram of fig. 6. After the micro-gap, 10ml of an oil well plugging material having a formulation of "R101 parts by weight + LV 2 parts by weight" was poured into the micro-gap and filled therein by the seepage of the resin, as shown in the b and c diagrams of FIG. 6, respectively. And after the resin is cured and the excess resin on the end face of the cement column is removed, connecting a pressure supply pipeline of a high-pressure water loss instrument. By gradually increasing the pressure of the nitrogen gas, the pressure bearing capacity of 2MPa is found, as shown in d of FIG. 6. The oil well plugging material provided by the embodiment of the application can effectively plug micro gaps, has a good reinforcing effect after plugging, and can bear large pressure.
Although the embodiments disclosed in the present application are described above, the descriptions are only for the purpose of facilitating understanding of the present application, and are not intended to limit the present application. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the disclosure as defined by the appended claims.
Claims (11)
1. An oil well plugging material based on in-situ curing reaction, which consists of 100 parts by weight of resin liquid, 1 or 2 parts by weight of curing agent, 0 to 0.1 part by weight of accelerator, 0 to 0.3 part by weight of polymerization inhibitor, 0 to 500 parts by weight of filler, 0 to 2 parts by weight of wetting agent, 0 to 2 parts by weight of defoaming agent and 0 to 1 part by weight of suspending agent;
the resin liquid consists of 70 parts by weight of dicyclopentadiene modified unsaturated polyester resin and 30 parts by weight of p-methylstyrene; the curing agent is Benox L40-LV or Curox Solar SC.
2. The oil well plugging material of claim 1, wherein the oil well plugging material consists of 100 parts by weight of the resin liquid and 2 parts by weight of Benox L40-LV.
3. The oil well plugging material according to claim 1, wherein the oil well plugging material consists of 100 parts by weight of the resin liquid, 2 parts by weight of Benox L40-LV, 1 part by weight of the suspending agent G1958, and 15 parts by weight of the hollow glass microspheres P62.
4. The oil well plugging material according to claim 1, wherein the oil well plugging material consists of 100 parts by weight of a resin liquid, 2 parts by weight of Benox L40-LV, 1 part by weight of a suspending agent G1958, and 200 parts by weight of iron ore powder D1200.
5. The oil well plugging material of any of claims 1-4, wherein said accelerator is selected from any one or more of tertiary amine accelerators and organometallic cobalt accelerators.
6. The well plugging material of claim 5, wherein said accelerator is selected from any one or more of cobalt naphthenate, cobalt isooctanoate, dimethylaniline and dimethyl p-toluidine.
7. The oil well plugging material of any one of claims 1 to 4, wherein said polymerization inhibitor is selected from any one or more of a polyhydric phenol and substituted phenol type polymerization inhibitor and a quinone type polymerization inhibitor; the filler is a lightening agent or a weighting agent.
8. The oil well plugging material of claim 7, wherein said lightening agent is hollow glass microspheres and said weighting agent is selected from any one or both of iron ore and barite.
9. The oil well plugging material of claim 7, wherein said polymerization inhibitor is selected from any one or both of p-tert-butylcatechol and p-benzoquinone.
10. The method of producing an oil well plugging material according to any one of claims 1 to 9, comprising: and uniformly mixing the components to obtain the oil well plugging material.
11. Method of application of a well plugging material according to any of claims 1 to 9, comprising: pumping the oil well plugging material to a site to be plugged, wherein the oil well plugging material generates an in-situ curing reaction at the site to be plugged so as to seal the site to be plugged, the time for pumping the oil well plugging material is controlled within the range of not more than 10h, and the temperature at the site to be plugged is within the range of 10-90 ℃.
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| JP2006056975A (en) * | 2004-08-19 | 2006-03-02 | Showa Highpolymer Co Ltd | Unsaturated polyester resin for gelcoat of high water resistance and weatherability, method for producing the unsaturated polyester resin and use thereof |
| CN104694096A (en) * | 2013-12-04 | 2015-06-10 | 中国石油化工股份有限公司 | Oilfield development plugging agent |
| CN108641691A (en) * | 2018-03-27 | 2018-10-12 | 中国石油大学(华东) | A kind of high-intensity resin blocking agent and the preparation method and application thereof |
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| JP2006056975A (en) * | 2004-08-19 | 2006-03-02 | Showa Highpolymer Co Ltd | Unsaturated polyester resin for gelcoat of high water resistance and weatherability, method for producing the unsaturated polyester resin and use thereof |
| CN104694096A (en) * | 2013-12-04 | 2015-06-10 | 中国石油化工股份有限公司 | Oilfield development plugging agent |
| CN108641691A (en) * | 2018-03-27 | 2018-10-12 | 中国石油大学(华东) | A kind of high-intensity resin blocking agent and the preparation method and application thereof |
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