Long-term high-temperature resistant toughened silica-cement composite material and preparation method

Abstract

The present invention belongs to the technical field of oil well cement preparation, discloses a long-term high-temperature resistant and toughened well cementing and silica-cement composite material and a preparation method. A solid component comprises cement, alumina, superfine, high-purity silica sand, a suspending agent and a toughening material according to weight fractions; the toughening material comprises a latex fiber toughening agent and a nano graphene sheet; and a liquid component is composed of water, nano iron oxide and an oil well cement admixture according to weight fractions. Cement slurry with a ratio of the present invention can achieve compressive strength reaching up to 31 MPa after being cured under a high-temperature and high-pressure environment of 200° C. and 150 MPa for one year; and the gas permeability is controlled below 0.02 mD.

Claims

1. A long-term high-temperature resistant and toughened well cementing and silica-cement composite material, comprising a solid component and a liquid component, wherein the solid component is composed of 40-60% of cement, 3-8% of alumina, 30-50% of superfine silica sand, 1.5-2.1% of an additive and 2.2-6% of a toughening material according to weight fractions; the liquid component is composed of 70-73% of water, 6-7% of nano iron oxide and 20-24% of an oil well cement admixture according to weight fractions; a weight ratio of the solid component to the liquid component is 1:0.3-0.6; the toughening material is composed of 0.2-1% of a nano graphene sheet and 2-6% of a latex fiber toughening material according to weight fractions; the latex fiber toughening material is a mixture of solidified latex and organic fibers; and a SiO.sub.2 content in the silica sand is larger than 97%; a median particle size of the silica sand is 5-20 μm; the purity of the nano graphene sheet is over 99.5%; the thickness of the nano graphene sheet is 4-20 nm; and a particle size of a nano iron oxide suspension is 30 nm.

2. The long-term high-temperature resistant and toughened well cementing and silica-cement composite material according to claim 1, wherein the cement is Class G oil well cement.

3. The long-term high-temperature resistant and toughened well cementing and silica-cement composite material according to claim 1, wherein the additive comprises a retarder; and the additive further comprises at least one of a suspending agent, a dispersing agent, a fluid loss agent and a defoamer.

4. A preparation method of the long-term high-temperature resistant and toughened well cementing and silica-cement composite material according to claim 1, wherein the preparation method of the long-term high-temperature resistant and toughened well cementing and silica-cement composite material comprises: step 1, mixing cement, alumina, silica sand, a suspending agent and a toughening material according to a ratio to obtain a solid component; step 2, mixing water, nano iron oxide and an additive according to a ratio to obtain a liquid component; and step 3, uniformly mixing the obtained solid component and liquid component according to proportions to obtain a high-temperature resistant oil well cement system.

5. An application of the long-term high-temperature resistant and toughened well cementing and silica-cement composite material according to claim 1 in oil well cementing.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a flow chart of a preparation method of a long-term high-temperature resistant and toughened well cementing and silica-cement composite material provided by an embodiment of the present invention.

(2) FIG. 2 is a thickening time diagram of a cement system provided by an embodiment of the present invention.

(3) FIG. 3 is a schematic diagram of detection results of compressive strength and a Young's modulus of a cement system provided by an embodiment of the present invention.

(4) FIG. 4 is a schematic diagram of detection results of gas permeability of a cement system provided by an embodiment of the present invention.

(5) FIG. 5 is a schematic diagram of detection results of water permeability of a cement system provided by an embodiment of the present invention.

(6) FIG. 6 is a schematic diagram of an XRD diffraction map of a cement system provided by an embodiment of the present invention.

(7) FIG. 7(a) is a schematic diagram of a cumulative distribution rate of distribution of mercury injection pore throat diameters of a cement system provided by an embodiment of the present invention; and FIG. 7(b) shows S, S/F and S/G in volume distribution rates.

(8) FIG. 8 is an electron microscope diagram of three magnifications (50 times, 200 times and 1000 times) of a cement system provided by an embodiment of the present invention.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(9) Aiming at the problems existing in the prior art, the present invention provides a long-term high-temperature resistant and toughened well cementing and silica-cement composite material and a preparation method thereof. The present invention will be described in detail below with reference to the accompanying drawings.

(10) The long-term high-temperature resistant and toughened well cementing and silica-cement composite material provided by an embodiment of the present invention is composed of a solid component and a liquid component; the solid component is composed of 40-60% of cement, 3-8% of alumina, 30-50% of superfine high-purity silica sand, 1.5-2.1% of an additive, of a toughening nano graphene sheet and 2-6% of a toughening latex fiber toughening material according to weight fractions.

(11) The liquid component is composed of 70-73% of water, 6-7% of nano iron oxide and of an oil well cement admixture according to weight fractions.

(12) A weight ratio of the solid component to the liquid component provided by an embodiment of the present invention is 1:0.3-0.6.

(13) The cement provided by an embodiment of the present invention is Class G oil well cement.

(14) The SiO.sub.2 content in the silica sand provided by an embodiment of the present invention is larger than 97%; a median particle size of the silica sand is 5-20 μm; the purity of nano graphene sheet is over 99.5%; the thickness is 4-20 nm; and a particle size of a nano iron oxide suspension is 30 nm. Preferably, a particle size D90 of the silica sand is 19.74 μm.

(15) The toughening material provided by an embodiment of the present invention is composed of 0.2-1% of a nano graphene sheet and 2-6% of a latex fiber toughening material according to weight fractions.

(16) The purity of nano graphene sheet provided by an embodiment of the present invention is over 99.5%.

(17) The latex fiber toughening material provided by an embodiment of the present invention is a mixture of solidified latex and organic fibers.

(18) The additive provided by an embodiment of the present invention comprises a retarder; and the additive further comprises at least one of a suspending agent, a dispersing agent, a fluid loss agent and a defoamer.

(19) As shown in FIG. 1, the preparation method of the long-term high-temperature resistant and toughened well cementing and silica-cement composite material provided by an embodiment of the present invention comprises:

(20) S101, mixing cement, alumina, silica sand, a suspending agent and a toughening material according to a ratio to obtain a solid component.

(21) S102, mixing water, nano iron oxide and an additive according to a ratio to obtain a liquid component; and

(22) S103, uniformly mixing the obtained solid component and liquid component according to proportions to obtain a high-temperature resistant oil well cement system.

(23) In the present invention, a weight ratio of the solid component to the liquid component may be 1:0.3, 1:0.35, 1:0.4, 1:0.45, 1:0.5, 1:0.55 or 1:0.6.

(24) In a preferred implementation, the solid component comprises, by weight, 40-60% of cement, 3-8% of alumina, 30-50% of silica sand, and 1.5-2.1% of a suspending agent and a toughening material; and the toughening material comprises, by weight, 0.2-1% of a nano graphene sheet and 2-6% of a latex fiber toughening material.

(25) In a specific implementation, the content of cement in the solid component may be 40%, 45%, 50%, 55% or 60% by weight; the content of alumina in the solid component may be 3%, 4%, 5%, 6%, 7% or 8% by weight; the content of silica sand in the solid component may be 30%, 35%, 40%, 45% or 50% by weight; the content of nano graphene sheet in the solid component may be 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1% by weight; and the content of latex fiber toughening material in the solid component may be 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5% or 6% by weight.

(26) In a preferred implementation, the cement is Class G oil well cement. In a specific implementation, Class G oil well cement comprises, by weight, 65.13% of CaO, 18.45% of SiO.sub.2 and 2.99% of Al.sub.2O.sub.3.

(27) In a preferred implementation, the content of SiO.sub.2 in the silica sand is over 97% of the weight.

(28) Preferably, a particle size D90 of silica sand is 19.3-52 μm. Specifically, the particle size D90 of silica sand may be 19.3 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm or 52 μm.

(29) In a specific implementation, the silica sand is conventional silica sand used for oil well cement, with the particle size D90 of 163 μm.

(30) In a preferred implementation, the particle size thickness of the nano graphene sheet is 4-20 nm; the micro-film size is 5-10 μm; and the number of layers is less than 20.

(31) In a preferred implementation, the latex fiber toughening material is of model Flok-2 produced by OMAX Oilfield Technology Co., Ltd. (Chengdu), which is a mixture of solidified latex and organic fibers.

(32) In a preferred implementation, a content of a nano iron oxide suspension, by weight, is 30%; an average particle size is 30 nm; and a specific surface area is 20-60m2/g.

(33) In a preferred implementation, the additive comprises a retarder. Further preferably, the additive further comprises at least one of a suspending agent, a dispersing agent, a fluid loss agent and a defoamer.

(34) In the present invention, most additives are polymers, which can be of a solid phase or a liquid phase. The phase is mainly determined by various slurry properties such as cement slurry density, rheology, thickening, water loss, etc. In general, adjustments should be made according to working conditions in actual engineering application.

(35) In a specific implementation, the additive may be obtained through commercially available manners.

(36) In a preferred implementation, the liquid component comprises, by weight, 70-90% of water and 10-30% of the additive.

(37) A second aspect of the present invention provides a preparation method of the high-temperature resistant oil well cement system, which comprises the following steps: (1) mixing cement, silica sand and other admixture according to a ratio to obtain a solid component; (2) mixing water and an additive according to a ratio to obtain a liquid component; and (3) mixing the solid component obtained in step (1) and the liquid component obtained in step (2) according to a ratio to obtain a high-temperature resistant oil well cement system.

(38) In a preferred implementation, in step (3), the mixing is mixing by stirring.

(39) In a preferred implementation, a specific process of step (3) is as follows: adding the liquid component obtained in step (2) into a mold, then adding the solid component obtained in step (1) into the liquid component under stirring, and mixing by stirring after the addition.

(40) The present invention will be further illustrated with reference to reference examples and test examples.

(41) The additives used in specific embodiments of the present invention are all from CNPC Boxing Company, wherein the suspending agent model is BCJ-300L; the dispersing agent model is BCD-210L; the retarder model is BCR-300L; the fluid loss agent model is BXF-200L; and the defoamer model is G603.

Embodiment 1

(42) A high-temperature resistant oil well cement system is composed of a solid component and a liquid component; and a weight ratio of the solid component to the liquid component is 1:0.44.

(43) Wherein the solid component comprises, by weight, 54.1% of Class G oil well cement (main chemical components: CaO: 65.13% by weight, SiO.sub.2: 18.45% by weight, and Al.sub.2O.sub.3: 2.99% by weight), 37.8% of silica sand (D90=19.2 μm) and 8.1% of alumina;

(44) The liquid component comprises, by weight, 69.2% of water, 4.8% of a suspending agent, 6.0% of nano iron oxide, 6.6% of a dispersing agent, 5.4% of a retarder, 7.2% of a fluid loss agent and 0.6% of a defoamer.

(45) A preparation process is as follows: (1) mixing cement, silica sand and other admixture according to a ratio to obtain a solid component; (2) mixing water and an additive according to a ratio to obtain a liquid component; and (3) adding the liquid component obtained in step (2) into a mold, then adding the solid component obtained in step (1) into the liquid component under a stirring speed of 4000 rpm, and stirring for 35 s under a speed of 12000 rpm after the addition.

Embodiment 2

(46) A high-temperature resistant oil well cement system is composed of a solid component and a liquid component; and a weight ratio of the solid component to the liquid component is 1:0.43.

(47) Wherein the solid component comprises, by weight, 52.4% of Class G oil well cement (main chemical components: CaO: 65.13% by weight, SiO.sub.2: 18.45% by weight, and Al.sub.2O.sub.3: 2.99% by weight), 36.6% of silica sand (D90=19.2 μm), 7.9% of alumina and 3.1% of a latex fiber toughening material;

(48) The liquid component comprises, by weight, 69.2% of water, 4.8% of a suspending agent, 6.0% of nano iron oxide, 6.6% of a dispersing agent, 5.4% of a retarder, 7.2% of a fluid loss agent and 0.6% of a defoamer.

(49) A preparation process is as follows: (1) mixing cement, silica sand and other admixture according to a ratio to obtain a solid component; (2) mixing water and an additive according to a ratio to obtain a liquid component; and (3) adding the liquid component obtained in step (2) into a mold, then adding the solid component obtained in step (1) into the liquid component under a stirring speed of 4000 rpm, and stirring for 35 s under a speed of 12000 rpm after the addition.

Embodiment 3

(50) A high-temperature resistant oil well cement system is composed of a solid component and a liquid component; and a weight ratio of the solid component to the liquid component is 1:0.44.

(51) Wherein the solid component comprises, by weight, 53.9% of Class G oil well cement (main chemical components: CaO: 65.13% by weight, SiO.sub.2: 18.45% by weight, and Al.sub.2O.sub.3: 2.99% by weight), 37.8% of silica sand (D90=163 μm), 8.1% of alumina and 0.2% of a nano graphene sheet.

(52) The liquid component comprises, by weight, 68.7% of water, 4.9% of a suspending agent, 6.1% of nano iron oxide, 6.8% of a dispersing agent, 5.5% of a retarder, 7.4% of a fluid loss agent and 0.6% of a defoamer.

(53) A preparation process is as follows: (1) mixing cement, silica sand and other admixture according to a ratio to obtain a solid component; (2) mixing water and an additive according to a ratio to obtain a liquid component; and (3) adding the liquid component obtained in step (2) into a mold, then adding the solid component obtained in step (1) into the liquid component under a stirring speed of 4000 rpm, and stirring for 35 s under a speed of 12000 rpm after the addition.

Embodiment 4

(54) A long-term high-temperature resistant and toughened well cementing and silica-cement composite material provided by an embodiment of the present invention is composed of a solid component and a liquid component; and a weight ratio of the solid component to the liquid component is 1:0.3, 1:0.35, 1:0.4, 1:0.45, 1:0.5, 1:0.55 or 1:0.6.

(55) The solid component is composed of 40% of cement, 8% of alumina, 44% of superfine high-purity silica sand, 2% of an additive and 6% of a toughening material according to weight fractions.

(56) The liquid component is composed of 70% of water, 6% of nano iron oxide and 24% of an oil well cement admixture according to weight fractions.

(57) A preparation process is as follows: (1) mixing cement, silica sand and other admixture according to a ratio to obtain a solid component; (2) mixing water and an additive according to a ratio to obtain a liquid component; and (3) adding the liquid component obtained in step (2) into a mold, then adding the solid component obtained in step (1) into the liquid component under a stirring speed of 4000 rpm, and stirring for 35 s under a speed of 12000 rpm after the addition.

Embodiment 5

(58) A long-term high-temperature resistant and toughened well cementing and silica-cement composite material provided by an embodiment of the present invention is composed of a solid component and a liquid component; and a weight ratio of the solid component to the liquid component is 1:0.3, 1:0.35, 1:0.4, 1:0.45, 1:0.5, 1:0.55 or 1:0.6.

(59) The solid component is composed of 60% of cement, 5% of alumina, 30.7% of superfine high-purity silica sand, 2.1% of an additive and 2.1% of a latex fiber toughening material according to weight fractions.

(60) The liquid component is composed of 72% of water, 6.5% of nano iron oxide and 21.5% of an oil well cement admixture according to weight fractions.

(61) A preparation process is as follows: (1) mixing cement, silica sand and other admixture according to a ratio to obtain a solid component; (2) mixing water and an additive according to a ratio to obtain a liquid component; and (3) adding the liquid component obtained in step (2) into a mold, then adding the solid component obtained in step (1) into the liquid component under a stirring speed of 4000 rpm, and stirring for 35 s under a speed of 12000 rpm after the addition.

Embodiment 6

(62) A long-term high-temperature resistant and toughened well cementing and silica-cement composite material provided by an embodiment of the present invention is composed of a solid component and a liquid component; and a weight ratio of the solid component to the liquid component is 1:0.3, 1:0.35, 1:0.4, 1:0.45, 1:0.5, 1:0.55 or 1:0.6.

(63) The solid component is composed of 55% of cement, 8% of alumina, 30.5% of superfine high-purity silica sand, 1.5% of an additive and 0.4% of a nano graphene sheet according to weight fractions.

(64) The liquid component is composed of 70% of water, 7% of nano iron oxide and 23% of an oil well cement admixture according to weight fractions.

(65) A preparation process is as follows: (1) mixing cement, silica sand and other admixture according to a ratio to obtain a solid component; (2) mixing water and an additive according to a ratio to obtain a liquid component; and (3) adding the liquid component obtained in step (2) into a mold, then adding the solid component obtained in step (1) into the liquid component under a stirring speed of 4000 rpm, and stirring for 35 s under a speed of 12000 rpm after the addition.

Reference Example 1

(66) Implementation is carried out according to the method of embodiment 1, but the difference is that: composition of the liquid component is different. The liquid component does not comprise nano iron oxide. The liquid component comprises, by weight, 74.7% of water, 4.9% of a suspending agent, 6.8% of a dispersing agent, 5.6% of a retarder, 7.4% of a fluid loss agent and 0.6% of a defoamer.

Test Example 1

(67) A thickening time diagram of the cement system in embodiment 1 under the condition of 180° C. and 120 MPa is shown in FIG. 2. It can be seen from the diagram that the thickening time of the system under a high temperature and a high pressure can exceed 5 h; and the heating-up time of the formula during curing is about 2 h, indicating that the system is still in a fluid state after reaching a target temperature and a target pressure, which meets conditions of high-temperature and high-pressure molding.

Test Example 2

(68) The oil well cement systems of embodiments 1-3 and reference example 1 are cured in situ under the condition of 200° C. and 150 MPa for 360 days; and the compressive strength and Young's modulus of each system are detected. The results are shown in FIG. 3, wherein the results of embodiments 1-3 and reference example 1 correspond to S, S/F, S/G and N in the diagram, respectively.

(69) It can be seen from the diagram that the compressive strength and Young's modulus of the 360-day-old sample of the oil well cement system with addition of the toughening material (formulas S/F and S/G) are obviously higher than those of other formulas. Specifically, after 360 days, the compressive strength of the formula with addition of the latex fiber toughening material can still remain above 30 MPa; and the Young's modulus remains about 10 GPa.

Test Example 3

(70) The oil well cement systems of embodiments 1-3 and reference example 1 are cured in situ under the condition of 200° C. and 150 MPa for 360 days; and the gas permeability of each system is detected. The results are shown in FIG. 4, wherein the results of embodiments 1-3 and reference example 1 correspond to S, S/F, S/G and N in the diagram, respectively.

(71) It can be seen from the diagram that the gas permeability of the 360-day-old sample with addition of the toughening material is obviously lower than that of other formulas, wherein the formula S/G with addition of the nano graphene material has the best performance; and the lowest gas permeability is only 0.0095 mD.

Test Example 4

(72) The oil well cement systems of embodiments 1-3 and reference example 1 are cured in situ under the condition of 200° C. and 150 MPa for 360 days; and the water permeability of each system is detected. The results are shown in FIG. 5, wherein the results of embodiments 1-3 and reference example 1 correspond to S, S/F, S/G and N in the diagram, respectively.

(73) It can be seen from the diagram that the water permeability of the 360-day-old sample with addition of the toughening material is obviously lower than that of other formulas, wherein the formula S/F with addition of the latex fiber toughening material has the best performance; and the lowest water permeability is only 0.0024 mD.

Test Example 5

(74) The oil well cement systems of embodiments 1-3 and reference example 1 are cured in situ under the condition of 200° C. and 150 MPa for 360 days; and an XRD diffraction map and mineral composition of each system are analyzed. The results are shown in FIG. 6, wherein the results of embodiments 1-3 and reference example 1 correspond to S, S/F, S/G and N in the diagram, respectively.

(75) It can be seen from FIG. 6 that, according to the XRD maps of different formulas with the same curing time, the mineral composition of each formula is basically the same (that is, the XRD diffraction map has little changes based on the formula). The result indicates that the addition of the toughening material does not influence formation of hydration products, but long-term stability of set cement is improved by filling internal pores of the set cement.

Test Example 6

(76) The oil well cement systems of embodiments 1-3 and reference example 1 are cured in situ under the condition of 200° C. and 150 MPa for 360 days; and the distribution of mercury injection pore throat diameters of each system is analyzed. The results are shown in FIG. 7, wherein the results of embodiments 1-3 correspond to S, S/F and S/G in cumulative distribution rates in FIG. 7(a) and volume distribution rates in FIG. 7(b), respectively.

(77) It can be seen from FIG. 7(a)-FIG. 7(b) that the internal pore throat diameter of the formula S/F with addition of the toughening material is obviously smaller than that of the formula without addition, indicating that the toughening material plays a role in reducing internal pores of set cement.

Test Example 7

(78) The oil well cement systems of embodiments 1-3 and reference example 1 are cured in situ under the condition of 200° C. and 150 MPa for 2 days and 360 days, respectively; and electron microscope analysis is made on microstructures of the 360-day samples. The results are shown in FIG. 8, wherein the results of embodiments 1-3 and reference example 1 correspond to S, S/F, S/G and N in the diagram, respectively.

(79) It can be seen from the diagram that there are still non-hydrated silica sand particles after curing for 360 days; and the microstructure of formula S/F with addition of the toughening material Flok-2 is denser.

Test Example 8

(80) After curing of the samples of the embodiments to a specified age, the samples are naturally cooled to a room temperature from the condition of 200° C. and 150 MPa; and the compressive strength, Young's modulus, water permeability and gas permeability of the 360-day samples are detected. After curing of the sample of the reference example to a specified age, the sample is naturally cooled to a room temperature from the condition of 200° C. and 150 MPa; and the compressive strength, Young's modulus, water permeability and gas permeability of the 360-day sample are detected. The results are shown in Table 1.

(81) TABLE-US-00001 TABLE 1 360-day 360-day 360-day 360-day compressive Young's water gas strength/ modulus/ permeability/ permeability/ No. MPa GPa mD mD Embodi- 20.1 6.05 0.0114 0.0548 ment 1 Embodi- 31.2 10.18  0.0024 0.0146 ment 2 Embodi- 27.2 9.43 0.0029 0.0095 ment 3 Reference 25.1 6.93 0.0034 0.0190 example 1

(82) It can be seen from Table 1, the strength of the 360-day-old sample of the formula of oil well cement system with addition of the toughening material in the present invention is obviously higher. In addition, the gas permeability and the water permeability of the 360-day sample are lower, indicating that the toughened oil well cement system in the present invention has excellent long-term high-temperature resistant performance and can meet the long-term sealing and isolation requirements of well cementing.

(83) The above content only involves the specific implementations of the present invention, but the scope of protection of the present invention is not limited to this. In the technical scope disclosed by the present invention, any modification, equivalent substitution, improvement, etc. made within the spirit and principle of the present invention by anyone of skill familiar with the technical field should be covered in the scope of protection of the present invention.