CN115181552A - Intelligent temperature control microcapsule for natural gas hydrate formation and preparation method and application thereof - Google Patents
Intelligent temperature control microcapsule for natural gas hydrate formation and preparation method and application thereof Download PDFInfo
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- CN115181552A CN115181552A CN202210865167.9A CN202210865167A CN115181552A CN 115181552 A CN115181552 A CN 115181552A CN 202210865167 A CN202210865167 A CN 202210865167A CN 115181552 A CN115181552 A CN 115181552A
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Images
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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
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
-
- 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
- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
- C09K8/14—Clay-containing compositions
- C09K8/18—Clay-containing compositions characterised by the organic compounds
- C09K8/22—Synthetic organic compounds
-
- 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
- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
- C09K8/14—Clay-containing compositions
- C09K8/18—Clay-containing compositions characterised by the organic compounds
- C09K8/22—Synthetic organic compounds
- C09K8/24—Polymers
Abstract
The invention relates to the technical field of drilling fluid, and discloses an intelligent temperature control microcapsule for a natural gas hydrate stratum and a preparation method and application thereof. The intelligent temperature control microcapsule comprises a core material and a wall material coated on the outer surface of the core material, and is characterized in that the core material is obtained by mixing and dissolving different normal alkanes; the wall material is nano silicon dioxide. The intelligent temperature control microcapsule has low phase change temperature and higher phase change potential, and can meet the use requirement of a hydrate stratum.
Description
Technical Field
The invention relates to the technical field of drilling fluid, in particular to an intelligent temperature control microcapsule for a natural gas hydrate stratum and a preparation method and application thereof.
Background
The enormous resource reserves make natural gas hydrate drilling and development a research hotspot. Hydrates are mainly present in subsea formations under low temperature and high pressure conditions, which presents a serious technical challenge to drilling engineering. One of the key problems is that in the horizontal well section of the hydrate reservoir, the cutting heat of a drilling tool causes the hydrate to be decomposed, so that the stratum loses framework support, and collapse and geological disasters are caused. However, the prior art only delays the decomposition speed of the hydrate to a certain extent by adding a chemical treatment agent, and does not change the phase equilibrium temperature of the hydrate. Therefore, the hydrate formed is continuously decomposed with the increase of temperature. Under the condition, the intelligent temperature control of the drilling fluid by using Phase Change Materials (PCMs) to inhibit the decomposition of the hydrate has important research value.
In recent years, researchers have conducted extensive studies on phase change materials, and temperature control techniques for storing/releasing energy in advance by phase change of materials and releasing/absorbing energy at an appropriate temperature have been developed. These compounds are mainly classified into organic compounds and inorganic compounds. Compared with organic phase change materials, inorganic phase change materials generally have the characteristics of low cost, high heat conductivity coefficient, capability of being cooled at low temperature and the like. However, organic phase change materials have found wider application due to their higher latent thermal properties.
CN107523273A discloses a phase change energy storage microcapsule, which takes paraffin as a core material and polyester resin with average molecular weight of 30000-40000 as a wall material. CN111013509A discloses a phase change energy storage microcapsule, which takes inorganic salt adsorbed with an interface enhancer as a core material and takes a high molecular polymer as a wall material. Because the microcapsules all use high molecular polymers as wall materials, the prepared microcapsules have extremely poor thermal conductivity and unsuitable phase change temperature, so that the microcapsules cannot play a role in a natural gas hydrate stratum.
CN113025285A discloses a phase change microcapsule coated with silica, which obtains a phase change material coated with silica through a sol-gel reaction on an emulsion interface. CN113249097A discloses a polyacrylate phase change microcapsule. The phase-change material of alkane and ester is taken as a core material, and the polyacrylate is taken as a wall material, so that the sealing material has good sealing performance, good crushing resistance and good coating effect.
Even though the microcapsule prepared by the method has good performance, the phase transition temperature is too high, so that the microcapsule is obviously inconsistent with the drilling condition of a hydrate stratum, and the microcapsule cannot be utilized in the hydrate stratum.
Disclosure of Invention
The invention aims to solve the problems that the existing chemical inhibition technology can only delay the decomposition rate of the hydrate and the existing microcapsule technology has the problem of uncomfortable phase transition temperature with hydrate formation drilling fluid. The intelligent temperature control microcapsule for the natural gas hydrate formation is low in phase change temperature, has high phase change potential and can meet the use requirement of the hydrate formation.
In order to achieve the above object, the present invention provides an intelligent temperature-controlling microcapsule, which comprises a core material and a wall material coated on the outer surface of the core material, wherein the core material is obtained by mixing different normal alkanes; the wall material is nano silicon dioxide.
The second aspect of the invention provides a preparation method of an intelligent temperature-control microcapsule, wherein the preparation method comprises the following steps:
(1) Mixing n-alkane with an emulsifier 1 to obtain an oil phase, mixing water with an emulsifier 2 to obtain a water phase, and contacting the oil phase with the water phase to obtain an oil-in-water emulsion; wherein the normal alkane is obtained by mixing and dissolving different normal alkanes;
(2) And slowly adding tetraethyl silicate into the oil-in-water emulsion, adding 3-aminopropyltriethoxysilane to adjust the pH value to be alkalescent, and performing synchronous hydrolytic condensation reaction to obtain the intelligent temperature-controlled microcapsule.
In a third aspect, the invention provides an intelligent temperature-control microcapsule prepared by the method.
The invention provides an application of the intelligent temperature control microcapsule in natural gas hydrate formation drilling fluid.
By the technical scheme, the intelligent temperature-control microcapsule taking silicon dioxide as a wall material and normal alkane as a core material is synthesized, and the phase change temperature of the microcapsule can be adjusted by changing the type and the ratio of the normal alkane in the core material. The microcapsule has good compatibility with drilling fluid, and has good temperature control effect at 1-10 wt%, particle diameter of 2-50 μm, and median of 5-15 μm.
Drawings
FIG. 1 is a schematic DSC curve of the intelligent temperature-controlled microcapsule prepared in example 1 of the present invention;
FIG. 2 is a schematic diagram of the particle size distribution of the intelligent temperature-controlled microcapsule prepared in example 1 of the present invention in deionized water;
FIG. 3 is an SEM photograph of intelligent temperature-controlled microcapsules prepared in example 1 of the invention;
FIG. 4 is a schematic diagram of the temperature control effect curves of the intelligent temperature-control microcapsules prepared in example 1 of the present invention at different concentrations.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As mentioned above, the first aspect of the present invention provides an intelligent temperature-control microcapsule, which comprises a core material and a wall material coated on the outer surface of the core material, wherein the core material is obtained by mixing different normal alkanes; the wall material is nano silicon dioxide.
The inventors of the present invention found that: in the process of drilling a natural gas hydrate stratum, the friction heat generated by a drilling tool is easy to cause hydrate decomposition, so that a series of problems of borehole wall instability and the like can be caused. Based on the above, the inventor of the invention introduces the phase-change microcapsule into the drilling fluid, which can play a role in controlling the temperature, thereby preventing the hydrate from decomposing due to the temperature rise. Research shows that the phase transition temperature of n-tetradecane to n-octadecane is close to the temperature of a hydrate formation, and n-alkane has high phase transition enthalpy, so that the n-alkane can be compounded to adjust the phase transition temperature of the core material.
According to the present invention, it should be noted that: the mass ratio at which any two or more different n-alkanes are miscible is not particularly limited and may be determined according to the desired phase transition temperature of the microcapsules.
According to the invention, the coating rate is 35-85%, preferably 55-70%; in the invention, the coating rate is controlled within the range, so that the core material can be well coated by the wall material to form a stable microcapsule structure, and the core material has high content and can effectively play a role in controlling temperature; if the coating rate is too low, a better microcapsule structure is not formed, and the coating fails; if the coating rate is too high, the proportion of the wall material is too large, and the temperature control effect of the core material is difficult to exert sufficiently.
According to the invention, the weight ratio of the core material to the wall material is 2: (1-10), preferably 2: (2-3); in the invention, the weight ratio of the core material to the wall material is controlled within the range, so that the effect is better; if the weight ratio of the core material to the wall material is too low, the core material is not coated by the wall material; if the weight ratio of the core material to the wall material is too high, the content of the coated core material is too low, which is not beneficial to exerting an effective temperature control effect.
According to the invention, the average particle size of the intelligent temperature-control microcapsule is 2-50 μm, preferably 5-25 μm.
According to the invention, the median value D of the particle diameter of the intelligent temperature-control microcapsule 50 Is 5-15 μm, preferably 8-12 μm.
According to the invention, the phase transition temperature of the microcapsules is between 6 and 18 ℃, preferably between 8 and 15 ℃.
According to the invention, the microcapsules have a latent heat of phase change of 70 to 150J/g, preferably 100 to 150J/g.
The second aspect of the invention provides a preparation method of an intelligent temperature-control microcapsule, wherein the preparation method comprises the following steps:
(1) Mixing n-alkane with an emulsifier 1 to obtain an oil phase, mixing water with an emulsifier 2 to obtain a water phase, and contacting the oil phase with the water phase to obtain an oil-in-water emulsion; wherein the normal alkane is obtained by mixing and dissolving different normal alkanes;
(2) And slowly adding tetraethyl silicate into the oil-in-water emulsion, adding 3-aminopropyltriethoxysilane to adjust the pH value to be alkalescent, and performing synchronous hydrolytic condensation reaction to obtain the intelligent temperature-controlled microcapsule.
According to the invention, the synchronous hydrolytic condensation reaction means that tetraethyl silicate can be hydrolyzed into SiO under alkaline condition 2 3-aminopropyltriethoxysilane can be used to adjust pH and is itself readily hydrolyzed to form SiO 2 And is therefore referred to as simultaneous hydrolytic condensation.
According to the invention, the emulsifier 1 is span 80.
According to the invention, the emulsifier 2 is selected from one or more of tween 80, dodecyl phenol polyoxyethylene ether, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and gelatin; preferably, the emulsifier 2 is selected from one or more of tween 80, polyoxyethylene dodecylphenol ether and sodium lauryl sulfate.
According to the invention, the mass ratio of the n-alkane to the emulsifier 1 is (2-20): 1, preferably (4-15): 1.
according to the invention, the mass concentration of emulsifier 2 in the aqueous phase is 1-15%, preferably 1-5%.
According to the invention, the ratio of emulsifier 1 to emulsifier 2 is 1: (1-5); preferably, the ratio of emulsifier 1 to emulsifier 2 is 2: (2-3).
According to the invention, the water is preferably deionized water.
According to the invention, in step (1), the conditions under which the oil phase is contacted with the aqueous phase comprise: the stirring speed is 300-600r/min, and the reaction temperature is 45-80 ℃; preferably, the stirring speed is 400-500r/min and the reaction temperature is 50-70 ℃.
According to the invention, in step (2), the reaction conditions include: stirring at 200-500r/min, reaction temperature of 30-60 deg.C, and stirring for 5-12h; preferably, the stirring speed is 300-400r/min, the reaction temperature is 40-55 ℃, and the stirring time is 6-8h.
According to the present invention, tetraethyl silicate (TEOS) is slowly added to the prepared oil-in-water emulsion, preferably under conditions comprising: 8-15g of tetraethyl silicate are added within 15-25 minutes.
According to the invention, 3-Aminopropyltriethoxysilane (APTS) is preferably added to adjust the pH to 9-11.
According to the invention, the method of the invention further comprises: slowly adding tetraethyl silicate (TEOS) into the prepared oil-in-water emulsion, adding 3-Aminopropyltriethoxysilane (APTS) to adjust the pH value to alkalescence, fully mixing, heating, washing and drying the obtained product to obtain the intelligent temperature-controlled natural gas hydrate microcapsule.
According to the invention, washing with ethanol may be carried out.
According to the invention, the drying temperature is 45-65 ℃.
In a third aspect, the invention provides an intelligent temperature-control microcapsule prepared by the method.
The invention provides an application of the intelligent temperature control microcapsule in natural gas hydrate formation drilling fluid.
According to the invention, the natural gas hydrate formation drilling fluid comprises intelligent temperature-control microcapsules.
According to the invention, the intelligent temperature-control microcapsule is preferably used in an amount of 1-10 wt%, preferably 3-5 wt%, based on the total weight of the natural gas hydrate formation drilling fluid.
According to the invention, the temperature of the natural gas hydrate formation is 2-15 ℃.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
(1) The structural performance of the microcapsule is characterized by SEM, particle size distribution and the like.
(2) The latent heat of the microcapsules was measured by DSC curve, and the coating efficiency of the microcapsules was calculated. In addition, in order to better simulate the field application effect, the temperature control effect of the microcapsule and the compatibility of the microcapsule and the drilling fluid are subjected to experimental study.
(3) The DSC curve of the microcapsules was measured using differential scanning calorimetry with TA Q2000. The thermal stability of the microcapsules was determined by thermal cycling experiments using DSC. The microcapsules are placed in an RTP incubator and heated/cooled in a nitrogen environment at a heating rate of 5 ℃/min within the range of-50 ℃ to 50 ℃, and are circulated for 10 times, 20 times and 30 times respectively.
(4) The particle size distribution of the microcapsules was determined using a Bettersize 2000 laser particle size analyzer. Uniformly dispersing the microcapsules in deionized water by ultrasonic wave for 15min, gradually adding the microcapsules into a laboratory dish of a laser particle sizer until the light shading rate reaches 10%, and measuring the particle size distribution of the microcapsules.
The drugs used in the examples of the present invention:
tetraethyl silicate and 3-aminopropyltriethoxysilane were purchased from Aladdin reagent (Shanghai, china).
N-alkanes were purchased from Shigao Innovation technologies, inc. (China, dongying).
Deionized water was self-made in the laboratory.
Example 1
This example illustrates the intelligent temperature-controlled microcapsules prepared in accordance with the present invention.
(1) Preparation of a stable oil/water (O/W) emulsion: mixing 8g of miscible n-alkane (n-tetradecane: n-hexadecane = 2); mixing the oil phase and the water phase in a 250mL three-neck flask, and stirring at 55 ℃ at a rotation speed of 300r/min sufficiently to obtain an oil-in-water emulsion;
(2) Preparing microcapsules: slowly adding 8g of tetraethyl silicate into the prepared oil-in-water emulsion at the speed of 0.5g/min, adding 2.7g of 3-aminopropyltriethoxysilane to adjust the pH value to 10, washing the product after stirring for 5 hours with ethanol for three times, and drying at the temperature of 45 ℃ for 12 hours to obtain the intelligent temperature-controlled natural gas hydrate microcapsule.
In the intelligent temperature-control silica-coated natural gas hydrate microcapsule prepared in this embodiment, the mass ratio of the oil phase to the water phase is 1:9; the mass ratio of the core material to the wall material is 1:1; the phase transition temperature of the intelligent temperature control microcapsule of the natural gas hydrate coated by the silicon dioxide is 14.15 ℃; the coating rate of the silica-coated natural gas hydrate intelligent temperature-control microcapsule is 62.4%; the latent heat of phase change of the silica-coated natural gas hydrate intelligent temperature-control microcapsule is 124.1J/g.
FIG. 1 is a schematic diagram of DSC curve of intelligent temperature-controlled microcapsule prepared in example 1 of the present invention; as can be seen from fig. 1: the melting temperature of the phase-change material coated by the microcapsule is 14.15 ℃, and the melting enthalpy is 124.1J/g; the solidification temperature is 14.21 ℃, and the enthalpy of solidification is 123.7J/g.
FIG. 2 is a schematic diagram of the particle size distribution of the intelligent temperature-controlled microcapsule prepared in example 1 of the present invention in deionized water; as can be seen from fig. 2: the particle diameter of the microcapsule particles is mostly distributed in the range of 5-15 μm, and the median diameter D 50 It was 8.085. Mu.m.
FIG. 3 is an SEM photograph of intelligent temperature-controlled microcapsules prepared in example 1 of the invention; as can be seen from fig. 3: the microcapsule particle has good coating effect and higher roundness.
Example 2
This example is intended to illustrate the intelligent temperature-controlled microcapsules prepared according to the invention.
(1) Preparation of a Stable oil/Water (O/W) emulsion: mixing 8g of miscible n-alkane (n-tetradecane: n-hexadecane = 2); mixing the oil phase and the water phase in a 250ml three-neck flask, and fully stirring at the temperature of 55 ℃ at the rotating speed of 300r/min to obtain an oil-in-water emulsion;
(2) Preparing microcapsules: slowly adding 10g tetraethyl silicate into the prepared oil-in-water emulsion at the speed of 0.5g/min, and then adding 2.7g of 3-aminopropyltriethoxysilane to adjust the pH value to 10; washing the product after stirring for 5h with ethanol for three times, and then drying at 45 ℃ for 12h to obtain the intelligent temperature-controlled microcapsule of the natural gas hydrate.
In the silica-coated natural gas hydrate intelligent temperature-control microcapsule prepared in this embodiment, the mass ratio of the oil phase to the water phase is 1:9; the mass ratio of the core material to the wall material is 4:5; the phase transition temperature of the intelligent temperature control microcapsule of the natural gas hydrate coated by the silicon dioxide is 14.15 ℃; the coating rate of the silica-coated natural gas hydrate intelligent temperature-control microcapsule is 57.9%; the latent heat of phase change of the intelligent temperature-control natural gas hydrate microcapsule coated by the silicon dioxide is 115.3J/g.
Example 3
This example illustrates the intelligent temperature-controlled microcapsules prepared in accordance with the present invention.
(1) Preparation of a Stable oil/Water (O/W) emulsion: mixing 8g of miscible n-alkane (n-tetradecane: n-hexadecane =2 = 5) and 1.2g of span 80 in a beaker as an oil phase, mixing 80g of deionized water with 1.5g of tween 80 to obtain an aqueous phase; mixing the oil phase and the water phase in a 250ml three-neck flask, and fully stirring at the temperature of 55 ℃ at the rotating speed of 300r/min to obtain an oil-in-water emulsion;
(2) Preparing microcapsules: 12g of tetraethyl silicate were slowly added to the prepared oil-in-water emulsion at a rate of 0.5g/min, and 2.7g of 3-aminopropyltriethoxysilane was added to adjust the pH to 10. Washing the product after stirring for 5h with ethanol for three times, and then drying at 45 ℃ for 12h to obtain the intelligent temperature-controlled microcapsule of the natural gas hydrate.
In the silica-coated natural gas hydrate intelligent temperature-control microcapsule prepared in this embodiment, the mass ratio of the oil phase to the water phase is 1:9; the mass ratio of the core material to the wall material is 2:3; the phase transition temperature of the silica-coated natural gas hydrate intelligent temperature control microcapsule is 14.15 ℃; the coating rate of the silica-coated natural gas hydrate intelligent temperature-control microcapsule is 52.2%; the latent heat of phase change of the intelligent temperature-control natural gas hydrate microcapsule coated by the silicon dioxide is 103.9J/g.
Example 4
This example illustrates the intelligent temperature-controlled microcapsules prepared in accordance with the present invention.
(1) Preparation of a Stable oil/Water (O/W) emulsion: mixing 8g of miscible n-alkane (n-tetradecane: n-hexadecane = 2) and 1.2g of span 80 in a beaker as an oil phase, and mixing 80g of deionized water with 1.8g of tween 80 to obtain an aqueous phase; mixing the oil phase and the water phase in a 250ml three-neck flask, and fully stirring at the temperature of 55 ℃ at the rotating speed of 300r/min to obtain an oil-in-water emulsion;
(2) Preparing microcapsules: slowly adding 8g tetraethyl silicate into the prepared oil-in-water emulsion at the speed of 0.5g/min, and then adding 2.7g 3-aminopropyltriethoxysilane to adjust the pH value to 10; washing the product after stirring for 5h with ethanol for three times, and then drying at 45 ℃ for 12h to obtain the intelligent temperature-controlled microcapsule of the natural gas hydrate.
In the intelligent temperature-control silica-coated natural gas hydrate microcapsule prepared in this embodiment, the mass ratio of the oil phase to the water phase is 1:9; the mass ratio of the core material to the wall material is 1:1; the phase transition temperature of the intelligent temperature control microcapsule of the natural gas hydrate coated by the silicon dioxide is 14.17 ℃; the coating rate of the silica-coated natural gas hydrate intelligent temperature control microcapsule is 60.9%; the latent heat of phase change of the natural gas hydrate intelligent temperature control microcapsule coated by the silicon dioxide is 121.1J/g.
Example 5
Intelligent temperature-controlled microcapsules were prepared in the same manner as in example 1, except that: the "n-tetradecane" in example 1: n-hexadecane =2:5 "modified to" n-tetradecane: n-octadecane =3:2";
in the silica-coated natural gas hydrate intelligent temperature-control microcapsule prepared in this embodiment, the mass ratio of the oil phase to the water phase is 1:9; the mass ratio of the core material to the wall material is 1:1; the phase transition temperature of the silica-coated natural gas hydrate intelligent temperature control microcapsule is 14.63 ℃; the coating rate of the silica-coated natural gas hydrate intelligent temperature-control microcapsule is 59.6%; the latent heat of phase change of the silica-coated natural gas hydrate intelligent temperature-control microcapsule is 118.7J/g.
Example 6
Smart temperature-controlled microcapsules were prepared in the same manner as in example 1, except that: the "n-tetradecane: n-hexadecane =2:5 "modified to" n-tetradecane: n-hexadecane: n-octadecane =2:1:1";
in the silica-coated natural gas hydrate intelligent temperature-control microcapsule prepared in this embodiment, the mass ratio of the oil phase to the water phase is 1:9; the mass ratio of the core material to the wall material is 1:1; the phase transition temperature of the silica-coated natural gas hydrate intelligent temperature control microcapsule is 14.45 ℃; the coating rate of the silica-coated natural gas hydrate intelligent temperature control microcapsule is 60.5%; the latent heat of phase change of the intelligent temperature-control natural gas hydrate microcapsule coated by the silicon dioxide is 120.4J/g.
Comparative example 1
Smart temperature-controlled microcapsules were prepared in the same manner as in example 1, except that: the "mixed normal paraffin" in example 1 was modified to be "n-octadecane".
The intelligent temperature-control microcapsule prepared by the result has the mass ratio of the oil phase to the water phase of 1:9; the mass ratio of the core material to the wall material is 1:1; the phase transition temperature of the silica-coated natural gas hydrate intelligent temperature control microcapsule is 28.2 ℃; the coating rate of the silica-coated natural gas hydrate intelligent temperature control microcapsule is 58.0 percent; the latent heat of phase change of the natural gas hydrate intelligent temperature control microcapsule coated by the silicon dioxide is 136.8J/g.
Comparative example 1 no mixed n-alkanes were used, only n-octadecane; as a result, comparative example 1 has a slightly higher latent heat of phase transition, but comparative example 1 has an excessively high phase transition temperature and is not suitable.
Comparative example 2
Intelligent temperature-controlled microcapsules were prepared in the same manner as in example 1, except that: "8g of tetraethyl silicate" in example 1 was modified to "16g of tetraethyl silicate".
The intelligent temperature-control microcapsule prepared by the result has the mass ratio of the oil phase to the water phase of 1:9; the mass ratio of the core material to the wall material is 1:2; the phase transition temperature of the silica-coated natural gas hydrate intelligent temperature control microcapsule is 14.15 ℃; the coating rate of the silica-coated natural gas hydrate intelligent temperature-control microcapsule is 42.6%; the latent heat of phase change of the silica-coated natural gas hydrate intelligent temperature-control microcapsule is 84.8J/g.
Comparative example 2 employs too much wall material, and as a result, the phase transition temperature of comparative example 2 is proper, but the latent heat of phase transition is too low.
Test example 1
Testing the compatibility of the microcapsule with the drilling fluid:
the components and the component contents in the water-based drilling fluid system specifically comprise: 2% seawater soil slurry +5% KCl +10% NaCl +3% lubricant +0.25% polyvinylpyrrolidone +1% modified lecithin. Drilling fluid performance was compared by adding 0wt% and 5wt% of the microcapsules prepared in the examples and comparative examples.
TABLE 1
| Drilling fluid formula | AV(mPa·s) | PV(mPa·s) | YP(Pa) | ρ(g/cm 3 ) |
| Drilling fluid | 31.7 | 20.8 | 10.9 | 1.126 |
| Drilling fluid +5wt% of the microcapsules of example 1 | 36.9 | 24.3 | 12.6 | 1.131 |
| Drilling fluid +5wt% of the microcapsules of example 2 | 36.6 | 24.1 | 12.5 | 1.129 |
| Drilling fluid +5wt% of example 3 microcapsules | 36.7 | 24.3 | 12.4 | 1.128 |
| Drilling fluid +5wt% of example 4 microcapsules | 36.5 | 24.2 | 12.3 | 1.131 |
| Drilling fluid +5wt% example 5 microcapsules | 37.2 | 24.5 | 12.7 | 1.133 |
| Drilling fluid +5wt% example 6 microcapsules | 36.7 | 24.2 | 12.5 | 1.130 |
As can be seen from table 1: the microcapsules prepared in examples 1-6 have good compatibility with drilling fluids. The addition of the microcapsule has little influence on the density of the drilling fluid, and after standing for 72 hours, the density of the upper layer and the lower layer is not different, which shows that the microcapsule can be stably dispersed in the drilling fluid. The intelligent temperature control microcapsule provided by the invention can be applied to the hydrate formation, and one of the keys lies in that the intelligent temperature control microcapsule has good compatibility with the conventional drilling fluid of the hydrate formation, which shows that the microcapsule prepared by the invention can be added into the drilling fluid.
Test example 2
And (3) testing the temperature control effect of the microcapsules:
0g, 1g, 3g, 5g of the microcapsules prepared in examples 1 to 6 and comparative examples 1 to 2 were fully dispersed in 100g of deionized water at a temperature of 2 ℃ to prepare microcapsule systems having concentrations of 0%, 1%, 3%, 5%. After the refrigeration capacity of the microcapsules was sufficiently stored, the temperature of the system was raised to 14 ℃, the electromagnetic heating stirrer was turned on to simulate the cutting heat released from the drill, and the temperature change with time was measured, and the results are shown in table 2.
TABLE 2
In addition, temperature measurement shows that the trend of the temperature rise of the system is obviously slowed down along with the increase of the content of the microcapsule, as shown in fig. 4, fig. 4 is a schematic diagram of the temperature control effect curve of the intelligent temperature control microcapsule prepared in example 1 of the present invention at different concentrations; the temperature rise amplitude of the group with microcapsule content of 5% is the lowest, after half an hour, compared with the control group added with 0% of microcapsules (the temperature increase of 0% of microcapsules after 30min is 6.54 ℃), the temperature increase of 1% is reduced by 0.45 ℃, the temperature increase of 3% is reduced by 1.41 ℃, and the temperature increase of 5% is reduced by 2.32 ℃, which indicates that the microcapsules have better temperature regulation performance.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. An intelligent temperature control microcapsule comprises a core material and a wall material coated on the outer surface of the core material, and is characterized in that the core material is obtained by mixing and dissolving different normal alkanes; the wall material is nano silicon dioxide.
2. The microcapsule of claim 1, wherein the n-alkane comprises C 14 -C 24 An alkane of (a);
preferably, the normal alkane comprises C 14 -C 18 Of (a) an alkane.
3. Microcapsules according to claim 1 or 2, wherein the coating rate is 35-85%, preferably 55-70%;
and/or the weight ratio of the core material to the wall material is 2: (1-3.5), preferably 2: (2-3);
and/or the average particle size of the intelligent temperature-control microcapsule is 2-50 μm, preferably 5-25 μm.
4. A microcapsule according to any one of claims 1 to 3, wherein the phase transition temperature of the microcapsule is from 6 to 18 ℃, preferably from 8 to 15 ℃;
and/or the latent heat of phase change of the microcapsules is 90-150J/g, preferably 100-150J/g.
5. A preparation method of intelligent temperature control microcapsules is characterized by comprising the following steps:
(1) Mixing n-alkane with an emulsifier 1 to obtain an oil phase, mixing water with an emulsifier 2 to obtain a water phase, and contacting the oil phase with the water phase to obtain an oil-in-water emulsion; wherein the normal alkane is obtained by mixing and dissolving different normal alkanes;
(2) And slowly adding tetraethyl silicate into the oil-in-water emulsion, adding 3-aminopropyltriethoxysilane to adjust the pH value to be alkalescent, and performing synchronous hydrolytic condensation reaction to obtain the intelligent temperature-controlled microcapsule.
6. The method of claim 5, wherein the emulsifier 1 is span 80;
and/or the emulsifier 2 is selected from one or more of tween 80, dodecyl phenol polyoxyethylene ether, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and gelatin.
7. The method according to claim 5 or 6, wherein the mass ratio of the n-alkane to the emulsifier 1 is (2-20): 1, preferably (4-15): 1;
and/or the mass concentration of the emulsifier 2 in the water phase is 1-15%, preferably 1-5%;
and/or the mass ratio of the using amount of the emulsifier 1 to the using amount of the emulsifier 2 is 1: (1-5), preferably 2: (2-3);
and/or the mass ratio of the dosage of the normal alkane to the dosage of the tetraethyl silicate is 2: (1-5).
8. The process of claim 5, wherein in step (1), the conditions under which the oil phase is contacted with the aqueous phase comprise: the stirring speed is 300-600r/min, and the reaction temperature is 45-80 ℃;
and/or, in step (2), the reaction conditions include: stirring at 200-500r/min, reaction temperature of 30-60 deg.C, and stirring for 5-12h;
and/or the pH value is 9-11.
9. An intelligent temperature-controlled microcapsule prepared by the method of any one of claims 5-8.
10. Use of the intelligent temperature controlling microcapsules of any one of claims 1-4 and 9 in drilling a natural gas hydrate formation.
11. The use of claim 10, wherein the natural gas hydrate formation has a temperature of 2-15 ℃;
and/or the intelligent temperature-control microcapsule is used in an amount of 1-10 wt%, preferably 3-5 wt%, based on the total weight of the natural gas hydrate formation drilling fluid.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995264A (en) * | 2006-12-06 | 2007-07-11 | 清华大学深圳研究生院 | Silicon dioxde coated phase-change energy-storage material microcapsule preparation method |
| CN104449590A (en) * | 2014-12-05 | 2015-03-25 | 中国工程物理研究院化工材料研究所 | Phase-change energy-storage material nanocapsule and preparation method thereof |
| US20170145277A1 (en) * | 2014-05-09 | 2017-05-25 | Jx Nippon Oil & Energy Corporation | METHOD FOR PRODUCING n-PARAFFIN-BASED LATENT HEAT STORAGE MATERIAL COMPOSITION AND MICROCAPSULE HEAT STORAGE MATERIAL |
| WO2017105352A1 (en) * | 2015-12-18 | 2017-06-22 | Nanyang Technological University | Synthesis of inorganic sio2 microcapsules containing phase change materials and applications therein |
| CN107513375A (en) * | 2017-08-11 | 2017-12-26 | 中国科学院化学研究所 | A kind of phase-change microcapsule of coated with silica and its preparation method and application |
-
2022
- 2022-07-21 CN CN202210865167.9A patent/CN115181552A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995264A (en) * | 2006-12-06 | 2007-07-11 | 清华大学深圳研究生院 | Silicon dioxde coated phase-change energy-storage material microcapsule preparation method |
| US20170145277A1 (en) * | 2014-05-09 | 2017-05-25 | Jx Nippon Oil & Energy Corporation | METHOD FOR PRODUCING n-PARAFFIN-BASED LATENT HEAT STORAGE MATERIAL COMPOSITION AND MICROCAPSULE HEAT STORAGE MATERIAL |
| CN104449590A (en) * | 2014-12-05 | 2015-03-25 | 中国工程物理研究院化工材料研究所 | Phase-change energy-storage material nanocapsule and preparation method thereof |
| WO2017105352A1 (en) * | 2015-12-18 | 2017-06-22 | Nanyang Technological University | Synthesis of inorganic sio2 microcapsules containing phase change materials and applications therein |
| CN107513375A (en) * | 2017-08-11 | 2017-12-26 | 中国科学院化学研究所 | A kind of phase-change microcapsule of coated with silica and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| YUBIN ZHANG: "Intelligent Temperature-Control of Drilling Fluid in Natural Gas Hydrate Formation by Nano-Silica/Modified n-Alkane Microcapsules", 《NANOMATERIALS》, no. 11, pages 2370 * |
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