CN117487528B - Preparation of low-temperature expandable modified graphite plugging agent and application of plugging agent in water-based drilling fluid - Google Patents
Preparation of low-temperature expandable modified graphite plugging agent and application of plugging agent in water-based drilling fluidInfo
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- 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
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- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
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- 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
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Abstract
本发明从属于油田化学领域，公开了一种低温可膨胀改性石墨及其制备方法以及其在水基钻井液堵漏领域的应用，低温可膨胀改性石墨的制备方法包括:(1)将天然鳞片石墨、预氧化剂预氧化反应，得到预氧化石墨。(2)将所述预氧化石墨、和主插层剂、主氧化剂接触进行氧化插层反应，反应一段时间后加入辅氧化剂，得到低温可膨胀石墨。(3)将所述低温可膨胀石墨使用改性剂对低温可膨胀石墨进行改性，再用引发剂将改性过的低温可膨胀石墨与表面活性剂聚合得到低温可膨胀改性石墨。The present invention belongs to the field of oilfield chemistry, and discloses a low-temperature expandable modified graphite, a preparation method thereof, and an application thereof in the field of plugging leaks in water-based drilling fluids. The preparation method of the low-temperature expandable modified graphite comprises: (1) subjecting natural flake graphite and a preoxidant to preoxidation reaction to obtain preoxidized graphite. (2) contacting the preoxidized graphite with a main intercalation agent and a main oxidant to an oxidation intercalation reaction, and adding an auxiliary oxidant after a period of reaction to obtain low-temperature expandable graphite. (3) modifying the low-temperature expandable graphite with a modifier, and then polymerizing the modified low-temperature expandable graphite with a surfactant with an initiator to obtain low-temperature expandable modified graphite.
Description
Technical Field
The invention relates to the field of oilfield chemistry, in particular to a preparation method of low-temperature expandable modified graphite and application of the low-temperature expandable modified graphite in water-based drilling fluid.
Background
The water-based drilling fluid is one of the drilling fluid systems which are widely applied to the field in the petroleum and natural gas engineering at present because of the advantages of environmental friendliness, low cost and the like. The problem of lost circulation of water-based drilling fluids is one of the greatest risks faced by various countries in performing drilling activities, and is also one of the most complex situations in drilling engineering. The lost circulation not only can cause a great deal of drilling fluid to leak out and restrict the drilling speed and reduce the production efficiency, but also can cause a series of important economic losses such as borehole collapse, drill sticking and the like. In recent years, with the deep exploration of global unconventional oil and gas resources, the number of well layers with complex structures is increased, and the situation that serious lost circulation occurs in the well drilling process in the middle east and North America is counted to respectively account for more than about 30% and 40% of the total number of wellbores. Currently, how to solve the lost circulation problem has become the biggest problem facing global drilling researchers. The traditional bridging plugging material has higher requirement on a leakage channel, is easy to further leak to the depth of a crack, and has no wide adaptability. Along with the development and progress of the plugging technology, the novel plugging material becomes a hot research topic at present, but most of the novel plugging materials are focused on the high-molecular polymer plugging material, but the novel plugging material has the defects of high cost, environmental pollution, high Wen Ne intolerance and the like, and the plugging material taking expanded graphite as a substrate is rarely reported.
The precursor of the expanded graphite, graphite is one of carbon allotropes, is the softest of carbon element minerals, has a layered structure formed by stacking hexagonal network planes of carbon, and because each carbon atom is connected with one P electron in a large bond form, the atomic structure in the same plane is very stable, the carbon layers are combined by Van der Waals force in the vertical direction, the bond energy is 16.7KJ/mol, and the bonding force is weaker, so intercalation substances can easily enter into a graphite interlayer compound under certain conditions, and a precondition is provided for preparing the expandable graphite. The expandable graphite is used as a novel plugging material, and expandable graphite particles can be added into a high-temperature-resistant drilling fluid formula to enter a high-temperature stratum along with the drilling fluid, when a certain temperature is reached, molecules or ions inserted between the expandable graphite layers can be instantaneously gasified to generate gases, and the gases can prop up the expandable graphite with a layered structure, so that the interlayer spacing of the expandable graphite is greatly expanded, and a vermicular structure-expanded graphite with multiple holes and high specific surface area is formed. The plugging agent can achieve the plugging effect of plugging the pore throats by utilizing the property that the plugging agent can expand 100-200 times than the original plugging agent at a certain temperature, and not only can the apparent viscosity and the parameters of the drilling fluid be changed by adding the expandable graphite particles, but also the plugging performance of the drilling fluid can be improved, the lubricity of the drilling fluid can be optimized, the chip carrying capacity of the drilling fluid can be improved, and the service lives of a drill bit and a drill rod can be prolonged. Most expandable graphite, however, typically has an expansion temperature as high as 400 ℃ at a minimum, whereas the formation temperature during current high temperature drilling is mostly 180-240 ℃, and conventional expandable graphite is not well-suited to drilling fluid systems. And the expandable graphite has the characteristics of oleophilic and hydrophobic property and poor interfacial adhesion between the expandable graphite and the polymer, which is unfavorable for being dispersed in a water-based drilling fluid system taking water as a disperse phase, and if the expandable graphite has poor dispersibility in the drilling fluid, the popcorn effect is easy to generate.
Current research on lowering the initial expansion temperature of expandable graphite is well established, and its poor dispersibility limits its use in the drilling fluid field. The graphite after the oxidation intercalation has the expandable property, and the surface of the graphite also contains a large amount of ketone, hydroxyl and carboxyl after the oxidation intercalation, wherein the carbon-oxygen functional group in the expandable graphite mainly exists in the form of single bond. If not modified, hydrogen bonding and aggregation between the surface hydroxyl groups can occur, which can degrade interfacial compatibility of the expandable graphite with the drilling fluid base slurry.
Therefore, the plugging material with good hydrophilicity, good dispersibility in water-based drilling fluid and high temperature resistance is of great significance to plugging engineering in drilling engineering.
Disclosure of Invention
The invention aims to solve the problems of high cost and unsatisfactory plugging effect of the existing plugging material for water-based drilling fluid, and provides low-temperature expandable modified graphite, a preparation method and application thereof and water-based drilling fluid.
In order to achieve the above object, a first aspect of the present invention provides a method for producing low-temperature expandable graphite, comprising:
(1) The natural crystalline flake graphite and a preoxidant are contacted for preoxidation reaction to obtain preoxidized graphite;
(2) The preoxidized graphite, the main intercalating agent and the main oxidant are contacted to carry out an oxidation intercalation reaction, and an auxiliary oxidant is added after a period of time to obtain low-temperature expandable graphite;
In a second aspect the present invention provides a low temperature expandable modified graphite produced by the process of the first aspect described above.
A third aspect of the present invention provides the expansion effect of the low temperature expandable modified graphite of the preceding second aspect and its use as a plugging agent in a water-based drilling fluid.
In a fourth aspect the present invention provides a water-based drilling fluid comprising the low temperature expandable modified graphite of the second aspect.
Through the technical scheme, the invention can obtain the following beneficial effects:
(1) The low-temperature expandable modified graphite prepared by the method provided by the invention has the advantages of 80-110 mu m of particle size range, good hydrophilicity, good dispersibility in water-based drilling fluid, smaller fluid loss, and capability of effectively plugging cracks with corresponding pore diameters.
(2) The water-based drilling fluid provided by the invention contains the components, has good rheological property, low fluid loss, good plugging effect and strong adaptability, and is a plugging material with great potential.
Detailed Description
For the purposes of endpoints and any values of the ranges disclosed herein are not limited to the precise range threshold, and such ranges or values are to be understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The first aspect of the invention provides a method for preparing low-temperature expandable graphite, which comprises the following steps:
(1) The natural crystalline flake graphite and a preoxidant are contacted for preoxidation reaction to obtain preoxidized graphite;
(2) The preoxidized graphite, the main intercalating agent and the main oxidant are contacted to carry out an oxidation intercalation reaction, and after a period of time, the auxiliary intercalating agent is added to obtain low-temperature expandable graphite;
(3) And modifying the low-temperature expandable graphite by using a modifier, and polymerizing the modified low-temperature expandable graphite with a surfactant by using an initiator to obtain the low-temperature expandable modified graphite.
According to the invention, in the step (1), the natural crystalline flake graphite is contacted with a preoxidant to perform a preoxidation reaction, the preoxidant is used for preoxidizing the natural crystalline flake graphite through oxidation to remove impurities in the natural crystalline flake graphite, then a main oxidant and a main intercalator are added, the edge of the lamellar graphite is oxidized by the main oxidant, the spacing between graphite layers is pulled, and meanwhile, intercalation agent ions and molecules enter a graphite carbon layer to obtain graphite intercalation oxide, after the steps are completed, a silane coupling agent is used for modifying the low-temperature expandable graphite, and the low-temperature expandable modified graphite is polymerized with the dimethylacrylamide dimethyl propane sulfonic acid.
According to the present invention, the natural crystalline flake graphite is preferably natural crystalline flake graphite, preferably, the natural crystalline flake graphite has a particle size of 300 μm and a purity of more than 99%.
According to the invention, the pre-oxidant is selected as hydrogen peroxide solution.
According to the present invention, the main intercalating agent is preferably at least one selected from perchloric acid, periodic acid, nitric acid and phosphoric acid, and more preferably perchloric acid and nitric acid. Wherein the weight ratio of nitric acid to perchloric acid is 1 (58-64), and more preferably 1:60.
According to the present invention, preferably, the main oxidizing agent is at least one selected from the group consisting of dinitrogen pentoxide, potassium permanganate, and potassium perchlorate, and further preferably potassium permanganate.
Preferably, the auxiliary intercalating agent is at least one selected from formic acid, glacial acetic acid and hypochlorous acid, and more preferably glacial acetic acid.
According to the present invention, in step (1), in order to obtain a better pre-oxidation effect on natural crystalline flake graphite, it is preferable that the weight ratio of the natural crystalline flake graphite to the pre-oxidizing agent is 1 (1-4), and more preferably 1 (2-3).
According to the invention, in step (1), the pre-oxidation reaction is carried out at a temperature of 25 ℃. The reaction system consisting of the natural crystalline flake graphite and the pre-oxidant is subjected to the pre-oxidation reaction of the graphite at the temperature required by the pre-oxidation reaction, and in the process, the pre-oxidant maximally removes impurities in the natural crystalline flake graphite, so that the reaction system is kept at the temperature required by the pre-oxidation reaction for a long time until the reaction is complete.
According to the invention, in the step (1), the operation process of the pre-oxidation reaction comprises the steps of mixing natural crystalline flake graphite with hydrogen peroxide solution according to the weight ratio of 1:2 at normal temperature, stirring for 2 hours at the rotating speed of 500r/min, and standing for 6-8 hours at the temperature of 25 ℃ in an incubator under the condition of ensuring sealing.
In the present invention, the pre-oxidation reaction treatment is centrifugal water washing. Specifically, the product containing the low-temperature expandable graphite is mixed with deionized water, the low-temperature expandable graphite is uniformly shaken to ensure that the low-temperature expandable graphite is relatively uniformly dispersed in water, a low-speed centrifugal machine is adjusted to 2 grades, the low-speed centrifugal machine is used for centrifugal for 15min at a rotation speed of 5000r/min, the operation is repeated for 4-5 times, and the low-temperature expandable graphite is dried at 60 ℃ after the centrifugal is finished (6-8 h).
According to the invention, in the step (2), the pre-oxidized graphite, the main intercalation agent and the main oxidant are contacted to perform an oxidation intercalation reaction, and after a period of time, the auxiliary intercalation agent is added to obtain low-temperature expandable graphite;
according to the present invention, in step (2), preferably, according to the present invention, the main intercalating agent is at least one selected from perchloric acid, periodic acid, nitric acid, and phosphoric acid, and more preferably perchloric acid and nitric acid.
Preferably, the main oxidizing agent is at least one selected from the group consisting of dinitrogen pentoxide, potassium permanganate and potassium perchlorate, and further preferably potassium permanganate.
In the present invention, the nitric acid refers to a nitric acid solution having a concentration of not less than 68 wt%.
According to the invention, in the step (2), in order to obtain a better oxidation intercalation effect, preferably, the weight ratio of the pre-oxidized graphite to the main intercalation agent to the main oxidant to the auxiliary intercalation agent is 1 (2-10): 4-8): 0.8-1.2, and more preferably 1 (5.5-6.5): 4-6): 0.9:1.1.
According to the invention, in step (2), the conditions of the oxidative intercalation reaction include a temperature of from 30 to 60℃and more preferably 40℃for a period of 30 minutes.
According to the invention, in the step (2), the operation process of the oxidation intercalation reaction comprises the steps of adding the preoxidized graphite into a mixed solution of a main intercalation agent and a main oxidant, wherein the weight ratio of the main intercalating agent nitric acid to perchloric acid is 1:60, stirring at the rotating speed of 500r/min until solid particles are uniformly dispersed in the solution, placing the mixed solution into a constant-temperature water bath for reaction, adding auxiliary intercalating agent glacial acetic acid after the reaction is carried out for a period of time, and keeping the constant-temperature water bath at 40 ℃ for 30min until the reaction is finished.
According to a preferred embodiment of the present invention, in step (2), it is preferable to add graphite oxide slowly while stirring the intercalation agent and oxidant mixed solution with a glass rod, so as to avoid adhesion of graphite oxide to the cup wall, resulting in a decrease in yield. Preferably, each reagent is added and needs to be fully stirred for at least 30min, the adding time of the auxiliary intercalating agent is controlled within 5min, and the influence of the intermediate product on the experimental result caused by temperature change is avoided.
According to the invention, in the step (2), after the oxidation intercalation reaction is finished, a second product system of the low-temperature expandable graphite is obtained, and after the reaction is finished, a centrifugal machine is used for centrifuging the product to ensure complete washing and remove strong acid solution (comprising perchloric acid, nitric acid, potassium permanganate, glacial acetic acid and pre-oxidized graphite which are not completely reacted in the process of the oxidation intercalation reaction) and remain in the incomplete reaction, so that the low-temperature expandable graphite is obtained.
In the invention, the products are centrifuged by a centrifuge after the oxidation intercalation reaction. Specifically, the product containing the low-temperature expandable graphite is mixed with deionized water, shaking is carried out to ensure that the low-temperature expandable graphite is relatively uniformly dispersed in water, a low-speed centrifugal machine is adjusted to 2 grades, the low-speed centrifugal machine is used for centrifugal for 15min at a rotation speed of 5000r/min, the operation is repeated until the pH value of supernatant fluid is=7, and the low-temperature expandable graphite is dried at 60 ℃ after the centrifugal treatment is completed (6-8 h). Wherein the lower layer solid is low-temperature expandable graphite solid powder, and the supernatant fluid is impurities.
According to the invention, in the step (3), the low-temperature expandable graphite is modified by a modifier in an acidic environment, and then the surfactant and the modified low-temperature expandable graphite are subjected to free radical polymerization under the action of an initiator to obtain the low-temperature expandable modified graphite.
According to the present invention, in step (3), preferably, the modifier is selected from at least one of silane coupling agents KH-550, KH-560, KH-570, and more preferably, silane coupling agent KH-550.
Preferably, the initiator is at least one selected from ammonium persulfate, potassium persulfate and sodium persulfate, and more preferably ammonium persulfate.
Preferably, the surfactant is selected from the group consisting of diacrylamidodimethylpropanesulfonic acid, sodium p-styrenesulfonate, N-dimethylacrylamide, further preferably diacrylamidodimethylpropanesulfonic acid.
According to the invention, in step (3), in order to obtain the low-temperature expandable modified graphite with optimal performance, the weight ratio of the silane coupling agent KH-550 to the diacrylamide-based dimethyl propane sulfonic acid to the ammonium persulfate is preferably 1 (0.1-0.3), 4-10, 30-70, and more preferably 1:0.2, 5-7, 40-60.
According to the invention, in the step (3), the operation process of the modification process comprises the steps of adding the low-temperature expandable graphite into an ethanol solution, adjusting the pH value to about 4 by hydrochloric acid at the rotating speed of 250r/min, adding a silane coupling agent according to the corresponding weight proportion, carrying out water bath reaction for 7 hours at the temperature of 70 ℃ to obtain the expandable graphite modified by the silane coupling agent, then respectively mixing the modified expandable graphite with the ethanol solution according to the weight ratio, mixing the diacrylamide-based dimethyl propane sulfonic acid with deionized water, adjusting the pH value to 7 by a sodium hydroxide aqueous solution, mixing the two solutions, and adding ammonium persulfate under the nitrogen environment for reaction for 8 hours at the temperature of 70 ℃.
In the present invention, the sodium hydroxide solution refers to a self-assembled aqueous sodium hydroxide solution having a concentration of 0.1 mol/L.
According to a preferred embodiment of the invention, in the step (3), a four-necked flask is selected for polymerization reaction, wherein one port is filled with nitrogen, a thermometer is inserted into the one port so as to ensure that the temperature cannot change greatly, the one port is used for slowly adding the ammonium persulfate initiator, and the other port slightly leaks out of the slit in the nitrogen filling process so as to facilitate oxygen overflow in the bottle, and after stopping filling of nitrogen, the bottle is tightly covered so as to ensure that the bottle is completely in the nitrogen atmosphere, thereby avoiding the reaction of persulfate radical in the ammonium persulfate initiator and oxygen from losing activity.
In a second aspect, the present invention provides a low temperature expandable modified graphite produced by the method of the first aspect, wherein the low temperature expandable modified graphite has a particle size in the range of 80-110 μm and meets the plugging requirements for 100-300 μm fractures in the formation in size.
According to the invention, the low-temperature expandable modified graphite has stronger hydrophilicity and can be well dispersed in water-based drilling fluid, the sulfonic acid group positively charged in the low-temperature expandable modified graphite can form an ionic bond with bentonite of the water-based drilling fluid, and the amide group and the sulfonic acid group form a hydrogen bond with montmorillonite which is a main component in the bentonite, so that an adsorption film is formed on the surface of the bentonite in the water-based drilling fluid, and free water is prevented from increasing the filtration loss through the adsorption film.
According to the invention, the low-temperature expandable modified graphite can improve the viscosity and the shear force of the water-based drilling fluid, improve the capability of carrying underground rock debris of the drilling fluid, and has better compatibility with the drilling fluid and strong adaptability.
A third aspect of the present invention provides the use of the low temperature expandable modified graphite of the preceding second aspect as a lost circulation additive in a water-based drilling fluid.
In a fourth aspect the present invention provides a water-based drilling fluid comprising the low temperature expandable modified graphite of the second aspect.
According to the invention, the water-based drilling fluid comprises the following components, by weight, 100 parts of water, 6-9 parts of bentonite, 0.2-0.5 part of sodium carbonate, 7-10 parts of a high-temperature-resistant filtrate reducer, 5-8 parts of a high-temperature-resistant surfactant, 7-10 parts of a high-temperature protective agent, and 100 parts of a weighting material, wherein the low-temperature-expandable modified graphite is added to the water-based drilling fluid.
Preferably, the high temperature resistant filtrate loss reducer is selected from at least one of sulfomethyl phenolic resin, sulfonated lignite, hydrolyzed polyacrylonitrile and sulfonated tannin, and further preferably sulfonated lignite.
Preferably, the high temperature resistant surfactant is at least one selected from span 80, tween 80 and tween 40, and further preferably tween 80.
Preferably, the high temperature protective agent is selected from one of sodium polyacrylate, potassium polyacrylate and ammonium polyacrylate, and more preferably potassium polyacrylate.
Preferably, the weighting material is a mixture of API barite and superfine barite, wherein the weight ratio of the API barite to the superfine barite is 1 (1-10), and more preferably 1 (1.5:9)
According to the invention, preferably, the weighting agent is at least one selected from API barite, superfine barium sulfate, superfine barite, magnetite powder, titanite powder and manganous oxide, and further preferably is the API barite compounded superfine barite, and the weight ratio is 1 (1-10), and further preferably is 1 (1.5:9).
The water drilling fluid provided by the invention has excellent filtration reducing performance, good rheological property and strong adaptability, and can greatly improve the stability of the well wall.
The present invention will be described in detail by examples. In the following preparation examples, comparative examples and test examples,
Preparation example 1
(1-1) Putting natural crystalline flake graphite (300 mu m, purity 99%) and hydrogen peroxide solution (concentration 30%wt) into a beaker according to a weight ratio of 1:2, wrapping a bottle mouth with a preservative film, stirring for 2 hours, standing for 6-8 hours at a temperature of 25 ℃ in a constant temperature box, mixing the obtained product with deionized water, shaking uniformly to ensure that the low-temperature expandable graphite is relatively uniformly dispersed in water, regulating a low-speed centrifuge to 2 grades, centrifuging at a rotation speed of 5000r/min for 15 minutes, repeating the operation for 4-5 times, and drying at 60 ℃ after centrifugation is finished (6-8 hours).
(1-2) Adding the pre-oxidized graphite, the perchloric acid, the nitric acid and the potassium permanganate into a beaker according to the weight ratio of 1:5.9:0.1:5:1, and reacting. Adding the preoxidized graphite into a mixed solution of potassium permanganate and perchloric acid, sealing a bottle mouth by a preservative film, stirring for 30min, heating in a water bath at 40 ℃ for reaction for 30min, and then adding glacial acetic acid for continuous reaction for 30min until the reaction is finished.
(1-3) Mixing the product containing the low-temperature expandable graphite with deionized water, shaking uniformly to ensure that the low-temperature expandable graphite is relatively uniformly dispersed in water, regulating a low-speed centrifugal machine to 2 grades, centrifuging at a rotation speed of 5000r/min for 15min, repeating the above operation until the pH value of supernatant fluid is=7, and drying at 60 ℃ after centrifugation is finished (6-8 h).
(1-4) Adding the low-temperature expandable graphite into 300ml of ethanol solution, adjusting the pH value to about 4 by using hydrochloric acid at the rotating speed of 250r/min, adding a silane coupling agent KH-550 with corresponding weight proportion, carrying out water bath reaction for 7 hours at 70 ℃ to obtain the expandable graphite modified by the silane coupling agent, then respectively mixing the modified expandable graphite with 10g of ethanol solution according to the weight ratio, mixing the diacrylamidyl dimethyl propane sulfonic acid with 80ml of deionized water, adjusting the pH value to 7 by using 0.1mol/L of sodium hydroxide aqueous solution, mixing the two solutions, and adding ammonium persulfate under the nitrogen environment for reaction for 8 hours at 70 ℃. Wherein the weight ratio of the low-temperature expandable graphite to the silane coupling agent kh-550 to the diacrylamide-based dimethyl propane sulfonic acid to the ammonium persulfate is 1:0.2:6:50.
(1-5) Mixing the low-temperature expandable modified graphite with deionized water, shaking to ensure that the low-temperature expandable modified graphite is relatively uniformly dispersed in water, regulating a low-speed centrifugal machine to 2 grades, centrifuging at a rotation speed of 5000r/min for 15min, repeating the above operation until the pH value of supernatant fluid is=7, and drying at 60 ℃ after the centrifugation is finished (20-24 h) to obtain the low-temperature expandable modified graphite (marked as S1).
Preparation example 2
(2-1) Placing natural crystalline flake graphite (300 mu m, purity 99%) and hydrogen peroxide solution (concentration 30%wt) into a beaker according to a weight ratio of 1:2, wrapping a bottle mouth with a preservative film, stirring for 2 hours, standing for 6-8 hours at a temperature of 25 ℃ in a constant temperature box, mixing the obtained product with deionized water, shaking uniformly to ensure that low-temperature expandable graphite is relatively uniformly dispersed in water, regulating a low-speed centrifuge to 2 grades, centrifuging at a rotation speed of 5000r/min for 15 minutes, repeating the operation for 4-5 times, and drying at 60 ℃ after centrifugation is completed (6-8 hours);
(2-2) adding the pre-oxidized graphite, the perchloric acid, the nitric acid and the potassium permanganate into a beaker according to the weight ratio of 1:5.4:0.1:4:0.9 for reaction. Adding the preoxidized graphite into a mixed solution of potassium permanganate and perchloric acid, sealing a bottle mouth by a preservative film, stirring for 30min, heating in a water bath at 40 ℃ for reaction for 30min, and then adding glacial acetic acid for continuous reaction for 30min until the reaction is finished.
(2-3) Mixing the product containing the low-temperature expandable graphite with deionized water, shaking uniformly to ensure that the low-temperature expandable graphite is relatively uniformly dispersed in water, adjusting a low-speed centrifugal machine to 2 grades, centrifuging at a rotation speed of 5000r/min for 15min, repeating the above operation until the pH value of supernatant fluid is=7, and drying at 60 ℃ after centrifugation is finished (6-8 h).
(2-4) Adding the low-temperature expandable graphite into 300ml of ethanol solution, adjusting the pH value to about 4 by using hydrochloric acid at the rotating speed of 250r/min, adding a silane coupling agent according to the corresponding weight proportion, carrying out water bath reaction for 7 hours at the temperature of 70 ℃ to obtain the expandable graphite modified by the silane coupling agent, then respectively mixing the modified expandable graphite with 10g of ethanol solution according to the weight ratio, mixing the diacrylamide dimethyl propane sulfonic acid with 75ml of deionized water, adjusting the pH value to 7 by using 0.1mol/L sodium hydroxide aqueous solution, mixing the two solutions, and adding ammonium persulfate to carry out reaction for 8 hours at the temperature of 70 ℃ in a nitrogen environment. Wherein the weight ratio of the low-temperature expandable graphite to the silane coupling agent kh-550 to the diacrylamide-based dimethyl propane sulfonic acid to the ammonium persulfate is 1:0.2:5:40.
(2-5) Mixing the low-temperature expandable modified graphite with deionized water, shaking to ensure that the low-temperature expandable modified graphite is relatively uniformly dispersed in water, regulating a low-speed centrifugal machine to 2 grades, centrifuging at a rotation speed of 5000r/min for 15min, repeating the above operation until the pH value of supernatant fluid is=7, and drying at 60 ℃ after the centrifugation is finished (20-24 h) to obtain the low-temperature expandable modified graphite (marked as S2).
Preparation example 3
(3-1) Placing natural crystalline flake graphite (300 mu m, purity 99%) and hydrogen peroxide solution (concentration 30%wt) into a beaker according to a weight ratio of 1:2, wrapping a bottle mouth with a preservative film, stirring for 2 hours, standing for 6-8 hours at a temperature of 25 ℃ in a constant temperature box, mixing the obtained product with deionized water, shaking uniformly and ensuring that low-temperature expandable graphite is relatively uniformly dispersed in water, adjusting a low-speed centrifuge to 2 grades, centrifuging at a rotation speed of 5000r/min for 15 minutes, repeating the operation for 4-5 times, and drying at 60 ℃ after centrifugation is completed (6-8 hours);
(3-2) adding the pre-oxidized graphite, the perchloric acid, the nitric acid and the potassium permanganate into a beaker according to the weight ratio of 1:6.4:0.1:6:1.1 for reaction. Adding the preoxidized graphite into a mixed solution of potassium permanganate and perchloric acid, sealing a bottle mouth by a preservative film, stirring for 30min, heating in a water bath at 40 ℃ for reaction for 30min, and then adding glacial acetic acid for continuous reaction for 30min until the reaction is finished.
(3-3) Mixing the product containing the low-temperature expandable graphite with deionized water, shaking up and ensuring that the low-temperature expandable graphite is relatively uniformly dispersed in water, adjusting the low-speed centrifugal machine to 2 grades, centrifuging at a rotation speed of 5000r/min for 15min, repeating the above operation until the pH value of the supernatant fluid is=7, and drying at 60 ℃ after the centrifugation is completed (6-8 h).
(3-4) Adding the low-temperature expandable graphite into 300ml of ethanol solution, adjusting the pH value to about 4 by using hydrochloric acid at the rotating speed of 250r/min, adding a silane coupling agent according to the corresponding weight proportion, carrying out water bath reaction for 7 hours at the temperature of 70 ℃ to obtain the expandable graphite modified by the silane coupling agent, then respectively mixing the modified expandable graphite with 10g of ethanol solution according to the weight ratio, mixing the diacrylamide dimethyl propane sulfonic acid with 75ml of deionized water, adjusting the pH value to 7 by using 0.1mol/L sodium hydroxide aqueous solution, mixing the two solutions, and adding ammonium persulfate to carry out reaction for 8 hours at the temperature of 70 ℃ in a nitrogen environment. Wherein the weight ratio of the low-temperature expandable graphite to the silane coupling agent kh-550 to the diacrylamide-based dimethyl propane sulfonic acid to the ammonium persulfate is 1:0.2:7:60.
(3-5) Mixing the low-temperature expandable modified graphite with deionized water, shaking to ensure that the low-temperature expandable modified graphite is relatively uniformly dispersed in water, regulating a low-speed centrifugal machine to 2 grades, centrifuging at a rotation speed of 5000r/min for 15min, repeating the above operation until the pH value of supernatant fluid is=7, and drying at 60 ℃ after the centrifugation is finished (20-24 h) to obtain the low-temperature expandable modified graphite (marked as S3).
Example 1
Mixing 100 parts by weight of water with 8 parts by weight of bentonite and 0.3 part by weight of sodium carbonate at a stirring rate of 1500r/min for 30min, adding 9 parts by weight of sulfonated lignite, stirring at a stirring rate of 2000r/min for 10min, adding 9 parts by weight of potassium polyacrylate, stirring at a stirring rate of 2000r/min for 10min, adding 7 parts by weight of Tween 80, stirring at a stirring rate of 2000r/min for 10min, adding 70 parts by weight of API barite and 30 parts by weight of ultrafine barite 5-8 times, stirring at a stirring rate of 2000r/min for 30min until no precipitate exists at the bottom of a high stirring cup, and finally adding 6 parts by weight of plugging agent S1, stirring at a stirring rate of 2000r/min for 10min to obtain a water-based drilling fluid (marked as F1).
The components and contents of F1 are shown in Table 1.
Examples 2 to 3
The procedure of example 1 was followed except that S2 and S3 were used as plugging agents, respectively, under the same conditions as in example 1. Water-based drilling fluids (designated F2 and F3, respectively) were obtained.
Example 4
Mixing 100 parts by weight of water with 6 parts by weight of bentonite and 0.2 part by weight of sodium carbonate at a stirring rate of 1500r/min for 30min, adding 7 parts by weight of sulfonated lignite, stirring at a stirring rate of 2000r/min for 10min, adding 7 parts by weight of potassium polyacrylate, stirring at a stirring rate of 2000r/min for 10min, adding 5 parts by weight of Tween 80, stirring at a stirring rate of 2000r/min for 10min, adding 60 parts by weight of API barite and 40 parts by weight of ultrafine barite for 5-8 times, stirring at a stirring rate of 2000r/min for 30min until no precipitate exists at the bottom of a high stirring cup, and finally adding 7 parts by weight of plugging agent S2, stirring at a stirring rate of 2000r/min for 10min to obtain a water-based drilling fluid (marked as F4).
The components and contents of F4 are shown in Table 1.
Examples 5 to 6
The procedure of example 4 was followed except that S2 and S3 were used as plugging agents, respectively, under the same conditions as in example 4. Water-based drilling fluids (designated F5 and F6, respectively) were obtained.
Example 7
Mixing 100 parts by weight of water with 9 parts by weight of bentonite and 0.5 part by weight of sodium carbonate at a stirring rate of 1500r/min for 30min, adding 10 parts by weight of sulfonated lignite, stirring at a stirring rate of 2000r/min for 10min, adding 10 parts by weight of potassium polyacrylate, stirring at a stirring rate of 2000r/min for 10min, adding 8 parts by weight of Tween 80, stirring at a stirring rate of 2000r/min for 10min, adding 80 parts by weight of API barite and 20 parts by weight of ultrafine barite 5-8 times, stirring at a stirring rate of 2000r/min for 30min until no precipitate exists at the bottom of a high stirring cup, and finally adding 7 parts by weight of plugging agent S3, stirring at a stirring rate of 2000r/min for 10min, thereby obtaining a water-based drilling fluid (marked as F7).
The components and contents of F7 are shown in Table 1.
Examples 8 to 9
The procedure of example 7 was followed except that S2 and S3 were used as plugging agents, respectively, under the same conditions as in example 7. Water-based drilling fluids (F8 and F9, respectively) were obtained.
Example 10
Mixing 100 parts by weight of water with 8 parts by weight of bentonite and 0.3 part by weight of sodium carbonate at a stirring rate of 1500r/min for 30min, adding 9 parts by weight of sulfonated lignite, stirring at a stirring rate of 2000r/min for 10min, adding 9 parts by weight of potassium polyacrylate, stirring at a stirring rate of 2000r/min for 10min, adding 7 parts by weight of Tween 80, stirring at a stirring rate of 2000r/min for 10min, adding 90 parts by weight of API barite and 10 parts by weight of ultrafine barite 5-8 times, stirring at a stirring rate of 2000r/min for 30min until no precipitate exists at the bottom of a high stirring cup, and finally adding 7 parts by weight of plugging agent S1, stirring at a stirring rate of 2000r/min for 10min to obtain a water-based drilling fluid (marked as F10).
The components and contents of F10 are shown in Table 1.
Examples 11 to 12
The procedure of example 10 was followed except that S2 and S3 were used as plugging agents, respectively, and the other conditions were the same as in example 10. Water-based drilling fluids (designated F11 and F12, respectively) were obtained.
Comparative example 1
The procedure of example 1 was followed except that the plugging agent S1 was not added, and the other conditions were the same as in example 1. A water-based drilling fluid (noted DF 1) was obtained.
Comparative example 2
The procedure of example 1 was followed except that the low-temperature expandable graphite obtained in the step (2-2) of preparation example 1 was used as a plugging agent, and the other conditions were the same as in example 1. A water-based drilling fluid (noted DF 2) was obtained.
Comparative example 3
The procedure of example 2 was followed except that the low-temperature expandable graphite obtained in the step (2-2) of preparation example 2 was used as a plugging agent, and the other conditions were the same as those in example 2. A water-based drilling fluid (noted DF 3) was obtained.
Comparative example 4
The procedure of example 3 was followed except that the low-temperature expandable graphite obtained in the step (2-2) of preparation example 3 was used as a plugging agent, and the other conditions were the same as those in example 3. A water-based drilling fluid (noted DF 4) was obtained.
Comparative example 5
The procedure of example 1 was followed except that S1 was replaced with natural crystalline flake graphite, with the other conditions being the same as in example 1. A water-based drilling fluid (noted DF 5) was obtained.
Comparative example 6
The procedure of example 1 was followed except that S1 was replaced with the usual laboratory plugging agent, micron-sized calcium carbonate, under otherwise identical conditions to example 1. A water-based drilling fluid (noted DF 6) was obtained.
Comparative example 7
The procedure of example 1 was followed except that the amount of S1 added was adjusted to 15 parts by weight, and the other conditions were the same as those of example 1. A water-based drilling fluid (noted DF 7) was obtained.
TABLE 1
TABLE 2
Note that in Table 2, the graphene pre-products used for DF2-DF4 are the low temperature expandable graphites produced in the step (2-2) of preparation examples 1-3, respectively.
Test case
The expansion volume test is carried out on the nano graphene products S1-S3 prepared in the preparation examples 1-3, the expansion performance is evaluated, the plugging performance test is carried out on the water-based drilling fluids F1-F12 prepared in the examples 1-12 and the water-based drilling fluids DF1-DF7 prepared in the comparative examples 1-7, the water-based drilling fluid is the first part of the field test of the petroleum and natural gas industrial drilling fluid, and the high temperature resistant drilling fluids prepared in the examples 1-12 and the comparative examples 1-7 are evaluated. In the following examples of the test that were conducted,
Apparent viscosity (AV, mpa·s), plastic viscosity (PV, mpa·s), dynamic shear force (YP, pa) were measured using a six-speed rotational viscometer and according to the method specified in GB/T29170-2012;
medium pressure fluid loss (API, mL) was measured using a medium pressure fluid loss meter and according to the method specified in GB/T29170-2012;
High temperature high pressure fluid loss (HTHP, mL) is measured using a high temperature high pressure filtration apparatus and according to the method specified in GB/T29170-2012;
The manufacturer of the six-speed rotational viscometer is Style platinum company, model ZNN-D6S
The manufacturer of the medium pressure filtration apparatus is Style platinum company, and the model is SD4/SD4A;
the manufacturer of the high-temperature high-pressure filtration instrument is Kennel instrument company, and the model KC-GS173.
1. Expansion Performance test
The S1-S3 obtained in the preparation example is respectively placed in an air environment and a water environment to test the expansion performance, wherein the expansion volumes at the temperatures of 180 ℃, 200 ℃ and 220 ℃ are respectively tested.
TABLE 3 Table 3
Note that V-void and V-water in table 3 are the expansion volumes of S1-S3 in the water environment and the air environment, respectively.
As can be seen from Table 3, the expansion volume of S1-S3 is small at 180℃and increases gradually with increasing temperature, since more and more of the intercalating agent decomposes at high temperature to produce more gas, expanding the exfoliated graphite increases the graphite volume. And it can be seen that the expansion volume of S1-S3 in water and the expansion volume in air environment are slightly reduced, because the expansion of graphite is limited by the pressure of external water, but the performance of drilling fluid is not reduced, excessive expansion of expanded graphite is avoided, the expanded graphite is excessively soft, the pressure bearing capacity is reduced, and the low-temperature expandable modified graphite can ensure the capability of expanding in water and does not excessively reduce the pressure bearing capacity.
2. Leak stopping performance test
The self-made micro-crack plugging simulation device is used for more accurately evaluating the plugging effect, and the self-made micro-crack simulation device is used in combination with the high-temperature high-pressure filtration instrument in the plugging evaluation experimental process. Specifically, after the micro-crack simulation rigid-slit plate is assembled, the micro-crack simulation rigid-slit plate is arranged at the lower end of the inner barrel of a GGS42 high-temperature high-pressure filtration instrument kettle body, the lower part of the kettle body is arranged according to the normal steps, the standard thickness gauge aluminum foil is used for calibrating the crack width, and the prepared drilling fluid slurry is poured into the kettle body. Wherein the slit widths of the microcrack devices were set to 150 μm,220 μm,300 μm, respectively, the water-based drilling fluids F1 to F12 prepared in examples 1 to 12 and the water-based drilling fluids DF1 to DF7 prepared in comparative examples 1 to 7 were tested at a temperature of 200℃under a pressure difference of 3.5MPa, and the fluid loss amounts at 100 μm,150 μm,220 μm were respectively designated as FL1, FL2, FL3.
Table 4 leak stopping Performance test of Water-based drilling fluids F1-F12 prepared in examples 1-12 and Water-based drilling fluids DF1-DF7 prepared in comparative examples 1-7
| FL1/mL | FL2/mL | FL3/mL | |
| F1 | 9 | 8 | 6 |
| F2 | 6 | 7 | 7 |
| F3 | 8 | 7 | 7.9 |
| F4 | 6 | 7 | 7 |
| F5 | 5 | 5.2 | 8 |
| F6 | 7.2 | 8.7 | 9 |
| F7 | 4 | 6.6 | 8.3 |
| F8 | 6 | 5 | 10 |
| F9 | 7 | 8 | 15 |
| F10 | 4.5 | 5.7 | 19 |
| F11 | 5.7 | 6.7 | 18 |
| F12 | 4.9 | 7 | 16 |
| DF1 | 30 | 31 | 38 |
| DF2 | 18 | 21 | 28 |
| DF3 | 16 | 16 | 24.8 |
| DF4 | 14.4 | 19 | 20 |
| DF5 | 27.8 | 25.6 | 29 |
| DF6 | 22 | 24 | 29 |
| DF7 | 15 | 17.8 | 16.6 |
As can be seen from Table 4, the more the low-temperature expandable modified graphite is added, the more obvious the plugging effect is, and the best matching effect between the low-temperature expandable modified graphite prepared by us and cracks of 100 mu m and 150 mu m can be found, because the natural crystalline flake graphite used in the preparation example is 300 mu m, the particle size of the natural crystalline flake graphite is about 100 mu m after modification, and after entering the cracks, the cracks slightly larger than the natural crystalline flake graphite can be plugged after expansion, but if the cracks are too large, the plugging effect is lost, and the fact that the plugging effect of the modified expandable graphite on the cracks of 300 mu m is not ideal is considered because the expansion volume of the low-temperature expandable modified graphite in water is reduced, so that the oversized cracks cannot be plugged. The plugging effect of the low-temperature expandable modified graphite is obviously superior to that of calcium carbonate and the low-temperature expandable graphite, and the natural crystalline flake graphite has poor plugging effect because the natural crystalline flake graphite has no expansion property and cannot realize plugging only by virtue of the physical property.
3. Drilling fluid performance test
The high temperature resistant drilling fluids prepared in examples 1 to 12 and comparative examples 1 to 7 were evaluated with reference to GB/T16783.1-2014 "Water based drilling fluid in oil and gas industry drilling fluid field test first section".
Table 5 results of high temperature drilling fluid performance test
As can be seen from the test results of Table 5, the high temperature resistant water-based drilling fluid prepared in examples 1 to 12 has good rheological property, and after aging at 220 ℃, the rheological property is not changed greatly, which means that the drilling fluid system has good high temperature resistant property, and the high temperature and high pressure fluid loss can be kept below 30mL basically, and for the comparative example DF1 without adding low temperature expandable modified graphite, the fluid loss is obviously higher than that with adding low temperature expandable modified graphite, and in the performance test of examples 1 to 12, the fluid loss is also influenced by the adding amount of low temperature expandable modified graphite, and is reduced with the increasing of the adding amount, and with the increasing of the adding amount of API barite in the drilling fluid formula.
Claims (10)
1. The preparation method of the low-temperature expandable modified graphite plugging agent is characterized by comprising the following steps of:
(1) Performing a pre-oxidation reaction on natural crystalline flake graphite and a pre-oxidant to obtain pre-oxidized graphite;
(2) The preparation method comprises the steps of enabling pre-oxidized graphite to contact with a main intercalation agent and a main oxidant for oxidation intercalation reaction, and adding an auxiliary intercalation agent after reacting for a period of time to obtain low-temperature expandable graphite, wherein the main intercalation agent is at least one of perchloric acid, periodic acid, nitric acid and phosphoric acid, the main oxidant is at least one of nitrous oxide, potassium permanganate and potassium perchlorate, and the auxiliary intercalation agent is at least one of formic acid, glacial acetic acid and hypochlorous acid;
(3) The low-temperature expandable graphite is modified by using a modifier, and the modified low-temperature expandable graphite is polymerized with a surfactant by using an initiator to obtain the low-temperature expandable modified graphite, wherein the modifier is at least one of silane coupling agents KH-550, KH-560 and KH-570, the surfactant is at least one of diacrylamide dimethyl propane sulfonic acid, sodium p-styrene sulfonate and N, N-dimethyl acrylamide, and the initiator is at least one of ammonium persulfate, potassium persulfate and sodium persulfate.
2. The method according to claim 1, wherein in the step (1), the weight ratio of the natural crystalline flake graphite to the pre-oxidizing agent is 1 (2-3).
3. The preparation method according to claim 1, wherein in the step (2), the weight ratio of the pre-oxidized graphite to the main intercalator to the main oxidant to the auxiliary intercalator is 1 (5.5-6.5): 4-6): 0.9:1.1.
4. The preparation method according to any one of claims 1 to 3, wherein the main intercalating agent is selected from nitric acid and perchloric acid, wherein the weight ratio of nitric acid to perchloric acid is 1 (11-13), the main oxidizing agent is selected from potassium permanganate, and the auxiliary intercalating agent is selected from glacial acetic acid.
5. The preparation method of the low-temperature expandable graphite according to claim 1, wherein in the step (3), the weight ratio of the modifier to the surfactant to the initiator is 1:0.2 (5-7) (40-60), the modifier is selected as a silane coupling agent KH-550, the surfactant is selected as diacrylamide-based dimethyl propane sulfonic acid, and the initiator is selected as ammonium persulfate.
6. A process according to any one of claim 1 to 3, wherein,
In the step (1), the pre-oxidation reaction condition comprises that the temperature is 25 ℃, and the washing mode adopts a low-speed centrifuge to wash the low-temperature expandable modified graphite;
in the step (2), the reaction oxidation intercalation condition comprises the temperature of 40 ℃ and the time of 1-2h;
in the step (3), the modification conditions comprise the temperature of 70 ℃ and the time of 7 hours;
in the step (3), the polymerization conditions comprise a temperature of 70 ℃ and a time of 8 hours.
7. A low temperature expandable modified graphite produced by the production process as set forth in any one of claims 1 to 6, wherein the particle diameter of said low temperature expandable modified graphite is in the range of 80 to 110 μm.
8. Use of the low temperature expandable modified graphite of claim 7 as a lost circulation additive in water-based drilling fluids.
9. A water-based drilling fluid comprising the low temperature expandable modified graphite of claim 7.
10. The water-based drilling fluid according to claim 9, wherein the water-based drilling fluid comprises 100 parts by weight of water, 6-9 parts by weight of bentonite, 0.2-0.5 part by weight of sodium carbonate, 7-10 parts by weight of high temperature resistant filtrate reducer, 5-8 parts by weight of high temperature resistant surfactant, 7-10 parts by weight of high temperature protective agent, 6-9 parts by weight of low temperature expandable modified graphite and 100 parts by weight of weighting material;
The high-temperature resistant filtrate reducer is selected from sulfonated lignite, the high-temperature resistant surfactant is selected from Tween 80, the high-temperature protective agent is selected from potassium polyacrylate, the weighting agent is selected from API barite and ultrafine barite, and the weighting agent is prepared from the API barite and the ultrafine barite in a weight ratio of 1 (1.5:9).
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