CN115558475B - Reversible emulsifier based on nano microcrystalline cellulose, and preparation method and application thereof - Google Patents
Reversible emulsifier based on nano microcrystalline cellulose, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a technology for petroleum drilling fluid, in particular to a reversible emulsifier based on nano microcrystalline cellulose, a preparation method and application thereof. The technical scheme is as follows: firstly, vacuumizing, adding an organic silanization reagent into an intermediate container, heating the intermediate container, and modifying the nano microcrystalline cellulose by the organic silanization reagent to obtain the nano microcrystalline cellulose with strong lipophilicity; secondly, adding 2-3 parts of the suspension into absolute ethyl alcohol, and stirring at a constant speed to obtain a suspension system; adding the mixture into a second reaction kettle, dropwise adding a first organic amine surfactant, and continuously stirring; then, a second organic amine surfactant is dripped into the mixture, and the mixture is stirred and dried; the beneficial effects are that: the stable reversible emulsion of the emulsifier has good stability, can realize repeated reversible phase inversion for many times, has the unique advantages of wide source, reproducibility, good biocompatibility and biodegradability, and can overcome the defects of high cost and easy environmental pollution of common nano particles.
Description
Technical Field
The invention relates to a technology for petroleum drilling fluid, in particular to a reversible emulsifier based on nano microcrystalline cellulose, a preparation method and application thereof.
Background
Water-based drilling fluids and oil-based drilling fluids are the two most used drilling fluids at present, and compared with water-based drilling fluids, oil-based drilling fluids have unique advantages: strong inhibition performance, and can stabilize the wellThe wall, prevent collapse, have very good protective properties to the hydrocarbon reservoir especially water sensitive stratum; the high-temperature-resistant lubricating oil has good high-temperature resistance and lubricating property, is suitable for deep wells and highly-deviated wells, and is beneficial to drilling long-section horizontal wells with regular well bores in shale strata. Therefore, under the situation that the shale reservoir development becomes a hot spot, the oil-based drilling fluid receives more attention than before. However, oil-based drilling fluids also have problems, most notably the change in wettability of the solid surface from water-wet to oil-wet, resulting in difficulty in removing the mud cake during the completion phase, low cement bond strength during cementing, emulsions plugging the formation, oil-bearing drill cuttings and drilling waste (2 x 10) 6 Ton/year) is not easy to be processed, and the further expansion of the application is severely restricted.
The reversible emulsified drilling fluid controls the phase state of the emulsion by a chemical method, so that the drilling fluid is converted between water-in-oil and oil-in-water emulsions in different stages of drilling and well completion, namely the water-in-oil emulsified drilling fluid has the performance of an oil-based drilling fluid in the drilling stage and is converted into an oil-in-water emulsified drilling fluid with the performance of a water-based drilling fluid in the well completion stage and subsequent operations. The phase inversion can combine the advantages of oil-based drilling fluid and water-based drilling fluid, fundamentally solves the contradiction between the drilling efficiency and the well completion efficiency, and brings new opportunities for the drilling industry, so that the phase inversion is regarded as a great leap of the drilling fluid technology. The core of the reversible emulsified drilling fluid is a reversible emulsion, and the key of the reversible emulsion is a reversible emulsifier.
The research and analysis of the reversal process and the influence factors of the reversible emulsion [ J ] petrochemical industry and application, 2014, 33 (7): 92-94.) proposes that polyoxyethylene fatty amine is used as an emulsifier, and acetic acid is used as a pH regulator to construct a reversible emulsion system. The preparation and evaluation of pH stimulus response type high temperature resistant reversible emulsifier [ J ] the drilling fluid and the completion fluid, 2021, 38 (05): 552-559 ] proposes the synthesis of RE-HT (N-alkylated diethanolamine) as a reversible emulsifier to prepare the reversible emulsified drilling fluid, and compared with the conventional surfactant type reversible emulsifier, the stable reversible emulsified drilling fluid system has good temperature resistance. However, when the drilling fluid is used in a mine, the drilling fluid can experience a high-strength shearing environment, and the molecular chain of the surfactant is easily damaged in the shearing process, so that the reusability of the reversible emulsified drilling fluid can be influenced.
Preparation and performance of reversible emulsified drilling fluid stabilized by "Liufei", wang Yanling, guo Bao Yu ", etc.]Advances in chemical engineering, 2017, 36 (11): 4200-4208) propose the use of modified nano SiO 2 The modified nano SiO is used as a reversible emulsifier for preparing reversible emulsified drilling fluid, and compared with a surfactant type reversible emulsifier 2 The dosage of the reversible emulsifier is small, and the stable reversible emulsion drilling fluid system has good temperature resistance and shearing resistance. But a large amount of nano SiO is introduced in the using process 2 If the treatment is improper during or after use, the nano-pollution is easy to cause.
Cellulose is a renewable natural high polymer material with the largest reserve and yield in the nature, is synthesized by natural plants through photosynthesis, has a supermolecular structure, is a system with crystal regions and amorphous regions which are staggered in space, and has the characteristics of regular and regular arrangement of the crystal regions, while the arrangement state of the amorphous regions is relatively loose. The amorphous region has higher chemical reaction accessibility, and the amorphous region in the cellulose is removed by a physical and chemical means, and the crystalline region is reserved to obtain the nano microcrystalline cellulose. Nanocrystalline cellulose is a plentiful renewable resource, has biodegradable properties, and it has low environmental, health and safety risks. The nano microcrystalline cellulose not only keeps the characteristics of cellulose, but also has unique performance generated by the nano material scale effect.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a reversible emulsifier based on nano microcrystalline cellulose, a preparation method and application thereof.
The invention provides a reversible emulsifier based on nano microcrystalline cellulose, which has the technical scheme that: the preparation method comprises the following steps of preparing the components in parts by weight;
the method comprises the following steps that firstly, a modifier liquid supply mixing device and an intermediate container are connected through a first pipeline, the intermediate container is connected with a modification reaction generator through a second pipeline, the upper end of the modification reaction generator is connected to a vacuum pump through a third pipeline and a second valve, and a first valve is installed on the first pipeline on the upper portion of the modifier liquid supply mixing device; during operation, the first valve is closed, the second valve is opened, and the vacuum pump is used for vacuumizing for 2-3h; closing the second valve, opening the first valve, and pumping the organic silanization reagent in the modifier liquid supply mixing device to the intermediate container; heating the intermediate container by using a heater, keeping the constant temperature of 85-95 ℃ by using the heater for heating for 10-12h, fully modifying the nano microcrystalline cellulose in the modification reaction generator, and preparing an organic silanization reagent according to the volume ratio of 4: the nano microcrystalline cellulose is less than or equal to 2; obtaining lipophilic nano microcrystalline cellulose which is named as nano particles (1);
secondly, 2-3 parts of the nanoparticles (1) are added into 200 parts of absolute ethyl alcohol, stirred at a constant speed of 250-300r/min for 20min, and ultrasonically dispersed at normal temperature for 30min to be uniformly mixed to obtain a fully dispersed suspension system; adding the suspension system into a 250mL second reaction kettle, slowly dropwise adding 1-2 parts of a first organic amine surfactant, and continuously stirring for 2-3h; slowly dripping 2-3 parts of second organic amine surfactant into the mixture, and continuously stirring for 4-5 hours to finish the reaction; washing the product with absolute ethyl alcohol for multiple times, and then carrying out vacuum drying for 12 hours at 50 ℃ to obtain the reversible emulsifier based on the nano microcrystalline cellulose;
the organic silanization reagent is methyl trimethoxy silane or dodecyl trimethoxy silane;
the first organic amine surfactant adopts lauramidopropyl dimethyl tertiary amine or lauramidopropyl dimethyl tertiary amine;
the second organic amine surfactant adopts hexadecylamine or dodecylamine polyoxyethylene ether.
Preferably, the dodecylamine polyoxyethylene ether is a compound formed by octadecylamine polyoxyethylene ether and dodecylamine polyoxyethylene ether according to a mass ratio of 4.
The invention relates to an application of a reversible emulsifier based on nano microcrystalline cellulose, which adopts the technical scheme that: for the formulation of pH-responsive stable reversible emulsions.
Preferably, the reversible emulsifier based on the nanocrystalline cellulose is applied by the following technical scheme: the components of the stable reversible emulsion with pH value response comprise the following components in parts by weight:
30-70 parts of a water phase,
30-70 parts of an oil phase,
1.0-2.5 parts of reversible emulsifier based on nano microcrystalline cellulose;
the oil phase is 5# white oil, 15# white oil, 32# white oil or 0# diesel oil;
the water phase is CaCl with the concentration of 0-30 percent 2 An aqueous solution.
Preferably, the reversible emulsifier based on the nanocrystalline cellulose is applied by the following technical scheme: a method for preparing a pH-responsive stable reversible emulsion comprising the steps of:
(1) mixing a reversible emulsifier based on nano microcrystalline cellulose with an oil phase, stirring at a rotating speed of 10000-12000r/min for 5-10min, and uniformly dispersing;
(2) and (2) adding the water phase into the system in the step (1), and stirring for 30 to 40min at the rotating speed of 10000 to 12000r/min to form a W/O emulsion, namely the stable reversible emulsion with pH value response.
The invention relates to an application of prepared stable reversible emulsion with pH value response, which adopts the technical proposal that: the phase inversion method comprises the following phase inversion steps:
adding hydrochloric acid into the stable reversible emulsion with pH value response to enable the pH value to be 5.0-6.0, stirring for 5-10 min at the rotating speed of 10000-12000r/min, and converting the W/O type emulsion into an O/W type emulsion; continuously adding aqueous alkali to enable the pH value to be 9.0-10.0, stirring at the rotating speed of 10000-12000r/min for 5-10min, and converting the emulsion into a W/O type;
the treatment is repeated in such a way that the emulsion can be phase-inverted between W/O type and O/W type.
Compared with the prior art, the invention has the beneficial effects that:
1. the reversible emulsifier based on the nano microcrystalline cellulose is characterized in that the nano microcrystalline cellulose is modified by an organic silanization reagent and a first organic amine surfactant and a second organic amine surfactant in sequence, so that an organic amine group capable of responding to a pH value is covered on the surface of the nano microcrystalline cellulose, and a pH response function of the modified nano microcrystalline cellulose is further endowed;
2. the reversible emulsifier based on the nano microcrystalline cellulose has biological friendliness, and has the following advantages compared with the common nano-particle type reversible emulsifier:
the common nano-particle type reversible emulsifier has the defect of high cost, and adopts a large amount of nano SiO 2 Nano pollution to the environment is easy to cause; the reversible emulsifier based on the nano microcrystalline cellulose is provided by the invention to prepare reversible emulsion, and then is used for drilling fluid to solve the defects of the existing reversible emulsion drilling fluid system; the nano microcrystalline cellulose not only maintains the characteristics of cellulose, but also has unique performance generated by the nano material scale effect; based on the advantages of the nano microcrystalline cellulose, the reversible emulsifier prepared by using the modified nano microcrystalline cellulose is used for drilling fluid, so that the stability of the drilling fluid can be effectively improved, the reversible emulsifier has the unique advantages of wide source, reproducibility, good biocompatibility and biodegradability, the problem of nano pollution caused by improper treatment in the using process or after use is solved, the reversible emulsifier is an ideal solution scheme of the reversible emulsifier, and the popularization and application of the reversible emulsified drilling fluid system can be promoted in a wider range;
3. the reversible emulsifier is W/O emulsifier, the prepared reversible emulsion is W/O emulsion, and the surface is activated by adding water-soluble acidReaction of amino group on sexual agent with hydrogen ion to generate-NRH + Increasing HLB value to become O/W emulsion, and phase inversion to obtain O/W type emulsion; continued addition of alkali, NRH on surfactant + Then converted into amino to become O/W type emulsion, and the emulsion is converted into W/O type emulsion; the emulsion can be converted between W/O type and O/W type for many times by repeating the treatment;
4. in addition, the reversible emulsifier based on the nano microcrystalline cellulose belongs to a granular emulsifier, compared with an emulsion formed by a surfactant type reversible emulsifier, the emulsion breaking voltage is greatly improved, the structure is stable, the reversible emulsifier can resist high temperature and has good shearing resistance, repeated reversible conversion can be realized for many times, and the stability of the stable reversible emulsion can be effectively improved.
Drawings
FIG. 1 is a schematic diagram of a small experimental flow connection according to the present invention;
FIG. 2 is a graphical representation of the stability of the W/O emulsion obtained at different stirring times;
FIG. 3 is a graph of the emulsion breaking voltage/conductivity as a function of the concentration of aqueous phase calcium chloride in the form of an initial water-in-oil emulsion;
FIG. 4 is a graph showing the variation of stability with the concentration of aqueous phase calcium chloride after the initial water-in-oil emulsion is left to stand for 24 hours;
FIG. 5 is a schematic diagram of a multiple repetition reversible phase inversion performance test of an invertible emulsion;
in the upper diagram: the device comprises a first valve 1, a second valve 2, a modifier liquid supply mixing device 3, an intermediate container 4, a heater 5, a modification reaction generator 6, a vacuum pump 7, a first pipeline 8, a second pipeline 9 and a third pipeline 10.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
Example 1, the reversible emulsifier based on nanocrystalline cellulose provided by the invention comprises the following preparation method, wherein the preparation method comprises the following steps of (by weight portion) preparing each component;
firstly, based on a designed small-scale experimental process, connecting a modifier liquid supply and mixing device 3 and an intermediate container 4 through a first pipeline 8, connecting the intermediate container 4 and a modification reaction generator 6 through a second pipeline 9, connecting the upper end of the modification reaction generator 6 to a vacuum pump 7 through a third pipeline 10 and a second valve 2, installing the first valve 1 on the first pipeline 8 at the upper part of the modifier liquid supply and mixing device 3, inserting one end of the first pipeline 8 into an organic silanization reagent in the modifier liquid supply and mixing device 3, and positioning the other end of the first pipeline 8 at the lower part of an inner cavity of the intermediate container 4; one end of the second pipeline 9 is positioned in the upper opening of the intermediate container 4, the other end is positioned in the upper opening of the modification reaction generator 6, and the upper ends of the intermediate container 4 and the modification reaction generator 6 are both provided with sealing covers; enough dodecyl trimethoxy silane is put into the modifier liquid supply mixing device 3, and 20g of nano microcrystalline cellulose is put into the modification reaction generator 6. Closing the first valve 1, opening the second valve 2, and vacuumizing for 2h by using a vacuum pump 7; closing the second valve 2, opening the first valve 1, arranging a scale on a 500ml capacity intermediate container 4, and introducing 80g of dodecyl trimethoxy silane by controlling the first valve 1; heating the intermediate container 4 by using a heater 5, and heating the heater 5 at a constant temperature of 95 ℃ for 10 hours to fully modify the nano microcrystalline cellulose to obtain lipophilic nano microcrystalline cellulose which is named as nano particles (1);
and secondly, adding 2 parts of the nanoparticles (1) into 200 parts of absolute ethyl alcohol, uniformly stirring at a constant speed of 250r/min for 20min, and ultrasonically dispersing at normal temperature for 30min and uniformly mixing to obtain a fully dispersed suspension system. Adding the suspension system into a 250mL second reaction kettle, slowly dropwise adding 1 part of laurylamine polyoxyethylene ether, and continuously stirring for 2h; slowly dropwise adding 3 parts of hexadecylamine into the solution, and continuously stirring for 5 hours to finish the reaction; and washing the product with absolute ethyl alcohol for 3 times, and then drying the product in vacuum at 50 ℃ for 12 hours to obtain the reversible emulsifier based on the nano microcrystalline cellulose.
The lauryl amine polyoxyethylene ether is a compound constructed by octadecyl amine polyoxyethylene ether and lauryl amine polyoxyethylene ether according to the mass ratio of 3.
in the first step, based on the small experimental procedure designed in example 1, a sufficient amount of methyltrimethoxysilane was placed in the modifier feed mixing device 3, and 30g of nanocrystalline cellulose was placed in the modification reactor 6. Closing the first valve 1, opening the second valve 2, and vacuumizing for 3h by using a vacuum pump 7; closing the second valve 2, opening the first valve 1 and introducing 60g of methyltrimethoxysilane into a 500ml volume intermediate container 4; heating the intermediate container 4 by using a heater 5, and keeping the heater 5 at the constant temperature of 85 ℃ for heating for 12h to fully modify the nano microcrystalline cellulose to obtain lipophilic nano microcrystalline cellulose;
and secondly, adding 2.5 parts of the prepared lipophilic nano microcrystalline cellulose into 200 parts of absolute ethyl alcohol, uniformly stirring for 20min at a constant speed of 300r/min, and ultrasonically dispersing for 30min at normal temperature to uniformly mix to obtain a fully dispersed suspension system. Adding the suspension system into a 250mL second reaction kettle, slowly dropwise adding 1.5 parts of dodecamidopropyl dimethyl tertiary amine, and continuously stirring for 2.5h; then, 2.5 parts of hexadecylamine was slowly added dropwise thereto, and the reaction was terminated after further stirring for 4.5 hours. And washing the product with absolute ethyl alcohol for 3 times, and then performing vacuum drying at 50 ℃ for 12 hours to obtain the reversible emulsifier based on the nano microcrystalline cellulose.
in the first step, based on the small experimental procedure designed in example 1, sufficient methyltrimethoxysilane was placed in the modifier-feed mixing device 3, and 30g of nanocrystalline cellulose was placed in the modification reactor 6. Closing the first valve 1, opening the second valve 2, and vacuumizing for 3 hours by using a vacuum pump 7; closing the second valve 2, opening the first valve 1 and introducing 60g of methyltrimethoxysilane into a 500ml volume intermediate container 4; heating the intermediate container 4 by using a heater 5, and keeping the heater 5 at the constant temperature of 85 ℃ for heating for 12 hours to fully modify the nano microcrystalline cellulose to obtain lipophilic nano microcrystalline cellulose;
and secondly, adding 3 parts of the lipophilic nano microcrystalline cellulose prepared in the embodiment 2 into 200 parts of absolute ethyl alcohol, uniformly stirring for 20min at a constant speed of 300r/min, and ultrasonically dispersing for 30min at normal temperature to uniformly mix to obtain a fully dispersed suspension system. Adding the suspension system into a 250mL second reaction kettle, slowly dropwise adding 2 parts of lauramide propyl dimethyl tertiary amine, and continuously stirring for 3h; and slowly dripping 2 parts of dodecylamine polyoxyethylene ether into the mixture, and continuously stirring for 4 hours to finish the reaction. Washing the product with absolute ethyl alcohol for 3 times, and then drying the product in vacuum at 50 ℃ for 12 hours to obtain the reversible emulsifier based on the nano microcrystalline cellulose;
the lauryl amine polyoxyethylene ether is a compound which is constructed by octadecyl amine polyoxyethylene ether and lauryl amine polyoxyethylene ether according to the mass ratio of 4.
Example 4, the use of the reversible emulsifiers based on nanocrystalline cellulose, as mentioned in the present invention, for the formulation of pH-responsive stable reversible emulsions.
The preparation method comprises the following steps of:
2.5g of the reversible emulsifier prepared in the embodiment 1 is mixed with 30mL of No. 5 white oil, stirred for 5min at the rotating speed of 10000r/min, 70mL of deionized water is added after uniform dispersion, and stirred for 30min at the rotating speed of 10000r/min to form milky W/O emulsion, namely the reversible emulsion.
Stability of the resulting W/O emulsion: the demulsification voltage is 302V, and the demulsification voltage comprises the following components: the higher the demulsification voltage needs, the higher the stability of the W/O emulsion. Compared with emulsion formed by a surfactant type reversible emulsifier, the emulsion breaking voltage is greatly improved, and the structure of the emulsion breaking voltage is stable.
Example 5 use of the reversible emulsifier based on nanocrystalline cellulose mentioned in this invention to formulate pH-responsive stable reversible emulsions.
The preparation method comprises the following steps of:
mixing 2g of the reversible emulsifier prepared in the embodiment 2 with 40mL of 15# white oil, stirring at the rotating speed of 12000r/min for 8min, dispersing uniformly, and adding CaCl with the mass concentration of 30% 2 60mL of aqueous solution at the rotating speed of 11000r/minStirring for 40min to form milky W/O emulsion as reversible emulsion.
Stability of the resulting W/O emulsion: the demulsification voltage is 448V.
Example 6 use of the reversible emulsifier based on nanocrystalline cellulose mentioned in this invention to formulate pH-responsive stable reversible emulsions.
The preparation method comprises the following steps of:
1.5g of the reversible emulsifier prepared in the embodiment 3 is mixed with 50mL of 32# white oil, stirred for 10min at the rotating speed of 11000r/min, and CaCl with the mass concentration of 15% is added after uniform dispersion 2 50mL of the aqueous solution is stirred for 35min at the rotating speed of 12000r/min to form milky W/O emulsion, and the reversible emulsion is obtained.
Stability of the resulting W/O emulsion: the demulsification voltage is 537V.
Example 7, the use of the reversible emulsifiers based on nanocrystalline cellulose, mentioned in the present invention, for the formulation of stable reversible emulsions with a pH response.
The preparation method comprises the following steps of:
1g of the reversible emulsifier prepared in the embodiment 1 is mixed with 60mL of 0# diesel oil, stirred for 5min at the rotating speed of 10000r/min, and CaCl with the mass concentration of 15% is added after uniform dispersion 2 40mL of the aqueous solution is stirred for 30min at the rotating speed of 10000r/min to form milky W/O emulsion, and the reversible emulsion is obtained.
Stability of the resulting W/O emulsion: demulsification voltage 724V.
Example 8, the use of the reversible emulsifiers based on nanocrystalline cellulose, as mentioned in the present invention, for the formulation of pH-responsive stable reversible emulsions.
The preparation method comprises the following steps of:
1.5g of the reversible emulsifier prepared in the embodiment 2 is mixed with 70mL of 15# white oil, stirred for 8min at the rotating speed of 12000r/min, and CaCl with the mass concentration of 30% is added after uniform dispersion 2 Stirring 30mL of aqueous solution for 35min at the rotating speed of 11000r/min to form milky W/O emulsion, namely the reversible emulsion.
Stability of the resulting W/O emulsion: the demulsification voltage is 878V.
Example 9 use of the reversible emulsifier based on nanocrystalline cellulose mentioned in this invention to formulate pH-responsive stable reversible emulsions.
The preparation method comprises the following steps of:
mixing 2g of the reversible emulsifier prepared in the embodiment 3 with 50mL of 5# white oil, stirring for 10min at the rotating speed of 11000r/min, uniformly dispersing, and adding CaCl with the mass concentration of 15% 2 50mL of aqueous solution is stirred for 40min at the rotating speed of 12000r/min to form milky W/O emulsion, and then the reversible emulsion is obtained.
Stability of the resulting W/O emulsion: demulsification voltage 649V.
Example 10 preparation of reversible emulsion
The difference compared to example 9 is that: the reversible emulsion preparation in example 9 used 5# white oil from scajon oil (Chongqing) co.
Stability of the resulting W/O emulsion: emulsion breaking voltage 563V.
EXAMPLE 11 preparation of reversible emulsion
The difference compared to example 9 is that: the 5# white oil used in the preparation of the reversible emulsion in example 9 was purchased from scawland petroleum (Chongqing) Inc., and the 5# white oil used in the preparation of the reversible emulsion in this example was purchased from Weifang Zhenghua chemical Co., ltd.
Stability of the resulting W/O emulsion: demulsification voltage 582V.
Example 12, the present invention refers to the use of a stable reversible emulsion with pH response prepared according to the following technical solution: the phase inversion method comprises the following phase inversion steps:
to the reversible emulsions prepared in examples 4 to 11, 20% by weight of hydrochloric acid was added to adjust the pH to 5.5, and the mixture was stirred at 12000r/min for 5min to convert the emulsion into O/W type; sodium hydroxide solution with the mass fraction of 20% is continuously added to ensure that the pH value is 9.5, the mixture is stirred for 5min at the rotating speed of 12000r/min, and the emulsion is converted into W/O type.
The reversible emulsions prepared in examples 4-11 were tested in the same manner and also had the same reversible phase inversion properties.
The above description is only a few of the preferred embodiments of the present invention, and any person skilled in the art may modify the above-described embodiments or modify them into equivalent ones. Therefore, the technical solution according to the present invention is subject to corresponding simple modifications or equivalent changes, as far as the scope of the present invention is claimed.
Claims (5)
1. A reversible emulsifier based on nano microcrystalline cellulose is characterized in that: the preparation method comprises the following steps of preparing the components in parts by weight;
firstly, a modifier liquid supply mixing device (3) and an intermediate container (4) are connected through a first pipeline (8), the intermediate container (4) and a modification reaction generator (6) are connected through a second pipeline (9), the upper end of the modification reaction generator (6) is connected to a vacuum pump (7) through a third pipeline (10) and a second valve (2), and a first valve (1) is installed on the first pipeline (8) at the upper part of the modifier liquid supply mixing device (3); during operation, the first valve (1) is closed, the second valve (2) is opened, and a vacuum pump (7) is used for vacuumizing for 2-3h; closing the second valve (2), opening the first valve (1) and pumping the organic silanization reagent in the modifier liquid-supplying and mixing device (3) to the intermediate container (4); heating the intermediate container (4) by using a heater (5), keeping the heater (5) at the constant temperature of 85-95 ℃ and heating for 10-12h to fully modify the nano microcrystalline cellulose in the modification reaction generator (6), wherein the volume ratio of the organic silylation reagent to the nano microcrystalline cellulose is not less than 4: the nano microcrystalline cellulose is less than or equal to 2; obtaining lipophilic nano microcrystalline cellulose which is named as nano particles (1);
secondly, 2-3 parts of the nano particles (1) are added into 200 parts of absolute ethyl alcohol, stirred at a constant speed of 250-300r/min for 20min, and ultrasonically dispersed at normal temperature for 30min and uniformly mixed to obtain a fully dispersed suspension system; adding the suspension system into a 250mL second reaction kettle, slowly dropwise adding 1-2 parts of a first organic amine surfactant, and continuously stirring for 2-3h; slowly dripping 2-3 parts of a second organic amine surfactant into the mixture, and continuously stirring for 4-5 hours to finish the reaction; washing the product with absolute ethyl alcohol for multiple times, and then drying the product in vacuum at 50 ℃ for 12 hours to obtain the reversible emulsifier based on the nano microcrystalline cellulose;
the organic silanization reagent is methyl trimethoxy silane or dodecyl trimethoxy silane;
the first organic amine surfactant adopts lauramidopropyl dimethyl tertiary amine or lauramidopropyl dimethyl tertiary amine;
the second organic amine surfactant is a compound which is constructed by hexadecylamine or octadecylamine polyoxyethylene ether and dodecylamine polyoxyethylene ether according to the mass ratio of 4.
2. Use of the reversible emulsifier based on nanocrystalline cellulose according to claim 1, characterized in that: for the formulation of pH-responsive stable reversible emulsions.
3. Use of the reversible emulsifier based on nanocrystalline cellulose according to claim 2, characterized in that: the components of the stable reversible emulsion responding to the pH value comprise the following components in parts by weight:
30-70 parts of a water phase,
30-70 parts of an oil phase,
1.0-2.5 parts of reversible emulsifier based on nano microcrystalline cellulose;
the oil phase is 5# white oil, 15# white oil, 32# white oil or 0# diesel oil;
the water phase is CaCl with the concentration of 0-30 percent 2 An aqueous solution.
4. Use of the reversible emulsifiers based on nanocrystallme cellulose according to claim 3, characterized by: a method for preparing a pH-responsive stable reversible emulsion comprising the steps of:
(1) mixing a reversible emulsifier based on the nano microcrystalline cellulose with an oil phase, stirring at the rotating speed of 10000-12000r/min for 5-10min, and uniformly dispersing;
(2) and (2) adding the water phase into the system in the step (1), and stirring for 30 to 40min at the rotating speed of 10000 to 12000r/min to form a W/O emulsion, namely the stable reversible emulsion with pH value response.
5. Use of a pH-responsive stable reversible emulsion prepared according to claim 4 characterized in that: the phase inversion method comprises the following phase inversion steps:
adding hydrochloric acid into the stable reversible emulsion with pH value response to enable the pH value to be 5.0-6.0, stirring for 5-10 min at the rotating speed of 10000-12000r/min, and converting the W/O type emulsion into an O/W type emulsion; continuously adding aqueous alkali to enable the pH value to be 9.0-10.0, stirring at the rotating speed of 10000-12000r/min for 5-10min, and converting the emulsion into a W/O type;
the treatment is repeated in such a way that the emulsion can be phase-inverted between W/O type and O/W type.
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Citations (6)
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| CN1351654A (en) * | 1999-05-25 | 2002-05-29 | 考格尼斯德国有限责任公司 | Utilization of pit emulsions in fermentation processes |
| CN110173244A (en) * | 2019-05-09 | 2019-08-27 | 西南石油大学 | The controllable emulsification increasing stick system in situ of viscosity and its application in water-drive pool |
| CN113355065A (en) * | 2021-08-10 | 2021-09-07 | 中国石油大学胜利学院 | Recyclable pH value responsive reversible emulsifier for oilfield drilling fluid |
| CN114574175A (en) * | 2022-04-26 | 2022-06-03 | 中国石油大学胜利学院 | pH value responsive reversible emulsifier based on waste argil for drilling fluid and application |
| CN114790379A (en) * | 2022-04-24 | 2022-07-26 | 西南石油大学 | Double-chamber microcapsule for drilling fluid and preparation method and application thereof |
| CN115216281A (en) * | 2022-06-30 | 2022-10-21 | 西南石油大学 | Reversible drilling fluid and preparation method and application thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1351654A (en) * | 1999-05-25 | 2002-05-29 | 考格尼斯德国有限责任公司 | Utilization of pit emulsions in fermentation processes |
| CN110173244A (en) * | 2019-05-09 | 2019-08-27 | 西南石油大学 | The controllable emulsification increasing stick system in situ of viscosity and its application in water-drive pool |
| CN113355065A (en) * | 2021-08-10 | 2021-09-07 | 中国石油大学胜利学院 | Recyclable pH value responsive reversible emulsifier for oilfield drilling fluid |
| CN114790379A (en) * | 2022-04-24 | 2022-07-26 | 西南石油大学 | Double-chamber microcapsule for drilling fluid and preparation method and application thereof |
| CN114574175A (en) * | 2022-04-26 | 2022-06-03 | 中国石油大学胜利学院 | pH value responsive reversible emulsifier based on waste argil for drilling fluid and application |
| CN115216281A (en) * | 2022-06-30 | 2022-10-21 | 西南石油大学 | Reversible drilling fluid and preparation method and application thereof |
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