CN114891168A - Water-based drilling fluid plugging inhibitor for improving integrity of shaft and preparation method and application thereof - Google Patents
Water-based drilling fluid plugging inhibitor for improving integrity of shaft and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a water-based drilling fluid plugging inhibitor for improving the integrity of a shaft and a preparation method and application thereof. The preparation method comprises the following steps: adding active carbon into concentrated nitric acid under the condition of stirring for reaction, and then filtering, washing and drying to obtain HNO 3 Activated carbon; the obtained HNO 3 Adding activated carbon into a sodium hydroxide solution to perform a first reaction; then continuing to add the allyl-containing monomer for heat preservation reaction, filtering, washing and drying to obtain allyl-terminated carbon; adding the obtained allyl end-capped carbon and acrylic acid into deionized water, deoxidizing nitrogen, and adding an initiator aqueous solution to perform polymerization reaction; then adding organic amine solution for reaction; after the reaction is finished, the obtained reaction liquid is poured into acetone for precipitation, and the product is obtained byFiltering and drying to obtain the product. The inhibitor obtained by the invention has plugging property and inhibiting property, can effectively plug micropores in rocks, improves the wall-making property of drilling fluid, and slows down or prevents the invasion of the drilling fluid filtration to the stratum.
Description
Technical Field
The invention relates to a water-based drilling fluid plugging inhibitor for improving the integrity of a shaft and a preparation method and application thereof, belonging to the field of oilfield chemistry of the petroleum industry.
Background
With the continuous expansion of the exploration and development range of the petroleum industry, the number of drilled wells under complex geological conditions is increased, and the integrity of the well bore becomes one of the important factors influencing the drilling speed and safety. The shale stratum is often developed with natural cracks, collapse instability easily occurs in the drilling process, the continuous operation of drilling construction is hindered, a drilling tool can be buried to be dead in serious conditions, serious accidents of collapse and drill sticking occur, and then huge economic loss is brought.
The transfer of drilling fluid filtrate and pressure to the formation is the primary factor of hydration instability of the shale well wall. The hard brittle shale microcracks develop well, and the microcracks are in a closed state under the action of the original pressure of the stratum. After the borehole is opened, the microcracks are opened under the action of secondary stress distribution, and drilling fluid filtrate seeps into the stratum under the action of bottom hole pressure difference, so that the stratum close to the borehole wall is hydrated by shale to cause borehole wall instability. For some bedding, pore, fracture development or fractured formations, the drilling fluid is mainly used for enhancing the capability of blocking pores and cementing, and the invasion of filtrate is mainly retarded, so that the reduction of the rock strength of the well wall caused by hydration is retarded as much as possible. By means of physicochemical blocking technology, compact mud cakes are formed on the surfaces of the microcracks after the boreholes are drilled, and invasion of drilling fluid to deep parts of the stratum is retarded. In addition, the clay content in the shale is high, and when the shale is immersed in the drilling fluid, the mud filtrate invades along the microcracks in the drilling process, so that the hydration and dispersion of the shale are gradually intensified, the binding force between the mudstones is weakened, the mudstones crack along the microcracks, and the mud shale chipping and collapsing are caused. Therefore, the inhibition of the drilling fluid should be enhanced, the hydration expansion speed and degree of the clay particles should be reduced, and the hydration expansion and hydration dispersion of the rock should be inhibited. The effective inhibitor can provide strong inhibition effect for the drilling fluid and reduce the hydration of the shale. Therefore, the selection of reasonable blocking agents and inhibitors is an important prerequisite and guarantee for improving the integrity of the wellbore. However, the existing inhibitor or plugging agent only has plugging or inhibiting performance, and the plugging or inhibiting performance is weak, so that the stable performance and the high drilling and production efficiency of the drilling fluid can be ensured by adding a plurality of treating agents, the cost is high, and the influence on the stratum is large.
Therefore, the inhibitor with the functions of plugging and inhibiting is developed, so that the invasion of filtrate into rock is reduced, the shale hydration dispersion and expansion can be inhibited, and the integrity of a shaft is improved, and the important significance is achieved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a water-based drilling fluid plugging inhibitor for improving the integrity of a shaft and a preparation method and application thereof. Through the deep research on the borehole wall destabilization mechanism, the invention develops a novel plugging inhibitor, and the inhibitor has plugging property and inhibiting property, can effectively plug micropores in rocks, improve the wall forming property of drilling fluid, and slow down or prevent the invasion of drilling filtrate to the stratum. In addition, the clay can be adsorbed on the surface of the shale, the electrical repulsive force among clay particles is reduced, and the hydration of the shale is greatly reduced. Compared with the conventional shale inhibitor, the plugging and inhibiting capability of the shale inhibitor is stronger, and the shale inhibitor has good development prospect. The novel plugging inhibitor of the invention enables the water-based drilling fluid to have better anti-collapse capability so as to improve the integrity of a shaft.
Description of terms:
room temperature: having a meaning well known in the art, meaning 25. + -. 5 ℃.
The technical scheme of the invention is as follows:
a method of preparing a water-based drilling fluid plugging inhibitor for enhancing wellbore integrity, comprising the steps of:
(1) adding active carbon into concentrated nitric acid under the condition of stirring for reaction, and then filtering, washing and drying to obtain HNO 3 Activated carbon (HNO) 3 -C)；
(2) HNO obtained in the step (1) 3 Adding activated carbon into a sodium hydroxide solution to perform a first reaction; then continuing to add the monomer containing allyl to carry out heat preservation reaction; after the reaction is finished, obtaining allyl end-capped carbon (C-A) through filtering, washing and drying;
(3) adding the allyl end-capped carbon obtained in the step (2) and acrylic acid into deionized water, deoxidizing nitrogen, and adding an initiator aqueous solution to perform polymerization reaction; then adding organic amine solution for reaction; after the reaction is finished, the obtained reaction liquid is poured into acetone for precipitation, and acrylic acid grafted activated carbon (C-AA-NH) is obtained after filtration and drying 2 ) Namely a water-based drilling fluid plugging inhibitor for improving the integrity of a shaft.
Preferably according to the invention, the concentration of the concentrated nitric acid in step (1) is 37 wt.%.
According to the invention, the active carbon in the step (1) is coal active carbon, wood active carbon or synthetic material active carbon; the particle size of the active carbon is 1000-1200 meshes; the ratio of the mass of the activated carbon to the volume of the concentrated nitric acid is 5-10 g:100 mL.
According to the invention, the reaction time in the step (1) is preferably 4-6 h.
According to the invention, the washing in the step (1) is preferably washing for 3-5 times by using deionized water to remove residual acid; the drying is drying for 20-30 hours at the temperature of 100-110 ℃; drying to obtain HNO 3 Activated carbon (HNO) 3 -C) granules, which are ground to a powder for use.
According to the invention, the concentration of the sodium hydroxide solution in the step (2) is preferably 0.4-0.5 mol/L; volume of the sodium hydroxide solution and HNO 3 The mass ratio of the activated carbon is 100mL: 5-10 g.
Preferably, the temperature of the first reaction in the step (2) is 40-60 ℃; the first reaction time is 8-10 h.
Preferably according to the present invention, the allyl-containing monomer in step (2) is allyl chloride or allyl bromide; the allyl-containing monomer and HNO 3 The mass ratio of the activated carbon is 4 to 10:1, and more preferably 5 to 7: 1.
According to the preferable method, in the step (2), after the allyl-containing monomer is added, the reaction is carried out for 12-24 hours in a heat preservation manner; the temperature of the incubation reaction is the same as the temperature of the first reaction.
According to the invention, in the step (2), the washing is preferably performed 3-5 times by using deionized water and ethanol respectively; the drying is carried out for 10-15 h at the temperature of 40-60 ℃.
According to the invention, the mass ratio of the allyl-terminated carbon to the acrylic acid in the step (3) is preferably 1: 5-15, and more preferably 1: 8-12; the mass ratio of the allyl-terminated carbon to the volume of the deionized water is 1.5-4.5 g:100 mL.
Preferably according to the invention, the initiator in step (3) is ammonium persulfate, potassium persulfate or azobisisobutyramidine hydrochloride; the mass of the initiator is 0.5-3% of the total mass of the allyl end-capped carbon and the acrylic acid, and the preferable mass is 2-3%; the concentration of the initiator aqueous solution is 0.01-0.05 g/mL.
According to the invention, the temperature of the polymerization reaction in the step (3) is preferably 40-65 ℃, and more preferably 55-60 ℃; the time of the polymerization reaction is 2-4 h, preferably 2.5-3.5 h, and more preferably 3 h.
Preferably according to the present invention, the organic amine in step (3) is ethylenediamine, triethylamine or tetramethylethylenediamine; the mass ratio of the organic amine to the allyl end-capped carbon is 2-8: 1, and the preferable mass ratio is 3-5: 1; the organic amine solution is obtained by dissolving organic amine in ethanol, and the concentration of the organic amine solution is 0.03-0.15 g/mL; after the polymerization reaction is finished, the organic amine solution is directly added without a temperature reduction process.
According to the preferable selection of the method, in the step (3), after the organic amine solution is added, the reaction time is 12-24 hours, and the reaction temperature is room temperature; the organic amine is added for reaction under the protection of nitrogen.
According to the invention, the volume ratio of the reaction liquid to acetone in the step (3) is preferably 1: 2-5; the drying is vacuum drying for 10-15 h at 35-55 ℃.
The invention also provides the water-based drilling fluid plugging inhibitor for improving the integrity of the shaft, which is prepared by the preparation method.
According to the invention, the application of the water-based drilling fluid plugging inhibitor for improving the integrity of the shaft in the water-based drilling fluid; preferably, the addition amount of the water-based drilling fluid plugging inhibitor for improving the integrity of a shaft is 10-20 g/L.
The invention has the following technical characteristics and beneficial effects:
1. the plugging inhibitor prepared by the invention has plugging property and inhibiting property, can effectively plug micropores in rocks, improve the wall building property of drilling fluid and slow down or prevent the invasion of the drilling fluid filtration to the stratum; and can be adsorbed on the surface of the shale, and a large amount of NH in the molecule 4 + Can neutralize negative charge of clay, compress double electron layers, reduce electrical repulsion among clay particles, greatly reduce shale hydration and have stronger plugging and inhibiting capability.
2. The plugging inhibitor has strong plugging property, and the activated carbon in the molecular structure can plug micropores of a well wall, so that the filtration loss of drilling fluid can be remarkably reduced, and the stability of the well wall is facilitated.
3. The blocking inhibitor has excellent inhibition performance, has a plurality of positively charged amino groups in a molecular structure, can neutralize negative charges on the surface of clay, compresses clay double electron layers, and can effectively inhibit clay hydration expansion and shale hydration dispersion.
4. The plugging inhibitor has strong temperature resistance, and the C is taken as a core in a molecule, has good temperature resistance and still shows good inhibition at high temperature.
5. In the preparation process of the plugging inhibitor, the acrylic acid grafted activated carbon is prepared by a free radical polymerization method, the reaction temperature and time are strictly controlled in the reaction process of the allyl end-capped carbon and the acrylic acid, the reaction temperature is low or the reaction time is short, the reaction of a polymer is not sufficient, and the effect of the synthesized target product is poor; if the reaction temperature is too high, the molecular weight distribution of the synthesized product becomes wide, the effect is poor, the reaction time is too long, and the molecular weight of the product is too large and the performance is poor.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents, materials and equipment are commercially available, unless otherwise specified.
In the examples, the particle size of the wood active carbon is 1000 to 1200 mesh, and the particle size of the coal active carbon is 1000 to 1200 mesh.
Example 1
A method of preparing a water-based drilling fluid plugging inhibitor for enhancing wellbore integrity, comprising the steps of:
(1) 100mL of concentrated nitric acid (37 wt% in concentration) was added to a beaker, and 5g of wood activated carbon was added thereto with stirring, and the mixture was reacted at room temperature for 4 hours. Then filtered, and the solid obtained by the filtration was washed 3 times with deionized water to remove residual acid, and finally dried in an oven at 105 ℃ for 24 hours to obtain HNO 3 Activated carbon (HNO) 3 -C) granules, which are further ground into a powder, ready for use.
(2) 100mL of sodium hydroxide solution (concentration: 0.45mol/L) was charged in a three-necked flask, and 5g of HNO was added 3 Activated carbon (HNO) 3 -C) reacting for 8h at 40 ℃; then, 31g of allyl chloride is continuously added into the flask, and the mixture is further reacted for 12 hours at the temperature of 40 ℃; and after the reaction is finished, filtering the reaction solution to obtain a solid product, washing the obtained solid product with deionized water and ethanol for 3 times respectively, and finally drying at 40 ℃ for 12 hours to obtain the allyl-terminated carbon (C-A).
(3) 1.5g of allyl-terminated carbon (C-A) and 16g of Acrylic Acid (AA) were charged into a three-necked flask containing 100mL of deionized water, and then the solution was purged with nitrogen for 10 minutes to remove dissolved oxygen; 0.5g of ammonium persulfateDissolving in 10mL of deionized water, adding an ammonium persulfate solution into a flask, and stirring at 40 ℃ for reaction for 3 hours; dissolving 6.7g of ethylenediamine in 200mL of ethanol, adding the ethylenediamine solution into a flask, naturally cooling to room temperature, stirring at room temperature for 12 hours, keeping condensation reflux during the reaction, and introducing N 2 Deoxidizing; after the reaction is finished, pouring the viscous solution into 900mL of acetone for precipitation, filtering, and drying the obtained solid in a vacuum drying oven at 35 ℃ for 12h to obtain the acrylic acid grafted activated carbon (C-AA-NH) 2 ) Namely a water-based drilling fluid plugging inhibitor for improving the integrity of a shaft.
Example 2
A method of preparing a water-based drilling fluid plugging inhibitor for enhancing wellbore integrity, comprising the steps of:
(1) 100mL of concentrated nitric acid (37 wt% in concentration) was added to a beaker, and 5g of wood activated carbon was added thereto with stirring, and the mixture was reacted at room temperature for 4 hours. Then filtered, and the solid obtained by the filtration was washed 3 times with deionized water to remove residual acid, and finally dried in an oven at 105 ℃ for 24 hours to obtain HNO 3 Activated carbon (HNO) 3 -C) granules, which are further ground into a powder, ready for use.
(2 Add 100mL of sodium hydroxide solution (0.45 mol/L) into three-necked flask, add 5g of HNO 3 Activated carbon (HNO) 3 -C) reacting for 8h at 60 ℃; then, 31g of allyl chloride is continuously added into the flask, and the mixture is further reacted for 12 hours at the temperature of 60 ℃; and after the reaction is finished, filtering the reaction solution to obtain a solid product, washing the obtained solid product with deionized water and ethanol for 3 times respectively, and finally drying at 60 ℃ for 12 hours to obtain the allyl-terminated carbon (C-A).
(3) 1.5g of allyl-terminated carbon (C-A) and 16g of Acrylic Acid (AA) were charged into a three-necked flask containing 100mL of deionized water, and then the solution was purged with nitrogen for 10 minutes to remove dissolved oxygen; dissolving 0.5g of ammonium persulfate in 10mL of deionized water, then adding the ammonium persulfate solution into a flask, and stirring and reacting for 2h at the temperature of 60 ℃; dissolving 6.7g of ethylenediamine in 200mL of ethanol, adding the ethylenediamine solution into a flask, naturally cooling to room temperature, stirring at room temperature for reaction for 12 hours, and reactingThe condensation reflux is kept in the process, and N is introduced 2 Deoxidizing; after the reaction is finished, pouring the viscous solution into 900mL of acetone for precipitation, filtering, and drying the obtained solid in a vacuum drying oven at 55 ℃ for 12h to obtain the acrylic acid grafted activated carbon (C-AA-NH) 2 ) Namely a water-based drilling fluid plugging inhibitor for improving the integrity of a shaft.
Example 3
A method of preparing a water-based drilling fluid plugging inhibitor for enhancing wellbore integrity, comprising the steps of:
(1) 100mL of concentrated nitric acid (37 wt% in concentration) was added to a beaker, and 5g of wood activated carbon was added thereto with stirring, and the mixture was reacted at room temperature for 6 hours. Then filtered, and the solid obtained by the filtration was washed 3 times with deionized water to remove residual acid, and finally dried in an oven at 105 ℃ for 24 hours to obtain HNO 3 Activated carbon (HNO) 3 -C) granules, which are further ground into a powder, ready for use.
(2) 100mL of sodium hydroxide solution (concentration: 0.45mol/L) was put into a three-necked flask, and 5g of HNO was added 3 Activated carbon (HNO) 3 -C) reacting for 8h at 60 ℃; then, 31g of allyl chloride is continuously added into the flask, and the mixture is further reacted for 24 hours at the temperature of 60 ℃; and after the reaction is finished, filtering the reaction solution to obtain a solid product, washing the obtained solid product with deionized water and ethanol for 3 times respectively, and finally drying at 60 ℃ for 12 hours to obtain the allyl-terminated carbon (C-A).
(3) 1.5g of allyl-terminated carbon (C-A) and 16g of Acrylic Acid (AA) were charged into a three-necked flask containing 100mL of deionized water, and then the solution was purged with nitrogen for 10 minutes to remove dissolved oxygen; dissolving 0.5g of ammonium persulfate in 10mL of deionized water, then adding the ammonium persulfate solution into a flask, and stirring and reacting for 3h at the temperature of 60 ℃; dissolving 6.7g of ethylenediamine in 200mL of ethanol, adding the ethylenediamine solution into a flask, naturally cooling to room temperature, stirring at room temperature for 24 hours, keeping condensation reflux during the reaction, and introducing N 2 Deoxidizing; after the reaction is finished, pouring the viscous solution into 900mL of acetone for precipitation, filtering, and drying the obtained solid in a vacuum drying oven at 55 ℃ for 12h to obtain the acrylic acid grafted activated carbon (C-AA-NH) 2 ) Is ready for useA water-based drilling fluid plugging inhibitor for improving the integrity of a shaft.
Example 4
A method of preparing a water-based drilling fluid plugging inhibitor for enhancing wellbore integrity, comprising the steps of:
(1) adding 100mL of concentrated nitric acid (the concentration is 37 wt%) into a beaker, adding 5g of wood activated carbon under the stirring condition, and reacting for 6 hours at room temperature; then filtered, and the solid obtained by the filtration was washed 3 times with deionized water to remove residual acid, and finally dried in an oven at 105 ℃ for 24 hours to obtain HNO 3 Activated carbon (HNO) 3 -C) granules, which are further ground into a powder, ready for use.
(2) 100mL of sodium hydroxide solution (concentration: 0.45mol/L) was put into a three-necked flask, and 5g of HNO was added 3 Activated carbon (HNO) 3 -C) reacting for 8h at 60 ℃; then, 31g of allyl chloride is continuously added into the flask, and the mixture is further reacted for 24 hours at the temperature of 60 ℃; and after the reaction is finished, filtering the reaction solution to obtain a solid product, washing the obtained solid product with deionized water and ethanol for 3 times respectively, and finally drying at 60 ℃ for 12 hours to obtain the allyl-terminated carbon (C-A).
(3) 1.5g of allyl-terminated carbon (C-A) and 16g of Acrylic Acid (AA) were charged into a three-necked flask containing 100mL of deionized water, and then the solution was purged with nitrogen for 10 minutes to remove dissolved oxygen; dissolving 0.1g of azobisisobutyramidine hydrochloride into 10mL of deionized water, adding the solution of azobisisobutyramidine hydrochloride into a flask, and stirring for reaction for 3 hours at 60 ℃; dissolving 6.7g of ethylenediamine in 200mL of ethanol, adding the ethylenediamine solution into a flask, naturally cooling to room temperature, stirring at room temperature for 24 hours, keeping condensation reflux during the reaction, and introducing N 2 Deoxidizing; after the reaction is finished, pouring the viscous solution into 900mL of acetone for precipitation, filtering, and drying the obtained solid in a vacuum drying oven at 55 ℃ for 12h to obtain acrylic acid grafted activated carbon (C-AA-NH) 2 ) Namely a water-based drilling fluid plugging inhibitor for improving the integrity of a shaft.
Example 5
A method of preparing a water-based drilling fluid plugging inhibitor for enhancing wellbore integrity, comprising the steps of:
(1) 100mL of concentrated nitric acid (37 wt% in concentration) was added to a beaker, and 5g of coal-based activated carbon was added thereto with stirring, and the mixture was reacted at room temperature for 6 hours. Then filtered, and the solid obtained by the filtration was washed 3 times with deionized water to remove residual acid, and finally dried in an oven at 105 ℃ for 24 hours to obtain HNO 3 Activated carbon (HNO) 3 -C) granules, which are further ground into a powder, ready for use.
(2) 100mL of sodium hydroxide solution (concentration: 0.45mol/L) was charged in a three-necked flask, and 5g of HNO was added 3 Activated carbon (HNO) 3 -C) reacting for 8h at 60 ℃; then, 31g of allyl chloride is continuously added into the flask, and the mixture is further reacted for 24 hours at the temperature of 60 ℃; and after the reaction is finished, filtering the reaction solution to obtain a solid product, washing the obtained solid product with deionized water and ethanol for 3 times respectively, and finally drying at 60 ℃ for 12 hours to obtain the allyl-terminated carbon (C-A).
(3) 1.5g of allyl-terminated carbon (C-A) and 16g of Acrylic Acid (AA) were charged into a three-necked flask containing 100mL of deionized water, and then the solution was purged with nitrogen for 10 minutes to remove dissolved oxygen; dissolving 0.5g of azobisisobutyramidine hydrochloride into 10mL of deionized water, adding the solution of azobisisobutyramidine hydrochloride into a flask, and stirring for reaction for 3 hours at 60 ℃; dissolving 6.7g of tetramethylethylenediamine in 200mL of ethanol, adding the tetramethylethylenediamine solution into a flask, naturally cooling to room temperature, stirring at room temperature for 24 hours, keeping condensation reflux during the reaction, and introducing N 2 Deoxidizing; after the reaction is finished, pouring the viscous solution into 900mL of acetone for precipitation, filtering, and drying the obtained solid in a vacuum drying oven at the temperature of 55 ℃ for 12 hours to obtain acrylic acid grafted activated carbon (C-AA-NH) 2 ) Namely a water-based drilling fluid plugging inhibitor for improving the integrity of a shaft.
Comparative example 1
A method of preparing a water-based drilling fluid plugging inhibitor for enhancing wellbore integrity, comprising the steps of:
(1) adding 100mL of sodium hydroxide solution (the concentration is 0.45mol/L) into a three-neck flask, adding 5g of wood activated carbon, and reacting for 8 hours at 60 ℃; then, 31g of allyl chloride is continuously added, and the reaction is further carried out for 24 hours at the temperature of 60 ℃; and after the reaction is finished, filtering the reaction solution to obtain a solid product, washing the obtained solid product with deionized water and ethanol for 3 times respectively, and finally drying at 60 ℃ for 12 hours to obtain the allyl-terminated carbon (C-A).
(2) 1.5g of allyl-terminated carbon (C-A) and 16g of Acrylic Acid (AA) were charged into a three-necked flask containing 100mL of deionized water, and then the solution was purged with nitrogen for 10 minutes to remove dissolved oxygen; dissolving 0.5g of ammonium persulfate in 10mL of deionized water, then adding the ammonium persulfate solution into a flask, and stirring and reacting for 3 hours at the temperature of 60 ℃; dissolving 6.7g of ethylenediamine in 200mL of ethanol, adding the ethylenediamine solution into a flask, naturally cooling to room temperature, stirring at room temperature for 24 hours, keeping condensation reflux during the reaction, and introducing N 2 Deoxidizing; after the reaction is finished, pouring the viscous solution into 900mL of acetone for precipitation, filtering, and drying the obtained solid in a vacuum drying oven at 55 ℃ for 12h to obtain the acrylic acid grafted activated carbon (C-AA-NH) 2 ) Namely a water-based drilling fluid plugging inhibitor for improving the integrity of a shaft.
Comparative example 2
A water-based drilling fluid plugging inhibitor for use in enhancing wellbore integrity is prepared as described in example 3, except that: after acrylic acid is grafted with the activated carbon in the step (3), no organic amine is added, and the concrete steps in the step (3) are as follows: 1.5g of allyl-terminated carbon (C-A) and 16g of Acrylic Acid (AA) were charged into a three-necked flask containing 100mL of deionized water, and then the solution was purged with nitrogen for 10 minutes to remove dissolved oxygen; dissolving 0.5g of ammonium persulfate in 10mL of deionized water, then adding the ammonium persulfate solution into a flask, and stirring and reacting for 3h at the temperature of 60 ℃; and after the reaction is finished, pouring the reaction liquid into 900mL of acetone for precipitation, filtering, and drying the obtained solid in a vacuum drying oven at 55 ℃ for 12h to obtain the water-based drilling fluid plugging inhibitor for improving the integrity of a shaft.
Comparative example 3
A water-based drilling fluid plugging inhibitor for use in enhancing wellbore integrity is prepared as described in example 3, except that: the amount of allyl chloride added in step (2) was 15.5 g.
Comparative example 4
A water-based drilling fluid plugging inhibitor for use in enhancing wellbore integrity is prepared as described in example 3, except that: in the step (1), the activated carbon is replaced by silicon dioxide.
Comparative example 5
A water-based drilling fluid plugging inhibitor for use in enhancing wellbore integrity is prepared as described in example 3, except that: in the step (3), an initiator is added to initiate the polymerization reaction of C-A and acrylic acid at 80 ℃.
Test examples
The plugging inhibitors prepared in the examples and comparative examples were tested as follows: normal temperature and pressure filtration experiment, bentonite pressure sheet linear expansion experiment and shale rolling recovery experiment.
1. Normal temperature and pressure filtration test
The normal temperature and pressure filtration experiment is used for evaluating the capacity of the plugging inhibitor for plugging the mud cake and reducing the filtrate.
Preparing base slurry: slowly adding 16g of bentonite into 400mL of distilled water while stirring, and aging for 24h at room temperature to prepare bentonite-based slurry.
Respectively taking 400mL of base slurry, adding 4g of different plugging inhibitor products, and stirring for 20min under the condition of 5000r/min to obtain a drilling fluid sample with the mass volume percentage concentration of 1%; and (3) carrying out aging treatment on the base slurry and the drilling fluid sample by using a roller heating furnace, wherein the temperature is 150 ℃, and the time is 16 h.
And (3) performance testing: the drilling fluid samples and base stocks obtained after aging were tested for normal temperature and pressure filtration loss according to the American Petroleum Institute (API) standard (API RP 13B-1,2009), and the effect of plugging inhibitors on the plugging properties of the base stocks was evaluated, and the experimental results are shown in Table 1.
Table 1 effect of blocking inhibitors on drilling fluid loss
The results show that the plugging inhibitor prepared in the example can effectively plug the mud cake and reduce the filtration loss, and the filtration loss of the base slurry can be reduced to 15.4mL in the example 3, because the plugging inhibitor particles are adsorbed on the clay surface and fill the micropores of the mud cake, the mud cake is more compact, and the liquid leaching is reduced. In examples 1 and 2, the reaction temperature and the reaction time are not in the optimal range, so the filtration loss is slightly larger than that of example 3, and in example 4, the effect of the synthesized target product is slightly worse than that of example 3 because the addition amount of the initiator is not in the optimal range; in comparative example 1, the polymerization activity was low due to the absence of acid activation treatment of activated carbon, the content of activated carbon in the final product was low, and the plugging effect was weak; in the comparative example 2, only a small-molecular organic amine monomer is not added, so that the influence on the plugging performance of the plugging inhibitor is small, and the filtration loss is still small; in the comparative example 3, the effect is poor because the double bonds introduced on the surface of C are less due to less added allyl monomers, which affects the subsequent polymerization reaction with acrylic acid; in comparative example 4, since the silica surface is difficult to activate compared with activated carbon, the introduction of double bonds and polymerization reaction on the subsequent surface are affected; in comparative example 5, the effect was poor because the reaction temperature was too high, which decomposed the initiator violently, resulting in broadening and non-uniformity of the molecular weight distribution of the synthesized product.
2. Bentonite tablet linear expansion experiment
And (3) performance testing: the 16h linear expansion amount of the bentonite is tested according to the evaluation method of shale inhibitor for drilling fluid (SY/T6335-1997) of the oil and gas industry standard of the people's republic of China, and the experimental results are shown in Table 2.
TABLE 2 amount of swelling of artificial core wire in different solutions
Note: in Table 2, "%" is a mass volume percent concentration, and for example, a 5% KCl solution is obtained by adding 5g KCl to 100mL water.
As can be seen from Table 2, the swelling amount of bentonite in clear water is large and can reach 12.62 mm. KCl is an inorganic salt inhibitor commonly used in oil fields, can inhibit the swelling of bentonite, and has a swelling capacity of 7.64mm in a 5% KCl solution. Compared with the bentonite in the solution of 1% in different embodiments, the linear swelling amount of the bentonite is greatly reduced, and the swelling inhibition effect is better than that of 5% KCl. The lowest linear expansion amount in example 3 is only 2.36mm, which shows that the prepared plugging inhibitor has excellent inhibition performance and can effectively inhibit hydration expansion of clay. This is due to the large amount of NH contained in the blocking inhibitor molecule 4 + The negative charges on the surface of the clay are neutralized, so that the electrical repulsion force among clay particles is reduced, the clay lattice can be embedded, the clay layer is tensioned, and the swelling of the bentonite is reduced. In comparative example 1, the activated carbon was not activated with nitric acid, so the reactivity was low, and the effect of the synthesized plugging inhibitor was poor; in comparative example 2, no amino group was introduced, so that the synthesized blocking inhibitor did not have the effect of ammonium ion and was poor in effect; in comparative example 3, due to the allyl monomer and HNO 3 The poor proportion of-C makes the subsequent polymerization reaction with acrylic acid less active and thus less effective; in comparative example 4, the silica surface was difficult to activate, making the effect poor; in comparative example 5, the product obtained had poor properties due to the excessively high reaction temperature.
3. Shale rolling recovery experiment
Respectively adding 3.5g of the plugging inhibitor prepared in the embodiment and the comparative example into 350mL of water, adding the obtained plugging inhibitor solution with the mass volume percentage concentration of 1% into an aging tank, adding 20g of weighed 6-10 mesh dry rock debris into the tank, sealing, and then rolling and heating at 150 ℃ for 16 h. After heating, pouring the liquid and the rock debris in the tank into a standard sieve of 40 meshes, washing for 1min by using tap water, drying the sieved rock debris at the temperature of 105 +/-3 ℃ for 4h, and weighing. The quality of the rejects after the rock debris is hot rolled in 350mL of tap water is determined by the method described above. And (3) calculating the rolling recovery rate of rock debris:
in the formula: r: shale recovery (%); m is 1 : initial rock sample mass (g); m is 2 : the mass (g) of the rock sample is recovered from the sample solution. The results of the shale rolling recovery experiments are shown in table 3.
TABLE 3 experimental results on the recovery rate of rock debris
Besides hydration and expansion, the rock also can be hydrated and dispersed when meeting water. The experimental result shows that when the inhibitor is not added, the rock debris is easy to hydrate and disperse in water, and the recovery rate is only 15.3%. In 5% KCl solution, recovery increased only to 22.6%. And the recovery rate of the rock debris in the solution of 1 percent of different examples is higher. In 1% of the plugging inhibitor solution prepared in example 3, the rock debris recovery rate reached more than 90%, because the plugging inhibitor had both the plugging effect of activated carbon particles and NH in the molecule 4 + The inhibition effect of the composition can effectively reduce water from entering the interior of the rock and inhibit the hydration of the rock. In comparative example 1, the active carbon participates in the reaction less, the plugging capability is poor, and the recovery rate is not good; comparative example 2, since there is no NH 4 + The effect is poor, the inhibition effect is poor, and the recovery rate is poor; in comparative example 3, the effect is poor because the addition of the allyl monomer is small, which affects the subsequent polymerization reaction with acrylic acid; in comparative example 4, it is difficult for silica to introduce double bonds on the surface to participate in the polymerization reaction, so that the effect is poor; in comparative example 5, the polymer molecular weight could not be expected due to the excessively high reaction temperature, and thus the effect was poor.
4. Evaluation of compatibility with drilling fluid
Preparing base slurry: adding 16g of bentonite slowly into 400mL of distilled water while stirring, and aging for 24h at room temperature to prepare bentonite-based slurry.
Preparing a drilling fluid sample: respectively taking 400mL of base slurry, adding 4g of different plugging inhibitor products, and stirring for 20min under the condition of 5000r/min to obtain a drilling fluid sample with the mass volume percentage concentration of 1%; and (3) carrying out aging treatment on the base slurry and the drilling fluid sample by using a roller heating furnace, wherein the temperature is 150 ℃, and the time is 16 h.
And (3) performance testing: the drilling fluid samples and base stocks obtained after aging were tested for rheological parameters (apparent viscosity, plastic viscosity) according to the American Petroleum Institute (API) standards (API RP 13B-1,2009) and the effect of the plugging inhibitor on the base stock rheology was evaluated and the results are shown in Table 4.
Table 4 effect of blocking inhibitors on drilling fluid rheology
As can be seen from Table 1, the viscosity of the drilling fluid is slightly increased after the plugging inhibitor prepared in different examples is added, the influence on the rheological property of the drilling fluid is small, and the inhibitor prepared in the examples has good compatibility with the drilling fluid. In comparative example 1, activated carbon was not activated, and more unreacted activated carbon particles remained, causing an increase in viscosity; in comparative example 2, no amino group was introduced, which reduced the inhibitory properties, but had less effect on viscosity; in comparative example 3, the polymer had a small molecular weight due to the small addition of the allyl monomer, and therefore had a small effect on viscosity; in comparative example 4, the silica surface was difficult to activate to introduce allyl monomers to participate in the polymerization reaction, and the unreacted silica increased the viscosity; in comparative example 5, since the reaction temperature was too high, the molecular weight distribution of the polymer was broad, and the influence on the viscosity was large.
Claims (10)
1. A method of preparing a water-based drilling fluid plugging inhibitor for enhancing wellbore integrity, comprising the steps of:
(1) adding active carbon into concentrated nitric acid under the condition of stirring for reaction, and then filtering, washing and drying to obtain HNO 3 Activated carbon;
(2) HNO obtained in the step (1) 3 Adding activated carbon into a sodium hydroxide solution to perform a first reaction; then continuing to add the monomer containing allyl to carry out heat preservation reaction; after the reaction is finished, filtering, washing and drying to obtain allyl end-capped carbon;
(3) adding the allyl end-capped carbon obtained in the step (2) and acrylic acid into deionized water, deoxidizing nitrogen, and adding an initiator aqueous solution to perform polymerization reaction; then adding organic amine solution for reaction; and after the reaction is finished, pouring the obtained reaction liquid into acetone for precipitation, and filtering and drying to obtain the acrylic acid grafted activated carbon, namely the water-based drilling fluid plugging inhibitor for improving the integrity of a shaft.
2. The method of preparing a water-based drilling fluid plugging inhibitor for improving wellbore integrity of claim 1, wherein the concentration of the concentrated nitric acid in step (1) is 37 wt%; the active carbon is coal active carbon, wood active carbon or synthetic material active carbon; the particle size of the active carbon is 1000-1200 meshes; the ratio of the mass of the activated carbon to the volume of the concentrated nitric acid is 5-10 g:100 mL.
3. The preparation method of the water-based drilling fluid plugging inhibitor for improving the integrity of the mineshaft according to the claim 1, wherein the reaction time in the step (1) is 4-6 h; washing is carried out for 3-5 times by using deionized water; the drying is carried out for 20-30 h at the temperature of 100-110 ℃.
4. The preparation method of the water-based drilling fluid plugging inhibitor for improving the integrity of the mineshaft according to the claim 1, wherein the concentration of the sodium hydroxide solution in the step (2) is 0.4-0.5 mol/L; the hydrogen isVolume of sodium oxide solution and HNO 3 The mass ratio of the activated carbon is 100mL: 5-10 g; the temperature of the first reaction is 40-60 ℃; the first reaction time is 8-10 h.
5. The method of claim 1, wherein the allyl-containing monomer of step (2) is allyl chloride or allyl bromide; the allyl-containing monomer and HNO 3 The mass ratio of the activated carbon is 4-10: 1, preferably 5-7: 1;
preferably, in the step (2), after the allyl-containing monomer is added, the reaction is carried out for 12-24 hours in a heat preservation manner; washing is respectively carried out for 3-5 times by using deionized water and ethanol; the drying is carried out for 10-15 h at the temperature of 40-60 ℃.
6. The preparation method of the water-based drilling fluid plugging inhibitor for improving the integrity of the shaft as claimed in claim 1, wherein the mass ratio of the allyl terminated carbon to the acrylic acid in the step (3) is 1: 5-15, preferably 1: 8-12; the mass ratio of the allyl-terminated carbon to the volume of the deionized water is 1.5-4.5 g:100 mL.
7. The method of claim 1, wherein the initiator in step (3) is ammonium persulfate, potassium persulfate, or azodiisobutylamine hydrochloride; the mass of the initiator is 0.5-3% of the total mass of the allyl end-capped carbon and the acrylic acid, and preferably 2-3%; the concentration of the initiator aqueous solution is 0.01-0.05 g/mL; the temperature of the polymerization reaction is 40-65 ℃, and preferably 55-60 ℃; the time of the polymerization reaction is 2-4 h, preferably 2.5-3.5 h, and more preferably 3 h.
8. The method for preparing the water-based drilling fluid plugging inhibitor for improving the integrity of the shaft as claimed in claim 1, wherein the organic amine in the step (3) is ethylenediamine, triethylamine or tetramethylethylenediamine; the mass ratio of the organic amine to the allyl end-capped carbon is 2-8: 1, preferably 3-5: 1; the organic amine solution is obtained by dissolving organic amine in ethanol, and the concentration of the organic amine solution is 0.03-0.15 g/mL; adding an organic amine solution, and reacting for 12-24 hours at room temperature; adding organic amine to react under the protection of nitrogen;
preferably, the volume ratio of the reaction liquid to acetone in the step (3) is 1: 2-5; the drying is vacuum drying for 10-15 h at 35-55 ℃.
9. A water-based drilling fluid plugging inhibitor prepared by the method of claim 1 for use in improving wellbore integrity.
10. Use of the water-based drilling fluid plugging inhibitor of claim 9 for enhancing wellbore integrity in a water-based drilling fluid; preferably, the addition amount of the water-based drilling fluid plugging inhibitor for improving the integrity of a shaft is 10-20 g/L.
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