CN113528100A - Near-well-wall stable polyamine shale inhibitor, and preparation method and application thereof - Google Patents
Near-well-wall stable polyamine shale inhibitor, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a near-wellbore wall stable polyamine shale inhibitor which has a structure shown in a formula (I); wherein m is an integer of 1-10; n is an integer of 0 to 5; 0 is an integer of 0 to 5; r is H or C1-C5 alkyl. Compared with the prior art, the near-wellbore wall stable polyamine shale inhibitor provided by the invention has a better near-wellbore wall stabilizing effect under a high-temperature condition, and simultaneously has better compatibility in drilling fluid.
Description
Technical Field
The invention belongs to the technical field of oilfield chemical drilling fluid treatment agents, and particularly relates to a near-well wall stable polyamine shale inhibitor, and a preparation method and application thereof.
Background
The problem of borehole wall instability in the oil and gas drilling process is always a main factor influencing the smooth drilling construction, and the problem is particularly obvious under the condition that deep wells, ultra-deep wells, horizontal wells, directional wells and highly deviated wells are increasingly increased. According to statistics, more than 90% of borehole instability occurs in shale and shale-containing formations. The borehole wall instability is closely related to the hydration, expansion and dispersion effects of clay minerals, and when the drilling tool encounters a stratum which is easy to collapse such as shale, the addition of an inhibitor into the drilling fluid is one of the most effective ways for solving the borehole wall instability. Therefore, the development of the high-performance mud shale strong inhibitor has great significance for inhibiting the hydration, expansion and dispersion of clay minerals, effectively improving the stability of the well wall, reducing the drilling cost, increasing the economic benefit and promoting safe drilling.
According to research, polyamine products are the organic materials with the strongest inhibition capability and the most extensive application. It is customary to refer to quaternary ammonium products such as small cations and large cations and amine-based polyethers collectively as polyamines. In the past 80 s, quaternary amine products (small cations and large cations) were widely used in drilling fluids, but their cationization degree was high, and their compatibility with anionic treatment agents was poor, so that their application was limited, and in the meantime, people introduced polar groups to reduce the proportion of cationic groups, such as solid phase chemical detergents. At the end of the last 90 s of the century, amino polyethers (epoxy resin curing agents, mature industrial products) were introduced abroad into drilling fluids to form high-performance water-based drilling fluids (HPWBM). The amino polyether is used as a main inhibitor of the high-performance water-based drilling fluid, plays a role in stabilizing a well wall by being embedded into a clay crystal layer, but has few amino adsorption active sites and large addition amount, and has a non-prominent inhibition effect in the drilling fluid, so that the inhibition performance and compatibility of the early-stage product cannot be considered at the same time.
Aiming at the situation, the development of the near-well wall stable polyamine shale inhibitor is developed from the functions of strengthening the inhibitive performance, compatibility and the like of the drilling fluid, so that the adsorption on the surface of solid-phase particles in the drilling fluid is reduced as much as possible, the polymer enters a near-well wall zone along with the filtrate as much as possible, the spacing between crystal layers is tightened, the problem of the instability of the well wall of the strong water-sensitive shale with higher formation temperature and a mud-containing formation is effectively solved, the stability of the well wall of the near-well wall zone is realized, and the polymer composite inhibitor has better economic benefit and social benefit and wide application prospect. At present, no report is found on the research of the near-well wall stable polyamine shale inhibitor.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a near wellbore wall stable polyamine shale inhibitor having good stability effect and compatibility, and a preparation method and an application thereof.
The invention provides a near-wellbore wall stable polyamine shale inhibitor, which has a structure shown in a formula (I):
wherein m is an integer of 1-10; n is an integer of 0 to 5; o is an integer of 0 to 5;
r is H or C1-C5 alkyl.
Preferably, R is H, CH3Or C2H5。
The invention also provides a preparation method of the near-wellbore wall stable polyamine shale inhibitor, which comprises the following steps:
s1) ring-opening polymerization is carried out on the alkylene oxide to obtain polyether alcohol reaction liquid;
s2) mixing the polyether alcohol reaction liquid with a chlorinating agent for chlorination reaction to obtain a chlorinated polyether reaction liquid;
s3) adding an amination reagent into the chlorinated polyether reaction solution, and heating for reaction to obtain the near-well wall stable polyamine shale inhibitor.
Preferably, the step S1) is specifically:
and mixing and heating the epoxy alkane, water and hydroxide to carry out ring-opening polymerization reaction to obtain polyether alcohol reaction liquid.
Preferably, the mass ratio of the alkylene oxide to the water to the hydroxide is 40: (160-200): (2-6); the hydroxide is selected from one or more of sodium hydroxide, potassium hydroxide and calcium hydroxide.
Preferably, the temperature of the ring-opening polymerization reaction is 95-105 ℃; the time of the ring-opening polymerization reaction is 0.5-2 h; the ring-opening polymerization reaction is carried out under the condition of stirring; the stirring speed is 300-900 r/min.
Preferably, the mass ratio of the chlorinating agent to the alkylene oxide is (5-12): 40; the temperature of the chlorination reaction is 60-90 ℃; the time of the chlorination reaction is 2-4 h.
Preferably, the mass ratio of the amination reagent to the alkylene oxide is (70-110): 40; the heating reaction temperature in the step S3) is 85-115 ℃; the heating reaction time is 2-4 h.
Preferably, the alkylene oxide is selected from one or more of ethylene oxide, propylene oxide and butylene oxide; the chlorinating agent is selected from thionyl chloride; the amination reagent is selected from one or more of ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine.
The invention also provides a drilling fluid which comprises the near-well wall stable polyamine shale inhibitor.
The invention provides a near-wellbore wall stable polyamine shale inhibitor which has a structure shown in a formula (I); wherein m is an integer of 1-10; n is an integer of 0 to 5; 0 is an integer of 0 to 5; r is H or C1-C5 alkyl. Compared with the prior art, the near-wellbore wall stable polyamine shale inhibitor provided by the invention has a better near-wellbore wall stabilizing effect under a high-temperature condition, and simultaneously has better compatibility in drilling fluid.
The invention also provides a preparation method of the near-wellbore wall stable polyamine shale inhibitor, which comprises the following steps: s1) ring-opening polymerization is carried out on the alkylene oxide to obtain polyether alcohol reaction liquid; s2) mixing the polyether alcohol reaction liquid with a chlorinating agent for chlorination reaction to obtain a chlorinated polyether reaction liquid; s3) adding an amination reagent into the chlorinated polyether reaction solution, and heating for reaction to obtain the near-well wall stable polyamine shale inhibitor. Compared with the prior art, the method has the advantages of simple process operation, mild reaction conditions, low energy consumption, water as a solvent and no waste water, waste gas and waste residue discharge.
Drawings
FIG. 1 is an infrared spectrum of a near-wellbore wall-stabilized polyamine shale inhibitor obtained in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a near-wellbore wall stable polyamine shale inhibitor, which has a structure shown in a formula (I):
Wherein m is an integer of 1-10; n is an integer of 0 to 5, preferably 0 to 4, i.e., n is 0, 1, 2, 3 or 4 in the present invention; o is an integer of 0 to 5, preferably 0 to 4, i.e., in the present invention o is 0, 1, 2, 3 or 4;
r is H or C1-C5 alkyl, preferably H or C1-C4 alkyl, more preferably H or C1-C3 alkyl, and still more preferably H, CH3Or C2H5。
The near-well wall stable polyamine shale inhibitor provided by the invention has a good near-well wall stabilizing effect under a high temperature condition, and simultaneously has good compatibility in drilling fluid.
The invention also provides a preparation method of the near-borehole wall stable polyamine shale inhibitor, which comprises the following steps: s1) ring-opening polymerization is carried out on the alkylene oxide to obtain polyether alcohol reaction liquid; s2) mixing the polyether alcohol reaction liquid with a chlorinating agent for chlorination reaction to obtain a chlorinated polyether reaction liquid; s3) adding an amination reagent into the chlorinated polyether reaction solution, and heating for reaction to obtain the near-well wall stable polyamine shale inhibitor.
In the present invention, the sources of all raw materials are not particularly limited, and they may be commercially available.
Ring-opening polymerization is carried out on alkylene oxide to obtain polyether alcohol reaction liquid, and preferably, ring-opening polymerization is carried out on alkylene oxide under alkaline condition to obtain polyether alcohol reaction liquid; in the present invention, this step is more preferably embodied as: mixing and heating epoxy alkane, water and hydroxide to carry out ring-opening polymerization reaction to obtain polyether alcohol reaction liquid; the alkylene oxide is preferably C2-C7 alkylene oxide, more preferably C2-C5 alkylene oxide, and still more preferably one or more of ethylene oxide, propylene oxide and butylene oxide; the hydroxide is preferably one or more of sodium hydroxide, potassium hydroxide and calcium hydroxide; the mass ratio of alkylene oxide, water and hydroxide is preferably 40: (160-200): (2-6); in some embodiments provided herein, the alkylene oxide, water and hydroxide are preferably present in a mass ratio of 40: 160: 2; in some embodiments provided herein, the alkylene oxide, water and hydroxide are preferably present in a mass ratio of 40: 170: 3; in some embodiments provided herein, the alkylene oxide, water and hydroxide are preferably present in a mass ratio of 40: 180: 4; in some embodiments provided herein, the alkylene oxide, water and hydroxide are preferably present in a mass ratio of 40: 190: 5; in other embodiments provided herein, the alkylene oxide, water, and hydroxide are preferably present in a mass ratio of 40: 200: 6; the temperature of the ring-opening polymerization reaction is preferably 95-105 ℃; the ring-opening reaction time is preferably 0.5-2 h; in the present invention, the ring-opening reaction is preferably carried out under stirring; the rotating speed of the stirring is preferably 300-900 r/min.
Mixing the polyether alcohol reaction liquid with a chlorinating agent for chlorination reaction to obtain chlorinated polyether reaction liquid; the mass ratio of the chlorinating agent to the alkylene oxide is (5-12): 40; in some embodiments provided herein, the mass ratio of the chlorinating agent to alkylene oxide is preferably 5: 40; in some embodiments provided herein, the mass ratio of the chlorinating agent to alkylene oxide is preferably 7: 40; in some embodiments provided herein, the mass ratio of the chlorinating agent to alkylene oxide is preferably 8: 40; in some embodiments provided herein, the mass ratio of the chlorinating agent to alkylene oxide is preferably 10: 40; in other embodiments provided herein, the mass ratio of the chlorinating agent to alkylene oxide is preferably 12: 40; the chlorinating agent is preferably thionyl chloride; the temperature of the chlorination reaction is preferably 60-90 ℃; the time of the chlorination reaction is preferably 2-4 h; after the chlorination reaction, the temperature is preferably reduced to room temperature, and a chlorinated polyether reaction solution is obtained.
Adding an amination reagent into the chlorinated polyether reaction solution, and heating for reaction; the mass ratio of the amination reagent to the alkylene oxide is preferably (70-110): 40; in some embodiments provided herein, the mass ratio of the aminating agent to alkylene oxide is preferably 70: 40; in some embodiments provided herein, the mass ratio of the aminating agent to alkylene oxide is preferably 80: 40; in some embodiments provided herein, the mass ratio of the aminating agent to alkylene oxide is preferably 90: 40; in some embodiments provided herein, the mass ratio of the aminating agent to alkylene oxide is preferably 100: 40; in some embodiments provided herein, the mass ratio of the aminating agent to alkylene oxide is preferably 110: 40; the amination reagent is preferably one or more of ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine; the temperature of the heating reaction is preferably 85-115 ℃; the heating reaction time is preferably 2-4 h.
After the heating reaction, the temperature is preferably reduced to room temperature, and a yellow brown viscous transparent liquid, namely the near-well wall stable polyamine shale inhibitor, is obtained.
The invention adopts epoxide, hydroxide, thionyl chloride and amination reagent as raw materials to prepare near-wellbore wall stable polyamine, the process operation is simple, the reaction condition is mild, the energy consumption is low, water is used as solvent, no waste water, waste gas and waste residue are discharged, and the synthesized product is a high-temperature resistant shale inhibitor with excellent near-wellbore wall stable effect; meanwhile, the near-well wall stable polyamine has better compatibility in the drilling fluid. The near-wellbore wall stable polyamine prepared by the invention can effectively solve the problem of wellbore instability of the shale with high formation temperature and strong water sensitivity and the shale-containing formation by embedding the crystal layer, thereby realizing the wellbore wall stability of the near-wellbore wall zone.
The invention also provides a drilling fluid which comprises the near-well wall stable polyamine shale inhibitor.
To further illustrate the present invention, a near-wellbore wall-stabilized polyamine shale inhibitor, a preparation method and applications thereof provided by the present invention are described in detail below with reference to examples.
The reagents used in the following examples are all commercially available.
Example 1
Adding 40g of ethylene oxide, 160g of water and 2g of sodium hydroxide into a reaction kettle, controlling the stirring speed to be 300r/min, and reacting at the temperature of 95 ℃ for 0.5h to obtain polyether alcohol reaction liquid; adding 5g of thionyl chloride into the polyether alcohol reaction solution, reacting at the temperature of 60 ℃ for 2h, and cooling to room temperature to obtain a chlorinated polyether reaction solution; and adding 70g of ethylenediamine into the chlorinated polyether reaction solution, keeping the reaction temperature at 85 ℃, reacting for 2h, and cooling to room temperature to obtain a yellow brown viscous transparent liquid, namely the near-well wall stable polyamine shale inhibitor. The product yield was 90.17%.
The near-wellbore wall stable polyamine prepared in example 1 of the present invention has a structure represented by formula 1:
in the formula 1, m is 1-10, n is 0, o is 0, and R is H.
The near-wellbore wall stable polyamine shale inhibitor obtained in example 1 is detected by infrared spectroscopy, and an infrared spectrogram is shown in fig. 1.
Example 2
Adding 40g of propylene oxide, 170g of water and 3g of potassium hydroxide into a reaction kettle, controlling the stirring speed to be 400r/min, and reacting at the temperature of 97 ℃ for 1.0h to obtain polyether alcohol reaction liquid; adding 7g of thionyl chloride into the polyether alcohol reaction solution, reacting for 3 hours at the temperature of 70 ℃, and cooling to room temperature to obtain a chlorinated polyether reaction solution; and adding 80g of diethylenetriamine into the chlorinated polyether reaction solution, keeping the reaction temperature at 90 ℃, reacting for 3h, and cooling to room temperature to obtain a yellow brown viscous transparent liquid, namely the near-well wall stable polyamine shale inhibitor. The product yield was 92.80%.
The near-wellbore wall stable polyamine prepared in example 2 of the present invention has a structure represented by formula 2:
in the formula 2, m is 1-10, n is 1, o is 1, R is CH3。
Example 3
Adding 40g of epoxy butane, 180g of water and 4g of sodium hydroxide into a reaction kettle, controlling the stirring speed to be 600r/min, and reacting at the temperature of 100 ℃ for 1.5h to obtain polyether alcohol reaction liquid; adding 8g of thionyl chloride into the polyether alcohol reaction solution, reacting at the temperature of 80 ℃ for 4 hours, and cooling to room temperature to obtain a chlorinated polyether reaction solution; and adding 90g of triethylene tetramine into the chlorinated polyether reaction solution, keeping the reaction temperature at 100 ℃, reacting for 4 hours, and cooling to room temperature to obtain a yellow brown viscous transparent liquid, namely the near-well wall stable polyamine shale inhibitor. The product yield was 92.44%.
The near-wellbore wall stable polyamine prepared in example 3 of the present invention has a structure represented by formula 3:
in the formula 3, m is 1-10, n is 2, o is 2, R is C2H5。
Example 4
Adding 40g of propylene oxide, 190g of water and 5g of potassium hydroxide into a reaction kettle, controlling the stirring speed to be 800r/min, and reacting at 105 ℃ for 2h to obtain polyether alcohol reaction liquid; adding 10g of thionyl chloride into the polyether alcohol reaction solution, reacting for 4 hours at the temperature of 90 ℃, and cooling to room temperature to obtain a chlorinated polyether reaction solution; and adding 100g of tetraethylenepentamine into the chlorinated polyether reaction solution, keeping the reaction temperature at 110 ℃, reacting for 4 hours, and cooling to room temperature to obtain a yellow brown viscous transparent liquid, namely the near-well wall stable polyamine shale inhibitor. The product yield was 93.98%.
The near-wellbore wall stable polyamine prepared in example 4 of the present invention has a structure represented by formula 4:
in the formula 4, m is 1-10, n is 3, o is 3, R is CH3。
Example 5
Adding 40g of propylene oxide, 200g of water and 6g of calcium hydroxide into a reaction kettle, controlling the stirring speed to be 900r/min, and reacting at 105 ℃ for 2h to obtain polyether alcohol reaction liquid; adding 12g of thionyl chloride into the polyether alcohol reaction solution, reacting for 4 hours at the temperature of 90 ℃, and cooling to room temperature to obtain a chlorinated polyether reaction solution; adding 110g of pentaethylenehexamine into the chlorinated polyether reaction solution, keeping the reaction temperature at 115 ℃, reacting for 4h, and cooling to room temperature to obtain a yellow brown viscous transparent liquid, namely the near-well wall stable polyamine shale inhibitor. The product yield was 94.59%.
The near-wellbore wall-stabilized polyamine prepared in example 5 of the present invention has a structure represented by formula 5:
in the formula 5, m is 1-10, n is 4, o is 4, R is CH3。
The near-well wall stable polyamine prepared in the embodiments 1-5 of the invention is hot rolled for 16h at 200 ℃ in 4% soil slurry (the mass of the near-well wall stable polyamine is 0.5% of the mass of the soil slurry), and the apparent viscosity AV and the filtration loss FL are tested, and the results are shown in Table 1; in 10% of the calcareous soil-based slurry (the mass of the near-well wall stable polyamine is 0.5% of the mass of the calcareous soil-based slurry), the relative inhibition rate is tested by hot rolling for 16h at 200 ℃, and the result is shown in table 2.
According to GB/T16783.1-2014, oil and gas industry drilling fluid field test part 1: and (4) testing the apparent viscosity and the filtration loss of the drilling fluid composition according to the standard of water-based drilling fluid.
The relative inhibition rate of the near-borehole wall stable polyamine on the calcareous soil-based slurry is evaluated according to the following method, and the specific method comprises the following steps: taking 350mL of distilled water, adding 0.5% of sodium carbonate, adding 10% of calcium bentonite after dissolution, stirring at a high speed for 20min, rolling at 200 ℃ for 16h, cooling and taking out to obtain calcium-soil-based slurry, stirring at a high speed for 5min, and measuring the 100r/min reading of the calcium-soil-based slurry as phi by using a six-speed rotational viscometer; adding 0.5% of sodium carbonate and 0.5% of near-wellbore wall stable polyamine sample into 350mL of distilled water, fully dissolving, adding 10% of calcium bentonite, stirring at high speed for 20min, rolling at 200 ℃ for 16h, cooling, taking out, stirring at high speed for 5min, and measuring the reading phi of 100r/min of the calcium soil base slurry added with near-wellbore wall stable polyamine by using a six-speed rotational viscometer1The relative inhibition of the near-wellbore wall-stabilized polyamine product to the calcareous soil is calculated according to the following formula:
in the formula:
b-relative inhibition ratio of near wellbore wall stabilized polyamine to calcareous soil based slurry,%;
the reading is stabilized when the rotational speed of the rotational viscometer of the phi-calcareous soil base slurry is 100 r/min;
Ф1And (4) stably reading when the rotational speed of the rotational viscometer of the calcareous soil-based slurry added with the near-borehole wall stable polyamine is 100 r/min.
TABLE 1 results of testing the rheology of 4% slurry on near-wellbore wall-stabilized polyamine samples
TABLE 2 results of relative inhibition of the near wellbore wall stabilized polyamine samples to the lime soil based slurries
The data in the table 1 show that after aging at 200 ℃ for 16h, the influence of a 0.5% near-well wall stable polyamine sample on the apparent viscosity of 4% soil slurry is small, and the change value of the apparent viscosity is less than or equal to 1.0 mPa.s; the near-well wall stable polyamine sample of 0.5 percent can reduce the filtration loss of 4 percent of soil slurry, and the filtration loss is reduced from 33.6mL of 4 percent of soil slurry to less than or equal to 32.6 mL; the close borehole wall stable polyamine shows better compatibility with the soil slurry.
As can be seen from the data in Table 2, after aging at 200 ℃ for 16h, the relative inhibition rate of 0.5% of the near-wellbore wall-stabilized polyamine sample on the calcareous soil-based slurry is more than or equal to 98.55%, the near-wellbore wall-stabilized polyamine shows excellent performance of inhibiting hydration, expansion and dispersion of clay, and the inhibition and anti-collapse effects on shale are outstanding.
Claims (10)
2. The near-wellbore wall-stabilized polyamine shale inhibitor of claim 1, wherein R is H, CH3Or C2H5。
3. A method of preparing a near-wellbore wall-stabilized polyamine shale inhibitor, comprising:
s1) ring-opening polymerization is carried out on the alkylene oxide to obtain polyether alcohol reaction liquid;
s2) mixing the polyether alcohol reaction liquid with a chlorinating agent for chlorination reaction to obtain a chlorinated polyether reaction liquid;
s3) adding an amination reagent into the chlorinated polyether reaction solution, and heating for reaction to obtain the near-well wall stable polyamine shale inhibitor.
4. The preparation method according to claim 3, wherein the step S1) is specifically:
and mixing and heating the epoxy alkane, water and hydroxide to carry out ring-opening polymerization reaction to obtain polyether alcohol reaction liquid.
5. The method according to claim 4, wherein the mass ratio of the alkylene oxide to the water to the hydroxide is 40: (160-200): (2-6); the hydroxide is selected from one or more of sodium hydroxide, potassium hydroxide and calcium hydroxide.
6. The production method according to claim 3, wherein the temperature of the ring-opening polymerization reaction is 95 ℃ to 105 ℃; the time of the ring-opening polymerization reaction is 0.5-2 h; the ring-opening polymerization reaction is carried out under the condition of stirring; the stirring speed is 300-900 r/min.
7. The preparation method according to claim 3, wherein the mass ratio of the chlorinating agent to the alkylene oxide is (5-12): 40; the temperature of the chlorination reaction is 60-90 ℃; the time of the chlorination reaction is 2-4 h.
8. The preparation method according to claim 3, wherein the mass ratio of the amination reagent to the alkylene oxide is (70-110): 40; the heating reaction temperature in the step S3) is 85-115 ℃; the heating reaction time is 2-4 h.
9. The method according to claim 3, wherein the alkylene oxide is selected from one or more of ethylene oxide, propylene oxide and butylene oxide; the chlorinating agent is selected from thionyl chloride; the amination reagent is selected from one or more of ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine.
10. A drilling fluid comprising the near-wellbore wall-stabilized polyamine shale inhibitor of any one of claims 1-2 or the near-wellbore wall-stabilized polyamine shale inhibitor prepared by the preparation method of any one of claims 3-9.
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Citations (5)
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US20020092681A1 (en) * | 2000-02-11 | 2002-07-18 | Patel Arvind D. | Shale hydration inhibition agent and method of use |
US20030155157A1 (en) * | 2002-01-31 | 2003-08-21 | Patel Arvind D. | High performance water based drilling mud and method of use |
CN104650832A (en) * | 2013-11-21 | 2015-05-27 | 中国石油大学(华东) | Strong-inhibition and strong-blockage aluminum-based anti-collapse water-based drilling fluid |
CN106432708A (en) * | 2015-08-10 | 2017-02-22 | 中石化石油工程技术服务有限公司 | Multi-branched polyether amine, preparation method and applications thereof |
CN109694473A (en) * | 2017-10-23 | 2019-04-30 | 中石化石油工程技术服务有限公司 | A kind of drilling fluid polyetheramine shale inhibitor and preparation method thereof and drilling fluid |
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2020
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US20020092681A1 (en) * | 2000-02-11 | 2002-07-18 | Patel Arvind D. | Shale hydration inhibition agent and method of use |
US20030155157A1 (en) * | 2002-01-31 | 2003-08-21 | Patel Arvind D. | High performance water based drilling mud and method of use |
CN104650832A (en) * | 2013-11-21 | 2015-05-27 | 中国石油大学(华东) | Strong-inhibition and strong-blockage aluminum-based anti-collapse water-based drilling fluid |
CN106432708A (en) * | 2015-08-10 | 2017-02-22 | 中石化石油工程技术服务有限公司 | Multi-branched polyether amine, preparation method and applications thereof |
CN109694473A (en) * | 2017-10-23 | 2019-04-30 | 中石化石油工程技术服务有限公司 | A kind of drilling fluid polyetheramine shale inhibitor and preparation method thereof and drilling fluid |
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