CN116063998A - Aluminum-based plugging anti-collapse agent and preparation method and application thereof - Google Patents

Aluminum-based plugging anti-collapse agent and preparation method and application thereof Download PDF

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Publication number
CN116063998A
CN116063998A CN202210804887.4A CN202210804887A CN116063998A CN 116063998 A CN116063998 A CN 116063998A CN 202210804887 A CN202210804887 A CN 202210804887A CN 116063998 A CN116063998 A CN 116063998A
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aluminum
plugging
collapse
agent
drilling fluid
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Inventor
王晓军
尹家峰
巩永丰
李晴
景烨琦
孙云超
韩龙
高清春
李晨光
步文洋
许佳
杨超
任艳
王西贵
洪伟
王丽君
张颖苹
闻丽
刘宏宇
戴运才
佟志刚
吕楠
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China National Petroleum Corp
CNPC Great Wall Drilling Co
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China National Petroleum Corp
CNPC Great Wall Drilling Co
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02Well-drilling compositions
    • C09K8/03Specific additives for general use in well-drilling compositions
    • C09K8/035Organic additives
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/42Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • C09K8/426Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells for plugging
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/12Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/34Lubricant additives

Abstract

The invention provides an aluminum-based plugging anti-collapse agent, a preparation method and application thereof, wherein the aluminum-based plugging anti-collapse agent comprises aluminum fulvate, and Al is utilized 3+ Al (OH) is formed after pH change 3 The precipitation can realize effective intelligent plugging of micro-cracks with different dimensions, and the traditional plugging mode that the particle size of the plugging agent is strictly matched with the size of the cracks is overturned, so that the water-based drilling fluid containing the plugging agent is not limited by complex stratum any more, and the self-matching plugging anti-collapse agent with excellent performance is provided. The aluminum-based plugging anti-collapse agent can effectively control the shale to be subjected to osmotic hydration, has good oxidation resistance and lubricity, ensures that the water-based drilling fluid containing the aluminum-based plugging anti-collapse agent has good plugging performance, temperature resistance and lubricity, and is beneficial to reducing the comprehensive cost of drilling and environmental protection pressure.

Description

Aluminum-based plugging anti-collapse agent and preparation method and application thereof
Technical Field
The invention belongs to the technical field of drilling fluid treatment agents, and particularly relates to an aluminum-based plugging anti-collapse agent, and a preparation method and application thereof.
Background
Along with the rapid development of oil and gas exploration technology and the continuous acceleration of development progress, exploration and development emphasis has been put into deep and ultra-deep development from the middle and shallow layers. The deep shale has the advantages that the deep shale is influenced by deep complex geological structure movement and a deposition environment, and the deep shale has the characteristics of hard and brittle bedding cracks, so that serious well instability problems exist in the well drilling process, and a series of complex underground conditions and accidents are brought. Thus, maintaining borehole wall stability is an important aspect of drilling operations. At present, oil-based drilling fluid generally has pollution problems, and oil-based drilling cuttings are difficult to treat and have high use cost. Compared with oil-based drilling fluid, the water-based drilling fluid has the advantages of small pollution and low cost; however, the water-based drilling fluid has weak anti-collapse performance, and thus, enhancement of the anti-collapse performance is an important research content for development of the water-based drilling fluid.
CN104263330a discloses a water-based drilling fluid and a preparation method thereof, the raw materials of the drilling fluid comprise the following components in percentage by mass: 40-60% of sodium bentonite, 10-20% of emulsified paraffin for drilling fluid, 10-20% of zwitterionic polymer strong coating agent for drilling fluid, 10-20% of anti-collapse filtrate reducer for drilling fluid, 10-20% of zwitterionic polymer viscosity reducer and 1000% of water. Compared with the existing similar products, the water-based drilling fluid has better hydration inhibition effect, effective plugging of microcracks, greatly reduced lost circulation probability, low pollution degree to stratum and high safety.
CN109294531a discloses a composite asphalt anti-collapse inhibitor of water-based drilling fluid and water-based drilling fluid, wherein the composite asphalt anti-collapse inhibitor comprises the following raw materials in parts by weight: 60-80 parts of natural asphalt, 2-5 parts of sodium dodecyl benzene sulfonate, 1-3 parts of ethylene-ethyl acrylate, 5-10 parts of surfactant, 5-15 parts of carbon fiber, 1-3 parts of zinc stearate, 1-3 parts of calcium stearate and 10-20 parts of limestone powder; the formula of the water-based drilling fluid containing the water-based drilling fluid is as follows: 1-5 parts of montmorillonite, 100-200 parts of water, 20-50 parts of barite, 1-5 parts of polyethylene glycol and 5-20 parts of a composite asphalt anti-collapse inhibitor. The water-based drilling fluid can obtain good collapse prevention and lubricating capacity, and the preparation method is simple and convenient for production.
CN110628398A discloses a water-based drilling fluid for shale gas wells and a production method thereof, wherein the raw materials comprise the following components: 1000 parts of water, 45-50 parts of sodium bentonite, 500 parts of water-soluble weighting inhibitor II, 100 parts of water-soluble weighting inhibitor III, 15-20 parts of non-fluorescent white asphalt of an anti-collapse agent, 10-20 parts of solid polymeric alcohol, 10-20 parts of filtrate reducer, 0.5-1 part of polyamine inhibitor, 20-30 parts of superfine calcium carbonate, 10-25 parts of extreme pressure lubricant and 0.5-1 part of coating inhibitor; the water-based drilling fluid has higher plugging property, inhibition property and lubricity, and can meet the safety drilling requirement of a shale gas horizontal well.
In general, in the water-based drilling fluid commonly used in the prior drilling engineering, commonly used plugging treatment agents comprise asphalt and emulsified paraffin, the particle size of the materials is larger, the plugging effect on stratum with larger crack gap size is better, but effective size matching with micro-nano-scale cracks cannot be formed, and a good inner mud cake cannot be formed, so that effective plugging of micro-crack stratum is difficult to realize. In addition, researchers also try to synthesize polymer materials as plugging treatment agents for micro-nano cracks, but most water-based treatment agents are easy to thermally degrade and desorb in a high-temperature environment, and the changes are irreversible, so the thermal stability and the oxidation stability of the water-based drilling fluid are also key factors for limiting the success or failure of deep well ultra-deep well drilling. Therefore, the research on the water-based drilling fluid treating agent and the drilling fluid system which are resistant to high temperature and have excellent anti-collapse effect has important significance in accelerating the exploration and development of deep stratum resources.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the aluminum-based plugging anti-collapse agent, and the preparation method and the application thereof, wherein the aluminum-based plugging anti-collapse agent not only can realize intelligent plugging of cracks with different sizes, but also has excellent temperature resistance and lubricating property, so that the water-based drilling fluid containing the aluminum-based plugging anti-collapse agent is not limited by complex stratum any more, and is beneficial to reducing the comprehensive drilling cost and environmental protection pressure.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an aluminum-based plugging and collapse preventing agent, which comprises aluminum fulvate.
Research shows that the well wall instability mechanism of deep shale is mainly due to the development of micro-nano cracks of rock, the micro cracks can rapidly spread under the action of drilling hydraulic pressure difference, and water phase can invade into the stratum along the micro cracks. On one hand, the water phase entering the shale causes hydration expansion of clay minerals, generates hydration stress, and reduces the cementing strength of the shale; on the other hand, the pore pressure of the stratum is continuously increased, the effective supporting stress of the well bore is continuously reduced, and finally rock damage is caused, so that scattered stripping and block falling are caused. Therefore, the anti-collapse performance of the water-based drilling fluid is improved, the plugging performance of the system to the micro-nano hole seam is required to be improved, and the inhibition performance is enhanced. The shale stratum is mostly a non-reservoir stratum, the coring probability is low, and even if the coring operation is performed, the microstructure of the core hole seam of the deep stratum which is taken to the ground is changed greatly due to the change of temperature and pressure; moreover, formation rock microcracks vary in terms of both seam width and extent of expansion, so that the particle size of the plugging agent is difficult to match closely with shale microcracks.
The aluminum-based plugging anti-collapse agent provided by the invention comprises aluminum fulvate, wherein aluminum ions Al 3+ Under alkaline condition with pH value higher than 8, the aluminum metasilicate AlO is mainly used 2 - In the form of aluminum hydroxide Al (OH) in the pH range of 6-8 3 The precipitate exists in a form; after the aluminum-based plugging anti-collapse agent enters a stratum, al (OH) can be generated due to the change of acid-base values 3 Precipitation, the transition is from ion to solid, namely, the drilling fluid containing the aluminum-based plugging anti-collapse agent enters into the formation cracks, intelligent plugging of the micro cracks is realized, and the traditional plugging mode that the particle size of the plugging agent is strictly matched with the size of the cracks is overturned, so that the cracks with different sizes are subjected toComprehensive and effective intelligent plugging. Meanwhile, the fulvic acid radical in the fulvic acid aluminum is used as organic acid, so that the activity is low, and the shale can be well controlled to be subjected to osmotic hydration; meanwhile, the anti-oxidation and lubricating performance of the system is good, the temperature resistance and the lubricating performance of the system can be improved, and the corrosion and the abrasion to drilling tools are reduced.
In conclusion, the aluminum-based plugging anti-collapse agent provided by the invention takes aluminum fulvate as an active ingredient, and utilizes Al on one hand 3+ After the pH value is changed, aluminum hydroxide precipitate is generated, intelligent plugging of microcracks with different dimensions can be realized, and the self-matching plugging anti-collapse agent is effective; on the other hand, the aluminum-based plugging anti-collapse agent can better control the shale to generate osmotic hydration, has good oxidation resistance and lubricating property, so that the water-based drilling fluid containing the aluminum-based plugging anti-collapse agent has good plugging property, temperature resistance and lubricating property, is not limited by complex stratum any more, and is beneficial to reducing the comprehensive cost of drilling and environmental protection pressure.
Preferably, the aluminum fulvate is obtained by reacting fulvic acid with an aluminium-containing compound.
Preferably, the fulvic acid is of mineral origin, more preferably weathered coal fulvic acid.
As a preferable technical scheme of the invention, the aluminum fulvate is obtained by reacting fulvic acid with aluminum-containing compounds, and the fulvic acid has good physiological activity, absorption, complexation, exchange and other functions, has low molecular weight, high activity and good water solubility, and can react with various aluminum-containing compounds to generate the aluminum fulvate.
Preferably, the aluminum-containing compound is aluminum oxide and/or an aluminum salt.
Preferably, the aluminum-containing compound comprises any one or a combination of at least two of aluminum oxide, aluminum chloride or aluminum sulfate.
Preferably, the fulvic acid is prepared by a process comprising: mixing the weathered coal with an acetone solution, adding sulfuric acid into the mixture to react, and precipitating to obtain supernatant containing fulvic acid.
Preferably, the particle size of the weathered coal is 40 to 60 mesh, for example, 45 mesh, 50 mesh, 55 mesh, or the like.
Preferably, the acetone solution is an aqueous solution of acetone.
Preferably, the acetone content of the acetone solution is 80-90% by mass, for example, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89% or 90%, and the specific point values between the above point values are limited in space and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.
Preferably, the mass of the weathered coal is 10 to 50%, for example, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45% or 48%, and specific point values between the above point values, based on 100% of the mass of the acetone solution, are limited in terms of length and for brevity, the present invention is not exhaustive of the specific point values included in the range, and more preferably 20 to 40%.
Preferably, the sulfuric acid is used in an amount such that the pH of the system is 3 to 3.5, e.g., 3.05, 3.1, 3.15, 3.2, 3.25, 3.3, 3.35, 3.4, or 3.45, and specific point values between the above points, are limited in scope and for brevity the present invention is not intended to be exhaustive.
Preferably, the concentration of sulfuric acid is 0.1 to 0.25mol/L, for example, 0.11mol/L, 0.13mol/L, 0.15mol/L, 0.17mol/L, 0.19mol/L, 0.2mol/L, 0.22mol/L or 0.24mol/L, and specific point values between the above point values, are not exhaustive and for the sake of brevity.
Preferably, the reaction time is 1 to 5 hours, for example, 1.25 hours, 1.5 hours, 1.75 hours, 2 hours, 2.25 hours, 2.5 hours, 2.75 hours, 3 hours, 3.25 hours, 3.5 hours, 3.75 hours, 4 hours, 4.25 hours, 4.5 hours or 4.75 hours, and specific point values between the above point values, are limited in length and for brevity, the present invention is not exhaustive of the specific point values included in the range, and more preferably 2.5 to 4 hours.
Preferably, the time of the precipitation is 4-10h, for example, may be 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h or 9.5h, and specific point values between the above point values, are limited in length and for brevity, the present invention is not exhaustive to list the specific point values included in the range, and further preferably 6-8h.
Preferably, the supernatant is dried (desolvation) to obtain the fulvic acid.
Preferably, the drying time is 8-10h, for example, 8.25h, 8.5h, 8.75h, 9h, 9.25h, 9.5h or 9.75h, and specific point values between the above point values, are limited in space and for brevity, the present invention is not exhaustive of the specific point values included in the range.
In a second aspect, the present invention provides a method for preparing the aluminum-based plugging anti-collapse agent according to the first aspect, the method comprising: and (3) reacting fulvic acid with an aluminum-containing compound to obtain the aluminum-based plugging anti-collapse agent.
Preferably, the molar ratio of fulvic acid to aluminium in the aluminium-containing compound is (2-5): 1, for example it may be 2.2:1, 2.5:1, 2.8:1, 3:1, 3.2:1, 3.5:1, 3.8:1, 4:1, 4.2:1, 4.5:1 or 4.8:1 etc., further preferably (2.5-3.5): 1.
Preferably, the reaction is carried out in the presence of a solvent, preferably water.
The amount of the solvent used in the present invention is not particularly limited, and a person skilled in the art may add the solvent according to actual needs to dissolve and sufficiently contact the raw materials for the reaction.
Preferably, the temperature of the reaction is 50-70 ℃, for example, it may be 51 ℃, 53 ℃, 55 ℃, 57 ℃, 59 ℃, 60 ℃, 61 ℃, 63 ℃, 65 ℃, 67 ℃ or 69 ℃, and specific point values between the above point values, are limited in space and for the sake of brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the reaction time is 0.5-3h, for example, 0.75h, 1h, 1.25h, 1.5h, 1.75h, 2h, 2.25h, 2.5h or 2.75h, and specific point values between the above point values, are limited in length and for brevity, the invention is not intended to be exhaustive of the specific point values included in the range.
Preferably, the pH of the reaction is < 7, e.g., pH 6.8, 6.5, 6.2, 6, 5.8, 5.5, 5.2, 5, 4.8, 4.5, 4.2 or 4, etc.
Preferably, the preparation method comprises the following steps:
(1) Mixing weathered coal with an acetone solution, adding sulfuric acid into the mixture under stirring until the pH value of the system is 3-3.5 for reaction, and drying supernatant after precipitation to obtain fulvic acid;
(2) And (3) reacting the fulvic acid obtained in the step (1) with an aluminum-containing compound for 0.5-3 hours under the conditions that the pH value is less than 7 and the temperature is 50-70 ℃ to generate aluminum fulvate, thereby obtaining the aluminum-based plugging collapse preventing agent.
In a third aspect, the invention provides an application of the aluminum-based plugging anti-collapse agent in drilling fluid.
In a fourth aspect, the present invention provides a water-based drilling fluid comprising the aluminium-based plugging anti-collapse agent according to the first aspect.
Preferably, the mass percentage of the aluminum-based plugging anti-collapse agent in the water-based drilling fluid is 0.1-3%, for example, 0.2%, 0.3%, 0.5%, 0.7%, 0.9%, 1%, 1.1%, 1.3%, 1.5%, 1.7%, 1.9%, 2%, 2.2%, 2.5%, 2.7%, 2.9%, and specific point values between the above point values, and the present invention is not limited to the specific point values included in the range, and more preferably 0.5-1.5% for the sake of brevity and brevity.
Preferably, the water-based drilling fluid comprises a fresh water drilling fluid or a brine drilling fluid.
Compared with the prior art, the invention has the following beneficial effects:
(1) The aluminum-based plugging collapse preventing agent provided by the invention takes aluminum fulvate as an active ingredient and utilizes Al 3+ Al (OH) is formed after pH change 3 Precipitation can realize effective intelligent plugging of microcracks with different dimensions, and the traditional plugging mode that the particle size of plugging agent is strictly matched with the size of the crack is overturned, so that the water-based drilling fluid containing the plugging agent is not limited by complex stratum any more, and the plugging agent is a type of plugging agentThe self-matching plugging anti-collapse agent with excellent performance.
(2) The aluminum-based plugging anti-collapse agent can effectively control the shale to be subjected to osmotic hydration, has good oxidation resistance and lubricity, ensures that the water-based drilling fluid containing the aluminum-based plugging anti-collapse agent has good plugging performance, temperature resistance and lubricity, and is beneficial to reducing the comprehensive cost of drilling and environmental protection pressure.
(2) The aluminum-based plugging anti-collapse agent has good compatibility with various water-based drilling fluid systems, the filtration loss of the water-based drilling fluid containing the aluminum-based plugging anti-collapse agent is reduced, the water-based drilling fluid has excellent plugging performance, the performance of resisting shale pressure transmission at 180 ℃ is remarkable, the time required for transmitting 1MPa pressure difference is prolonged by more than 5.5 times compared with that of a blank rock sample, the permeability of the blank shale is reduced by more than 5 times after the effect of the aluminum-based plugging anti-collapse agent, the recovery rate of rock debris is obviously improved, and the effect of controlling mudstone hydration dispersion is good.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
An aluminum-based plugging anti-collapse agent and a preparation method thereof are provided, wherein the aluminum-based plugging anti-collapse agent is aluminum fulvate, and the preparation method specifically comprises the following steps:
(1) Adding 30% (calculated by the mass of the acetone solution) of weathered coal into a system by taking an acetone solution (acetone aqueous solution) with the mass percent of acetone as a solvent, gradually adding concentrated sulfuric acid with the concentration of 0.2mol/L to a pH value of 3.2 under a stirring state for reaction, reacting for 2 hours, naturally precipitating for 6 hours after the reaction is completed, transferring clear supernatant into an evaporating dish, putting the evaporating dish into an oven, fully drying and crushing to obtain reddish brown powdery substances, namely fulvic acid;
(2) The fulvic acid obtained in the step (1) is mixed with alumina (Al 2 O 3 ) Mixing at a molar ratio of 6:1, dissolving in water, reacting for 1h at a pH value of 4 and a temperature of 50 ℃ to generate aluminum fulvate, and obtaining brownish red viscous liquid which is the aluminum-based plugging prevention agentAnd (3) a collapsing agent.
Example 2
An aluminum-based plugging anti-collapse agent and a preparation method thereof are provided, wherein the aluminum-based plugging anti-collapse agent is aluminum fulvate, and the preparation method specifically comprises the following steps:
(1) Adding 30 percent (calculated by the mass of the acetone solution) of weathered coal into a system by taking an acetone solution (acetone aqueous solution) with the mass percent of acetone as a solvent, gradually adding sulfuric acid with the concentration of 0.25mol/L to a pH value of 3.5 under a stirring state for reaction, reacting for 2.5 hours, naturally precipitating for 8 hours after the reaction is completed, transferring clear supernatant into an evaporation dish, putting the evaporation dish into an oven, fully drying and crushing to obtain reddish brown powdery substances, namely fulvic acid;
(2) The fulvic acid obtained in the step (1) is mixed with alumina (Al 2 O 3 ) Mixing at a molar ratio of 6:1, dissolving in water, reacting for 2 hours at a pH value of 5 and a temperature of 60 ℃ to generate aluminum fulvate, and obtaining brownish red viscous liquid which is the aluminum-based plugging anti-collapse agent.
Example 3
An aluminum-based plugging anti-collapse agent and a preparation method thereof are provided, wherein the aluminum-based plugging anti-collapse agent is aluminum fulvate, and the preparation method specifically comprises the following steps:
(1) Adding 30 percent (calculated by the mass of the acetone solution) of weathered coal into a system by taking an acetone solution (acetone aqueous solution) with the mass percent of acetone as a solvent, gradually adding sulfuric acid with the concentration of 0.15mol/L to a pH value of 3 under a stirring state for reaction for 3 hours, naturally precipitating for 7 hours after the reaction is completed, transferring clear supernatant into an evaporation dish, putting the evaporation dish into an oven, fully drying and crushing to obtain reddish brown powdery substances, namely fulvic acid;
(2) The fulvic acid obtained in the step (1) is mixed with alumina (Al 2 O 3 ) Mixing at a molar ratio of 6:1, dissolving in water, reacting for 2 hours at a pH value of 6 and a temperature of 70 ℃ to generate aluminum fulvate, and obtaining brownish red viscous liquid which is the aluminum-based plugging anti-collapse agent.
Example 4
An aluminum-based plugging anti-collapse agent and a preparation method thereof are provided, wherein the aluminum-based plugging anti-collapse agent is aluminum fulvate, and the preparation method specifically comprises the following steps:
fulvic acid (prepared in the same manner as in example 1) was reacted with aluminum chloride (AlCl) 3 ) Mixing the materials according to a molar ratio of 3:1, dissolving the mixture in water, and reacting the mixture for 1h at the pH value of 4 and the temperature of 50 ℃ to generate the yellow aluminum humate, thus obtaining the brownish red viscous liquid which is the aluminum-based plugging anti-collapse agent.
Example 5
An aluminum-based plugging anti-collapse agent and a preparation method thereof are provided, wherein the aluminum-based plugging anti-collapse agent is aluminum fulvate, and the preparation method specifically comprises the following steps:
fulvic acid (prepared in the same manner as in example 2) was reacted with alumina (AlCl) 3 ) Mixing the materials according to a molar ratio of 3:1, dissolving the mixture in water, and reacting the mixture for 2 hours at a pH value of 5 and a temperature of 60 ℃ to generate aluminum fulvate, wherein the red brown viscous liquid is the aluminum-based plugging anti-collapse agent.
Example 6
An aluminum-based plugging anti-collapse agent and a preparation method thereof are provided, wherein the aluminum-based plugging anti-collapse agent is aluminum fulvate, and the preparation method specifically comprises the following steps:
fulvic acid (prepared in the same manner as in example 3) was reacted with alumina (AlCl) 3 ) Mixing the materials according to a molar ratio of 3:1, dissolving the mixture in water, and reacting the mixture for 2 hours at the pH value of 6 and the temperature of 70 ℃ to generate the yellow aluminum humate, thus obtaining the brownish red viscous liquid which is the aluminum-based plugging anti-collapse agent.
Example 7
An aluminum-based plugging anti-collapse agent and a preparation method thereof are provided, wherein the aluminum-based plugging anti-collapse agent is aluminum fulvate, and the preparation method specifically comprises the following steps:
fulvic acid (preparation method same as example 1) was reacted with aluminum sulfate Al 2 (SO 4 ) 3 Mixing at a molar ratio of 6:1, dissolving in water, reacting for 1h at a pH value of 4 and a temperature of 50 ℃ to generate aluminum fulvate, and obtaining brownish red viscous liquid which is the aluminum-based plugging anti-collapse agent.
Example 8
An aluminum-based plugging anti-collapse agent and a preparation method thereof are provided, wherein the aluminum-based plugging anti-collapse agent is aluminum fulvate, and the preparation method specifically comprises the following steps:
fulvic acid (preparation method same as example 2) was reacted with aluminum sulfate Al 2 (SO 4 ) 3 Mixing at a molar ratio of 6:1, dissolving in water, reacting for 2 hours at a pH value of 5 and a temperature of 60 ℃ to generate aluminum fulvate, and obtaining brownish red viscous liquid which is the aluminum-based plugging anti-collapse agent.
Example 9
An aluminum-based plugging anti-collapse agent and a preparation method thereof are provided, wherein the aluminum-based plugging anti-collapse agent is aluminum fulvate, and the preparation method specifically comprises the following steps:
fulvic acid (preparation method same as example 3) was reacted with aluminum sulfate Al 2 (SO 4 ) 3 Mixing at a molar ratio of 6:1, dissolving in water, reacting for 2 hours at a pH value of 6 and a temperature of 70 ℃ to generate aluminum fulvate, and obtaining brownish red viscous liquid which is the aluminum-based plugging anti-collapse agent.
Comparative example 1
An aluminum-based plugging anti-collapse agent and a preparation method thereof are provided, wherein the specific preparation method is as follows:
humic acid (derived from weathered coal) and alumina (Al) 2 O 3 ) Mixing the materials according to the molar ratio of 6:1, dissolving the mixture in water, and reacting the mixture for 3 hours at the pH value of 6 and the temperature of 65 ℃ to obtain brownish red viscous liquid, namely the aluminum-based plugging anti-collapse agent.
Application example 1
The polysulfonate drilling fluid (fresh water drilling fluid system) comprises the following components in percentage by mass: 4.0% of bentonite, 0.2% of sodium carbonate, 0.15% of caustic soda, 2.0% of sulfonated phenolic resin, 1.5% of sulfonated lignite, 3.0% of sulfonated asphalt, 0.15% of coating inhibitor, 4.0% of liquid lubricant and a predetermined amount of barite (density 1.30 g/cm) 3 ) The balance being water; and respectively adding the aluminum-based plugging and anti-collapse agents provided in the examples 1-9 and the comparative example 1 into the base slurry to enable the mass percentage of the aluminum-based plugging and anti-collapse agent in the drilling fluid system to be 1%.
Adding the aluminum-based plugging and anti-collapse agents provided in examples 1-9 and comparative example 1 into the base slurry respectively, stirring for 20min at 11000r/min, aging for 16h at 180 ℃, taking out, cooling to room temperature, stirring for 10min at 11000r/min, and measuring the Plastic Viscosity (PV) and dynamic shear force of the drilling fluid(YP), static shear force (Gel) and medium pressure loss (FL) API ) The specific results of the changes are shown in Table 1.
TABLE 1
Figure BDA0003736570110000111
Figure BDA0003736570110000121
Application example 2
A composite salt drilling fluid (a salt drilling fluid system) comprises the following components in percentage by mass: 2.0% of bentonite, 0.2% of sodium carbonate, 0.15% of caustic soda, 2.0% of salt-resistant filtrate reducer, 0.5% of gum-protecting agent, 1.5% of non-permeable treatment agent, 0.05% of flow-type regulator, 8.0% of potassium chloride, 4.0% of liquid lubricant and a compound salt weighting agent (density 1.30 g/cm) 3 ) The balance being water; and respectively adding the aluminum-based plugging and anti-collapse agents provided in the examples 1-9 and the comparative example 1 into the base slurry to enable the mass percentage of the aluminum-based plugging and anti-collapse agent in the drilling fluid system to be 1%.
Adding the aluminum-based plugging and anti-collapse agents provided in examples 1-9 and comparative example 1 into the base slurry respectively, stirring for 20min at 11000r/min, aging for 16h at 180 ℃, taking out, cooling to room temperature, stirring for 10min at 11000r/min, and measuring the Plastic Viscosity (PV), dynamic shear force (YP), static shear force (Gel) and medium pressure Fluid Loss (FL) of the drilling fluid API ) The specific results of the changes are shown in Table 2.
TABLE 2
System of PV(mPa·s) YP(Pa) Gel(Pa/Pa) FL API (mL)
Base slurry 40 15 4.0/5.5 4.8
Base stock + example 1 42 17 4.5/6.0 4.4
Base stock + example 2 41 16 4.5/6.0 4.6
Base stock + example 3 43 17.5 5.0/6.5 4.6
Base stock + example 4 44 19 5.0/7.0 4.6
Base stock + example 5 43 18.5 5.0/6.5 4.2
Base stock + example 6 45 19 5.0/7.0 4.2
Base stock + example 7 46 19.5 5.0/7.0 4.4
Base stock + example 8 47 20 5.5/7.5 4.2
Base stock + example 9 47 19.5 5.5/7.0 3.8
Base stock + comparative example 1 44 20 6/8.5 5.2
As can be seen from the test data in Table 1 and Table 2, the aluminum-based plugging and anti-collapse agent provided in examples 1-9 has slightly increased viscosity and shear force, reduced fluid loss, and less overall rheological fluctuation, and has better compatibility than the plugging and anti-collapse agent prepared by reacting humic acid with aluminum-containing compound in comparative example 1, regardless of fresh water drilling fluid system (polysulfonate drilling fluid) or brine drilling fluid system (composite salt drilling fluid).
Application example 3
The application example is a plugging performance test example of the aluminum-based plugging anti-collapse agent, in particular to a sand tray permeability plugging experiment (PPA), which is an improved high-temperature high-pressure HTHP water loss experiment, and plugging performance evaluation of drilling fluid is carried out by using sand tray media with different specifications, wherein the conventional test condition is 7.0MPa/30min. At a permeability of 10 μm 2 The sand tray of the polyamine high-performance water-based drilling fluid containing 1% of the aluminum-based plugging anti-collapse agent is evaluated at 180 ℃ by adopting a sand tray permeability plugging PPA experimental instrument as a percolation medium.
The polyamine high-performance water-based drilling fluid comprises the following components in percentage by mass: 2% of soil powder, 0.1% of sodium carbonate, 0.05% of caustic soda, 2% of SN resin, 2% of salt-resistant filtrate reducer (KFT), 0.5% of polyanionic cellulose (PAC-LV), 1% of polyamine inhibitor, 0.1% of tackifier (XC) and a predetermined amount of barite (density 1.30 g/cm) 3 ) The balance being water; and respectively adding the aluminum-based plugging and anti-collapse agents provided in examples 1-9 and comparative example 1 into the base slurry to enable the mass percentage of the aluminum-based plugging and anti-collapse agent in the system to be 1%, and performing PPA experiments according to the method, wherein the test results are shown in Table 3.
TABLE 3 Table 3
System of FL PPA (mL) Instantaneous water loss (mL)
Base slurry 94 11.2
Base stock + example 1 48 7.4
Base stock + example 2 45 5.8
Base stock + example 3 51 7.8
Base stock + example 4 47 7.2
Base stock + example 5 48 7.6
Base stock + example 6 50 7.2
Base stock + example 7 49 6.8
Base stock + example 8 46 6.2
Base stock + example 9 45 6.0
Base stock + comparative example 1 67 8.2
The PPA test results in Table 3 show that the addition of the aluminum-based plugging anti-collapse agent provided by the invention can reduce PPA fluid loss of drilling fluid base fluid, the reduction value of PPA fluid loss is more than 45%, the proportion of instantaneous water loss to total water loss is increased, the rapid water loss of experimental slurry is facilitated to form an inner mud cake, and the leakage of drilling fluid is reduced. Under the action of pressure difference, the aluminum-based plugging anti-collapse agent can fill and plug pore throats on the surface of the sand disc to form an effective physical plugging layer. In the plugging and anti-collapse agent prepared by reacting humic acid with an aluminum-containing compound in comparative example 1, the reduction of PPA filtrate loss and instantaneous water loss is not ideal enough, and the ratio of the instantaneous water loss to the total water loss is low. Therefore, under the test condition, the aluminum-based plugging anti-collapse agent provided by the invention has stronger plugging performance.
Application example 4
The application example is another plugging and anti-collapse performance test example of the aluminum-based plugging and anti-collapse agent, and specifically is a pressure transmission experiment. Because of the heterogeneity of the length, width and extension of the fracture in the rock, the simulated plugging apparatus is not capable of fully verifying the plugging effect of the plugging agent on the formation. According to the application example, a rock core is used as a plugging object, a high-temperature high-pressure well wall stability simulation experiment device is adopted to carry out a pressure transmission experiment, and the pressure barrier performance of the aluminum-based plugging anti-collapse agent is evaluated. The experimental device mainly comprises 5 parts, including a high-temperature high-pressure kettle body, a hydraulic control system, a fluid circulation system, a temperature transmission and control system and a data acquisition and processing system; the data acquisition and processing system can automatically and continuously record pressure and differential pressure signals at the same time and has the functions of data recording, real-time display, disc storage, playback, processing and the like. And (3) placing the test core into a core holder, pumping test liquid into contact with the upper end face of the core through an upstream test liquid inlet, maintaining the pressure at the top end of the core to be 2MPa and the initial pressure at the bottom end to be 1MPa, and obtaining the pressure transmission rate of the test liquid by monitoring the change of the bottom pressure so as to evaluate the pressure blocking performance of the plugging agent at 180 ℃.
The shale permeability calculation formula is:
Figure BDA0003736570110000151
wherein K is shale permeability, mum 2 The method comprises the steps of carrying out a first treatment on the surface of the Mu is the viscosity of the test solution and mPa.s; beta is static compression rate of test solution and MPa -1 The method comprises the steps of carrying out a first treatment on the surface of the V is the volume of the downstream container, cm 3 The method comprises the steps of carrying out a first treatment on the surface of the L is the length of the core, cm; a is the cross-sectional area of the core, cm 2 The method comprises the steps of carrying out a first treatment on the surface of the t is the action time of the core and the drilling fluid, s; p (P) m Is the upstream pressure, MPa; p (P) 0 Pore pressure, MPa; p (L, t) is the pressure downstream of the moment t, MPa.
The base slurry for testing comprises the following components in percentage by mass: 4% of soil powder, 0.2% of sodium carbonate, 0.15% of caustic soda and the balance of water; and respectively adding the aluminum-based plugging and collapse preventing agents provided in the examples 1-9 and the comparative example 1 into the base slurry to enable the mass percentage of the aluminum-based plugging and collapse preventing agent in the system to be 1%, performing a pressure transmission test experiment according to the method, and further calculating the permeability of the shale before and after plugging by using the pressure transmission test data, wherein the concrete results are shown in the table 4.
TABLE 4 Table 4
Figure BDA0003736570110000161
Figure BDA0003736570110000171
The pressure transmission test results in the table 4 show that after 1% of the aluminum-based plugging anti-collapse agent provided by the invention is added into the base slurry, the time required for transmitting 1MPa pressure difference is obviously improved compared with that of a blank rock sample and the base slurry, and the time required for transmitting 1MPa pressure difference is prolonged by more than 5.5 times compared with that of the blank rock sample; the permeability of the blank shale is reduced by more than 5 times after the aluminum-based plugging anti-collapse agent acts. In the comparative example 1, the plugging and anti-collapse agent formed by the reaction of humic acid and aluminum-containing compound only prolongs the time required for transmitting the pressure difference of 1MPa by 3.5 times compared with the blank rock sample. Therefore, under the condition of 180 ℃, the aluminum-based plugging anti-collapse agent has remarkable performance of resisting shale pressure transmission and has stronger plugging anti-collapse performance.
Application example 5
The application example is a hydration dispersion control performance test example of the aluminum-based plugging anti-collapse agent, and the specific method is as follows: 50g (0.01 g precisely) of shale rock debris with the particle size of 6-10 meshes, which is obtained from four subsections below the recessed sand in the eastern part of Liaohe, are quantitatively weighed, are put into pints of different drilling fluid systems, are washed by standard saline water after being thermally rolled at 180 ℃ for 16 hours, are sieved by a 40-mesh standard sieve, and the remainder of the sieve is dried and weighed at 105 ℃, and the ratio of the mass of the remainder of the sieve to the mass of the initial rock debris is recorded as the rock debris recovery rate, and the test results are shown in Table 5.
TABLE 5
Figure BDA0003736570110000172
Figure BDA0003736570110000181
From table 5, it can be seen that after the aluminum-based plugging anti-collapse agent provided by the invention is used, the rock debris recovery rate is obviously improved, wherein the effects of examples 7-9 are more obvious, the rock debris recovery rate is far higher than that of 8.0% KCl inorganic inhibitor, and is inferior to that of a No. 5 white oil sample, so that the aluminum-based plugging anti-collapse agent provided by the invention has a good effect of controlling the hydration dispersion of mudstone. In the plugging anti-collapse agent prepared by reacting humic acid with an aluminum-containing compound in comparative example 1, the recovery rate of rock debris is only slightly better than that of 8.0% KCl, and the inhibition effect cannot meet the anti-collapse requirement.
In conclusion, the aluminum-based plugging anti-collapse agent provided by the invention can be suitable for different water-based drilling fluid systems, has good high-temperature resistance, can intelligently plug the holes and gaps with different sizes, further delays the transmission of drilling fluid and filtrate thereof to the deep part of a stratum, combines the double inhibition effects of trivalent cations and organic acid radicals (fulvic acid radicals), can obviously improve the anti-collapse performance of the water-based drilling fluid, and is beneficial to popularization and application of the water-based drilling fluid in deep complex stratum.
The applicant states that the present invention is described by the above examples as an aluminium-based plugging anti-collapse agent, and the preparation method and application thereof, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be practiced by relying on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (10)

1. An aluminum-based plugging anti-collapse agent is characterized by comprising aluminum fulvate.
2. The aluminum-based plugging anti-collapse agent according to claim 1, wherein the aluminum fulvate is obtained by reacting fulvic acid with an aluminum-containing compound;
preferably, the fulvic acid is mining source fulvic acid, and further preferably weathered coal fulvic acid;
preferably, the aluminum-containing compound is aluminum oxide and/or an aluminum salt;
preferably, the aluminum-containing compound comprises any one or a combination of at least two of aluminum oxide, aluminum chloride or aluminum sulfate.
3. The aluminum-based plugging collapse prevention agent according to claim 2, wherein the fulvic acid is prepared by a process comprising: mixing weathered coal with an acetone solution, adding sulfuric acid into the mixture to react, and precipitating to obtain a supernatant containing fulvic acid;
preferably, the acetone solution is an aqueous solution of acetone;
preferably, the acetone in the acetone solution is 80-90% by mass;
preferably, the mass of the weathered coal is 10 to 50%, further preferably 20 to 40%, based on 100% of the mass of the acetone solution;
preferably, the reaction time is 1 to 5 hours, more preferably 2.5 to 4 hours;
preferably, the time of the precipitation is 4 to 10 hours, further preferably 6 to 8 hours;
preferably, the supernatant is dried to obtain the fulvic acid.
4. A method for preparing the aluminum-based plugging anti-collapse agent according to any one of claims 1 to 3, wherein the preparation method comprises: and (3) reacting fulvic acid with an aluminum-containing compound to obtain the aluminum-based plugging anti-collapse agent.
5. The process according to claim 4, wherein the molar ratio of fulvic acid to aluminium in the aluminium-containing compound is (2-5): 1, preferably (2.5-3.5): 1.
6. The method of claim 4 or 5, wherein the temperature of the reaction is 50-70 ℃;
preferably, the reaction time is 0.5-3 hours;
preferably, the pH of the reaction is < 7.
7. The preparation method according to any one of claims 4 to 6, characterized in that the preparation method comprises the steps of:
(1) Mixing weathered coal with an acetone solution, adding sulfuric acid into the mixture under stirring until the pH value of the system is 3-3.5 for reaction, and drying supernatant after precipitation to obtain fulvic acid;
(2) And (3) reacting the fulvic acid obtained in the step (1) with an aluminum-containing compound for 0.5-3 hours under the conditions that the pH value is less than 7 and the temperature is 50-70 ℃ to generate aluminum fulvate, thereby obtaining the aluminum-based plugging collapse preventing agent.
8. Use of an aluminium-based plugging anti-collapse agent according to any one of claims 1 to 3 in drilling fluids.
9. A water-based drilling fluid, characterized in that the water-based drilling fluid comprises the aluminum-based plugging anti-collapse agent as claimed in any one of claims 1 to 3.
10. The water-based drilling fluid according to claim 9, wherein the mass percentage of the aluminum-based plugging anti-collapse agent in the water-based drilling fluid is 0.1-3%, preferably 0.5-1.5%.
CN202210804887.4A 2022-07-08 2022-07-08 Aluminum-based plugging anti-collapse agent and preparation method and application thereof Pending CN116063998A (en)

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