CN111704695B - Multifunctional drilling treatment agent and preparation and application thereof - Google Patents
Multifunctional drilling treatment agent and preparation and application thereof Download PDFInfo
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- CN111704695B CN111704695B CN202010498709.4A CN202010498709A CN111704695B CN 111704695 B CN111704695 B CN 111704695B CN 202010498709 A CN202010498709 A CN 202010498709A CN 111704695 B CN111704695 B CN 111704695B
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- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
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Abstract
A multifunctional well drilling treating agent is prepared from starch and cellulose through graft polymerizing with acrylamide under the action of trigger, and is prepared from starch, cellulose, acrylamide, oxidant, reducer, water-soluble compound monomer containing double bonds and dispersion stabilizer. The multifunctional drilling treatment agent effectively combines the comprehensive effects of starch, cellulose and polymer products of natural high polymer products, has excellent cutting performance, can improve the suspension property and sand carrying property of the drilling fluid, and can not greatly improve the apparent viscosity of the drilling fluid; the filter has excellent filtrate loss performance and good temperature and salt resistance effect; meanwhile, the coating has good coating inhibition performance, can effectively coat clay and drill cuttings, prevents solid phase pollution, is easy to degrade, has no pollution, has excellent comprehensive performance, can meet the requirements of maintenance and treatment of the current on-site drilling fluid, has wide application prospect, and is particularly suitable for large-displacement wells and solid-phase-free drilling fluid.
Description
Technical Field
The application belongs to the field of drilling treatment agents, and particularly relates to a multifunctional drilling treatment agent, and preparation and application thereof.
Background
With the increase in world energy demand and the development of drilling technology, treatment agents for drilling fluids have become an integral part of the drilling process. Meanwhile, due to the continuous increase of drilling depth, the drilling of stratum becomes more and more complex and environmental protection is increasingly emphasized, and the drilling operation has higher and higher requirements on the drilling fluid treating agent.
In addition, with the rapid increase of world oil and gas resource demands, the number of horizontal wells and large-displacement wells is rapidly increased, the drilling engineering is also developed from land to ocean, and the requirements for reservoir protection are more and more strict, so that the brine drilling fluid and the solid-free drilling technology are more and more widely applied. The drilling process has higher requirements on rheological property and salt resistance of a drilling fluid system, and particularly has higher requirements on filtrate loss reduction performance and sand carrying performance. The solid-phase-free brine drilling fluid has good rheological property, inhibition, lubrication and cooling properties, is favorable for improving the drilling speed, can greatly improve the high-efficiency rock breaking capacity of the drill bit, can improve the service life of the drill bit, and can effectively protect the well wall due to the good inhibition, so that the application is wider and wider; however, the method has the defects of large water loss, poor rock carrying capacity and the like. The large-displacement well can fully utilize the existing platform or land-based development marginal oil fields and offshore oil and gas fields to connect a plurality of oil and gas reservoirs in series, so that the cost of repeated construction can be saved greatly, and the investment can be saved; however, large displacement wells have large horizontal sections, which have very high requirements for reservoir protection for the sand carrying capacity and suspension properties of the mud.
The rapid development of the advanced drilling technology has higher requirements on drilling fluid, and is mainly characterized in that the requirements on the shear force of the drilling fluid are higher, so that the suspension property of the drilling fluid is improved, sand is convenient to carry, and adverse phenomena such as sand-settling stuck drilling and the like are reduced; the filter loss of the drilling fluid is as low as possible, the effect of protecting the well wall is achieved, meanwhile, the differential pressure stuck drill caused by the formation of an excessively thick mud cake is prevented, the coating inhibition of the drilling fluid is strong, the stability of the well wall is maintained, and meanwhile, solid phase pollution is prevented. At present, no product in the market can simultaneously meet the technical requirements, but a plurality of products are adopted for compounding and using so as to realize the technical requirements. The complex use of multiple materials not only makes the drilling fluid adjustment and maintenance process complex, but also easily causes the change of the drilling fluid due to the compatibility problem of different materials, and even seriously affects the smooth progress of drilling.
Disclosure of Invention
The application provides a multifunctional drilling treatment agent and preparation and application thereof, wherein the multifunctional drilling treatment agent is an acrylamide grafted starch/cellulose copolymer, has the functions of reducing filtration, cutting, thickening, coating inhibition and the like, has excellent comprehensive performance, can achieve multiple effects by using a single drilling treatment agent, is simple and convenient to operate, has easily-adjustable drilling fluid performance, and can effectively reduce the change of drilling fluid performance caused by compatibility problems of various materials in the maintenance process of the drilling fluid.
The application provides a multifunctional drilling treatment agent, which is prepared by graft copolymerization of starch and cellulose with acrylamide under the action of an initiator by adopting a dispersion polymerization process.
In the multifunctional well treatment agent provided herein, the initiator includes an oxidizing agent and a reducing agent; the multifunctional drilling treatment agent comprises raw materials and a solvent, wherein the raw materials of the multifunctional drilling treatment agent comprise the following components in percentage by mass: 30-80% of starch, 10-40% of cellulose, 5-45% of acrylamide, 0-15% of water-soluble compound monomer containing double bonds, optionally 0.5-15% of oxidant, 0.5-5% of reducing agent and 0.5-5% of dispersion stabilizer. Alternatively, the double bond-containing water-soluble compound monomer may not be added.
Preferably, the multifunctional drilling treatment agent comprises the following raw materials in percentage by mass: 40-70% of starch, 15-35% of cellulose, 10-35% of acrylamide, 2-10% of a water-soluble compound monomer containing double bonds, 1-2% of an oxidant, 1-2% of a reducing agent and 1-3% of a dispersion stabilizer.
Optionally, the multifunctional drilling treatment agent comprises starch, cellulose, acrylamide, a water-soluble compound monomer containing double bonds, an oxidant, a reducing agent and a dispersion stabilizer.
In the multifunctional drilling treatment agent provided by the application, the water-soluble compound monomer containing double bonds is selected from one or more of amino acrylic acid, amino acrylic acid salt, styrene sulfonate and allylic quaternary ammonium salt;
in the multifunctional drilling treatment agent provided by the application, the oxidant is selected from one or more of hydrogen peroxide, ammonium persulfate, potassium persulfate and sodium persulfate;
in the multifunctional drilling treatment agent provided by the application, the reducing agent is selected from one or more of ferrous sulfate, sodium sulfite and ammonium sulfite.
In the multifunctional drilling treatment agent provided by the application, the dosage of the solvent is 1-5 times of the total weight of the raw materials of the multifunctional drilling treatment agent;
optionally, the solvent is selected from one or more of isopropanol, ethanol, ethylene glycol, and propylene glycol;
preferably, the solvent consists of isopropanol and ethanol, the solvent is used in an amount which is 1.5-3 times of the total weight of the raw materials of the multifunctional drilling treatment agent, and the weight ratio of the isopropanol to the ethanol is (2:8) - (8:2).
In the multifunctional drilling treatment agent provided by the application, the starch is one or more than two of pregelatinized starch, sulfonated starch, carboxymethyl starch and temperature resistant starch;
optionally, the starch has a particle size of 60-120 mesh;
optionally, the cellulose is selected from one or more of hydroxypropyl cellulose, hydroxymethyl cellulose, polyanionic cellulose, and sodium carboxymethyl cellulose.
In the multifunctional drilling treatment agent provided by the application, the dispersion stabilizer is selected from one or more of polyethylene glycol, anionic surfactant and cationic surfactant;
optionally, the dispersion stabilizer is selected from one or more of polyethylene glycol, alkyl sulfonate, and quaternary ammonium salt.
In still another aspect, the present application provides a method for preparing the multifunctional drilling treatment agent, including:
(1) Adding a solvent, acrylamide, starch, cellulose and a water-soluble compound monomer containing double bonds into a reaction container, adding an oxidant and a dispersion stabilizer, and stirring until the mixture is completely dissolved;
(2) Adjusting the pH value of the solution in the reaction vessel to 8-10;
(3) Introducing a protective gas into the reaction vessel;
(4) Dripping the aqueous solution of the reducing agent, and finishing dripping within 40-60 minutes;
(5) Continuously stirring at 30-50 ℃ for reaction for 2-3 hours;
(6) Separating the generated precipitate under the atmosphere of protective gas;
(7) Drying the precipitate obtained in the step (6) at 60-80 ℃ and a vacuum degree of 0.01-0.05MPa to obtain the multifunctional drilling treating agent. Optionally, the preparation of the multifunctional drilling treatment agent consists of the steps.
In the preparation method of the multifunctional drilling treatment agent provided by the application, the protective gas is one or more selected from nitrogen, helium and argon;
optionally, the mass concentration of the aqueous solution of the reducing agent in the step (4) is 2-10%.
Optionally, the separation in the step (6) is centrifugal separation, wherein the rotation speed of the centrifugal separation is 2000-10000 rpm, and the time of the centrifugal separation is 10-30min.
In yet another aspect, the application provides the use of the multifunctional drilling treatment agent as described above as a drilling fluid additive;
optionally, the multifunctional drilling treatment agent effectively combines the comprehensive effects of starch, cellulose and polymer products of natural high polymer products, and has the functions of cutting, tackifying, reducing filtration, coating inhibition and the like.
The multifunctional drilling treatment agent provided by the application combines the comprehensive effects of natural high polymer products such as starch, cellulose and polymer products, has excellent cutting performance, can improve the suspension property and sand carrying property of the drilling fluid, and can not greatly improve the apparent viscosity of the drilling fluid; has excellent filtrate loss performance, good temperature and salt resistance effect, and can resist the temperature of more than 120 ℃ in a saturated brine and seawater drilling fluid system. The multifunctional drilling treatment agent has excellent filtrate reduction performance under the conditions of high temperature and high pressure, seawater, saturated brine and the like, can effectively reduce the filtrate reduction amount of drilling fluid, and is suitable for drilling engineering under different complex operation environments; meanwhile, the coating has good coating inhibition performance, can effectively coat clay and drill cuttings, and prevents solid phase pollution. The product adopts a special dispersion polymerization process, has high polymerization degree and high purity, has a main body structure of natural polymers of starch and cellulose, has natural polymer degradation performance, is environment-friendly, nontoxic and pollution-free, is a product with excellent comprehensive performance, has multiple functions, simplifies on-site drilling fluid regulation and maintenance processes, meets the requirements of maintenance and treatment, can meet the environmental requirements of land operation and offshore operation, and has wide application prospect in drilling engineering. Is especially suitable for large-displacement wells and solid-free drilling fluids.
Additional features and advantages of the application will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the application. Other advantages of the present application may be realized and attained by the instrumentalities and aspects depicted in the specification.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present application more apparent, embodiments of the present application are described in detail. It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be arbitrarily combined with each other.
The embodiment of the application provides a multifunctional drilling treatment agent, which is prepared by graft copolymerization of starch and cellulose and acrylamide under the action of an initiator by adopting a dispersion polymerization process.
In embodiments of the present application, the initiator includes an oxidizing agent and a reducing agent; the multifunctional drilling treatment agent comprises raw materials and a solvent, wherein the raw materials of the multifunctional drilling treatment agent comprise the following components in percentage by mass: 30-80% of starch, 10-40% of cellulose, 5-45% of acrylamide, 0-15% of water-soluble compound monomer containing double bonds, optionally 0.5-15% of oxidant, 0.5-5% of reducing agent and 0.5-5% of dispersion stabilizer. Alternatively, the double bond-containing water-soluble compound monomer may not be added.
Preferably, the multifunctional drilling treatment agent comprises the following raw materials in percentage by mass: 40-70% of starch, 15-35% of cellulose, 10-35% of acrylamide, 2-10% of a water-soluble compound monomer containing double bonds, 1-2% of an oxidant, 1-2% of a reducing agent and 1-3% of a dispersion stabilizer.
Optionally, the multifunctional drilling treatment agent comprises starch, cellulose, acrylamide, a water-soluble compound monomer containing double bonds, an oxidant, a reducing agent and a dispersion stabilizer.
In an embodiment of the present application, the double bond-containing water-soluble compound monomer is selected from one or more of amino acrylic acid, amino acrylic acid salt, styrene sulfonate and allylic quaternary ammonium salt; alternatively, the monomer is selected from one or more of sodium N- (3-aminopropyl) methacrylate, diallyldimethylammonium chloride and sodium styrenesulfonate.
In an embodiment of the present application, the oxidizing agent is selected from one or more of hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate;
in an embodiment of the present application, the reducing agent is selected from one or more of ferrous sulfate, sodium sulfite, and amine sulfite.
In the embodiment of the application, the dosage of the solvent is 1-5 times of the total weight of the raw materials of the multifunctional drilling treatment agent;
optionally, the solvent is selected from one or more of isopropanol, ethanol, ethylene glycol, and propylene glycol;
preferably, the solvent consists of isopropanol and ethanol, the solvent is used in an amount which is 1.5-3 times of the total weight of the raw materials of the multifunctional drilling treatment agent, and the weight ratio of the isopropanol to the ethanol is (2:8) - (8:2).
In the embodiment of the application, the starch is one or more than two selected from pregelatinized starch, sulfonated starch, carboxymethyl starch and temperature resistant starch;
optionally, the starch has a particle size of 60-120 mesh;
optionally, the cellulose is selected from one or more of hydroxypropyl cellulose, hydroxymethyl cellulose, polyanionic cellulose, and sodium carboxymethyl cellulose.
In an embodiment of the present application, the dispersion stabilizer is selected from one or more of polyethylene glycol, anionic surfactant, and cationic surfactant;
optionally, the dispersion stabilizer is selected from one or more of polyethylene glycol, alkyl sulfonate, and quaternary ammonium salt.
In still another aspect, an embodiment of the present application provides a method for preparing the multifunctional drilling treatment agent, including:
(1) Adding a solvent, acrylamide, starch, cellulose and a water-soluble compound monomer containing double bonds into a reaction container, adding an oxidant and a dispersion stabilizer, and stirring until the mixture is completely dissolved;
(2) Adjusting the pH value of the solution in the reaction vessel to 8-10;
(3) Introducing a protective gas into the reaction vessel;
(4) Dripping the aqueous solution of the reducing agent, and finishing dripping within 40-60 minutes;
(5) Continuously stirring at 30-50 ℃ for reaction for 2-3 hours;
(6) Separating the generated precipitate under the atmosphere of protective gas;
(7) Drying the precipitate obtained in the step (6) at 60-80 ℃ and a vacuum degree of 0.01-0.05MPa to obtain the multifunctional drilling treating agent. Optionally, the preparation of the multifunctional drilling treatment agent consists of the steps.
In an embodiment of the present application, the shielding gas is selected from one or more of nitrogen, helium and argon;
optionally, the mass concentration of the aqueous solution of the reducing agent in the step (4) is 2-10%.
Optionally, the separation in the step (6) is centrifugal separation, wherein the rotation speed of the centrifugal separation is 2000-10000 rpm, and the time of the centrifugal separation is 10-30min.
In the examples herein, the polyethylene glycol has a molecular weight between 200 and 800 and is purchased from the sea-safe petrochemical plant, PEG 600.
Pregelatinized starch in the following examples pregelatinized starch α -starch from nijin county, jia and energy saving materials limited; is convenient for dissolution, and the starch granules are 40-60 meshes.
The low viscosity polyanionic cellulose in the following examples was purchased from Puyang Orientization Co., ltd; cellulose particles 40-60 mesh.
In the following examples carboxymethyl starch was purchased from the Boyang chemical industry plant, CMS, starch granules 40-60 mesh.
Example 1
The embodiment provides a multifunctional drilling treatment agent which is prepared from the following raw materials in parts by weight: 51kg of carboxymethyl starch (CMS), 20kg of carboxymethyl cellulose (LV-CMC); 25kg of acrylamide and 1kg of sodium persulfate; ferrous sulfate 1kg, polyethylene glycol 2kg, isopropanol 100kg, ethanol 100kg.
The preparation method of the multifunctional drilling treatment agent comprises the following steps: firstly, adding 100kg of isopropanol and 100kg of ethanol into a reaction kettle, and stirring to uniformly mix, wherein the mixture is used as a polymerization solvent; 51kg of carboxymethyl starch, 20kg of carboxymethyl cellulose and 25kg of acrylamide are added into a reaction kettle, 1kg of sodium persulfate and 2kg of polyethylene glycol are added, and the raw materials are stirred to be completely dissolved; then 1kg of ferrous sulfate is dissolved in 20kg of distilled water, and the mixture is stirred uniformly and placed in a constant pressure dropping funnel; adding 10wt.% NaOH aqueous solution to adjust the pH value of the reaction kettle solution to 9-10; introducing nitrogen into the reaction kettle, and then beginning to dropwise add the ferrous sulfate aqueous solution within 40-60 minutes; maintaining nitrogen atmosphere, and stirring and reacting for 2 hours at 50 ℃; stopping the reaction, precipitating the generated polymer from the system, and carrying out centrifugal separation under the protection of nitrogen at a centrifugal speed of 5000-8000 rpm for 20min; drying at 80deg.C under vacuum degree of 0.01-0.05MPa, and pulverizing to obtain the final product.
Example 2
The embodiment provides a multifunctional drilling treatment agent which is prepared from the following raw materials in parts by weight: 51kg of carboxymethyl starch (CMS), 20kg of carboxymethyl cellulose (LV-CMC); 20kg of acrylamide, 5kg of sodium N- (3-aminopropyl) methacrylate and 1kg of sodium persulfate; ferrous sulfate 1kg, polyethylene glycol 2kg, isopropanol 100kg, ethanol 100kg.
The preparation method of the multifunctional drilling treatment agent comprises the following steps: firstly, adding 100kg of isopropanol and 100kg of ethanol into a reaction kettle, and stirring to uniformly mix, wherein the mixture is used as a polymerization solvent; 51kg of carboxymethyl starch, 20kg of carboxymethyl cellulose, 20kg of acrylamide, 5kg of double bond-containing water-soluble compound monomer N- (3-aminopropyl) sodium methacrylate are added into a reaction kettle, 1kg of sodium persulfate and 2kg of polyethylene glycol are added, and the raw materials are stirred to be completely dissolved; then 1kg of ferrous sulfate is dissolved in 20kg of distilled water, and the mixture is stirred uniformly and placed in a constant pressure dropping funnel; adding 10wt.% NaOH aqueous solution to adjust the pH value of the reaction kettle solution to 9-10; introducing nitrogen into the reaction kettle, and then beginning to dropwise add the ferrous sulfate aqueous solution within 40-60 minutes; maintaining nitrogen atmosphere, and stirring and reacting for 2 hours at 50 ℃; stopping the reaction, precipitating the generated polymer from the system, and carrying out centrifugal separation under the protection of nitrogen at a centrifugal speed of 5000-8000 rpm for 20min; drying at 80deg.C under vacuum degree of 0.01-0.05MPa, and pulverizing to obtain the final product.
Example 3
The embodiment provides a multifunctional drilling treatment agent which is prepared from the following raw materials in parts by weight: 51kg of carboxymethyl starch (CMS), 20kg of carboxymethyl cellulose (LV-CMC); 20kg of acrylamide, 5kg of diallyl dimethyl ammonium chloride and 1kg of sodium persulfate; ferrous sulfate 1kg, polyethylene glycol 2kg, isopropanol 100kg, ethanol 100kg.
The preparation method of the multifunctional drilling treatment agent comprises the following steps: firstly, adding 100kg of isopropanol and 100kg of ethanol into a reaction kettle, and stirring to uniformly mix, wherein the mixture is used as a polymerization solvent; 51kg of carboxymethyl starch, 20kg of carboxymethyl cellulose, 20kg of acrylamide and 5kg of double bond-containing water-soluble compound monomer diallyl dimethyl ammonium chloride are added into a reaction kettle, 1kg of sodium persulfate and 2kg of polyethylene glycol are added, and the raw materials are stirred to be completely dissolved; then 1kg of ferrous sulfate is dissolved in 20kg of distilled water, and the mixture is stirred uniformly and placed in a constant pressure dropping funnel; adding 10wt.% NaOH aqueous solution to adjust the pH value of the reaction kettle solution to 9-10; introducing nitrogen into the reaction kettle, and then beginning to dropwise add the ferrous sulfate aqueous solution within 40-60 minutes; maintaining nitrogen atmosphere, and stirring and reacting for 2 hours at 50 ℃; stopping the reaction, precipitating the generated polymer from the system, and carrying out centrifugal separation under the protection of nitrogen at a centrifugal speed of 5000-8000 rpm for 20min; drying at 80deg.C under vacuum degree of 0.01-0.05MPa, and pulverizing to obtain the final product.
Example 4
The embodiment provides a multifunctional drilling treatment agent which is prepared from the following raw materials in parts by weight: 64kg of carboxymethyl starch (CMS), 20kg of carboxymethyl cellulose (LV-CMC); 10kg of acrylamide, 2kg of sodium N- (3-aminopropyl) methacrylate and 1kg of ammonium persulfate; ferrous sulfate 1kg, polyethylene glycol 2kg, isopropanol 100kg, ethanol 100kg.
The preparation method of the multifunctional drilling treatment agent comprises the following steps: firstly, adding 100kg of isopropanol and 100kg of ethanol into a reaction kettle, and stirring to uniformly mix, wherein the mixture is used as a polymerization solvent; adding 64kg of carboxymethyl starch, 20kg of carboxymethyl cellulose, 10kg of acrylamide, 2kg of double bond-containing water-soluble compound monomer N- (3-aminopropyl) sodium methacrylate into a reaction kettle, adding 1kg of ammonium persulfate and 2kg of polyethylene glycol, and stirring to completely dissolve the raw materials; then 1kg of ferrous sulfate is dissolved in 20kg of distilled water, and the mixture is stirred uniformly and placed in a constant pressure dropping funnel; adding 10wt.% NaOH aqueous solution to adjust the pH value of the reaction kettle solution to 9-10; introducing nitrogen into the reaction kettle, and then beginning to dropwise add the ferrous sulfate aqueous solution within 40-60 minutes; maintaining nitrogen atmosphere, and stirring and reacting for 2 hours at 50 ℃; stopping the reaction, precipitating the generated polymer from the system, and carrying out centrifugal separation under the protection of nitrogen at a centrifugal speed of 5000-8000 rpm for 20min; drying at 80deg.C under vacuum degree of 0.01-0.05MPa, and pulverizing to obtain the final product.
Example 5
The embodiment provides a multifunctional drilling treatment agent which is prepared from the following raw materials in parts by weight: 41kg of carboxymethyl starch (CMS), 15kg of carboxymethyl cellulose (LV-CMC); 30kg of acrylamide, 10kg of sodium N- (3-aminopropyl) methacrylate and 1kg of hydrogen peroxide; ferrous sulfate 1kg, sodium dodecyl sulfate 2kg, ethylene glycol 100kg, ethanol 100kg.
The preparation method of the multifunctional drilling treatment agent comprises the following steps: firstly, adding 100kg of ethylene glycol and 100kg of ethanol into a reaction kettle, and stirring to uniformly mix, wherein the mixture is used as a polymerization solvent; 41kg of carboxymethyl starch, 15kg of carboxymethyl cellulose, 30kg of acrylamide, 30kg of double bond-containing water-soluble compound monomer N- (3-aminopropyl) sodium methacrylate are added into a reaction kettle, 1kg of hydrogen peroxide and 2kg of sodium dodecyl sulfonate are added, and the raw materials are stirred to be completely dissolved; then 1kg of ferrous sulfate is dissolved in 20kg of distilled water, and the mixture is stirred uniformly and placed in a constant pressure dropping funnel; adding 10wt.% NaOH aqueous solution to adjust the pH value of the reaction kettle solution to 9-10; introducing nitrogen into the reaction kettle, and then beginning to dropwise add the ferrous sulfate aqueous solution within 40-60 minutes; maintaining nitrogen atmosphere, and stirring and reacting for 2 hours at 50 ℃; stopping the reaction, precipitating the generated polymer from the system, and carrying out centrifugal separation under the protection of nitrogen at a centrifugal speed of 5000-8000 rpm for 20min; drying at 80deg.C under vacuum degree of 0.01-0.05MPa, and pulverizing to obtain the final product.
Example 6
The embodiment provides a multifunctional drilling treatment agent which is prepared from the following raw materials in parts by weight: 51kg of pregelatinized starch (alpha-starch), 20kg of low viscosity polyanionic cellulose (LV-PAC); 20kg of acrylamide, 5kg of sodium styrene sulfonate and 1kg of hydrogen peroxide; sodium sulfite 1kg, polyethylene glycol 2kg, ethanol 400kg.
The preparation method of the multifunctional drilling treatment agent comprises the following steps: adding 400kg of ethanol into a reaction kettle, and stirring to uniformly mix, wherein the mixture is used as a polymerization solvent; 51kg of pregelatinized starch (alpha-starch), 20kg of low-viscosity polyanionic cellulose (LV-PAC), 20kg of acrylamide and 5kg of double bond-containing water-soluble compound monomer sodium styrene sulfonate are added into a reaction kettle, 1kg of hydrogen peroxide and 2kg of polyethylene glycol are added, and the raw materials are stirred to be completely dissolved; then 1kg of sodium sulfite is dissolved in 20kg of distilled water, and the mixture is stirred uniformly and placed in a constant pressure dropping funnel; adding 10wt.% NaOH aqueous solution to adjust the pH value of the reaction kettle solution to 9-10; introducing nitrogen into the reaction kettle, and then beginning to dropwise add sodium sulfite aqueous solution, wherein the dropwise addition is completed within 40-60 minutes; maintaining nitrogen atmosphere, and stirring and reacting for 2 hours at 50 ℃; stopping the reaction, precipitating the generated polymer from the system, and carrying out centrifugal separation under the protection of nitrogen at a centrifugal speed of 5000-8000 rpm for 20min; drying at 80deg.C under vacuum degree of 0.01-0.05MPa, and pulverizing to obtain the final product.
Example 7
The embodiment provides a multifunctional drilling treatment agent which is prepared from the following raw materials in parts by weight: 86kg of carboxymethyl starch (CMS), 8kg of carboxymethyl cellulose (LV-CMC); 2kg of acrylamide, 1kg of sodium N- (3-aminopropyl) methacrylate and 1kg of sodium persulfate; ferrous sulfate 1kg, polyethylene glycol 2kg, isopropanol 100kg, ethanol 100kg.
The preparation method of the multifunctional drilling treatment agent comprises the following steps: firstly, adding 100kg of isopropanol and 100kg of ethanol into a reaction kettle, and stirring to uniformly mix, wherein the mixture is used as a polymerization solvent; 85kg of starch, 8kg of cellulose, 2kg of acrylamide, 1kg of double bond-containing water-soluble compound monomer N- (3-aminopropyl) sodium methacrylate are added into a reaction kettle, 1kg of sodium persulfate and 2kg of polyethylene glycol are added, and the raw materials are stirred to be completely dissolved; then 1kg of ferrous sulfate is dissolved in 20kg of distilled water, and the mixture is stirred uniformly and placed in a constant pressure dropping funnel; adding 10wt.% NaOH aqueous solution to adjust the pH value of the reaction kettle solution to 9-10; introducing nitrogen into the reaction kettle, and then beginning to dropwise add the ferrous sulfate aqueous solution within 40-60 minutes; maintaining nitrogen atmosphere, and stirring and reacting for 2 hours at 50 ℃; stopping the reaction, precipitating the generated polymer from the system, and carrying out centrifugal separation under the protection of nitrogen at a centrifugal speed of 5000-8000 rpm for 20min; drying at 80deg.C under vacuum degree of 0.01-0.05MPa, and pulverizing to obtain the final product.
Example 8
The embodiment provides a multifunctional drilling treatment agent which is prepared from the following raw materials in parts by weight: 16kg of carboxymethyl starch (CMS), 5kg of carboxymethyl cellulose (LV-CMC); 50kg of acrylamide, 25kg of sodium N- (3-aminopropyl) methacrylate and 1kg of sodium persulfate; ferrous sulfate 1kg, polyethylene glycol 2kg, isopropanol 100kg, ethanol 100kg.
The preparation method of the multifunctional drilling treatment agent comprises the following steps: firstly, adding 100kg of isopropanol and 100kg of ethanol into a reaction kettle, and stirring to uniformly mix, wherein the mixture is used as a polymerization solvent; adding 16kg of starch, 5kg of cellulose, 50kg of acrylamide and 25kg of double bond-containing water-soluble compound monomer N- (3-aminopropyl) sodium methacrylate into a reaction kettle, adding 1kg of sodium persulfate and 2kg of polyethylene glycol, and stirring to completely dissolve the raw materials; then 1kg of ferrous sulfate is dissolved in 20kg of distilled water, and the mixture is stirred uniformly and placed in a constant pressure dropping funnel; adding 10wt.% NaOH aqueous solution to adjust the pH value of the reaction kettle solution to 9-10; introducing nitrogen into the reaction kettle, and then beginning to dropwise add the ferrous sulfate aqueous solution within 40-60 minutes; maintaining nitrogen atmosphere, and stirring and reacting for 2 hours at 50 ℃; stopping the reaction, precipitating the generated polymer from the system, and carrying out centrifugal separation under the protection of nitrogen at a centrifugal speed of 5000-8000 rpm for 20min; drying at 80deg.C under vacuum degree of 0.01-0.05MPa, and pulverizing to obtain the final product.
Comparative example 1
The comparative example provides a multifunctional drilling treatment agent which is prepared from the following raw materials in parts by weight: carboxymethyl starch (CMS) 71kg, sodium N- (3-aminopropyl) methacrylate 25g, ferrous sulfate 1kg, polyethylene glycol 2kg, isopropanol 100kg, ethanol 100kg.
The preparation method of the multifunctional drilling treatment agent comprises the following steps: firstly, adding 100kg of isopropanol and 100kg of ethanol into a reaction kettle, and stirring to uniformly mix, wherein the mixture is used as a polymerization solvent; 71kg of starch and 25g N- (3-aminopropyl) sodium methacrylate are added into a reaction kettle, 1kg of sodium persulfate and 2kg of polyethylene glycol are added, and the raw materials are stirred to be completely dissolved; then 1kg of ferrous sulfate is dissolved in 20kg of distilled water, and the mixture is stirred uniformly and placed in a constant pressure dropping funnel; adding 10wt.% NaOH aqueous solution to adjust the pH value of the reaction kettle solution to 9-10; introducing nitrogen into the reaction kettle, and then beginning to dropwise add the ferrous sulfate aqueous solution within 40-60 minutes; maintaining nitrogen atmosphere, and stirring and reacting for 2 hours at 50 ℃; stopping the reaction, precipitating the generated polymer from the system, and carrying out centrifugal separation under the protection of nitrogen at a centrifugal speed of 5000-8000 rpm for 20min; drying at 80deg.C under vacuum degree of 0.01-0.05MPa, and pulverizing to obtain the final product.
Comparative example 2
Selecting 50kg of carboxymethyl starch (CMS) and 25kg of carboxymethyl cellulose (LV-CMC); 25kg of polyacrylamide (molecular weight 50-90 ten thousand) is directly mixed.
Test example:
the products obtained in examples 1-8 and comparative examples 1-2 were tested according to the drilling fluid API 13A standard, clauses 16.3, 16.4, with the products obtained in examples 1-6 accounting for 0.75wt.% of the total test system, and the properties are shown in Table 1:
table 1 performance index of multifunctional drilling treatments
Note that: the test sample is subjected to normal temperature test after being thermally rolled for 16 hours at 120 ℃ before testing.
The products provided in examples 1-8, which combine the comprehensive effects of starch, cellulose and polymer products of natural polymer products, have excellent cutting performance, can improve the suspension property and sand carrying property of the drilling fluid, and can not greatly improve the apparent viscosity of the drilling fluid; the filter has excellent filtrate loss performance and good temperature and salt resistance effect; meanwhile, the coating has good coating inhibition performance, can effectively coat clay and drill cuttings, prevents solid phase pollution, can resist the temperature of more than 120 ℃ in a saturated saline and seawater drilling fluid system, has strong cutting capacity, has limited influence on apparent viscosity of the drilling fluid, and can also play a role in coating inhibition. And meanwhile, the main structure of the product is starch and cellulose, so that the product is easy to degrade, nontoxic and pollution-free, belongs to an environment-friendly product, has excellent comprehensive performance, can meet the requirements of maintenance and treatment of the current on-site drilling fluid, has a very wide application prospect, and is particularly suitable for large-displacement wells and solid-free drilling fluids.
It is to be understood that the above embodiments are merely illustrative of the exemplary embodiments employed to illustrate the principles of the present application, however, the present application is not limited thereto. Various modifications and improvements may be made by those skilled in the art without departing from the spirit and substance of the application, and are also considered to be within the scope of the application.
Claims (13)
1. The multifunctional drilling treatment agent is prepared by adopting a dispersion polymerization process and is prepared by graft copolymerization of starch and cellulose and acrylamide under the action of an initiator;
the initiator comprises an oxidizing agent and a reducing agent; the multifunctional drilling treatment agent comprises raw materials and a solvent, wherein the raw materials of the multifunctional drilling treatment agent comprise the following components in percentage by mass: 30-80% of starch, 10-40% of cellulose, 5-45% of acrylamide, 0-15% of a water-soluble compound monomer containing double bonds, 0.5-5% of an oxidant, 0.5-5% of a reducing agent and 0.5-5% of a dispersion stabilizer;
the water-soluble compound monomer containing double bonds is selected from one or more of amino acrylic acid, amino acrylic acid salt, styrene sulfonate and allylic quaternary ammonium salt;
the dosage of the solvent is 1-5 times of the total weight of the raw materials of the multifunctional drilling treatment agent,
the solvent is selected from one or more of isopropanol, ethanol, ethylene glycol and propylene glycol.
2. The multifunctional well treatment agent of claim 1, wherein the initiator comprises an oxidizing agent and a reducing agent; the multifunctional drilling treatment agent comprises raw materials and a solvent, wherein the raw materials of the multifunctional drilling treatment agent comprise the following components in percentage by mass: 30-80% of starch, 10-40% of cellulose, 5-45% of acrylamide, 0.5-15% of water-soluble compound monomer containing double bonds, 0.5-5% of oxidant, 0.5-5% of reducing agent and 0.5-5% of dispersion stabilizer;
the starch is one or more than two of pregelatinized starch, sulfonated starch, carboxymethyl starch and temperature resistant starch;
the cellulose is selected from one or more of hydroxypropyl cellulose, hydroxymethyl cellulose, polyanionic cellulose and sodium carboxymethyl cellulose.
3. The multifunctional well treatment agent of claim 1, wherein the materials of the multifunctional well treatment agent comprise, in mass fraction:
40-70% of starch, 15-35% of cellulose, 10-35% of acrylamide, 2-10% of a water-soluble compound monomer containing double bonds, 1-2% of an oxidant, 1-2% of a reducing agent and 1-3% of a dispersion stabilizer.
4. The multifunctional drilling treating agent of claim 1, wherein the oxidizing agent is selected from one or more of hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate.
5. The multifunctional well treatment agent of claim 1, wherein the reducing agent is selected from one or more of ferrous sulfate, sodium sulfite, and amine sulfite.
6. The multifunctional well treatment agent of claim 1, wherein,
the solvent consists of isopropanol and ethanol, the dosage of the solvent is 1.5-3 times of the total weight of the raw materials of the multifunctional drilling treatment agent, and the weight ratio of the isopropanol to the ethanol is (2:8) - (8:2).
7. The multifunctional well treatment agent of claim 1, wherein the starch has a particle size of 60-120 mesh.
8. The multifunctional well treatment agent of claim 1, wherein the dispersion stabilizer is selected from one or more of polyethylene glycol, anionic surfactant, and cationic surfactant.
9. The multifunctional well treatment agent of claim 1, wherein the dispersion stabilizer is selected from one or more of polyethylene glycol, alkyl sulfonate, and quaternary ammonium salt.
10. A method of preparing a multifunctional drilling treating agent according to any one of claims 1 to 9, comprising:
(1) Adding a solvent, acrylamide, starch, cellulose and a water-soluble compound monomer containing double bonds into a reaction container, adding an oxidant and a dispersion stabilizer, and stirring until the mixture is completely dissolved;
(2) Adjusting the pH value of the solution in the reaction vessel to 8-10;
(3) Introducing a protective gas into the reaction vessel;
(4) Dripping the aqueous solution of the reducing agent, and finishing dripping within 40-60 minutes;
(5) Continuously stirring at 30-50 ℃ for reaction for 2-3 hours;
(6) Separating the generated precipitate under the atmosphere of protective gas;
(7) Drying the precipitate obtained in the step (6) at 60-80 ℃ and a vacuum degree of 0.01-0.05MPa to obtain the multifunctional drilling treating agent.
11. The method of preparing a multifunctional well treatment agent according to claim 10, wherein the shielding gas is selected from one or more of nitrogen, helium and argon.
12. The method for preparing a multifunctional well drilling treating agent according to claim 10, wherein the mass concentration of the aqueous solution of the reducing agent in the step (4) is 2-10%.
13. Use of a multifunctional drilling-treatment agent according to any one of claims 1 to 9 as a drilling-fluid additive.
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