CN108641686B - Flow pattern regulator for ultra-high temperature and ultra-high density water-based drilling fluid and completion fluid and preparation method thereof - Google Patents
Flow pattern regulator for ultra-high temperature and ultra-high density water-based drilling fluid and completion fluid and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polycarboxylate flow pattern regulator for ultra-high temperature and ultra-high density water-based drilling fluid and completion fluid and a preparation method thereof, wherein alkenyl benzene sulfonate, strongly hydrophilic cationic alkenyl quaternary ammonium salt and allyl polyoxyethylene ether containing a specific long-chain structure are subjected to aqueous solution free radical polymerization to generate a zwitter-ion polycarboxylate multipolymer with a comb-type structure, the molecular chain of the generated multipolymer contains 7-20 structural units, and the weight average molecular weight range is 6,500-12,500-one. The polycarboxylate flow pattern regulator can greatly reduce the viscosity and shear force of the ultrahigh-temperature and ultrahigh-density water-based drilling fluid completion fluid, improve the dispersion state of a solid-phase weighting material in the water-based drilling fluid completion fluid, improve the rheological property of the ultrahigh-temperature and ultrahigh-density water-based drilling fluid completion fluid, obviously reduce the surface tension of the ultrahigh-temperature and ultrahigh-density water-based drilling fluid completion fluid, increase the lubricating property of the ultrahigh-temperature and ultrahigh-density water-based drilling fluid, has the mud shale inhibition property and the high-temperature stability property, and can resist the high temperature of more than 251 ℃.
Description
The technical field is as follows:
the invention relates to a flow pattern regulator for an ultrahigh-temperature and ultrahigh-density water-based drilling fluid and completion fluid and a preparation method thereof, belonging to the technical field of drilling fluids and completion fluids in petroleum and natural gas drilling engineering, exploration and development of earth deep resources and geothermal well drilling engineering.
Background art:
in recent years, with the continuous development of deep development of oil and gas exploration in the world and the continuous promotion of important deep projects such as deep resource exploration, continental scientific drilling engineering, earth deep exploration plans and the like in China, and the increasing number of ultra-high temperature reservoirs in drilling engineering of geothermal wells, the probability of drilling ultra-high pressure strata (the pressure of stratum pores exceeds 138MPa) and ultra-high temperature strata (the temperature exceeds 220 ℃) in the drilling engineering process increases year by year, so that the situations of using an ultra-high density water-based drilling fluid completion fluid system, an ultra-high temperature water-based drilling fluid completion fluid system and an ultra-high temperature ultra-high density water-based drilling fluid completion fluid system in the drilling process are more and more. However, for ultra-high temperature formations, the maintenance and treatment of the ultra-high density water-based drilling fluid completion fluid are often extremely complicated, and the ultra-high density water-based drilling fluid completion fluid often falls into a vicious circle of weighting → thickening → viscosity reduction → weighting agent sedimentation → density reduction → re-weighting, so that the smooth operation of drilling is affected, and even serious downhole complex accidents can be caused. Because the solid phase content of the ultra-high density drilling fluid system is very high and even reaches 50-60%, the viscosity and the shear force of the drilling fluid completion fluid are usually large, a series of complex physical and chemical reactions can be caused under the condition of an ultra-high temperature bottom hole environment, so that the flowing property of the drilling fluid completion fluid is remarkably deteriorated, the rheological property of the ultra-high temperature and ultra-high density drilling fluid system is extremely difficult to regulate and control, and the two aspects are usually shown, namely, the ultra-high temperature and ultra-high density resistant drilling fluid completion fluid system with good rheological property is difficult to prepare successfully, and the stability of the rheological property of the ultra-high temperature and ultra-high density water-based drilling fluid completion fluid in the normal drilling process is difficult. Therefore, how to effectively improve the fluidity of the ultrahigh-temperature ultrahigh-density water-based drilling fluid and completion fluid, maintain the sedimentation stability of a high-density solid-phase weighting material, and solve the problem of regulating and controlling the rheological property of the ultrahigh-temperature ultrahigh-density water-based drilling fluid and completion fluid is one of key technologies for smoothly carrying out drilling engineering, and the development of a high-performance flow type regulator capable of resisting ultrahigh temperature is an effective technical approach for solving the problem.
At present, viscosity reducers or diluents of various high molecular compounds are often used as flow pattern regulators of ultrahigh-temperature and ultrahigh-density water-based drilling fluid and completion fluid in drilling engineering sites, such as sulfomethylated tannin, lignosulfonate, polymers with low relative molecular mass, polymer grafted natural high molecular materials with low relative molecular mass and the like, but the existing viscosity reducers or diluents still have the characteristics of insufficient functionality, insufficient temperature resistance and the like.
There are also a number of patent documents relating to flow pattern modifiers for drilling fluids, for example: chinese patent document CN102485826A discloses a low-temperature micro-bubble drilling fluid flow pattern regulator and application thereof; the flow pattern regulator is prepared from xanthan gum and an inorganic boron crosslinking agent, the mass ratio of the xanthan gum to the inorganic boron crosslinking agent is 1: 1-2: 1, the water-soluble content of the flow pattern regulator is not less than 90%, the water content is not more than 15%, the pH value of a 0.5% aqueous solution prepared from the flow pattern regulator is 5.0-7.0, the apparent viscosity is 15-25 mPa & s, and the microbubble stabilization time is not less than 24h, and the flow pattern regulator is used as a flow pattern regulator of microbubble drilling fluid, and the dosage of the low-temperature microbubble drilling fluid flow pattern regulator is 0.1-0.4 g based on one hundred g of water in the microbubble drilling fluid. For another example: chinese patent document CN107955586A discloses the use of cellulose nanofibers as a flow pattern modifier for drilling fluids. The cellulose nanofiber is applied to a flow pattern regulator for drilling fluid, and the addition amount of the cellulose nanofiber in the drilling fluid is 0.1-3.0% by volume. However, the above-mentioned xanthan gum and cellulose belong to natural polymer materials, which are greatly affected by temperature, and when the temperature exceeds 120 ℃, the molecular structures of the xanthan gum and cellulose polymer materials and their modified products are easily damaged under high temperature conditions, so that the high temperature of the xanthan gum and cellulose flow pattern regulator is lost, and thus it cannot be applied to high temperature or ultra-high temperature drilling fluid completion fluids; in addition, the flow pattern regulator is mainly used for viscosity increasing and cutting improving of low-density drilling fluid and completion fluid, and is not suitable for high-temperature high-density water-based drilling fluid and completion fluid and ultrahigh-temperature ultrahigh-density water-based drilling fluid and completion fluid, namely the high-solid-phase high-temperature or ultrahigh-temperature water-based drilling fluid and completion fluid does not have viscosity decreasing and cutting reducing effects. For another example: when some polymer products with low relative molecular mass are used as flow pattern regulators or viscosity reducers of high-temperature and high-density water-based drilling fluid completion fluids, the polymer products are limited by specific molecular structures, the technical problem of poor temperature resistance is mainly faced, when the temperature exceeds 180 ℃, the polymer products generally fail due to high temperature, so the temperature resistance of the flow pattern regulators for the drilling fluid completion fluids is generally lower than 180 ℃, and therefore, the polymer products are not suitable for the ultrahigh-temperature and ultrahigh-density water-based drilling fluid completion fluids. However, the high-performance polycarboxylate product has excellent performances of low doping amount, strong dispersion, environmental protection and the like, and is recently used as a high-efficiency water reducing agent for regulating the slurry performance of concrete cement slurry, and also used as a strong dispersing agent for regulating the rheological property of coal water slurry. But the research and application of the polycarboxylate used as the high-efficiency flow pattern regulator in the ultra-high density water-based drilling fluid completion fluid are not reported, and the polycarboxylate has wide application prospect in the ultra-high density water-based drilling fluid completion fluid according to the dispersion mechanism of the polycarboxylate acting on the high-concentration solid-phase particle turbid fluid; in addition, the good temperature resistance of the polycarboxylate enables the polycarboxylate to have the potential of being applied to the ultrahigh-temperature water-based drilling fluid and completion fluid, so that the polycarboxylate is used as the flow pattern regulator for the ultrahigh-temperature ultrahigh-density water-based drilling fluid and completion fluid and overcomes the technical problems of the traditional flow pattern regulator for the traditional drilling fluid and completion fluid, and the technical problems to be solved by the technical personnel in the field still remain.
The invention content is as follows:
aiming at the defects of the prior art, the invention provides the flow pattern regulator for the drilling fluid completion fluid, which can resist ultra-high temperature, greatly reduce the viscosity and the shear force of the ultra-high density drilling fluid completion fluid, reduce the surface tension of the ultra-high temperature water-based drilling fluid completion fluid, improve the dispersion state of a solid phase weighting material in the ultra-high temperature ultra-high density water-based drilling fluid completion fluid, improve the rheological property of the ultra-high temperature ultra-high density water-based drilling fluid completion fluid, increase the lubricating property of the ultra-high temperature ultra-high density water-based drilling fluid, and have certain mud shale inhibition performance and high temperature stability.
The technical scheme of the invention is as follows:
a flow pattern regulator for ultra-high temperature and ultra-high density water-based drilling fluid and completion fluid has the structure shown in the formula (I):
the flow pattern regulator is a zwitterion terpolymer with a comb-shaped structure, which is generated by carrying out aqueous solution free radical polymerization on alkenyl benzene sulfonate, strong hydrophilic cation alkenyl quaternary ammonium salt and allyl polyoxyethylene ether containing a long-chain structure;
in the formula (I), x, y and z respectively represent the mole numbers of an anionic reaction monomer alkenyl benzene sulfonate, an allyl polyoxyethylene ether macromonomer and a cationic reaction monomer alkenyl quaternary ammonium salt in the structural formula, and m represents the number of repeating chain links of polyoxyalkyl in allyl polyoxyethylene ether containing a long-chain structure.
According to the invention, the molecular structure main chain of the flow pattern regulator preferably contains 7-20 structural units, and the weight-average molecular weight is in the range of 6,500-12,500; the molar ratio x/y is (0.35-0.85): (0.55-1.55), the weight of the alkenyl quaternary ammonium salt accounts for 3-15% of the total weight of the alkenyl benzenesulfonate and the allyl polyoxyethylene ether, and m is 5-26.
According to the invention, it is preferred that the allyl polyoxyethylene ether with a long-chain structure has an unsaturation degree of more than 1.25mmol/g and a hydroxyl value of 85 to 155 mgKOH/g.
According to the invention, preferably, the molecular structure main chain of the flow pattern regulator contains 10-15 structural units, and the weight average molecular weight is in the range of 7,000-10,000; the molar ratio x: y is (0.45-0.65): 0.75-1.25), the weight of the alkenyl quaternary ammonium salt accounts for 3-8% of the total weight of the alkenyl benzene sulfonate and the allyl polyoxyethylene ether, and m is 5-15.
According to the invention, the main chain of the molecular structure of the flow pattern regulator preferably contains 7-12 structural units, the weight average molecular weight is 10,000-12,000, the molar ratio x: y is (0.48-0.52): 0.85-1.15), the weight of the alkenyl quaternary ammonium salt accounts for 5-12% of the total weight of the alkenyl benzene sulfonate and the allyl polyoxyethylene ether, and m is 12-15.
According to the invention, the preparation method of the flow pattern regulator for the ultrahigh-temperature ultrahigh-density water-based drilling fluid and completion fluid comprises the following steps:
adding reactants of alkenyl benzene sulfonate, strongly hydrophilic cationic alkenyl quaternary ammonium salt and long-chain-structure-containing allyl polyoxyethylene ether into a reaction kettle filled with a solvent according to a ratio, adding a catalyst into the solvent to be fully dissolved, then pouring the solution into the reaction kettle, adjusting the concentration of the mixed solution of the reactants by using the solvent, heating the mixed solution in the reaction kettle in a water bath heating or steam heating manner, maintaining the reaction time, terminating the reaction, and cooling to room temperature to obtain the flow pattern regulator for the ultra-high temperature and ultra-high density water-based drilling fluid completion fluid. The flow pattern regulator is a light yellow to reddish brown liquid product with certain concentration.
According to the present invention, preferably, the solvent is water;
preferably, the catalyst is a combination of persulfate and sodium bisulfite; or, the initiator is one or the combination of a water-soluble azo initiator and an amphiphilic azo initiator;
preferably, the mass ratio of the persulfate to the sodium bisulfite is 1: 1.
according to the present invention, preferably, the persulfate is potassium persulfate or ammonium persulfate;
preferably, the water-soluble azo initiator is azobisisobutyramidine hydrochloride or azobisisobutyrimidazoline hydrochloride, and the amphiphilic azo initiator is azobisisobutyronitrile formamide.
According to the invention, it is preferred that the total weight of the reactants represents from 30 to 60% by weight of the total weight of the solution formed by the reactants and the solvent;
when the catalyst is the combination of persulfate and sodium bisulfite, the addition amount of the catalyst is 0.5 to 4 weight percent of the total weight of the reactants;
when the catalyst is water-soluble azo initiator or/and amphiphilic azo initiator, the addition amount of the catalyst is 0.1-2 wt% of the total weight of the reactants.
According to the invention, the reaction temperature is preferably 60 to 95 ℃; the reaction time is from 1.5 hours to 6 hours.
According to the inherent property of the ultra-high temperature and ultra-high density water-based drilling fluid completion fluid containing high-concentration solid-phase weighted particles and the specific physicochemical characteristics of the ultra-high temperature and high density water-based drilling fluid completion fluid, the invention designs the molecular structure of the drilling fluid completion fluid by taking the research on the action mechanism of the ultra-high temperature and ultra-high density water-based drilling fluid completion fluid as a starting point, and the prepared flow pattern regulator suitable for the ultra-high temperature and ultra-high density water-based drilling fluid completion fluid system has good effect.
The reaction process of the invention is as follows:
the flow pattern regulator for the ultrahigh-temperature and ultrahigh-density water-based drilling fluid and completion fluid has the following action mechanism and beneficial effects:
(1) reducing the surface tension mechanism of action. After a small amount of the popular regulator is added, the surface tension of the ultrahigh-temperature ultrahigh-density water-based drilling fluid completion fluid is reduced, the wettability of the surfaces of ultrahigh-temperature solid-phase particles can be effectively improved under an ultrahigh-temperature environment, the compatibility problem and the agglomeration performance of high-concentration inert particles caused by the change of subcritical water characteristics of other high-temperature resistant treatment agents are improved, and meanwhile, the lubricating performance of the surfaces of the ultrahigh-temperature solid-phase particles can be improved.
(2) Effectively inhibit hydration slurrying of the clay mineral and improve the dispersion mechanism of the clay mineral and weighting agent particles. The amphoteric ion characteristic enables the water-based well completion fluid to effectively inhibit the slurrying performance of clay mineral particles under the ultra-high temperature condition, the specific molecular structure with the comb-shaped structure enables the clay mineral particles to be adsorbed on the surfaces of the clay mineral and a weighting agent under the action of hydrogen bonds, electrostatic force and the like, the Zeta potential of solid phase particles is reduced, the clay mineral particles can keep a good dispersion state under the condition of the ultra-high solid phase particles, the long molecular chain characteristic of a polyoxyethylene chain can increase the steric hindrance effect between the surfaces of the solid phase particles, and the agglomeration characteristic of the clay mineral particles under the ultra-high temperature condition is inhibited, so that the viscosity, the shearing force and the rheological stability of the well completion fluid of the ultra-high temperature and ultra-high density water-based well completion fluid are greatly reduced, and the filtration wall building performance of the.
Description of the drawings:
FIG. 1 is an infrared spectrum of a flow pattern regulator for the ultra-high temperature and ultra-high density water-based drilling fluid and completion fluid obtained in example 2 of the present invention.
FIG. 2 is a characteristic spectrogram of a flow pattern regulator for the ultra-high temperature and ultra-high density water-based drilling fluid and completion fluid, which is obtained in example 2 of the present invention, by nuclear magnetic resonance C spectroscopy.
The specific implementation mode is as follows:
the present invention is further illustrated by, but is not limited to, the following specific examples.
The starting materials used in the examples are, unless otherwise specified, conventional commercial products.
The flow pattern regulator for the ultrahigh-temperature and ultrahigh-density water-based drilling fluid completion fluid in the embodiment has a structure shown in a formula (I):
the flow pattern regulator is a zwitterion terpolymer with a comb-shaped structure, which is generated by carrying out aqueous solution free radical polymerization on alkenyl benzene sulfonate, strong hydrophilic cation alkenyl quaternary ammonium salt and allyl polyoxyethylene ether containing a long-chain structure;
in the formula (I), x, y and z respectively represent the mole numbers of an anionic reaction monomer alkenyl benzene sulfonate, an allyl polyoxyethylene ether macromonomer and a cationic reaction monomer alkenyl quaternary ammonium salt in the structural formula, and m represents the number of repeating chain links of polyoxyalkyl in allyl polyoxyethylene ether containing a long-chain structure.
Example 1:
weighing 56.68 g of sodium alkenyl benzenesulfonate, adding into a reaction kettle with a volume of 2.5 liters and equipped with a stirrer, a reflux condenser, a nitrogen protection device, a temperature sensor and a heating device, adding 500 ml of tap water, starting the stirring device, and stirring at a high speed to fully dissolve the sodium alkenyl benzenesulfonate; 392 g of allyl polyoxyethylene ether (the repeating chain number of polyoxyalkyl is m ═ 12-15) are weighed and poured into a reaction kettle; weighing 22.43 g of methacryloyloxyethyl trimethyl ammonium chloride, pouring into a reaction kettle, and stirring at a high speed for 10 minutes; weighing 18.89 g of ammonium persulfate, fully dissolving the ammonium persulfate in 200 ml of tap water, pouring the ammonium persulfate into a reaction kettle, uniformly stirring the ammonium persulfate and the reaction kettle at a high speed, and then adding tap water until the total amount of the tap water reaches 1575 ml; introducing nitrogen, stirring at a high speed for 5 minutes, heating to 78-83 ℃, reacting for 4 hours, and cooling to room temperature to obtain the flow pattern regulator for the ultra-high temperature and ultra-high density water-based drilling fluid completion fluid, wherein the mass concentration of the flow pattern regulator is about 30%.
In the flow pattern modifier, the molar ratio x: y of the alkenylbenzenesulfonate salt to the allylpolyoxyethyleneether was 0.50: 1.00, the weight of the alkenylquaternary ammonium salt was 5.0% based on the total weight of the alkenylbenzenesulfonate salt and the allylpolyoxyethyleneether, the weight-average molecular weight of the polycarboxylate was about 10,500, and the number of structural units was about 9 to 11.
Example 2:
weighing 61.8 g of sodium alkenyl benzenesulfonate in a 1.5L reaction kettle equipped with a stirrer, a reflux condenser, a nitrogen protection device, a temperature sensor and a heating device, adding 600 ml of tap water, starting the stirring device, and stirring at high speed to fully dissolve the sodium alkenyl benzenesulfonate; 216 g of allyl polyoxyethylene ether (the number of repeating chain links of polyoxyalkyl is m-5-9) is weighed and poured into a reaction kettle; weighing 18.1 g of methacryloyloxyethyl trimethyl ammonium chloride, pouring into a reaction kettle, and stirring at a high speed for 10 minutes; weighing 3.55 g of azodiisobutyl amidine hydrochloride, fully dissolving the azodiisobutyl amidine hydrochloride in 100 ml of tap water, pouring the mixture into a reaction kettle, uniformly stirring the mixture at a high speed, adding the tap water till the total amount of the tap water reaches 850 ml, introducing nitrogen, stirring the mixture at a high speed for 5 minutes, heating the mixture to 63-68 ℃, reacting the mixture for 4 hours, and cooling the mixture to room temperature to obtain the flow pattern regulator for the ultrahigh-temperature ultrahigh-density water-based drilling fluid completion fluid, wherein the mass concentration of the flow pattern regulator is about 35%.
In the flow pattern modifier, the molar ratio x: y of the alkenylbenzenesulfonate salt to the allylpolyoxyethyleneether was 0.50: 1.20, the weight of the alkenylquaternary ammonium salt was 6.5% based on the total weight of the alkenylbenzenesulfonate salt and the allylpolyoxyethyleneether, the weight-average molecular weight of the polycarboxylate was about 7,900, and the number of structural units was about 11 to 13.
Example 3:
adding 500 kg of tap water into a stainless steel corrosion-resistant reaction kettle which is provided with a stirrer, a reflux condenser, a nitrogen protection device, a thermometer and a heating device and has the capacity of 3-3.5 tons, starting the stirrer, adding 142 kg of sodium p-styrene sulfonate into the reaction kettle at the speed of 25 kg/min, and stirring until the sodium p-styrene sulfonate is dissolved uniformly; 497 kg of allyl polyoxyethylene ether (the number of repeating chain links of polyoxyalkyl group, m: 5-9) was added to the reaction vessel at a rate of 50 kg/min, and stirred for 10 min; adding 41.5 kg of methacryloyloxyethyl trimethyl ammonium chloride, pouring into a reaction kettle, and stirring at a high speed for 10 minutes; 8.166 kg of azodiisobutyl amidine hydrochloride is weighed and fully dissolved in 100 kg of tap water, poured into a reaction kettle and stirred for 10 minutes; adding tap water to 1950 kg in total weight, introducing nitrogen, stirring for 30 minutes, heating to 65-70 ℃, reacting for 4 hours, and cooling to room temperature to obtain the flow pattern regulator for the ultra-high temperature and ultra-high density water-based drilling fluid completion fluid, wherein the mass concentration is about 35%.
In the flow pattern modifier, the molar ratio x: y of the alkenylbenzenesulfonate salt to the allylpolyoxyethyleneether was 0.50: 1.20, the weight of the alkenylquaternary ammonium salt was 6.5% based on the total weight of the alkenylbenzenesulfonate salt and the allylpolyoxyethyleneether, the weight-average molecular weight of the polycarboxylate was about 7,500, and the number of structural units was about 10 to 13.
Comparative example 1:
generally, the water-soluble polymer with low relative molecular mass has certain viscosity reduction and shear reduction effects on high-temperature and high-density drilling fluid, but is greatly influenced by the temperature and the density value of the drilling fluid completion fluid, and when the temperature exceeds 220 ℃, the density reaches 2.35g/cm3In the above case, the effect is often difficult to exert, and the drilling fluid is often reacted to the ultrahigh-temperature ultrahigh-density water-based drilling fluid. Therefore, in order to enable the flow pattern regulator to have ultrahigh temperature resistance and good viscosity reduction and cutting performance in the ultrahigh-density water-based drilling fluid completion fluid, the comprehensive effect of the novel flow pattern regulator for the ultrahigh-temperature ultrahigh-density water-based drilling fluid completion fluid is obviously influenced by the introduction of the allyl polyoxyethylene ether with a molecular branch with a specific length and the content of the allyl polyoxyethylene ether with the molecular branch in the low relative molecular mass polymer molecular chain, wherein the influence of the length of the allyl polyoxyethylene ether molecular branch is most obvious, and the viscosity reduction and cutting effect of a synthesized product is also reduced by overlong or overlong of the allyl polyoxyethylene ether molecular branch. For this reason, in the process of synthesizing the flow pattern regulator, the weight of the alkenyl quaternary ammonium salt is set as alkenylW% of total weight of benzenesulfonate and allylpolyoxyethylene ether, and by changing the size of the allylpolyoxyethylene ether molecular branch chain under constant other variables, comparative examples 1-1 (x/y: 0.50: 1.20, w: 6.5, m: 5-7), comparative examples 1-2 (x/y: 0.50: 1.20, w: 6.5, m: 10-12), comparative examples 1-3 (x/y: 0.50: 1.20, w: 6.5, m: 14-16), comparative examples 1-4 (x/y: 0.50: 1.20, w: 6.5, m: 19-21), and x/y: 1-5 (x/y: 0.50: 1.24, w: 24, w: 26) were synthesized.
Preparing the ultra-high density water-based drilling fluid: taking 400mL of drilling fluid in a Tarrichwood oil field full of 6-well three-throw drilling field, placing the drilling fluid in a high-speed stirring cup, stirring the drilling fluid for 20 minutes at a high speed at a stirring speed of 8000 rpm, and weighting the drilling fluid to 2.55g/cm according to a weighting agent proportion that the mass ratio of barite to iron ore powder is 2:13And continuously stirring at high speed for 30 minutes to obtain the ultrahigh-density water-based drilling fluid.
Preparation and testing of test slurry: 0.5 percent of each proportional sample is respectively added into the ultra-high density water-based drilling fluid, the mixture is uniformly stirred at a high speed at a stirring speed of 8000 rpm, and the rheological property of each test slurry is measured, and the result is shown in table 1.
TABLE 1 test results in ultra high density water-based drilling fluids
Comparative example 2:
in the invention, after the allyl polyoxyethylene ether with long branched chain is introduced into the linear polymer with low relative molecular mass consisting of alkenyl benzene sulfonate and alkenyl quaternary ammonium salt, the flow type regulator has a comb-shaped structure, and when the flow type regulator is in a drilling fluid completion fluid with high clay mineral content, part of the long branched chain structure of the polyoxyethylene ether can be embedded into the interlayer of the clay mineral, thereby preventing the clay mineral from strong dispersion under the high-temperature condition; and part of the polyoxyethylene ether branched chain structure is adsorbed on the surface of clay mineral particles, and can prevent the clay mineral from coalescing under the high-temperature condition. The flow pattern regulator has stronger adsorption effect on high-concentration solid-phase particles dispersed in the ultrahigh-density water-based drilling fluid, and alkenyl quaternary ammonium salt contained in a molecular chain of the flow pattern regulator is one of main reasons for positively charging. However, when the number of chain links of the alkenyl quaternary ammonium salt side chain is large, namely when the reaction ratio of the alkenyl quaternary ammonium salt monomer is too large, the relative molecular mass of the synthesized flow pattern regulator is high, the control is not easy in the reaction, the copolymerization of alkenyl benzene sulfonate and allyl polyoxyethylene ether is influenced, the surface activity of the synthesized product is reduced, and the action effect of the synthesized product in the ultrahigh-temperature ultrahigh-density water-based drilling fluid is weakened. For this purpose, in the synthesis of the flow pattern modifier, control was performed under constant conditions by changing the reaction ratios of the alkenyl quaternary ammonium salts, assuming that the weight of the alkenyl quaternary ammonium salt was w% of the total weight of the alkenyl benzenesulfonate salt and the allyl polyoxyethylene ether, and by changing the ratio of the alkenyl quaternary ammonium salt, comparative example 2-1 (x: y: 0.50: 1.20, w: 5, m: 10-12), comparative example 2-2 (x: y: 0.50: 1.20, w: 10, m: 10-12), comparative example 2-3 (x: y: 0.50: 1.20, w: 15, m: 10-12), comparative example 2-4 (x: y: 0.50: 1.20, w: 20, m: 10-12), and comparative example 2-5 (x: y: 0.50, w: 1.20, w: 20, m: 10-12) were synthesized.
The ultra high density water-based drilling fluid formulation, test slurry formulation and test method were identical to those described in comparative example 1, with the results shown in table 2.
TABLE 2 test results in ultra high density water-based drilling fluids
The performance and effect of the flow pattern regulator for the drilling fluid and completion fluid are evaluated through the test examples.
Test methods in test examples: GB/T32198-2015: general rules of infrared spectrum quantitative analysis technology; and (2) nuclear magnetic resonance C spectrum standard. GB/T5005-: and (4) the drilling fluid material specification. SY 5444-1992: evaluation soil for drilling fluid. SY/T5695-: the drilling fluid uses a zwitterionic polymer viscosity reducer XY 27. Sixthly, adopting GB/T16738-1997: and (4) carrying out a field test procedure on the water-based drilling fluid.
Test example 1
The infrared spectrum characteristic spectrum of the flow pattern modifier for the ultra-high temperature and ultra-high density water-based drilling fluid and completion fluid obtained in example 2 is tested and shown in fig. 1.
Test example 2
The nuclear magnetic resonance C spectrum characteristic spectrum of the flow pattern modifier for the ultra-high temperature and ultra-high density water-based drilling fluid and completion fluid obtained in example 2 was tested and shown in fig. 2.
Test example 3
The flow pattern modifier for the ultra-high temperature ultra-high density water-based drilling fluid completion fluid obtained in example 1 was tested for relative molecular mass.
The relative molecular mass of the flow pattern modifier for the ultra-high temperature ultra-high density water-based drilling fluid completion fluid of example 1 was analyzed by gel permeation chromatography, and the results are shown in table 3.
Table 3 relative molecular mass analysis of example 1 samples
Test example 4
The surface activity performance test of the flow pattern regulator for the ultra-high temperature and ultra-high density water-based drilling fluid completion fluid obtained in example 3 was carried out, and the results are shown in table 4.
TABLE 4 surface tension of the solutions of example 3 in distilled water at different concentrations
Test example 5
Test for testing influence on rheological property of base slurry in ultra-high temperature environment
Preparing base slurry: respectively adding 32g of second-grade bentonite for the drilling fluid into 400mL of tap water, stirring at a high speed of 8000 rpm for 30 minutes, then adding 40g of evaluation soil for the drilling fluid, continuing to stir at a high speed for 2 hours, and standing for 24 hours to obtain the pre-hydrated test base slurry.
Preparation and testing of test slurry: adding 1.5% of the flow pattern regulator for the ultrahigh-temperature and ultrahigh-density water-based drilling fluid completion fluid (samples in examples 1, 2 and 3) and 0.5% of the zwitterionic polymer viscosity reducer XY27 for the drilling fluid into the pre-hydrated base slurry respectively, stirring at a high speed at a stirring speed of 6000 rpm to obtain uniform stirring, and testing the rheological property of each test slurry. The test slurries were loaded into a high temperature aging tank, heat roll aged at 240 ℃ for 16 hours, and the rheology of each test slurry was tested in the same manner.
The rheological parameter calculation method comprises the following steps: the viscosity reduction rate is calculated according to the calculation method in SY/T5695-1995, namely
Viscosity reduction rate (phi '100-phi 100)/phi' 100 x 100% (1)
In the above formula (1): Φ'100 is a reading at 100RPM of the six-speed rotational viscometer after the base slurry to which the evaluation sample was not added was subjected to high-temperature aging at 240 ℃ for 16 hours, and Φ 100 is a reading at 100RPM of the six-speed rotational viscometer after the test slurry to which the evaluation sample was added was subjected to high-temperature aging at 240 ℃ for 16 hours.
The rate of change of the remaining rheological parameters, i.e. the rate of reduction of the Apparent Viscosity (AV), the rate of reduction of the Plastic Viscosity (PV), the rate of reduction of the dynamic shear force (YP), the rate of reduction of the static shear force (Gel 10 "and Gel 10'), the rate of reduction of Φ 6 and the rate of reduction of Φ 3, follow the general formula:
the results are shown in tables 5 and 6.
TABLE 5 test results of the effect of flow pattern modifier for ultra-high temperature ultra-high density water-based drilling fluid completion fluid on the rheology of base fluid
TABLE 6 evaluation results of rheological parameter adjusting effect of flow pattern regulator for ultra-high temperature and ultra-high density water-based drilling fluid and completion fluid on base slurry aged at 240 DEG C
Test example 6
Inhibiting the pulping of bentonite
Preparation and testing of test slurry: the evaluation samples (1.5% of example 3, 0.5% XY-27, 1% of silicofluoride viscosity reducer SF260 for drilling fluid and 0.5% of polyamine) and 5% of secondary bentonite for drilling fluid were added to 400mL of clear water with high agitation for 30min, the slurry was hot-rolled at 70 ℃ for 16 hours, then cooled to room temperature, and the rheological properties of the slurry were tested after 5min with high agitation. And adding 5% of bentonite, stirring for 30min, rolling for 16 hours at 70 ℃, cooling to room temperature, and testing the rheological property of the slurry. This was repeated until the slurry viscosity was too great to be on the instrument scale. The minimum reading of phi 3 indicates that the performance of the bentonite for inhibiting the slurry making is optimal. The results are shown in Table 7.
TABLE 7 test results of the slurry-making property of the inhibited bentonite
Test example 7
Dispersibility of clay mineral particles in water
Preparation and testing of test slurry: adding 7 g of sodium bentonite passing through a 100-mesh sieve into 350 ml of deionized water, stirring at a high speed of 8000 plus 10000RPM for 20 minutes, adding a certain content of each evaluation sample (0.1% of anhydrous sodium carbonate, 1% of example 1, 1% of example 2, 1% of example 3, 5% of potassium chloride, 5% of sodium chloride and 0.5% of polyamine), stirring at a high speed of 8000 plus 10000RPM for 20 minutes, transferring into a 100 ml measuring cylinder, standing for 24 hours, observing the dispersion and flocculation conditions of the sodium bentonite particles of each evaluation sample, recording the flocculation scale value, and calculating the flocculation rate according to the following formula:
C＝(Hw-Hi)/Hw×100％ (2)
in the above formula (2):
c: representing the flocculation rate of the test drug on fully hydrated sodium bentonite;
Hw: represents a flocculation scale value of sodium bentonite when fully hydrated, typically 100;
Hi: the flocculation scale value of each test drug to sodium bentonite.
The results are shown in Table 8.
TABLE 8 results of clay mineral particle dispersibility in water
| Serial number | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| Sample (I) | Na2CO3 | Example 1 sample | Example 2 sample | Example 3 sample | KCl | | Polyamines |
| H | |||||||
| i | 100 | 100 | 100 | 100 | 47 | 54 | 32 |
| Flocculation rate/% | 0 | 0 | 0 | 0 | 53 | 46 | 68 |
Test example 8
Testing in ultra-high temperature ultra-high density water-based drilling fluid completion fluids
Preparing low solid phase fresh water base slurry: adding 400ml of tap water into a high-stirring cup, sequentially adding 0.2-0.3 g of anhydrous sodium carbonate and 4-6 g of second-grade bentonite for the drilling fluid at the stirring speed of 8000 rpm, stirring for 2 hours, and standing for 24 hours in a sealed manner to obtain the low solid phase fresh water base slurry with good prehydration, wherein the solid phase content is about 1-1.5%.
Preparing base slurry of the ultra-high temperature and ultra-high density water-based drilling fluid: weighing 400ml of low solid phase fresh water base slurry, stirring for 20 minutes on a high-speed stirrer at 8000 revolutions per minute, then sequentially adding 0.3-0.5 part of caustic soda, 0.2-0.5 part of ultra-high temperature resistant anionic polymer filtrate reducer, 0.2-0.7 part of ultra-high temperature resistant complex salt resistant zwitterionic hydrophobic association polymer filtrate reducer, 3-6 parts of sulfomethyl phenolic resin type II, 2-5 parts of sulfonated lignite resin type II, 2-6 parts of high temperature plugging collapse prevention agent, 0.5-2 parts of polyalcohol, 1-3 parts of lubricant, 3-7 parts of potassium chloride and 1100 g of composite weighting agent (the mass ratio of iron ore powder to barite is 2: 1), stirring at high speed for 20-30 minutes after adding one treating agent, and preparing the ultra-high temperature and ultra-high density water-based completion drilling fluid base slurry according to the method, wherein the density is 2.50-2.55 g/cm.3。
The test method comprises the following steps: taking 400ml of the base slurry of the ultrahigh-temperature ultrahigh-density water-based drilling fluid completion fluid, uniformly stirring at a high speed of 8000 rpm, adding 1-3 parts of the sample of example 3, stirring at a high speed for 30 minutes to obtain a system of the ultrahigh-temperature ultrahigh-density water-based drilling fluid completion fluid, and measuring the rheological property and the fluid loss property of the test slurry. The test slurry was charged into a high temperature aging tank, hot roll aged in a high temperature roller oven at 240 ℃ for 16 hours, and the rheology and fluid loss of the test slurry were measured in the same manner. The results are shown in Table 9.
TABLE 9 test results in ultra high temperature ultra high density water-based drilling fluid completion fluids
Note: the formulation No. 1 is an ultrahigh-temperature and ultrahigh-density water-based drilling fluid completion fluid system added with the sample in the example 3, the formulation No. 2 is ultrahigh-temperature and ultrahigh-density water-based drilling fluid completion fluid base slurry without the sample in the example, and the HTHP fluid loss test condition is 180 ℃/3.5 MPa.
Test example 9
Testing in ultra high temperature water-based drilling fluid completion fluids
Preparing base slurry of the ultra-high temperature water-based drilling fluid completion fluid: weighing 400ml of fresh water base slurry, stirring the slurry at a high speed for 20 minutes in a high-speed stirrer with 8000 revolutions per minute of 6000 plus materials, then sequentially adding 0.1 to 0.3 part of sodium hydroxide, 0.3 to 0.7 part of anhydrous sodium sulfite, 0.5 to 1 part of ultra-high temperature resistant anionic polymer filtrate reducer, 0.5 to 2 parts of zwitterion hydrophobic association polymer filtrate reducer resisting ultra-high temperature complex salt, 1 to 3 parts of sulfomethyl phenolic resin II type, 3 to 5 parts of special resin, 2 to 4 parts of high softening point sulfonated asphalt powder, 0.5 to 2 parts of modified graphite, 1 to 4 parts of polymeric alcohol, 0.3 to 1.5 parts of polyamine, 0.3 to 1 part of sorbitol fatty acid ester and 40 grams of barite, stirring the slurry at a high speed for 20 minutes after adding one treatment agent every time, and preparing the water-based drilling fluid completion slurry of the water-based drilling fluid according to the method, the density was 1.15g/cm3。
The test method comprises the following steps: taking 400ml of the base slurry of the ultrahigh-temperature water-based drilling fluid completion fluid, uniformly stirring at a high speed of 8000 rpm, adding 0.8-2 parts of the sample of the embodiment 3, stirring at a high speed for 20 minutes to obtain a system of the ultrahigh-temperature water-based drilling fluid completion fluid, and measuring the rheological property and the fluid loss property of the test slurry. The test slurry was charged into a high temperature aging tank, hot roll aged in a high temperature roller furnace at 248 ℃ and 251 ℃ for 16 hours, and the rheology and fluid loss of the test slurry were tested in the same manner. The results are shown in Table 10.
TABLE 10 test results in ultra high temperature water-based drilling fluid completion fluids
Note: the formulation No. 1 is the ultra-high temperature water-based drilling fluid completion fluid base slurry without the sample of the example, the formulations No. 2 and No. 3 are the ultra-high temperature water-based drilling fluid completion fluid systems with the sample of the example, and the HTHP fluid loss test condition is 180 ℃/3.5 MPa.
And (4) analyzing results:
the test results of test examples 1 to 3 show that the flow pattern regulator for the ultrahigh-temperature and ultrahigh-density water-based drilling fluid and completion fluid is prepared by polymerizing alkenyl anionic monomer sodium styrene sulfonate, allyl polyoxyethylene ether (the number m of the repeating chain of polyoxyalkyl is 5-15) and alkenyl cationic monomer methacryloyloxyethyl trimethyl ammonium chloride, wherein the weight average molecular weight is about 10000, and the number average molecular weight is about 8000.
Experimental test results of the test example 4 show that the flow pattern regulator for the ultra-high temperature and ultra-high density water-based drilling fluid and completion fluid has the performance of reducing the surface tension of an aqueous solution and has obvious surface activity characteristics.
The test result of test example 5 shows that the flow pattern modifier for the ultra-high temperature and ultra-high density water-based drilling fluid completion fluid can obviously improve the rheological property of the ultra-high temperature water-based drilling fluid completion fluid, can greatly reduce the viscosity, the dynamic shear force and the static shear force of the water-based drilling fluid completion fluid, has the viscosity reduction rate of over 85 percent, the plastic viscosity reduction rate of over 32 percent, the dynamic shear force reduction rate of over 80 percent and the static shear force reduction range of over 95 percent, and therefore can obviously improve the thickening performance of the water-based drilling fluid completion fluid after ultra-high temperature aging and ensure that the ultra-high temperature water-based drilling fluid keeps good rheological property.
Test results of test examples 6 and 7 show that the flow pattern regulator for the ultrahigh-temperature and ultrahigh-density water-based drilling fluid and completion fluid can effectively inhibit the slurrying performance of bentonite particles in water, promote clay minerals to reach a good dispersion state in water and improve the rheological property of the drilling fluid and completion fluid.
Test results of test examples 8 and 9 show that the flow pattern regulator for the ultra-high temperature and ultra-high density water-based drilling fluid and completion fluid can effectively inhibit the high-temperature thickening property of the ultra-high temperature and ultra-high density water-based drilling fluid and completion fluid, and can keep good rheological property and fluid loss wall building property of the ultra-high temperature and ultra-high density water-based drilling fluid and completion fluid; in addition, the flow pattern regulator for the ultra-high temperature and ultra-high density water-based drilling fluid and completion fluid can resist the high temperature of 251 ℃ in the ultra-high temperature water-based drilling fluid.
The test results of the comprehensive test examples 1 to 9 show that the flow pattern regulator for the ultrahigh-temperature and ultrahigh-density water-based drilling and completion fluid can effectively reduce the viscosity and shear force of the ultrahigh-temperature and ultrahigh-density water-based drilling and completion fluid subjected to ultrahigh-temperature aging, has good rheological property regulation and control performance on the ultrahigh-temperature and ultrahigh-density water-based drilling and completion fluid, has the temperature resistance of over 251 ℃ in a drilling and completion fluid system, and also has good surface activity performance and auxiliary filtrate reduction performance.
Claims (9)
1. A flow pattern regulator for ultra-high temperature and ultra-high density water-based drilling fluid and completion fluid is characterized by having the structure shown in the formula (I):
the flow pattern regulator is a zwitterion terpolymer with a comb-shaped structure, which is generated by carrying out aqueous solution free radical polymerization on alkenyl benzene sulfonate, strong hydrophilic cation alkenyl quaternary ammonium salt and allyl polyoxyethylene ether containing a long-chain structure;
in the formula (I), x, y and z respectively represent the mole numbers of an anion reaction monomer alkenyl benzene sulfonate, an allyl polyoxyethylene ether macromonomer and a cation reaction monomer alkenyl quaternary ammonium salt in the structural formula, and m represents the number of repeated chain links of polyoxyalkyl in allyl polyoxyethylene ether containing a long-chain structure;
the molecular structure main chain of the flow pattern regulator contains 7-20 structural units, and the weight average molecular weight range is 6,500-12,500; the molar ratio x/y is (0.35-0.85): (0.55-1.55), the weight of the alkenyl quaternary ammonium salt accounts for 3-15% of the total weight of the alkenyl benzenesulfonate and the allyl polyoxyethylene ether, and m is 5-26.
2. A flow pattern modifier according to claim 1, wherein the allyl polyoxyethylene ether having a long chain structure has an unsaturation degree of more than 1.25mmol/g and a hydroxyl value of 85 to 155 mgKOH/g.
3. A flow pattern modifier according to claim 1, wherein the molecular structure backbone of the flow pattern modifier comprises 10-15 structural units, and the weight average molecular weight is in the range of 7,000-10,000; the molar ratio x: y is (0.45-0.65): 0.75-1.25), the weight of the alkenyl quaternary ammonium salt accounts for 3-8% of the total weight of the alkenyl benzene sulfonate and the allyl polyoxyethylene ether, and m is 5-15.
4. A flow pattern modifier according to claim 1, wherein the molecular structure backbone of the flow pattern modifier comprises 7-12 structural units, the weight average molecular weight is 10,000-12,000, the molar ratio x: y (0.48-0.52) to (0.85-1.15), the weight of the alkenyl quaternary ammonium salt is 5-12% of the total weight of the alkenyl benzenesulfonate and the allyl polyoxyethylene ether, and m: 12-15.
5. The method for preparing the flow pattern regulator for the ultra-high temperature and ultra-high density water-based drilling fluid completion fluid of any one of claims 1 to 4, comprising the following steps:
adding reactants of alkenyl benzene sulfonate, strongly hydrophilic cationic alkenyl quaternary ammonium salt and long-chain-structure-containing allyl polyoxyethylene ether into a reaction kettle filled with a solvent according to a ratio, adding a catalyst into the solvent to be fully dissolved, then pouring the solution into the reaction kettle, adjusting the concentration of the mixed solution of the reactants by using the solvent, heating the mixed solution in the reaction kettle in a water bath heating or steam heating manner, maintaining the reaction time, terminating the reaction, and cooling to room temperature to obtain the flow pattern regulator for the ultra-high temperature and ultra-high density water-based drilling fluid completion fluid.
6. A method of preparing a flow pattern modifier according to claim 5, wherein the solvent is water;
the catalyst is the combination of persulfate and sodium bisulfite; or, the initiator is one or the combination of a water-soluble azo initiator and an amphiphilic azo initiator;
the mass ratio of the persulfate to the sodium bisulfite is 1: 1.
7. a method of preparing a flow pattern modifier according to claim 6 wherein the persulfate is potassium persulfate or ammonium persulfate;
the water-soluble azo initiator is azobisisobutylamidine hydrochloride or azobisisobutylimidazoline hydrochloride, and the amphiphilic azo initiator is azobisisobutyro-cyano formamide.
8. A method of preparing a flow pattern modifier according to claim 6, wherein the total weight of the reactants is 30-60 wt% of the total weight of the solution of the reactants and the solvent;
when the catalyst is the combination of persulfate and sodium bisulfite, the addition amount of the catalyst is 0.5 to 4 weight percent of the total weight of the reactants;
when the catalyst is water-soluble azo initiator or/and amphiphilic azo initiator, the addition amount of the catalyst is 0.1-2 wt% of the total weight of the reactants.
9. A method of preparing a flow pattern modifier according to claim 5, wherein the reaction temperature is 60-95 ℃; the reaction time is from 1.5 hours to 6 hours.
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