CN108641686A - Superhigh temperature ultrahigh-density water-base drilling fluid completion fluid polycarboxylate flow pattern regulator and preparation method thereof - Google Patents

Superhigh temperature ultrahigh-density water-base drilling fluid completion fluid polycarboxylate flow pattern regulator and preparation method thereof Download PDF

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CN108641686A
CN108641686A CN201810560669.4A CN201810560669A CN108641686A CN 108641686 A CN108641686 A CN 108641686A CN 201810560669 A CN201810560669 A CN 201810560669A CN 108641686 A CN108641686 A CN 108641686A
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flow pattern
drilling fluid
polycarboxylate
water
pattern regulator
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CN108641686B (en
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毛惠
邱正松
黄维安
何勇明
刘伟
邓虎成
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Chengdu Univeristy of Technology
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    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02Well-drilling compositions
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    • C08F212/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02Monomers containing only one unsaturated aliphatic radical
    • C08F212/04Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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    • C09K2208/34Lubricant additives

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Abstract

The present invention relates to superhigh temperature ultrahigh-density water-base drilling fluid completion fluid polycarboxylate flow pattern regulators and preparation method thereof, the amphoteric ion polycarboxylate multipolymer with comb-type structure generated through aqueous free radical polymerisation by alkenyl benzene sulfonic acid salt, strongly hydrophilic cationic alkenyl quaternary ammonium salt and allyl polyethenoxy ether containing specific backbone, contain 7 20 structural units in the multiple copolymer strand of generation, weight average molecular weight range is 6,500 12,500.The viscosity and shear force of superhigh temperature ultrahigh-density water-base drilling fluid completion fluid can be greatly reduced in this polycarboxylate flow pattern regulator, improve solid phase weighting material dispersity in water-base drilling fluid completion fluid, improve the rheological characteristic of superhigh temperature ultrahigh-density water-base drilling fluid completion fluid, it is substantially reduced the surface tension of superhigh temperature water base drilling fluid completion fluid, increase the greasy property of superhigh temperature ultrahigh-density water-base drilling fluid, and mud shale rejection and high temperature stability performance are had both, 251 DEG C or more of high temperature can be resisted.

Description

Superhigh temperature ultrahigh-density water-base drilling fluid completion fluid polycarboxylate flow pattern regulator and Preparation method
Technical field:
The present invention relates to a kind of superhigh temperature ultrahigh-density water-base drilling fluid completion fluid polycarboxylate flow pattern regulator and its Preparation method belongs in oil and gas drilling engineering, Earth resource exploration and exploitation and geothermal well drilling engineering and bores Well liquid and completion fluid technical field.
Background technology:
In recent years, with oil-gas exploration and development in the world develop in depth and breadth and the exploration of the deep resource in China, Continental Science Chance is bored in the lasting propulsion of the great deep ground project such as drilling project, Earth survey plan and geothermal well drilling engineering Superhigh temperature reservoir is more and more, is bored during drilling engineering and meets super-pressure stratum (formation pore pressure is more than 138MPa) and superelevation The probability of warm stratum (temperature is more than 220 DEG C) increases year by year, therefore, ultrahigh-density water-base drilling fluid completion is used in drilling process The case where liquid system, superhigh temperature water base drilling fluid completion fluid system and superhigh temperature ultrahigh-density water-base drilling fluid completion fluid system, gets over Come more.However, for superhigh temperature stratum, the maintenance of ultrahigh-density water-base drilling fluid completion fluid and processing often complex, It is often stuck with the vicious circle of " exacerbation → thickening → viscosity reduction → heavy weight additive sedimentation → density declines → aggravates again ", influences drilling well Be smoothed out, in some instances it may even be possible to cause serious underground complex accident.Since ultra high density drilling fluid system solid concentration is very high, Solid concentration is even as high as 50-60%, thus the viscosity of drilling fluid and completion fluid and shear force are usually larger, the downhole environment of superhigh temperature Condition can cause the physical and chemical reaction of a series of complex again, and the mobile performance of drilling fluid and completion fluid is caused significantly to deteriorate, and surpass The regulation and control of the rheological characteristic of high temperature ultra high density drilling fluid system will become abnormal difficult, usually show both ways, first, being difficult to Preparing successfully has the preferably anti-superhigh temperature ultra high density drilling fluid and completion fluid system of rheological property, second is that being difficult to maintain normally to bore Into the stabilization of superhigh temperature ultrahigh-density water-base drilling fluid completion fluid rheological property in the process.Therefore, how superhigh temperature is effectively improved The mobility of ultrahigh-density water-base drilling fluid completion fluid, and the sedimentation stability of high density solid phase weighting material can be maintained, it solves The regulation and control problem of good superhigh temperature ultrahigh-density water-base drilling fluid completion fluid rheological characteristic is the key technology that drilling engineering is smoothed out One of, and developing can resist the high-performance flow pattern regulator of superhigh temperature to be the effective technical way for solving this problem.
Currently, drilling engineering scene usually uses the thinner of various high-molecular compounds or diluent super as superhigh temperature The flow pattern regulator of high-density water-based drilling fluid completion fluid, such as sulfomethylation tannin, lignosulfonates, some low average moleculars The polymer of the polymer of quality and low relative molecular mass grafting natural macromolecular material etc., but these existing thinners or Diluent still has the features such as infull functionality, temperature resistance scarce capacity.
Also there is numerous patents file report about drilling fluid flow pattern regulator, such as:Chinese patent document CN102485826A discloses a kind of low temperature microbubble drilling fluid flow pattern conditioning agent and its application;The flow pattern regulator by xanthans and Inorganic boron crosslinking agent is formulated, and the mass ratio of xanthans and inorganic boron crosslinking agent is 1: 1~2: 1, and the flow pattern regulator is water-soluble Object content >=90%, moisture≤15%, it is 5.0~7.0 that flow pattern regulator, which is configured to the pH value after 0.5% aqueous solution, table Sight 15~25mPas of viscosity, microvesicle stabilization time >=for 24 hours, it is used as microbubble drilling fluid flow pattern conditioning agent, in micro-foam drilling fluid Water base meter per hectogram, low temperature microbubble drilling fluid flow pattern conditioning agent dosage are 0.1~0.4 gram.Again for example:Chinese patent document CN107955586A discloses a kind of cellulose nano-fibrous application as drilling fluid flow pattern regulator.Cellulose Nanowire Dimension is applied to drilling fluid flow pattern regulator, and the cellulose nano-fibrous amount of filling in drilling fluid is 0.1~3.0%, by volume Than.But above-mentioned xanthans and cellulose etc. belong to natural macromolecular material, this kind of material be influenced by temperature it is larger, When temperature is more than 120 DEG C, xanthans and the molecular structure of cellulose family macromolecule material and its modified product are in hot conditions Under be highly prone to destroy, to cause the high temperature failure of xanthans and cellulose family flow pattern regulator, thus it can not be applied In high temperature or ultra-high temperature drilling liquid completion fluid;In addition, such as above-mentioned flow pattern regulator makees the adjusting of water-base drilling fluid rheological characteristic With the thickening for the Drilling and completion fluids for being generally mainly used in low-density and the effect of cutting is proposed, it is water base not to be suitable for high-temperature high-density Drilling fluid and completion fluid and superhigh temperature ultrahigh-density water-base drilling fluid completion fluid, i.e., it is water base to the high temperature containing high solid phase or superhigh temperature Drilling fluid and completion fluid and the effect cut without viscosity reduction, drop.Again for example:The polymeric articles of some low relative molecular masses by with When flow pattern regulator or thinner as high-temperature high-density water-base drilling fluid completion fluid, it is limited to its specific molecule knot Structure mainly faces the technical problem of heat-resisting property difference, and when temperature is more than 180 DEG C, its failure can be generally caused because of high temperature, Thus the temperature resistance ability of this kind of drilling fluid and completion fluid flow pattern regulator is usually less than 180 DEG C, therefore, is also not particularly suited for surpassing In high temperature ultrahigh-density water-base drilling fluid completion fluid.However, high-performance polycarboxylic acid salt product is because it is with low-dosage, strong dispersion And environmentally protective equal excellent performances, it is used in concrete water mud as a kind of high efficiency water reducing agent in recent years and regulates and controls its slurry Performance, be also used in the regulation and control of CWS Reological Properties and used as a kind of strong dispersant.But polycarboxylate is used in super It is not yet had been reported that as the research of efficient flow pattern regulator and application in high-density water-based drilling fluid completion fluid, and according to polycarboxylic acids Salt action is in the peptizaiton mechanism of high concentration solid phase particles turbid solution so that it is in ultrahigh-density water-base drilling fluid completion fluid It has broad application prospects;In addition, the good temperature resistance ability of polycarboxylate is again so that it has in superhigh temperature water base drilling fluid Therefore polycarboxylate is used for superhigh temperature ultrahigh-density water-base drilling fluid completion fluid flow pattern tune by the potentiality applied in completion fluid Section agent and to overcome traditional drilling fluid and completion fluid with the technical barrier that traditional flow pattern regulator faces be still those skilled in the art's need Want urgent problem to be solved.
Invention content:
In view of the deficiencies of the prior art, the present invention provides one kind and can resist superhigh temperature, ultra high density drilling fluid is greatly reduced The viscosity and shear force of completion fluid reduce the surface tension of superhigh temperature water base drilling fluid completion fluid, improve superhigh temperature ultra high density water Solid phase weighting material dispersity in base drilling fluid completion fluid improves the rheology of superhigh temperature ultrahigh-density water-base drilling fluid completion fluid Property, increase the greasy property of superhigh temperature ultrahigh-density water-base drilling fluid, and have both certain mud shale rejection and high temperature is steady Drilling fluid and completion fluid polycarboxylic acid salt's flow pattern regulator of qualitative energy.
Technical scheme is as follows:
A kind of superhigh temperature ultrahigh-density water-base drilling fluid completion fluid polycarboxylate flow pattern regulator has formula (I) described Structure:
The flow pattern regulator is by alkenyl benzene sulfonic acid salt, strongly hydrophilic cationic alkenyl quaternary ammonium salt and containing backbone The amphoteric ion polycarboxylate three with comb-type structure that allyl polyethenoxy ether is generated through aqueous free radical polymerisation Membered copolymer;
In formula (I), x, y and z respectively represent anionic reactive monomer alkenyl benzene sulfonic acid salt, allyl polyoxy in structural formula The molal quantity of vinethene polymeric monomer and cationoid reaction monomer alkenyl quaternary ammonium salt, m represent the allyl polyoxy containing backbone The repeating segment number of polyoxy alkyl in vinethene.
, according to the invention it is preferred to, in the flow pattern regulator molecular structure main chain, containing 7-20 structural unit, Weight average molecular weight range is in 6,500-12,500;Molar ratio x ﹕ y=(0.35-0.85) ﹕ (0.55-1.55), alkenyl quaternary ammonium salt Weight accounts for the 3-15% of alkenyl benzene sulfonic acid salt and allyl polyethenoxy ether total weight, m=5-26.
, according to the invention it is preferred to, the degree of unsaturation of the allyl polyethenoxy ether of backbone is more than 1.25mmol/g, Hydroxyl value is 85-155mgKOH/g.
, according to the invention it is preferred to, in the flow pattern regulator molecular structure main chain, containing 10-15 structural unit, Weight average molecular weight range is in 7,000-10,000;Molar ratio x ﹕ y=(0.45-0.65) ﹕ (0.75-1.25), alkenyl quaternary ammonium salt Weight accounts for the 3-8% of alkenyl benzene sulfonic acid salt and allyl polyethenoxy ether total weight, m=5-15.
, according to the invention it is preferred to, in the flow pattern regulator molecular structure main chain, containing 7-12 structural unit, Weight average molecular weight range 10,000-12,000, molar ratio x ﹕ y=(0.48-0.52) ﹕ (0.85-1.15), alkenyl quaternary ammonium salt Weight accounts for the 5-12% of alkenyl benzene sulfonic acid salt and allyl polyethenoxy ether total weight, m=12-15.
According to the present invention, the system of above-mentioned superhigh temperature ultrahigh-density water-base drilling fluid completion fluid polycarboxylate flow pattern regulator Preparation Method includes the following steps:
Reactant alkenyl benzene sulfonic acid salt, strongly hydrophilic cationic alkenyl quaternary ammonium salt and allyl containing backbone are gathered Ethylene oxide ether is proportionally added in the reaction kettle equipped with solvent, and reaction is poured into after catalyst is added in solvent fully dissolving In kettle, reactant mixed liquid concentration is adjusted with solvent, is heated by heating water bath or steam-heated mode mixed in reaction kettle Conjunction liquid, maintains the reaction time, terminates reaction, is cooled to room temperature to use to get superhigh temperature ultrahigh-density water-base drilling fluid completion fluid and gather Carboxylate flow pattern regulator.The flow pattern regulator is certain density faint yellow to rufous fluid product.
, according to the invention it is preferred to, the solvent is water;
Preferably, the catalyst is the combination of persulfate and sodium hydrogensulfite;Alternatively, drawing for water-soluble azo class Send out agent, amphipathic azo initiator alternative one or combination;
Preferably, the mass ratio of persulfate and sodium hydrogensulfite is 1:1.
, according to the invention it is preferred to, the persulfate is potassium peroxydisulfate or ammonium persulfate;
Preferably, the water-soluble azo class initiator is two isobutyl imidazoline of azo-bis-isobutyrate hydrochloride or azo Hydrochloride, the amphipathic azo-initiator are azo isobutyl cyano formamides.
, according to the invention it is preferred to, reactant total weight accounts for the 30- for the total solution weight that reactant is formed with solvent 60wt%;
When catalyst is the combination of persulfate and sodium hydrogensulfite, the addition of catalyst is reactant total weight 0.5-4wt%;
When catalyst is water-soluble azo class initiator or/and amphipathic azo initiator, the addition of catalyst is The 0.1-2wt% of reactant total weight.
, according to the invention it is preferred to, reaction temperature is 60-95 DEG C;Reaction time is 1.5 hours to 6 hours.
Intrinsic category of the present invention according to the superhigh temperature ultrahigh-density water-base drilling fluid completion fluid weighting particles of solid phase containing high concentration Property and its specific physicochemical characteristic having under superhigh-temperature and-pressure, from polycarboxylate to the water base brill of superhigh temperature ultra high density The research of the well liquid completion fluid mechanism of action is starting point, devises the molecule knot of the polycarboxylate suitable for drilling fluid and completion fluid The polycarboxylate flow pattern regulator suitable for superhigh temperature ultrahigh-density water-base drilling fluid completion fluid system of structure, preparation has well Effect.
The reaction process of the present invention is as follows:
The mechanism of action of the superhigh temperature ultrahigh-density water-base drilling fluid completion fluid polycarboxylate flow pattern regulator of the present invention And have the beneficial effect that:
(1) surface tension effects mechanism is reduced.After a small amount of polycarboxylate prevalence conditioning agent is added, superhigh temperature is reduced The surface tension of ultrahigh-density water-base drilling fluid completion fluid, can effectively improve under hyperthermal environments improves superelevation solid phase Grain wettability of the surface energy, improves other high temperature resistance inorganic agents consistency problem caused by the variation of subcritical water characteristic With the coalescence performance of high concentration inertia native place particle, while the greasy property on superelevation solid phase particles surface can be improved again.
(2) effectively inhibit the aquation pulping of clay mineral and improve the peptizaiton machine of clay mineral and weighting agent particles Reason.The characteristic of amphoteric ion polycarboxylate is so as to effectively inhibit pulping of the clay mineral particle under ultra-high temperature condition Can, have the effects that the specific molecular structure of comb-type structure can be such that clay mineral particle is adsorbed under hydrogen bond and electrostatic force again Clay mineral and heavy weight additive surface, reduce the Zeta potential of solid phase particles, enable clay mineral particle in superelevation solid phase particles Under the conditions of keep good dispersity, the long chain characteristic of polyoxyethylene chain that can increase the space between solid phase particles surface again Steric hindrance inhibits coalescence characteristic of the clay mineral particle under ultra-high temperature condition, to which superhigh temperature superelevation be greatly reduced The viscosity of density water-base drilling fluid completion fluid, the stabilization of shear force and its rheological characteristic, and improve the water base brill of superhigh temperature ultra high density The leak-off wall building property of well liquid completion fluid.
Description of the drawings:
Fig. 1 is the superhigh temperature ultrahigh-density water-base drilling fluid completion fluid polycarboxylate flow pattern that the embodiment of the present invention 2 obtains The infrared spectrum feature spectrogram of conditioning agent.
Fig. 2 is the superhigh temperature ultrahigh-density water-base drilling fluid completion fluid polycarboxylate flow pattern that the embodiment of the present invention 2 obtains Conditioning agent nuclear magnetic resonance C spectrum signature spectrograms.
Specific implementation mode:
Below by specific embodiment, the invention will be further described, but not limited to this.
It is raw materials used in embodiment, it is unless otherwise specified regular market purchase product.
Superhigh temperature ultrahigh-density water-base drilling fluid completion fluid polycarboxylate flow pattern regulator in embodiment has formula (I) The structure:
The flow pattern regulator is by alkenyl benzene sulfonic acid salt, strongly hydrophilic cationic alkenyl quaternary ammonium salt and containing backbone The amphoteric ion polycarboxylate three with comb-type structure that allyl polyethenoxy ether is generated through aqueous free radical polymerisation Membered copolymer;
In formula (I), x, y and z respectively represent anionic reactive monomer alkenyl benzene sulfonic acid salt, allyl polyoxy in structural formula The molal quantity of vinethene polymeric monomer and cationoid reaction monomer alkenyl quaternary ammonium salt, m represent the allyl polyoxy containing backbone The repeating segment number of polyoxy alkyl in vinethene.
Embodiment 1:
56.68 grams of alkenyl benzene sulfonic acid sodium is weighed to be added equipped with blender, reflux condenser, nitrogen protection device, temperature In the reaction kettle that the capacity of sensor and heating device is 2.5 liters, 500 milliliters of tap water is added, opens agitating device, high speed Stirring makes it fully dissolve;392 grams of allyl polyethenoxy ether (the repeating segment number m=12-15 of polyoxy alkyl) is weighed to fall Enter in reaction kettle;It weighs 22.43 grams of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride to pour into reaction kettle, high-speed stirred 10 is divided Clock;It weighs 18.89 grams of ammonium persulfate and is substantially dissolved in 200 milliliters of tap water, poured into reaction kettle and high speed It stirs evenly, the rear tap water that is added is to originally water inventory to 1575 milliliters;Logical nitrogen, high-speed stirred are warming up to 78-83 after five minutes DEG C, 4 hours postcoolings of reaction are to room temperature to get the poly- carboxylic of superhigh temperature ultrahigh-density water-base drilling fluid completion fluid of the present invention Hydrochlorate flow pattern regulator, mass concentration are about 30%.
In this flow pattern regulator, the molar ratio x ﹕ y=0.50 ﹕ 1.00 of alkenyl benzene sulfonic acid salt and allyl polyethenoxy ether, The weight of alkenyl quaternary ammonium salt accounts for the 5.0% of alkenyl benzene sulfonic acid salt and allyl polyethenoxy ether total weight, and the weight of polycarboxylate is equal Molecular weight is about 10,500, and structural unit number is about 9-11.
Embodiment 2:
It is 1.5 to the capacity equipped with blender, reflux condenser, nitrogen protection device, temperature sensor and heating device 61.8 grams of alkenyl benzene sulfonic acid sodium is weighed in the reaction kettle risen, 600 milliliters of tap water is added, and opens agitating device, high-speed stirring Mixing makes it fully dissolve;216 grams of allyl polyethenoxy ether (the repeating segment number m=5-9 of polyoxy alkyl) is weighed to pour into instead It answers in kettle;It weighs 18.1 grams of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride to pour into reaction kettle, high-speed stirred 10 minutes;Claim It takes 3.55 grams of azo-bis-isobutyrate hydrochloride and is substantially dissolved in 100 milliliters of tap water, poured into reaction kettle simultaneously High-speed stirred is uniform, and the rear tap water that is added leads to nitrogen, high-speed stirred is warming up to after five minutes to originally water inventory to 850 milliliters 63-68 DEG C, 4 hours postcoolings of reaction are to room temperature to get superhigh temperature ultrahigh-density water-base drilling fluid completion fluid of the present invention With polycarboxylate flow pattern regulator, mass concentration is about 35%.
In this flow pattern regulator, the molar ratio x ﹕ y=0.50 ﹕ 1.20 of alkenyl benzene sulfonic acid salt and allyl polyethenoxy ether, The weight of alkenyl quaternary ammonium salt accounts for the 6.5% of alkenyl benzene sulfonic acid salt and allyl polyethenoxy ether total weight, and the weight of polycarboxylate is equal Molecular weight is about 7,900, and structural unit number is about 11-13.
Embodiment 3:
It it is 3-3.5 tons to the capacity equipped with blender, reflux condenser, nitrogen protection device, thermometer and heating device The corrosion-resistant reaction kettle of stainless steel in be first added 500 kilograms of tap water, turn on agitator, with 25 kg/min of rate by 142 Kilogram sodium p styrene sulfonate be added in reaction kettle, stirring is to being uniformly dissolved;With 50 kg/min of rate by 497 kilograms Allyl polyethenoxy ether (the repeating segment number m=5-9 of polyoxy alkyl) be added reaction kettle in, stir 10 minutes;It adds 41.5 kilograms of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride pours into reaction kettle, high-speed stirred 10 minutes;Weigh 8.166 thousand Gram azo-bis-isobutyrate hydrochloride and be substantially dissolved in the tap water of double centner, pour into reaction kettle, stir 10 points Clock;Tap water total weight is added to 1950 kilograms, leads to nitrogen, stirring is warming up to 65-70 DEG C after 30 minutes, cold after reacting 4 hours But to room temperature to get superhigh temperature ultrahigh-density water-base drilling fluid completion fluid polycarboxylate flow pattern regulator of the present invention, Mass concentration is about 35%.
In this flow pattern regulator, the molar ratio x ﹕ y=0.50 ﹕ 1.20 of alkenyl benzene sulfonic acid salt and allyl polyethenoxy ether, The weight of alkenyl quaternary ammonium salt accounts for the 6.5% of alkenyl benzene sulfonic acid salt and allyl polyethenoxy ether total weight, and the weight of polycarboxylate is equal Molecular weight is about 7,500, and structural unit number is about 10-13.
Comparative example 1:
Usually, the water-soluble polymer with low relative molecular mass all has high-temperature high-density drilling fluid certain Viscosity reduction, the drop effect of cutting, but it is affected by the density value of temperature and drilling fluid and completion fluid, when temperature is more than 220 DEG C, density Up to 2.35g/cm3When above, then often it is difficult to play effect, often reacts on superhigh temperature ultra high density water-based drilling instead Liquid.Therefore, to make the flow pattern regulator of the present invention that there is anti-superhigh temperature and its can be in ultrahigh-density water-base drilling fluid completion fluid In there is good viscosity reduction and drop to cut performance, the allyl polyethenoxy ether with specific length molecule branch introduces and its low The content height of shared molar ratio is to the novel super-high temperature ultra high density water-based drilling in relative molecular mass polymer molecular chain The comprehensive function influential effect of liquid completion fluid flow pattern regulator is notable, wherein mainly by allyl polyethenoxy ether molecule branch Effect length it is the most apparent, allyl polyethenoxy ether molecule branch it is long or too short also reduce synthetic product drop It glues, cut effect.For this purpose, during synthesizing the flow pattern regulator, if the weight of alkenyl quaternary ammonium salt be alkenyl benzene sulfonic acid salt and The w% of allyl polyethenoxy ether total weight, control other Variable Conditions it is constant under conditions of, pass through change allyl polyoxy second The length of alkene ether molecule branch changes the size of m in flow pattern regulator molecular structure formula (I) of the present invention, synthesis comparison Example sample 1-1 (x ﹕ y=0.50 ﹕ 1.20, w=6.5, m=5-7), comparative example 1-2 (x ﹕ y=0.50 ﹕ 1.20, w=6.5, m =10-12), comparative example 1-3 (x ﹕ y=0.50 ﹕ 1.20, w=6.5, m=14-16), comparative example 1-4 (x ﹕ y= 0.50 ﹕ 1.20, w=6.5, m=19-21), comparative example 1-5 (x ﹕ y=0.50 ﹕ 1.20, w=6.5, m=24-26).
The preparation of ultrahigh-density water-base drilling fluid:Tarim Oilfield jump three spudding well scene drilling fluid 400mL of full 6 well is taken, Be placed in it is high stir in cup under 8000 revs/min of stir speed (S.S.) high-speed stirred after twenty minutes, according to the matter of barite and Iron Ore Powder Amount ratio is 2:Under 1 heavy weight additive proportioning, which is weighed out to 2.55g/cm3, continue high-speed stirred after 30 minutes to obtain the final product Ultrahigh-density water-base drilling fluid.
Test the preparation and test of slurry:0.5% each comparative example is added into ultrahigh-density water-base drilling fluid respectively, High-speed stirred is uniform under 8000 revs/min of mixing speed, surveys the rheological characteristic of each experiment slurry, the results are shown in Table 1.
Test result of the table 1 in ultrahigh-density water-base drilling fluid
Comparative example 2:
In the present invention, when the polymerization in the linear low relative molecular mass being made of alkenyl benzene sulfonic acid salt and alkenyl quaternary ammonium salt After introducing the allyl polyethenoxy ether with long-chain branch in object, this flow pattern regulator is just provided with comb-type structure, when the flow pattern When conditioning agent is in the higher drilling fluid and completion fluid of clay mineral content, part polyoxyethylene ether long branched chain structure just can be embedded in glutinous The interlayer of native mineral, to prevent the strong peptizaiton of clay mineral under the high temperature conditions;And part polyoxyethylene ether branch chains Structure is then adsorbed on clay mineral particle surface, and can prevent the coalescence effect of clay mineral under the high temperature conditions.In the present invention Flow pattern regulator has stronger suction-operated, molecule to the high concentration solid phase particles disperseed in ultrahigh-density water-base drilling fluid The positively charged alkenyl quaternary ammonium salt contained in chain is one of the main reasons.But when the chain link of alkenyl quaternary ammonium salt side chain is more, i.e., When the reaction ratio of alkenyl quaternary ammonium salt monomer is excessive, the relative molecular mass of the polycarboxylate flow pattern regulator of synthesis then compared with Height is difficult to control in reaction, and influences the copolymerization of alkenyl benzene sulfonic acid salt and allyl polyethenoxy ether, reduces synthetic product Surface-active, and then the decrease that function and effect of the synthetic product in superhigh temperature ultrahigh-density water-base drilling fluid will be led to.For this purpose, During synthesizing the flow pattern regulator, if the weight of alkenyl quaternary ammonium salt is alkenyl benzene sulfonic acid salt and allyl polyethenoxy ether The w% of total weight, control other Variable Conditions it is constant under conditions of, pass through change alkenyl quaternary ammonium salt reaction ratio, synthesis pair Ratio sample 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), comparative example 2-5 (x ﹕ y=0.50 ﹕ 1.20, w=25, m=10-12).
It is consistent described in the preparation of ultrahigh-density water-base drilling fluid, the preparation of experiment slurry and test method and comparative example 1, as a result As shown in table 2.
Test result of the table 2 in ultrahigh-density water-base drilling fluid
Drilling fluid and completion fluid is evaluated with the impact of performance of polycarboxylate flow pattern regulator below by test example.
Test method in test example:①GB/T 32198-2015:IR spectrum quantitative analysis technology general rule;2. nuclear-magnetism The C that resonates composes standard.③GB/T 5005-2010:Drilling fluid materials specification.④SY5444-1992:Drilling fluid evaluation soil.⑤ SY/T 5695-1995:Drilling fluid amphoteric ion polymer thinner XY27.6. using GB/T 16738-1997:Water base brill Well liquid On-Site Test Procedure.
Test example 1
The superhigh temperature ultrahigh-density water-base drilling fluid completion fluid polycarboxylate flow pattern regulator that testing example 2 obtains Infrared spectrum feature spectrogram, as shown in Figure 1.
Test example 2
The superhigh temperature ultrahigh-density water-base drilling fluid completion fluid polycarboxylate flow pattern regulator that testing example 2 obtains Nuclear magnetic resonance C spectrum signature spectrograms, as shown in Figure 2.
Test example 3
The superhigh temperature ultrahigh-density water-base drilling fluid completion fluid polycarboxylate flow pattern regulator that testing example 1 obtains Relative molecular mass.
Using gel permeation chromatograph, analysis has obtained the superhigh temperature ultrahigh-density water-base drilling fluid completion fluid of embodiment 1 With the relative molecular mass of polycarboxylate flow pattern regulator, the results are shown in Table 3.
The relative molecular mass of 3 embodiment of table, 1 sample is analyzed
Test example 4
The superhigh temperature ultrahigh-density water-base drilling fluid completion fluid polycarboxylate flow pattern regulator that testing example 3 obtains Some surface active property is tested, and the results are shown in Table 4.
In 4 distilled water of table under various concentration 3 sample solution of embodiment surface tension
Test example 5
Test the test influenced on base slurry rheological property under hyperthermal environments
The preparation of base slurry:32g drilling fluids two level bentonite is added in 400mL tap water respectively, at 8000 revs/min Stir speed (S.S.) under high-speed stirred 30 minutes, 40g drilling fluids evaluation soil is then added, continues high-speed stirred 2h, it is small to stand 24 When after up to the testing experiment base slurry after prehydration.
Test the preparation and test of slurry:1.5% superhigh temperature of the present invention is added into the base slurry after prehydration respectively Ultrahigh-density water-base drilling fluid completion fluid evaluates sample (1 sample of embodiment, 2 sample of embodiment, implementation with polycarboxylate flow pattern regulator 3 sample of example) and 0.5% drilling fluid with amphoteric ion polymer thinner XY27, the high-speed stirring under 6000 revs/min of mixing speed Average price is mixed, the rheological characteristic of each experiment slurry is tested.Experiment is starched and is packed into high temperature ageing tank, heat rolling aging 16 is small under 240 DEG C of environment When, the rheological characteristic of each experiment slurry is tested with same method.
The computational methods of rheological parameter:The computational methods of viscosity break ratio are according to the computational methods in SY/T 5695-1995, i.e.,
Viscosity break ratio=(Φ ' 100- Φ 100)/Φ ' 100 × 100% (1)
In above formula (1):Φ ' 100 is that the base slurry of evaluation sample is not added after 240 DEG C of high temperature ageings 16 hours in six speed rotations It is the reading under 100RPM to turn viscosity metering rotating speed, and Φ 100 be that the experiment of evaluation sample is added to starch through 240 DEG C of high temperature ageings 16 hours Reading in the case where six fast rotary viscosity metering rotating speeds are 100RPM afterwards.
The reduced rate of the change rate of remaining rheological parameter, i.e. apparent viscosity (AV), the reduced rate of plastic viscosity (PV) are moved and are cut The reduced rate of power (YP), reduced rate, the reduced rate of Φ 6 and the reduced rate of Φ 3 of gel strength (Gel 10 " and Gel 10') follow Following general formula:
As a result as shown in Table 5,6.
5 superhigh temperature ultrahigh-density water-base drilling fluid completion fluid of table starches rheology impact with polycarboxylate flow pattern regulator to base Test result
6 superhigh temperature ultrahigh-density water-base drilling fluid completion fluid of table starches base with polycarboxylate flow pattern regulator old through 240 DEG C Rheology is joined after change
The evaluation result of number regulating effect
Test example 6
Inhibit the performance of bentonite pulping
Test the preparation and test of slurry:Evaluation sample (1.5% embodiment, 3 sample, 0.5%XY- are added in 400mL clear water 27,1% drilling fluid fluosilicic thinner SF260 and 0.5% polyamine) and 5% drilling fluid two level bentonite, height stir 30min, starch Liquid heat rolling 16 hours at 70 DEG C, then cool to room temperature, and height tests slurries rheological property after stirring 5min.Add 5% swelling Soil, height stir after 30min heat rolling 16 hours at 70 DEG C, are cooled to room temperature, test slurries rheological property.So it is repeated up to slurries Until viscosity exceeds instrument range very much greatly.Φ 3 reads reckling and shows that it inhibits the best performance of bentonite pulping.As a result such as table Shown in 7.
Table 7 inhibits bentonite pulping the performance test results
Test example 7
To the dispersion performance of clay mineral particle in water
Test the preparation and test of slurry:7 grams of sodium bentonites for sieving with 100 mesh sieve net are added in 350 ml deionized waters, Then each evaluation sample (0.1% Carbon Dioxide of certain content is added in high-speed stirred 20 minutes at 8000-10000RPM Sodium, 1% embodiment, 1 sample, 1% embodiment, 2 sample, 1% embodiment, 3 sample, 5% potassium chloride, 5% sodium chloride and 0.5% polyamine), It is transferred to after twenty minutes under 8000-10000RPM high-speed stirreds in 100 milliliters of tool plug graduated cylinders, standing observes each evaluation sample afterwards for 24 hours Dispersion to Na-bentonite soil particle and flocculation situation, record flocculation scale value calculate flocculating rate according to the following formula:
C=(Hw-Hi)/Hw× 100% (2)
In above formula (2):
C:Indicate flocculating rate of the test drug to abundant aquation sodium bentonite;
Hw:The flocculation scale value of sodium bentonite when indicating abundant aquation, usually 100;
Hi:Flocculation scale value of each test drug to sodium bentonite.
The results are shown in Table 8.
Dispersion performance test result of the table 8 to clay mineral particle in water
Serial number 1 2 3 4 5 6 7
Sample Na2CO3 1 sample of embodiment 2 sample of embodiment 3 sample of embodiment KCl NaCl Polyamine
Hi 100 100 100 100 47 54 32
Flocculating rate/% 0 0 0 0 53 46 68
Test example 8
Test in superhigh temperature ultrahigh-density water-base drilling fluid completion fluid
The preparation of low solid phase fresh water-based slurry:400 milliliters of tap water of addition in cup are stirred in height, speed is stirred at 8000 revs/min 0.2-0.3 grams of natrium carbonicum calcinatum and 4-6 grams of drilling fluid two level bentonite are sequentially added under degree, are stirred 2 hours, it is closed to stand 24 Hour is the good low solid phase fresh water-based slurry of prehydration, and solid concentration is about 1-1.5%.
The preparation of superhigh temperature ultrahigh-density water-base drilling fluid completion liquid-based slurry:400 milliliters of low solid phase fresh water-based slurrys are measured, High-speed stirred 20 minutes on 8000 revs/min of homogenizer, then sequentially add 0.3-0.5 parts of caustic soda, 0.2-0.5 parts it is anti- The amphoteric ion hydrophobic association polymerization of superhigh temperature anionic polymer fluid loss additive, 0.2-0.7 parts of anti-anti- complex salts of superhigh temperature II type of object fluid loss additive, 3-6 part sulfonated-pheno-formoldehyde resin, 2-5 parts of II types of sulfonated lignite resin, 2-6 parts of high temperature block anti-sloughing agents, 0.5-2 parts of polymeric alcohols, 1-3 parts of lubricants, 3-7 parts of potassium chloride, 1100 grams of compound heavy weight additive (Iron Ore Powder and barite mass ratioes 2: 1 compounding), high-speed stirred 20-30 minutes after a kind of inorganic agent are often added, superelevation of the present invention can be made according to the above method Warm ultrahigh-density water-base drilling fluid completion liquid-based slurry, density 2.50-2.55g/cm3
Test method:Superhigh temperature ultrahigh-density water-base drilling fluid completion liquid-based is taken to starch 400 milliliters, at 8000 revs/min High-speed stirred is uniform under mixing speed, and 1-3 parts of 3 samples of embodiment are added, and high-speed stirred 30 minutes is to get superhigh temperature ultra high density water Base drilling fluid completion fluid system surveys the rheological characteristic and leak-off of experiment slurry.Experiment is starched and is packed into high temperature ageing tank, at 240 DEG C Heat rolling aging 16 hours, the rheological characteristic and leak-off of experiment slurry are tested with same method in high temp roller furnace.As a result such as table 9 It is shown.
Test result of the table 9 in superhigh temperature ultrahigh-density water-base drilling fluid completion fluid
Note:For the superhigh temperature ultrahigh-density water-base drilling fluid completion fluid system of 3 sample of embodiment is added, No. 2 are formulated No. 1 formula For the superhigh temperature ultrahigh-density water-base drilling fluid completion liquid-based slurry of embodiment sample is not added, the test condition of HTHP filter losses is 180℃/3.5MPa。
Test example 9
Test in superhigh temperature water base drilling fluid completion fluid
The preparation of superhigh temperature water base drilling fluid completion liquid-based slurry:400 milliliters of fresh water-based slurrys are measured, at 6000-8000 revs/min Then high-speed stirred 20 minutes on the homogenizer of clock sequentially add 0.1-0.3 parts of sodium hydroxides, 0.3-0.7 parts of anhydrous sodiums Sodium sulphate, 0.5-1 portions of anti-superhigh temperature anionic polymer fluid loss additives, 0.5-2 parts of anti-anti- complex salts of superhigh temperature both sexes from Sub- hydrophobic associated polymer fluid loss additive, 1-3 parts of II types of sulfonated-pheno-formoldehyde resin, 3-5 parts of Special Resins, 2-4 parts of high softening-points Sulfonated gilsonite powder, 0.5-2 part modified graphite, 1-4 parts of polymeric alcohols, 0.3-1.5 parts of polyamine, 0.3-1 parts of sorbitan fatty acid esters, 40 grammes per square metre spar are often added high-speed stirred 20 minutes after a kind of inorganic agent, superelevation of the present invention can be made according to the above method Warm water base drilling fluid completion liquid-based is starched, density 1.15g/cm3
Test method:Superhigh temperature water base drilling fluid completion liquid-based is taken to starch 400 milliliters, in 8000 revs/min of mixing speed Lower high-speed stirred is uniform, and 0.8-2 parts of 3 samples of embodiment are added, and high-speed stirred 20 minutes is to get superhigh temperature water base drilling fluid completion fluid System surveys the rheological characteristic and leak-off of experiment slurry.Experiment is starched and is packed into high temperature ageing tank, in 248 DEG C and 251 DEG C of high temp rollers Heat rolling aging 16 hours, the rheological characteristic and leak-off of experiment slurry are tested with same method in stove.The results are shown in Table 10.
Test result of the table 10 in superhigh temperature water base drilling fluid completion fluid
Note:No. 1 formula is the superhigh temperature water base drilling fluid completion liquid-based slurry that embodiment sample is not added, and No. 2 are formulated and No. 3 Formula to be added the superhigh temperature water base drilling fluid completion fluid system of embodiment sample, the test conditions of HTHP filter losses is 180 DEG C/ 3.5MPa。
Interpretation of result:
Show superhigh temperature ultrahigh-density water-base drilling fluid completion fluid of the present invention from the test result of test example 1 to 3 It is by alkenyl anionic monomer sodium styrene sulfonate, allyl polyethenoxy ether (polyoxy alkyl with polycarboxylate flow pattern regulator Repeating segment number m=5-15) and alkenyl cationic monomer MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride occur polymerisation And generate, weight average molecular weight is about 10000 or so, and number-average molecular weight is about 8000 or so.
Show superhigh temperature ultrahigh-density water-base drilling fluid completion of the present invention from the experimental results of test example 4 Liquid polycarboxylate flow pattern regulator has the performance that can reduce aqueous solution surface tension, surface active properties apparent.
Show that superhigh temperature ultrahigh-density water-base drilling fluid completion fluid of the present invention is used from the test result of test example 5 Polycarboxylate flow pattern regulator can be obviously improved the rheological characteristic of superhigh temperature water base drilling fluid completion fluid, can greatly reduce water base Viscosity, yield value and the gel strength of drilling fluid and completion fluid, viscosity break ratio up to 85% or more, plastic viscosity reduced rate up to 32% or more, For yield value reduced rate up to 80% or more, the reduction amplitude of gel strength is up to 95% or more, it is thus possible to significantly improve water base brill Thickening properties of the well liquid completion fluid after superhigh temperature aging make superhigh temperature water base drilling fluid keep good rheological characteristic.
Show superhigh temperature ultrahigh-density water-base drilling fluid completion fluid of the present invention from the test result of test example 6 and 7 It on the one hand can effectively inhibit the pulping performance of bentonite clay particle in water, another aspect and energy with polycarboxylate flow pattern regulator Enough promote clay mineral to reach good dispersity in water, is conducive to the rheological characteristic for improving drilling fluid and completion fluid.
Show superhigh temperature ultrahigh-density water-base drilling fluid completion fluid of the present invention from the test result of test example 8 and 9 The high-temperature thickening characteristic of superhigh temperature ultrahigh-density water-base drilling fluid completion fluid can effectively be inhibited with polycarboxylate flow pattern regulator, Superhigh temperature ultrahigh-density water-base drilling fluid completion fluid can be made to keep good rheological property and leak-off wall building property;In addition, this The invention superhigh temperature ultrahigh-density water-base drilling fluid completion fluid is with polycarboxylate flow pattern regulator in superhigh temperature water-based drilling 251 DEG C of high temperature can be resisted in liquid.
The test result of compbined test example 1 to 9 shows superhigh temperature ultrahigh-density water-base drilling fluid completion of the present invention It is complete that liquid with polycarboxylate flow pattern regulator can effectively reduce the superhigh temperature ultrahigh-density water-base drilling fluid after superhigh temperature aging The viscosity and shear force of well liquid have the adjusting of good rheological characteristic and controlling to superhigh temperature ultrahigh-density water-base drilling fluid completion fluid Can, the heat-resisting property in drilling fluid and completion fluid system up to 251 DEG C or more, while its also have good some surface active property and Assist filtrate loss controllability.

Claims (10)

1. a kind of superhigh temperature ultrahigh-density water-base drilling fluid completion fluid polycarboxylate flow pattern regulator, which is characterized in that the stream Type conditioning agent has the structure described in formula (I):
The flow pattern regulator is by alkenyl benzene sulfonic acid salt, strongly hydrophilic cationic alkenyl quaternary ammonium salt and containing the allyl of backbone The amphoteric ion polycarboxylate ternary with comb-type structure that base polyoxyethylene ether is generated through aqueous free radical polymerisation is total Polymers;
In formula (I), x, y and z respectively represent anionic reactive monomer alkenyl benzene sulfonic acid salt, allyl polyethenoxy in structural formula The molal quantity of ether polymeric monomer and cationoid reaction monomer alkenyl quaternary ammonium salt, m represent the allyl polyethenoxy containing backbone The repeating segment number of polyoxy alkyl in ether.
2. polycarboxylate flow pattern regulator according to claim 1, which is characterized in that the flow pattern regulator molecule knot In structure main chain, containing 7-20 structural unit, weight average molecular weight range is 6,500-12,500;Molar ratio x ﹕ y=(0.35- 0.85) ﹕ (0.55-1.55), the weight of alkenyl quaternary ammonium salt account for the 3- of alkenyl benzene sulfonic acid salt and allyl polyethenoxy ether total weight 15%, m=5-26.
3. polycarboxylate flow pattern regulator according to claim 1, which is characterized in that the allyl polyoxy second of backbone The degree of unsaturation of alkene ether is more than 1.25mmol/g, hydroxyl value 85-155mgKOH/g.
4. polycarboxylate flow pattern regulator according to claim 1, which is characterized in that the flow pattern regulator molecule knot In structure main chain, containing 10-15 structural unit, weight average molecular weight range is 7,000-10,000;Molar ratio x ﹕ y=(0.45- 0.65) ﹕ (0.75-1.25), the weight of alkenyl quaternary ammonium salt account for the 3- of alkenyl benzene sulfonic acid salt and allyl polyethenoxy ether total weight 8%, m=5-15.
5. polycarboxylate flow pattern regulator according to claim 1, which is characterized in that the flow pattern regulator molecule knot In structure main chain, containing 7-12 structural unit, weight average molecular weight range is 10,000-12,000, molar ratio x ﹕ y=(0.48- 0.52) ﹕ (0.85-1.15), the weight of alkenyl quaternary ammonium salt account for the 5- of alkenyl benzene sulfonic acid salt and allyl polyethenoxy ether total weight 12%, m=12-15.
6. claim 1-5 any one of them superhigh temperature ultrahigh-density water-base drilling fluid completion fluid is adjusted with polycarboxylate flow pattern The preparation method of agent, includes the following steps:
By reactant alkenyl benzene sulfonic acid salt, strongly hydrophilic cationic alkenyl quaternary ammonium salt and allyl polyoxy second containing backbone Alkene ether is proportionally added in the reaction kettle equipped with solvent, and reaction kettle is poured into after catalyst is added in solvent fully dissolving In, reactant mixed liquid concentration is adjusted with solvent, the mixing in reaction kettle is heated by heating water bath or steam-heated mode Liquid maintains the reaction time, terminates reaction, is cooled to room temperature to get the poly- carboxylic of superhigh temperature ultrahigh-density water-base drilling fluid completion fluid Hydrochlorate flow pattern regulator.
7. the preparation method of polycarboxylate flow pattern regulator according to claim 6, which is characterized in that the solvent is Water;
The catalyst is the combination of persulfate and sodium hydrogensulfite;Alternatively, being water-soluble azo class initiator, amphipathic Azo initiator alternative one or combination;
Preferably, the mass ratio of persulfate and sodium hydrogensulfite is 1:1.
8. the preparation method of polycarboxylate flow pattern regulator according to claim 6, which is characterized in that the persulfuric acid Salt is potassium peroxydisulfate or ammonium persulfate;
The water-soluble azo class initiator is two isobutyl imidazoline hydrochloride of azo-bis-isobutyrate hydrochloride or azo, described Amphipathic azo-initiator be azo isobutyl cyano formamide.
9. the preparation method of polycarboxylate flow pattern regulator according to claim 6, which is characterized in that reactant total weight Account for the 30-60wt% for the total solution weight that reactant is formed with solvent;
When catalyst is the combination of persulfate and sodium hydrogensulfite, the addition of catalyst is the 0.5- of reactant total weight 4wt%;
When catalyst is water-soluble azo class initiator or/and amphipathic azo initiator, the addition of catalyst is reaction The 0.1-2wt% of object total weight.
10. the preparation method of polycarboxylate flow pattern regulator according to claim 6, which is characterized in that reaction temperature is 60-95℃;Reaction time is 1.5 hours to 6 hours.
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