CN103194202B - Adsorptive acid liquor retarding admixture and preparation method thereof - Google Patents
Adsorptive acid liquor retarding admixture and preparation method thereof Download PDFInfo
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- CN103194202B CN103194202B CN201310109406.9A CN201310109406A CN103194202B CN 103194202 B CN103194202 B CN 103194202B CN 201310109406 A CN201310109406 A CN 201310109406A CN 103194202 B CN103194202 B CN 103194202B
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- AVMUPOYOFDZPRS-UHFFFAOYSA-N CCC(C)(C)C1CCCC1 Chemical compound CCC(C)(C)C1CCCC1 AVMUPOYOFDZPRS-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses an adsorptive acid liquor retarding admixture for acidification in oil and gas wells and a preparation method thereof. According to the technical scheme, the acid liquor retarding admixture comprises the following monomers in percentage by mole: 4.2 to 4.7 percent of octadecyl dimethyl allyl ammonium chloride (BAZ) monomer, 1.9 to 2.3 percent of allyl polyethylene glycol (APEG) monomer, 93 to 93.5 percent of acrylic amide (AM) monomer, and 2,2'-azobis(2-methylpropionamide) dihydrochloride (AIBA) serving as an initiator in an amount which is 0.4 to 0.5 percent of the total mass of the monomers. The preparation method comprises the following steps of: adding BAZ, APEG and AM into a reaction container, adding water to prepare a solution of which the monomer concentration is 10 mass percent, adding the initiator, mixing uniformly, reacting for 6 to 7 hours at the temperature of between 50 and 55 DEG C, and thus obtaining the acid liquor retarding admixture. The preparation method is simple and feasible; the reaction conditions are mild; and the acid liquor retarding admixture is high in thermal stability, can be adsorbed to stratum crack walls, can be used for retarding the reaction speed of acid liquor and the crack walls and achieving the effect of deep acidification and is used for preparing acidifying liquor.
Description
Technical field
The present invention relates to a kind of slow admixture of adsorptive type acid solution for industrial gas oil acidizing treatment and preparation method thereof.
Background technology
Acidifying is one of important well stimulation of hydrocarbon-bearing pool.It is to utilize acid solution to remove recovery well, near the pollution in Injection Well shaft bottom, and the rate of permeation of renwing stratum or corrosion formation rock cementing matter are to improve the well stimulation of zone permeability.Its objective is with acid and remove the injury in the processes such as drilling well, completion, well workover and augmented injection, near stratum well being caused, dredge fluid seepage channel, thereby recover and raising oil gas well capacity.At present, taking acid-etched fracture scale as the criteria for classifying, ACID FRACTURING TECHNOLOGY can be divided into common acid fracturing and the large class of Depth Acid Fracturing two.
Common acid fracturing is mainly the pollution de-plugging to immediate vicinity of wellbore or forms small-scale acid-etched fracture, improves the flow conductivity of stratum around the well.But it is serious that common acid is pressed with acid liquid loss, sour rock speed of response is fast, and effectively acid etching operating distance is shorter, the reservoir of even can with serious pollution natural fracture growing.
Depth Acid Fracturing is fast for common acid fracturing and reservoir speed of response, the EFFECTIVE RANGE of acid solution is short, cause most of acid solution consumption near wellbore formation, and deep-section can not get abundant acidifying, make the feature of well stimulation deleterious, the retarded acid liquid system with different qualities of development, mainly comprises gel acid, emulsified acid, chemically retarded acid, foamed acid, acid becomes sticky.
Gel acid is a kind of macromolecular solution, has higher viscosity.The technical characteristics of gel acid is in acidizing fluid, to add after jelling agent, makes acid fluid system become lyophilic sol and reduces the velocity of diffusion of H+, thereby reduce sour rock speed of response, increases active acid penetration range, reaches the effect of deep acidizing.Gel acid has advantages of the inhibiter of saving consumption, reduces pumping frictional resistance, alleviates formation damage, but very sensitive to shearing, and in residual acid, broken glue difficulty, easily causes secondary pollution to reservoir.
Emulsified acid typically refers to oil and two kinds of immiscible liquid of acid solution mix by suitable proportion, and the oil that mixture forms under the effect of emulsifying agent wraps sour emulsion.Its mechanism of action is to utilize the high viscosity of emulsified acid and the inhibition of foreign minister's oil to postpone contacting of acid solution and crack wall, postpones sour rock speed of response.Its advantage is that filter loss is little, and slow performance is good, can enter earth formation deep; Shortcoming is that construction frictional resistance is higher, high compared with common acid, causes acid fracturing operation pressure high, and discharge capacity is low.
Chemically retarded acid refers to and in acid solution, adds tensio-active agent or add the CO2 that the reaction of sour rock is generated to form the tensio-active agent of stable foam and the acid fluid system that forms.Its mechanism of action is that SURFACTANT ADSORPTION forms protective membrane after formation fracture wall, delays sour rock speed of response; Its shortcoming is that control leak-off is poor, is mainly applicable to the low temperature dolomite stratum that sour rock speed of response is controlled by surface, combines can be applicable to middle temperature dolomite reservoir with multistage alternating implantttion technique.
Foamed acid is to replace conventional acid solution by inflation or the acid solution that gasified, to reduce sour rock speed of reaction, realizes deep penetration.Foamed acid is made up of acid solution, gas, pore forming material, suds-stabilizing agent, water-soluble polymers etc.It has, and liquid content is low, apparent viscosity is high, filter loss is little, can effectively slow down sour rock speed of reaction the advantage such as the row of returning rapidly, but under hot conditions, the stability of foamed acid reduces, and acid liquid loss amount increases, thereby affects retarded acidizing effect.
The acid that becomes sticky is called again leak-off control acid, refers to and in acid solution, adds a kind of synthetic compound, can in stratum, form crosslinked jelling agent and increase viscosity, the acid fluid system that can automatically break glue viscosity reduction after acid solution consumption is residual acid.
The acid that becomes sticky has good filtrate loss controllability, and viscosity temperature characteristic is stable and residual sour viscosity is lower, but more responsive to hydrogen sulfide.
Summary of the invention
The object of the invention is: in acidizing treatment, conventional acid solution hydrochloric acid and the mud acid using is strong acid, stratum reacts very fast with it, generally can only eliminate the injury of rate of permeation around of nearly well, for reaching deep formation acidifying, improve oil-gas field production capacity, spy provides slow admixture of a kind of adsorptive type acid solution and preparation method thereof.
For achieving the above object, the present invention is by the following technical solutions: the slow admixture of a kind of adsorptive type acid solution, is characterized in that: the slow admixture of this acid solution is to be formed by solution property code name BAZ, allyl polyglycol code name APEG, tri-kinds of monomer polymerizations of acrylamide code name AM; The molar percentage of monomer used is: BAZ monomer is 4.2～4.7%; APEG monomer is 1.9～2.3%, and the relative molecular mass of APEG monomer used is 1000g/mol; AM monomer is 93～93.5%; Initiator is azo-bis-isobutyrate hydrochloride, and add-on is 0.4～0.5% of monomer total mass.Its structural formula of the slow admixture of this acid solution is as follows:
Wherein X=4.2～4.7%, Y=1.9～2.3%, n=20～25.
The preparation method of the slow admixture of a kind of adsorptive type acid solution, its step is in the silk opening reagent bottle that is first 100mL at volume, to add the acrylamide AM of the solution property BAZ of 0.002mol and the allyl polyglycol APEG of 0.001mol and 0.04mol; Then being made into monomer mass percentage concentration to the deionized water that adds 41.3g in above-mentioned solution is 10% solution, adds initiator azo-bis-isobutyrate hydrochloride 0.018g after stirring and dissolving; After finally above-mentioned solution being mixed, being to react 6-7h at 50-55 DEG C in temperature, obtaining colloid product, use absolute ethanol washing 3-5 time, until there is precipitation, is to dry after 24h in 50 DEG C of baking ovens in temperature, makes the slow admixture of this acid solution.
With the slow admixture comparison of existing acid solution, the present invention has following beneficial effect: (1) preparation method's simple possible of the present invention, reaction conditions gentleness.(2) this product adds after acid fluid system, all has preferably slow effect in sandstone and carbonate, can be to the acidification of carrying out of deep formation, and acid fluid system viscosity is without considerable change, is conducive to the row of returning of residual acid.(3) the product thermal stability that prepared by the method is good, and temperature resistance ability is stronger, has good compatibleness with other admixture of acid fluid system.
Embodiment
The preparation method of 1 one kinds of slow admixtures of adsorptive type acid solution of embodiment
In the silk opening reagent bottle that is first 100mL at volume, adding 0.747g is that the solution property BAZ of 0.002mol and 1g are that allyl polyglycol APEG and the 2.84g of 0.001mol is the acrylamide AM of 0.04mol; Then being made into monomer mass percentage concentration to the deionized water that adds 41.3g in above-mentioned solution is 10% solution, adds initiator azo-bis-isobutyrate hydrochloride 0.018g after stirring and dissolving; After finally above-mentioned solution being mixed, being to react 6h at 50 DEG C in temperature, obtaining colloid product, use absolute ethanol washing 3 times, until there is precipitation, is to dry after 24h in 50 DEG C of baking ovens in temperature, makes the slow admixture of this acid solution.
The preparation method of 2 one kinds of slow admixtures of adsorptive type acid solution of embodiment
In the silk opening reagent bottle that is first 100mL at volume, adding 0.672g is that the solution property BAZ of 0.0018mol and 1g are that allyl polyglycol APEG and the 2.84g of 0.001mol is the acrylamide AM of 0.04mol; Then being made into monomer mass percentage concentration to the deionized water that adds 40.6g in above-mentioned solution is 10% solution, adds initiator azo-bis-isobutyrate hydrochloride 0.018g after stirring and dissolving; After finally above-mentioned solution being mixed, being to react 6h at 50 DEG C in temperature, obtaining colloid product, use absolute ethanol washing 3 times, until there is precipitation, is to dry after 24h in 50 DEG C of baking ovens in temperature, makes the slow admixture of this acid solution.
The preparation method of 3 one kinds of slow admixtures of adsorptive type acid solution of embodiment
In the silk opening reagent bottle that is first 100mL at volume, adding 0.672g is that the solution property BAZ of 0.0018mol and 0.8g are that allyl polyglycol APEG and the 2.84g of 0.0008mol is the acrylamide AM of 0.04mol; Then being made into monomer mass percentage concentration to the deionized water that adds 38g in above-mentioned solution is 10% solution, adds initiator azo-bis-isobutyrate hydrochloride 0.017g after stirring and dissolving; After finally above-mentioned solution being mixed, being to react 6h at 50 DEG C in temperature, obtaining colloid product, use absolute ethanol washing 3 times, until there is precipitation, is to dry after 24h in 50 DEG C of baking ovens in temperature, makes the slow admixture of this acid solution.
The slow effect of 4 one kinds of slow admixtures of adsorptive type acid solution of embodiment in sandstone
For evaluating the slow performance of the slow admixture of this acid solution in sandstone, with reference to the static weight loss method in SY/T5886-93 sandstone retarded acid method of evaluating performance.Process is as follows: first mud acid and slow admixture acid fluid system are placed in to the silk opening reagent bottle of 2 100mL, after put into the thermostat water bath of 80 DEG C, after the acid liquor temperature in screw thread reagent bottle is constant, add corresponding sandstone landwaste.The sequentially determining reaction times is 30 or 45 or 60 or the corrosion rate of 90min.Then wash, filter, dry, weigh, calculate the core corrosion rate under different condition, finally prove that slow admixture acid fluid system, compared with regular mud acid, has the slow effect of good acid solution.
The slow effect of 5 one kinds of slow admixtures of adsorptive type acid solution of embodiment in carbonatite
For evaluating the slow performance of the slow admixture of this acid solution in In Carbonate Rock, first produce 2 long 2mm, wide 1mm, the rectangular parallelepiped carbonate rock sample of high 1mm, calculates its surface-area, is accurate to 0.01m2, puts into the dry 30min of moisture eliminator.Then each rock sample measures respectively 3mL hydrochloric acid and adds the hydrochloric acid (hydrochloric acid mass percentage concentration is 20%) of slow admixture to be placed in reaction flask by every square centimeter of surface-area, reaction flask is moved into 80 DEG C of thermostat water baths after acid liquor temperature is constant, add rock sample, the sequentially determining reaction times is 30 or 45 or 60 or the corrosion rate of 90min, finally wash, filter, dry, weigh, calculate the corrosion rate of rock under different condition.Found that by experiment, add this invention to make after the slow admixture of acid solution, acid solution has preferably slow effect.
Claims (1)
1. the slow admixture of adsorptive type acid solution, is characterized in that: the slow admixture of this acid solution is to be formed by solution property code name BAZ, allyl polyglycol code name APEG, tri-kinds of monomer polymerizations of acrylamide code name AM; The molar percentage of monomer used is: BAZ monomer is 4.2～4.7%; APEG monomer is 1.9～2.3%, and the relative molecular mass of APEG monomer used is 1000g/mol; AM monomer is 93～93.5%; Initiator is azo-bis-isobutyrate hydrochloride, and add-on is 0.4～0.5% of monomer total mass; Its preparation method is: the acrylamide AM that adds the solution property BAZ of 0.002mol and the allyl polyglycol APEG of 0.001mol and 0.04mol in the silk opening reagent bottle that is first 100mL at volume; Then being made into monomer mass percentage concentration to the deionized water that adds 41.3g in above-mentioned solution is 10% solution, adds initiator azo-bis-isobutyrate hydrochloride 0.018g after stirring and dissolving; After finally above-mentioned solution being mixed, being to react 6-7h at 50-55 DEG C in temperature, obtaining colloid product, use absolute ethanol washing 3-5 time, until there is precipitation, is to dry after 24h in 50 DEG C of baking ovens in temperature, makes the slow admixture of this acid solution.
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| CN105001849A (en) * | 2015-07-02 | 2015-10-28 | 西南石油大学 | Hydrophobically associated type cation acid solution retardant and preparation method thereof |
| CN105693947B (en) * | 2016-03-04 | 2019-01-08 | 西南石油大学 | It is acidified retardant, preparation method and retarded acid |
| CN105647511A (en) * | 2016-04-07 | 2016-06-08 | 西南石油大学 | Acidification additive and preparation method thereof |
| CN105950126A (en) * | 2016-05-16 | 2016-09-21 | 中国石油化工股份有限公司 | Delaying controlled-release acid for acidizing unblocking, preparation method of acid and acidizing unblocking method |
| CN107793537B (en) * | 2016-08-30 | 2020-02-14 | 中国石油天然气股份有限公司 | Acid liquor thickener and preparation method thereof |
| CN107312121B (en) * | 2017-06-22 | 2019-12-20 | 西南石油大学 | Polymer type non-crosslinked self-diverting acidification diverting agent and preparation method thereof |
| CN110343220B (en) * | 2019-07-26 | 2022-08-16 | 西南石油大学 | Retarding additive, preparation method thereof and retarding acid |
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