CN103194202A - 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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- CN103194202A CN103194202A CN2013101094069A CN201310109406A CN103194202A CN 103194202 A CN103194202 A CN 103194202A CN 2013101094069 A CN2013101094069 A CN 2013101094069A CN 201310109406 A CN201310109406 A CN 201310109406A CN 103194202 A CN103194202 A CN 103194202A
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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 the 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 on recovery 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 that in the processes such as drilling well, completion, well workover and augmented injection near the stratum well is caused, mediation fluid seepage channel, thus recover and raising oil gas well capacity.At present, be the criteria for classifying with the acid-etched fracture scale, ACID FRACTURING TECHNOLOGY can be divided into common acid fracturing and degree of depth acid fracturing two big classes.
Common acid fracturing mainly is to the pollution de-plugging of immediate vicinity of wellbore or forms small-scale acid-etched fracture, improves the flow conductivity of stratum around the well.But common acid is pressed with that acid liquid loss is serious, and sour rock speed of response is fast, and effectively acid etching operating distance is shorter, even the reservoir of can with serious pollution natural fracture growing.
Degree of depth acid fracturing is fast at 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 characteristics 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 major technique characteristics of gel acid are add jelling agent in acidizing fluid after, make acid fluid system become lyophilic sol and reduce the velocity of diffusion of H+, thereby reduce sour rock speed of response, increase the active acid penetration range, reach the effect of deep acidizing.Gel acid has the advantage of saving inhibiter consumption, reduction pumping frictional resistance, alleviating formation damage, but very sensitive to shearing, broken glue difficulty easily causes secondary pollution to reservoir in residual acid.
Emulsified acid typically refers to oil and two kinds of immiscible liquid of acid solution mix by suitable proportion, and the oil that forms that is mixed under the effect of emulsifying agent wraps sour emulsion.Its mechanism of action is to utilize high viscosity and the inhibition delay acid solution of foreign minister's oil and contacting of crack wall of emulsified acid, 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 the construction frictional resistance is higher, than the common acid height, causes acid fracturing operation pressure height, and discharge capacity is low.
Chemically retarded acid refers in acid solution to add that CO2 that tensio-active agent or adding generate sour rock reaction forms the tensio-active agent of stable foam and the acid fluid system that constitutes.Its mechanism of action is that SURFACTANT ADSORPTION forms protective membrane behind the formation fracture wall, delays sour rock speed of response; Its shortcoming is that the control leak-off is relatively poor, mainly is fit to the low temperature dolomite stratum that sour rock speed of response is subjected to surface control, combine with the multistage alternating implantttion technique can be applicable in warm dolomite reservoir.
Foamed acid is to replace conventional acid solution with 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 slow down sour rock speed of reaction and advantage such as the row of returning rapidly effectively, but under hot conditions, the stability of foamed acid reduces, and the acid liquid loss amount increases, thereby influences the retarded acidizing effect.
The acid that becomes sticky is called leak-off control acid again, refers to add a kind of synthetic compound in acid solution, can form crosslinked jelling agent and increase viscosity, the acid fluid system that can break the glue viscosity reduction after acid solution consumption is residual acid automatically in the stratum.
The acid that becomes sticky has good filtration reduction energy, and viscosity temperature characteristic is stable and residual sour viscosity is lower, but responsive to hydrogen sulfide.
Summary of the invention
The objective of the invention is: in the acidizing treatment, conventional acid solution hydrochloric acid and the mud acid that uses is strong acid, stratum and its reaction are very fast, generally can only eliminate the injury of rate of permeation on every side of nearly well, for reaching the deep formation acidifying, improve the oil-gas field production capacity, the 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 octadecyl dimethyl-allyl ammonium chloride code name BAZ, allyl polyglycol code name APEG, three kinds of monomer polymerizations of acrylamide code name AM; The molar percentage of used monomer is: the BAZ monomer is 4.2～4.7%; The APEG monomer is 1.9～2.3%, and the relative molecular mass of used APEG monomer is 1000g/mol; The 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:
X=4.2～4.7% wherein, 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, adds octadecyl dimethyl-allyl ammonium chloride BAZ and the allyl polyglycol APEG of 0.001mol and the acrylamide AM of 0.04mol of 0.002mol earlier in volume is the silk mouthful reagent bottle of 100mL; It is 10% solution that the deionized water that adds 41.3g then in the above-mentioned solution is made into the monomer mass percentage concentration, adds initiator azo-bis-isobutyrate hydrochloride 0.018g after the stirring and dissolving; After at last above-mentioned solution being mixed, reaction 6-7h gets the colloid product under temperature is 50-55 ℃, uses absolute ethanol washing 3-5 time, until precipitation occurring, after temperature is to dry by the fire 24h in 50 ℃ of baking ovens, makes the slow admixture of this acid solution.
Compare with the slow admixture 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) after this product adds acid fluid system, slow effect is preferably arranged all in sandstone and carbonate, can be to the acidification of carrying out of deep formation, and acid fluid system viscosity do not have considerable change, is conducive to the row of returning of residual acid.(3) the product thermal stability of this method preparation is good, and the temperature resistance ability is stronger, with other admixture of acid fluid system compatibleness is preferably arranged.
Embodiment
The preparation method of 1 one kinds of slow admixtures of adsorptive type acid solution of embodiment
In being the silk mouthful reagent bottle of 100mL, volume adds earlier 0.747g and is the acrylamide AM that the octadecyl dimethyl-allyl ammonium chloride BAZ of 0.002mol and allyl polyglycol APEG that 1g is 0.001mol and 2.84g are 0.04mol; It is 10% solution that the deionized water that adds 41.3g then in the above-mentioned solution is made into the monomer mass percentage concentration, adds initiator azo-bis-isobutyrate hydrochloride 0.018g after the stirring and dissolving; After at last above-mentioned solution being mixed, reaction 6h get the colloid product under temperature is 50 ℃, use absolute ethanol washing 3 times, until precipitation occurring, after temperature is to dry by the fire 24h in 50 ℃ of baking ovens, make 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 being the silk mouthful reagent bottle of 100mL, volume adds earlier 0.672g and is the acrylamide AM that the octadecyl dimethyl-allyl ammonium chloride BAZ of 0.0018mol and allyl polyglycol APEG that 1g is 0.001mol and 2.84g are 0.04mol; It is 10% solution that the deionized water that adds 40.6g then in the above-mentioned solution is made into the monomer mass percentage concentration, adds initiator azo-bis-isobutyrate hydrochloride 0.018g after the stirring and dissolving; After at last above-mentioned solution being mixed, reaction 6h get the colloid product under temperature is 50 ℃, use absolute ethanol washing 3 times, until precipitation occurring, after temperature is to dry by the fire 24h in 50 ℃ of baking ovens, make 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 being the silk mouthful reagent bottle of 100mL, volume adds earlier 0.672g and is the acrylamide AM that the octadecyl dimethyl-allyl ammonium chloride BAZ of 0.0018mol and allyl polyglycol APEG that 0.8g is 0.0008mol and 2.84g are 0.04mol; It is 10% solution that the deionized water that adds 38g then in the above-mentioned solution is made into the monomer mass percentage concentration, adds initiator azo-bis-isobutyrate hydrochloride 0.017g after the stirring and dissolving; After at last above-mentioned solution being mixed, reaction 6h get the colloid product under temperature is 50 ℃, use absolute ethanol washing 3 times, until precipitation occurring, after temperature is to dry by the fire 24h in 50 ℃ of baking ovens, make 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 estimating the slow performance of the slow admixture of this acid solution in sandstone, with reference to the static weight-loss method in the SY/T5886-93 sandstone retarded acid method of evaluating performance.Process is as follows: at first mud acid and slow admixture acid fluid system are placed the silk mouthful reagent bottle of 2 100mL, after put into 80 ℃ thermostat water bath, treat that acid liquor temperature in the screw thread reagent bottle is constant after, add corresponding sandstone landwaste.The sequentially determining reaction times is 30 or 45 or 60 or the corrosion rate of 90min.Wash then, filter, dry, weigh, calculate the core corrosion rate under the different condition, prove that at last slow admixture acid fluid system compares with regular mud acid, the slow effect of acid solution is preferably arranged.
The slow effect of 5 one kinds of slow admixtures of adsorptive type acid solution of embodiment in carbonatite
For estimating the slow performance of the slow admixture of this acid solution in the carbonate rock, at 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.Each rock sample is measured 3mL hydrochloric acid respectively by every square centimeter of surface-area and is placed reaction flask with the hydrochloric acid (the hydrochloric acid mass percentage concentration is 20%) that adds slow admixture then, reaction flask is moved into after 80 ℃ of thermostat water baths treat that 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, wash at last, filter, dry, weigh, calculate the corrosion rate of rock under the different condition.Found that by experiment add after this invention makes the slow admixture of acid solution, acid solution has slow effect preferably.
Claims (2)
1. slow admixture of adsorptive type acid solution, it is characterized in that: the slow admixture of this acid solution is to be formed by octadecyl dimethyl-allyl ammonium chloride code name BAZ, allyl polyglycol code name APEG, three kinds of monomer polymerizations of acrylamide code name AM; The molar percentage of used monomer is: the BAZ monomer is 4.2～4.7%; The APEG monomer is 1.9～2.3%, and the relative molecular mass of used APEG monomer is 1000g/mol; The AM monomer is 93～93.5%; Initiator is azo-bis-isobutyrate hydrochloride, and add-on is 0.4～0.5% of monomer total mass.
2. preparation method of the slow admixture of acid solution according to claim 1, it is characterized in that, in volume is the silk mouthful reagent bottle of 100mL, add earlier octadecyl dimethyl-allyl ammonium chloride BAZ and the allyl polyglycol APEG of 0.001mol and the acrylamide AM of 0.04mol of 0.002mol; It is 10% solution that the deionized water that adds 41.3g then in the above-mentioned solution is made into the monomer mass percentage concentration, adds initiator azo-bis-isobutyrate hydrochloride 0.018g after the stirring and dissolving; After at last above-mentioned solution being mixed, reaction 6-7h gets the colloid product under temperature is 50-55 ℃, uses absolute ethanol washing 3-5 time, until precipitation occurring, after temperature is to dry by the fire 24h in 50 ℃ of baking ovens, 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 |
| CN105647511A (en) * | 2016-04-07 | 2016-06-08 | 西南石油大学 | Acidification additive and preparation method thereof |
| CN105693947A (en) * | 2016-03-04 | 2016-06-22 | 西南石油大学 | Acidulated retarding agent, preparation method thereof and retarding acid |
| 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 |
| CN107312121A (en) * | 2017-06-22 | 2017-11-03 | 西南石油大学 | A kind of non-crosslinked low damage acidified diverting agent of polymer-type and preparation method thereof |
| CN107793537A (en) * | 2016-08-30 | 2018-03-13 | 中国石油天然气股份有限公司 | A kind of gelling agent for acid fluid and preparation method thereof |
| CN110343220A (en) * | 2019-07-26 | 2019-10-18 | 西南石油大学 | A kind of slow additive, preparation method and retarded acid |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104263329A (en) * | 2014-09-19 | 2015-01-07 | 中国石油集团渤海钻探工程有限公司 | High-temperature resistant and salt-tolerance filtrate reducer for drilling fluid and preparation method thereof |
| 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 |
| CN105693947A (en) * | 2016-03-04 | 2016-06-22 | 西南石油大学 | Acidulated retarding agent, preparation method thereof and retarding acid |
| 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 |
| CN107793537A (en) * | 2016-08-30 | 2018-03-13 | 中国石油天然气股份有限公司 | A kind of gelling agent for acid fluid and preparation method thereof |
| 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 |
| CN107312121A (en) * | 2017-06-22 | 2017-11-03 | 西南石油大学 | A kind of non-crosslinked low damage acidified diverting agent of polymer-type 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 |
| CN110343220A (en) * | 2019-07-26 | 2019-10-18 | 西南石油大学 | A kind of slow additive, preparation method and retarded acid |
| 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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