CN102585797B - Diverting acid for carrying out acidification and transformation on high-temperature oil and gas well with long well segment - Google Patents
Diverting acid for carrying out acidification and transformation on high-temperature oil and gas well with long well segment Download PDFInfo
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Abstract
The invention relates to diverting acid for carrying out acidification and transformation on a high-temperature oil and gas well with a long well segment, which comprises the following components: 4.5 to 5.0 percent by mass of diverter octadecanoyl amido ethyl dimethylamine betaine, 1.0 to 2.0 percent by mass of corrosion inhibitor Mannich base, 1.0 to 2.0 percent by mass of ferric ion stabilizer erythorbic acid or sodium erythorbate, 20 percent by mass of hydrochloric acid and the balance water. According to the invention, the characteristic that the diverting acid has different molecule aggregation morphologies and aggregation numbers under different pH values is utilized; the high temperature resistance diverting acid with viscoelasticity is prepared by adding the corrosion inhibitor Mannich base and the ferric ion stabilizer erythorbic acid or sodium erythorbate; and after the diverting acid is injected into a formation, the viscosity of the acid is rapidly improved along with the consumption of the acid and the injection pressure at the bottom of the well also rises along with the consumption of the acid, so that the acid is forced to permeate and divert toward the formation, a reservoir is uniformly acidified and the acidification effect is obviously improved.
Description
Affiliated technical field
The present invention relates to the acid that turns to of acidification of oil gas well construction, especially for the acid that turns to of long well section, heterogeneous high temperature deep well acidizing treatment.
Background technology
Bore the completion construction and can cause hydrocarbon contamination, reduce the oil gas output.Acidifying is mainly used to remove the pollution of nearly well band, enlarges the oil flow channel of low permeability layer, recovers or increase oil gas well yield.But because the pollution of reservoir and extent of injury normally are uneven distribution, the in addition nonuniformity between reservoir, the perviousness of each layer differs greatly, particularly open well segment length, long horizontal traverse well and horizontal well that opening degree is high, conventional acid metallization processes or acid solution not only are difficult to remove the contamination and plugging of skewness, can increase the rate of permeation extreme difference on the contrary, the aggravation interlayer contradiction.Therefore how effectively evenly putting in the stratum, shunt acid solution, acid solution reasonably is distributed in respectively pollutes interval, is the key that improves the acidizing treatment effect.As not taking acid solution to turn to measure, most of acid solution will be missed to most permeable zone, and make the acidizing effect variation.
At present ripe acid solution turns to normal employing mechanical steering technology (such as the down-hole separation scraper, stop up ball etc.), but the method complicated operation, heaviness, and expensive.Compare with the mechanical steering technology, the chemistry diversion technology then easy to use, construction risk is low.Rig-site utilization is more to have chemical particle to turn to, foam turns to, polymkeric substance becomes glue steering technique etc. on the spot.It is to add the molten and water-insolube chemical particle of a kind of oil in acid solution that chemical particle turns to, and these particulates form the very little filter cake of rate of permeation, the injectability of regulating each layer by filter cake in the processing aspect.Such as Halliburton company publication, use soap class solution and CaCl
2The particle that reaction generates is as diverting agent, but in fact this cake layer often can cause permanent reservoir damage.Utilize foam different in the stability of high low permeability layer, and foam at most permeable zone to the inhibition of the liquid phase flow principle greater than low permeability layer, developed the foam steering technique, the foam technology easily row of returning and secondary injury is low, but construction infusion pressure height, non-refractory, steering capability are limited, have limited the application that foam turns to.Polymkeric substance becomes the glue steering technique to add polymkeric substance on the spot in acid solution, under the effect of high-valence cationic Fe (III) and Zr (IV), occur on the spot crosslinked, producing high viscosity frozen glue makes acid solution turn to shunting, this technology shunting effect is better, but polymer residue can cause reservoir permeability to reduce, and causes secondary injury.Chang Lynn observes at polymkeric substance to become on the spot under the adhesive tape part with Nasr-El-Din simultaneously, and linking agent Fe (III) can precipitate.
Summary of the invention
The object of the present invention is to provide the acid that turns to for long well section, the transformation of high-temperature oil gas well acidizing, the present invention utilizes diversion agent under different pH, form different molecular aggregates form and aggregation number, adding inhibiter mannich base and Fe stabilizer saccharosonic acid or SODIUM ISOVITAMIN C prepares and has visco-elasticity, resistant to elevated temperaturesly turns to acid, after injecting the stratum, raise rapidly with acid solution consumption acids fluid viscosity, sand face injection pressure rises thereupon, force acid solution to turn to the stratum infiltration, make reservoir obtain homogeneous acidification, significantly improve acidizing effect.
For reaching above technical purpose, the invention provides following technical scheme.
Be used for the acid that turns to of long well section, the transformation of high-temperature oil gas well acidizing, its component and content are as follows:
Diversion agent, 4.5～5.0 quality %;
Inhibiter, 1.0～2.0 quality %;
Fe stabilizer, 1.0～2.0 quality %;
Hydrochloric acid, 20 quality %;
All the other components are water.
Among the present invention, described diversion agent is stearoyl amido ethyl decil lactone, and with stearic acid, N, N-dimethyl-ethylenediamine, Mono Chloro Acetic Acid are the raw material preparation.
Described inhibiter is mannich base, mannich base is β-diethylin phenyl ketone, β-rosin amine phenyl ketone or the two mixture, and described the two mixture is comprised of the β of the β of 80-85 quality %-diethylin phenyl ketone and 15-20 quality %-rosin amine phenyl ketone.
Described Fe stabilizer is saccharosonic acid or SODIUM ISOVITAMIN C.
Described hydrochloric acid is commercially available chemical pure or technical pure.
But the present invention is based on the characteristics that the self-organization in certain density acid solution of amphoterics molecule forms multiple supramolecular structure, formed the acid that turns to special flow change nature.Micelle solution is with H
+The variation generation rheological property of concentration is suddenlyd change and is had the character of gel, shows significant visco-elasticity.After acid solution was injected the stratum, along with the carrying out of sour rock reaction, acid concentration constantly descended, the surfactant molecule micellar conformation changes in the solution, the micella growth forms and mutually twines the vermiculate glues that is woven in together, and acid liquid viscosity raises rapidly, changes gel liquid into by low-viscosity (mobile) liquid.This variation has increased acid solution resistance to flow in the stratum, can automatically regulate the distribution of acid solution in interlayer or layer.Along with acid strength further reduces, acid is reacted the Ca that generates with rock
2+, Mg
2+Concentration rises, and disintegrates to the acid solution vermiculate glues that is exhausted, and system is broken glue thoroughly, and residual acid is returned smoothly and flow back to ground, and reservoir is evenly transformed, and significantly improves acidizing effect.
The present invention is after response of stratum forms residual acid, and micella is disintegrated and is the tensio-active agent small molecules, without injury, and can adapt to Reservoir Acidization operation more than 120 ℃ to reservoir.
Turn in the acid in the present invention, stearoyl amido ethyl decil lactone is amphoterics, and structure is as follows:
RN
+(CH
3)
2CH
2COO
-，R＝-CH
2CH
2NHOCC
17H
33
This diversion agent stearoyl amido ethyl decil lactone is by stearic acid, N, N-dimethyl-ethylenediamine, Mono Chloro Acetic Acid are the raw material preparation: (1) amidation, in reactor, add stearic acid and little excessive N, the N-dimethyl-ethylenediamine, NaOH is catalyzer, 110 ℃ of reaction 5h obtain the midbody product tertiary amine.(2) quaternary ammoniated, in reactor, add Mono Chloro Acetic Acid, dripping NaOH solution, to be neutralized to pH be about 7, adds the midbody product tertiary amine, behind 60～80 ℃ of reaction 10h, obtains stearoyl amido ethyl decil lactone after decompression, dry, the cooling.
Its synthetic route is as follows:
Its concrete preparation method is as follows:
(1) in 250mL single port flask, adds stearic acid 0.1mol, heat fused, logical nitrogen deoxygenation 20min.Add N, N-dimethyl-ethylenediamine 0.12mol, 0.2%, 110 ℃ of reaction of catalyst n aOH quality 5h.Decompression vacuum pumping steams excessive N, and the N-dimethyl-ethylenediamine is placed after the cooling and spent the night, and obtains midbody product.
(2) in the there-necked flask with thermometer, agitator, add Mono Chloro Acetic Acid 0.15mol, dissolve with suitable quantity of water, then dripping NaOH liquid, to be neutralized to pH be about 7, the midbody product tertiary amine that the complete adding 0.1mol the first step that neutralizes obtains behind the reaction 10h, obtains liquid of vicidity in 60～80 ℃ of water-baths, pressure reducing and steaming moisture gets stearoyl amido ethyl decil lactone after drying, the cooling.
The present invention turns to the preparation method of acid as follows:
(1) add the concentrated hydrochloric acid of design flow in the acid-resistant container, thin up obtains the hydrochloric acid of 20 quality %;
(2) mannich base of adding 1.0～2.0 quality %;
(3) saccharosonic acid or the SODIUM ISOVITAMIN C of adding 1.0～2.0 quality %;
(4) the stearoyl amido ethyl decil lactone of adding 4.5～5.0 quality %;
(5) it is even to be stirred well to acid solution, obtains turning to acid.
The present invention forms the acid system that turns to that adapts to long well section, high temperature deep well acidifying, and compared with prior art, beneficial effect of the present invention is that acid formula is simple, turning efficiency good, nothing injury, high temperature resistant, and acidizing effect is remarkable.Its core technology index of the present invention is:
(1) turns to bright sour viscosity＜50mPa.s under the sour normal temperature;
(2) turn to acid fluid system reaction tackify after, high viscosity＞100mPa.s;
(3) 120 ℃ turn to acid corrosion speed≤40g/ (m
2.h).
Description of drawings
Fig. 1 turns to acid bright sour viscograph (embodiment 2)
Fig. 2 turns to viscograph (embodiment 2) behind the acid-respons tackify
Fig. 3 is imperial hilllock X well acidizing construction curve.
Embodiment
Following per-cent is mass percent.
Stearoyl amido ethyl decil lactone by 4.5%, 1.0% β-diethylin phenyl ketone, 1.0% saccharosonic acid, 20% hydrochloric acid, surplus is water, configuration turns to acid.
Present embodiment turns to sour sample, bright sour initial viscosity 20.4mPa.s, 120 ℃ of acid solution Dynamic Corrosion speed 5.4g/m
2System viscosity is 155mPa.s when .h, reacting to acid concentration 8% with rock; System viscosity is 25mPa.s when reacting to acid concentration 5%; System viscosity is 11mPa.s when reacting to acid concentration 1.5%.
Embodiment 2
Stearoyl amido ethyl decil lactone by 5.0%, 2.0% β-diethylin phenyl ketone, 2.0% saccharosonic acid, 20% hydrochloric acid, surplus is water, configuration turns to acid.
Present embodiment turns to sour sample, bright sour initial viscosity 28.4mPa.s, 120 ℃ of acid solution Dynamic Corrosion speed 4.8g/m
2System viscosity is 336mPa.s when .h, reacting to acid concentration 8% with rock; System viscosity is 25.0mPa.s when reacting to acid concentration 5%; System viscosity is 24.3mPa.s when reacting to acid concentration 1.5%.Acid liquid viscosity-time curve is referring to Fig. 1 and Fig. 2.
Embodiment 3
Stearoyl amido ethyl decil lactone by 4.5%, 1.5% β-diethylin phenyl ketone, 1.5% saccharosonic acid, 20% hydrochloric acid, surplus is water, configuration turns to acid.
Present embodiment turns to sour sample, bright sour initial viscosity 20.4mPa.s, 120 ℃ of acid solution Dynamic Corrosion speed 5.1g/m
2System viscosity is 162.5mPa.s when .h, reacting to acid concentration 8% with rock; System viscosity is 22.0mPa.s when reacting to acid concentration 5%; System viscosity is 12.6mPa.s when reacting to acid concentration 1.5%.
Embodiment 4
Stearoyl amido ethyl decil lactone by 5.0%, 1.0% β-diethylin phenyl ketone, 1.0% saccharosonic acid, 20% hydrochloric acid, surplus is water, configuration turns to acid.
Present embodiment turns to sour sample, bright sour initial viscosity 28.1mPa.s, 120 ℃ of acid solution Dynamic Corrosion speed 5.8g/m
2System viscosity is 312.1mPa.s when .h, reacting to acid concentration 8% with rock; System viscosity is 22.4mpa.s when reacting to acid concentration 5%; System viscosity is 17.0mPa.s when reacting to acid concentration 1.5%.
Embodiment 5
By turning to the acid prescription among the embodiment 2, carry out test in place at Sichuan Long Gang structure X well.Test pit adopts completion to turn to acidification technique, and design is measured 160m with acid
3, construction well section span 34m (4693-4727m), discharge capacity 4.4-5.0m
3/ min, operation pressure 60-70MPa.
The acidizing treatment curve is referring to Fig. 3.After acid solution entered the stratum, fluctuating widely appearred in the little but pressure of starting stage displacement variation, shows that the acid solution steering-effecting is obvious; Construction later stage acid solution effectively has been communicated with reservoir centre joint hole, makes pressure occur declining to a great extent, and acidizing treatment technique is achieved success.
Claims (2)
1. be used for the acid that turns to of long well section, the transformation of high-temperature oil gas well acidizing, it is characterized in that: it is comprised of following component and content:
Diversion agent stearoyl amido ethyl decil lactone, 4.5～5.0 quality %;
Inhibiter, 1.0～2.0 quality %;
Fe stabilizer, 1.0～2.0 quality %;
Hydrochloric acid, 20 quality %;
All the other components are water;
Described inhibiter is any one or both the mixture among β-diethylin phenyl ketone, the β-rosin amine phenyl ketone; Described Fe stabilizer is saccharosonic acid or SODIUM ISOVITAMIN C.
2. the acid that turns to for long well section, the transformation of high-temperature oil gas well acidizing according to claim 1 is characterized in that: described the two mixture is comprised of the β of the β of 80～85 quality %-diethylin phenyl ketone and 15～20 quality %-rosin amine phenyl ketone.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103571453A (en) * | 2013-11-01 | 2014-02-12 | 中国石油集团川庆钻探工程有限公司 | Immovable pipe column weak acid acidizing fluid for water injection well and preparation method thereof |
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| CN102899014B (en) * | 2012-11-09 | 2014-12-10 | 西南石油大学 | Fiber steering acid |
| CN103897686B (en) * | 2012-12-28 | 2016-12-28 | 中国石油天然气股份有限公司 | A kind of acidifying visco-elastic surfactant acid acid fluid system and preparation method thereof |
| CN104212428B (en) * | 2014-08-14 | 2017-06-20 | 中国石油天然气集团公司 | It is a kind of to be adapted to high temperature acidified Mannich base corrosion inhibiter preparation method and applications |
| CN108384528B (en) * | 2018-03-12 | 2020-07-10 | 中国石油天然气股份有限公司 | Diverting agent for diverting and acidifying water injection well and preparation method thereof |
| CN109486476B (en) * | 2018-11-14 | 2020-01-10 | 四川大学 | Viscoelastic surfactant for high-temperature self-diverting acid, preparation method and application |
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| CN102020983A (en) * | 2009-09-12 | 2011-04-20 | 中国石油化工股份有限公司 | Viscosity-variable diverting acid for improving stratigraphic acidified section |
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| CN101824312B (en) * | 2010-05-07 | 2011-03-16 | 西南石油大学 | Sulfur solvent for cleaning sulphur deposition in wellhole |
| CN101875841B (en) * | 2010-07-06 | 2011-06-29 | 西南石油大学 | Resistance reducing acid used for transformation of ultra-deep well |
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| CN102020983A (en) * | 2009-09-12 | 2011-04-20 | 中国石油化工股份有限公司 | Viscosity-variable diverting acid for improving stratigraphic acidified section |
Non-Patent Citations (2)
| Title |
|---|
| 《甜菜碱类粘弹性表面活性剂自转向酸酸化技术研究》;曲冠政;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20111115;第14-15页 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103571453A (en) * | 2013-11-01 | 2014-02-12 | 中国石油集团川庆钻探工程有限公司 | Immovable pipe column weak acid acidizing fluid for water injection well and preparation method thereof |
| CN103571453B (en) * | 2013-11-01 | 2016-02-17 | 中国石油集团川庆钻探工程有限公司 | Faint sour acidizing fluid of water injection well fixed tubular column and preparation method thereof |
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