CN102899012A - Self-born acid and preparation method and application thereof - Google Patents
Self-born acid and preparation method and application thereof Download PDFInfo
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- CN102899012A CN102899012A CN2012104579739A CN201210457973A CN102899012A CN 102899012 A CN102899012 A CN 102899012A CN 2012104579739 A CN2012104579739 A CN 2012104579739A CN 201210457973 A CN201210457973 A CN 201210457973A CN 102899012 A CN102899012 A CN 102899012A
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- acid
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- spontaneous acid
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Abstract
The invention provides a self-born acid and a preparation method and application thereof. The self-born acid comprises paraformldehyde, ammonia chloride and water. The self-born acid is a potential acid which gradually generates a hydrochloric acid in a high-temperature carbonate rock storage layer. The self-born acid can effectively improve the deep penetrating power of acid liquor in the carbonate rock storage layer, so that the deep part of the storage layer can be reconstructed, and the oil output of an oil-gas field is improved.
Description
Technical field
The invention belongs to carbonate reservoir and transform field, particularly a kind of spontaneous acid, Preparation Method And The Use.
Background technology
In the exploitation of oil-gas field process, usually adopt acid-fracture technology to transform carbonate reservoir, thereby improve the oil-gas field oil offtake.Acid-fracture technology is specially: acid is injected in the crack that is produced by the viscous liquid spearhead, or acid itself is used to form the crack.When acid during along flow in fracture, can the kluftkarren wall, enlarge the hydrocarbon flow passage, improve the flow conductivity of reservoir.
In the acid fracturing treating processes, the groundwork medium is hydrochloric acid, after it enters the reservoir slit, with rock wall generation chemical reaction.For example: be calcite (CaCO for main component
3) and rhombspar (CaMg (CO)
3) carbonate reservoir, after injecting hydrochloric acid, the main chemical reactions of generation is:
CaCO
3+2HCl＝CaCl
2+CO
2t+H
2O
CaMg(CO
3)
2+4HCl＝MgCl
2+CaCl
2+2CO
2+2H
2O
Can be calculated 1m
3The hydrochloric acid solubilized 438kg calcium carbonate of volume 28% concentration generates 486kg calcium chloride, 79kg water and 193kg carbonic acid gas, and dissolved calcium carbonate, volume is equivalent to 0.162m
3, this shows, with 1m
3Reservoir behind 28% the hydrochloric acid reaction can increase 0.162m
3The space, thus the hydrocarbon flow passage increased.
Now in the technology, usually use gelled acid in the acidizing fracturing process, the gelled acid main component is hydrochloric acid, therefore, and when gelled acid Implantation Carbonate Reservoir is inner, itself and carbonate reaction speed, therefore, the speed that gelled acid is consumed, and then cause acid solution can't arrive the deep in crack, namely can't realize the purpose to the transformation of reservoir deep, thereby reduce oil offtake.
Summary of the invention
In view of the foregoing defects the prior art has, the invention provides a kind of spontaneous acid, but the Effective Raise acid solution to the deep penetration ability of carbonate reservoir, thereby can transform the reservoir deep, improved the oil-gas field oil offtake.
The present invention's the first purpose comprises Paraformaldehyde 96, ammonium chloride and water for a kind of spontaneous acid is provided.
Preferably, the quality proportioning of described Paraformaldehyde 96 and described ammonium chloride is 5: 11---7: 10.
Preferably, also comprise xanthan gum.
Preferably, the massfraction of described xanthan gum is 0.2%-0.5%.
Preferably, the massfraction of described xanthan gum is 0.4%.
Preferably, described Paraformaldehyde 96 comprises formaldehyde and/or glutaraldehyde.
The present invention's the second purpose may further comprise the steps for a kind of preparation method of spontaneous acid is provided:
Add water, Paraformaldehyde 96 and the ammonium chloride of dosing amount in the Agitation Tank, the mixed solution that obtains stirs and is described spontaneous acid.
Preferably, also comprise:
The xanthan gum that also adds the dosing amount in the described Agitation Tank.
The present invention's the 3rd purpose is for providing a kind of purposes of spontaneous acid, and described spontaneous acid is used for the acid solution of carbonate reservoir acid etching.
Preferably, described spontaneous acid etching carbonate reservoir specifically may further comprise the steps:
S2 is injected into carbonate reservoir inside with described spontaneous acid;
S2, under the high temperature action of carbonate reservoir inside, the Paraformaldehyde 96 in the described spontaneous acid and ammonium chloride reaction generate hydrochloric acid, and the hydrochloric acid of generation carries out acid etching to carbonate reservoir.
Beneficial effect of the present invention is as follows:
Spontaneous acid provided by the invention under high temperature carbonate rock reservoir conditions, produces the potential acid of hydrochloric acid for a kind of gradually.But the Effective Raise acid solution is to the deep penetration ability of carbonate reservoir, thereby can transform the reservoir deep, improved the oil-gas field oil offtake.
Description of drawings
Fig. 1 is the temperature of reaction of the sour rock of spontaneous acid for preparing of the present invention and the graph of relation between the acid etching acid strength;
The micro-structure diagram after the core acidifying is carried out in the spontaneous acid that Fig. 2 prepares for employing the present invention;
Fig. 3 is for adopting the micro-structure diagram after 20%HCl carries out the core acidifying.
Embodiment
Embodiment 1-6
Change component and the proportioning of dosing amount, carry out six groups of experiments, experimental technique is: the component of adding dosing amount in the Agitation Tank, the mixed solution that obtains stirs and obtains six kinds of spontaneous acid.The proportioning of each component is as shown in table 1 in 6 groups of experiments.
Table 1
Test example
This test example be used for to be investigated the relation of the acid etching acid solution Pressure, Concentration, Temperature of the spontaneous acid that the present invention prepares.
For the embodiment of the invention 1, change the temperature of reaction of the sour rock of spontaneous acid, after 2 hours, measure the acid etching acid strength of spontaneous acid, experimental result sees Table 2 and Fig. 1.
Table 2
Can find out from table 2 and Fig. 1, the spontaneous acid that the present invention prepares, along with the rising of temperature of reaction, the concentration of hydrochloric acid of its generation is higher.Spontaneous acid is being higher than under 120 ℃ the temperature, produces the concentration of HCl in 2 hours near 20%.
Other embodiments of the invention have been carried out identical experiment, and experimental result is similar.
Comparative example 1
The spontaneous acid for preparing take the embodiment of the invention 1 take commercially available conventional gelled acid as reference substance, is carried out respectively sour rock reaction as trial target, investigates its residual acid amount after the sour rock of the difference reaction times, and experimental result sees Table 3.
Table 3
As can be seen from the above table, conventional gelled acid acid rock reaction 15 minutes, the sour rock reaction times of the spontaneous acid that the present invention prepares can reach 1 hour 40 minutes.As seen, the sour rock reaction times of the spontaneous acid that the present invention prepares can Effective Raise acid corrosion action distance considerably beyond conventional gelled acid.Concrete reason is: the spontaneous acid that the present invention prepares under high temperature carbonate rock reservoir conditions, produces the potential acid of hydrochloric acid for a kind of gradually.Need certain temperature because spontaneous acid produces acid, and produce acid and progressively carry out, therefore can reduce sour rock speed of reaction, prolong acid solution operating distance, reduce simultaneously the corrosive nature to down-hole string.
Other embodiments of the invention have been carried out identical experiment, and experimental result is similar.
Comparative example 2
The spontaneous acid for preparing take the embodiment of the invention 1 take 20%HCl as reference substance, is carried out respectively the acid etching experiment as trial target, investigates the two acid etching effect.
Rock beam is taken from Sichuan Basin high temperature carbonate rock reservoir, 140 ℃-160 ℃ of formation temperature, about 6000 meters of well depths.Under 20MPa locking pressure, 120 ℃ the experiment condition in the rock beam respectively injection test product and reference substance, after 1 hour, measure rock beam loss quality; In addition, adopt the scanning electron microscope method to analyze microtexture before and after the core acidifying, experimental result sees Table 4 and Fig. 2, Fig. 3.
Table 4
Can find out that from table 4 and Fig. 2, Fig. 3 the spontaneous acid that the present invention prepares and reservoir carbonatite reactivity time are long, the acid etching effect is better than technical hydrochloric acid.
Other embodiments of the invention have been carried out identical experiment, and experimental result is similar.
Claims (10)
1. a spontaneous acid is characterized in that, comprises Paraformaldehyde 96, ammonium chloride and water.
2. spontaneous acid according to claim 1 is characterized in that, the quality proportioning of described Paraformaldehyde 96 and described ammonium chloride is 5: 11---7: 10.
3. spontaneous acid according to claim 1 is characterized in that, also comprises xanthan gum.
4. spontaneous acid according to claim 3 is characterized in that, the massfraction of described xanthan gum is 0.2%-0.5%.
5. spontaneous acid according to claim 4 is characterized in that, the massfraction of described xanthan gum is 0.4%.
6. each described spontaneous acid is characterized in that described Paraformaldehyde 96 comprises formaldehyde and/or glutaraldehyde according to claim 1-5.
7. the preparation method of each described spontaneous acid of a claim 1-6 is characterized in that, may further comprise the steps:
Add water, Paraformaldehyde 96 and the ammonium chloride of dosing amount in the Agitation Tank, the mixed solution that obtains stirs and is described spontaneous acid.
8. preparation method according to claim 7 is characterized in that, also comprises:
The xanthan gum that also adds the dosing amount in the described Agitation Tank.
9. the purposes of each described spontaneous acid of a claim 1-6 is characterized in that, described spontaneous acid is used for the acid solution of carbonate reservoir acid etching.
10. purposes according to claim 9 is characterized in that, described spontaneous acid etching carbonate reservoir specifically may further comprise the steps:
S2 is injected into carbonate reservoir inside with described spontaneous acid;
S2, under the high temperature action of carbonate reservoir inside, the Paraformaldehyde 96 in the described spontaneous acid and ammonium chloride reaction generate hydrochloric acid, and the hydrochloric acid of generation carries out acid etching to carbonate reservoir.
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| CN201210457973.9A CN102899012B (en) | 2012-11-14 | 2012-11-14 | Spontaneous acid, Preparation Method And The Use |
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|---|---|---|---|
| CN201210457973.9A CN102899012B (en) | 2012-11-14 | 2012-11-14 | Spontaneous acid, Preparation Method And The Use |
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| CN102899012B CN102899012B (en) | 2016-03-02 |
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104975840A (en) * | 2015-06-18 | 2015-10-14 | 中国石油化工股份有限公司 | Self-born acid composite acid fracturing process for high-temperature deep well carbonate rock reservoir |
| CN105400504A (en) * | 2014-08-13 | 2016-03-16 | 中国石油集团渤海钻探工程有限公司 | Reusable hydroxypropyl guar gum fracturing fluid |
| CN106833596A (en) * | 2016-12-21 | 2017-06-13 | 中国石油天然气股份有限公司 | It is a kind of can self-generating acid fracturing fluid and its preparation method and application |
| CN109880610A (en) * | 2019-04-10 | 2019-06-14 | 北京大德广源石油技术服务有限公司 | Oil gas field acidification, pressure break spontaneous acid and preparation method thereof |
| CN110643344A (en) * | 2018-06-26 | 2020-01-03 | 中国石油化工股份有限公司 | Double-retarding emulsifying self-generated acid and preparation method thereof |
| CN110804431A (en) * | 2019-11-12 | 2020-02-18 | 深圳市百勤石油技术有限公司 | Thickening autogenous acid generating system for oil-gas reservoir acid fracturing production increasing measures and preparation method |
| CN111171803A (en) * | 2020-01-17 | 2020-05-19 | 成都理工大学 | Cross-linking authigenic acid for reducing acid rock reaction rate |
| CN111849453A (en) * | 2019-04-30 | 2020-10-30 | 深圳市百勤石油技术有限公司 | Polychlorinated ketol self-acid generator and use method thereof |
| US10895140B2 (en) | 2017-04-07 | 2021-01-19 | Saudi Arabian Oil Company | Compositions and methods for controlled delivery of acid |
| CN112342010A (en) * | 2020-09-23 | 2021-02-09 | 南阳市华庆中能能源技术开发有限公司 | Polychlorinated ether alcohol self-acid generator and use method thereof |
| CN112852399A (en) * | 2021-01-27 | 2021-05-28 | 重庆科技学院 | Fluid for thickened oil deep self-heating huff and puff oil recovery and preparation and use method thereof |
| CN112940707A (en) * | 2020-12-30 | 2021-06-11 | 北京瓜尔润科技股份有限公司 | Stable reservoir stratum modification liquid and preparation and use methods thereof |
| CN113214818A (en) * | 2021-06-03 | 2021-08-06 | 西南石油大学 | Fracturing preposed self-acid-generating system and breaking reduction method thereof |
| CN113355080A (en) * | 2021-06-03 | 2021-09-07 | 西南石油大学 | Multifunctional foam fracturing fluid and preparation method thereof |
| CN113355081A (en) * | 2021-06-10 | 2021-09-07 | 北京世纪中星能源技术有限公司 | Deep penetration working solution for sandstone reservoir acid fracturing modification and application |
| US11156070B2 (en) | 2018-10-10 | 2021-10-26 | Saudi Arabian Oil Company | Methods for delivering in-situ generated acids for stimulation of downhole structures |
| US11505737B2 (en) | 2017-06-23 | 2022-11-22 | Saudi Arabian Oil Company | Compositions and methods for controlling strong acid systems |
| CN115561189A (en) * | 2022-10-20 | 2023-01-03 | 西南石油大学 | Method for testing reaction rate of authigenic acid rock |
| US11851613B2 (en) | 2020-08-06 | 2023-12-26 | Saudi Arabian Oil Company | Compositions and methods for controlled delivery of acid using sulfonate derivatives |
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| CN105400504A (en) * | 2014-08-13 | 2016-03-16 | 中国石油集团渤海钻探工程有限公司 | Reusable hydroxypropyl guar gum fracturing fluid |
| CN105400504B (en) * | 2014-08-13 | 2018-03-13 | 中国石油集团渤海钻探工程有限公司 | It is repeatable to utilize hydroxypropyl guar fracturing fluid |
| CN104975840B (en) * | 2015-06-18 | 2018-02-23 | 中国石油化工股份有限公司 | A kind of spontaneous compound acid fracturing method of acid for high temperature deep well carbonate reservoir |
| CN104975840A (en) * | 2015-06-18 | 2015-10-14 | 中国石油化工股份有限公司 | Self-born acid composite acid fracturing process for high-temperature deep well carbonate rock reservoir |
| CN106833596B (en) * | 2016-12-21 | 2020-12-01 | 中国石油天然气股份有限公司 | Fracturing fluid capable of generating acid by itself and preparation method and application thereof |
| CN106833596A (en) * | 2016-12-21 | 2017-06-13 | 中国石油天然气股份有限公司 | It is a kind of can self-generating acid fracturing fluid and its preparation method and application |
| US10895140B2 (en) | 2017-04-07 | 2021-01-19 | Saudi Arabian Oil Company | Compositions and methods for controlled delivery of acid |
| US11505737B2 (en) | 2017-06-23 | 2022-11-22 | Saudi Arabian Oil Company | Compositions and methods for controlling strong acid systems |
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| CN110643344B (en) * | 2018-06-26 | 2021-11-02 | 中国石油化工股份有限公司 | Double-retarding emulsifying self-generated acid and preparation method thereof |
| US11156070B2 (en) | 2018-10-10 | 2021-10-26 | Saudi Arabian Oil Company | Methods for delivering in-situ generated acids for stimulation of downhole structures |
| CN109880610A (en) * | 2019-04-10 | 2019-06-14 | 北京大德广源石油技术服务有限公司 | Oil gas field acidification, pressure break spontaneous acid and preparation method thereof |
| CN111849453A (en) * | 2019-04-30 | 2020-10-30 | 深圳市百勤石油技术有限公司 | Polychlorinated ketol self-acid generator and use method thereof |
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| CN111171803A (en) * | 2020-01-17 | 2020-05-19 | 成都理工大学 | Cross-linking authigenic acid for reducing acid rock reaction rate |
| US11851613B2 (en) | 2020-08-06 | 2023-12-26 | Saudi Arabian Oil Company | Compositions and methods for controlled delivery of acid using sulfonate derivatives |
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| CN112852399A (en) * | 2021-01-27 | 2021-05-28 | 重庆科技学院 | Fluid for thickened oil deep self-heating huff and puff oil recovery and preparation and use method thereof |
| CN113214818A (en) * | 2021-06-03 | 2021-08-06 | 西南石油大学 | Fracturing preposed self-acid-generating system and breaking reduction method thereof |
| CN113355080A (en) * | 2021-06-03 | 2021-09-07 | 西南石油大学 | Multifunctional foam fracturing fluid and preparation method thereof |
| CN113355081A (en) * | 2021-06-10 | 2021-09-07 | 北京世纪中星能源技术有限公司 | Deep penetration working solution for sandstone reservoir acid fracturing modification and application |
| CN113355081B (en) * | 2021-06-10 | 2022-06-14 | 北京世纪中星能源技术有限公司 | Deep penetration working solution for sandstone reservoir acid fracturing modification and application |
| CN115561189A (en) * | 2022-10-20 | 2023-01-03 | 西南石油大学 | Method for testing reaction rate of authigenic acid rock |
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