CN1014253B - Method for improving permeability of oil-well strata and its solvent - Google Patents
Method for improving permeability of oil-well strata and its solventInfo
- Publication number
- CN1014253B CN1014253B CN 88103530 CN88103530A CN1014253B CN 1014253 B CN1014253 B CN 1014253B CN 88103530 CN88103530 CN 88103530 CN 88103530 A CN88103530 A CN 88103530A CN 1014253 B CN1014253 B CN 1014253B
- Authority
- CN
- China
- Prior art keywords
- solvent
- acid
- oil
- boric acid
- hydrochloric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
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- Lubricants (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a method and a solvent for increasing the penetrability of oil well strata. Solvents in the prior art are prepared from boric acid dissolved by methanol and hydrochloric acid, and the boric acid has the disadvantages of low solubility and poor low-temperature performance and is not suitable for oilfield on-site construction where air temperature is low. The solvent is prepared from boric acid dissolved by fluoboric acid and hydrochloric acid, and the boric acid has the advantages of high solubility and stability at low temperature and has the functions of acidifying and precipitating the oil well strata for the second time. By using the solvent and the treatment method to treat oil wells, the penetrability of the oil well strata is improved, and the production increasing effect of crude oil is obvious. The solvent can also be used for removing insoluble fluoride deposits on the surfaces of industrial containers and pipelines.
Description
What the present invention relates to is method and the solvent thereof that improves penetration with the chemical Treatment oil-well strata.
In oil extraction, along with the passing of the time of oil recovery, down-hole pressure, penetration reduces gradually, and crude output also reduces gradually.In order to improve crude output, various physics and chemical treatment method have been used.In order to improve penetration, traditional method is to inject the down-hole with mud acid (hydrochloric acid and hydrofluoric acid) or fluoboric acid etc., carry out acidification, the silica that oil circuit influences the crude oil infiltration is stopped up in dissolving rapidly, sand, clay, squame and other foreign material that the sulfate of indissoluble and the carbonate of alkaline-earth metal are formed.But the reaction enclosure of this acidification can generate the fluoride of indissoluble, for example C
aF
2, N
A2SiF
6Deng ...The fluoride of these secondary precipitations also stops up oil circuit, influences the penetration of oil-well strata.Adopt chemical method to remove fluoride, in the technology of squame, representative technology is United States Patent (USP) 2961355(1960).This technology is to utilize boric acid (borax) and hydrochloric acid to make solvent to remove fluoride and squame (promptly carrying out after-treatment).But the solubility of boric acid in hydrochloric acid is very low, for example in the time of 26 ℃, only dissolves 2% boric acid in 15% hydrochloric acid, and this can influence result of use greatly.United States Patent (USP) 4330419(1982) a kind of low new method of boric acid solubility that solves has been proposed.This method is boric acid to be dissolved in making component in the methyl alcohol earlier, makes solvent with mixed in hydrochloric acid again, with it oil well is carried out after-treatment, and the effect of dissolving fluoride, squame is fine.But this method also has shortcoming.When first temperature is low (as being lower than 22 ℃).Boric acid solubility in methyl alcohol reduces and the generation precipitation.Therefore this method is not easy working at the lower scene, oil field of temperature.It two is that methyl alcohol in this solvent only plays dissolving boric acid, does not play other effects in the down-hole.
The purpose of this invention is to provide a kind of processing method and solvent thereof that can suppress dissolving fluoride and squame.It can greatly increase the solubility of boric acid, can be lower than under-30 ℃ the situation and using, can play the deep acidizing effect to limestone, sandstone again, making the acidification of oil well and secondary precipitation handle to merge and once finish, can improve the penetrating power of oil well effectively, improve crude output.
The present invention finishes like this.Earlier boric acid is dissolved in fluoboric acid and makes component, make solvent with mixed in hydrochloric acid again.The component of this solvent comprises:
(a) with 5～32% hydrochloric acid (weight percent concentration);
(b) with 20～50% fluoboric acid (weight percent concentration);
(c) before above-mentioned hydrochloric acid adds, boric acid (or borax of a great deal of) is dissolved in the above-mentioned fluoboric acid, its concentration is 1～17%(weight percent concentration).All the other are water.
The more obvious component of effect of the present invention is: hydrochloric acid 12～25%(weight percent concentration); Fluoboric acid 10～22%(weight percent concentration); Boric acid 1～12%(weight percent concentration).Before above-mentioned hydrochloric acid adds, boric acid (or borax of a great deal of) is dissolved in the above-mentioned fluoboric acid, all the other are water.
Below the invention will be further described.
When containing boric acid and hydrochloric acid in the solvent, can dissolve the indissoluble fluoride (with C
aF
2Be example), its chemical reaction is undertaken by following formula, generates water-soluble products.
Here the n value from 1 to 4.When n=4,
In other words, in order to generate water-soluble products, 4mol HCl and 1mol H
3BO
3Need and 2mol C
aF
2Reaction.Therefore needing product is water-soluble products, and the boric acid of q.s must be arranged in solvent, is to improve the key of treatment effect so improve the solubility of boric acid.
We find that boric acid has fabulous solubility in fluoboric acid.For example, at room temperature maxima solubility can to reach 15%(fluoboric acid concentration be 50%).In the time of 2 ℃, be that solubility is 9.3% in 50% the fluoboric acid in concentration.Therefore use hydrochloric acid, boric acid, fluoboric acid are that fluoride that the solvent of component is handled oil-well strata deposits and squame is extremely effective.
Inject the fluoboric acid in the solvent of oil well in addition and handle fluoboric acid that secondary precipitation generates by the following formula hydrolysis:
Degree of hydrolysis depends on the concentration of fluoboric acid, but also is subjected to Temperature Influence.The HF that hydrolysis obtains falls clay and a part of quartz particle with regard to corrosion, and reaction is undertaken by following formula:
In any reaction time, only there is the HF of the fluoboric acid hydrolysis of limited quantity to exist.Therefore reaction delays, and has correspondingly increased the penetration range in the stratum.While can make and be touched because of fluoboric acid but undissolved small bits of clay obviously merges the formation fused layer, has controlled the animal migration of particulate, plays and stablizes the effect that clay no longer expands it.
Inject another part hydrochloric acid and traditional the same corrosion limestone that plays of technology, the effect of sandstone and other foreign material of oil well.
From finding out that fluoboric acid and part hydrochloric acid also play the deep acidizing effect to the micrograined texture of oil-well strata.Therefore use method of the present invention and solvent, can remove traditional acidification process from, deep acidizing and secondary precipitation processing once can be finished according to strata condition.
Solvent preparation technology of the present invention is described below.Is that zero degree is to room temperature by above-mentioned prescription in temperature, boric acid is added in the fluoboric acid, fully stir boric acid dissolving, thin up, add hydrochloric acid again, at this moment be rendered as light yellow transparency liquid immediately, stirred continuously one hour, make solvent of the present invention, its integrated concentration is 35.4～37.00%, and proportion is 1.22～1.30/25 ℃.After the solvent of above-mentioned technology preparation can mix with various additives (ferrous stability, corrosion inhibiter, surfactant), in 70 ℃ of water-baths, left standstill 4 hours, not emulsification of solution, not stratified, do not produce precipitation, compatibility is good between the solvent each component of the present invention.
Solvent cryogenic property of the present invention is stable, for example gets the 50ml solvent and places the 100ml beaker, is placed in-35 ℃ the salt solution to cool off, and slowly heats up then, and temperature is designated as-31.5, and-30 ,-27 ,-23 ,-18, in the time of-15 ,-13 ℃, all there is not precipitation to generate,
Certainly along with the reduction of temperature, the each component of proportioning should float to lower limit.
Be described below with the method for solvent of the present invention well treatment:
Pei Zhi solvent with 0～3 times of its dilution, injects oil-well strata according to earth formation as stated above, stops 1～100 hour on the stratum, and perhaps up to fluoride, squame secondary precipitation or limestone, sandstone have tangible dissolving.After processing finishes, extract residual solvent in the stratum out ground.
Though there is not the sour corrosion inhibitor, solvent of the present invention still can use, and metal pipe material under the oil well and equipment are had certain corrosiveness.Therefore, should add the sour corrosion inhibitor and be used, to prolong the life cycle of metal pipe material or equipment.Sour corrosion inhibitor commonly used generally contains: alkynol class, quaternary ammonium compound, alkane compound, the compound of antimony or the compound of arsenic, surfactant or the like.
Solvent of the present invention has greatly improved the solubility of boric acid, has increased the corrosion to fluoride and squame greatly, and the serviceability temperature wide ranges, and good manufacturability can be at the oilfield construction that extremely hangs down (30 ℃) under the temperature.Handle the penetration that oil-well strata can greatly improve oil well with solvent of the present invention, improve crude output.
For example handle certain oil well, the well section is 3080～3085 meters, 5.6 meters of core intersections.Rock formation analysis: coarse silt-impalpable powder sandstone is main, secondly for containing the superfine meal sandstone of white clouds matter.Cement mostly is calcite, and micrite white clouds matter is main, is the dolomite gluing secondly.
This well crude oil daily output before handling: 11.4 tons, moisture 0.5%.Undertaken by the acidizing treatment step that the oil field is traditional, wherein inject 3 cubic meters of solvent of the present invention (integrated concentration is 12%), contain the 2%HAC+2%HCHO+0.5%IS-129(corrosion inhibiter)+the 0.5%AE-1910(surfactant).2～3 days after treatment later crude oil daily outputs of oil well increase to more than 30 ton.
The solvent of this invention also can be used for removing pipeline, the indissoluble fluoride deposition on the surface of industrial container.Its method be solvent action with the preparation of above-mentioned technology in surface with indissoluble fluoride deposition, keep certain hour after, rinse well with clear water.
The invention will be further described with embodiment below.
Example 1, solvent of the present invention is to C
aF
2(98.42%) dissolved corrosion test the results are shown in Table 1
Table 1
Inferior CaF
2Weight corrosion amount corrosion corrosion agent corrosion agent corrosion
Number (g) is temperature (℃) volume (ml) temperature (%) time (hour) (%)
1????1＃3.9388????27.61????29????40????19.54????23
2＃4.3284????25.59????40
2????1＃4.3748????25.54????27????40????19.54????23
2＃
3????1＃3.8988????32.86????27????40????19.54????24
2＃4.3627????26.83
4????1＃4.4690????24.93????28????40????19.54????23
2＃4.0191????22.99????40
1＃3.3935????36.55????28????40????19.54????27
2＃4.4554????23.88????40
Example 2, solvent of the present invention is to N
A2SiF
6(99%) dissolved corrosion test the results are shown in Table 2
Table 2
Inferior Na
2SiF
6Corrosion amount corrosion corrosion agent corrosion agent corrosion
Number weight (g) are temperature (℃) volume (ml) concentration (%) time (hour) (%)
1 1＃4.7804 22.10 32.5 40 19.45 24 1/3
2＃3.6883????28.86????40
2 1＃4.4215 24.84 30 40 19.45 24 1/12
2＃4.2691????22.29????40
3 1＃4.2260 29.79 31.5 40 19.45 23 3/4
2＃4.1843????30.03????40
4 1＃4.3614 28.78 31 40 19.45 23 5/6
2＃3.9993????29.81????40
5 1＃4.0768 32.99 30 40 19.45 23 11/12
2＃4.3263????31.56????40
Example 3 solvents of the present invention and other solvents under the concentration same case to N
A2SiF
6, C
aF
2, k
2SiF
6Corrosion rate comparing result see Table 3
Table 3
NO sediment solvent reaction thermotonus time corrosion rate
(℃) (hour) (%)
1 CaF
2Solvent 71 1 9.8 of the present invention
2 CaF
2Hydrochloric acid 70 1 3.6
3 CaF
2Mud acid 70 1 2.5
4 k
2SiF
6Solvent 70 1 30.6 of the present invention
5 k
2SiF
6Hydrochloric acid 70 1 6.8
6 k
2SiF
6Mud acid 70 1 8.0
7 Na
2SiF
6Solvent 70 1 68.6 of the present invention
8 Na
2SiF
6Hydrochloric acid 70 1 52.7
9 Na
2SiF
6Mud acid 70 1 63.4
The corrosion rate of finding out solvent of the present invention from last table is the highest
Example 4 solvent mesoboric acid concentration differences of the present invention are to C
aF
2(98%) solvent test the results are shown in Table 4
Table 4
Inferior CaF
2The heavy boric acid concentration corrosion amount corrosion agent dense corrosion agent body corrosion temperature corrosion time
Quantity (g) (%) (%) degree (%) long-pending (ml) degree (%) (hour)
1 2.1840 1.51 14.63 36.20 20 0 50 1/4
2 3.1136 1.0 9.98 36.20 20 0 50 1/4
3????2.7944????2.77????16.70????34.57????20????0????24
4????3.1196????2.77????15.50????34.57????20????0????24
5????3.8988????4.10????32.86????35.40????20????27????24
Find out that from last table boric acid 1% begins all to work, it is preferable to surpass 4% effect.
Hydrochloric acid and fluoboric acid all are strong acid, and their existence all can be worked, and this point is self-evident.
Claims (4)
1, a kind of solvent that improves the oil-well strata penetration wherein contains hydrochloric acid and fluoboric acid, it is characterized in that component comprises:
(a) hydrochloric acid is 5～32% (weight percent concentration)
(b) fluoboric acid is 20～50% (weight percent concentration)
(c) boric acid is 1～17% (weight percent concentration)
All the other are water.
2, solvent according to claim 1 is characterized in that hydrochloric acid 12～25%, fluoboric acid 10～22%, and boric acid 1～12% more than is weight percent concentration, and all the other are water.
3, solvent according to claim 1 and 2 is characterized in that also containing a kind of or several sour corrosion inhibitor.
4, a kind of method of removing the fluoride of indissoluble from oil-well strata is characterized in that:
(a) will contain 5～32% hydrochloric acid, 20～50% fluoboric acid, all the other are the solvent of water for 1～12 boric acid, after diluting 0～3 times, inject oil-well strata;
(b) above-mentioned solvent is retained in the oil-well strata 1～100 hour;
(c) from the oil-well strata structure, extract residual solvent out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88103530 CN1014253B (en) | 1988-06-08 | 1988-06-08 | Method for improving permeability of oil-well strata and its solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88103530 CN1014253B (en) | 1988-06-08 | 1988-06-08 | Method for improving permeability of oil-well strata and its solvent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1030809A CN1030809A (en) | 1989-02-01 |
| CN1014253B true CN1014253B (en) | 1991-10-09 |
Family
ID=4832645
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88103530 Expired CN1014253B (en) | 1988-06-08 | 1988-06-08 | Method for improving permeability of oil-well strata and its solvent |
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| Country | Link |
|---|---|
| CN (1) | CN1014253B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100335746C (en) * | 2001-12-21 | 2007-09-05 | 索菲泰克公司 | A novel fluid system having controllable reversible viscosity |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1116497C (en) * | 1999-02-10 | 2003-07-30 | 王素君 | Sandstone acid |
| CN1329476C (en) * | 2004-09-24 | 2007-08-01 | 中国石油化工股份有限公司 | Acidification composition for oil well |
| CN100352884C (en) * | 2004-09-24 | 2007-12-05 | 中国石油化工股份有限公司 | Oil well acidification composition |
| RU2009138310A (en) * | 2007-03-23 | 2011-04-27 | Борд Оф Риджентс, Зе Юниверсити Оф Техас Систем (Us) | METHOD FOR PROCESSING SOLVENT FORMATION |
| CN101407716B (en) * | 2008-10-31 | 2010-12-08 | 湖北中科博策新材料研究院 | Complex formulation material for improving oil well secondary and third stoping oil productivity |
| CN105275438B (en) * | 2014-12-28 | 2017-12-19 | 新疆科力新技术发展股份有限公司 | The anti-technology that disappears of sensitive reservoir expansion |
| CN114591721A (en) * | 2022-03-08 | 2022-06-07 | 中海油能源发展股份有限公司 | Infiltration-increasing and sand-stabilizing acidizing composite working fluid for unconsolidated sandstone reservoir and preparation method and application thereof |
-
1988
- 1988-06-08 CN CN 88103530 patent/CN1014253B/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100335746C (en) * | 2001-12-21 | 2007-09-05 | 索菲泰克公司 | A novel fluid system having controllable reversible viscosity |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1030809A (en) | 1989-02-01 |
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