CN108570320A - A kind of complex acid mixed liquor and its application suitable for carbonate reservoir acidification - Google Patents
A kind of complex acid mixed liquor and its application suitable for carbonate reservoir acidification Download PDFInfo
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- CN108570320A CN108570320A CN201710149123.5A CN201710149123A CN108570320A CN 108570320 A CN108570320 A CN 108570320A CN 201710149123 A CN201710149123 A CN 201710149123A CN 108570320 A CN108570320 A CN 108570320A
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- acid
- mixed liquor
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- water
- carbonate reservoir
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- 239000002253 acid Substances 0.000 title claims abstract description 38
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 28
- 230000020477 pH reduction Effects 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 13
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004220 glutamic acid Substances 0.000 claims abstract description 9
- 235000013922 glutamic acid Nutrition 0.000 claims abstract description 9
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229960001484 edetic acid Drugs 0.000 claims abstract description 8
- 238000005086 pumping Methods 0.000 claims abstract description 3
- 239000011435 rock Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 abstract description 2
- 230000000536 complexating effect Effects 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 23
- 238000002360 preparation method Methods 0.000 description 9
- 239000003129 oil well Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000004579 marble Substances 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- UZVUJVFQFNHRSY-OUTKXMMCSA-J tetrasodium;(2s)-2-[bis(carboxylatomethyl)amino]pentanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC[C@@H](C([O-])=O)N(CC([O-])=O)CC([O-])=O UZVUJVFQFNHRSY-OUTKXMMCSA-J 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- -1 iron ion Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000009671 shengli Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/32—Anticorrosion additives
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mining & Mineral Resources (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Fluid Mechanics (AREA)
- Physics & Mathematics (AREA)
- Geochemistry & Mineralogy (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of complex acid mixed liquors suitable for carbonate reservoir acidification, are made of ethylenediamine tetra-acetic acid, glutamic acid diacetic acid and water, wherein ethylenediamine tetra-acetic acid accounts for 3%~5%, and glutamic acid diacetic acid accounts for 10%~50%, and water accounts for 45%~87%.The complex acid mixed liquor of the present invention, can be applied as the acidifying solution of carbonate reservoir：It, first will complexing acid solution mixed liquor and water by volume 1 when operation：Then it is pumped into acidification purpose of horizon, termination of pumping carried out removing tubing string operation after 1~3 hour by 1~3 ratio mixing, mixing using pump truck along oil pipe and casing annulus.The present invention has the following advantages：It is low to tube corrosion degree with higher solution ration,（3）Secondary precipitation will not be generated, slow ability is strong, can be not required to the residual acid of the row of returning directly into production flow line.
Description
Technical field
The present invention relates to a kind of complex acids suitable for granular carbonate rock or conventional carbonate reservoir acidification to mix
Liquid and its application belong to oil development technical field.
Background technology
Particulate carbonate rock is a kind of special Oil Reservoir Types, and the main component of such oil reservoir is CaCO3, and
It presents " graininess ", with the clastic reservoir rocks such as sandstone apparently similar, conventional carbonate reservoir is dense.To such
When oil reservoir is transformed, regular hydrochloric acid system reaction speed is fast, easily causes reservoir across collapsing, treatment radius also compares
Small, it is difficult that residual acid returns drain subsequent processing.Therefore, it is necessary to research and develop the acidification reaction system for being suitble to such reservoir, to improve processing
Radius, while protecting reservoir.
Invention content
For the above-mentioned prior art, the present invention provides a kind of complex acid mixing suitable for carbonate reservoir acidification
Liquid, and its as the application in carbonate reservoir acidifying solution.
The present invention is achieved by the following technical solutions：
A kind of complex acid mixed liquor suitable for carbonate reservoir acidification, by ethylenediamine tetra-acetic acid, (EDTA, molecular formula are
C10H16N2O8), glutamic acid diacetic acid (GLDA, molecular formula C9H13NO8) and water composition, wherein by weight percentage, second two
Amine tetraacethyl accounts for 3%~5%, and glutamic acid diacetic acid accounts for 10%~50%, and water accounts for 45%~87%.Preferably, ethylenediamine tetrem
Acid accounts for 5%, and glutamic acid diacetic acid accounts for 40%, and water accounts for 55%.
The complex acid mixed liquor suitable for carbonate reservoir acidification, when preparation, by ethylenediamine tetra-acetic acid, glutamic acid
Oxalic acid and water mixing mixing to get.
The complex acid mixed liquor suitable for carbonate reservoir acidification can be used as carbonate rock (granular carbonate
Rock or conventional carbonate rock) acidifying solution of reservoir applied, and when concrete application, application method is：When operation, first by network
Close acid solution mixed liquor and water (salinity of water is required in 1000mg/L or less) by volume 1：1~3 ratio mixing, mixing,
Then, it is pumped into acidification purpose of horizon along oil pipe and casing annulus using pump truck, is pumped into volume and is counted according to 2~3m for the treatment of radius
It calculates and determines, termination of pumping carried out removing tubing string operation after 1~3 hour.
The complex acid mixed liquor for being suitable for carbonate reservoir acidification of the present invention, has the following advantages：
(1) there is higher solution ration, it is suitable with 10%~12% Hydrochloric Acid Etching ability.
(2) low to tube corrosion degree, N80 standard steel discs are carried out according to Q/SH 0352-2010 sinopecs company standards
Related experiment is reduced to 10.7552g in 30 days to steel disc quality by 10.8125g, and extent of corrosion is below 0.53%.
(3) secondary precipitation will not be generated, it is low to reservoir damage degree：Conventional acid fluid system dissolve a large amount of high-valency metals from
After son, with the raising (when being increased to 3~4) of pH, generation secondary precipitation can be precipitated in the high volence metal ions such as iron ion, to stifled
Fill in Reservoir Seepage channel；And the complex acid of the present invention can form complex compound with high volence metal ions such as iron ions, prevent its analysis
Go out, it is low to reservoir damage degree.
(4) slow ability is strong, and hydrogen ion depletion rate is 1/5th of hydrochloric acid system.
(5) pH value is high after being acidified, and is 6~7, can be not required to the residual acid of the row of returning directly into production flow line.
Specific implementation mode
With reference to embodiment, the present invention is further illustrated.
Involved instrument, reagent, material etc., are existing in the prior art unless otherwise noted in following embodiments
Conventional instrument, reagent, material etc., can be obtained by regular commercial sources.Involved experimental method in following embodiments, inspection
Survey method etc. is unless otherwise noted existing routine experiment method in the prior art, detection method etc..
Embodiment 1 prepares the complex acid mixed liquor for being suitable for carbonate reservoir acidification
Component composition and ratio relationship is：5g EDTA, 40gGLDA, 55g water.
Preparation method is：Under room temperature, GLDA is added to the water, is stirring evenly and then adding into EDTA, mixing to get.
After testing, the performance parameter of the complex acid mixed liquor of above-mentioned preparation is as follows：
Related experiment is carried out to N80 standard steel discs according to Q/SH 0352-2010 sinopecs company standards, 30 days to steel disc
Quality is reduced to 10.7552g by 10.8125g, and extent of corrosion is below 0.53%.
Weigh marble No. 1 sample 10g and No. 2 sample 10g, under room temperature, be separately added into 200ml complexing acid systems and
10% hydrochloric acid systems of 200ml；When the complete bubble-free of sample generates, No. 1 sample takes 3.1 hours, and it is small that No. 2 samples take 0.6
When, and marble surplus is weighed, No. 1 sample 6.3g, No. 2 sample 6.11g.The result shows that：Complex acid and 10% hydrochloric acid system
It is respectively 37% and 38.9% to marble corrosion rate, substantially quite.In the case of suitable corrosion rate, complex acid, which takes, is
5 times of 10% hydrochloric acid system, i.e. reaction speed are 1/5th of 10% hydrochloric acid system.
Embodiment 2 prepares the complex acid mixed liquor for being suitable for carbonate reservoir acidification
Component composition and ratio relationship is：5g EDTA, 50gGLDA, 45g water.
Preparation method is：Under room temperature, GLDA is added to the water, is stirring evenly and then adding into EDTA, mixing to get.
After testing, the performance parameter of the complex acid mixed liquor of above-mentioned preparation is as follows：
At normal temperatures, system is suitable with 12% Hydrochloric Acid Etching rate to the corrosion rate of particulate carbonate rock, and reaction speed is
/ 5th of common hydrochloric acid system.
Embodiment 3 prepares the complex acid mixed liquor for being suitable for carbonate reservoir acidification
Component composition and ratio relationship is：3g EDTA, 10gGLDA, 87g water.
The preparation method is the same as that of Example 1.
Embodiment 4 prepares the complex acid mixed liquor for being suitable for carbonate reservoir acidification
Component composition and ratio relationship is：3g EDTA, 30gGLDA, 67g water.
The preparation method is the same as that of Example 1.
Embodiment 5 prepares the complex acid mixed liquor for being suitable for carbonate reservoir acidification
Component composition and ratio relationship is：4g EDTA, 46gGLDA, 50g water.
The preparation method is the same as that of Example 1.
The oil fields application example Shengli Oil Field A1
The oil fields A1, oil reservoir gas permeability 10 × 10-3μm2, porosity Φ=13%, it is low to belong to low hole reservoir thickness h=6m
Permeability is hidden, 70 DEG C, original formation pressure 21.5MPa of reservoir temperature, which is particulate carbonate rock, in order to improve oil
Well production implements it acidification measure.
Implementation is as follows：
Certain A oil well is selected, according to reservoir condition, decides through discussion and implements treatment radius r=3m, be pumped into acid solution volume=Π r2
H=3.1415 × 3 Φ2× 13% × 6=22.05m3, 22m is pressed at scene3Acid solution is prepared, then according to complex acid mixed liquor and water=
1:3 ratio mixing, needs that acid solution mixed liquor (preparation of embodiment 1) 5.5m is complexed3。
By complex acid mixed liquor 5.5m316.5m is added3In water, scene is pumped into purpose of horizon with pump truck after mixing, stops
Pump reaction 3 hours.Need not the residual acid of the row of returning, tripping in flow string production.
Meanwhile certain B oil well is selected, using 10% HCl treatment, processing mode and 10% hydrochloric acid dosage are same as above.
As a result：After the method processing of the present invention, oil well is averaged day liquid 15m3, day oil 10m3, do not go out " sand ".And it uses
The oil well of hydrochloric acid system processing, oil well are averaged day liquid 10m3, day oil 6.5m3, go out " sand ", need well-flushing.As it can be seen that utilizing the present invention
Method processing after significant effect.
Although above-mentioned be described the specific implementation mode of the present invention in conjunction with the embodiments, not the present invention is protected
The limitation of range, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art
The various modifications or changes that can be made need not be made the creative labor still within protection scope of the present invention.
Claims (4)
1. a kind of complex acid mixed liquor suitable for carbonate reservoir acidification, it is characterised in that：By ethylenediamine tetra-acetic acid, paddy ammonia
Sour oxalic acid and water composition, wherein by weight percentage, ethylenediamine tetra-acetic acid accounts for 3%~5%, and glutamic acid diacetic acid accounts for 10%~
50%, water accounts for 45%~87%.
2. the complex acid mixed liquor according to claim 1 suitable for carbonate reservoir acidification, it is characterised in that：By second
Ethylenediamine tetraacetic acid (EDTA), glutamic acid diacetic acid and water composition, wherein ethylenediamine tetra-acetic acid accounts for 5%, and glutamic acid diacetic acid accounts for 40%, and water accounts for
55%。
3. the complex acid mixed liquor as claimed in claim 1 or 2 suitable for carbonate reservoir acidification is stored up as carbonate rock
Application in the acidifying solution of layer.
4. application according to claim 3, it is characterised in that：When concrete application, application method is：Acid solution will be complexed first
Mixed liquor and water by volume 1：Then it is pumped by 1~3 ratio mixing, mixing using pump truck along oil pipe and casing annulus
It is acidified purpose of horizon, volume is pumped into and determination is calculated according to 2~3m for the treatment of radius, termination of pumping carried out removing tubing string work after 1~3 hour
Industry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710149123.5A CN108570320A (en) | 2017-03-13 | 2017-03-13 | A kind of complex acid mixed liquor and its application suitable for carbonate reservoir acidification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710149123.5A CN108570320A (en) | 2017-03-13 | 2017-03-13 | A kind of complex acid mixed liquor and its application suitable for carbonate reservoir acidification |
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| Publication Number | Publication Date |
|---|---|
| CN108570320A true CN108570320A (en) | 2018-09-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710149123.5A Pending CN108570320A (en) | 2017-03-13 | 2017-03-13 | A kind of complex acid mixed liquor and its application suitable for carbonate reservoir acidification |
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| CN (1) | CN108570320A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109541119A (en) * | 2018-10-29 | 2019-03-29 | 中国海洋石油集团有限公司 | The quantitative evaluation method of secondary precipitation rejection ability in a kind of sandstone acidizing |
| CN111004617A (en) * | 2019-12-17 | 2020-04-14 | 中国地质大学（武汉） | Environment-friendly acidizing working fluid suitable for low permeability carbonate rock reservoir and preparation method |
| CN111250535A (en) * | 2020-02-18 | 2020-06-09 | 四川省蜀通岩土工程公司 | Heavy metal composite contaminated site soil remediation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103261362A (en) * | 2010-12-17 | 2013-08-21 | 阿克佐诺贝尔化学国际公司 | Treatment of illitic formations using a chelating agent |
| CN103261363A (en) * | 2010-12-17 | 2013-08-21 | 阿克佐诺贝尔化学国际公司 | Fluid suitable for treatment of carbonate formations containing a chelating agent |
| CN104350123A (en) * | 2012-06-18 | 2015-02-11 | 阿克佐诺贝尔化学国际公司 | Process to produce oil or gas from a subterranean formation using a chelating agent |
-
2017
- 2017-03-13 CN CN201710149123.5A patent/CN108570320A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103261362A (en) * | 2010-12-17 | 2013-08-21 | 阿克佐诺贝尔化学国际公司 | Treatment of illitic formations using a chelating agent |
| CN103261363A (en) * | 2010-12-17 | 2013-08-21 | 阿克佐诺贝尔化学国际公司 | Fluid suitable for treatment of carbonate formations containing a chelating agent |
| CN104350123A (en) * | 2012-06-18 | 2015-02-11 | 阿克佐诺贝尔化学国际公司 | Process to produce oil or gas from a subterranean formation using a chelating agent |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109541119A (en) * | 2018-10-29 | 2019-03-29 | 中国海洋石油集团有限公司 | The quantitative evaluation method of secondary precipitation rejection ability in a kind of sandstone acidizing |
| CN111004617A (en) * | 2019-12-17 | 2020-04-14 | 中国地质大学（武汉） | Environment-friendly acidizing working fluid suitable for low permeability carbonate rock reservoir and preparation method |
| CN111250535A (en) * | 2020-02-18 | 2020-06-09 | 四川省蜀通岩土工程公司 | Heavy metal composite contaminated site soil remediation method |
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Application publication date: 20180925 |