CN1317481C - Use of modified flyash as profile control agent - Google Patents
Use of modified flyash as profile control agent Download PDFInfo
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- CN1317481C CN1317481C CNB2004100622716A CN200410062271A CN1317481C CN 1317481 C CN1317481 C CN 1317481C CN B2004100622716 A CNB2004100622716 A CN B2004100622716A CN 200410062271 A CN200410062271 A CN 200410062271A CN 1317481 C CN1317481 C CN 1317481C
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- coal ash
- modified coal
- control agent
- profile control
- plugging
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Abstract
The present invention relates to the use of modified fly ash as profile control agent, which solves the problems of bad plugging effect, high cost and short effective period of the existing polymer profile control agent. The modified fly ash can be used for plugging a water absorbing profile in the development of a high moisture oil layer of an oil field with water injection, plugging a water absorbing profile in the development of a particularly high moisture oil layer of the oil field with the water injection, plugging a high permeability layer in the development of the oil field with the water injection and adjusting and plugging a liquid absorbing profile in the development of the oil field with the water injection. The granular modified fly ash as the profile control agent has the characteristics of good plugging effect, low cost, strong adaptability, high plugging intensity and long effective period.
Description
Technical field:
The present invention relates to the new purposes of modified coal ash, relate in particular to the new purposes in fluid entry profile adjustment in waterflooding oil field, high permeability zone shutoff or the macropore shutoff field.
Background technology:
Along with the continuous rising of domestic waterflooding reservoir comprehensive water cut, inject water poor efficiency or invalid circulation in high permeability zone or macropore in order to reduce, profile control agent commonly used mainly is Al on the mining site at present
3+, Cr
3+, compound ion is as polymer gel class and solid particle class such as clay, oil field produced mud and the flyash etc. of crosslinking agent.The performance of polymer gel class profile control agent is to becoming the glue environment very responsive, and chemical agent cost height, period of validity weak point make its use scale and scope be subjected to very big restriction in addition.
Flyash is the excreta of coal-burning power plant, and its main chemical is an aluminosilicate: quartzy 92%, mullite 8%, outward appearance mostly is loosely organized, noncrystalline matter glassy phase spheroid.
Summary of the invention:
The problem that existing profile control agent plugging effect is poor in order to solve, cost height and period of validity are short, the invention provides a kind of new purposes of modified coal ash, i.e. new application in waterflooding oil field high moisture and the shutoff of ultra-high water cut stage oil reservoir intake profile, high permeability zone shutoff or macropore shutoff.This graininess modified coal ash has the advantages that as the application of profile control agent plugging effect is good, cost is low, compliance is strong, plugging strength is high and period of validity is long.
The technical solution used in the present invention is: flyash modified processing method is: the NaOH aqueous solution of 2.0mol/L is mixed by liquid-solid ratio 3.0 (ml/g) with flyash, stir 60min 70 ℃ of conditions, left standstill 12 hours, then solid and fluid separation applications are promptly got modified coal ash, the chemical compound of modified coal ash is: quartz 74%, mullite 7%, zeolite 19%.
In fact, the present invention relates to the application of modified coal ash in waterflooding oil field high water-cut stage well intake profile is adjusted.
Relate to the application of modified coal ash in waterflooding oil field high water-cut stage oil well liquid-producing section is adjusted.
Relate to the application of modified coal ash in the shutoff of waterflooding oil field well high permeability zone.
Relate to the application of modified coal ash in the shutoff of waterflooding oil field oil well high permeability zone.
The invention has the beneficial effects as follows: the modified coal ash particle has irregular contour structures, when the modified coal ash particle is migrated in blowhole, its cellular and ribbon profile is very easily captured by pore constriction, cause the hole flow section to reduce, increase follow-up particle flow resistance, and cause new capture effect to take place, final form " bridge blinding ", plugging effect is good, and machine plugging simultaneously has the advantages that cost is low, compliance is strong, plugging strength is high and period of validity is long.
The size distribution of modified coal ash and fly ash grain: sieve formula is adopted in flyash and modified coal ash particle size analysis, and its particle diameter scope and mass percent thereof see Table 1 and table 2.
Table 1 fly ash grain size distribution and mass percent
| Order is counted scope | Particle diameter D scope (μ m) | Mass percent (%) |
| ＜40 orders | D＞450 | 2.44 |
| 40～160 orders | 450＞D＞90 | 15.97 |
| 160～240 orders | 90＞D＞63 | 4.47 |
| 240～300 orders | 63＞D＞50 | 5.75 |
| 300～360 orders | 50＞D＞40 | 7.71 |
| ＞360 orders | D＜40 | 63.66 |
Table 2 modified coal ash particle size distribution and mass percent
| Order is counted scope | Particle diameter D scope (μ m) | Mass percent (%) |
| ＜160 orders | D＞90 | 1.50 |
| 160～240 orders | 90＞D＞63 | 19.80 |
| 240～300 orders | 63＞D＞50 | 11.80 |
| 300～360 orders | 50＞D＞40 | 17.40 |
| ＞360 orders | D＜40 | 49.50 |
The data contrast as can be seen from table 1 and table 2, no matter be flyash or modified coal ash, most particle diameters are all less than 90 μ m, but wherein also comprise the bigger particle of a small amount of diameter, therefore, should take the filtration measure to be eliminated in actual use.Comparatively speaking, the diameter Distribution scope of modified coal ash particle is more concentrated.
Modified coal ash and flyash composition analysis: flyash and modified coal ash composition analysis comprise mineral and chemical element composition analysis, mineral composition is analyzed and is adopted X diffraction quantitative analysis method, the chemical element composition analysis adopts X fluorescence macroelement analytic approach, and its check and analysis the results are shown in Table 3 and table 4.
Table 3 flyash and modified coal ash mineral composition
| The sample title | Quartzy (%) | Mullite (%) | Zeolite (%) |
| Flyash | 92 | 8 | |
| Modified coal ash | 74 | 7 | 19 |
Table 4 flyash and modified coal ash chemical compound
| Sample Fe 2O 3 C aO P Al 2O 3 | Macroelement content (%) M n K 2O | Loss on ignition Ti S SiO 2 55.295 | ||||||||||
| MgO | N a2O | (％) | Product fine coal | 5.696 | 0.246 | 0.562 | 8.410 | 1.581 | 0.461 | 0.639 | ||
| 19.667 19.349 | 0.0 0.0 | 0.938 1117 | 5.940 7.469 | Ash modification fine coal | 5.670 | 0.252 | 0.567 | 8.525 | 1.576 | 0.096 | 0.690 | 54.243 |
From the listed test data of table 3 as can be seen, except that the mineral composition that contains flyash, also increased a kind of mineral composition zeolite newly in the modified coal ash, according to the difference of chemical formulation, modified coal ash mesolite content is 10%～19%; As can be seen from Table 4, the basic chemical compound of flyash and modified coal ash is close, and Main Ingredients and Appearance is SiO
2, Al
2O
3, CaO, F
E2O
3Lose the carbon amount with burning.
Modified coal ash and flyash surface structure feature:
Accompanying drawing 1 is flyash SEM (SEM) photo, and wherein last figure a multiplication factor is 400, figure below b is 2500; Accompanying drawing 2 is modified coal ash SEM (SEM) photo, and wherein last figure a multiplication factor is 400, figure below b is 2700.
From accompanying drawing 1 and accompanying drawing 2 as can be seen, flyash and modified coal ash particle appearance feature difference are obvious.Fly ash grain is mainly noncrystalline matter glassy phase, and loosely organized, outward appearance is based on sphere.And the modified coal ash particle, crystalline form is obvious, compact structure, and have forms such as cellular hole and band.Just because of modified coal ash has above-mentioned architectural feature, when its particle is migrated in blowhole, its cellular and ribbon profile is very easily captured by pore constriction, cause the hole flow section to reduce, increase follow-up particle flow resistance, and cause new capture effect to take place, and final form " bridge blinding ", plugging effect is good in waterflooding oil field high moisture and the shutoff of ultra-high water cut stage oil reservoir intake profile, high permeability zone shutoff or macropore shutoff.
Modified coal ash and shutoff experiment of flyash profile control and effect analysis:
Material therefor: clear water, super-high relative molecular weight are (greater than 3000 * 10
4) polyacrylamide, artificial core, flyash and modified coal ash, the particle diameter of flyash and modified coal ash＞360 orders, the permeability 5000 * 10 of artificial core
-3μ m
2
With super-high relative molecular weight (greater than 3000 * 10
4) polyacrylamide is as the liquid that carries of flyash and modified coal ash, at first the liquid that carries with design quantity injects rock core, injects clear water then, the pressure difference value at rock core two ends in the record injection process.
Experimental program 1: the experiment of polymer shutoff profile control, polymer quality concentration C
P=600mg/L, the injection volume of polymer solution are 2 times of voids volumes (PV).
Experimental program 2: polymer+flyash mixed liquor shutoff profile control experiment, polymer quality concentration C
P=600mg/L, flyash mass concentration C
Flyash=0.6%, injecting mixeding liquid volume is 2 times of voids volumes (PV).
Experimental program 3: polymer+modified coal ash mixed liquor shutoff profile control experiment, polymer quality concentration C
P=600mg/L, modified coal ash mass concentration C
Modified coal ash=0.6%, injecting mixeding liquid volume is 2 times of voids volumes (PV).
Theory analysis and experimental data show that the injection pressure increment is bigger, shows the particle plugging effect better.In actual oil reservoir, oil reservoir have usually that certain non-homogeneity promptly vertically goes up and the plane on permeability or pore size there is some difference.After profile control agent enters high permeability zone, because of being detained in hole, profile control agent cause flow resistance to increase and the liquid absorption minimizing, and impel follow-up injection water to enter the less permeable layer of spread effect difference before this, finally reach the purpose that improves oil recovery factor.
Experimental result is as shown in Figure 3:
From accompanying drawing 3 as can be seen, inject the stage at profile control agent, along with three kinds of profile control agents (polymer solution, flyash and modified coal ash) enter blowhole and delay therein, the hole flow section reduces, and flow resistance increases, and injection pressure improves.From pressure amplification, the maximum of modified coal ash, plugging effect is best, secondly is flyash, secondly is polymer solution again.In the follow-up water drive stage, along with entering of follow-up water, the part retentate is migrated in the hole, even by extraction, the hole flow section increases, and injection pressure reduces.From the force value that keeps, modified coal ash also is maximum, and flyash is placed in the middle, the polymer solution minimum.
Modified coal ash can be obtained plugging effect preferably, and main cause is that its particle has irregular contour structures as shown in Figure 2.When the modified coal ash particle was migrated in blowhole, its cellular and ribbon profile was very easily captured by pore constriction, causes the hole flow section to reduce, and increases follow-up particle flow resistance, and caused new capture effect to take place, final form " bridge blinding ".
Description of drawings:
Fig. 1 flyash SEM photo (* 400, * 2500);
Fig. 2 modified coal ash SEM photo (* 400, * 2700);
Graph of relation between Fig. 3 pressure and profile control agent injection pore volume multiple (PV number).
The specific embodiment:
The present invention is further described below in conjunction with embodiment:
The NaOH aqueous solution of 2.0mol/L is mixed by liquid-solid ratio 3.0 (ml/g) with flyash, stir 30min, left standstill 12 hours, then solid and fluid separation applications are promptly got modified coal ash 70 ℃ of conditions.This modified coal ash as profile control agent in waterflooding oil field to fluid entry profile adjust, high permeability zone carries out shutoff or macropore is carried out shutoff.
Embodiment 1, the NaOH aqueous solution of 2.0mol/L is mixed by liquid-solid ratio 3.0 (ml/g) with flyash, stir 60min, left standstill 12 hours, then solid and fluid separation applications are promptly got modified coal ash 70 ℃ of conditions.With modified coal ash and relative molecular mass greater than 3000 * 10
4Polyacrylamide mix, with jet pump itself and water are mixed into the modified coal ash profile control agent then, wherein polyacrylamide accounts for the mass concentration C of profile control agent
P=600mg/L, modified coal ash account for the mass concentration C of profile control agent
Modified coal ash=0.6%.At last with the mixed liquor injection waterflooding oil field high water-cut stage well intake profile profile control target zone of slush pump with this profile control agent.The injection water pressure reaches 13MPa after using this profile control agent, and period of validity is more than 10 years.
Embodiment 2, the NaOH aqueous solution of 2.0mol/L is mixed by liquid-solid ratio 3.0 (ml/g) with flyash, stir 60min, left standstill 12 hours, then solid and fluid separation applications are promptly got modified coal ash 70 ℃ of conditions.With modified coal ash and relative molecular mass greater than 3000 * 10
4Polyacrylamide mix, with jet pump itself and water are mixed into the modified coal ash profile control agent then, wherein polyacrylamide accounts for the mass concentration C of profile control agent
P=600mg/L, modified coal ash account for the mass concentration C of profile control agent
Modified coal ash=0.6%.With slush pump the mixed liquor of this profile control agent is injected into waterflooding oil field high water-cut stage oil well liquid-producing section profile control target zone at last.The injection water pressure reaches 13MPa after using this profile control agent, and period of validity is more than 10 years.
Embodiment 3, the NaOH aqueous solution of 2.0mol/L is mixed by liquid-solid ratio 3.0 (ml/g) with flyash, stir 60min, left standstill 12 hours, then solid and fluid separation applications are promptly got modified coal ash 70 ℃ of conditions.With modified coal ash and relative molecular mass greater than 3000 * 10
4Polyacrylamide mix, with jet pump itself and water are mixed into the modified coal ash profile control agent then, wherein polyacrylamide accounts for the mass concentration C of profile control agent
P=600mg/L, modified coal ash account for the mass concentration C of profile control agent
Modified coal ash=0.6%.With slush pump the mixed liquor of this profile control agent is injected into waterflooding oil field well high permeability zone at last and carries out shutoff.The injection water pressure reaches 13MPa after using this profile control agent, and period of validity is more than 10 years.
Embodiment 4, the NaOH aqueous solution of 2.0mol/L is mixed by liquid-solid ratio 3.0 (ml/g) with flyash, stir 60min, left standstill 12 hours, then solid and fluid separation applications are promptly got modified coal ash 70 ℃ of conditions.With modified coal ash and relative molecular mass greater than 3000 * 10
4Polyacrylamide mix, with jet pump itself and water are mixed into the modified coal ash profile control agent then, wherein polyacrylamide accounts for the mass concentration C of profile control agent
P=600mg/L, modified coal ash account for the mass concentration C of profile control agent
Modified coal ash=0.6%.With slush pump the mixed liquor of this profile control agent is injected into waterflooding oil field oil well high permeability zone at last and carries out shutoff.The injection water pressure reaches 13MPa after using this profile control agent, and period of validity is more than 10 years.
Claims (5)
1, a kind of method of modifying of modified coal ash is characterized in that: the NaOH aqueous solution of 2.0mol/L is mixed by liquid-solid ratio 3.0 (ml/g) with flyash, stir 30min 70 ℃ of conditions, leave standstill and made modified coal ash in 12 hours.
2, the application of a kind of modified coal ash in waterflooding oil field high water-cut stage well intake profile is adjusted, it is characterized in that: described modified coal ash is made by the described method of claim 1.
3, the application of a kind of modified coal ash in waterflooding oil field high water-cut stage oil well liquid-producing section is adjusted, it is characterized in that: described modified coal ash is made by the described method of claim 1.
4, the application of a kind of modified coal ash in the shutoff of waterflooding oil field well high permeability zone, it is characterized in that: described modified coal ash is made by the described method of claim 1.
5, the application of a kind of modified coal ash in the shutoff of waterflooding oil field oil well high permeability zone, it is characterized in that: described modified coal ash is made by the described method of claim 1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100622716A CN1317481C (en) | 2004-07-05 | 2004-07-05 | Use of modified flyash as profile control agent |
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|---|---|---|---|
| CNB2004100622716A CN1317481C (en) | 2004-07-05 | 2004-07-05 | Use of modified flyash as profile control agent |
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|---|---|
| CN1587637A CN1587637A (en) | 2005-03-02 |
| CN1317481C true CN1317481C (en) | 2007-05-23 |
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| CNB2004100622716A Expired - Fee Related CN1317481C (en) | 2004-07-05 | 2004-07-05 | Use of modified flyash as profile control agent |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100419039C (en) * | 2006-10-31 | 2008-09-17 | 大庆油田有限责任公司 | Zeolite profile control agent and method for injecting zeolite profile control agent into profile control well |
| CN104419391B (en) * | 2013-09-03 | 2018-05-08 | 中国石油化工股份有限公司 | Well cementation compound lightening material and preparation method and deep-well compound cement and application |
| CN107858142A (en) * | 2017-11-22 | 2018-03-30 | 烟台智本知识产权运营管理有限公司 | A kind of coal-fired waste residue profile control agent and preparation method thereof |
| CN112625665B (en) * | 2019-10-08 | 2023-04-18 | 中国石油化工股份有限公司 | Fly ash suspension stable plugging profile control agent and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4537918A (en) * | 1982-04-06 | 1985-08-27 | Etudes Et Fabrication Dowell Schlumberger | Cement compositions for cementing wells, allowing pressure gas-channeling in the cemented annulus to be controlled |
| CN1152663A (en) * | 1996-10-25 | 1997-06-25 | *** | Activated fly ash and application thereof |
| US5900053A (en) * | 1997-08-15 | 1999-05-04 | Halliburton Energy Services, Inc. | Light weight high temperature well cement compositions and methods |
| CN1249281A (en) * | 1999-08-11 | 2000-04-05 | 孙救来 | Process for modifying and applying fly ash |
| WO2004055321A1 (en) * | 2002-11-15 | 2004-07-01 | Halliburton Energy Services, Inc. | Methods of cementing high temperature wells and cement compositions therefor |
-
2004
- 2004-07-05 CN CNB2004100622716A patent/CN1317481C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4537918A (en) * | 1982-04-06 | 1985-08-27 | Etudes Et Fabrication Dowell Schlumberger | Cement compositions for cementing wells, allowing pressure gas-channeling in the cemented annulus to be controlled |
| CN1152663A (en) * | 1996-10-25 | 1997-06-25 | *** | Activated fly ash and application thereof |
| US5900053A (en) * | 1997-08-15 | 1999-05-04 | Halliburton Energy Services, Inc. | Light weight high temperature well cement compositions and methods |
| US6143069A (en) * | 1997-08-15 | 2000-11-07 | Halliburton Energy Services, Inc. | Light weight high temperature well cement compositions and methods |
| CN1249281A (en) * | 1999-08-11 | 2000-04-05 | 孙救来 | Process for modifying and applying fly ash |
| WO2004055321A1 (en) * | 2002-11-15 | 2004-07-01 | Halliburton Energy Services, Inc. | Methods of cementing high temperature wells and cement compositions therefor |
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| CN1587637A (en) | 2005-03-02 |
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Assignee: Beijing Dongsheng Century Science and Technology Co., Ltd. Assignor: Lu Xiangguo Contract fulfillment period: 2007.5.25 to 2013.5.24 contract change Contract record no.: 2008110000201 Denomination of invention: Use of modified flyash as profile control agent Granted publication date: 20070523 License type: Exclusive license Record date: 20081212 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.5.25 TO 2013.5.24; CHANGE OF CONTRACT Name of requester: BEIJING DONGSHENG SHIJI SCIENCE CO., LTD. Effective date: 20081212 |
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Granted publication date: 20070523 |