CN104694096A - Oilfield development plugging agent - Google Patents
Oilfield development plugging agent Download PDFInfo
- Publication number
- CN104694096A CN104694096A CN201310646652.8A CN201310646652A CN104694096A CN 104694096 A CN104694096 A CN 104694096A CN 201310646652 A CN201310646652 A CN 201310646652A CN 104694096 A CN104694096 A CN 104694096A
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- Prior art keywords
- agent
- blocking agent
- unsaturated polyester
- plugging
- blocking
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- 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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/5086—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C09K2208/18—Bridging agents, i.e. particles for temporarily filling the pores of a formation; Graded salts
Abstract
The invention provides an oilfield development plugging agent which is prepared from unsaturated resin emulsion, a curing agent and a coupling agent as raw materials, the unsaturated resin emulsion is formed by mixing 196 unsaturated polyester resin, an emulsifier and water, and the coupling agent is gamma-aminopropyl triethoxysilane. The plugging agent is suitable for the formation at the temperature of 30-90 DEG C, and the resin solution can be self curing at the temperature, and can be used for the permanent sealing of large holes or large cracks which do not need plugging releasing. The oilfield development plugging agent has strong plugging ability, salt resistance, wide applicable scope, long validity period and low cost. Compared with the blocking agent in other profile control systems, the oilfield development plugging agent has obvious advantages on plugging of oil reservoirs with large holes or large cracks, and is in line with the needs of oil field sites.
Description
Technical field
The present invention relates to a kind of oil-field development blocking agent.
Background technology
In the performance history of carbonatite oil field, water is usually along Thief zone macropore, microfracture tonguing, and these ducts, Thief zone crack obviously can not divide interval on vertical section, thus just can not take simple machinery card every, therefore techniques of chemical water plugging will become the important measures of Carbonate Reservoir steady oil control water.But due to the singularity of Carbonate Reservoir, make the water outlet rule of oil well be different from sandstone oil reservoir, traditional reservoir engineering method is no longer applicable.Therefore, the water-plugging technique developing applicable Carbonate Reservoir is very necessary.
A kind of Carbonate Oil well density selective water shutoff agent is provided in patent application CN102746835A, its component formula meter, cement 100 parts, flyash 60-75 part, clay 50-58 part, micro-silicon 52-62 part, hardening accelerator 5-8 part, water retaining 16-28 part, water 1100-1200 part.This plugging agent is easy to resident between water-oil interface, sets up water blockoff dividing plate, ensures solidification effect, and after solidification, ultimate compression strength is large.
Patent CN102410022A provides a kind of method for protecting fissured carbonate reservoir.Fractured carbonate reservoir protecting materials wherein: form by the tensio-active agent of mass fraction by the carbon material of 0.5-20 part, the special fibre colloid novel material of 70-85 part and 5-10 part.The pressure use this protecting materials can stop fracture propagation, stratum being born higher than fracture gradient also can not cause mud loss.
In sum, although the blocking agent of various oil field exploratory development has been developed in this area, the macropore still needing exploration can better, can occur in shutoff In Oil Field Exploration And Development in this area or the blocking agent of large fracture.
Summary of the invention
The invention provides a kind of oil-field development blocking agent, described blocking agent is that raw material prepares by unsaturated polyester emulsion, solidifying agent and coupling agent, and described unsaturated polyester emulsion is mixed to form by 196 unsaturated polyester resins, emulsifying agent and water, described coupling agent is γ-aminopropyl triethoxysilane.
In the present invention, described γ-aminopropyl triethoxysilane and silicoorganic compound KH-550.Blocking agent of the present invention is prepared from by these three kinds of raw materials, but those skilled in the art easily learn, except using except water in the process preparing unsaturated polyester emulsion, a certain amount of moisture content can also be added before above-mentioned three kinds of raw material reactions, after reaction neutralization reaction.
The present invention is directed to and carry out permanent shutoff without the need to the macropore of de-plugging, large fracture.The present invention selects 196 unsaturated polyester resins (unsaturated polyester 196#) to prepare unsaturated polyester emulsion, this resin is light yellow clear viscous liquid, and its solid content is 64% ~ 70%, its good toughness, shock strength is high, is the relatively low unsaturated resins for universal use of adjacent benzene-type of a kind of price.This resin has good physical strength, after contacting with sand grains, under solidifying agent and coupling agent acting in conjunction, the macromole produced by the affine winding effect of physics is insolubles, then the insoluble superpolymer do not melted is formed by polyreaction, thus by sand grains consolidation securely, described superpolymer has mesh structure.In addition, from the angle analysis of mechanical performance index, unsaturated polyester 196# is slightly poorer than epoxy resin, but is better than resol, and its cost is between therebetween, has good practical value.
In a kind of embodiment of the present invention, the mass percent that three kinds of raw materials of described blocking agent account for blocking agent is respectively, unsaturated polyester emulsion 50 ~ 80wt%, solidifying agent 10 ~ 35wt%, coupling agent 1 ~ 15wt%; Preferably, unsaturated polyester emulsion 65 ~ 80wt%, solidifying agent 15 ~ 25wt%, coupling agent 5 ~ 10wt%.
Preferably, solidifying agent of the present invention is one or more in hydrogen peroxide, benzoyl peroxide and methylethyl ketone peroxide; Emulsifying agent of the present invention is one or more in tween, OP-10 and sapn.
In a specific embodiment of the present invention, the mass ratio of described 196 unsaturated polyester resins and emulsifying agent is 2 ~ 50:1, is preferably 3 ~ 20:1.
In a specific embodiment of the present invention, the consumption of described 196 unsaturated polyester resins is 20 ~ 40wt% of described unsaturated polyester emulsion.
The present invention also provides the preparation method of above-mentioned blocking agent, comprise first by described 196 unsaturated polyester resins and emulsifier for mixing mixing, then after adding water, stirring and evenly mixing forms unsaturated polyester emulsion; Again described solidifying agent and coupling agent are added in described unsaturated polyester emulsion and form described blocking agent.
Preferably, stirring velocity is 500 ~ 800r/min, and water is that constant speed adds.
The present invention also provides the application of above-mentioned blocking agent in Carbonate Reservoir exploitation.Because Carbonate Reservoir development late stage easily produces macropore and/or large fracture, now use the blocking agent in the present invention to carry out shutoff and be suitable for especially.Certainly, if sandstone oil reservoir development late stage exists macropore and/or large fracture, the blocking agent in the present invention equally also can be used to carry out shutoff.
Blocking agent in the present invention is adapted to the stratum that shutoff has more macropore or large fracture.Strong, the anti-salt of this blocking agent shut-off capacity, applied widely, validity period are long, cost is lower, and compare with other profile control systems, the blocking agent in the present invention is with the obvious advantage to the oil reservoir shutoff that there is macropore or large fracture, meets the needs of Oil Field.
In addition, by showing the application of blocking agent in the present invention, blocking agent formation sand grains of the present invention and have stronger ability to cure in pore throat, under 70 DEG C of conditions, system solution and the sand grains ultimate compression strength that 1:10 mixes the consolidated core made in mass ratio is greater than 5MPa.This system is applicable to the stratum of temperature 30 ~ 90 DEG C, and resin solution can solidify at this temperature voluntarily, carries out permanent shutoff for macropore or large fracture.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
In the present invention, core permeability represents under certain pressure reduction, the ability that rock allows fluid to pass through.Its value larger explanation rock core allows stronger by the ability of fluid.
In the present invention, breakthrough pressure gradient: refer to along fluid flow direction, the pressure change on unit path length.Its value is larger, and the intensity of blocking agent higher (shutoff must be more firm) is described.
In the present invention, reservoir core plugging rate refers to the ability of blocking agent shutoff rock core.The sealing characteristics of the larger explanation blocking agent of its value is better.
Embodiment 1
The preparation method of blocking agent: 10g unsaturated polyester 196# and 1.5g emulsifier tween 80 join in three-necked bottle, under 25 DEG C of conditions, 600r/min stirs, add 20ml deionized water with 1mL/min constant speed, under 25 DEG C of conditions, 600r/min stirs 0.5h, namely forms unsaturated polyester emulsion; Then be 9g by solidifying agent hydrogen peroxide, coupling agent silicoorganic compound KH-550 is that 4.5g joins in above-mentioned unsaturated polyester emulsion, stir 0.5h at 20 ~ 30 DEG C, obtain profile control and water plugging blocking agent.
In this blocking agent, 196 unsaturated polyester resins in unsaturated polyester emulsion and the mass ratio of emulsifying agent are 6.67:1, and the consumption of 196 unsaturated polyester resins is the 31.75wt% of described unsaturated polyester emulsion; And unsaturated polyester emulsion is 70wt% in described blocking agent, solidifying agent is 20wt%, and coupling agent is 10wt%.
Be: under 50 DEG C of conditions that core permeability is 1.45 μm to the test case of the blocking agent in the present embodiment
2with the volume of voids that blocking agent injection rate is 0.4 times of PV(rock core) time; The breakthrough pressure gradient > 60MPa/m of system, and reservoir core plugging rate is 100%.
Embodiment 2
The preparation method of blocking agent is identical with embodiment 1, but the consumption changing each raw material makes the mass ratio of 196 unsaturated polyester resins in unsaturated polyester emulsion and emulsifying agent be 3:1, and the consumption of 196 unsaturated polyester resins is the 20wt% of described unsaturated polyester emulsion; And unsaturated polyester emulsion is 72wt% in described blocking agent, solidifying agent is 21wt%, and coupling agent is 7wt%.
Be: under 60 DEG C of conditions that core permeability is 0.46 μm to the test case of the blocking agent in the present embodiment
2with the volume of voids that blocking agent injection rate is 0.4 times of PV(rock core) time; The breakthrough pressure gradient > 60MPa/m of system, and reservoir core plugging rate is 100%.
Embodiment 3
The preparation method of blocking agent is identical with embodiment 1, but the consumption changing each raw material makes the mass ratio of 196 unsaturated polyester resins in unsaturated polyester emulsion and emulsifying agent be 10:1, and the consumption of 196 unsaturated polyester resins is the 25wt% of described unsaturated polyester emulsion; And unsaturated polyester emulsion is 65wt% in described blocking agent, solidifying agent is 25wt%, and coupling agent is 10wt%.
Be: under 50 DEG C of conditions that core permeability is 1.98 μm to the test case of the blocking agent in the present embodiment
2with the volume of voids that blocking agent injection rate is 0.4 times of PV(rock core) time; The breakthrough pressure gradient > 60MPa/m of system, and reservoir core plugging rate is 100%.
Embodiment 4
The preparation method of blocking agent is similar to embodiment 1, but the consumption changing each raw material makes the mass ratio of 196 unsaturated polyester resins in unsaturated polyester emulsion and emulsifying agent be 15:1, and the consumption of 196 unsaturated polyester resins is the 36wt% of described unsaturated polyester emulsion; And unsaturated polyester emulsion is 80wt% in described blocking agent, solidifying agent is 15wt%, and coupling agent is 5wt%; In addition, the solidifying agent hydrogen peroxide used in embodiment 1 is changed into use benzoyl peroxide.
Be: under 45 DEG C of conditions that core permeability is 1.04 μm to the test case of the blocking agent in the present embodiment
2with the volume of voids that blocking agent injection rate is 0.4 times of PV(rock core) time; The breakthrough pressure gradient > 60MPa/m of system, and reservoir core plugging rate is 100%.
Embodiment 5
The preparation method of blocking agent is similar to embodiment 1, but the consumption changing each raw material makes the mass ratio of 196 unsaturated polyester resins in unsaturated polyester emulsion and emulsifying agent be 20:1, and the consumption of 196 unsaturated polyester resins is the 40wt% of described unsaturated polyester emulsion; And unsaturated polyester emulsion is 75wt% in described blocking agent, solidifying agent is 20wt%, and coupling agent is 5wt%; In addition, the emulsifier tween 80 used in embodiment 1 is changed into use OP-10.
Be: under 55 DEG C of conditions that core permeability is 1.21 μm to the test case of the blocking agent in the present embodiment
2with the volume of voids that blocking agent injection rate is 0.4 times of PV(rock core) time; The breakthrough pressure gradient > 60MPa/m of system, and reservoir core plugging rate is 100%.
By above-described embodiment 1 ~ 5 explanation, when blocking agent injection rate is 0.4 times of PV, the equal > 60MPa/m of breakthrough pressure gradient of the system in embodiment 1 ~ 5, and reservoir core plugging rate is 100%, illustrate that the blocking agent of this consumption is applicable to the stratum that temperature is 45 ~ 60 DEG C, and to be applicable to core permeability be 0.46 ~ 1.98 μm
2stratum.In fact, for the stratum of certain temperature and core permeability, suitable modulation and blocking agent injection rate (the plug agent amount excessive then shutoff high cost optimized in the present invention, plug agent amount is too small, and plugging effect may decline), it is the stratum of 30 ~ 90 DEG C and the stratum being applicable to any core permeability (as macroscopic void or large fracture) that blocking agent of the present invention can be made to be applicable to temperature.
Claims (10)
1. an oil-field development blocking agent, it is characterized in that, described blocking agent is that raw material prepares by unsaturated polyester emulsion, solidifying agent and coupling agent, and described unsaturated polyester emulsion is mixed to form by 196 unsaturated polyester resins, emulsifying agent and water, described coupling agent is γ-aminopropyl triethoxysilane.
2. blocking agent according to claim 1, is characterized in that, the mass percent that three kinds of raw materials of described blocking agent account for blocking agent is respectively, unsaturated polyester emulsion 50 ~ 80wt%, solidifying agent 10 ~ 35wt%, coupling agent 1 ~ 15wt%.
3. blocking agent according to claim 2, is characterized in that, the mass percent that three kinds of raw materials of described blocking agent account for blocking agent is respectively, unsaturated polyester emulsion 65 ~ 80wt%, solidifying agent 15 ~ 25wt%, coupling agent 5 ~ 10wt%.
4. according to the blocking agent in claims 1 to 3 described in any one, it is characterized in that, described solidifying agent is one or more in hydrogen peroxide, benzoyl peroxide and methylethyl ketone peroxide.
5. according to the blocking agent in claims 1 to 3 described in any one, it is characterized in that, described emulsifying agent is one or more in tween, OP-10 and sapn.
6. according to the blocking agent in claims 1 to 3 described in any one, it is characterized in that, the mass ratio of described 196 unsaturated polyester resins and emulsifying agent is 2 ~ 50:1, is preferably 3 ~ 20:1.
7. according to the blocking agent in claims 1 to 3 described in any one, it is characterized in that, the consumption of described 196 unsaturated polyester resins is 20 ~ 40wt% of described unsaturated polyester emulsion.
8. according to the preparation method of blocking agent described in any one in claim 1 ~ 7, it is characterized in that, first by described 196 unsaturated polyester resins and emulsifier for mixing mixing, then after adding water, stirring and evenly mixing forms unsaturated polyester emulsion; Again described solidifying agent and coupling agent are added in described unsaturated polyester emulsion and form described blocking agent.
9. preparation method according to claim 8, is characterized in that, stirring velocity is 500 ~ 800r/min, and water is that constant speed adds.
10. the application of the blocking agent that method prepares as described in blocking agent as described in any one in claim 1 ~ 7 or claim 8 or 9 in Carbonate Reservoir exploitation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310646652.8A CN104694096B (en) | 2013-12-04 | 2013-12-04 | A kind of oil field development blocking agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310646652.8A CN104694096B (en) | 2013-12-04 | 2013-12-04 | A kind of oil field development blocking agent |
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| CN104694096A true CN104694096A (en) | 2015-06-10 |
| CN104694096B CN104694096B (en) | 2018-02-09 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105504645A (en) * | 2015-12-19 | 2016-04-20 | 中国石油天然气股份有限公司 | Terpolymer elastic granular profile control material and preparation method thereof |
| CN108641691A (en) * | 2018-03-27 | 2018-10-12 | 中国石油大学(华东) | A kind of high-intensity resin blocking agent and the preparation method and application thereof |
| CN109054786A (en) * | 2018-06-26 | 2018-12-21 | 西安石油大学 | A kind of the deep profile controlling system and its preparation and application of in-situ generation particle |
| CN109054787A (en) * | 2018-08-17 | 2018-12-21 | 河北工业大学 | A kind of plugging material of organic/inorganic composite |
| CN109943301A (en) * | 2019-03-28 | 2019-06-28 | 中国石油大学(华东) | Resin emulsion sealing agent composition and preparation method thereof and the application in fracture formation |
| CN110105935A (en) * | 2019-05-10 | 2019-08-09 | 陕西鼎和源瑞环境工程有限公司 | A kind of high strength multifunctional blocking agent |
| CN111139047A (en) * | 2020-01-02 | 2020-05-12 | 西安石油大学 | Emulsified thermosetting phenolic resin water plugging system and preparation method thereof |
| CN111592866A (en) * | 2020-06-04 | 2020-08-28 | 汉中聚智达远环能科技有限公司 | High-adhesion plugging material and preparation method thereof |
| CN111808580A (en) * | 2020-06-11 | 2020-10-23 | 中国海洋石油集团有限公司 | Oil well plugging material based on in-situ curing reaction and preparation and application methods thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105504645A (en) * | 2015-12-19 | 2016-04-20 | 中国石油天然气股份有限公司 | Terpolymer elastic granular profile control material and preparation method thereof |
| CN105504645B (en) * | 2015-12-19 | 2018-02-02 | 中国石油天然气股份有限公司 | A kind of terpolymer elastic granule profile control material and preparation method thereof |
| CN108641691A (en) * | 2018-03-27 | 2018-10-12 | 中国石油大学(华东) | A kind of high-intensity resin blocking agent and the preparation method and application thereof |
| CN108641691B (en) * | 2018-03-27 | 2020-11-06 | 中国石油大学(华东) | High-strength resin plugging agent and preparation method and application thereof |
| CN109054786A (en) * | 2018-06-26 | 2018-12-21 | 西安石油大学 | A kind of the deep profile controlling system and its preparation and application of in-situ generation particle |
| CN109054787A (en) * | 2018-08-17 | 2018-12-21 | 河北工业大学 | A kind of plugging material of organic/inorganic composite |
| CN109943301A (en) * | 2019-03-28 | 2019-06-28 | 中国石油大学(华东) | Resin emulsion sealing agent composition and preparation method thereof and the application in fracture formation |
| CN110105935A (en) * | 2019-05-10 | 2019-08-09 | 陕西鼎和源瑞环境工程有限公司 | A kind of high strength multifunctional blocking agent |
| CN111139047A (en) * | 2020-01-02 | 2020-05-12 | 西安石油大学 | Emulsified thermosetting phenolic resin water plugging system and preparation method thereof |
| CN111592866A (en) * | 2020-06-04 | 2020-08-28 | 汉中聚智达远环能科技有限公司 | High-adhesion plugging material and preparation method thereof |
| CN111808580A (en) * | 2020-06-11 | 2020-10-23 | 中国海洋石油集团有限公司 | Oil well plugging material based on in-situ curing reaction and preparation and application methods thereof |
| CN111808580B (en) * | 2020-06-11 | 2022-12-06 | 中国海洋石油集团有限公司 | Oil well plugging material based on in-situ curing reaction and preparation and application methods thereof |
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| CN104694096B (en) | 2018-02-09 |
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