CN108728075A - A kind of tackifying system of liquid and supercritical carbon dioxide - Google Patents
A kind of tackifying system of liquid and supercritical carbon dioxide Download PDFInfo
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- CN108728075A CN108728075A CN201810706136.2A CN201810706136A CN108728075A CN 108728075 A CN108728075 A CN 108728075A CN 201810706136 A CN201810706136 A CN 201810706136A CN 108728075 A CN108728075 A CN 108728075A
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- 0 CC(C)(C(C)(*)[Si](C)(CCCOCCOC(C#CCc1ccccc1)=O)O*(*)[Si](C)(C)C)O[Si](C)(CCO)C(C)(C)O[Si](C)(C)* Chemical compound CC(C)(C(C)(*)[Si](C)(CCCOCCOC(C#CCc1ccccc1)=O)O*(*)[Si](C)(C)C)O[Si](C)(CCO)C(C)(C)O[Si](C)(C)* 0.000 description 1
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- 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
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
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- 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
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/885—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses a kind of liquid and the tackifying system of supercritical carbon dioxide, which includes tackifier, surfactant, organic solvent and drag reducer；The tackifier are long chain fatty acids or polyester at least one of amino, ether or alkoxy group, or by the group modified polysiloxanes of amino, polyethers, acrylic acid, aryl, alkyl one of which；The weight average molecular weight of the tackifier is 3000-100000.The tackifying system of the present invention is used in compounding using tackifier polymer, surfactant, organic solvent and drag reducer, 15~120 times of the viscosity of carbon dioxide system can be effectively improved, system resistance coefficient is effectively reduced simultaneously, and 5~22% can be reduced under different in flow rate.
Description
Technical field
The invention belongs to natural petroleum gas field, volume increase field of chemicals, and in particular to a kind of liquid and overcritical
Carbon dioxide tackifying system.
Background technology
Anhydrous fracturing technique is to carry out rock fracture as pressure break medium using non-water base fluid, realize oil and gas development or increasing
Production.Liquid carbon dioxide (LCO2) and supercritical carbon dioxide (scCO2) anhydrous fracturing technique is good with its effect of increasing production, to reservoir
Fanout free region and to the conventional unrivaled technical advantage of pressure break such as protection of water resource, can in a foreseeable future be increasingly becoming non-
The core technology of conventional gas and oil exploitation.The technology be by proppants such as the natural grains of sand, resin tags or high-strength ceramics and
LCO2Reservoir is injected together, is completed seam, is taken the processes such as sand, replacement.Wherein, scCO2Pressure break system just can reach super in the wellbore
Critical state.CO2It can also be reacted with the water in reservoir and generate carbonic acid, swelling clay mineral can be effectively reduced, released crack and block, increase
The energy for adding reservoir dissolved gas drive is finally reached the purpose of volume increase.It is substantially residual without solid phase due to being free of any water phase in fluid
Slag will not only damage reservoir, moreover it is possible to the row's of returning efficiency after enhancing pressure, to improve fracturing effect.
Current domestic and international CO2The present Research of anhydrous pressure break is away from it extensively using still having the suitable gap, first cause to be exactly
Lack efficient, low cost, free of contamination CO2Thickener.LCO2With scCO2Viscosity is low, and prop-carrying capacity is poor, needs to increase its viscosity
To carry proppant.But CO2For nonpolar molecule, there is extremely low dielectric constant and surface tension, Conventional thickeners can not be with
Its is miscible carry it is viscous.
CN201510434208.9 discloses a kind of liquid carbon dioxide fracturing fluid.The used tackifier of system are height fluorine
Change the acrylate of (77% or more) and partly sulfonated styrene block copolymer.CN201611016355.5, which is disclosed, to be used for
The supercritical carbon dioxide pressure break system and preparation method of low permeability reservoirs.Moieties in dispersant mentioned by system are complete
Fluoroalkyl.Though fluoro-based polymers are a kind of CO of effect2Thickener, but it is expensive, and dosage is larger, easily injures stratum and to ring
Border harm is big.
CN201610078402.2 discloses a kind of supercritical carbon dioxide thickener and its preparation and application.The thickener
For copolymer, including close CO2Monomer and adhesion promoting monomers.The parent CO2Monomer is lewis base, selected from acrylic acid, metering system
It is one or more in acid, tert-butyl acrylate, vinylacetate, methyl methacrylate；The thickening body is selected from 1- heptan
Alkene, 1- octenes, 1- decene, styrene, 4- acetylbenzenes ethylene, vinyl benzoic acid and one kind or more in vinyl benzoate
Kind.But the production building-up process of the system is complex, and precise controlling is difficult to realize, and product controllability is poor, and product dissolves institute
Need condition more harsh, performance needs to be further increased.
CN201710331970.3 discloses a kind of method improving liquid carbon dioxide viscosity.Stick is carried involved by system
For acrylamide, the copolymer of -2 methyl propane sulfonic acid of 2- acrylamidos, hexadecyldimethyl benzyl ammonium allyl ammonium chloride, and use
A large amount of auxiliary agents.Above-mentioned copolymer includes three kinds of monomers, using free radical polymerization it is difficult to control its structure and the stability of composition, gesture
Efficient Adhesive Promotion must be produced bigger effect.It is greatly improved in addition, cosolvent also results in cost.
CN201710818835.1 discloses a kind of carbon dioxide method for thickening and thickened systems.The thickened systems include fat
Cosolvent, surfactant and the macromolecule solvent of fat hydrocarbon and alcohol composition.System composition is complicated, small molecule cosolvent dissolubility compared with
It is good, CO can be improved simultaneously2Viscosity and density, but its pressure break cost also accordingly increases.
Invention content
The purpose of the present invention is be directed to LCO in the prior art2With scCO2Viscosity existing for fracturing fluid system is low, solubility
The problems such as low, tackifier efficiency is low, and system frictional resistance is high, and pressure break is of high cost, environmental pollution and big formation damage, provides one kind and is used for
The tackifying system of liquid carbon dioxide or supercritical carbon dioxide thickening.The tackifying system can be improved the viscosity of carbon dioxide
It improves to 15~120 times, while effectively reducing system resistance coefficient.
The tackifying system of liquid provided by the invention and supercritical carbon dioxide, including it is tackifier, surfactant, organic
Solvent and drag reducer.Wherein, the tackifier are the long-chain fats at least one of amino, ether or alkoxy group
Acid or polyester, or by the group modified polysiloxanes of amino, polyethers, acrylic acid, aryl, alkyl one of which；The thickening
The weight average molecular weight of agent is 3000-100000.
The structural formula of the long chain fatty acids is as follows：
In formula, R1For H or the chain alkyl containing 1-4 carbon atom, it is preferable that R1=CH3。
The structural formula of the polyester is as follows：
In formula, R2For the chain alkyl containing 2-22 carbon atom；R3For H or the chain alkyl containing 1-4 carbon atom.It is preferred that
Ground, R2=C4H9, R3=H.
Preferably, simultaneous at least one of amino, ether or alkoxy base in the tackifier molecular structure
Group and phenyl or group containing aluminium base.
It may further be preferable that the tackifier are Siloxane-Oxyalkylene Copolymers, structural formula is as follows：
Preferably, the surfactant is oil-soluble nonionic surfactant.
The organic solvent is one or more in small molecular alcohol with chain alkyl structure, ester, ketone, aldehydes.Alcohol,
Ester, ketone, the structural formula difference of aldehydes are as follows：
R4- OH,
In formula, R4, R5, R6, R7, R8And R9For the long chain alkane containing 2~22 carbon atoms, n >=1, it is preferred that R4=
C18H38, R5=C12H26, R6=C2H6, R7=C18H38, R8=C12H26, R9=C2H6.I.e. preferred organic solvent is backbone
C18H38OH、C12H26COOC2H6、C18H38CHO、C12H26COC2H6In one kind.
The drag reducer is nano-composite fiber or montmorillonite, graphite, carbon nano tube modified fiber, nano-composite fiber end
Face 60-100nm, length 0.6-1cm；30-100 μm of modified fibre end face, length 0.5-1cm, fibre-forming polymer molecular weight are
20000-100000。
The tackifying system is added in liquid or supercritical carbon dioxide and forms fracturing fluid system, it is each in fracturing fluid system
The mass percent of component is as follows：Tackifier 0.5-6%, surfactant 0.5-3%, organic solvent 0.5-5%, drag reducer
0.05-0.2%, remaining is liquid or supercritical carbon dioxide.
The invention has the beneficial effects that：
(1) parent such as the amino containing non-fluorine, ether, alkoxy carbon dioxide group in tackifier polymer molecular structure,
Make it in LCO2With scCO2It is effectively dissolved in system；And contain phenyl, containing aluminium base group etc. thin carbon dioxide group, make its
LCO2With scCO2It mutually associates in system or is combined with other auxiliary agents, further increase Efficient Adhesive Promotion.
(2) tackifying system of the invention is multiple using Tackified polymeric, surfactant, Small molecule organic solvents and drag reducer
With synergistic effect, it can be effectively increased the viscosity of carbon dioxide pressure break liquid system, 15~120 times can be improved, 0.6~4.8mPa
S, while system resistance coefficient is effectively reduced, it can reduce by 5~22% under different in flow rate.
(3) not fluorine-containing in tackifying system, have the characteristics that environmentally protective, is a kind of green, economical and effective liquid and super
Critical carbon dioxide tackifying system, the active ingredient by recycling, in recycling system further decrease pressure break cost.
Description of the drawings
Fig. 1 be in embodiment 1 liquid carbon dioxide system viscosity with the change curve of shear time.
Fig. 2 is the relationship between liquid carbon dioxide system discharge capacity and resistance coefficient in embodiment 1.
Specific implementation mode
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings, it should be understood that preferred reality described herein
Apply example only for the purpose of illustrating and explaining the present invention and is not intended to limit the present invention.
Embodiment 1
Present embodiments provide a kind of liquid carbon dioxide fracturing fluid system, on the basis of fracturing fluid total weight, fracturing fluid
In system, each component mass percent is：Siloxane-Oxyalkylene Copolymers tackifier 2%, ethyl alcohol are mixed with mass ratioes such as cyclohexanone
Organic solvent 5%, nano-composite fiber drag reducer 0.15% (fibre length 0.5cm, a diameter of 50 μm), surfactant
0.5%, remaining is liquid carbon dioxide.Tackifying system each component being added to after being stirred evenly in liquid carbon dioxide can obtain
The effect of thickening needed for obtaining and drop frictional resistance.Room temperature, viscosity reaches 0.92mPa.s under 7MPa；Flow velocity 1m/s, resistance coefficient are
0.019.Fig. 1 be in the present embodiment liquid carbon dioxide system viscosity with the change curve of shear time.Fig. 2 is in the present embodiment
Relationship between liquid carbon dioxide system discharge capacity and resistance coefficient.
Embodiment 2
Present embodiments provide a kind of liquid carbon dioxide fracturing fluid system, on the basis of fracturing fluid total weight, fracturing fluid
In system, each component mass percent is：Siloxane-Oxyalkylene Copolymers tackifier 2%, ethyl alcohol are mixed with mass ratioes such as cyclohexanone
Organic solvent 5%, surfactant 3%, remaining be liquid carbon dioxide.Tackifying system each component is added to liquid dioxy
Change the effect that can be obtained required thickening and drop frictional resistance after being stirred evenly in carbon.This example demonstrates that without using nano combined
In the case of fiber drag reducer, fracturing fluid system resistance coefficient is increased to 0.023.
Embodiment 3
Present embodiments provide a kind of liquid carbon dioxide fracturing fluid system, on the basis of fracturing fluid total weight, fracturing fluid
In system, each component mass percent is：It is amino modified polysiloxane tackifier 0.5%, cyclohexanone solvent 5%, nano combined
Fiber drag reducer 0.05% (fibre length 0.5cm, a diameter of 50 μm), surfactant 1%, remaining be liquid carbon dioxide.
Tackifying system each component is added to the effect that can be obtained required thickening and drop frictional resistance after being stirred evenly in liquid carbon dioxide.
Room temperature, viscosity reaches 1.03mPa.s under 7MPa；Flow velocity 1m/s, resistance coefficient 0.020.A small amount of water is added into the present embodiment,
It is acted on liquid carbon dioxide, the tertiary amine ingredient protonation in tackifier increases its polarity, effectively improves its pressure break and returns and flows back to receipts
Possibility.
Embodiment 4
Present embodiments provide a kind of supercritical carbon dioxide fracturing fluid system, on the basis of fracturing fluid total weight, pressure break
In liquid system, each component mass percent is：Octadecylamino acid tackifier 6%, C12H26COOC2H6Organic solvent 2% is received
Rice composite fibre drag reducer 0.05%, surfactant 2%, remaining be supercritical carbon dioxide.Tackifying system each component is added
Enter the effect that can be obtained required thickening and drop frictional resistance after being stirred evenly into liquid carbon dioxide.Room temperature, viscosity reaches under 7MPa
To 1.47mPa.s；Flow velocity 1m/s, resistance coefficient 0.024.
Embodiment 5
Present embodiments provide a kind of liquid carbon dioxide fracturing fluid system, on the basis of fracturing fluid total weight, fracturing fluid
In system, each component mass percent is：Silane coupler modified polyester tackifier 4%, C18H38CHO organic solvents 1% are received
Rice composite fibre drag reducer 0.05%, surfactant 1%, remaining be liquid carbon dioxide.Tackifying system each component is added
It can be obtained the effect of required thickening and drop frictional resistance to after being stirred evenly in liquid carbon dioxide.Room temperature, viscosity reaches under 7MPa
1.16mPa.s；；Flow velocity 1m/s, resistance coefficient 0.022.
In conclusion the present invention provides a kind of green, economical and effective liquid and super faces in view of the deficiencies of the prior art
Boundary's carbon dioxide tackifying system, is used in compounding using tackifier polymer, surfactant, organic solvent and drag reducer,
Synergistic effect can effectively improve 15~120 times of the viscosity of carbon dioxide system, while effectively reduce system resistance coefficient, not cocurrent flow
5~22% can be reduced under speed；Active ingredient by recycling, in recycling system can further decrease pressure break cost.
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, though
So the present invention has been disclosed as a preferred embodiment, and however, it is not intended to limit the invention, any technology people for being familiar with this profession
Member, without departing from the scope of the present invention, when the technology contents using the disclosure above make a little change or modification
For the equivalent embodiment of equivalent variations, as long as being the content without departing from technical solution of the present invention, according to the technical essence of the invention
To any simple modification, equivalent change and modification made by above example, in the range of still falling within technical solution of the present invention.
Claims (10)
1. the tackifying system of a kind of liquid and supercritical carbon dioxide, which is characterized in that the tackifying system includes tackifier, surface
Activating agent, organic solvent and drag reducer；The tackifier are the length at least one of amino, ether or alkoxy group
Chain fatty acid or polyester, or by the group modified polysiloxanes of amino, polyethers, acrylic acid, aryl, alkyl one of which；
The weight average molecular weight of the tackifier is 3000-100000.
2. the tackifying system of liquid as described in claim 1 and supercritical carbon dioxide, which is characterized in that the long-chain fat
The structural formula of acid is as follows：
In formula, R1 is H or the chain alkyl containing 1-4 carbon atom.
3. the tackifying system of liquid as described in claim 1 and supercritical carbon dioxide, which is characterized in that the knot of the polyester
Structure formula is as follows：
In formula, R2For the chain alkyl containing 2-22 carbon atom；R3For H or the chain alkyl containing 1-4 carbon atom.
4. the tackifying system of liquid as described in claim 1 and supercritical carbon dioxide, which is characterized in that the tackifier point
Simultaneous at least one of amino, ether or alkoxy group and phenyl or group containing aluminium base in minor structure.
5. the tackifying system of liquid as claimed in claim 4 and supercritical carbon dioxide, which is characterized in that the tackifier are
Siloxane-Oxyalkylene Copolymers, structural formula are as follows：
6. the tackifying system of liquid as described in claim 1 and supercritical carbon dioxide, which is characterized in that the surface-active
Agent is oil-soluble nonionic surfactant.
7. the tackifying system of liquid as described in claim 1 and supercritical carbon dioxide, which is characterized in that the organic solvent
For the alcohol, ester, ketone, one or more in aldehydes with chain alkyl structure.
8. the tackifying system of liquid as claimed in claim 7 and supercritical carbon dioxide, which is characterized in that the organic solvent
For the C of backbone18H38OH、C12H26COOC2H6、C18H38CHO、C12H26COC2H6In one kind.
9. the tackifying system of liquid as described in claim 1 and supercritical carbon dioxide, which is characterized in that the drag reducer is
Nano-composite fiber or montmorillonite, graphite, carbon nano tube modified fiber, nano-composite fiber end face 60-100nm, length 0.6-
1cm；30-100 μm of modified fibre end face, length 0.5-1cm, fibre-forming polymer molecular weight are 20000-100000.
10. the tackifying system of liquid as described in any one of claims 1-9 and supercritical carbon dioxide, which is characterized in that
The tackifying system, which is added in liquid or supercritical carbon dioxide, forms fracturing fluid system, the quality of each component in fracturing fluid system
Percentage is as follows：Tackifier 0.5-6%, surfactant 0.5-3%, organic solvent 0.5-5%, drag reducer 0.05-0.2%,
Remaining is liquid or supercritical carbon dioxide.
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| CN109439309A (en) * | 2018-11-28 | 2019-03-08 | 中国华能集团有限公司 | A kind of CO2Fracturing fluid thickener and preparation method thereof |
| CN110331972A (en) * | 2019-06-26 | 2019-10-15 | 中国石油集团渤海钻探工程有限公司 | Low pressure densification gas reservoir liquid CO2And CO2Foam system mixing fracturing technology |
| CN110862543A (en) * | 2019-12-03 | 2020-03-06 | 中国石油大学(华东) | Preparation method of hyperbranched hydrogen-containing siloxane supercritical carbon dioxide thickener |
| CN110862541A (en) * | 2019-12-04 | 2020-03-06 | 中国石油大学(华东) | Preparation method of acrylate/siloxane polymer supercritical carbon dioxide thickener |
| CN111019627A (en) * | 2019-12-17 | 2020-04-17 | 陕西延长石油(集团)有限责任公司研究院 | Drag reducer and preparation method and application thereof |
| CN112111033A (en) * | 2019-06-21 | 2020-12-22 | 中国石油天然气集团有限公司 | Carbon dioxide viscosity-increasing and fluid loss-reducing copolymer and preparation method and application thereof |
| CN112679663A (en) * | 2020-12-14 | 2021-04-20 | 中国石油大学(华东) | Preparation method and application of supercritical carbon dioxide thickening agent |
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|---|---|---|---|---|
| CN109439309A (en) * | 2018-11-28 | 2019-03-08 | 中国华能集团有限公司 | A kind of CO2Fracturing fluid thickener and preparation method thereof |
| CN109439309B (en) * | 2018-11-28 | 2021-04-20 | 中国华能集团有限公司 | CO (carbon monoxide)2Fracturing fluid thickening agent and preparation method thereof |
| CN112111033A (en) * | 2019-06-21 | 2020-12-22 | 中国石油天然气集团有限公司 | Carbon dioxide viscosity-increasing and fluid loss-reducing copolymer and preparation method and application thereof |
| CN112111033B (en) * | 2019-06-21 | 2022-08-05 | 中国石油天然气集团有限公司 | Carbon dioxide viscosity-increasing and fluid loss-reducing copolymer and preparation method and application thereof |
| CN110331972A (en) * | 2019-06-26 | 2019-10-15 | 中国石油集团渤海钻探工程有限公司 | Low pressure densification gas reservoir liquid CO2And CO2Foam system mixing fracturing technology |
| CN110862543A (en) * | 2019-12-03 | 2020-03-06 | 中国石油大学(华东) | Preparation method of hyperbranched hydrogen-containing siloxane supercritical carbon dioxide thickener |
| CN110862543B (en) * | 2019-12-03 | 2021-11-09 | 中国石油大学(华东) | Preparation method of hyperbranched hydrogen-containing siloxane supercritical carbon dioxide thickener |
| CN110862541A (en) * | 2019-12-04 | 2020-03-06 | 中国石油大学(华东) | Preparation method of acrylate/siloxane polymer supercritical carbon dioxide thickener |
| CN110862541B (en) * | 2019-12-04 | 2021-07-16 | 中国石油大学(华东) | Preparation method of acrylate/siloxane polymer supercritical carbon dioxide thickener |
| CN111019627A (en) * | 2019-12-17 | 2020-04-17 | 陕西延长石油(集团)有限责任公司研究院 | Drag reducer and preparation method and application thereof |
| CN111019627B (en) * | 2019-12-17 | 2021-11-26 | 陕西延长石油(集团)有限责任公司研究院 | Drag reducer and preparation method and application thereof |
| CN112679663A (en) * | 2020-12-14 | 2021-04-20 | 中国石油大学(华东) | Preparation method and application of supercritical carbon dioxide thickening agent |
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