CN106939160A - A kind of high mineralization water quality clean fracturing fluid - Google Patents
A kind of high mineralization water quality clean fracturing fluid Download PDFInfo
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- CN106939160A CN106939160A CN201710079291.1A CN201710079291A CN106939160A CN 106939160 A CN106939160 A CN 106939160A CN 201710079291 A CN201710079291 A CN 201710079291A CN 106939160 A CN106939160 A CN 106939160A
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- fracturing fluid
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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
- C09K8/60—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
- C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
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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
- C09K8/60—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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- 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
- C09K8/84—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
- C09K8/887—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
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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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/26—Gel breakers other than bacteria or enzymes
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- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present invention relates to a kind of oil field compression fracture construction clean fracturing fluid, especially a kind of anti-rich calcium and magnesium high-salinity water quality clean fracturing fluid of artificial-synthetic copolymer's class；Polymer includes following components by weight：Thickening agent 0.45 0.65%, cleanup additive 0.30 1.00%, clay stabilizer 0.20 1.00%, crosslinking agent 0.30 0.60%, gel breaker 0.01 0.03% and rich calcium and magnesium concentrated water；The present invention has the following advantages that：1st, thickening agent is ultrafast instant, can complete swelling in 5~10min, it is adaptable to which on-line continuous matches somebody with somebody liquid construction technology；2nd, the system additive is few, can mitigate construction intensity significantly, shortens the engineering time；3rd, the system breaks glue thoroughly, and no residue reduces the injury to stratum；4th, the system is applicable to the high 3800mg/L of Ca2+, Mg2+ content, and salinity matches somebody with somebody liquid water for 20000mg/L's, and the dosage of thickening agent can do corresponding adjustment according to the difference of water-mineralizing degree.
Description
Technical field
The present invention relates to a kind of oil field compression fracture construction clean fracturing fluid, especially a kind of anti-richness of artificial-synthetic copolymer's class
Calcium and magnesium high-salinity water quality clean fracturing fluid.
Background technology
Hydraulic fracturing technology is the major measure for realizing the volume increase of low-permeability oil gas well, and fracturing fluid is to determine Hydro Fracturing Stimulation Treatment
One of key link of success or failure, by the development of decades, has formed a variety of fracturing fluid systems.Current fracturing reform both at home and abroad
Mainly based on the water-based fracturing liquid system by thickening agent of guar gum, there is the deficiency of the following aspects in it：
1st, fracturing fluid system breaks glue residue content height, typically in 500~more than 800mg/L；
2nd, fracturing fluid generally requires the more additives of addition, and stratum can be damaged to a certain extent；
3rd, when metal ions such as Ca2+, the Mg2+ for being higher than normal value several times in liquid water containing concentration, its energy and guar gum
Macromolecule group is acted on, and causes guar gum to occur fully to be swelled or dissolve in water, and occur being layered and sediment.
Above-mentioned factor significantly have impact on fracturing transformation effect, to the injury on stratum also than larger, particularly be used when with liquid
When water salinity is higher, fracturing fluid property can be had a strong impact on, so as to influence the solid-carrying performance of fracturing fluid, pressure break success is in turn resulted in
Rate is reduced.
The content of the invention
The present invention relates to a kind of rich calcium and magnesium high-salinity water quality fracturing fluid system preparation method of artificial-synthetic copolymer's class, with
Solution guanidine gum fracturing fluid dissolves in concentrated water, swelling rate is slow, and rheological property is poor, and water insoluble matter content is high, residue is high,
Additive uses the shortcoming more than species, the following is concrete technical scheme：
The present invention offsets calcium ions and magnesium ions to polymer molecular chain not by introducing extraordinary anticalcium magnesium ion group in the polymer
Good influence, makes polymer molecular chain in aqueous still in extended configuration, rather than rolls up state, keeps high viscosity, by
Increase hydrophilic radical in polymer, improve the water solubility of polymer, reduce water-insoluble and residue content, split with solving guanidine glue laminated
The secondary injury that liquid residue is caused to bottom, under the collective effect of hydrophilic radical and different kinds of ions group, polymer can be in water
In it is quick dissolve viscous, realize and match somebody with somebody online, polymer includes following components by weight：Thickening agent 0.45-0.65%, cleanup additive
0.30- 1.00%, clay stabilizer 0.20-1.00%, crosslinking agent 0.30-0.60%, gel breaker 0.01-0.03% and rich calcium
Magnesium concentrated water.
Wherein, thickening agent is a kind of anticalcium magnesium artificial-synthetic copolymer, is specially that one kind passes through acrylamide, PAA
A kind of hydrophobic associated polymer is obtained with a kind of approach of efficient hydrophobic monomer copolymerization, its structural formula is：
Further, cleanup additive is fluorocarbon surfactant, beet alkali surface activator, OTAC
In one or two kinds of mixtures.
Further, clay stabilizer is a kind of efficient clay stabilizer of novel halogen-free small cation.
Crosslinking agent is surfactant.
Further, gel breaker is the one or more in ammonium persulfate, the sour sodium of excessively stream, potassium peroxydisulfate, hydrogen peroxide.
Wherein, hydrophobic monomer is methylacryoyloxyethyl dimethyl stearyl ammonium bromide, and concrete structure formula is as follows：
Further, hydrophobic associated polymer is by using ammonium persulfate/sodium hydrogensulfite oxidation-reduction trigger system,
Formed using aqueous solution polymerization reaction synthesis, specifically include following steps：
(1) acrylamide is weighed, by distilling water dissolves and carrying out mechanical agitation, water-bath is warming up to reaction temperature；
(2) distilled water is mixed with acrylic acid, and NaOH solution is added under sub-zero water-bath cooling, acrylic acid is neutralized
It is 5~6 to pH value, is transferred in reactor；
(3) N is passed through into reactor2, certain mass hydrophobic monomer methylacryoyloxyethyl dimethyl ten is weighed in beaker
Eight alkyl bromination ammoniums, with distillation water dissolves, after air is drained in question response device, by N2Conduit is pulled out to more than liquid level, is added thin
Aqueous monomer；
(4) ammonium persulfate and sodium hydrogensulfite of certain mass are weighed, with appropriate distillation water dissolves, reaction is then added sequentially to
In device；
(5) after charging is finished, then lead to N2, thing to be polymerized occurs after pole-climbing, stop stirring, a timing is reacted under this polymerization temperature
Between；
(6) blob of viscose is taken out after completion of the reaction, granulation is crushed, micelle is placed in 50 DEG C of vacuum drying ovens and dried 4~6 hours, is taken out
Crushed with pulverizer, obtain polymer.
Wherein, the preparation of hydrophobic monomer specifically includes following steps:
(1) M1g bromo-octadecanes are weighed, are placed in in constant pressure funnel, electric stirring, the 250ml there-necked flasks of thermometer；
(2) it is put into water bath with thermostatic control, temperature is set to 30 DEG C~35 DEG C, opens electric stirring；
(3) M2g methacrylic acid-N are weighed, TMSDMA N dimethylamine base ethyl ester, addition 35~40ml acetone dissolves it, then put
Enter into constant pressure funnel, control drop rate, it is dripped off in 1h；
(4) after adding after material, water-bath is warming up to 40 DEG C~43 DEG C 20~26h of reaction；
(5) after the completion of reacting, it is put into Buchner funnel and starts suction filtration, then rinsed repeatedly 3 times with acetone；
(6) it is 50 DEG C of dry 6h that temperature is set in vacuum drying chamber, obtains white powder product, here is reactional equation
Formula：
Beneficial effect：The present invention has the following advantages that：1st, thickening agent is ultrafast instant, 5~10min can complete swelling,
Match somebody with somebody liquid construction technology suitable for on-line continuous；2nd, the system additive is few, can mitigate construction intensity significantly, shortens the engineering time；
3rd, the system breaks glue thoroughly, and no residue reduces the injury to stratum；4th, the system is applicable to Ca2+, Mg2+ content height
3800mg/L, salinity matches somebody with somebody liquid water for 20000mg/L's, and the dosage of thickening agent can do phase according to the difference of water-mineralizing degree
The adjustment answered.
Brief description of the drawings
Fig. 1 is Inventive polymers infrared spectrum；
Fig. 2 is hydrophobic monomer infrared spectrum of the present invention；
Fig. 3 is hydrophobic monomer nuclear magnetic spectrogram of the present invention.
Embodiment
Embodiment 1
The synthesis of hydrophobic monomer：
(1) M1g bromo-octadecanes are weighed, are placed in in constant pressure funnel, electric stirring, the 250ml there-necked flasks of thermometer；
(2) it is put into water bath with thermostatic control, temperature is set to 30 DEG C, opens electric stirring；
(3) M2g methacrylic acid-N are weighed, TMSDMA N dimethylamine base ethyl ester, addition 35ml acetone dissolves it, is then put into
In constant pressure funnel, drop rate is controlled, it is dripped off in 1h；
(4) after adding after material, water-bath is warming up to 40 DEG C of reaction 20h；
(5) after the completion of reacting, it is put into Buchner funnel and starts suction filtration, then rinsed repeatedly 3 times with acetone；
(6) it is 50 DEG C of dry 6h that temperature is set in vacuum drying chamber, obtains white powder product.
The synthesis of hydrophobic polymer：
(1) acrylamide of certain mass is weighed in beaker, with appropriate distillation water dissolves, four mouthfuls of polymer reactors are transferred to
In, then with a small amount of distillation water washing beaker repeatedly, residual acrylamide is transferred in reactor, mechanical agitation is started, will
Water-bath is warming up to reaction temperature；
(2) a certain amount of distilled water is added in 50ml small beakers, the acrylic acid of certain mass is then weighed in this beaker,
Sub-zero water-bath cooling is lower to add a certain amount of NaOH solution, and it is 5~6 that acrylic acid is neutralized into pH value, is transferred to reaction
In device；
(3) N2 is passed through into reactor, certain mass hydrophobic monomer methylacryoyloxyethyl dimethyl ten is weighed in beaker
Eight alkyl bromination ammoniums, with distillation water dissolves, after air is drained in question response device, N2 conduits, which are pulled out to more than liquid level, (prevents liquid
Bubbling), add hydrophobic monomer；
(4) ammonium persulfate and sodium hydrogensulfite of certain mass are weighed, with appropriate distillation water dissolves, reaction is then added sequentially to
In device；
(5) after charging is finished, then logical a period of time N2, thing to be polymerized occurs after pole-climbing, stops stirring, anti-under this polymerization temperature
Answer certain time；
(6) blob of viscose is taken out after completion of the reaction, granulation is crushed, micelle is placed in 50 DEG C of vacuum drying ovens and dried 4~6 hours, is taken out
Crushed with pulverizer, obtain polymer samples.
The synthesis of fracturing fluid and use：
In 30m329550kg water is added in container, in the case where being stirred with pump circulation or agitator, 150kg cleanup additives,
150kg clay stabilizers, then add 150kg thickening agents, continue cycling through or stir 2 minutes, make liquid mixing abundant, are formed
Solution A 1.
During pressing crack construction, while infusion solution A 1, by crosslinking agent and solution A 1 according to A1:Crosslinking agent=100 liter:
0.5 liter of volume ratio carries out being mixed to form fracturing fluid.
Above fracturing fluid recommend with liquid with water Ca2+, Mg2+ content within 100mg/L, well temperature is 80~100 DEG C
Gas well is used.
Embodiment 2
The synthesis of fracturing fluid and use：
In 30m329535kg water is added in container, in the case where being stirred with pump circulation or agitator, 150kg cleanup additives,
150kg clay stabilizers, then add 165kg thickening agents, continue cycling through or stir 2 minutes, make liquid mixing abundant, are formed
Solution A 2.
During pressing crack construction, while infusion solution A 2, by crosslinking agent and solution A 2 according to A2:Crosslinking agent=100 liter:
0.5 liter of volume ratio carries out being mixed to form fracturing fluid.
Above fracturing fluid recommend with liquid with water Ca2+, Mg2+ content in 500mg/L or so, well temperature is 80~100 DEG C
Gas well is used.
Embodiment 3
The synthesis of fracturing fluid and use：
In 30m329520kg water is added in container, in the case where being stirred with pump circulation or agitator, 150kg cleanup additives,
150kg clay stabilizers, then add 180kg thickening agents, continue cycling through or stir 2 minutes, make liquid mixing abundant, are formed
Solution A 3.
During pressing crack construction, while infusion solution A 3, by crosslinking agent and solution A 3 according to A3:Crosslinking agent=100 liter:
0.5 liter of volume ratio carries out being mixed to form fracturing fluid.
Above fracturing fluid recommend with liquid with water Ca2+, Mg2+ content in 1000~1500mg/L or so, well temperature for 80~
100 DEG C of gas well is used.
Embodiment 4：
The synthesis of fracturing fluid and use：
In 30m329505kg water is added in container, in the case where being stirred with pump circulation or agitator, 150kg cleanup additives,
150kg clay stabilizers, then add 195kg thickening agents, continue cycling through or stir 2 minutes, make liquid mixing abundant, are formed
Solution A 4.
During pressing crack construction, while infusion solution A 4, by crosslinking agent and solution A 4 according to A4:Crosslinking agent=100 liter:
0.5 liter of volume ratio carries out being mixed to form fracturing fluid.
Above fracturing fluid recommend with liquid with water Ca2+, Mg2+ content in 3000~4000mg/L or so, well temperature for 80~
100 DEG C of gas well is used.
The fracturing fluid that the present invention is provided has stronger resistivity to calcium ions and magnesium ions, while dissolving swelling rate soon, can make
Prepared with rich calcium and magnesium concentrated water on-line continuous, operating efficiency is high；Artificial-synthetic copolymer is right without water-insoluble, without residue
Formation damage is low；Additive types are few, simple and convenient with liquid.
Claims (9)
1. a kind of high mineralization water quality clean fracturing fluid, it is characterised in that described fracturing fluid includes thickening agent 0.45- by weight
0.65%th, cleanup additive 0.30-1.00%, clay stabilizer 0.20-1.00%, crosslinking agent 0.30-0.60%, gel breaker 0.01-
0.03% and rich calcium and magnesium concentrated water.
2. a kind of high mineralization water quality clean fracturing fluid according to claim 1, it is characterised in that described thickening agent is one
Anticalcium magnesium artificial-synthetic copolymer is planted, is specially that one kind passes through acrylamide, PAA and a kind of efficient hydrophobic monomer copolymerization
Approach obtain a kind of hydrophobic associated polymer, its structural formula is：
3. a kind of high mineralization water quality clean fracturing fluid according to claim 1, it is characterised in that described cleanup additive is fluorine
One or two kinds of mixtures in carbon surface active agent, beet alkali surface activator, OTAC.
4. a kind of high mineralization water quality clean fracturing fluid according to claim 1, it is characterised in that described clay stabilizer
For a kind of efficient clay stabilizer of novel halogen-free small cation.
5. a kind of high mineralization water quality clean fracturing fluid according to claim 1, it is characterised in that described crosslinking agent is table
Face activating agent.
6. a kind of high mineralization water quality clean fracturing fluid according to claim 1, it is characterised in that described gel breaker was
One or more in the sour sodium of ammonium sulfate, excessively stream, potassium peroxydisulfate, hydrogen peroxide.
7. a kind of high mineralization water quality clean fracturing fluid according to claim 2, it is characterised in that described hydrophobic monomer is
Methylacryoyloxyethyl dimethyl stearyl ammonium bromide, concrete structure formula is as follows：
8. a kind of high mineralization water quality clean fracturing fluid according to claim 2, it is characterised in that described hydrophobic association gathers
Compound is formed by using ammonium persulfate/sodium hydrogensulfite oxidation-reduction trigger system using aqueous solution polymerization reaction synthesis,
Specifically include following steps：
(1) acrylamide is weighed, by distilling water dissolves and carrying out mechanical agitation, water-bath is warming up to reaction temperature；
(2) distilled water is mixed with acrylic acid, and NaOH solution is added under sub-zero water-bath cooling, acrylic acid is neutralized
It is 5~6 to pH value, is transferred in reactor；
(3) N is passed through into reactor2, certain mass hydrophobic monomer methylacryoyloxyethyl dimethyl 18 is weighed in beaker
Alkyl bromination ammonium, with distillation water dissolves, after air is drained in question response device, by N2Conduit is pulled out to more than liquid level, is added hydrophobic
Monomer；
(4) ammonium persulfate and sodium hydrogensulfite of certain mass are weighed, with appropriate distillation water dissolves, reaction is then added sequentially to
In device；
(5) after charging is finished, then lead to N2, thing to be polymerized occurs after pole-climbing, stop stirring, a timing is reacted under this polymerization temperature
Between；
(6) blob of viscose is taken out after completion of the reaction, granulation is crushed, micelle is placed in 50 DEG C of vacuum drying ovens and dried 4~6 hours, is taken out
Crushed with pulverizer, obtain polymer.
9. a kind of high mineralization water quality clean fracturing fluid according to claim 7 or 8, it is characterised in that described hydrophobic list
The preparation of body specifically includes following steps:
(1) M1g bromo-octadecanes are weighed, are placed in in constant pressure funnel, electric stirring, the 250ml there-necked flasks of thermometer；
(2) it is put into water bath with thermostatic control, temperature is set to 30 DEG C~35 DEG C, opens electric stirring；
(3) M2g methacrylic acid-N are weighed, TMSDMA N dimethylamine base ethyl ester, addition 35~40ml acetone dissolves it, then put
Enter into constant pressure funnel, control drop rate, it is dripped off in 1h；
(4) after adding after material, water-bath is warming up to 40 DEG C~43 DEG C 20~26h of reaction；
(5) after the completion of reacting, it is put into Buchner funnel and starts suction filtration, then rinsed repeatedly 3 times with acetone；
(6) it is 50 DEG C of dry 6h that temperature is set in vacuum drying chamber, obtains white powder product.
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| CN201610241769 | 2016-04-19 | ||
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107828404A (en) * | 2017-11-20 | 2018-03-23 | 中国石油天然气股份有限公司 | Fracturing fluid for high-salinity produced water liquid preparation of oil field |
| CN108659810A (en) * | 2018-04-17 | 2018-10-16 | 四川申和新材料科技有限公司 | Elasticity takes sand fracturing fluid and the thickening agent and preparation method thereof for the fracturing fluid |
| CN109536152A (en) * | 2018-10-18 | 2019-03-29 | 中国石油天然气股份有限公司 | gel fracturing fluid system |
| CN114561203A (en) * | 2022-04-11 | 2022-05-31 | 西南石油大学 | High-salinity water-based delayed cross-linking gel fracturing fluid and preparation method thereof |
| CN114686199A (en) * | 2022-04-22 | 2022-07-01 | 大庆华理生物技术股份有限公司 | Composite fracturing fluid system slickwater |
| CN114805678A (en) * | 2022-06-30 | 2022-07-29 | 山东诺尔生物科技有限公司 | Tackifier for drilling fluid and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107828404A (en) * | 2017-11-20 | 2018-03-23 | 中国石油天然气股份有限公司 | Fracturing fluid for high-salinity produced water liquid preparation of oil field |
| CN108659810A (en) * | 2018-04-17 | 2018-10-16 | 四川申和新材料科技有限公司 | Elasticity takes sand fracturing fluid and the thickening agent and preparation method thereof for the fracturing fluid |
| CN109536152A (en) * | 2018-10-18 | 2019-03-29 | 中国石油天然气股份有限公司 | gel fracturing fluid system |
| CN114561203A (en) * | 2022-04-11 | 2022-05-31 | 西南石油大学 | High-salinity water-based delayed cross-linking gel fracturing fluid and preparation method thereof |
| CN114561203B (en) * | 2022-04-11 | 2023-08-29 | 西南石油大学 | High-mineralization water-based delayed crosslinking gel fracturing fluid and preparation method thereof |
| CN114686199A (en) * | 2022-04-22 | 2022-07-01 | 大庆华理生物技术股份有限公司 | Composite fracturing fluid system slickwater |
| CN114805678A (en) * | 2022-06-30 | 2022-07-29 | 山东诺尔生物科技有限公司 | Tackifier for drilling fluid and preparation method thereof |
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