CN105968258A - Clean and environmentally friendly composite polymer for fracturing fluid and preparing method thereof - Google Patents
Clean and environmentally friendly composite polymer for fracturing fluid and preparing method thereof Download PDFInfo
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- CN105968258A CN105968258A CN201610369396.6A CN201610369396A CN105968258A CN 105968258 A CN105968258 A CN 105968258A CN 201610369396 A CN201610369396 A CN 201610369396A CN 105968258 A CN105968258 A CN 105968258A
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Abstract
The invention belongs to the technical field of new materials, and particularly relates to an environmentally friendly composite polymer for fracturing fluid special for salt-tolerant anti-shearing dense rock stratum and shale gas (oil) stratum development and a preparing method thereof. The polymer fracturing fluid is used for fracturing injection stimulation of dense rock stratum and shale gas stratum. The macromolecular entanglement effect of the polymer can be effectively reduced by means of a surface active agent, high temperature resistance, salt tolerance and shearing resistance of the fracturing fluid are realized, macromolecular entanglement is avoided, residues are reduced, and residues can be degraded into micromolecular nitrogen compounds after flowback. The composite polymer fracturing fluid has high temperature resistance, salt tolerance and shearing resistance, can avoid macromolecular chain entanglement and residues and can serve as a thickening agent to be used for shale bed fracturing.
Description
Technical field
The invention belongs to technical field of novel materials, particularly relate to a kind of anti-shearing tight stratum of salt tolerant and shale gas (oily)
Special fracturing fluid environment-friendly type composition polymer and preparation method are developed in stratum.
Background technology
Tight stratum and shale gas engineering pressure break utilize pressure to be pressed off on stratum exactly, form crack, and will with proppant
It supports, to reduce the volume increase of a kind of necessity of hydrocarbon fluids flow resistance, well stimulation.Suspended prop therein
Thick substances is also called fracturing fluid.
Tight stratum and shale gas engineering pressure break are at the early-stage in China, particularly shale gas engineering pressure break China 2011
Just carrying out exploratory exploitation, domestic fracturing fluid used contributes to the oil field pressure increased during oil exploitation used by oil and gas production
Split liquid.Have not been reported of the special fracturing fluid of shale gas engineering pressure break, particularly environment-friendly type.
Special fracturing fluid is developed on tight stratum and shale gas (oily) stratum and oil field compression fracture polymer is all a kind of water-soluble
Property polymer, can make water thickening, but requires that polymer has viscosity under certain condition, but after breaking gel without residue or have
Extremely low insoluble matter, is beneficial to the row of returning, and is finally reached suspended prop and enters behind stratum, completely the row of returning do not injure stratum but also
The material that after degraded, the little molecule of formation is nitrogenous can do Fertilizer application.
So fracturing fluid is related to the success or failure of pressure break for the serviceability of tight stratum and rammell.The most the most frequently used
Oil field a lot of by fracturing fluid polymer kind, natural polysaccharide and derivant thereof and the big class of synthetic polymer two can be divided into, its
Middle guanidine glue and derivant thereof most widely used.But its applied defect is that the fracturing liquid rubber-breaking of use guanidine glue and derivant thereof is the completeest
Entirely, and residue can be stayed in crack after breaking gel, and the polymer remained in crack will seriously reduce oozing of proppant pack
Thoroughly rate, thus injure stratum, causes fracturing effect to be deteriorated, and prop-carrying capacity weakens, the most also bring the underground being difficult to overcome and
The pollution on ground, thus cause government of the countries concerned and environmentalist and the opposition of tissue and protest！And guanidine glue price is floated
Dynamic very big, your time reach 18 just in case tons.Pressure break especially for tight stratum and rammell does not also have successful example.
Single utilization synthetic polymer is the most much shown in, such as fracturing fluid: number of patent application 200410079063 is high poly-
Thing fracturing fluid and compound method thereof.The scene such as polyacrylamide and chromium acetate, acetic acid zirconium, acetic acid, formic acid, chlorine dioxide is utilized to join
System, for oil field compression fracture.Its shortcoming is, preparation complexity, chromium ion makees cross-linking agent and can pollute subsoil water, in being put into
State's water environment pollution thing blacklist, general organic boron, organic zirconium, organic titanium crosslinking on oil field.
Substantial amounts of document report oil field compression fracture needs to add cross-linking agent and improves the viscosity of fracturing fluid, strengthens its prop-carrying capacity,
Therefore use cost increases.It addition, synthetic polymer product is not easy to preparation, stores and pump, it is unfavorable for popularization and application at the scene.
Although the fracturing fluid prepared can be by mixing brokenly glue with formation hydrocarbon or water, but this process required time is longer, most important
Be that environment is caused severe contamination by the fracturing fluid after the row of returning.
After oil field compression fracture, mostly use the quickly row's of returning technique, after pressing crack construction terminates, open flow immediately at present, subtract as far as possible
Few fracturing fluid on stratum in instantaneous time, reduce the injury to stratum.
Domestic fracturing fluid special to tight stratum, oil field has been reported, such as number of patent application 200410043878.X deep layer
Compact gas pool fracturing liquid, principal polymeric is: natural guanidine glue and derivant thereof.
Tight stratum and shale gas engineering fracturing fluid that foreign applications is relatively more are drag reduction water fracturing fluids, drag reduction water fracturing fluid
Refer in clear water, add the additive such as a certain amount of proppant and minimal amount of drag reducer, surfactant, clay stabilizer
A kind of fracturing fluid, be called again slippery water fracturing fluid.Drag reduction water fracturing fluid is initially by Halliburton, Schlumberger
With Messina company for a kind of New Fracturing Fluid of the Barnett shale area joint development of east, Texas.1997
Year, Mitchell energy company implements drag reduction hydraulic pressure first in Barnett area and splits, employs 3029m3 water, 90t sand, its
Shale gas ultimate recovery improves 20%, and the relatively large fracturing of pressure break expense decreases 65%.Drag reduction water fracturing fluid exists
The successful Application in Barnett shale area quickly expands to U.S. Haynesville, Marcellus, Woodruff and
The areas such as Fayetteville.In recent years, drag reduction hydraulic pressure splits fast development, and drag reduction water fracturing fluid system obtains at north America region
Significant economic benefit and instead of traditional gelatinous fracturing fluid and become most popular fracturing fluid, by 2004 years
The usage amount Yi Zhan U.S. fracturing fluid of drag reduction water fracturing fluid uses more than the 30% of total amount.
Tight stratum and shale gas engineering pressure break are higher because of the special performance requirement to fracturing fluid of its geologic structure, it is desirable to
The easily row of returning, residue requires higher, particularly requires to impact the environment after the row of returning, and common oil field fracturing fluid is wanted
Ask lower.Both at home and abroad shale gas is developed special fracturing fluid not report, so environment-friendly type clean fracturing fluid and application thereof
Technology becomes the significant technology issues anxious to be resolved of current pressure break circle common concern.
Summary of the invention
It is an object of the invention to, overcome the deficiencies in the prior art, it is provided that a kind of anti-shearing tight stratum of salt tolerant and page
Special fracturing fluid environment-friendly type composition polymer and preparation method are developed in rock gas (oily) stratum.The present invention is directed to tight stratum and page
Rock gas (oily) stratum is developed, and have studied a kind of salt tolerant shear-stable environment-friendly type composition polymer, overcomes at high salt and high-pressure section
Under part, common natural polysaccharide and derivant thereof are prone to the decline of thinning suspending power with synthetic polymer and overcome in synthesis poly-
Compound is difficult to the shortcoming of preparation, and has the advantage that cheap consumption is few.The present invention also provides for its synthesis preparation method.
For solving above-mentioned technical problem, the technical scheme is that
The preparation method of dimethylhydroxylamine ylmethyl methene polyacrylamide, comprises the steps:
A: synthesize poly-methylolation methene acrylamide
In monomer reaction still, it is sequentially added into N, N methylene-bisacrylamide (AAM), acrylamide and alkali polymerization obtain
Methene polyacrylamide (MPAM)；
B, hydroxymethylation
Take the prepared MPAM of step A and formaldehyde according to mol ratio 1:(0.01-1) reaction, reaction temperature controls at 40-70
DEG C, the response time is 20-60min, is cooled to room temperature, airtight placement 2h, prepares N-(dimethylamino methyl) methene polyacrylamide
Amine；
C, Mannich reaction
Take N-(dimethylamino methyl) methene polyacrylamide and polyethylene polyamine that step B prepares, 70 DEG C of reactions
2h, cooling obtains dimethylhydroxylamine ylmethyl methene polyacrylamide (MAMPAM), by mol, described polyethylene polyamine after placing 2h
0.3-1% for N-(dimethylamino methyl) methene polyacrylamide.
In described step A: by quality ratio, take AAM, acrylamide (AM) and pure water according to (0.1-1): 1:(5-
15), after fully dissolving, add the NaOH of in terms of AAM mole 10%, at 60 DEG C, add redox system initiator and azo
Class initiator carries out multistage initiation, stirring reaction, disappears to ammonia taste, till being neutrality with pH reagent paper survey steam, thus make
MPAM。
Described redox system initiator is the potassium peroxydisulfate of mass ratio 1:1 or Ammonium persulfate. and sodium sulfite, institute
Stating azo-initiator is azo dibutyronitrile.
Described redox system initiator, azo-initiator are 1:1:5 with the mol ratio of AAM.
Dimethylhydroxylamine ylmethyl methene polyacrylamide prepared by above-mentioned preparation method.
Clean and environment-friendly fracturing fluid composition polymer, by dimethylhydroxylamine ylmethyl methene polyacrylamide and surface activity
Agent is compounding to be prepared, and surfactant used is imidazoline modified linetype polyurethanes compound, mass concentration be l0～
The mass fraction of 50% dimethylhydroxylamine ylmethyl methene polyacrylamide and surfactant is than being (0.1-0.9): (0.9-
0.1)。
Mass concentration is the dimethylhydroxylamine ylmethyl methene polyacrylamide MAMPAM of l0～50% and surfactant is multiple
Prepare to obtain composition polymer.
Surfactant used is: imidazoline modified linetype polyurethanes compound, and its chemical general formula is:
Wherein:
R1Represent the fatty acyl group corresponding to the fatty acid containing 4 to 28 carbon atoms or fatty acid ester；
R2Represent polyethylene polyamine base or the many amidos of ethoxy；
R3For diisocyanate and the residue of hydroxyl reaction；
R4The initiator polyhydric alcohol used in synthesizing for polyethers or polyamine initiator residue；
A, B are the oxyalkylene group of 2～4 carbon atoms, and the oxyalkylene group of 2～4 carbon atoms is by addition polymerization or other polymerizations
Method prepares with R4-Am-BnFor formula by polyethylene oxide base, polypropylene oxide base, the polyethers of polyoxybutylene base synthesis, institute
State oxyalkylene group and derive from oxirane, expoxy propane, epoxy butane or by epoxychloropropane；During synthesizing polyether right
The polymerization methods of oxyalkylene group and polyethylene oxide base, polypropylene oxide base, polyoxybutylene base is the most shared in polyethers to be divided
Number does not make any restriction.A and B can be the same or different.
M represents the positive integer of 10 to 90, and n represents the positive integer of 10 to 460, and x represents the positive integer of 0 to 20.
Preferably, oxyalkylene group A derives from expoxy propane, and oxyalkylene group B derives from oxirane；In the polyethers of synthesis
Polypropylene oxide base molecular weight is generally 1000～5000, wherein polyethylene oxide base account for whole pfpe molecule amount 10%～
About 80%.Generally preferably polypropylene oxide base molecular weight is about 3000, and polyethylene oxide base accounts for whole pfpe molecule amount
The polyethers of 20%.
The surfactant of the present invention is existing patented product, patent publication No. CN 101012300A.
The preparation method of clean and environment-friendly fracturing fluid composition polymer, dimethylhydroxylamine ylmethyl methene polyacrylamide and
Surfactant mixing after be dried, through pelletize, be dried, pulverize, pack after obtain composition polymer.
Special clean and environment-friendly fracturing fluid is developed in the anti-shearing tight stratum of salt tolerant, according to mass fraction by following each component group
Become: clean and environment-friendly fracturing fluid composition polymer 1 part, cross-linking agent 0.01-0.1 part, clay stabilizer 0.01-0.1 part, part
Oxide 0.001-0.05 part, water 90-99 part are prepared from.Described partial oxide is Ammonium persulfate., and cross-linking agent is organic boron
Cross-linking agent, clay stabilizer is potassium chloride, wherein clean and environment-friendly fracturing fluid composition polymer, Ammonium persulfate., potassium chloride and
Water first mixes, and is subsequently adding organic borate cross-linker, and special clean environment firendly is developed in the anti-shearing tight stratum of salt tolerant obtaining the present invention
Type fracturing fluid.
The invention belongs to the polymer fracturing fluid of a kind of synthetic, for tight stratum and the Fracturing Technology of rammell,
Between 1 0000000 between the molecular weight 500000 and 1 of the polymer fracturing fluid of a kind of synthetic.Due to height
The macromole winding effect that polymers is intrinsic, so water soluble polymer all has the effect of shear thickening, this is fracturing fluid institute
Unallowed, the present invention can be effectively reduced the macromole winding effect of polymer with a kind of surfactant, makes fracturing fluid have
There is a good heatproof, anti-salt and anti-shearing and avoid macromole to be wound around and reduce residue, and after the row of returning, it is degraded into little molecule
Nitrogen compound.Described composition polymer fracturing fluid has a good heatproof, anti-salt and anti-shearing and avoid macromolecular chain group
Residual, can be as thickening agent for rammell pressure break.
Special clean and environment-friendly fracturing fluid composition polymer is developed in the anti-shearing tight stratum of salt tolerant (shale), mainly
Molecular formula is as follows:
In formula, x and y, can be identical, it is also possible to differ；The numerical value of x and y is from 2-400 ten thousand.With the increase of carbon number, altogether
The elastic increase of copolymer solution.
The invention has the beneficial effects as follows: the dimethylhydroxylamine ylmethyl methene polyacrylamide of the present invention is multiple with surfactant
Forming composition polymer after conjunction, this clean and environment-friendly fracturing fluid composition polymer environmental friendliness, salt tolerant is anti-shearing.The present invention uses
Surfactant the macromole winding effect of polymer can be made to reduce, make the active force between functional group strengthen so that pressure
Splitting liquid system shear stability to strengthen, under high salt, intensity does not reduces, and frictional resistance is little, easy to use, the most superior character of the row of returning.Special
Do not apply to the pressure break on shale gas (oily) stratum under tight stratum and condition of high voltage.After pressure break produce persistent period length, due to
Described polymer is nitrogenous material, can form the micromolecular compound of nitrogen after degraded, can make fertilizer, and environment protecting is dashed forward
Go out, and excellent cost performance.
The technique that the present invention uses is different and is easier to realize extemporaneous preparation and is more prone to, and make use of surfactant
Compounded technology.On the premise of environment-friendly type, performance is made to increase considerably, the interpolation by surfactant of our product, fall
This agent aqueous solution absorption in the earth formation low, is beneficial to the most quickly row of returning, and reduces the pollution to stratum and secondary injury.
Dimethylhydroxylamine ylmethyl methene polyacrylamide and the surfactant clean and environment-friendly pressure through being compounded to form
Split liquid composition polymer and can have both advantages concurrently, fabulous through both tests compatibility, it is particularly well-suited to tight stratum and height
The pressure break on shale gas (oily) stratum under press strip part.
Detailed description of the invention
Embodiment 1
The preparation method of dimethylhydroxylamine ylmethyl methene polyacrylamide, comprises the steps:
A: synthesize poly-methylolation methene acrylamide: be sequentially added into N, N methylene bisacrylamide in monomer reaction still
Amide (AAM), acrylamide and alkali polymerization obtain methene polyacrylamide (MPAM)；AAM, acrylamide (AM) and pure water quality
Amount ratio is 0.1:1:5, after fully dissolving, adds the NaOH of in terms of AAM mole 10%, adds redox system and draw at 60 DEG C
Sending out agent and azo-initiator carries out multistage initiation, stirring reaction, disappear to ammonia taste, surveying steam with pH reagent paper is that neutrality is
Stop, thus the MPAM made.Described redox system initiator is the potassium peroxydisulfate of mass ratio 1:1 or Ammonium persulfate. and sulfurous acid
Hydrogen sodium, azo-initiator is azo dibutyronitrile, and redox system initiator, azo-initiator with the mol ratio of AAM are
1:1:5。
B, hydroxymethylation: take the prepared MPAM of step A and formaldehyde reacts according to mol ratio 1:0.02, reaction temperature control
System is at 40 DEG C, and the response time is 30min, is cooled to room temperature, airtight placement 2h, prepares N-(dimethylamino methyl) methene poly-third
Acrylamide；
C, Mannich reaction: N-(dimethylamino methyl) the methene polyacrylamide taking step B prepared is many with many ethylene
Amine, reacts 2h at 70 DEG C, cools down and obtains dimethylhydroxylamine ylmethyl methene polyacrylamide (MAMPAM) after placing 2h, by mol,
Described polyethylene polyamine is the 0.3% of N-(dimethylamino methyl) methene polyacrylamide.
The dimethylhydroxylamine ylmethyl methene polyacrylamide prepared according to above-mentioned preparation method.
Embodiment 2
The preparation method of dimethylhydroxylamine ylmethyl methene polyacrylamide, comprises the steps:
A: synthesize poly-methylolation methene acrylamide: be sequentially added into N, N methylene bisacrylamide in monomer reaction still
Amide (AAM), acrylamide and alkali polymerization obtain methene polyacrylamide (MPAM)；AAM, acrylamide (AM) and pure water quality
Amount ratio is 1): 1:15, after fully dissolving, add the NaOH of in terms of AAM mole 10%, at 60 DEG C, add redox system draw
Sending out agent and azo-initiator carries out multistage initiation, stirring reaction, disappear to ammonia taste, surveying steam with pH reagent paper is that neutrality is
Stop, thus the MPAM made.Described redox system initiator is the potassium peroxydisulfate of mass ratio 1:1 or Ammonium persulfate. and sulfurous acid
Hydrogen sodium, azo-initiator is azo dibutyronitrile, and redox system initiator, azo-initiator with the mol ratio of AAM are
1:1:5。
B, hydroxymethylation: taking the prepared MPAM of step A and formaldehyde reacts according to mol ratio 1:1, reaction temperature controls
At 70 DEG C, the response time is 60min, is cooled to room temperature, airtight placement 2h, prepares N-(dimethylamino methyl) methene polypropylene
Amide；
C, Mannich reaction: N-(dimethylamino methyl) the methene polyacrylamide taking step B prepared is many with many ethylene
Amine, reacts 2h at 70 DEG C, cools down and obtains dimethylhydroxylamine ylmethyl methene polyacrylamide (MAMPAM) after placing 2h, by mol,
Described polyethylene polyamine is the 1% of N-(dimethylamino methyl) methene polyacrylamide.
The dimethylhydroxylamine ylmethyl methene polyacrylamide prepared according to above-mentioned preparation method.
Embodiment 3
The preparation method of dimethylhydroxylamine ylmethyl methene polyacrylamide, comprises the steps:
A: synthesize poly-methylolation methene acrylamide: be sequentially added into N, N methylene bisacrylamide in monomer reaction still
Amide (AAM), acrylamide and alkali polymerization obtain methene polyacrylamide (MPAM)；AAM, acrylamide (AM) and pure water quality
Amount ratio is 0.5:1:10, after fully dissolving, adds the NaOH of in terms of AAM mole 10%, adds redox system at 60 DEG C
Initiator and azo-initiator carry out multistage initiation, stirring reaction, disappear to ammonia taste, and surveying steam with pH reagent paper is that neutrality is
Stop, thus the MPAM made.Described redox system initiator is the potassium peroxydisulfate of mass ratio 1:1 or Ammonium persulfate. and sulfurous acid
Hydrogen sodium, azo-initiator is azo dibutyronitrile, and redox system initiator, azo-initiator with the mol ratio of AAM are
1:1:5。
B, hydroxymethylation: take the prepared MPAM of step A and formaldehyde reacts according to mol ratio 1:0.5, reaction temperature control
System is at 60 DEG C, and the response time is 40min, is cooled to room temperature, airtight placement 2h, prepares N-(dimethylamino methyl) methene poly-third
Acrylamide；
C, Mannich reaction: N-(dimethylamino methyl) the methene polyacrylamide taking step B prepared is many with many ethylene
Amine, reacts 2h at 70 DEG C, cools down and obtains dimethylhydroxylamine ylmethyl methene polyacrylamide (MAMPAM) after placing 2h, by mol,
Described polyethylene polyamine is the 0.7% of N-(dimethylamino methyl) methene polyacrylamide.
The dimethylhydroxylamine ylmethyl methene polyacrylamide prepared according to above-mentioned preparation method.
Embodiment 4
Clean and environment-friendly fracturing fluid composition polymer, with the dimethylhydroxylamine ylmethyl methene polypropylene of embodiment 1 preparation
Amide and surfactant compound prepare, and surfactant used is imidazoline modified linetype polyurethanes compound, matter
The amount concentration ratio that is the dimethylhydroxylamine ylmethyl methene polyacrylamide of l0% and the mass fraction of surfactant is for 0.1:0.9.
The preparation method of clean and environment-friendly fracturing fluid composition polymer: dimethylhydroxylamine ylmethyl methene polyacrylamide and
Surfactant mixing after be dried, through pelletize, be dried, pulverize, pack after obtain composition polymer.
Embodiment 5
Clean and environment-friendly fracturing fluid composition polymer, with the dimethylhydroxylamine ylmethyl methene polypropylene of embodiment 2 preparation
Amide and surfactant compound prepare, and surfactant used is imidazoline modified linetype polyurethanes compound, matter
The amount concentration ratio that is the dimethylhydroxylamine ylmethyl methene polyacrylamide of 50% and the mass fraction of surfactant is for 0.9:0.1.
The preparation method of clean and environment-friendly fracturing fluid composition polymer: dimethylhydroxylamine ylmethyl methene polyacrylamide and
Surfactant mixing after be dried, through pelletize, be dried, pulverize, pack after obtain composition polymer.
Embodiment 6
Clean and environment-friendly fracturing fluid composition polymer, with the dimethylhydroxylamine ylmethyl methene polypropylene of embodiment 3 preparation
Amide and surfactant compound prepare, and surfactant used is imidazoline modified linetype polyurethanes compound, matter
The amount concentration ratio that is the dimethylhydroxylamine ylmethyl methene polyacrylamide of 30% and the mass fraction of surfactant is for 0.5:0.4.
The preparation method of clean and environment-friendly fracturing fluid composition polymer: dimethylhydroxylamine ylmethyl methene polyacrylamide and
Surfactant mixing after be dried, through pelletize, be dried, pulverize, pack after obtain composition polymer.
Embodiment 7
Special clean and environment-friendly fracturing fluid is developed in the anti-shearing tight stratum of salt tolerant, according to mass fraction by following each component group
Become: the clean and environment-friendly fracturing fluid composition polymer 1 part of embodiment 4 preparation, cross-linking agent 0.01 part, clay stabilizer 0.01
Part, partial oxide 0.001 part, 90 parts of water are prepared from, and described partial oxide is Ammonium persulfate., and cross-linking agent is that organic boron is handed over
Connection agent, clay stabilizer is potassium chloride, wherein clean and environment-friendly fracturing fluid composition polymer, Ammonium persulfate., potassium chloride and water
First mixing, be subsequently adding organic borate cross-linker, special clean and environment-friendly is developed in the anti-shearing tight stratum of salt tolerant obtaining the present invention
Fracturing fluid.
Embodiment 7
Special clean and environment-friendly fracturing fluid is developed in the anti-shearing tight stratum of salt tolerant, according to mass fraction by following each component group
Become: embodiment 5 preparation clean and environment-friendly fracturing fluid composition polymer 1 part, cross-linking agent 0.1 part, clay stabilizer 0.1 part,
Partial oxide 0.05 part, 99 parts of water are prepared from, and described partial oxide is Ammonium persulfate., and cross-linking agent is organic boron crosslinking
Agent, clay stabilizer is potassium chloride, and wherein clean and environment-friendly fracturing fluid composition polymer, Ammonium persulfate., potassium chloride and water are first
Mixing, is subsequently adding organic borate cross-linker, and special clean and environment-friendly pressure is developed in the anti-shearing tight stratum of salt tolerant obtaining the present invention
Split liquid.
Embodiment 7
Special clean and environment-friendly fracturing fluid is developed in the anti-shearing tight stratum of salt tolerant, according to mass fraction by following each component group
Become: the clean and environment-friendly fracturing fluid composition polymer 1 part of embodiment 6 preparation, cross-linking agent 0.05 part, clay stabilizer 0.05
Part, partial oxide 0.02 part, 95 parts of water are prepared from, and described partial oxide is Ammonium persulfate., and cross-linking agent is that organic boron is handed over
Connection agent, clay stabilizer is potassium chloride, wherein clean and environment-friendly fracturing fluid composition polymer, Ammonium persulfate., potassium chloride and water
First mixing, be subsequently adding organic borate cross-linker, special clean and environment-friendly is developed in the anti-shearing tight stratum of salt tolerant obtaining the present invention
Fracturing fluid.
Product properties of the present invention test and correction data:
1) viscosity experiment
Viscosity is the difference of the leading indicator of this agent, first experimental viscosity and other products.
Table 1 product of the present invention clean and environment-friendly fracturing fluid contrasts with the product viscosity of commercially available better performances
2) salt tolerance experiment
Owing to stratum media is salt environment, in use, again because the intrusion of the water containing high salinity makes thickening
There is the impact of salt in the environment that uses of agent.Due to salting out, the viscosity that most polymers causes due to molecule winding effect,
In saline, reduce winding power, and lose viscosity.So, polymer salt tolerant is also important indicator.
Table 2 product of the present invention clean and environment-friendly fracturing fluid contrasts with the product salt resistance ability of commercially available better performances
3) the aqueous solution resting period
The aqueous solution of almost all of water-soluble polymer all can be sent out by bacterial corrosion in the natural environment of proper temperature
Ferment, loses viscosity, such as, polyacrylamide conventional on market, polyacrylic acid, and polysaccharide biopolymer, such as melon
Glue and derivant, starch and derivant, polysaccharide Biological water soluble polymer, it is widely used as the thickening agent of fracturing fluid,
In this kind of thickening agent containing a large amount of saprophytic bacterias, the microorganism such as mycete, yeast.Environment especially dosing temperature is conducive to these thin
The breeding of bacterium.Therefore, the polysaccharide Biological water dissolubility polymer solution being made into is the most putrid and deteriorated, causes fracturing fluid do not cross-link or hand over
Join insufficient, it is impossible to for pressing crack construction.
In Africa (such as, middle oil Oilfield of Sudan) mean temperature under the conditions of 30 DEG C, almost all of water-soluble polymeric
Thing just lost viscosity within 24 hours.
Happiness oxygen mushroom yeast, mycete, saprophytic bacteria and the anaerobism mushroom sulfate reducting bacteria distributed pole in oil field are wide.Antibacterial
Breeding with binary fission, colony grows with exponential rate.The antibacterial injury to polysaccharide Biological water soluble polymer, mainly
The galactomannan molecule making polysaccharide Biological water soluble polymer issues raw hydrolysis in the effect of enzyme, causes glycosidic bond to break
Split, molecular chain degradation.As degradation reaction is continuously carried out, galactose and mannose finally can be generated.Polysaccharide after degraded
Biological water soluble polymer loses thickening capabilities.
After the reason that specify that polysaccharide Biological water dissolubility depolymerization, on the premise of not affecting viscosity, significantly carry
The stabilization time of the solution viscosity of high water-soluble polymer.
Product of the present invention has been viscosity stability contrast experiment with the similar products of commercially available better performances, and experimental result is shown in Table
3。
Table 3 product of the present invention clean and environment-friendly fracturing fluid contrasts with the product water solution viscosity reduction rate of commercially available better performances
4) cross-linked gel intensity
Table 4 product of the present invention clean and environment-friendly fracturing fluid and the product cross-linked gel intensity contrast of commercially available better performances
5) water insoluble matter content
In fracturing process, the row of returning is thorough, and residue is the main cause improving in-place permeability less, so, product water is insoluble
Thing content is low, and the row of returning is thorough, and residue is the lowest, and the injury to stratum is the least.The water insoluble matter content of product of the present invention can control
Within 8%, residue controls within 600mg/L.
The product water insoluble matter of table 5 product of the present invention clean and environment-friendly fracturing fluid and commercially available better performances and broken glue residue
Contrast
| Sample ID | Water-insoluble (%) | Broken glue residue (mg/L) |
| The embodiment of the present invention 5 | 5.2 | 270 |
| The embodiment of the present invention 6 | 5.6 | 273 |
| The embodiment of the present invention 7 | 5.0 | 275 |
| Polyacrylamide | 6.2 | 350 |
| Commercially available hydroxypropyl guar | 10.2 | 550 |
1) the Shengli Oil Field inspection center that this invention product clean and environment-friendly fracturing fluid has been authorized by Department of Qulity Supervision of Shandong Province
Inspection, indices can reach or exceed industry standard
2) this invention product has studied intensively the inspection of institute by Karamay, Xinjiang, and indices can reach or exceed industry mark
Accurate
3) this invention product fracturing fluid using effect is shown in Table 6
Table 6 product of the present invention clean and environment-friendly fracturing fluid and commercially available similar products return row's Data Comparison
Claims (9)
1. the preparation method of dimethylhydroxylamine ylmethyl methene polyacrylamide, it is characterised in that: comprise the steps:
A: synthesize poly-methylolation methene acrylamide
In monomer reaction still, it is sequentially added into N, N methylene-bisacrylamide (AAM), acrylamide and alkali polymerization obtains methene
Polyacrylamide (MPAM)；
B, hydroxymethylation
Take the prepared MPAM of step A and formaldehyde according to mol ratio 1:(0.01-1) reaction, prepare N-(dimethylamino methyl) methene
Polyacrylamide；
C, Mannich reaction
N-(dimethylamino methyl) the methene polyacrylamide taking step B prepared mixes with polyethylene polyamine, 70 DEG C of reactions
2h, cooling obtains dimethylhydroxylamine ylmethyl methene polyacrylamide (MAMPAM), by mol, described polyethylene polyamine after placing 2h
0.3-1% for N-(dimethylamino methyl) methene polyacrylamide.
2. the preparation method of dimethylhydroxylamine ylmethyl methene polyacrylamide described in claim 1, it is characterised in that: described step
In A: by quality ratio, take AAM, acrylamide (AM) and pure water according to (0.1-1): 1:(5-15), after fully dissolving, add
The NaOH of in terms of AAM mole 10%, adds redox system initiator at 60 DEG C and azo-initiator carries out multistage drawing
Send out, stirring reaction, disappear to ammonia taste, till being neutrality with pH reagent paper survey steam, thus the MPAM made.
3. the preparation method of dimethylhydroxylamine ylmethyl methene polyacrylamide described in claim 2, it is characterised in that: described oxidation
Reduction system initiator is the potassium peroxydisulfate of mass ratio 1:1 or Ammonium persulfate. and sodium sulfite, and described azo-initiator is
Azo dibutyronitrile.
4. the preparation method of dimethylhydroxylamine ylmethyl methene polyacrylamide described in claim 2, it is characterised in that: described oxidation
Reduction system initiator, azo-initiator are 1:1:5 with the mol ratio of AAM.
5. the preparation method of dimethylhydroxylamine ylmethyl methene polyacrylamide described in claim 1, it is characterised in that: described step
In B: reaction temperature controls at 40-70 DEG C, and the response time is 20-60min, it is cooled to room temperature, airtight placement 2h.
6. the dimethylhydroxylamine ylmethyl methene polyacrylamide prepared according to the preparation method of claim 1-5.
7. clean and environment-friendly fracturing fluid composition polymer, it is characterised in that: with dimethylhydroxylamine ylmethyl methene polyacrylamide
Preparing with surfactant compound, surfactant used is imidazoline modified linetype polyurethanes compound, and quality is dense
Dimethylhydroxylamine ylmethyl methene polyacrylamide and the mass fraction of surfactant ratio that degree is l0～50% are (0.1-
0.9): (0.9-0.1).
The preparation method of clean and environment-friendly fracturing fluid composition polymer the most according to claim 7, it is characterised in that: two
First azanol ylmethyl methene polyacrylamide and surfactant mixing after be dried, through pelletize, be dried, pulverize, pack after obtain
Composition polymer.
9. the anti-shearing tight stratum of salt tolerant develop special clean and environment-friendly fracturing fluid, it is characterised in that: according to mass fraction by under
Row each component form: the composition polymer 1 part of the clean and environment-friendly fracturing fluid described in claim 8, cross-linking agent 0.01-0.1 part,
Clay stabilizer 0.01-0.1 part, partial oxide 0.001-0.05 part, water 90-99 part are prepared from, described partial oxide
Being Ammonium persulfate., cross-linking agent is organic borate cross-linker, and clay stabilizer is potassium chloride, and wherein clean and environment-friendly fracturing fluid is with compound
Polymer, Ammonium persulfate., potassium chloride and water first mix, and are subsequently adding organic borate cross-linker, and the salt tolerant obtaining the present invention is anti-shearing
Special clean and environment-friendly fracturing fluid is developed in tight stratum.
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| CN116063624A (en) * | 2023-01-12 | 2023-05-05 | 东营聚源石油科技有限公司 | Delay tackifying temperature-resistant salt-resistant polymer for oil displacement and preparation method thereof |
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| CN109762102A (en) * | 2018-12-19 | 2019-05-17 | 青岛科凯达橡塑有限公司 | A kind of high resistance to mineralized water, low cohesive energy, with polyacrylamide from antibacterial functions and preparation method thereof |
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| CN116063624A (en) * | 2023-01-12 | 2023-05-05 | 东营聚源石油科技有限公司 | Delay tackifying temperature-resistant salt-resistant polymer for oil displacement and preparation method thereof |
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Application publication date: 20160928 |