CN107268104A - A kind of hollow PVA fibers and its production and use - Google Patents
A kind of hollow PVA fibers and its production and use Download PDFInfo
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- CN107268104A CN107268104A CN201610213439.1A CN201610213439A CN107268104A CN 107268104 A CN107268104 A CN 107268104A CN 201610213439 A CN201610213439 A CN 201610213439A CN 107268104 A CN107268104 A CN 107268104A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
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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
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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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
- C09K2208/08—Fiber-containing well treatment fluids
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Abstract
A kind of hollow PVA fibers, are 1000~3500 by the degree of polymerization, alcoholysis degree is prepared for 99.0~99.9 (mol) % PVA spinning, and wherein PVA fiber cross-sectionals are hollow structure, 0.1 ~ 100 μm of hollow portion diameter.The present invention is added in oil-gas field fracturing liquid so that fracturing fluid has takes sand function well, beneficial to fracturing fluid recovery (backflow), the usage amount for being difficult to be completely dissolved and being difficult to from other compositions such as the guar gums of shaft bottom discharge can be reduced, so as to mitigate the injury to environment；It is added in oil gas field well cementation agent, the intensity and toughness of well cementing material can be strengthened, leakproof can also be played a part of；It is added in oil-gas field fracturing diverting agent, considers mistake effect with good drop, form one layer of shielding layer at the position for being intended to temporarily block up, fracturing fluid is smoothly turned to；The composition of present invention residual in the environment eventually resolves into nontoxic hydrocarbon, and environment will not be damaged.
Description
Technical field
The present invention relates to PVA fibers, and in particular to a kind of hollow PVA fibers and preparation method thereof and use
On the way.
Background technology
China's Low Permeability Oil/gas stock number is huge, accounts for and has verified more than the 70% of gross reserves, be China not
Come the main potential work area produced in increasing the storage.This kind of petroleum resources have three it is low the characteristics of, that is, it is low to verify rate,
Natural production rate is low, and recovery ratio is low.Practical application shows, in this kind of exploitation of oil-gas field, is badly in need of work(
The good well cementation agent of energy, pressure break diverting agent, and the oil-gas field fracturing for preferably taking sand effect can be played
Liquid, meanwhile, the injury of low environment is also reduced as far as possible.
In recent years, domestic and international researcher is carried out around oil gas field field pressure break, well cementation, temporary plugging technique
Numerous studies.CN200610063700.0A discloses a kind of composite fracturing fluid, and its compounding gelatinizing agent is
0.4~1.0wt% of fracturing fluid quality, metal crosslinking agent is 0.05~0.7wt% of fracturing fluid quality,
0.05~0.5wt% that gel breaker is fracturing fluid quality is aoxidized, remaining is water.CN201410088243.5A
Disclose a kind of instant modified cellulose crosslinking clean fracturing fluid, use component for：FAG-500 types are modified
Two parts, DL-16 types in the parts by weight of cellulose 0.2~0.6, FAZ-1 types thickening initiator 0.1~0.5
The parts by weight of cleanup additive 0.3~0.7, the parts by weight of FAJ-305 types cross-linking regulator 0.5~1.2, FAC-201
0.2~0.7 part of organic zirconium crosslinker of type polarity chelating, NBA-102 types capsule breaker 0.002~0.07
Part, the parts by weight of water 100.CN201510078854.6A discloses a kind of raising fracturing fluid prop-carrying capacity
Fibre-bearing fracturing fluid, the addition of fiber is 0.3~0.8 parts by weight in its fracturing fluid, fiber it is anti-
Tensile strength is 20~300MPa, and real density is 0.98~1.33g/cm3, length is 3~15mm, directly
Footpath be 25~150 μm, the fiber be polypropylene fibre, polyethylene fibre, polyacrylonitrile fibre,
One or more in vinal and polyester fiber.CN201310698113.9A discloses one
Fiber composite diverting agent is planted, its main formula is 55~75 parts of liquid of carrying, diverting agent particle 20~30
Part, temporary stifled 0.5~2 part of composition of fiber, temporarily stifled fiber be vinal, modified polyester fiber,
One or more in polyurethane fiber.Qi Hongke etc. exists《Drilling technique》" the tenacity of fibre of magazine
In utilization of the cement mortar technology in Central Plains oil gas field " article, mention and add fibrous material in cement,
Toughness reinforcing leakproof can be played a part of.Although colleague has done many effort both at home and abroad, so far,
Existing fracturing technique, which still can not be properly arrived at, can both reduce injury of the fracturing fluid to reservoir, and energy
The purpose of solid-carrying performance is improved, in terms of existing fiber is due to its degradability and high temperature-resistant acid-resistant alkali
Limitation, in oil gas field field using effect and bad.
The content of the invention
It is according to the first aspect of the invention, of the invention in order to solve problems of the prior art
Purpose is to provide a kind of hollow PVA fibers.
Percentage of the present invention is mass percent in the case of without specified otherwise.
The purpose of the present invention is realized by following technical measures：
A kind of hollow PVA fibers, it is characterised in that：It is 1000~3500 by the degree of polymerization, alcoholysis degree is
99.0~99.9 (mol) % PVA spinning is prepared, and the PVA fiber cross-sectionals are hollow structure,
0.1~100 μm of hollow portion diameter.
According to one embodiment of the invention, metallic element, the gold are contained in above-mentioned PVA fibers
Category element is one or more kinds of element combinations in copper, titanium, vanadium, boron.
According to one embodiment of the invention, the metallic element contained in above-mentioned PVA fibers, in PVA
Mass content in fiber is 0.05~5.0%.
According to one embodiment of the invention, above-mentioned PVA fibers can also containing molecular weight be 500~
5000 polyethylene glycol.
According to the second aspect of the invention, it is an object of the invention to provide above-mentioned hollow PVA fibers
Preparation method.
According to one embodiment of the invention, above-mentioned hollow PVA fibers can be prepared by following methods：
(1) preparation of spinning solution：By the degree of polymerization be 1000~2500, alcoholysis degree be 99.2~
99.9 (mol) % PVA and the raw material including copper sulphate, titanium tetrachloride, boric acid are soluble in water
Be made into spinning solution, mass concentrations of the wherein PVA in stoste is 13~18%, copper sulphate relative to
PVA mass concentration is 2~5%, and mass concentration of the titanium tetrachloride relative to PVA is 0.5~2.0%,
Mass concentration of the boric acid relative to PVA is 0.5~2.0%, and stoste is warming up into 95~110 DEG C, holding
0.01~0.15MPa of pressure, dissolving enters spinning process after 3~15 hours.
(2) spinning：PVA stostes are pumped to filament spinning component with metering, by PVA stostes from spinning head
Aperture is sprayed into coagulating bath, and the spinneret of filament spinning component can be passed through the compound of gas using spinneret orifice centre
Spinneret.The composition of coagulating bath be sodium sulphate and sodium hydroxide, wherein 320~380g/l of sodium sulfate concentration,
30~70g/l of concentration of sodium hydroxide, 40~50 DEG C of coagulation bath temperature, using -1~2 times of spinning head
Draw ratio, residence time of the silk in coagulating bath sprayed from spinning head is 10~30s.
(3) spinning is post-processed:Neutralization washing and drying is carried out to as-spun fibre, heat-setting process, heat is stretched
170~260 DEG C of setting temperature, hot-stretch multiple 2~15, heat-setting time 3~20 minutes, in being made
Empty PVA fibers.
According to one embodiment of the invention, above-mentioned spinning solution enters after dissolving 3~15 hours
Before spinning process, viscosity at 50 DEG C is 5000~20000mPas.
According to one embodiment of the invention, except addition copper sulphate, tetrachloro in above-mentioned spinning solution
To change outside titanium and boric acid, can also add sodium vanadate, mass concentration of the sodium vanadate relative to PVA be 0.2~
1.2%, the hollow space diameter that with the addition of obtained PVA doughnuts after sodium vanadate is more uniform.
According to the third aspect of the invention we, the present invention provides above-mentioned hollow PVA fibers in oil-gas field fracturing
Purposes in liquid.
Inventor has surprisingly found that, when the above-mentioned hollow PVA fibers of the present invention are added to oil-gas field fracturing liquid,
The composition of PVA fibers and oil-gas field fracturing liquid is fully acted on, and PVA fibers can be kept with proppant
Good suspended state, solid-carrying performance is greatly improved, and greatly shortens the row's of returning time.
According to the fourth aspect of the invention, the present invention provides the oil gas field for including above-mentioned hollow PVA fibers
Fracturing fluid.
According to one embodiment of the invention, the oil-gas field fracturing liquid of above-mentioned hollow PVA fibers is included,
Mass content of the PVA fibers in oil-gas field fracturing liquid is 0.1~2.5%.
According to one embodiment of the invention, the viscosity of above-mentioned oil-gas field fracturing liquid at normal temperatures is
80~200mPas.The normal temperature refers to 20~30 DEG C.
According to one embodiment of the invention, above-mentioned oil-gas field fracturing liquid is of the prior art any
A kind of aqua type fracturing fluid.
According to one embodiment of the invention, aqua type oil-gas field fracturing liquid includes thickening agent, can also wrapped
Include crosslinking agent or gel breaker；Viscosity of the thickening agent to improve fracturing fluid, the worry of reduction fracturing fluid is lost,
Proppant is suspended and carries, it is guanidine glue to commonly use thickening agent；The PVA fibers of the present invention are added to oil gas field
After fracturing fluid, thickening agent can be used no or little.Crosslinking agent is boric acid, borax, organic boron, organic
One kind or several in zirconium, aluminum sulfate, aluminum nitrate, titanium tetrachloride, titanium sulfate, zinc sulfate, organic titanium
Plant combination；Gel breaker be potassium peroxydisulfate, ammonium persulfate, potassium bichromate, potassium permanganate including enzyme or
Biology enzyme or the organic acids such as capsule, the amylase of person's acid.
It is steady that clay can also be added according to one embodiment of the invention, in above-mentioned oil-gas field fracturing liquid
Determine the auxiliary agents such as agent, cleanup additive, bactericide, foaming agent, defoamer, demulsifier.Clay stabilizer energy
Oil-gas Layer CLAY MINERALS AND THEIR SIGNIFICANCE hydration swelling and scattered migration are prevented, can be potassium chloride, anionic surface
Activating agent.The addition of bactericide can not only keep the stability on glue surface but also can prevent bacterium in stratum
Growth, such as chlorine, quaternary ammonium salt.Cleanup additive is to reduce the surface tension or oil-water interfaces of fracturing fluid
Tension force, increase and the contact angle of rock, the hollow billet resistance run into during reduction fracturing fluid recovery (backflow), such as 12
Sodium alkyl sulfate.The effect of foaming agent is that certain power is provided to stratum, discharging liquid will be helped from ground
Return and eject in layer, such as cationic surfactant.
According to one embodiment of the invention, above-mentioned hollow PVA fibers are added to oil-gas field fracturing liquid
In mode, can be only the pressure break preparatory stage add, can also simultaneously in pressure break early stage, pressure break
PVA fibers are added in fracturing fluid by phase and pressure break tail phase substep.
According to the fifth aspect of the invention, the present invention provides above-mentioned hollow PVA fibers in oil-gas field fracturing
The purposes temporarily blocked up in liquid.
According to the sixth aspect of the invention, the present invention provides the oil gas field for including above-mentioned hollow PVA fibers
Pressure break temporarily blocks up liquid.
According to one embodiment of the invention, the above-mentioned oil-gas field fracturing containing hollow PVA fibers is temporary
Stifled liquid, the PVA fibers are 0.2~3.0% in the mass content that oil-gas field fracturing is temporarily blocked up in liquid.
According to the seventh aspect of the invention, the present invention provides above-mentioned hollow PVA fibers and cemented the well in oil gas field
Purposes in agent.
According to the eighth aspect of the invention, the present invention provides the oil gas field for including above-mentioned hollow PVA fibers
Well cementation agent.
According to one embodiment of the invention, the above-mentioned oil gas field well cementation agent containing hollow PVA fibers,
Mass content of the PVA fibers in oil gas field cements the well agent is 0.3~3.0%.
According to one embodiment of the invention, husky, lime can be also added in above-mentioned oil gas field well cementation agent
Etc. other components.
Through experimental results demonstrate, the present invention containing hollow PVA fibers oil gas field construction base fluid in,
Hollow PVA fibers are used with guanidine gluing, and liquid or oil gas are temporarily blocked up as oil-gas field fracturing liquid, oil-gas field fracturing
During the well cementation agent of field, suspend and carrying proppant performance is more preferable.
Beneficial effects of the present invention
The PVA fibers of the present invention have hollow structure, and contain a certain amount of copper, titanium, vanadium, boron etc.
Element, it is constructed in oil gas field, and (oil-gas field fracturing liquid, oil gas field well cementation agent or oil-gas field fracturing are temporarily blocked up
Agent) in good dispersion, tack it is good, construction effect is good, so as to promote oil gas field secondary recovery to increase income.
2nd, the oil gas field base fluid of the present invention for containing hollow PVA fibers as oil-gas field fracturing liquid when have
There are three big advantages, one is to have to take sand function well at work, beneficial to fracturing fluid recovery (backflow), specifically
Principle is：By PVA fibers as load fluid injects together, form compound in the crack of near wellbore
Property proppant, proppant is matrix, fiber be enhancing phase.At the end of pressing crack construction, the branch in crack
Support agent reaches mechanical balance because bearing to interact in the form of contact between lateral pressure, particle.Pressure
Split liquid to start after the row of returning, due to washing away for flow of fluid, this balance is destroyed, proppant particles
Just occur plasticity shearing deformation, form a series of domes, and then the stability of the husky arch of raising,
Fracturing fluid recovery (backflow) speed is improved, and proppant can be controlled to return row well；Two be pressure prepared by the present invention
The use for being difficult to be completely dissolved and being difficult to from other compositions such as the guar gums of shaft bottom discharge can be reduced by splitting liquid
Amount, so as to mitigate the injury to environment；Three be that PVA fibers belong to degradation material, remains in environment
In composition eventually resolve into nontoxic hydrocarbon, environment will not be damaged.
3rd, when the oil gas field base fluid of the present invention for containing hollow PVA fibers is as oil gas field well cementation agent,
The intensity and toughness of well cementing material can be strengthened, leakproof can also be played a part of.
4th, the oil gas field base fluid of the present invention for containing hollow PVA fibers is as oil-gas field fracturing diverting agent
When mainly have a two big advantages, one is due to that there is PVA fibers good drop to consider mistake effect, be intended to it is temporarily stifled
Position formed one layer of shielding layer, fracturing fluid is smoothly turned to；Two be that PVA fibers have good drop
Xie Xing, remaining in the composition of ground end will not pollute to environment.
Brief description of the drawings
Accompanying drawing 1 is the displaing micro photo figure of PVA fiber cross-sectionals hollow diameters made from embodiment 1.
Embodiment
The present invention is specifically described below by embodiment, it is necessary to it is pointed out here that be this reality
Apply example to be served only for that the present invention is further described, it is impossible to be interpreted as the limit to the scope of the present invention
System, the person skilled in the art in the field can make according to the content of the invention described above to the present invention
Nonessential modifications and adaptations.
PVA fiber cross-sectionals hollow diameters are tested using light microscope.
Embodiment 1
The preparation of hollow PVA fibers：
(1) preparation of spinning solution：It is 1800 by the degree of polymerization, alcoholysis degree is 99.5 (mol) % PVA
And copper sulphate, titanium tetrachloride, boric acid are soluble in water is made into spinning solution, wherein PVA is in stoste
Mass concentration be 15%, mass concentration of the copper sulphate relative to PVA be 3.5%, titanium tetrachloride is relative
It is 1.0% in PVA mass concentration, mass concentration of the boric acid relative to PVA is 1.2%, by stoste liter
Temperature keeps 0.01~0.15MPa of pressure to 105~110 DEG C, and dissolving enters after 14~15 hours to be spun
Wire process.Now take a part of stoste to cool the temperature to 50 DEG C and survey its viscosity for 8000mPas.
(2) spinning：PVA stostes are pumped to filament spinning component with metering, by PVA stostes from spinning head
Aperture is sprayed into coagulating bath, and the spinneret of filament spinning component can be passed through the compound of gas using spinneret orifice centre
Spinneret.The composition of coagulating bath is sodium sulphate and sodium hydroxide, wherein sodium sulfate concentration 350g/l, hydrogen
The concentration 50g/l of sodium oxide molybdena, 45 DEG C of coagulation bath temperature, using 1 times of spinneret draft, from
Residence time of the silk that spinning head sprays in coagulating bath is 20s.
(3) spinning is post-processed:Neutralization washing and drying is carried out to as-spun fibre, the processes such as thermal finalization are stretched,
Hollow PVA fibers are made in 190 DEG C of heat setting temperature, hot-stretch multiple 10, heat-setting time 15 minutes.
Contain copper, titanium elements and boron element, copper coin in a diameter of 70 μm of hollow space, PVA fibers
Element, the mass content of titanium elements and boron element in PVA fibers be 2.5%, PVA fibers in also contain
Molecular weight is 2500 polyethylene glycol.
Embodiment 2
Prepare hollow PVA fibers with reference to embodiment 1, wherein PVA fibers by the degree of polymerization 2000,
Alcoholysis degree 99.5 (mol) % polyvinyl alcohol is prepared through spinning, during the section of the PVA fibers is
Contain copper in hollow structure, a diameter of 50 μm of hollow space, PVA fibers, copper is fine in PVA
Mass content in dimension is also containing the polyethylene glycol that molecular weight is 1000 in 0.08%, PVA fibers.
Embodiment 3
Prepare hollow PVA fibers with reference to embodiment 1, wherein PVA fibers by the degree of polymerization 1700,
Alcoholysis degree 99.0 (mol) % polyvinyl alcohol is prepared through spinning, during the section of the PVA fibers is
Contain copper and titanium elements, copper in hollow structure, a diameter of 70 μm of hollow space, PVA fibers
It in 1.5%, PVA fibers also containing molecular weight is 1500 to be with mass content of the titanium elements in PVA fibers
Polyethylene glycol.
Embodiment 4
Prepare hollow PVA fibers with reference to embodiment 1, wherein PVA fibers by the degree of polymerization 2400,
Alcoholysis degree 99.9 (mol) % polyvinyl alcohol is prepared through spinning, during the section of the PVA fibers is
Contain copper and boron element, copper coin in hollow structure, a diameter of 100 μm of hollow space, PVA fibers
Element and mass content of the boron element in PVA fibers be 1.0%, PVA fibers in be also containing molecular weight
2800 polyethylene glycol.
Embodiment 5
Prepare hollow PVA fibers with reference to embodiment 1, wherein PVA fibers by the degree of polymerization 1500,
Alcoholysis degree 99.6 (mol) % polyvinyl alcohol is prepared through spinning, during the section of the PVA fibers is
Contain copper and boron element, copper in hollow structure, a diameter of 80 μm of hollow space, PVA fibers
It is 0.08% with mass content of the boron element in PVA fibers, the mol ratio of copper and boron element is 5：
3。
Embodiment 6
Prepare hollow PVA fibers with reference to embodiment 1, wherein PVA fibers by the degree of polymerization 2400,
Alcoholysis degree 99.9 (mol) % polyvinyl alcohol is prepared through spinning, during the section of the PVA fibers is
Contain copper, titanium elements and boron element in hollow structure, a diameter of 60 μm of hollow space, PVA fibers,
The mass content of copper, titanium elements and boron element in PVA fibers is 2.5%, copper, titanium member
The mol ratio of element and boron element is 3:3:Also containing the poly- second two that molecular weight is 3000 in 2, PVA fibers
Alcohol.
Embodiment 7
Prepare hollow PVA fibers with reference to embodiment 1, wherein PVA fibers by the degree of polymerization 2800,
Alcoholysis degree 99.8 (mol) % polyvinyl alcohol is prepared through spinning, during the section of the PVA fibers is
Contain titanium elements in hollow structure, a diameter of 0.8 μm of hollow space, PVA fibers, titanium elements are in PVA
Mass content in fiber is 0.8%.
Embodiment 8
Prepare hollow PVA fibers with reference to embodiment 1, wherein PVA fibers by the degree of polymerization 2400,
Alcoholysis degree 99.6 (mol) % polyvinyl alcohol is prepared through spinning, during the section of the PVA fibers is
Contain v element in hollow structure, a diameter of 20 μm of hollow space, PVA fibers, v element is fine in PVA
Mass content in dimension is also containing the polyethylene glycol that molecular weight is 3500 in 0.8%, PVA fibers.System
The oil gas field base fluid obtained can be used for oil-gas field fracturing liquid, oil-gas field fracturing temporarily to block up liquid, oil gas field well cementation agent
And in the other constructions of oil gas field.
Embodiment 9
A kind of fibre-bearing guar gum fracturing fluid is present embodiments provided, preparation method is as follows：
Step one：Under stirring condition, 0.2 parts by weight thickening agent hydroxyl is added into 100 parts by weight water
Propyl group guar gum (CNPC's material Kunshan company), 0.12 parts by weight sodium carbonate, 0.1 parts by weight
Potassium chloride, then stirs 20min, obtains the guar gum thickening agent aqueous solution；
Step 2：Under agitation, the friendship of 0.2 parts by weight is added into the above-mentioned thickening agent aqueous solution
Join agent zinc sulfate, obtain guar gum fracturing fluid (not fibre-bearing guar gum fracturing fluid)；
Step 3：PVA made from 0.5 parts by weight of example 1 is added into above-mentioned guar gum fracturing fluid fine
Dimension, fiber prescinds to 6mm length, is added in oil-gas field fracturing liquid and is uniformly dispersed, obtain fibre-bearing
Guar gum fracturing fluid.
Step 4：By above-mentioned fibrous guanidine gum fracturing fluid along with proppant (clay, quartz sand etc.)
It is added to together in Oil/gas Well, 0.02 parts by weight gel breaker ammonium persulfate is added in the pressing crack construction later stage.
Test example 10：(comparative example 1)
A kind of fibre-bearing guar gum fracturing fluid is present embodiments provided, preparation method is as follows：
Step one：Under stirring condition, 0.2 parts by weight thickening agent hydroxyl is added into 100 parts by weight water
Propyl group guar gum (CNPC's material Kunshan company), 0.12 parts by weight sodium carbonate, 0.1 parts by weight
Potassium chloride, then stirs 20min, obtains the guar gum thickening agent aqueous solution；
Step 2：During fracturing work, under agitation, add into the above-mentioned thickening agent aqueous solution
Enter 0.2 parts by weight of crosslinking agent FAL-120 (the limited public affairs of Langfang City Wanke petroleum gas engineering
Department), obtain guar gum fracturing fluid (not fibre-bearing guar gum fracturing fluid)；
Step 3：0.5 parts by weight of polypropylene nitrile fiber is added into above-mentioned guar gum fracturing fluid, and (tension is strong
Spend for 100MPa, real density is 0.98g/cm3, and length is 5mm, a diameter of 78 μm), stirring
It is well mixed, obtain fibre-bearing guar gum fracturing fluid.
Step 4：By above-mentioned fibrous guanidine gum fracturing fluid along with proppant (clay, quartz sand etc.)
It is added to together in Oil/gas Well, 0.02 parts by weight gel breaker ammonium persulfate is added in the pressing crack construction later stage.
Obtained fracturing fluid viscosity 55mPas, the rate of settling 0.52 (cm/min), the row of returning the time is
32h。
Embodiment 11
The prop-carrying capacity that sand method verifies fracturing fluid is taken using static, is carried out at room temperature in the lab, it is real
Test step as follows：
(1) a certain proportion of thickening agent HPG is added in clear water, thickening agent is prepared water-soluble
Liquid；
(2) fiber and proppant according to made from experiment demand adds embodiment 1 (from 0.3~
0.6mm haydite, meets SY/T5108-2006 standards, under 69MPa percentage of damage for 4.0%), then
Add appropriate crosslinking agent aluminum sulfate to stir to form fracturing fluid, by the mixing of fracturing fluid, fiber and proppant
Thing is poured into graduated cylinder；
(3) mixture obtained in (2) is stood into 120min in room temperature, record proppant is in fracturing fluid
Settling height and calculate sinking speed (settling height divided by sedimentation time), be specifically shown in table 1 below.
| 1 group | 2 groups | 3 groups | |
| Thickener concentration (wt%) | 0.50wt% | 0.50wt% | 1.20wt% |
| Fibre concentration (wt%) | 0 | 0.5 | 0 |
| The rate of settling (cm/min) | 0.078 | 0.018 | 0.019 |
, it is evident that when thickener concentration is all 0.50wt%, proppant is in 1 group of pressure from table 1
Splitting the rate of settling in liquid (not fibrous fracturing fluid), to be far longer than 2 groups of fracturing fluids (fibrous
Fracturing fluid) in the rate of settling, it can thus be seen that the addition of fiber substantially increases fracturing fluid
Prop-carrying capacity.Proppant is 2 groups of fracturing fluids (thickener concentration is 0.50wt% fibre-bearing fracturing fluid)
Neutralize the sedimentation speed in 3 groups of fracturing fluids (thickener concentration is free of fiber fracturing liquid for 1.20wt%'s)
Rate quite, thus can be explained, the use of fiber can in reduction fracturing fluid the concentration of thickening agent it is same
When ensure fracturing fluid prop-carrying capacity.
With reference to embodiment 9 and embodiment 11, run according to following parameter, prepared by detection above-described embodiment
PVA fibers as the performance of oil-gas field fracturing liquid, in table 2, embodiment 1 is referred to using implementing
Hollow PVA fibers prepared by example 1, by that analogy embodiment 1-8；The detection temperature of viscosity is 25 DEG C
Left and right, rate of settling unit (cm/min).
From Table 2, it can be seen that the PVA fibers containing special construction of the present invention are added to fracturing fluid
In, the prop-carrying capacity of fracturing fluid can be significantly improved.Moreover, during the row of returning after terminating with regard to pressing crack construction
Between from the point of view of, generally want two or three talent to return drained, and our product used after in 2 hours
Drained with regard to that can return, good need not wait two hours.Just from the point of view of the row's of returning efficiency, fiber of the present invention has been used
Oil and gas well fracturing fluid return row to lead ratio high by more than 20% without using (embodiment 8-2)；With embodiment 8-1
Exemplified by, the row of returning of embodiment 8-1 oil and gas well fracturing fluid leads higher than embodiment 8-2 by 24% after 15 hours
Left and right.Just return from the point of view of discharge opeing silt content, used the oil and gas well fracturing fluid of fiber of the present invention to return discharge opeing and contained
Sand amount without using (embodiment 8-2) than lowering 10~30%；By taking embodiment 8-1 as an example, relative to reality
Apply attenuating 27% or so for a 8-2.For oil gas well production, the pressure break of fiber of the present invention has been used
Liquid Oil/gas Well ratio is not high by more than 50% using fiber (embodiment 8-2) of the present invention；With embodiment 8-1
Exemplified by, the output increased 53% or so of the Oil/gas Well of the fracturing fluid than having used embodiment 8-2.
To be added to containing hollow PVA fibers in conventional oil gas well cementing agent, through experimental results demonstrate,
PVA fibers are when the mass content during oil gas field cements the well agent is 0.3~3.0%, and hollow PVA fibers are with consolidating
The composition of well agent is fully acted on, and then strengthens the intensity and toughness of well cementing material, can also play leakproof
Effect；It will be added to containing hollow PVA fibers in the pressure break diverting agent of conventional oil gas field, due to PVA
There is fiber good drop to consider mistake effect, forms one layer of shielding layer at the position for being intended to temporarily block up, makes fracturing fluid
Smoothly turn to；And the PVA fibers that use of the present invention have good degradability, remain in ground end into
Dividing will not pollute to environment.
Claims (14)
1. a kind of hollow PVA fibers, it is characterised in that：It is 1000~3500 by the degree of polymerization, alcoholysis degree is prepared for 99.0~99.9 (mol) % PVA spinning, the PVA fiber cross-sectionals are hollow structure, 0.1~100 μm of hollow portion diameter.
2. hollow PVA fibers as claimed in claim 1, it is characterised in that：The hollow PVA fibers contain metallic element, and the metallic element is one or more kinds of elements in copper, titanium, vanadium, boron；Mass content of the metallic element in PVA fibers is 0.05~5.0%.
3. hollow PVA fibers as claimed in claim 1 or 2, it is characterised in that：The hollow PVA fibers can also contain the polyethylene glycol that molecular weight is 500 ~ 5000.
4. the preparation method of hollow PVA fibers as described in claim any one of 1-3, using following steps：
（1）The preparation of spinning solution：It is 1000~2500 by the degree of polymerization, raw material of the alcoholysis degree for 99.2~99.9 (mol) % PVA and including copper sulphate, titanium tetrachloride, boric acid is soluble in water to be made into spinning solution, mass concentrations of the wherein PVA in stoste is 13~18%, mass concentration of the copper sulphate relative to PVA is 2~5%, mass concentration of the titanium tetrachloride relative to PVA is 0.5~2.0%, mass concentration of the boric acid relative to PVA is 0.5~2.0%, stoste is warming up to 95~110 DEG C, the MPa of pressure 0.01~0.15 is kept, dissolving enters spinning process after 3~15 hours；
（2）Spinning：PVA stostes are pumped to filament spinning component with metering, by PVA stostes from spinning head aperture sprays into coagulating bath, the spinneret of filament spinning component is using the composite spinneret that gas is passed through in the middle of spinneret orifice；The composition of coagulating bath is sodium sulphate and sodium hydroxide, wherein 320~380g/l of sodium sulfate concentration, 30~70g/l of concentration of sodium hydroxide, 40~50 DEG C of coagulation bath temperature, using -1~2 times of spinneret draft, residence time of the silk sprayed from spinning head in coagulating bath is 10~30s；
（3）Spinning is post-processed:Neutralization washing and drying is carried out to as-spun fibre, heat-setting process is stretched, hollow PVA fibers are made in 170~260 DEG C of heat setting temperature, hot-stretch multiple 2~15, heat-setting time 3~20 minutes.
5. method as claimed in claim 4, it is characterised in that：The spinning solution after dissolving 3~15 hours before spinning process is entered, and viscosity at 50 DEG C is 5000~20000mPas.
6. the method as described in claim 4 or 5, it is characterised in that：Sodium vanadate is also added in the spinning solution, mass concentration of the sodium vanadate relative to PVA is 0.2~1.2%.
7. purposes of the hollow PVA fibers in oil-gas field fracturing liquid as described in claim any one of 1-3.
8. include the oil-gas field fracturing liquid of any one of the claim 1-3 hollow PVA fibers, it is characterised in that：Mass content of the PVA fibers in oil-gas field fracturing liquid is 0.1~2.5%.
9. oil-gas field fracturing liquid as claimed in claim 8, it is characterised in that：The oil-gas field fracturing liquid also includes thickening agent, crosslinking agent and gel breaker；The thickening agent is guanidine glue；The crosslinking agent is the one or more combination in boric acid, borax, organic boron, organic zirconium, aluminum sulfate, aluminum nitrate, titanium tetrachloride, titanium sulfate, zinc sulfate, organic titanium；The gel breaker is potassium peroxydisulfate, ammonium persulfate, potassium bichromate, potassium permanganate, amylase or organic acid.
10. oil-gas field fracturing liquid as claimed in claim 8 or 9, it is characterised in that：The viscosity of the oil-gas field fracturing liquid at normal temperatures is 80~200mPas.
11. the purposes that the hollow PVA fibers as described in claim any one of 1-3 are temporarily blocked up in liquid in oil-gas field fracturing.
12. the oil-gas field fracturing comprising any one of the claim 1-3 hollow PVA fibers temporarily blocks up liquid, it is characterised in that：The PVA fibers are 0.2~3.0% in the mass content that oil-gas field fracturing is temporarily blocked up in liquid.
13. purposes of the hollow PVA fibers in oil gas field cements the well agent as described in claim any one of 1-3.
14. the oil gas field well cementation agent comprising any one of the claim 1-3 hollow PVA fibers, it is characterised in that：Mass content of the PVA fibers in oil gas field cements the well agent is 0.3~3.0%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111101219A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | High-strength high-modulus polyvinyl alcohol filament and preparation method thereof |
| CN111620430A (en) * | 2020-06-04 | 2020-09-04 | 浙江大学 | Hollow fiber membrane reactor based on metal thin film catalysis, manufacturing method and application |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1141233A (en) * | 1995-06-05 | 1997-01-29 | 可乐丽股份有限公司 | Polyvinyl alcohol-based hollow fiber memberane and process for producing same |
| CN1328868A (en) * | 2000-06-21 | 2002-01-02 | 可乐丽股份有限公司 | Porous hollow fibre membrane and its manufacturing method |
| CN101918488A (en) * | 2007-12-20 | 2010-12-15 | 菲利普莫里斯生产公司 | Hollow/porous fibers and applications thereof |
| CN103275692A (en) * | 2013-06-25 | 2013-09-04 | 中国海洋石油总公司 | Seawater base fracturing fluid |
| CN103725277A (en) * | 2013-12-18 | 2014-04-16 | 四川省博仁达石油科技有限公司 | Fibre compound temporary plugging agent |
| CN104727800A (en) * | 2015-01-22 | 2015-06-24 | 中国石油集团川庆钻探工程有限公司长庆井下技术作业公司 | Temporary blocking turnaround fracturing method based on surface modified polyvinyl alcohol fibers |
| CN105086985A (en) * | 2015-05-29 | 2015-11-25 | 中国石油天然气股份有限公司 | Synergistic fiber vegetable gum fracturing fluid and preparation method thereof |
-
2016
- 2016-04-07 CN CN201610213439.1A patent/CN107268104B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1141233A (en) * | 1995-06-05 | 1997-01-29 | 可乐丽股份有限公司 | Polyvinyl alcohol-based hollow fiber memberane and process for producing same |
| CN1328868A (en) * | 2000-06-21 | 2002-01-02 | 可乐丽股份有限公司 | Porous hollow fibre membrane and its manufacturing method |
| CN101918488A (en) * | 2007-12-20 | 2010-12-15 | 菲利普莫里斯生产公司 | Hollow/porous fibers and applications thereof |
| CN103275692A (en) * | 2013-06-25 | 2013-09-04 | 中国海洋石油总公司 | Seawater base fracturing fluid |
| CN103725277A (en) * | 2013-12-18 | 2014-04-16 | 四川省博仁达石油科技有限公司 | Fibre compound temporary plugging agent |
| CN104727800A (en) * | 2015-01-22 | 2015-06-24 | 中国石油集团川庆钻探工程有限公司长庆井下技术作业公司 | Temporary blocking turnaround fracturing method based on surface modified polyvinyl alcohol fibers |
| CN105086985A (en) * | 2015-05-29 | 2015-11-25 | 中国石油天然气股份有限公司 | Synergistic fiber vegetable gum fracturing fluid and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111101219A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | High-strength high-modulus polyvinyl alcohol filament and preparation method thereof |
| CN111101219B (en) * | 2018-10-26 | 2022-08-12 | 中国石油化工股份有限公司 | High-strength high-modulus polyvinyl alcohol filament and preparation method thereof |
| CN111620430A (en) * | 2020-06-04 | 2020-09-04 | 浙江大学 | Hollow fiber membrane reactor based on metal thin film catalysis, manufacturing method and application |
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