CN107268104B - A kind of hollow PVA fiber and its preparation method and application - Google Patents
A kind of hollow PVA fiber and its preparation method and application Download PDFInfo
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- CN107268104B CN107268104B CN201610213439.1A CN201610213439A CN107268104B CN 107268104 B CN107268104 B CN 107268104B CN 201610213439 A CN201610213439 A CN 201610213439A CN 107268104 B CN107268104 B CN 107268104B
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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 fiber, by the degree of polymerization be 1000~3500, alcoholysis degree be 99.0~99.9 (mol) % PVA spinning be prepared, wherein PVA fiber cross-sectional be 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, which has, takes sand function well, is conducive to fracturing fluid recovery (backflow), can be reduced the usage amount of other ingredients such as the guar gum that is difficult to be completely dissolved and be difficult to be discharged from shaft bottom, 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 enhanced, leakproof can also be played the role of；It is added in oil-gas field fracturing diverting agent, there is good drop to consider mistake effect, form one layer of shielding layer at the position for being intended to temporarily block up, turn to fracturing fluid smoothly；The ingredient of present invention residual in the environment eventually resolves into nontoxic hydrocarbon, will not damage to environment.
Description
Technical field
The present invention relates to PVA fibers, and in particular to a kind of hollow PVA fiber and its preparation method and application.
Background technique
China's Low Permeability Oil/gas stock number is huge, accounts for and has verified 70% of gross reserves or more, is produced in China's future increasing the storage
Main potential work area.This kind of petroleum resources have the characteristics that three is low, that is, verify that rate is low, and natural production rate is low, and recovery ratio is low.It is real
Border application shows in this kind of exploitation of oil-gas field, is badly in need of the good well cementation agent of function, pressure break diverting agent, and can play compared with
The oil-gas field fracturing liquid of sand effect is taken well, meanwhile, also to reduce the injury of low environment to the greatest extent.
In recent years, domestic and international researcher has carried out numerous studies around oil gas field field pressure break, well cementation, temporary plugging technique.
CN200610063700.0A discloses a kind of composite fracturing fluid, and compounding gelatinizing agent is 0.4~1.0wt% of fracturing fluid quality,
Metal crosslinking agent is 0.05~0.7wt% of fracturing fluid quality, and oxidation gel breaker is 0.05~0.5wt% of fracturing fluid quality,
Remaining is water.CN201410088243.5A discloses a kind of instant modified cellulose crosslinking clean fracturing fluid, using component are as follows:
0.2~0.6 parts by weight of FAG-500 type modified cellulose, FAZ-1 type thickening initiator 0.1~0.5 in two parts, DL-16 type help row
0.3~0.7 parts by weight of agent, 0.5~1.2 parts by weight of FAJ-305 type cross-linking regulator, FAC-201 type polarity chelating organic zirconium are handed over
Join 0.2~0.7 part of agent, 0.002~0.07 part of NBA-102 type capsule breaker, 100 parts by weight of water.CN201510078854.6A
A kind of fibre-bearing fracturing fluid for improving fracturing fluid prop-carrying capacity is disclosed, the additive amount of fiber is 0.3~0.8 weight in fracturing fluid
Part is measured, the tensile strength of fiber is 20~300MPa, and real density is 0.98~1.33g/cm3, length is 3~15mm, diameter
It is 25~150 μm, the fiber is that polypropylene fibre, polyethylene fibre, polyacrylonitrile fibre, vinal and polyester are fine
One of dimension is a variety of.CN201310698113.9A discloses a kind of fiber composite diverting agent, and main formula is to carry liquid
55~75 parts, 20~30 parts of diverting agent particle, temporarily 0.5~2 part of stifled fiber forms, and temporarily stifled fiber is vinal, modification
One of polyester fiber, polyurethane fiber are a variety of." the tenacity of fibre cement slurry skill in " drilling technique " magazine such as Qi Hongke
In utilization of the art in Central Plains oil gas field " article, mentions and fibrous material is added in cement, toughening leakproof can be played the role of.
Although colleague has done many effort both at home and abroad, so far, existing fracturing technique, which still cannot be properly arrived at, both may be used
Injury of the fracturing fluid to reservoir is reduced, and the purpose of solid-carrying performance can be improved, existing fiber is due to its degradability and resistance to
Limitation in terms of high temperature acid and alkali-resistance, in oil gas field field using effect and bad.
Summary of the invention
In order to solve the problems in the existing technology, according to the first aspect of the invention, it is an object of the invention to mention
For a kind of hollow PVA fiber.
Percentage of the present invention is mass percent in the case of no specified otherwise.
The purpose of the present invention is realized by following technical measures:
A kind of hollow PVA fiber, it is characterised in that: by the degree of polymerization be 1000~3500, alcoholysis degree be 99.0~99.9
(mol) the PVA spinning of % is prepared, the PVA fiber cross-sectional be hollow structure, 0.1~100 μm of hollow portion diameter.
An embodiment according to the present invention, contains metallic element in above-mentioned PVA fiber, the metallic element be copper,
One of titanium, vanadium, boron or more than one element combinations.
An embodiment according to the present invention, the metallic element contained in above-mentioned PVA fiber, the matter in PVA fiber
Measuring content is 0.05~5.0%.
An embodiment according to the present invention, the poly- second two that above-mentioned PVA fiber is also 500~5000 containing molecular weight
Alcohol.
According to the second aspect of the invention, the purpose of the present invention is to provide the preparation methods of above-mentioned hollow PVA fiber.
An embodiment according to the present invention, above-mentioned hollow PVA fiber can be prepared by following methods:
(1) preparation of spinning solution: being 1000~2500 by the degree of polymerization, and alcoholysis degree is the PVA of 99.2~99.9 (mol) %
And raw material including copper sulphate, titanium tetrachloride, boric acid is soluble in water is made into spinning solution, wherein PVA is in stoste
Mass concentration is 13~18%, and copper sulphate is 2~5% relative to the mass concentration of PVA, quality of the titanium tetrachloride relative to PVA
Concentration is 0.5~2.0%, and boric acid is 0.5~2.0% relative to the mass concentration of PVA, and stoste is warming up to 95~110 DEG C, is protected
0.01~0.15MPa of pressure is held, enters spinning process after dissolution 3~15 hours.
(2) spinning: being pumped to filament spinning component for the metering of PVA stoste, and PVA stoste is sprayed into coagulating bath from spinning head aperture
In, the spinneret of filament spinning component is using the composite spinneret that can be passed through gas among spinneret orifice.The ingredient 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, coagulation bath temperature 40~50
DEG C, using -1~2 times of spinneret draft, residence time of the silk sprayed from spinning head in coagulating bath is 10~30s.
(3) spinning post-processes: carrying out neutralization washing and drying to as-spun fibre, stretches heat-setting process, heat setting temperature 170
~260 DEG C, heat-setting time 3~20 minutes, hollow PVA fiber was made in hot-stretch multiple 2~15.
An embodiment according to the present invention, before above-mentioned spinning solution enters spinning process after dissolution 3~15 hours,
Viscosity at 50 DEG C is 5000~20000mPas.
An embodiment according to the present invention, in addition to addition copper sulphate, titanium tetrachloride and boric acid in above-mentioned spinning solution
Outside, sodium vanadate can also be added, sodium vanadate is 0.2~1.2% relative to the mass concentration of PVA, is made after being added to sodium vanadate
PVA doughnut hollow space diameter it is more uniform.
According to the third aspect of the invention we, the present invention provides purposes of the above-mentioned hollow PVA fiber in oil-gas field fracturing liquid.
Inventor has surprisingly found that, when the above-mentioned hollow PVA fiber of the present invention is added to oil-gas field fracturing liquid, PVA fiber with
The ingredient of oil-gas field fracturing liquid sufficiently acts on, and PVA fiber and proppant can be made to keep good suspended state, solid-carrying performance
It greatly improves, 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 fracturing liquid comprising above-mentioned hollow PVA fiber.
An embodiment according to the present invention, the oil-gas field fracturing liquid comprising above-mentioned hollow PVA fiber, the PVA are fine
Tieing up the mass content in oil-gas field fracturing liquid is 0.1~2.5%.
An embodiment according to the present invention, the viscosity of above-mentioned oil-gas field fracturing liquid at normal temperature are 80~200mPa
s.The room temperature refers to 20~30 DEG C.
An embodiment according to the present invention, above-mentioned oil-gas field fracturing liquid are any one aqua type in the prior art
Fracturing fluid.
An embodiment according to the present invention, aqua type oil-gas field fracturing liquid includes thickening agent, may also include crosslinking agent
Or gel breaker；Viscosity of the thickening agent to improve fracturing fluid, the worry for reducing fracturing fluid are lost, and are suspended and are carried proppant, commonly use thick
Agent is guanidine glue；After PVA fiber of the invention is added to oil-gas field fracturing liquid, thickening agent can be used no or little.Crosslinking agent is
One of boric acid, borax, organic boron, organic zirconium, aluminum sulfate, aluminum nitrate, titanium tetrachloride, titanium sulfate, zinc sulfate, organic titanium or
Several combinations；Gel breaker is potassium peroxydisulfate, ammonium persulfate, potassium bichromate, potassium permanganate, the capsule including enzyme or acid, starch
The biological enzyme such as enzyme or organic acid.
An embodiment according to the present invention can also add clay stabilizer, the row of helping in above-mentioned oil-gas field fracturing liquid
The auxiliary agents such as agent, fungicide, foaming agent, defoaming agent, demulsifier.Clay stabilizer can prevent oil-gas Layer CLAY MINERALS AND THEIR SIGNIFICANCE hydration swelling
It migrates with dispersion, can be potassium chloride, anionic surfactant.The addition of fungicide can both keep the stability on glue surface
The growth that can prevent bacterium in stratum again, such as chlorine, quaternary ammonium salt.Cleanup additive is the surface tension or grease in order to reduce fracturing fluid
Interfacial tension increases the contact angle with rock, the hollow billet resistance encountered when reducing fracturing fluid recovery (backflow), such as lauryl sodium sulfate.
The effect of foaming agent is that certain power is provided to stratum, and discharging liquid will be helped to return from stratum and ejected, as cationic surface is living
Property agent.
An embodiment according to the present invention, above-mentioned hollow PVA fiber are added to the mode in oil-gas field fracturing liquid, can
To be only to be added in the pressure break preparatory stage, PVA fiber can also be added in pressure break early period, pressure break mid-term and pressure break tail phase substep simultaneously
It is added in fracturing fluid.
According to the fifth aspect of the invention, the present invention provides above-mentioned hollow PVA fiber and temporarily blocks up in liquid in oil-gas field fracturing
Purposes.
According to the sixth aspect of the invention, the present invention provides the oil-gas field fracturing comprising above-mentioned hollow PVA fiber and temporarily blocks up liquid.
An embodiment according to the present invention, the above-mentioned oil-gas field fracturing containing hollow PVA fiber temporarily blocks up liquid, described
PVA fiber is 0.2~3.0% in the mass content that oil-gas field fracturing temporarily blocks up in liquid.
According to the seventh aspect of the invention, the present invention provides purposes of the above-mentioned hollow PVA fiber in oil gas field well cementation agent.
According to the eighth aspect of the invention, the present invention provides the oil gas field well cementation agent comprising above-mentioned hollow PVA fiber.
An embodiment according to the present invention, the above-mentioned oil gas field well cementation agent containing hollow PVA fiber, the PVA are fine
The mass content tieed up in oil gas field well cementation agent is 0.3~3.0%.
An embodiment according to the present invention can also add other components such as sand, lime in the well cementation agent of above-mentioned oil gas field.
Through experimental results demonstrate, the present invention containing hollow PVA fiber oil gas field construction base fluid in, hollow PVA fiber
It is used with guanidine gluing, when temporarily blocking up liquid or oil gas field well cementation agent as oil-gas field fracturing liquid, oil-gas field fracturing, suspends and carry proppant
Performance is more preferable.
Beneficial effects of the present invention
PVA fiber of the invention has hollow structure, and containing elements such as a certain amount of copper, titanium, vanadium, boron, in oil gas
Good dispersion, adhesion are good in field construction (oil-gas field fracturing liquid, oil gas field well cementation agent or oil-gas field fracturing diverting agent), construction effect
Fruit is good, so that oil gas field secondary recovery be promoted to increase income.
2, the oil gas field base fluid of the present invention for containing hollow PVA fiber as oil-gas field fracturing liquid when have it is three big excellent
Point takes sand function well first is that having at work, is conducive to fracturing fluid recovery (backflow), concrete principle are as follows: by PVA fiber with load fluid
It injects together, forms plyability proppant in the crack of near wellbore, proppant is matrix, and fiber is reinforced phase.Pressure break is applied
At the end of work, the proppant in crack is interacted in the form of contact between particle because bearing lateral pressure and reaches mechanics and put down
Weighing apparatus.After fracturing fluid starts the row of returning, due to washing away for fluid flowing, this balance is destroyed, and plasticity just occurs for proppant particles
Shearing deformation forms a series of domes, and then improves the stability of husky arch, improves fracturing fluid recovery (backflow) speed, and can be very
Proppant is controlled well returns row；It is difficult to be completely dissolved and be difficult to be discharged from shaft bottom second is that fracturing fluid prepared by the present invention can reduce
Other ingredients such as guar gum usage amount, to mitigate the injury to environment；Third is that PVA fiber belongs to degradation material, residual
Ingredient in the environment eventually resolves into nontoxic hydrocarbon, will not damage to environment.
3, it when the oil gas field base fluid of the present invention for containing hollow PVA fiber is as oil gas field well cementation agent, can be enhanced solid
The intensity and toughness of well material, can also play the role of leakproof.
4, the oil gas field base fluid of the present invention for containing hollow PVA fiber as oil-gas field fracturing diverting agent when mainly have two
Big advantage, first is that forming one layer of shielding layer since there is PVA fiber good drop to consider mistake effect at the position for being intended to temporarily block up, making to press
Liquid is split smoothly to turn to；Second is that PVA fiber has good degradability, the ingredient for remaining in ground end not can cause environmental pollution.
Detailed description of the invention
Attached drawing 1 is the displaing micro photo figure of PVA fiber cross-sectional hollow diameters made from embodiment 1.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that the present embodiment is served only for
Invention is further explained, should not be understood as limiting the scope of the invention, the person skilled in the art in the field
Some nonessential modifications and adaptations can be made to the present invention according to the content of aforementioned present invention.
PVA fiber cross-sectional hollow diameters are tested using optical microscopy.
Embodiment 1
The preparation of hollow PVA fiber:
(1) preparation of spinning solution: by the degree of polymerization be 1800, alcoholysis degree be 99.5 (mol) % PVA and copper sulphate,
Titanium tetrachloride, boric acid are soluble in water to be made into spinning solution, and wherein mass concentration of the PVA in stoste is 15%, and copper sulphate is opposite
It is 3.5% in the mass concentration of PVA, titanium tetrachloride is 1.0% relative to the mass concentration of PVA, quality of the boric acid relative to PVA
Concentration is 1.2%, and stoste is warming up to 105~110 DEG C, keeps 0.01~0.15MPa of pressure, and dissolution enters after 14~15 hours
Spinning process.Taking a part of stoste to cool the temperature to 50 DEG C to survey its viscosity at this time is 8000mPas.
(2) spinning: being pumped to filament spinning component for the metering of PVA stoste, and PVA stoste is sprayed into coagulating bath from spinning head aperture
In, the spinneret of filament spinning component is using the composite spinneret that can be passed through gas among spinneret orifice.The ingredient of coagulating bath is sodium sulphate
And sodium hydroxide, wherein sodium sulfate concentration 350g/l, the concentration 50g/l of sodium hydroxide, 45 DEG C of coagulation bath temperature, using 1 times
Spinneret draft, residence time of the silk sprayed from spinning head in coagulating bath is 20s.
(3) spinning post-processes: carrying out neutralization washing and drying to as-spun fibre, stretches the processes such as thermal finalization, heat setting temperature
190 DEG C, heat-setting time 15 minutes, hollow PVA fiber was made in hot-stretch multiple 10.Hollow space diameter is 70 μm, and PVA is fine
Contain copper, titanium elements and boron element in dimension, the mass content of copper, titanium elements and boron element in PVA fiber is
The polyethylene glycol for being also 2500 containing molecular weight in 2.5%, PVA fiber.
Embodiment 2
Hollow PVA fiber is prepared referring to embodiment 1, wherein PVA fiber is by the degree of polymerization 2000, alcoholysis degree 99.5
(mol) polyvinyl alcohol of % is prepared through spinning, and the section of the PVA fiber is hollow structure, and hollow space diameter is 50 μm,
Contain copper in PVA fiber, copper is also to contain molecular weight in 0.08%, PVA fiber in the mass content in PVA fiber
For 1000 polyethylene glycol.
Embodiment 3
Hollow PVA fiber is prepared referring to embodiment 1, wherein PVA fiber is by the degree of polymerization 1700, alcoholysis degree 99.0
(mol) polyvinyl alcohol of % is prepared through spinning, and the section of the PVA fiber is hollow structure, and hollow space diameter is 70 μm,
Contain copper and titanium elements in PVA fiber, the mass content of copper and titanium elements in PVA fiber is 1.5%, PVA fine
The polyethylene glycol for being also 1500 containing molecular weight in dimension.
Embodiment 4
Hollow PVA fiber is prepared referring to embodiment 1, wherein PVA fiber is by the degree of polymerization 2400, alcoholysis degree 99.9
(mol) polyvinyl alcohol of % is prepared through spinning, and the section of the PVA fiber is hollow structure, and hollow space diameter is 100 μ
Contain copper and boron element in m, PVA fiber, the mass content of copper and boron element in PVA fiber is 1.0%, PVA
The polyethylene glycol for being also 2800 containing molecular weight in fiber.
Embodiment 5
Hollow PVA fiber is prepared referring to embodiment 1, wherein PVA fiber is by the degree of polymerization 1500, alcoholysis degree 99.6
(mol) polyvinyl alcohol of % is prepared through spinning, and the section of the PVA fiber is hollow structure, and hollow space diameter is 80 μm,
Contain copper and boron element in PVA fiber, the mass content of copper and boron element in PVA fiber is 0.08%, copper coin
The molar ratio of element and boron element is 5:3.
Embodiment 6
Hollow PVA fiber is prepared referring to embodiment 1, wherein PVA fiber is by the degree of polymerization 2400, alcoholysis degree 99.9
(mol) polyvinyl alcohol of % is prepared through spinning, and the section of the PVA fiber is hollow structure, and hollow space diameter is 60 μm,
Contain copper, titanium elements and boron element, the mass content of copper, titanium elements and boron element in PVA fiber in PVA fiber
Be 2.5%, the molar ratio of copper, titanium elements and boron element is 3:3:2, in PVA fiber also containing molecular weight be 3000 it is poly-
Ethylene glycol.
Embodiment 7
Hollow PVA fiber is prepared referring to embodiment 1, wherein PVA fiber is by the degree of polymerization 2800, alcoholysis degree 99.8
(mol) polyvinyl alcohol of % is prepared through spinning, and the section of the PVA fiber is hollow structure, and hollow space diameter is 0.8 μ
Contain titanium elements in m, PVA fiber, mass content of the titanium elements in PVA fiber is 0.8%.
Embodiment 8
Hollow PVA fiber is prepared referring to embodiment 1, wherein PVA fiber is by the degree of polymerization 2400, alcoholysis degree 99.6
(mol) polyvinyl alcohol of % is prepared through spinning, and the section of the PVA fiber is hollow structure, and hollow space diameter is 20 μm,
Contain vanadium in PVA fiber, vanadium is also to contain molecular weight in 0.8%, PVA fiber in the mass content in PVA fiber
For 3500 polyethylene glycol.Oil gas field base fluid obtained can be used for oil-gas field fracturing liquid, oil-gas field fracturing, and temporarily stifled liquid, oil gas field are solid
In well agent and the other constructions of oil gas field.
Embodiment 9
A kind of fibre-bearing guar gum fracturing fluid is present embodiments provided, the preparation method is as follows:
Step 1: under stirring condition, 0.2 parts by weight thickening agent hydroxypropyl guar gum (China is added into 100 parts by weight water
Oil substance Kunshan company), then 0.12 parts by weight sodium carbonate, 0.1 parts by weight potassium chloride stirs 20min, obtain guar gum thickening
Agent aqueous solution；
Step 2: under agitation, being added 0.2 parts by weight of crosslinking agent zinc sulfate in Xiang Shangshu thickening agent aqueous solution, it obtains
To guar gum fracturing fluid (not fibre-bearing guar gum fracturing fluid)；
Step 3: being added PVA fiber made from 0.5 parts by weight of example 1 in Xiang Shangshu guar gum fracturing fluid, fiber prescind to
6mm length is added in oil-gas field fracturing liquid and is uniformly dispersed, and obtains fibre-bearing guar gum fracturing fluid.
Step 4: above-mentioned fibrous guanidine gum fracturing fluid is added to together along with proppant (clay, quartz sand etc.)
In oil/gas well, 0.02 parts by weight gel breaker ammonium persulfate is added in the pressing crack construction later period.
Test example 10:(comparative example 1)
A kind of fibre-bearing guar gum fracturing fluid is present embodiments provided, the preparation method is as follows:
Step 1: under stirring condition, 0.2 parts by weight thickening agent hydroxypropyl guar gum (China is added into 100 parts by weight water
Oil substance Kunshan company), then 0.12 parts by weight sodium carbonate, 0.1 parts by weight potassium chloride stirs 20min, obtain guar gum thickening
Agent aqueous solution；
Step 2: during fracturing work, under agitation, 0.2 parts by weight are added in Xiang Shangshu thickening agent aqueous solution
Crosslinking agent FAL-120 (Wanke Petroleum & Natural-Gas Technical Engineering Co., Ltd., Langfang City), obtains guar gum fracturing fluid (not fibre-bearing melon
Fracturing fluid)；
Step 3: be added in Xiang Shangshu guar gum fracturing fluid 0.5 parts by weight of polypropylene nitrile fiber (tensile strength 100MPa,
Real density is 0.98g/cm3, and length 5mm, diameter is 78 μm), it is uniformly mixed, obtains fibre-bearing guar gum fracturing fluid.
Step 4: above-mentioned fibrous guanidine gum fracturing fluid is added to together along with proppant (clay, quartz sand etc.)
In oil/gas well, 0.02 parts by weight gel breaker ammonium persulfate is added in the pressing crack construction later period.
Fracturing fluid viscosity 55mPas obtained, the rate of settling 0.52 (cm/min), the row of returning is 32h the time.
Embodiment 11
The prop-carrying capacity that sand method verifying fracturing fluid is taken using static state, is carried out, experimental procedure is as follows at room temperature in the lab:
(1) a certain proportion of thickening agent hydroxypropyl guar gum is added in clear water, prepares thickening agent aqueous solution；
(2) fiber made from embodiment 1 is added according to experiment demand and proppant (selects the haydite of 0.3~0.6mm, symbol
SY/T5108-2006 standard is closed, percentage of damage is 4.0%), to add appropriate crosslinking agent aluminum sulfate and stir to form pressure at 69MPa
Liquid is split, the mixture of fracturing fluid, fiber and proppant is poured into graduated cylinder；
(3) mixture obtained in (2) is stood into room temperature 120min, it is high records sedimentation of the proppant in fracturing fluid
It spends and calculates sinking speed (settling height is divided by the sedimentation time), be specifically shown in the following table 1.
| 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 |
From table 1, it is evident that when thickener concentration is all 0.50wt%, proppant is in 1 group of fracturing fluid (not fibre-bearing
Fracturing fluid) in the rate of settling be far longer than the rate of settling in 2 groups of fracturing fluids (fibrous fracturing fluid), it is possible thereby to see
Out, the addition of fiber substantially increases the prop-carrying capacity of fracturing fluid.In 2 groups of fracturing fluids, (thickener concentration is proppant
The fibre-bearing fracturing fluid of 0.50wt%) it neutralizes in 3 groups of fracturing fluids (thickener concentration is 1.20wt% without fiber fracturing liquid)
The rate of settling it is suitable, thus can illustrate, fiber use can reduce fracturing fluid in thickening agent concentration while guarantee
The prop-carrying capacity of fracturing fluid.
It referring to embodiment 9 and embodiment 11, is run according to following parameter, detects PVA fiber prepared in the above embodiments and make
For the performance of oil-gas field fracturing liquid, in table 2, embodiment 1 refers to the hollow PVA fiber prepared using embodiment 1, and so on
Embodiment 1-8；The detection temperature of viscosity is 25 DEG C or so, rate of settling unit (cm/min).
From Table 2, it can be seen that the PVA fiber of the invention containing special construction is added in fracturing fluid, it can be obvious
Improve the prop-carrying capacity of fracturing fluid.Moreover, wanting two or three talent under normal circumstances from the point of view of with regard to the row's of returning time after pressing crack construction
Return drained, and our product can return in 2 hours drained after having used, and good not needing is two hours equal.Just the row's of returning efficiency is come
See, used the oil and gas well fracturing fluid of fiber of the present invention return row lead ratio without using (embodiment 8-2) it is high by 20% or more；With embodiment
For 8-1, the row of returning of the oil and gas well fracturing fluid of embodiment 8-1 leads higher than embodiment 8-2 by 24% or so after 15 hours.Just return drain
From the point of view of silt content, uses the oil and gas well fracturing fluid of fiber of the present invention to return drain silt content ratio and lowered without using (embodiment 8-2)
10~30%；By taking embodiment 8-1 as an example, lower 27% or so for embodiment 8-2.For oil gas well production, make
Do not use fiber (embodiment 8-2) of the present invention high by 50% or more with the fracturing fluid oil/gas well ratio of fiber of the present invention；To implement
For example 8-1, the output increased 53% or so of the oil/gas well of the fracturing fluid than having used embodiment 8-2.
It will be added in conventional oil gas well cementing agent containing hollow PVA fiber, through experimental results demonstrate PVA fiber is in oil
When mass content in gas well cementing agent is 0.3~3.0%, hollow PVA fiber and the ingredient of well cementation agent are sufficiently acted on, Jin Erzeng
The intensity and toughness of strong well cementing material, can also play the role of leakproof；Conventional oil gas field will be added to containing hollow PVA fiber
In pressure break diverting agent, since there is PVA fiber good drop to consider mistake effect, one layer of shielding layer is formed at the position for being intended to temporarily block up, is made
Fracturing fluid smoothly turns to；And the PVA fiber that the present invention uses has good degradability, the ingredient for remaining in ground end will not be to ring
Border pollutes.
Claims (21)
1. a kind of hollow PVA fiber, it is characterised in that: by the degree of polymerization be 1000~3500, alcoholysis degree be 99.0~99.9mol%
PVA spinning be prepared, the PVA fiber cross-sectional be hollow structure, 0.1~100 μm of hollow portion diameter；
The preparation method of the hollow PVA fiber, using following steps:
(1) preparation of spinning solution: being 1000~3500 by the degree of polymerization, and alcoholysis degree is the PVA and packet of 99.0~99.9mol%
Include that the raw material including copper sulphate, titanium tetrachloride, boric acid is soluble in water to be made into spinning solution, wherein quality of the PVA in stoste is dense
Degree is 13~18%, and copper sulphate is 2~5% relative to the mass concentration of PVA, and titanium tetrachloride is 0.5 relative to the mass concentration of PVA
~2.0%, boric acid is 0.5~2.0% relative to the mass concentration of PVA, and stoste is warming up to 95~110 DEG C, keeps pressure 0.01
~0.15MPa enters spinning process after dissolution 3~15 hours；
(2) spinning: being pumped to filament spinning component for the metering of PVA stoste, and PVA stoste is sprayed into coagulating bath from spinning head aperture,
The spinneret of filament spinning component is using the composite spinneret for being passed through gas among spinneret orifice；The ingredient of coagulating bath is sodium sulphate and hydrogen-oxygen
Change sodium, wherein 320~380g/L of sodium sulfate concentration, 30~70g/L of concentration of sodium hydroxide, are adopted by 40~50 DEG C of coagulation bath temperature
With 1~2 times of spinneret draft, residence time of the silk sprayed from spinning head in coagulating bath is 10~30s；
(3) spinning post-processes: neutralization washing and drying carried out to as-spun fibre, stretches heat-setting process, heat setting temperature 170~
260 DEG C, heat-setting time 3~20 minutes, hollow PVA fiber was made in hot-stretch multiple 2~15.
2. hollow PVA fiber as described in claim 1, it is characterised in that: the degree of polymerization of the PVA is 1000~2500, alcohol
Xie Du is 99.2~99.9mol%.
3. hollow PVA fiber as claimed in claim 1 or 2, it is characterised in that: the hollow PVA fiber can also contain molecule
The polyethylene glycol that amount is 500 ~ 5000.
4. hollow PVA fiber as described in claim 1, it is characterised in that: the spinning solution is laggard at dissolution 3~15 hours
Before entering spinning process, viscosity at 50 DEG C is 5000~20000mPas.
5. hollow PVA fiber as described in claim 1 or 4, it is characterised in that: sodium vanadate is also added in the spinning solution,
Sodium vanadate is 0.2~1.2% relative to the mass concentration of PVA.
6. purposes of the hollow PVA fiber in oil-gas field fracturing liquid as described in claim any one of 1-2.
7. purposes of the hollow PVA fiber in oil-gas field fracturing liquid as claimed in claim 3.
8. the oil-gas field fracturing liquid comprising any one of the claim 1-2 hollow PVA fiber, it is characterised in that: the PVA is fine
Tieing up the mass content in oil-gas field fracturing liquid is 0.1~2.5%.
9. the oil-gas field fracturing liquid comprising hollow PVA fiber described in claim 3, it is characterised in that: the PVA fiber is in oil gas
Mass content in the fracturing fluid of field is 0.1~2.5%.
10. 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 boric acid, borax, organic boron, organic zirconium, aluminum sulfate, nitre
The combination of one or more of sour aluminium, titanium tetrachloride, titanium sulfate, zinc sulfate, organic titanium；The gel breaker is potassium peroxydisulfate, mistake
Ammonium sulfate, potassium bichromate, potassium permanganate, amylase or organic acid.
11. oil-gas field fracturing liquid as claimed in claim 9, 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 boric acid, borax, organic boron, organic zirconium, aluminum sulfate, nitre
The combination of one or more of sour aluminium, titanium tetrachloride, titanium sulfate, zinc sulfate, organic titanium；The gel breaker is potassium peroxydisulfate, mistake
Ammonium sulfate, potassium bichromate, potassium permanganate, amylase or organic acid.
12. oil-gas field fracturing liquid as claimed in claim 8, it is characterised in that: the oil-gas field fracturing liquid at normal temperature viscous
Degree is 80~200mPas.
13. oil-gas field fracturing liquid as claimed in claim 9, it is characterised in that: the oil-gas field fracturing liquid at normal temperature viscous
Degree is 80~200mPas.
14. hollow PVA fiber temporarily blocks up the purposes in liquid in oil-gas field fracturing as described in claim any one of 1-2.
15. hollow PVA fiber as claimed in claim 3 temporarily blocks up the purposes in liquid in oil-gas field fracturing.
16. the oil-gas field fracturing comprising any one of the claim 1-2 hollow PVA fiber temporarily blocks up liquid, it is characterised in that: described
PVA fiber is 0.2~3.0% in the mass content that oil-gas field fracturing temporarily blocks up in liquid.
17. the oil-gas field fracturing comprising hollow PVA fiber described in claim 3 temporarily blocks up liquid, it is characterised in that: the PVA fiber
It is 0.2~3.0% in the mass content that oil-gas field fracturing temporarily blocks up in liquid.
18. purposes of the hollow PVA fiber in oil gas field well cementation agent as described in claim any one of 1-2.
19. purposes of the hollow PVA fiber as claimed in claim 3 in oil gas field well cementation agent.
The agent 20. oil gas field comprising any one of the claim 1-2 hollow PVA fiber is cemented the well, it is characterised in that: the PVA
Mass content of the fiber in oil gas field well cementation agent is 0.3~3.0%.
The agent 21. oil gas field comprising any one of the claim 3 hollow PVA fiber is cemented the well, it is characterised in that: the PVA is fine
The mass content tieed up in oil gas field well cementation agent is 0.3~3.0%.
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| 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 |
| CN111620430B (en) * | 2020-06-04 | 2021-08-31 | 浙江大学 | Hollow fiber membrane reactor based on metal thin film catalysis, manufacturing method and application |
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