CN107268105B - High-strength high-modulus PVA fiber and preparation method and application thereof - Google Patents
High-strength high-modulus PVA fiber and preparation method and application thereof Download PDFInfo
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- CN107268105B CN107268105B CN201610214227.5A CN201610214227A CN107268105B CN 107268105 B CN107268105 B CN 107268105B CN 201610214227 A CN201610214227 A CN 201610214227A CN 107268105 B CN107268105 B CN 107268105B
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- 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
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B16/04—Macromolecular compounds
- C04B16/06—Macromolecular compounds fibrous
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- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
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- D01D5/12—Stretch-spinning methods
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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Abstract
The invention discloses a high-strength high-modulus PVA fiber and a preparation method and application thereof. The invention provides a PVA fiber which is prepared from polyvinyl alcohol with polymerization degree of 1000-2500 and alcoholysis degree of 99.2-99.9 (mol)%, the single fiber linear density of the fiber is 1-5 dtex, the dry breaking strength is more than or equal to 10cN/dtex, and the dispersibility is less than or equal to 3 grade. The invention has the advantages of degradability and strong sand carrying capacity, is very suitable for the fields of fracturing fluid of oil and gas fields, well cementing agent of oil and gas fields, temporary plugging agent of oil and gas fields, battery diaphragm, cement concrete reinforcement and the like, and can not cause new pollution to the environment.
Description
Technical Field
The invention relates to a PVA fiber, in particular to a PVA fiber and a preparation method and application thereof.
Background
The low-permeability oil gas resource amount in China is huge, accounts for over 70 percent of the total reserve volume which is proved to be a main potential work area for increasing storage and increasing production in future. The oil and gas resources have the characteristics of low exploratory rate, low natural input rate and low recovery rate. Fracturing is an important technical measure for increasing the yield of oil and gas fields and increasing the injection of water injection wells. The performance of the fracturing fluid is a key factor for the success or failure of fracturing. At present, the common fracturing fluid at home and abroad is water-based fracturing fluid, wherein the water-based fracturing fluid taking natural vegetable gum as a thickening agent is most widely applied. However, as the natural vegetable gum contains 6-8% of water-insoluble substances, the water-based fracturing fluid cannot break the gum thoroughly, so that more residues are retained in the stratum, the stratum is damaged, and the modification effect of the reservoir is seriously influenced.
China patent CN200610063700.0A discloses a composite fracturing fluid, a compound gelling agent is 0.4-1.0 wt% of the fracturing fluid, a metal cross-linking agent is 0.05-0.7 wt% of the fracturing fluid, an oxidation gel breaker is 0.05-0.5 wt% of the fracturing fluid, and the balance is water, CN 201410088243.5A discloses a quick-dissolving modified cellulose cross-linking clean fracturing fluid, which adopts the components of 0.2-0.6 part of FAG-500 type modified cellulose, 0.1-0.5 part of FAZ-1 type tackifying initiator, 0.3-0.7 part of D L-16 type drainage assistant, 0.5-1.2 part of FAJ-305 type cross-linking regulator, 0.2-0.7 part of FAC-201 type polar chelating organic cross-linking agent, 0.2-0.7 part of NBA-102 type capsule gel breaker, 0.002 weight of FAJ-305 type crosslinking regulator, 0.2-0.7 part of NBA-201 type polar chelating organic cross-linking agent, 0.2 part of NBA-0.7 part of NBA-102 type gel breaker, 0.002, 0.07 part of CN-0.7 part of a polyvinyl alcohol fiber, the fiber and the fiber can be used as a fracturing fluid, the fracturing fluid can reduce the fracture strength of the fracturing fluid of a fracturing fluid, the fiber of a fracturing fluid, the fiber fracturing fluid can reduce the fiber fracturing fluid, the fiber fracturing fluid, the fiber fracturing.
Disclosure of Invention
In order to solve the problems of the prior art, according to a first aspect of the present invention, it is an object of the present invention to provide a PVA fiber.
The percentages are all mass percentages unless otherwise specified.
The purpose of the invention is realized by the following technical measures:
a PVA fiber is prepared from polyvinyl alcohol with polymerization degree of 1000-2500 and alcoholysis degree of 99.2-99.9 (mol)% and grooves are formed on the surface of the PVA fiber in a morphological structure.
According to one embodiment of the present invention, the surface of the above-described PVA fiber morphology structure is a longitudinal groove.
According to an embodiment of the present invention, the width of the PVA fiber grooves is 0.5 to 5 μm.
According to one embodiment of the present invention, the ratio of the above-mentioned amorphous region of PVA fiber is 20% or more.
According to one embodiment of the invention, the single fiber density of the PVA fiber is 1-5 dtex, the dry breaking strength is more than or equal to 10cN/dtex, and the dispersibility is less than or equal to 3 grade.
According to an embodiment of the present invention, the PVA fiber has a density of 1.2 to 1.4g/cm3The modulus is 150 to 500cN/dtex, and the fiber length is 2 to 40 mm.
According to a second aspect of the present invention, there is provided a method for producing the above PVA fiber, comprising the steps of:
(1) preparing a spinning solution: dispersing PVA with the polymerization degree of 1000-2500 and the alcoholysis degree of 99.2-99.9 (mol%), boric acid (or borax) and titanium dioxide in water to prepare a spinning stock solution, wherein the mass concentration of the PVA in the stock solution is 10-30%, the mass concentration of the boric acid (or borax) relative to the PVA is 0.8-2.0%, and the addition amount of the titanium dioxide is 0.2-5% of the mass of the PVA, heating the stock solution to 95-110 ℃, keeping the pressure at 0.01-0.15 MPa, dissolving for 3-15 hours, standing and defoaming for 3-7 hours at normal pressure, and then entering a spinning process;
(2) spinning: the method comprises the following steps of (1) conveying a PVA stock solution to a spinning assembly by using a metering pump, spraying the PVA stock solution into a coagulation bath from small holes of a spinning nozzle, adding sodium hydroxide to adjust the pH value of the coagulation bath to be 8.5-12.5, adjusting the temperature of the coagulation bath to be 35-55 ℃, adopting-1-2 times of the drawing times of the spinning nozzle, and keeping the filament sprayed from the spinning nozzle in the coagulation bath for 10-30 s; the coagulating bath comprises sodium sulfate and ammonium sulfate, wherein the concentration of the sodium sulfate is 300-400 g/l, and the concentration of the ammonium sulfate is 20-150 g/l;
(3) and (3) spinning post-treatment, namely drying the nascent fiber, stretching and heat-setting, wherein the heat-setting temperature is 170-260 ℃, the heat-stretching ratio is 2-15, and the heat-setting time is 3-20 minutes, so that the high-strength and high-modulus PVA fiber is prepared.
And (2) taking a part of stock solution, cooling the temperature to 50 ℃, and measuring the viscosity of the stock solution to be 5000-2000 mPas before entering a spinning process after the stock solution is dissolved for 3-15 hours in the step (1).
According to a third aspect of the invention, the invention provides the use of a PVA fiber as described above in a fracturing fluid for oil and gas fields. The inventor surprisingly finds that when the PVA fiber is added into the fracturing fluid of the oil and gas field, the PVA fiber and the fracturing fluid of the oil and gas field have full effects, so that the PVA fiber and the propping agent can be kept in a good suspension state, the sand carrying performance is greatly improved, and the flowback time is greatly shortened.
According to one embodiment of the invention, the oil and gas field fracturing fluid is any one of water-based fracturing fluids in the prior art.
According to a fourth aspect of the present invention there is provided a field fracturing fluid comprising PVA fibres as described above.
According to one embodiment of the invention, the PVA fiber is added into the oil and gas field fracturing fluid and is uniformly dispersed, wherein the mass content of the PVA fiber in the oil and gas field fracturing fluid is 0.2-2.0%.
A large number of experiments prove that the PVA fiber and the guanidine gum are used in the water-based oil-gas field fracturing fluid, and the suspending and carrying proppant has better performance.
According to one embodiment of the invention, the water-based field fracturing fluid comprises a viscosifier, and may further comprise a cross-linking agent or a breaker; the thickening agent is used for improving the viscosity of the fracturing fluid, reducing the filtration loss of the fracturing fluid, suspending and carrying a propping agent, and the common thickening agent is guanidine gum; after the PVA fiber is added into fracturing fluid of oil and gas fields, no thickening agent or less thickening agent is used. The cross-linking agent is one or a combination of a plurality of boric acid, borax, organic boron, organic zirconium, aluminum sulfate, aluminum nitrate, titanium tetrachloride, titanium sulfate, zinc sulfate and organic titanium; the gel breaker is biological enzyme or organic acid such as potassium persulfate, ammonium persulfate, potassium dichromate, potassium permanganate, capsule containing enzyme or acid, amylase, etc.
According to an embodiment of the invention, the oil-gas field fracturing fluid can also be added with assistants such as clay stabilizer, cleanup additive, bactericide, foaming agent, defoaming agent, demulsifier and the like. The clay stabilizer can prevent the clay mineral in the oil-gas layer from hydration expansion and dispersion migration, and can be potassium chloride or anionic surfactant. The bactericide, such as chlorine and quaternary ammonium salt, is added to maintain the stability of the surface of the glue solution and prevent the growth of bacteria in the stratum. The cleanup additive is used for reducing the surface tension or oil-water interfacial tension of the fracturing fluid, increasing the contact angle with rocks and reducing capillary resistance encountered during flowback of the fracturing fluid, such as sodium dodecyl sulfate. The foaming agent acts to provide some momentum to the formation and to displace drainage-promoting fluids from the formation, such as cationic surfactants.
According to an embodiment of the invention, the PVA fiber can be added into the fracturing fluid of the oil and gas field only in the preparation stage of fracturing, or can be added into the fracturing fluid in steps in the early stage of fracturing, the middle stage of fracturing and the tail stage of fracturing.
According to one embodiment of the invention, the oil and gas field fracturing fluid is constructed in a formation at a temperature below 130 ℃.
According to a fifth aspect of the present invention, the present invention provides the use of the above PVA fibers in an oil and gas field fracturing temporary plugging agent.
According to a sixth aspect of the invention, the invention provides an oil and gas field fracturing temporary plugging agent containing the PVA fiber, wherein the PVA fiber is uniformly dispersed when being added into the oil and gas field fracturing temporary plugging agent, and the mass content of the PVA fiber in the oil and gas field fracturing temporary plugging agent is 0.2-2.5%.
According to a seventh aspect of the present invention, the present invention provides the use of the above PVA fibres in a cementing agent for oil and gas fields.
According to the eighth aspect of the invention, the oil and gas field cementing agent containing the PVA fiber is provided, the high-strength and high-modulus PVA fiber is added into the oil and gas field cementing agent and is uniformly dispersed, and the mass content of the PVA fiber in the oil and gas field cementing agent is 0.1-3.0%.
According to a ninth aspect of the present invention, there is provided the use of the above PVA fibers in a cement concrete reinforcing agent.
According to a tenth aspect of the present invention, there is provided a cement concrete reinforcing agent comprising the PVA fibers, wherein the PVA fibers are uniformly dispersed in lime and water to form a reinforced cement, and the PVA fibers are contained in the cement in an amount of 0.2 to 2.0% by mass.
According to an eleventh aspect of the present invention, the present invention provides the use of the above PVA fibers in the field of battery separators.
The invention has the advantages of
1. The PVA fiber provided by the invention has a special structure, and when the PVA fiber is used in the fracturing fluid of an oil and gas field, the fiber can be better combined with a propping agent, so that the sand carrying capacity of the fracturing fluid is greatly improved.
2. The PVA fiber provided by the invention has a special structure, and can be better combined with cement and other support systems when being used in the fields of oil field well cementation, oil field temporary plugging, cement concrete reinforcement and battery diaphragms, so that the functions of well cementation, temporary plugging, cement reinforcement and the like can be better played.
3. The PVA fiber provided by the invention has high dry breaking strength and modulus, overcomes the defects of the conventional PVA fiber in mechanical property, and can play a good mechanical effect when being used in special fields such as oil and gas field fracturing fluid, oil and gas field well cementing agent, oil and gas field temporary plugging agent, battery diaphragm, cement concrete reinforcement and the like.
4. When the PVA fiber provided by the invention is used for fracturing of an oil and gas field, the PVA fiber also has the advantages of good sand suspending effect, short gel breaking time, high flowback efficiency, small damage to stratum, remarkable yield increasing effect and the like.
5. After the PVA fiber provided by the invention is combined with a thickening agent, a cross-linking agent and the like, a system can be further thickened to form jelly, and the jelly becomes a typical viscoelastic fluid; after fracturing and crack making and sand filling are formed, under the condition of bottom layer pressure and temperature, the chemical bonds of the high molecular groups connected into a net structure are broken under the action of the gel breaker and degraded into smaller molecular groups, so that the viscosity is reduced, the high-viscosity fracturing fluid is rapidly and thoroughly broken, the viscosity is reduced, and the hydration residual liquid of gel breaking is conveniently drained back as soon as possible.
6. When the PVA fiber provided by the invention is used for oil-gas field fracturing, the dosage of conventional thickening agent guanidine gum can be reduced, and the damage of fracturing fluid to stratum can be reduced.
7. The PVA fiber provided by the invention has degradable performance, and can not cause new pollution to the environment when being used in the fields of oil and gas field fracturing fluid, oil and gas field cementing agent, oil and gas field temporary plugging agent, battery diaphragm, cement concrete reinforcement and the like.
Drawings
FIG. 1: scanning electron microscope photographs of the high strength and high modulus PVA fibers prepared in example 1.
FIG. 2 is a drawing: SEM photograph of PVA fiber obtained in comparative example 1.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the examples are only for illustrative purposes and should not be construed as limiting the scope of the present invention, and that those skilled in the art can make insubstantial modifications and adaptations of the present invention based on the above disclosure. The raw materials used in the invention are all commercial products.
The tests of dry breaking strength, single fiber linear density and modulus of PVA fiber are carried out according to GB/T14462-1993. PVA fiber dispersibility was tested by reference (Q/SH 1115221-2012). The proportion of the amorphous regions of the PVA fibers was determined by thermal analysis. The morphology and structure of the PVA fiber are tested by a scanning electron microscope.
Example 1: the high-strength high-modulus PVA fiber is prepared by the following steps:
(1) preparing a spinning solution: dispersing PVA with the polymerization degree of 1700 and the alcoholysis degree of 99.5 (mol)% in water to prepare spinning stock solution, wherein the mass concentration of the PVA in the stock solution is 16%, the addition amount of the boric acid is 1.2% of the mass of the PVA, the addition amount of the titanium dioxide is 0.25% of the mass of the PVA, heating the stock solution to 100 ℃, keeping the pressure at 0.10MPa, dissolving for 8 hours, standing and defoaming for 3 hours at normal pressure, and then entering the spinning process.
(2) Spinning: the PVA dope is delivered to the spinning pack by a metering pump and sprayed into a coagulation bath from the small holes of the spinneret. The components of the coagulating bath are sodium sulfate and ammonium sulfate, wherein the concentration of the sodium sulfate is 350g/l, the concentration of the ammonium sulfate is 85g/l, sodium hydroxide is added to adjust the PH of the coagulating bath to be 10.5, the temperature of the coagulating bath is 38 ℃, the drawing times of a spinning nozzle are-0.5 times, and the retention time of the filaments sprayed from the spinning nozzle in the coagulating bath is 15 s.
(3) And (3) spinning post-treatment, namely drying the nascent fiber, stretching and heat-setting, and the like, wherein the heat-setting temperature is 190 ℃, the heat-stretching multiple is 8 times, and the heat-setting time is 10 minutes, so that the high-strength high-modulus PVA fiber is prepared.
Scanning the prepared high-strength high-modulus PVA fiber by an electron microscope, wherein the surface of the prepared high-strength high-modulus PVA fiber is provided with a longitudinal groove, the width of the groove is 0.5-5 mu m, the amorphous area of the PVA fiber accounts for 22%, the single-fiber linear density of the prepared PVA fiber is 1.5dtex, the dry breaking strength is 15cN/dtex, the dispersibility is 3 grade, and the fiber modulus is 350 cN/dtex.
Example 2: the high-strength high-modulus PVA fiber is prepared by the following steps:
(1) preparing a spinning solution: dispersing PVA with the polymerization degree of 2400 and the alcoholysis degree of 99.8 (mol)% in water to prepare spinning stock solution, wherein the mass concentration of the PVA in the stock solution is 14%, the addition amount of the boric acid is 1.8% of the mass of the PVA, the addition amount of the titanium dioxide is 0.4% of the mass of the PVA, heating the stock solution to 105 ℃, keeping the pressure at 0.08MPa, dissolving for 10 hours, standing at normal pressure for defoaming for 6 hours, and then entering the spinning process.
(2) Spinning: the PVA dope is delivered to the spinning pack by a metering pump and sprayed into a coagulation bath from the small holes of the spinneret. The components of the coagulating bath are sodium sulfate and ammonium sulfate, wherein the concentration of the sodium sulfate is 330g/l, the concentration of the ammonium sulfate is 45g/l, sodium hydroxide is added to adjust the PH of the coagulating bath to be 11.5, the temperature of the coagulating bath is 45 ℃, the drawing times of a spinning nozzle are-0.75 times, and the retention time of the filaments sprayed from the spinning nozzle in the coagulating bath is 10 s.
(3) And (3) spinning post-treatment, namely drying the nascent fiber, stretching and heat-setting, and the like, wherein the heat-setting temperature is 200 ℃, the heat-stretching multiple is 7 times, and the heat-setting time is 15 minutes, so that the high-strength high-modulus PVA fiber is prepared.
Scanning the prepared high-strength high-modulus PVA fiber by an electron microscope, wherein the surface of the prepared high-strength high-modulus PVA fiber is provided with a longitudinal groove, the width of the groove is 0.5-5 mu m, the amorphous area of the PVA fiber accounts for 28%, the single-fiber linear density of the prepared PVA fiber is 2.8dtex, the dry breaking strength is 20cN/dtex, the dispersibility is 1 grade, and the fiber modulus is 300 cN/dtex.
Example 3: the high-strength high-modulus PVA fiber is prepared by the following steps:
(1) preparing a spinning solution: dispersing PVA with the polymerization degree of 2000 and the alcoholysis degree of 99.9 (mol)% in water to prepare spinning stock solution, wherein the mass concentration of the PVA in the stock solution is 13%, the addition amount of the boric acid is 1.0% of the mass of the PVA, the addition amount of the titanium dioxide is 3.0% of the mass of the PVA, heating the stock solution to 100 ℃, keeping the pressure at 0.06MPa, dissolving for 9 hours, standing at normal pressure for defoaming for 5 hours, and then entering the spinning process.
(2) Spinning: the PVA dope is delivered to the spinning pack by a metering pump and sprayed into a coagulation bath from the small holes of the spinneret. The components of the coagulating bath are sodium sulfate and ammonium sulfate, wherein the concentration of the sodium sulfate is 300g/l, the concentration of the ammonium sulfate is 150g/l, sodium hydroxide is added to adjust the PH of the coagulating bath to be 12.5, the temperature of the coagulating bath is 40 ℃, the drawing multiple of a spinning nozzle is adopted, the drawing multiple is-0.2 times, and the retention time of the silk sprayed from the spinning nozzle in the coagulating bath is 20 s.
(3) And (3) spinning post-treatment, namely drying the nascent fiber, stretching and heat-setting, and the like, wherein the heat-setting temperature is 230 ℃, the heat-stretching multiple is 4 times, and the heat-setting time is 5 minutes, so that the high-strength high-modulus PVA fiber is prepared.
Scanning the prepared high-strength high-modulus PVA fiber by an electron microscope, wherein the surface of the prepared high-strength high-modulus PVA fiber is provided with a longitudinal groove, the width of the groove is 0.5-5 mu m, the amorphous area of the PVA fiber accounts for 30%, the single-fiber linear density of the prepared PVA fiber is 2.2dtex, the dry breaking strength is 18cN/dtex, the dispersibility is 2 grade, and the fiber modulus is 380 cN/dtex.
Examples 4-8 were prepared by operating according to the following parameters with reference to the above examples.
DP represents the degree of polymerization and Ad represents the degree of alcoholysis of polyvinyl alcohol in mol/mol%.
Example 9: comparative example 1
PVA and boric acid with the polymerization degree of 2000 and the alcoholysis degree of 99.5 (mol)% are dissolved in water to prepare spinning stock solution, wherein the mass concentration of the PVA in the stock solution is 15%, the mass concentration of the boric acid in the stock solution is 1.2%, the stock solution is heated to 90 ℃, dissolved for 5 hours, kept at normal pressure and defoamed for 3 hours, and then is conveyed to a spinning assembly through a metering pump, and the PVA stock solution is sprayed into 330g/l sodium sulfate coagulation bath from a small hole of a spinning nozzle. And drying the nascent fiber, stretching and heat-setting at the temperature of 170 ℃, the heat-stretching multiple of 2 times and the heat-setting time of 3 minutes to obtain the PVA fiber.
The PVA fibers obtained in example 1 and comparative example 1 were subjected to scanning by an electron microscope, and the results are shown in FIG. 1 and FIG. 2, respectively. As can be seen from FIGS. 1 and 2, the PVA fibers prepared according to the present invention had longitudinal grooves, whereas the PVA fibers prepared by the conventional method of comparative example 1 had smooth surfaces and no grooves.
Example 10
The embodiment provides a fiber-containing guar gum fracturing fluid, which is prepared by the following steps:
the method comprises the following steps: adding 0.2 weight part of thickening agent hydroxypropyl guar gum (Kunshan corporation, China Petroleum substance), 0.12 weight part of sodium carbonate and 0.1 weight part of potassium chloride into 100 weight parts of water under stirring, and stirring for 20min to obtain a guar thickening agent water solution;
step two: in the fracturing operation process, under the stirring condition, 0.2 part by weight of cross-linking agent zinc sulfate is added into the thickening agent aqueous solution to obtain guar gum fracturing fluid (without fiber guar gum fracturing fluid);
step three: and (2) adding 0.5 part by weight of PVA fiber prepared in the example 1 into the guar gum fracturing fluid, cutting the fiber to 6mm, adding the fiber into the oil-gas field fracturing fluid, and uniformly dispersing to obtain the fiber-containing guar gum fracturing fluid.
Step four: the fiber-containing guanidine gum fracturing fluid is added into an oil-gas well along with a propping agent (argil, quartz sand and the like), and 0.02 part by weight of a gel breaker ammonium persulfate is added at the later stage of fracturing construction. The guar gum fracturing fluid containing fibers can be applied to fracturing construction of wells at 128 ℃.
Example 11
Referring to example 10, the high-strength high-modulus PVA fibers prepared in example 1 were chopped to a length of 6mm, added to a fracturing fluid in an oil and gas field, and uniformly dispersed, when the PVA fibers were added, the PVA fibers were added to the fracturing fluid in three steps, namely, a pre-fracturing stage, a middle fracturing stage, and a post fracturing stage, respectively, the fracturing fluid in the oil and gas field further added with guanidine gum and a crosslinking agent, the mass content of the PVA fibers in the fracturing fluid in the oil and gas field was 1.2%, and the prepared fracturing fluid in the oil and gas field was used in a formation with a maximum temperature of 98 ℃.
Example 12
Referring to example 10, the high-strength high-modulus PVA fibers prepared in example 2 were chopped to a length of 12mm, added to an oil and gas field fracturing fluid and dispersed uniformly, guanidine gum accounting for 0.3% of the oil and gas field fracturing fluid was also added to the oil and gas field fracturing fluid, the mass content of the PVA fibers in the oil and gas field fracturing fluid was 0.6%, and the prepared oil and gas field fracturing fluid was used in a formation with a maximum temperature of 70 ℃.
Example 13
Referring to example 10, the high-strength high-modulus PVA fibers prepared in example 3 were chopped to a length of 20mm, added to an oil and gas field fracturing fluid, and dispersed uniformly, guanidine gum and a cross-linking agent were also added to the oil and gas field fracturing fluid, the mass content of the PVA fibers in the oil and gas field fracturing fluid was 1.5%, and the prepared oil and gas field fracturing fluid was used in a formation with a maximum temperature of 120 ℃.
Example 14:
referring to example 10, the high-strength high-modulus PVA fiber prepared in example 3 is cut into 12mm in length, added into the oil and gas field fracturing fluid and dispersed uniformly, no guanidine gum is used in the oil and gas field fracturing fluid, the mass content of the PVA fiber in the oil and gas field fracturing fluid is 1.5%, and the prepared oil and gas field fracturing fluid is used in a stratum with the highest temperature of 120 ℃ for construction.
Example 15:
referring to example 10, the PVA fibers prepared in comparative example 1 were cut to 6mm in length, added to the same oil and gas field fracturing fluid as in example 1, and dispersed uniformly, when the PVA fibers were added, the PVA fibers were added to the fracturing fluid in three steps, namely, the pre-fracturing stage, the middle fracturing stage, and the post-fracturing stage, respectively, and the mass content of the PVA fibers in the oil and gas field fracturing fluid was 1.2%, and the prepared oil and gas field fracturing fluid was used in a formation with a maximum temperature of 128 ℃.
Test example 16: comparative example 2
The embodiment provides a fiber-containing guar gum fracturing fluid, which is prepared by the following steps:
the method comprises the following steps: adding 0.2 weight part of thickening agent hydroxypropyl guar gum (Kunshan corporation, China Petroleum substance), 0.12 weight part of sodium carbonate and 0.1 weight part of potassium chloride into 100 weight parts of water under stirring, and stirring for 20min to obtain a guar thickening agent water solution;
in the fracturing operation process, under the stirring condition, adding 0.2 weight part of cross-linking agent FA L-120 (Wanke oil and gas technology engineering Co., Ltd., corridor, Inc.) and 0.02 weight part of gel breaker ammonium persulfate into the thickening agent aqueous solution to obtain guar fracturing fluid (without fiber guar fracturing fluid);
step three: and adding 0.5 part by weight of polyacrylonitrile fibers (the tensile strength is 100MPa, the length is 5mm, and the diameter is 78 micrometers) into the guar gum fracturing fluid, and stirring and mixing uniformly to obtain the fiber-containing guar gum fracturing fluid.
Step four: the fiber-containing guanidine gum fracturing fluid is added into an oil-gas well along with a propping agent (argil, quartz sand and the like), and 0.02 part by weight of a gel breaker ammonium persulfate is added at the later stage of fracturing construction. The guar gum fracturing fluid containing fibers can be applied to fracturing construction of wells at 80 ℃.
Example 17
The static sand-carrying method is adopted to verify the sand-carrying capacity of the fracturing fluid, and the method is carried out at room temperature in a laboratory, and comprises the following experimental steps:
(1) adding a thickening agent hydroxypropyl guar gum in a certain proportion into clear water to prepare a thickening agent water solution;
(2) adding the fibers and the proppant prepared in the example 1 according to experimental requirements (0.3-0.6 mm of ceramsite is selected and meets the SY/T5108-2006 standard, the breakage rate is 4.0% under 69 MPa), adding a proper amount of cross-linking agent aluminum sulfate, stirring to form fracturing fluid, and pouring a mixture of the fracturing fluid, the fibers and the proppant into a measuring cylinder;
(3) the mixture obtained in (2) was left to stand at room temperature for 120min, the height of the proppant settled in the fracturing fluid was recorded and the settling rate (height of settled divided by settling time) was calculated.
| Group 1 | 2 groups of | Group 3 | |
| Thickener concentration (wt%) | 0.40wt％ | 0.40wt％ | 0.90wt％ |
| Fiber concentration (wt%) | 0 | 0.4 | 0 |
| Sedimentation Rate (cm/min) | 0.076 | 0.012 | 0.013 |
It is apparent from the table that when the concentrations of the thickening agents are all 0.40 wt%, the settling rate of the proppant in 1 group of fracturing fluid (fracturing fluid without fibers) is much greater than that in 2 groups of fracturing fluid (fracturing fluid with fibers), and thus it can be seen that the sand carrying capacity of the fracturing fluid is greatly improved by the addition of the fibers. The settling rates of the proppant in 2 groups of fracturing fluids (the fiber-containing fracturing fluid with the thickening agent concentration of 0.40 wt%) and 3 groups of fracturing fluids (the fiber-free fracturing fluid with the thickening agent concentration of 0.90 wt%) are equivalent, so that the use of the fiber can ensure the sand carrying capacity of the fracturing fluid while reducing the concentration of the thickening agent in the fracturing fluid.
The fracturing fluids of examples 10-16 were tested for sand-carrying capacity with reference to the test method of example 17.
As can be seen from the table, the PVA fiber containing the special structure is added into the fracturing fluid, so that the sand carrying capacity of the fracturing fluid can be obviously improved. In addition, in terms of flowback time after fracturing construction is finished, flowback is finished in two or three days generally, and the product can be flowback within 2 hours after being used, so that the flowback time is not required to be two hours. In terms of the flowback efficiency, the flowback efficiency using the fiber of the present invention was greatly improved, and was higher by 20% or more than that of example 15 (comparative example 1 fiber); taking example 10 as an example, the flowback rate of the oil and gas well fracturing fluid of example 10 after 15 hours is about 20% higher than that of example 15. In terms of the sand content of the flowback fluid, the sand content of the flowback fluid using the fiber of the invention is greatly reduced by 10-30% compared with that of the example 15; taking example 10 as an example, the reduction is about 25% compared with example 15. In addition, the yield of the oil and gas well using the fracturing fluid can be improved by more than 50 percent; for example 10, the production rate was improved by 60% compared to the oil and gas well using the fracturing fluid of example 15.
When the PVA with the special structure provided by the invention is used in the fields of oil field well cementation, oil field temporary plugging, cement concrete reinforcement and battery diaphragms, the PVA fiber can be better combined with cement and other support systems, so that the functions of well cementation, temporary plugging, cement reinforcement and the like can be better played.
Claims (5)
1. The application of the PVA fiber in the fracturing fluid of the oil and gas field is characterized in that the PVA fiber is prepared from polyvinyl alcohol with the polymerization degree of 1000-2500 and the alcoholysis degree of 99.2-99.9 mol%, and grooves are formed in the surface of the PVA fiber in the shape structure;
the preparation method of the PVA fiber comprises the following steps:
(1) preparing a spinning solution: dispersing PVA, boric acid or borax and titanium dioxide with the polymerization degree of 1000-2500 and the alcoholysis degree of 99.2-99.9 mol% in water to prepare a spinning stock solution, wherein the mass concentration of the PVA in the stock solution is 10-30%, the mass concentration of the boric acid or borax relative to the PVA is 0.8-2.0%, and the addition amount of the titanium dioxide is 0.2-5% of the mass of the PVA, heating the stock solution to 95-110 ℃, keeping the pressure at 0.01-0.15 MPa, dissolving for 3-15 hours, standing at normal pressure for defoaming for 3-7 hours, and then entering a spinning process;
(2) spinning, namely pumping PVA stock solution to a spinning assembly by using a metering pump, spraying the PVA stock solution into a coagulation bath from small holes of a spinning nozzle, adding sodium hydroxide to adjust the pH = 8.5-12.5 of the coagulation bath, adjusting the temperature of the coagulation bath to 35-55 ℃, adopting a spinning nozzle stretching multiple of-1-2 times, and keeping the retention time of filaments sprayed from the spinning nozzle in the coagulation bath to be 10-30 s, wherein the coagulation bath contains sodium sulfate and ammonium sulfate, the concentration of the sodium sulfate is 300-400 g/L, and the concentration of the ammonium sulfate is 20-150 g/L;
(3) and (3) spinning post-treatment, namely drying the nascent fiber, and performing a stretching and heat setting process at the heat setting temperature of 170-260 ℃, the heat stretching ratio of 2-15 and the heat setting time of 3-20 minutes to obtain the high-strength and high-modulus PVA fiber.
2. Use according to claim 1, characterized in that: the grooves are longitudinal grooves; the width of the longitudinal groove is 0.5-5 mu m.
3. Use according to claim 1, characterized in that: the proportion of the PVA fiber amorphous area is more than or equal to 20 percent.
4. Use according to claim 1, characterized in that: the PVA fiber single-fiber density is 1-5 dtex, the dry breaking strength is more than or equal to 10cN/dtex, and the dispersibility is less than or equal to 3 grade.
5. Use according to claim 1, characterized in that: the PVA fiber modulus is 150-500 cN/dtex, and the fiber length is 2-40 mm.
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| CN112095159B (en) * | 2020-08-04 | 2022-09-16 | 东华大学 | A kind of wet spinning high-strength coarse denier polyvinyl alcohol fiber and preparation method thereof |
| CN114836184B (en) * | 2022-04-26 | 2024-04-12 | 中海油(天津)油田化工有限公司 | Degradable temporary plugging agent for offshore large-leakage oil-water well workover and use method thereof |
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| CN1109114A (en) * | 1993-07-29 | 1995-09-27 | 可乐丽股份有限公司 | Polyvinyl Alcohol Based Water Soluble Fiber |
| CN103031611A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工集团公司 | Polyvinyl alcohol fiber and preparation method as well as application thereof |
| CN103075830A (en) * | 2013-01-21 | 2013-05-01 | 王伟男 | Geothermal recovery method and geothermal recovery device capable of absorbing earthquake wave energy |
| CN104405360A (en) * | 2014-10-27 | 2015-03-11 | 中石化胜利油田分公司采油工艺研究院 | Fracturing method capable of improving sand-carrying performance of fracturing liquid |
| CN105441047A (en) * | 2015-11-30 | 2016-03-30 | 长江大学 | Oil-soluble hydraulic fracture temporary plugging reorientation agent and preparation method thereof |
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| CN1109114A (en) * | 1993-07-29 | 1995-09-27 | 可乐丽股份有限公司 | Polyvinyl Alcohol Based Water Soluble Fiber |
| CN103031611A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工集团公司 | Polyvinyl alcohol fiber and preparation method as well as application thereof |
| CN103075830A (en) * | 2013-01-21 | 2013-05-01 | 王伟男 | Geothermal recovery method and geothermal recovery device capable of absorbing earthquake wave energy |
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