CN111763506B - Temporary plugging diverting agent and preparation method and application thereof - Google Patents
Temporary plugging diverting agent and preparation method and application thereof Download PDFInfo
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- CN111763506B CN111763506B CN202010657698.XA CN202010657698A CN111763506B CN 111763506 B CN111763506 B CN 111763506B CN 202010657698 A CN202010657698 A CN 202010657698A CN 111763506 B CN111763506 B CN 111763506B
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- polyglycolic acid
- temporary plugging
- agent
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 241000196324 Embryophyta Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
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- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
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- 235000014655 lactic acid Nutrition 0.000 description 1
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- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
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- 239000005060 rubber Substances 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
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Classifications
-
- 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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/5086—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/13—Methods or devices for cementing, for plugging holes, crevices or the like
- E21B33/138—Plastering the borehole wall; Injecting into the formation
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mining & Mineral Resources (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical & Material Sciences (AREA)
- Fluid Mechanics (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a temporary plugging diverting agent and a preparation method and application thereof. The temporary plugging diverter comprises the following raw materials: polyglycolic acid having a first weight average molecular weight and polyglycolic acid having a second weight average molecular weight; wherein the difference between the second weight average molecular weight and the first weight average molecular weight is not less than 10,000 and not more than 290,000; the polyglycolic acid is a homopolymer of glycolic acid and/or a copolymer having glycolic acid as a main repeating unit. The temporary plugging diverting agent can be used for temporary plugging diverting fracturing of oil and gas wells.
Description
Technical Field
The invention belongs to the technical field of oil-gas field fracturing modification, and relates to a foaming type degradable temporary plugging diverter as well as a preparation method and application thereof.
Background
As is well known, oil and gas resources such as oil and gas are produced by exploiting wells (oil wells or gas wells, which may be collectively referred to as "wells") containing porous and permeable underground layers. However, in recent years, as oil and gas fields are continuously produced, the quality of reservoirs is gradually reduced year by year, and for this reason, related oil and gas producers often adopt a reservoir fracturing modification mode to improve the permeability of underground reservoirs so as to continuously and effectively extract oil and gas resources from the underground reservoirs.
In the technical field of reservoir fracturing modification, the temporary blocking steering fracturing technology is characterized in that a temporary blocking steering agent is added in real time in fracturing construction to temporarily block an old crack or an added sand crack, and fluid is steered through the change of fracture pressure and crack extension pressure so as to create a new crack. The temporary blocking diverting agent and the action principle thereof in the cracks are that after the temporary blocking diverting agent is added in the fracturing construction based on the grain material bridging diverting material developed according to the principle of granular material bridging, because the dynamic crack width of the hydraulic fracturing crack near a shaft is the largest and the crack width becomes smaller and smaller when the hydraulic fracturing crack is farther away from a well, when the temporary blocking diverting agent and the propping agent simultaneously enter the fracturing crack in a certain proportion, under the combined action of the propping agent and the temporary blocking diverting agent, the grain diameter of the solid grains of the temporary blocking diverting agent is larger than 1/3-2/3 of the dynamic width of the crack, the solid grains of the temporary blocking diverting agent can form bridging at the position and block the road for the subsequent temporary blocking diverting agent grains to move forward, thereby forming accumulation. However, as the subsequent temporary plugging diversion agent is continuously added, more and more temporary plugging diversion agent particles generate bridge plugging and accumulation, a plugging zone with certain thickness and length can be formed in a main channel of the fracture, the continuous extension and development of the fracture are hindered and limited, the fracture is positioned in the fracture volume between the shaft and the plugging zone, the net pressure of the fracture is continuously increased along with the continuous addition of the subsequent sand carrying fluid, when the net pressure in the fracture reaches the opening pressure of the micro-fracture or the fracture pressure of a new fracture, the micro-fracture or the new fracture is opened, and along with the continuous addition of the subsequent sand carrying fluid, the opened micro-fracture or the new fracture can be extended and expanded into a new branch fracture.
In the temporary plugging diversion fracturing technology, a temporary plugging material with excellent performance is the key for realizing effective temporary plugging fracturing. However, in practical application, the conventional oil-soluble temporary plugging diversion agent and the water-soluble temporary plugging diversion agent both need to rely on formation fluid to realize plugging removal, but in some reservoirs, the problem of incomplete plugging removal may exist, and the application of the conventional oil-soluble temporary plugging diversion agent and the water-soluble temporary plugging diversion agent is limited. Different from conventional oil-soluble temporary plugging diversion agents and water-soluble temporary plugging diversion agents, the temporary plugging diversion agent prepared from the self-degradable material can be self-degraded under the conditions of formation temperature and pressure, and is gradually a research hotspot in the technical field of fracturing temporary plugging diversion of oil and gas wells. At present, relevant research works have been carried out at home and abroad aiming at the research of the degradable temporary plugging diversion agent in the fracturing process.
The invention patent application with publication number CN102653673A discloses a biodegradable temporary plugging agent, which contains a biodegradation agent, an organic swelling material and a thickening agent, wherein the biodegradation agent is a particle mixture of soybean and corn, and the biodegradation agent are effectively combined together to prepare temporary plugging particles with controllable degradation time. Although the temporary plugging agent disclosed in the patent can be completely degraded in a certain time under the stratum condition, the compatibility between the particle mixture of the soybeans and the corns and the organic expansion material is poor, and the particles are difficult to be uniformly mixed, so that the expansion speeds of different point positions are different greatly, and uniform and rapid plugging of blast hole leakage channels is difficult to realize.
The invention patent application with publication number CN105482799A discloses a self-degradation hydraulic temporary plugging diverting agent and a preparation method thereof, wherein the temporary plugging diverting agent is prepared by taking polypropylene carbonate resin as a self-degradation adhesive, adding a plasticizer, a modifier, an accelerator and a density regulator, and extruding and granulating by a screw. The temporary plugging diverter is added with nano calcium carbonate as a plasticizer, so that the strength of a temporary plugging agent product is improved, nano calcium carbonate particles are small enough to flow out along with return liquid, and no harm and secondary pollution are caused to the stratum, but the plasticizer and the density regulator in the system are both inorganic matters, so that the plasticizer and the density regulator are poor in compatibility with the polypropylene carbonate resin, and are difficult to uniformly disperse in the polypropylene carbonate resin, and the strength and the density of a final product are influenced.
The invention patent application with publication number CN108531152A discloses a low-density and high-strength degradable temporary plugging agent and a preparation method thereof, the temporary plugging agent is prepared by constructing a blending material system by using polylactic acid as a continuous parent phase, starch as a filler, styrene butadiene rubber as a toughening agent and glycerol as a solubilizer and then performing extrusion molding. The temporary plugging agent has certain rigidity, can form bridge plugging in the existing cracks, can be automatically degraded and cannot cause secondary damage to a reservoir stratum, but the temporary plugging agent product can be easily bonded when meeting water at normal temperature and is not beneficial to pump injection.
Under the existing chemical technical conditions, polyglycolic acid is known to have a completely decomposable ester structure with a minimum number of carbon units, and can be prepared by polycondensation of glycolic acid or ring-opening polymerization of glycolide. Unlike conventional polymer materials (e.g., plastics, rubbers, etc.) having stable properties, polyglycolic acid as a material is gradually degraded after a certain period of time and finally becomes water and carbon dioxide harmless to human bodies, animals, plants and natural environments. Therefore, polyglycolic acid, a novel environmentally-friendly and degradable material with good biodegradability and biocompatibility, has been encouraged and supported by national policy, and has been gradually applied to the technical fields of medicine, agriculture, packaging, oil and gas exploitation, and the like.
At present, some researches have been carried out at home and abroad aiming at the technical field that polyglycolic acid materials are used for oil-gas well fracturing temporary plugging diversion.
The invention patent application with publication number CN106520094A discloses a soluble temporary plugging agent for acid fracturing, which consists of magnesium alloy granules, magnesium alloy sheets and fibers, wherein the fibers can adopt polyglycolic acid fibers. The temporary plugging agent is mainly applied to the acid fracturing operation, and can be completely dissolved in a short time by means of the flowback of residual acid in the stratum operation after the acid fracturing operation is completed, so that an oil-gas channel of a reservoir can be quickly recovered.
The invention patent application with publication number CN 1072458330A discloses a composite temporary plugging agent and temporary plugging method for horizontal well repeated fracturing, wherein the temporary plugging agent comprises a component a and a component B, the component a is selected from at least one of polyester polymers (such as polyglycolic acid), and the component B is selected from at least one of acrylamide polymers, polymethyl fibers and polyvinyl alcohol. In the composite temporary plugging agent, the component A is a rigid temporary plugging agent component capable of being slowly dissolved or degraded, the rigid propping agent function is exerted in the middle early stage of temporary plugging, the synergistic temporary plugging function is exerted in the later stage, the component B is a temporary plugging agent component capable of being rapidly expanded, the rapid temporary plugging effect can be exerted, and the two components have the synergistic effect and jointly maintain the high-efficiency temporary plugging function of oil well cracks.
The invention patent application with publication number CN109233773A discloses a nonlinear self-degradation temporary plugging agent reformed by multi-cluster fracturing in a section, which is prepared by using a mixture consisting of polyglycolide, polylactide-glycolide and polyvinyl alcohol as a body, and an initiator, a lubricant, a forming agent, a reinforcing agent and a degradation promoter in an auxiliary way through extrusion and granulation. The temporary plugging agent does not adhere to water at normal temperature, is beneficial to pump injection, is slowly degraded in limited time, has a nonlinear relation between the dissolution rate and the time at the reservoir temperature, and meets the technical requirements of multi-cluster fracturing construction in a horizontal well section.
The invention patent application with publication number US20160298017A1 discloses a temporary plugging agent for well drilling, which contains a synthetic resin having a temporary plugging function in a temperature range of 93 ℃ (200 ° F) to 204 ℃ (400 ° F) for no more than 40 days; further disclosed is a temporary plugging agent having a temporary plugging function of not less than 2 days and not more than 40 days, wherein the synthetic resin contains a polyglycolic acid-based resin.
The temporary plugging agent which has low density and good dispersibility and is beneficial to pump injection is urgently needed in the field.
Disclosure of Invention
The invention aims to provide a foaming type degradable temporary plugging diverter which has the characteristics of low density of a foaming material and the characteristics of self degradation and complete dissolution of a degradable material.
The invention also aims to provide a preparation method of the foaming type degradable temporary plugging diversion agent.
The invention also aims to provide application of the foaming type degradable temporary plugging diversion agent.
In a first aspect of the present invention, there is provided a temporary blocking diverting agent having a cell structure whose raw material components comprise polyglycolic acid; the polyglycolic acid is a homopolymer of glycolic acid and/or a copolymer having glycolic acid as a main repeating unit.
In another embodiment, the temporary blocking diverter is prepared by a foaming process using raw materials comprising polyglycolic acid of different molecular weights.
In another embodiment, the temporary blocking diverting agent employs polyglycolic acid having a first weight average molecular weight and polyglycolic acid having a second weight average molecular weight, where the second weight average molecular weight is larger than the first weight average molecular weight, and the difference between the second weight average molecular weight and the first weight average molecular weight is not less than 10,000 and not more than 290,000;
the mass ratio of the polyglycolic acid having the second weight average molecular weight to the polyglycolic acid having the first weight average molecular weight is 1.
In another embodiment, the copolymer comprises one or more units selected from the group consisting of: vinyl oxalate ester units, hydroxycarboxylic acid units, lactone units, carbonate units, and amide units.
In another embodiment, the starting material further comprises 0.1 to 1.2wt% of a dispersing agent, based on the total weight of polyglycolic acid; preferably, the dispersant is polyether nonionic surfactant.
In another embodiment, the temporary plugging diverter has an apparent density of 0.45 to 1.6g/cm 3 。
In another embodiment, the time to complete degradation of the temporary blocking diverter in water at 90-110 ℃ is not less than 2 hours.
In a second aspect of the present invention, there is provided a method for preparing the temporary plugging diversion agent provided by the present invention as described above, the method comprising the steps of: make supercritical CO 2 Into a particle obtained by mixing polyglycolic acid having a first weight average molecular weight, polyglycolic acid having a second weight average molecular weight, and a dispersant to obtain the temporary blocking diverter provided by the present invention as described above.
In another embodiment, the method comprises the steps of:
(1) Putting polyglycolic acid with a first weight average molecular weight, polyglycolic acid with a second weight average molecular weight, and a dispersant in a closed high-pressure reaction kettle;
(2) Introducing CO into the autoclave 2 Diffusing into polyglycolic acid after reaching a supercritical state; and
(3) And cooling and depressurizing the high-pressure reaction kettle to normal temperature and normal pressure to obtain the temporary plugging diversion agent.
In a third aspect of the invention, there is provided a use of the temporary plugging diversion agent provided by the invention as described above in temporary plugging diversion fracturing of an oil and gas well.
Therefore, the temporary plugging agent provided by the invention has the advantages of low density, good dispersibility and convenience for pump injection.
Detailed Description
The present inventors have made extensive and intensive studies by using two polyglycolic acids having different molecular weights by a foaming process, for example, by using supercritical CO 2 Foaming process, i.e. mixing two polyglycolic acids of different molecular weights, followed by supercritical CO 2 Under the condition of (3), the molecular chain of the polyglycolic acid is subjected to large-range plastic deformation to change the oriented crystalline structure of the polyglycolic acid, thereby regulating the supercritical CO 2 The solubility in the crystalline phase/amorphous phase of the polyglycolic acid is used for preparing the polyglycolic acid temporary blocking steering agent foaming particles with uniform particles, fine foaming and fine properties, the density is low, the dispersibility is good, the pumping injection is facilitated, and the polyglycolic acid temporary blocking steering agent foaming particles can be applied to temporary blocking and steering of oil and gas wellsAnd (5) fracturing. On the basis of this, the present invention has been completed.
Specifically, the present invention provides (1) an intumescent degradable temporary blocking diverter prepared using expanded polyglycolic acid comprising at least one of a homopolymer of glycolic acid or a copolymer of glycolic acid. As a specific embodiment of the invention relating to the foamed degradable temporary plugging diversion agent provided by the present invention, there is provided a foamed degradable temporary plugging diversion agent described in the following (2) to (9).
(2) The foamable degradable temporary plugging diversion agent according to the above (1), wherein the foamed polyglycolic acid is prepared by a foaming process using at least two polyglycolic acids different in molecular weight.
(3) The foamable degradable temporary blocking steering agent according to the above (2), wherein the foaming is carried out using polyglycolic acid having a first weight average molecular weight and polyglycolic acid having a second weight average molecular weight.
(4) The foamable degradable temporary plugging diverter according to the item (3), wherein the difference between the second weight average molecular weight and the first weight average molecular weight is not less than 10,000 and not more than 290,000.
(5) The foamable degradable temporary blocking diverter according to the (4), wherein preferably, the first weight average molecular weight is 10,000 to 80,000, more preferably 30,000 to 50,000, and preferably, the second weight average molecular weight is 90,000 to 300,000, more preferably 130,000 to 220,000.
(6) The foaming type degradable temporary blocking diverter according to any one of the (2) to (5), wherein the mass ratio of the polyglycolic acid having a larger molecular weight to the other polyglycolic acid in the two polyglycolic acids is 1.
(7) The foaming-type degradable temporary blocking diverter as described in (1), wherein the apparent density of the temporary blocking diverter is from 0.45 to 1.6g/cm 3 And the sphericity is 0.4-0.9.
(8) The foaming-type degradable temporary plugging diverter according to the (1), wherein the time for complete degradation of the temporary plugging diverter in clear water with the temperature of 90-110 ℃ is not less than 2 hours.
(9) The foamable degradable temporary blocking diverter according to the item (1), wherein the repeating units of the glycolic acid copolymer contain at least one of a vinyl oxalate unit, a hydroxycarboxylic acid unit (e.g., a lactic acid unit, a 3-hydroxypropionic acid unit, a 3-hydroxybutyric acid unit, a 4-hydroxybutyric acid unit, a 6-hydroxyhexanoic acid unit, etc.), a lactone unit (e.g., a β -propiolactone unit, a β -butyrolactone unit, a γ -butyrolactone unit, an ∈ -caprolactone unit, etc.), a carbonate unit (e.g., a trimethylene carbonate unit, etc.) or an amide unit (e.g., an ∈ -caprolactam unit, etc.) in addition to the glycolic acid unit.
In the present invention, the mass content of the glycolic acid repeating unit (i.e., [ -O-CH2-CO- ]) in the "glycolic acid copolymer" or the "copolymer having glycolic acid as a main repeating unit" is 50% or more, preferably 75% or more, more preferably 85% or more, and still more preferably 90% or more.
The invention also provides a preparation method (10) of the foaming type degradable temporary plugging diversion agent, which comprises the following steps:
step i): at normal temperature, placing at least two polyglycolic acids with different molecular weights into a high-pressure reaction kettle, adding a dispersing agent, and then sealing the high-pressure reaction kettle;
step ii): introducing low-pressure CO into the closed high-pressure reaction kettle 2 So as to completely replace the air in the high-pressure reaction kettle and then introduce high-pressure CO 2 Starting stirring until the pressure of the high-pressure reaction kettle rises to a set value, and then gradually heating the high-pressure reaction kettle by adopting a heat source until the CO in the high-pressure reaction kettle 2 Fully mixing polyglycolic acid with different molecular weights under the action of dispersant to obtain homogeneous and uniform particles, and maintaining the pressure for a period of time to make supercritical CO 2 (ii) diffusional dissolution into the polyglycolic acid particles;
step iii): and removing the heat source, quickly reducing the temperature of the high-pressure reaction kettle to room temperature, and then relieving the pressure to normal pressure to prepare foamed polyglycolic acid (namely the foamed degradable temporary plugging diversion agent).
As a specific embodiment of the invention relating to the method for producing a foamed degradable temporary blocking and diverting agent provided by the present invention, there is provided a method for producing a foamed degradable temporary blocking and diverting agent described in the following (11) to (17).
(11) In the process for producing a foamed type degradable temporary plugging diversion agent according to the above (10), the dispersant used in the step i) is a polyether nonionic surfactant which is a condensate of an alkylphenol and ethylene oxide, and is further selected from commercially available OP series dispersants, for example, but not limited to, commercially available OP-9, OP-10, OP-11 and the like.
(12) In the method for preparing the foaming type degradable temporary plugging diversion agent according to the item (10), the amount of the dispersant used in the step i) is 0.1 to 1.2%, preferably 0.8 to 1% of the total weight of the polyglycolic acid.
(13) In the process for preparing the foaming type degradable temporary plugging diversion agent according to the item (10), in the step ii), after the air in the high-pressure reaction kettle is completely replaced, high-pressure CO is introduced 2 Until the pressure of the autoclave is raised to about 10MPa, and then the autoclave is gradually heated to about 150-250 c using a heat source and maintained at a pressure of about 10-50MPa for about 10-240 minutes.
(14) The method for preparing the foaming type degradable temporary plugging diversion agent according to the above (13), further preferably, in the step ii), after the air in the high-pressure reaction kettle is completely replaced, introducing high-pressure CO 2 Until the pressure of the autoclave is raised to about 10MPa, and then the autoclave is gradually heated to about 180-220 ℃ with a heat source and maintained at a pressure of about 20-30MPa for about 40-120 minutes.
(15) In the process for preparing a foaming type degradable temporary plugging diversion agent as described in (10), in the step iii), the temperature reduction rate of the high-pressure reaction kettle is about 5 to 15 ℃/min.
(16) In the process for preparing an intumescent degradable temporary plugging diversion agent as described in (10), in the step iii), the pressure relief rate of the high-pressure reaction kettle is about 2 to 30 MPa/min.
(17) The process for producing an intumescent degradable temporary plugging diversion agent as described in (16), further preferably, in the step iii), the pressure-releasing rate of the high-pressure reactor is about 10 to 20 MPa/min.
The heat source used in the above preparation method is a heating/heat supply heat source conventional in the art, including but not limited to an electric heating device, a hydrothermal device, a heat transfer oil circulation heating device and the like conventional in the art, and preferably an electric heating device.
The invention also provides application of the foaming type degradable temporary plugging diverter.
As one embodiment (18) of the invention related to the application of the foaming type degradable temporary plugging diversion agent provided by the invention, the foaming type degradable temporary plugging diversion agent is directly applied to temporary plugging diversion fracturing of an oil-gas well.
In another embodiment (19) of the invention related to the application of the foamed degradable temporary plugging diversion agent provided by the invention, the foamed degradable temporary plugging diversion agent is compounded with other additives and/or other degradable polymers except foamed polyglycolic acid and then used for temporary plugging diversion fracturing of an oil-gas well.
According to the invention, after the temporary plugging diversion agent is compounded with other auxiliary agents and/or other degradable polymers except for foamed polyglycolic acid, the plugging bearing strength is more than 5MPa under the condition that the width of a steel rock crack is 1-3 mm.
As a specific mode of the application of the foamed degradable temporary blocking diverting agent provided by the present invention in another embodiment (19), other auxiliary agents include, but are not limited to, any one or more of plasticizers, fillers or compatibilizers.
As a specific mode of another embodiment (19) of the application of the foaming type degradable temporary plugging diversion agent provided by the invention, the foamed polyglycolic acid has a mass content of 50-99.9% by mass and the balance of other auxiliary agents, wherein the mass percentage is 100% by mass.
As a specific mode of another embodiment (19) of the application of the foamed degradable temporary plugging diversion agent provided by the present invention, the other degradable polymer is, for example, a degradable polymer having a biological decomposition property or a hydrolysis property, wherein the biological decomposition property means that the degradable polymer can be decomposed by using microorganisms in a well, and the hydrolysis property means that the degradable polymer can be decomposed by using a liquid in a well, particularly water, more preferably a water body containing an acid or a base. Further, the resin is brittle due to a decrease in strength inherent in the resin due to a low degree of polymerization or the like, and as a result, the resin can be easily disintegrated to lose its original shape by applying a very small mechanical force, and the resin also conforms to the degradable polymer.
As yet another specific mode of the application of the foamed degradable temporary blocking diverter provided by the present invention, the other degradable polymers include, but are not limited to, any one or more of polylactic acid, poly (e-caprolactone), polylactic acid-polyglycolic acid copolymer (PLGA), poly (butylene adipate/terephthalate) (PBAT), poly (butylene succinate) (PBS), poly (propylene carbonate) (PPC), polyethylene adipate (PEA), polyhydroxyalkanoate (PHA), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), or polyethylene naphthalate (PEN).
As still another specific mode of the application of the foamed degradable temporary plugging diversion agent provided by the invention, the foamed polyglycolic acid accounts for 50-90% by mass, other degradable polymers account for 8-49% by mass and other auxiliary agents account for 100% by mass of the total mass fraction.
As used herein, "ambient temperature" or "ambient temperature" means 15 to 40 deg.C, preferably 20 to 30 deg.C.
As used herein, "atmospheric pressure" means open to the atmosphere, without bearing pressure; for example, at 25 ℃, atmospheric pressure is one atmosphere.
It should be noted that in the development of any such actual implementation, numerous implementation-specific decisions must be made to achieve the developers' specific goals, such as compliance with system-related and business-related constraints, which will vary from one implementation to another. Moreover, it will be appreciated that such a development effort might be complex and time-consuming, but would nevertheless be a routine undertaking for those of ordinary skill in the art having the benefit of this disclosure.
In the context of the present invention and this detailed description, the term "about" when used to modify a numerical value means a margin of error measured within ± 5% of the numerical value.
The polyglycolic acid used in the present invention is a compound having the formula (formula 1) - (-O-CH) 2 -CO-) -a polymer of repeating units represented by. The proportion of the repeating unit represented by (formula 1) in the polymer is usually about 50% by weight or more, preferably about 80% by weight or more, more preferably about 85% by weight or more, further preferably about 90% by weight or more, particularly preferably about 95% by weight or more, most preferably about 99% by weight or more. When the proportion of the repeating unit represented by (formula 1) is less than about 50wt%, toughness, crystallinity, heat resistance, hardness, and the like tend to be decreased. In most cases, it is most preferable to use a homopolymer of polyglycolic acid having a proportion of 100% by weight of the repeating unit represented by (formula 1). The copolymer of glycolic acid may have, in addition to the repeating unit represented by formula 1, other repeating units such as a vinyl oxalate-based unit, a hydroxycarboxylic acid-based unit (e.g., a lactic acid unit, a 3-hydroxypropionic acid unit, a 3-hydroxybutyric acid unit, a 4-hydroxybutyric acid unit, a 6-hydroxyhexanoic acid unit, etc.), a lactone-based unit (e.g., a β -propiolactone unit, a β -butyrolactone unit, a γ -butyrolactone unit, an ∈ -caprolactone unit, etc.), a carbonate-based unit (e.g., a trimethylene carbonate unit, etc.), an amide-based unit (e.g., an ∈ -caprolactam unit, etc.), etc., but is not limited thereto.
In the present invention, polyglycolic acid can be produced by polycondensation of glycolic acid or ring-opening polymerization of glycolide.
In this regard, in general, the homopolymer of glycolic acid in the present invention may be referred to as a homopolymer of glycolide, and the copolymer of glycolic acid may be referred to as a copolymer of glycolide. The scope of protection of the present claims therefore covers the case of homopolymers of glycolide, copolymers of glycolide.
The features mentioned above, or those mentioned in the embodiments, may be combined in any combination. All features disclosed in this specification may be combined in any combination, provided that there is no conflict between such features and the combination, and all possible combinations are to be considered within the scope of the present specification. Each feature disclosed in this specification may be replaced by an alternative feature serving the same, equivalent, or similar purpose. Thus, unless expressly stated otherwise, the features disclosed are merely generic examples of equivalent or similar features.
The main advantages of the invention are:
1. the invention is characterized in that polyglycolic acid with different molecular weights is subjected to supercritical CO 2 The medium mixing makes the molecular chain generate large-scale plastic deformation, increases the free volume of the molecular chain, reduces the entanglement of the molecular chain, changes the oriented crystalline structure of the polyglycolic acid, and further can adjust the supercritical CO 2 Solubility in the crystalline phase/amorphous phase of polyglycolic acid, forming polyglycolic acid foam material with different cell sizes (about 10-1000 μm of pore diameter), uniform particles and fine foam.
2. The foaming type degradable temporary plugging diverter provided by the invention not only has the low-density characteristic of a foaming material (the apparent density of the temporary plugging diverter is 0.45-1.6 g/cm) 3 Preferably 0.68 to 1.2g/cm 3 ) And the characteristics of autonomous degradation and complete dissolution of the degradable material (the complete degradation time is not less than 2 hours in clear water at the temperature of 90-110 ℃), does not adhere to water at normal temperature, is beneficial to pump injection, can be completely degraded, has no harm to a reservoir stratum, has simple preparation process steps, and is beneficial to realizing industrial production.
3. In practical application, the foaming type degradable temporary plugging diversion agent provided by the invention can be compounded with other auxiliary agents and/or other degradable polymers except foamed polyglycolic acid, and has excellent plugging bearing strength (for example, under the condition that the width of a steel rock fracture is 1-3mm, the plugging bearing strength is more than 5MPa, and particularly the plugging bearing strength can be as high as 26.1 MPa), so that fracturing operation can be performed practically, old fractures or fractures with sand are plugged temporarily, and fluid is diverted through the change of fracture extension pressure, so that new fractures are created, and the yield and energy increase of an oil and gas well are realized.
In one aspect of the present invention, the foamed type degradable temporary plugging diverter of examples 1-10 is prepared by using foamed polyglycolic acid, and the specific preparation process comprises the following steps:
i. at normal temperature, putting A type polyglycolic acid and B type polyglycolic acid into a high-pressure reaction kettle, wherein the A type polyglycolic acid is polyglycolic acid with the weight-average molecular weight M, the B type polyglycolic acid is polyglycolic acid with the weight-average molecular weight N, the mass ratio of the A type polyglycolic acid to the B type polyglycolic acid is O, adding a commercially available dispersing agent OP-11 accounting for 1 percent of the total weight of the A type polyglycolic acid and the B type polyglycolic acid, and then sealing the high-pressure reaction kettle;
ii, introducing low pressure CO 2 (CO 2 Pressure intensity<4 MPa) completely replacing air in the high-pressure reaction kettle, and then introducing high-pressure CO 2 (CO 2 Pressure intensity>10 MPa) and the pressure in the high-pressure reaction kettle reaches 10MPa, meanwhile, the stirring paddle is started, and then the high-pressure reaction kettle is gradually heated to P until CO in the high-pressure reaction kettle 2 Reaching supercritical state, and maintaining at pressure of Q for a certain time R to obtain supercritical CO 2 Diffusing and dissolving into two kinds of polyglycolic acid;
and iii, removing a heat source of the high-pressure reaction kettle, quickly cooling to room temperature, and then releasing the pressure to normal pressure at the pressure relief speed of S.
The foaming type degradable temporary plugging diverter prepared in the examples 1-10 is tested for apparent density and sphericity by SY/T5108-2006 fracturing propping agent performance index and test recommendation method, which is specifically shown in Table 1.
Table 1 examples 1-10 preparation of foamed degradable temporary plugging diversion agent process parameters and apparent density and sphericity
Note: in Table 1, M represents the weight average molecular weight of type A polyglycolic acid; n is the weight average molecular weight of the B-type polyglycolic acid; o is the mass ratio of the A-type polyglycolic acid to the B-type polyglycolic acid; p is the temperature of the high-pressure reaction kettle; q is the pressure of the high-pressure reaction kettle; r is the pressure maintaining time; and S is the pressure relief speed.
Both polyglycolic acid type a and polyglycolic acid type B in each example in table 1 are homopolymers of glycolic acid.
The degradation performance of the foamed degradable temporary plugging diversion agent prepared by the invention is tested, the test result is shown in table 2, and the specific test method is as follows:
i) Putting the prepared temporary plugging agent into a constant-temperature drying box, and drying for 48 hours at the temperature of 60 ℃;
II) weighing 5.00g of dried temporary plugging agent, placing the temporary plugging agent in 100mL of clear water, and placing the clear water in a thermostat with set temperature;
III) taking out the degraded sample on time, and extracting supernatant to separate residual solid phase;
IV) cleaning the separated residual solid phase by using distilled water, putting the cleaned residual solid phase into a constant-temperature drying box, drying the residual solid phase for 24 hours at the temperature of 60 ℃, weighing, and recording the weight of the residual solid phase as w;
v) calculating the degradation rate R of the temporary plugging agent in clear water A The calculation formula is as follows:
TABLE 2 degradation test results for foaming type degradable temporary plugging diverter
From the test results in table 2, it can be seen that under the same temperature conditions, the temporary blocking diverting agent with higher apparent density is degraded at a lower rate than the temporary blocking diverting agent with lower apparent density. The time for complete degradation of the temporary plugging diversion agent prepared by the invention in clear water at 90-110 ℃ is not less than 2 hours, for example, the time for complete degradation of the temporary plugging diversion agent prepared in the embodiment 1 in clear water at 110 ℃ is 16 hours; the time for complete degradation of the temporary plugging diversion agent prepared in the example 9 in clear water at 90 ℃ is 5 hours; the time for complete degradation of the temporary plugging diversion agent prepared in the example 10 in clear water at 100 ℃ is 10 hours.
Based on the test results in table 2, the degradation time of the foamed degradable temporary blocking diverter of the present invention can be adjusted by adjusting the weight average molecular weight of two polyglycolic acids and the preparation process. For example, in the case where the temperature P of the autoclave, the pressure Q of the autoclave and the pressure-releasing rate S are determined, the degradation time of the foaming type degradable temporary plugging diverter can be adjusted by changing the weight average molecular weights of the a-type polyglycolic acid and the B-type polyglycolic acid, the mass ratio of the a-type polyglycolic acid to the B-type polyglycolic acid and the dwell time R of the autoclave, as shown in examples 1 and 8, from table 2, it can be seen that the degradation rates of the foaming type degradable temporary plugging diverter of examples 1 and 8 are 43% and 32% respectively for 24 hours, the degradation rates of the foaming type degradable temporary plugging diverter for 96 hours are 85% and 58% respectively for 96 hours and the degradation rates of the foaming type degradable diverter for 168 hours are 95% and 74% respectively in 90 ℃ clear water.
It should be noted that the above degradation test is only a demonstration of the degradation performance of the foamed degradable temporary plugging diverter of the present invention, and the two polyglycolic acids with different molecular weights used in the preparation method of the present invention are essentially mixtures composed of many compounds with the same chain structure and different polymerization degrees, and the mixed system of the two polyglycolic acids can be regarded as "chaotic body", and its properties may not exactly correspond to the process parameters in the preparation method, so the actual degradation of some foamed degradable temporary plugging diverters (i.e. foamed polyglycolic acid) prepared according to the method of the present invention is not limited to the data in table 2.
The following table 3 shows the preparation process parameters, apparent density and sphericity of the foamed degradable temporary plugging diversion agent of examples 11-17.
TABLE 3 examples 11-17 preparation of foamed degradable temporary blocking steering agents with Process parameters and apparent Density and sphericity
Note: in Table 3, M represents the weight average molecular weight of type A polyglycolic acid; n is the weight average molecular weight of the B-type polyglycolic acid; o is the mass ratio of the A-type polyglycolic acid to the B-type polyglycolic acid; p is the temperature of the high-pressure reaction kettle; q is the pressure of the high-pressure reaction kettle; r is the pressure maintaining time; and S is the pressure relief speed.
In Table 3, the type A polyglycolic acid in example 11 is a copolymer of glycolic acid and lactic acid (i.e., a polyglycolic-lactic acid copolymer, PLGA for short), the proportion of glycolic acid repeating units is about 85% by weight, and the type B polyglycolic acid is a homopolymer of glycolic acid; in example 12, both of the polyglycolic acid type a and the polyglycolic acid type B were polyglycolic acid-lactic acid copolymers, and the proportion of glycolic acid repeating units was about 72wt%; the type A polyglycolic acid in example 13 is a copolymer of glycolic acid and ε -caprolactone having a proportion of glycolic acid repeating units of about 53wt%, while the type B polyglycolic acid is a copolymer of glycolic acid and trimethylene carbonate having a proportion of glycolic acid repeating units of about 90wt%; the polyglycolic acid type A in example 14 is a homopolymer of glycolic acid, while the polyglycolic acid type B is a copolymer of glycolic acid and epsilon-caprolactam, the proportion of glycolic acid repeat units being about 92wt%; the polyglycolic acid type a in example 15 is a copolymer of glycolic acid and vinyl oxalate, the proportion of glycolic acid repeating units is about 88wt%, while the polyglycolic acid type B is a copolymer of glycolic acid and 3-hydroxybutyric acid, the proportion of glycolic acid repeating units is about 82wt%; the a-type polyglycolic acid and the B-type polyglycolic acid in examples 16 and 17 are both homopolymers of glycolic acid.
As another aspect of the present invention, the foaming type degradable temporary plugging diversion agent prepared in example 1 is compounded with other auxiliary agents and/or other degradable polymers except for the foaming polyglycolic acid (the compounded temporary plugging diversion agent can be prepared by using the existing blending extrusion granulation process, but the process for blending extrusion granulation is not limited by special technology and is not repeated herein), and the dosage relationship among the components can be seen in examples 18 to 24 in table 4.
TABLE 4 relationship of the mass ratios of the foaming type degradable temporary plugging diverter and other components in examples 18-24
The filler used can improve the mechanical strength and heat resistance of the temporary blocking diverting agent. As the filler, a granular or powdery filler can be used. As particulate or powdered fillers, there may be included, but not limited to, any one or more of mica, talc, calcium carbonate, zinc oxide, kaolin, quartz powder, and the like. Preferably, the granular or powdered filler is selected from quartz powder.
The compatibilizer used is effective to reduce surface tension and improve interfacial adhesion between the dispersed and continuous phases in the blend. As the compatibilizer, a grafted maleic anhydride compatibilizer may be used, for example, including, but not limited to, any one of polyethylene grafted maleic anhydride (PE-g-MAH), polypropylene grafted maleic anhydride (PP-g-MAH), ethylene-vinyl acetate copolymer grafted maleic anhydride (EVA-g-MAH). Preferably, the compatibilizer is selected from ethylene-vinyl acetate copolymer grafted maleic anhydride (EVA-g-MAH).
The plasticizer used can weaken the acting force between macromolecules of the polymer, so that the mobility of polymer molecules is increased, and the processability of the polymer can be effectively improved. As the plasticizer, a plasticizer of a commercially available phthalate ester, aliphatic dibasic acid ester, citric acid ester or polyol ester, for example, including but not limited to butyl phthalate, dioctyl phthalate, adipate, azelate, sebacate, stearate, phosphate ester and the like, may be used. Preferably, the plasticizer is selected from butyl phthalate or dioctyl phthalate.
The weight average molecular weights of the polylactic acid (PLA), polybutylene adipate/terephthalate (PBAT) and polyethylene terephthalate (PET) used are preferably from 60,000 to 300,000, more preferably from 100,000 to 300,000, from 120,000 to 280,000 and particularly preferably from 150,000 to 250,000.
In the aspect of plugging performance testing, the specific implementation mode is mainly divided into the following two aspects:
1. the foaming-type degradable temporary plugging diverter prepared in the embodiment 2, the embodiment 4, the embodiment 7 and the embodiment 14 is directly subjected to a plugging performance test, and the specific test method is as follows:
a) Directly mixing the foaming type degradable temporary plugging diverter with a proper amount of clear water, and stirring for 30 minutes at 1000 revolutions per minute by using a stirrer to prepare temporary plugging slurry;
b) Putting the wedge-shaped crack steel rock into a holder, wherein the wide surface of the steel rock crack is the inlet end of the temporary plugging diverter, applying a confining pressure of 30MPa, and closing an outlet valve;
c) Pouring the temporary plugging slurry into a clamp holder kettle body, and connecting an inlet pipeline and a pressure sensor;
d) Opening pressure monitoring software, starting a displacement pump in a constant flow mode, and opening an outlet valve;
e) Starting a displacement pump to gradually increase the pumping pressure from 0MPa to 1.0-2.0MPa each time, and stabilizing the pressure of each pressure point for 5-10 minutes;
f) And when the inlet pressure cannot be stabilized to a certain pressure point, taking the pressure stabilizing point nearest to the pressure point as the pressure bearing capacity of the temporary plugging agent.
2. The temporary plugging diverting agents prepared in the embodiments 20 and 24 are subjected to plugging performance tests, and the specific test method is as follows:
a) Directly mixing the temporary plugging diverter prepared by compounding with a proper amount of clear water, and stirring for 30 minutes at 1000 revolutions per minute by using a stirrer to prepare temporary plugging slurry;
b) Putting the wedge-shaped crack steel rock into a holder, wherein the wide surface of the steel rock crack is the inlet end of the temporary plugging diverting agent, applying confining pressure of 30MPa, and closing an outlet valve;
c) Pouring the temporary plugging slurry into a clamp holder kettle body, and connecting an inlet pipeline and a pressure sensor;
d) Opening pressure monitoring software, starting a displacement pump in a constant flow mode, and opening an outlet valve;
e) Starting a displacement pump to gradually increase the pumping pressure from 0MPa to 1.0-2.0MPa each time, and stabilizing the pressure of each pressure point for 5-10 minutes;
f) And when the inlet pressure cannot be stabilized to a certain pressure point, taking the pressure stabilizing point closest to the pressure point as the pressure bearing capacity of the temporary plugging agent.
The results of the plugging performance test of the above corresponding examples are shown in table 5.
Table 5 plugging test results
| Item | Crack width (mm) | Plugging pressure (MPa) |
| Example 2 | 1-3 | 5.6 |
| Example 4 | 1-3 | 22.4 |
| Example 4 | 3-5 | 15.8 |
| Example 7 | 3-5 | 8.3 |
| Example 14 | 1-3 | 20.3 |
| Example 20 | 1-3 | 22.5 |
| Example 24 | 1-3 | 26.1 |
In conclusion, the foaming type degradable temporary plugging diverter disclosed by the invention has the low density characteristic (namely lower apparent density) of a foaming material, has higher sphericity and good suspension property, and is favorable for smoothly reaching the specified position of an underground reservoir stratum and realizing effective plugging; in addition, the foaming type degradable temporary plugging diverting agent provided by the invention has a cellular structure, so that the strength of the foaming type degradable temporary plugging diverting agent is reduced to some extent, but the temporary plugging diverting agent still has better plugging performance (for example, when the temporary plugging diverting agent is not compounded with other components, the plugging pressure is more than 5MPa under the condition that the crack width is 1-3mm, and even can be as high as 22.4 MPa). In practical application, the foaming type degradable temporary plugging diversion agent can be compounded with other auxiliary agents and/or other degradable polymers except for the foaming polyglycolic acid according to actual working conditions. For example, in order to suitably increase the strength, the foaming type degradable temporary plugging diversion agent of the present invention can be compounded with a filler and/or a degradable polymer (e.g., PET) with a larger hardness, which can provide enough accommodation space for the filler due to the existence of a cellular structure, which is favorable for the filler to be sufficiently dispersed in the foaming type degradable temporary plugging diversion agent to suitably increase the strength of the foaming type degradable temporary plugging diversion agent, while the PET itself has a relatively higher strength, which is favorable for improving the strength of the composition system when compounded with the foaming type degradable temporary plugging diversion agent, and other non-degradable polymers with a larger hardness can be suitably added, but it is noted that the higher the strength of the composition system is not better, which increases the cost on the one hand, and on the other hand, because of the increase of non-degradable reservoir components (e.g., filler, other non-degradable polymers), the residual components can adversely affect the underground after the temporary plugging diversion fracturing. Therefore, the amount of the filler and/or the harder degradable polymer in the composition system can be adjusted to obtain the desired strength according to the actual working conditions.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, which is defined in the appended claims, and any other technical entity or method implemented by another person is deemed to be covered by the claims if it is exactly the same as or equivalent to the claims.
Claims (7)
1. The temporary blocking diverting agent is characterized by having a cellular structure, wherein the raw material components of the temporary blocking diverting agent comprise polyglycolic acid; the polyglycolic acid is a homopolymer of glycolic acid and/or a copolymer with glycolic acid as a main repeating unit; - (-O-CH) 2 -CO-) -, wherein the proportion of the repeating unit represented by the formula (I) is 50wt% or more;
the temporary blocking steering agent adopts polyglycolic acid with a first weight average molecular weight and polyglycolic acid with a second weight average molecular weight to be subjected to supercritical CO 2 A foaming process, wherein the first weight average molecular weight is 10,000-80,000, the second weight average molecular weight is 90,000-300,000, and the mass ratio of the polyglycolic acid with the second weight average molecular weight to the polyglycolic acid with the first weight average molecular weight is 1;
the apparent density of the temporary plugging diverting agent is 0.45-1.6g/cm 3 。
2. The temporary plugging diverter of claim 1, wherein said copolymer further comprises one or two units selected from the group consisting of: carbonate units and amide units.
3. The temporary blocking diverting agent according to claim 1, wherein the raw material further comprises 0.1-1.2wt% of a dispersing agent based on the total weight of polyglycolic acid; the dispersing agent is polyether nonionic surfactant.
4. The temporary plugging diverter according to claim 1, wherein the time for complete degradation of the temporary plugging diverter in water at 90-110 ℃ is not less than 2 hours.
5. A process for preparing a diverting agent for temporary plugging according to any of claims 1 to 4, characterized in that it comprises the steps of: make supercritical CO 2 Into particles obtained by mixing polyglycolic acid having a first weight average molecular weight, polyglycolic acid having a second weight average molecular weight, and a dispersant to obtain a polymer as set forth in any one of claims 1 to 4Temporarily blocking the diverter.
6. The method of claim 5, wherein the method comprises the steps of:
(1) Putting polyglycolic acid with a first weight average molecular weight, polyglycolic acid with a second weight average molecular weight, and a dispersant in a closed high-pressure reaction kettle;
(2) Introducing CO into the autoclave 2 Diffusing into polyglycolic acid after reaching a supercritical state;
(3) And cooling and depressurizing the high-pressure reaction kettle to normal temperature and normal pressure to obtain the temporary plugging diverting agent.
7. Use of the diverting agent according to any of claims 1-4 in diverting fracturing of a diverting of an oil or gas well.
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| SG11202001095UA (en) | 2017-08-10 | 2020-03-30 | Mitsubishi Chem Corp | Diverting agent and method of filling fracture in well using the same |
| CN112280545B (en) * | 2020-11-09 | 2023-01-17 | 内蒙古浦景聚合材料科技有限公司 | Nonmetal degradable self-adaptive temporary plugging ball |
| CN115505242B (en) * | 2021-06-07 | 2024-03-29 | 国家能源投资集团有限责任公司 | Full-biodegradable foam material and preparation method and application thereof |
| CN113403051A (en) * | 2021-06-23 | 2021-09-17 | 新疆中凌工程技术有限公司 | Self-adaptive temporary plugging ball and manufacturing method thereof |
| CN113801644B (en) * | 2021-09-10 | 2022-11-25 | 北京九恒质信能源技术有限公司 | Oil-gas well full-degradation temperature-control temporary plugging knot and preparation method thereof |
| CN115058235B (en) * | 2022-06-17 | 2023-09-29 | 东方宝麟科技发展(北京)有限公司 | Degradable rope knot temporary plugging fiber material for oil and gas field and preparation method thereof |
| CN117264620A (en) * | 2023-09-19 | 2023-12-22 | 西安石油大学 | Oilfield fracturing high-temperature-resistant degradable temporary plugging agent and preparation method thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1476907A (en) * | 2003-06-30 | 2004-02-25 | 暨南大学 | Bio-active 3-D porous tissue engineering support material and its preparation method |
| JP2004162215A (en) * | 2002-11-14 | 2004-06-10 | Teijin Ltd | Fiber structure of polyglycolic acid and method for producing the same |
| CN102240415A (en) * | 2011-05-30 | 2011-11-16 | 陕西师范大学 | Composite porous support material and preparation method thereof |
| CN103128973A (en) * | 2012-12-20 | 2013-06-05 | 华南理工大学 | Preparation method of high polymer product provided with multi-scale foam structure and applications of high polymer product provided with multi-scale foam structure |
| CN103254459A (en) * | 2013-05-28 | 2013-08-21 | 浙江大学 | Method for preparing tissue engineering scaffold with double-pore structure by combining with supercritical carbon dioxide foaming technology |
| CN104140551A (en) * | 2013-05-10 | 2014-11-12 | 北京化工大学 | Preparation method of organic/inorganic composite porous scaffold material for bone tissue engineering |
| CN107541031A (en) * | 2016-06-29 | 2018-01-05 | 上海浦景化工技术股份有限公司 | A kind of modified PGA or PLGA fully biodegradable foamed material and preparation method thereof |
| CN107722331A (en) * | 2017-09-15 | 2018-02-23 | 浙江大学 | The step pressure release foaming technique of supercritical carbon dioxide two prepares the method with double-pore structure bone tissue engineering scaffold |
| CN108310458A (en) * | 2018-03-21 | 2018-07-24 | 奚桢浩 | A method of tissue engineering bracket material is prepared using degradable synthesized polymer material |
| CN109233773A (en) * | 2018-11-06 | 2019-01-18 | 中国石油集团川庆钻探工程有限公司工程技术研究院 | The non-linear self-degradation diverting agent of more cluster fracturing reforms and preparation method in a kind of section |
| CN110305652A (en) * | 2018-09-13 | 2019-10-08 | 中海石油(中国)有限公司上海分公司 | Pressure break Complex Temporary Blocking agent and preparation method thereof |
| CN110591310A (en) * | 2019-09-04 | 2019-12-20 | 常州大学 | Modified polylactic acid foaming material and forming method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2008318678B2 (en) * | 2007-10-31 | 2014-02-13 | Cardinal Health 529, Llc | Vascular closure device |
-
2020
- 2020-07-09 CN CN202010657698.XA patent/CN111763506B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004162215A (en) * | 2002-11-14 | 2004-06-10 | Teijin Ltd | Fiber structure of polyglycolic acid and method for producing the same |
| CN1476907A (en) * | 2003-06-30 | 2004-02-25 | 暨南大学 | Bio-active 3-D porous tissue engineering support material and its preparation method |
| CN102240415A (en) * | 2011-05-30 | 2011-11-16 | 陕西师范大学 | Composite porous support material and preparation method thereof |
| CN103128973A (en) * | 2012-12-20 | 2013-06-05 | 华南理工大学 | Preparation method of high polymer product provided with multi-scale foam structure and applications of high polymer product provided with multi-scale foam structure |
| CN104140551A (en) * | 2013-05-10 | 2014-11-12 | 北京化工大学 | Preparation method of organic/inorganic composite porous scaffold material for bone tissue engineering |
| CN103254459A (en) * | 2013-05-28 | 2013-08-21 | 浙江大学 | Method for preparing tissue engineering scaffold with double-pore structure by combining with supercritical carbon dioxide foaming technology |
| CN107541031A (en) * | 2016-06-29 | 2018-01-05 | 上海浦景化工技术股份有限公司 | A kind of modified PGA or PLGA fully biodegradable foamed material and preparation method thereof |
| CN107722331A (en) * | 2017-09-15 | 2018-02-23 | 浙江大学 | The step pressure release foaming technique of supercritical carbon dioxide two prepares the method with double-pore structure bone tissue engineering scaffold |
| CN108310458A (en) * | 2018-03-21 | 2018-07-24 | 奚桢浩 | A method of tissue engineering bracket material is prepared using degradable synthesized polymer material |
| CN110305652A (en) * | 2018-09-13 | 2019-10-08 | 中海石油(中国)有限公司上海分公司 | Pressure break Complex Temporary Blocking agent and preparation method thereof |
| CN109233773A (en) * | 2018-11-06 | 2019-01-18 | 中国石油集团川庆钻探工程有限公司工程技术研究院 | The non-linear self-degradation diverting agent of more cluster fracturing reforms and preparation method in a kind of section |
| CN110591310A (en) * | 2019-09-04 | 2019-12-20 | 常州大学 | Modified polylactic acid foaming material and forming method thereof |
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