CN106675549B - Underwater suspensible proppant for oil-gas well fracturing and preparation method thereof - Google Patents
Underwater suspensible proppant for oil-gas well fracturing and preparation method thereof Download PDFInfo
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- CN106675549B CN106675549B CN201611103999.8A CN201611103999A CN106675549B CN 106675549 B CN106675549 B CN 106675549B CN 201611103999 A CN201611103999 A CN 201611103999A CN 106675549 B CN106675549 B CN 106675549B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
Abstract
The invention relates to a water suspendable proppant for oil-gas well fracturing and a preparation method thereof. The underwater suspendable proppant comprises proppant aggregate, an expansion layer and an interface transition layer between the aggregate and the expansion layer; the swelling layer comprises hydrogel dry powder and adhesive which is used for binding the hydrogel dry powder and is swellable in water; the interface transition layer comprises epoxy resin and/or thermoplastic phenolic resin as interface transition layer resin.
Description
Technical Field
The invention relates to the field of fracturing production increase of oil and gas wells, in particular to a proppant capable of suspending in water for fracturing and a preparation method thereof.
Background
Fracturing is one of the main measures for increasing the production of oil and gas wells, and is to inject fracturing fluid into a stratum by using a high-pressure pump, so that the fracture of the stratum is enlarged, a new fracture is formed, and a propping agent is filled in the fracture, so that the permeability of the stratum is improved. Proppants and fracturing fluids are materials necessary for fracturing.
The conventional proppant in the current market mainly comprises ceramsite and quartz sand, wherein the ceramsite proppant has high crushing resistance (the crushing rate of 52MPa is generally less than 5%), good sphericity and strong flow conductivity, but has high relative density, requires high viscosity of fracturing fluid, has high construction difficulty and serious abrasion to a delivery pump and a pipeline, and ensures that the construction cost and the safety risk of equipment are increased invisibly; the natural quartz sand has lower relative density, is convenient for carrying and conveying the fracturing fluid, but is suitable for the stratum with the stratum stress lower than 35MPa due to low strength. A layer of resin film is coated on the surface of a conventional propping agent, which is called as a resin coated propping agent, and the resin coated propping agent can greatly reduce the breaking rate, turbidity and acid solubility of the propping agent, improve the flow conductivity of the propping agent and prolong the fracturing timeliness. The fracturing fluid functions to transmit pressure, create fractures in the in situ formation and carry proppant into the fractures.
Chinese patent application 201510266248.7 discloses a self-suspending proppant for hydraulic fracturing, which comprises inner core aggregate particles and a composite resin coating layer coated on the surfaces of the inner core aggregate particles; the composite resin coating layer comprises the following components in parts by weight: 1.5-4.5 parts of water-soluble resin, 0.8-2 parts of water-swellable polymer, 0.1-0.2 part of cross-linking agent and 0.05-0.1 part of dispersing agent; wherein the mass ratio of the water-soluble resin to the inner core aggregate particles is 1.5-4.5: 100. The water-soluble resin is any one of water-soluble epoxy resin, water-soluble polyurethane resin, water-soluble phenolic resin, water-soluble acrylic resin and water-soluble modified polymers thereof. The water-swellable polymer is polyacrylamide, hydroxypropyl cellulose or hydroxyethyl cellulose. The cross-linking agent is nitroglycerin, triacetin, polyethylene oxide or polypropylene oxide. The patent has the problems that the water-soluble resin (water-soluble epoxy resin, water-soluble polyurethane resin, water-soluble phenolic resin and water-soluble acrylic resin) only physically coats the surface of quartz sand or ceramsite, no curing reaction occurs, when the self-suspending proppant is put into clear water and stirred, the water-soluble resin is dissolved in the water, the swellable polymer coating the surface of the quartz sand or ceramsite is separated from the quartz sand or ceramsite, the quartz sand or ceramsite can settle, and the swellable polymer cannot play a role in suspending.
Chinese patent application 201410479945.6 discloses a self-suspending proppant which is formed by adhering at least one layer of water-soluble polymer material on an aggregate, swells and dissolves in water after being mixed with natural water at normal temperature, and is in a suspended state and maintains the state for a certain period of time. The using amount of the water-soluble high polymer material is 0.1-1.5 Wt% of that of the aggregate, the water-soluble high polymer material is selected from one or more of polycaprolactone, guar gum, polyvinyl acetate, polyvinyl alcohol and polyacrylamide, the guar gum is hydroxypropyl guar gum and/or carboxymethyl hydroxypropyl guar gum, and the polyacrylamide is anionic polyacrylamide. The water-soluble polymer material is formed by adhering an adhesive to aggregate, the amount of the adhesive is 0.1-0.7 Wt% of the amount of the aggregate, the adhesive is selected from any one or more of phenolic resin, epoxy resin and unsaturated polyester resin, and the phenolic resin is thermoplastic phenolic resin and/or thermosetting phenolic resin; the epoxy resin is epoxy resin with the epoxy equivalent of 0.09-0.14mol/100 g; the unsaturated polyester resin is one or more of o-benzene unsaturated polyester resin, m-benzene unsaturated polyester resin, dimethyl benzene unsaturated polyester resin, bisphenol A unsaturated polyester resin, halogenated unsaturated polyester resin and vinyl ester resin; the resin is a) epoxy resin, or b) unsaturated polyester resin, or c) thermoplastic and/or thermosetting phenolic resin, and the corresponding curing agent is a) aliphatic amine and its addition product, tertiary amine and its salt, aromatic amine and its modification, imidazole, high molecular prepolymer, b) peroxide, peroxide ester, c) paraformaldehyde or hexamethylenetetramine. The patent has the problems that polycaprolactone and polyvinyl acetate are insoluble in water in the water-soluble polymer material (the polycaprolactone has excellent biocompatibility, memory property, biodegradability and the like, but is insoluble in water; the polyvinyl acetate is colorless viscous liquid or light yellow transparent glassy particles, the softening point is about 38 ℃, and the polyvinyl acetate cannot be mutually dissolved with fat and water); guanidine gum, polyvinyl alcohol and polyacrylamide are dissolved in water, and can absorb water to swell only when the guanidine gum, the polyvinyl alcohol and the polyacrylamide are crosslinked to form gel, but the guanidine gum, the polyvinyl alcohol and the polyacrylamide are not crosslinked, so that the effect of absorbing water to swell the volume of the proppant is not achieved, and the viscosity of water is only increased. The water-soluble polymer material is adhered on the aggregate through the adhesive, and the adhesive is selected from one or more of phenolic resin, epoxy resin and unsaturated polyester resin, and the adhesive can not expand when meeting water after being cured according to the patent conditions, so that the expansion of the water-soluble polymer material in the adhesive is limited, and the water-soluble polymer material on the surface of the adhesive is easy to separate from the proppant body due to dissolution.
Chinese patent application 201280042615.X discloses a modified proppant comprising proppant particles and a hydrogel coating. Wherein the hydrogel coating is applied to the surface of the proppant particle and localized on the surface to produce a modified proppant. The hydrogel coating may contain a water-swellable polymer. In embodiments, the hydrogel coating is applied as a liquid to a surface that may contain a solvent or carrier fluid; the liquid hydrogel coating may be changed to a dried hydrogel coating by removing the solvent or carrier fluid. In embodiments, the dried hydrogel coating is capable of expanding in volume upon contact with an aqueous fluid to form a swollen hydrogel coating having a thickness of at least about 10% greater than the dried hydrogel coating. In an embodiment, the hydrogel coating comprises a polymer selected from the group consisting of: polyacrylamide, polyacrylic acid, copolymers of acrylamide and acrylate, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, guar gum, carboxymethyl hydroxypropyl guar gum, hydrophobically associating swellable emulsion polymers, and latex polymers. In embodiments, the modified proppant further comprises a crosslinker; the crosslinking agent may contain a covalent crosslinking agent, and the covalent crosslinking agent may contain a functional group selected from the group consisting of: epoxides, anhydrides, aldehydes, diisocyanates and carbodiimides. In embodiments, the covalent cross-linking agent may be selected from the group consisting of: polyethylene glycol, diglycidyl ether, epichlorohydrin, maleic anhydride, formaldehyde, glyoxal, glutaraldehyde, toluene diisocyanate, and methylene diphenyl diisocyanate, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide. In embodiments, the modified proppant further comprises an alcohol selected from the group consisting of: ethylene glycol, propylene glycol, glycerol, propanol and ethanol. The problem with this patent is that the hydrogel coating is applied as a liquid to a surface that may contain a solvent or carrier fluid, and the liquid hydrogel coating can be changed to a dried hydrogel coating by removing the solvent or carrier fluid. On one hand, the process is complex in coating and drying process; on the other hand, no adhesive is used for bonding the hydrogel with the proppant body, and the hydrogel is easy to separate from the surface of the proppant when stirred in water in the fracturing process, so that the function of increasing the volume of the proppant is not achieved.
In the fracturing and production increasing process of oil and gas wells, in order to reduce the using amount of the fracturing fluid and reduce the damage of the fracturing fluid to the stratum, the proppant is required to have higher strength and lower density, and the optimal clean water fracturing is realized. But is currently suitable for pressingThe apparent density of the proppant for crack construction is more than 2.50g/cm3The suspension condition in water cannot be met, and the clear water fracturing cannot be realized.
Disclosure of Invention
Problems to be solved by the invention
The invention aims to solve the problems that self-suspending proppant or a hydrogel layer on the surface of the proppant is easy to separate from a proppant body in the fracturing and stirring process, the volume of the proppant cannot be increased to achieve the purpose of suspending, or selected binders are dissolved in water or have no expansibility in water after being cured, so that the performance of a water-swellable polymer is influenced, or selected water-soluble high polymer materials such as guanidine gum, polyvinyl alcohol, polyacrylamide and the like are not gelatinized and cannot be swelled after being dissolved in water.
Means for solving the problems
The invention develops an underwater suspensible proppant and a preparation method thereof, the proppant can suspend in water, and a hydrogel layer on the surface of the proppant does not separate from the proppant in the fracturing and stirring process, so that the volume of the proppant is really increased, and the purpose of suspension in the fracturing process is achieved.
The underwater suspendable proppant comprises proppant aggregate, an expansion layer and an interface transition layer between the aggregate and the expansion layer; the swelling layer comprises hydrogel dry powder and adhesive which is used for binding the hydrogel dry powder and is swellable in water; the interface transition layer comprises epoxy resin and/or thermoplastic phenolic resin as interface transition layer resin.
The intumescent layer may comprise a polyurethane binder and a hydrogel dry powder. In this case, the polyurethane binder may account for 0.1 to 2% of the weight of the aggregate, and the hydrogel dry powder may account for 0.1 to 4% of the weight of the aggregate; the interface transition layer can account for 0.1-4% of the aggregate weight. The proppant of this composition proportion not only has the function of hanging certainly in aqueous, moreover because the bonding fastness problem between aggregate and the inflation layer has been solved to the interface transition layer, and proppant suspension nature is stable in fracturing transportation process, and the intensity of aggregate, the breakage of greatly reduced aggregate can be strengthened to the interface transition layer simultaneously.
When the interface transition layer comprises epoxy resin, the curing agent can be selected from alicyclic polyamine, aromatic polyamine, modified alicyclic polyamine and/or modified aromatic polyamine, and the amount of the curing agent accounts for 10-40% of the weight of the epoxy resin; when the interface transition layer contains thermoplastic phenolic resin, the curing agent can be hexamethylenetetramine, and the curing agent accounts for 10-20% of the weight of the phenolic resin.
In addition, the interface transition layer can comprise a coupling agent, and the coupling agent can account for 0.5-2% of the transition layer resin by weight. The coupling agent can be a silane coupling agent selected from gamma-aminopropyltriethoxysilane, N-bis (beta-hydroxyethyl) -gamma-aminopropyltrimethoxysilane, anilinomethyltriethoxysilane, and gamma-glycidoxypropyltrimethoxysilane. The weight ratio of the coupling agent to the transition layer resin is 0.1-3: 100, preferably 0.5-2: 100. The selection and the proportion of the coupling agent can well enhance the bonding strength between the resin and the aggregate.
The polyurethane adhesive may be comprised of a polyisocyanate and a water-soluble sulfonate polyester polyol.
In order to achieve the object of the present invention, the present invention provides a method for synthesizing a sulfonate polyester polyol. The method comprises the following steps: reacting sulfonate, dibasic acid and dihydric alcohol at 140-175 ℃ in the presence of an esterification and alcoholysis catalyst, adding dibasic acid and/or dibasic acid anhydride and trihydric alcohol to perform polycondensation reaction at 140-200 ℃ when reactants are clear and transparent and the acid value is less than 90mgKOH/g until the acid value is less than 1mgKOH/g and the hydroxyl value is 50-100 mgKOH/g, and obtaining a target product, wherein the molar ratio of the use amount of the sulfonate to the total use amount of the dibasic acid and/or dibasic acid anhydride is 1: 20-4, preferably 1: 10-5, wherein the molar ratio of the trihydric alcohol to the dihydric alcohol is 1: 30-10, preferably 1: 20-15, the molar ratio of the dibasic acid added for the first time to the dibasic acid and/or the dibasic acid anhydride added for the second time is 1: 0.8-5, preferably 1: 1-3, more preferably 1:2, and the molar ratio of the total usage amount of the dihydric alcohol and the trihydric alcohol to the dibasic acid and/or the dibasic acid anhydride is 1.05-1.3: 1. The sulfonate is preferably sodium isophthalate or dimethyl isophthalate sulfonate or a mixture thereof.
The preparation method of the suspending proppant in water comprises the following steps:
1) heating aggregate, adding interface transition layer composition containing a coupling agent under stirring to enable the transition layer to be coated on the aggregate, and then adding a curing agent to cure, wherein the coupling agent accounts for 0.5-2% of the weight of the transition layer;
2) adding water-swellable adhesive and hydrogel dry powder and stirring;
3) the material was cooled, crushed and sieved.
Effects of the invention
The proppant particles can be suspended in water, the hydrogel layer on the surface of the proppant cannot be separated from the body of the proppant particles in the fracturing and stirring processes, the purpose of increasing the volume of the proppant and achieving the suspension in the fracturing process is really realized, the use amount of the hydrogel is greatly reduced compared with the use amount of the guar gum or modified guar gum used in the conventional fracturing, the damage to the stratum is small, the hydrogel breaks completely, the improvement of the flow conductivity is facilitated, the fracturing construction process is simple, and the cost is low.
Detailed Description
The self-suspending proppant provided by the invention comprises a proppant aggregate, an expansion layer and an interface transition layer for solving the problem of an interface between the aggregate and the expansion layer.
The proppant aggregate may be one commonly used in the art so long as it meets the criteria specified in SY/T5108-2014, proppant performance test recommendations for hydraulic fracturing and gravel packing operations. The proppant aggregate in the invention is preferably natural quartz sand and/or ceramsite.
In order to improve the strength of the proppant and enable the aggregate to be firmly bonded with the expansion layer, epoxy resin and/or thermoplastic phenolic resin are/is used as interface transition layer resin to coat the aggregate, so that the strength and the interface performance of the proppant are ensured. In this case, the resin may account for 0.5 to 4%, preferably 1.0 to 3%, by weight of the aggregate. If the resin is used for independently improving the interface problem between the proppant aggregate and the expansion layer, the resin can account for 0.2-1% of the weight of the aggregate, and the cost of the proppant is lower under the condition of using the resin.
When the interface transition layer resin is epoxy resin, the bisphenol A epoxy resin which is cheap and has good film covering process is preferred, and can be selected from one or more of E-21, E-20, E-14 and E-13 which are commercially available. The curing agent for the epoxy resin may be a cycloaliphatic polyamine, a modified cycloaliphatic polyamine, an aromatic polyamine and/or a modified aromatic polyamine. Wherein, the alicyclic polyamine is preferably selected from one or more of isophorone diamine, bisaminocyclohexane, diaminodicyclohexylmethane, o-diamine methylcyclopentane and menthane diamine. The aromatic polyamine is preferably selected from one or more of m-xylylenediamine, diaminodiphenylmethane and m-phenylenediamine. The modified alicyclic polyamine and the modified aromatic polyamine are preferably commercially available corresponding modified polyamines, and the use amount is preferably 5-30% of the weight of the epoxy resin. When the interface transition layer resin is phenolic resin (preferably, the softening point of the phenolic resin is more than 90 ℃, the polymerization rate at 150 ℃ is less than 90 seconds, the content of free phenol is less than 0.5 weight percent, the interface transition layer resin meeting the condition meets the environmental protection requirement and can meet good film coating performance), the curing agent can be hexamethylenetetramine, and the using amount of the curing agent is preferably 10-20 percent of the weight of the phenolic resin. The curing agent in this ratio can enhance the strength of the thermoplastic phenolic resin film well.
The coupling agent may be selected from a variety of coupling agents known to those skilled in the art. In order to improve the bonding strength between the interface transition layer resin and the proppant aggregate, the coupling agent is preferably a silane coupling agent. Examples of the silane coupling agent include gamma-aminopropyltriethoxysilane, anilinomethyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, and the like. The dosage of the coupling agent is preferably 0.1-2% of the weight of the interfacial transition layer resin, and more preferably 0.5-1%. The selection and the proportion of the coupling agent can well enhance the bonding strength between the resin and the aggregate.
According to a preferred embodiment of the present invention, when the interfacial transition layer resin of the present invention is an epoxy resin, the epoxy value of the resin is greater than 0.12 mol/100 g; when the interface transition layer resin is thermoplastic phenolic resin, the softening point of the resin is more than 85 ℃, the polymerization rate at 150 ℃ is less than 120 seconds, and the content of free phenol is less than 0.5%. The interface transition layer resin meeting the conditions meets the environmental protection requirement and can meet good film coating performance.
According to a preferred embodiment of the invention, the swelling layer of the inventive water-suspendable proppant comprises a polyurethane binder and a dry hydrogel powder, the polyurethane binder consisting of a polyisocyanate and a water-soluble sulfonate polyester polyol.
The sulfonate used to prepare the sulfonate polyester polyol is preferably sodium isophthalate or dimethyl isophthalate sulfonate or a mixture thereof. In the preparation method of the sulfonate polyester polyol, the molar ratio of the sodium m-phthalic acid sulfonate or the sodium dimethyl m-phthalic acid sulfonate to the dibasic acid and/or the dibasic acid anhydride is 1: 20-4, preferably 1: 10-5; the molar ratio of the trihydric alcohol to the dihydric alcohol is 1: 30-10, preferably 1: 20 to 15 parts. The triol may be glycerol or trimethylolpropane or a mixture thereof. The dibasic acid can be isophthalic acid, terephthalic acid, adipic acid, sebacic acid, fumaric acid, itaconic acid, citraconic acid or chloromaleic acid or a mixture thereof, and the dibasic anhydride can be hexahydrophthalic anhydride, phthalic anhydride, nadic anhydride, tetrahydrophthalic anhydride and maleic anhydride or a mixture thereof; the dihydric alcohol can be ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol-400, polyethylene glycol-600, polyethylene glycol-800, polyethylene glycol-1000, neopentyl glycol or a mixture thereof.
The synthesis process of the sulfonate polyester polyol is a two-step method, and can specifically comprise the following steps: adding sodium m-phthalic acid sulfonate or sodium dimethyl m-phthalic acid sulfonate, dibasic acid (half of the total acid amount), dihydric alcohol and an esterification and alcoholysis catalyst into a reaction kettle, introducing nitrogen for protection, heating to 120 ℃, stirring, heating to 140 ℃, gradually heating to 170 ℃, preserving heat at 170-175 ℃, keeping the temperature until the acid value is less than 90mgKOH/g and the reactant is clear and transparent, cooling to below 160 ℃, adding the rest dibasic acid (or anhydride) and trihydric alcohol, preserving heat at 140-160 ℃ for one hour, gradually heating to 190 ℃, controlling the internal temperature to be not more than 103 ℃ in the heating process, preserving heat at 190-200 ℃, and vacuumizing until the acid value is reduced to below 1mgKOH/g when the acid value is less than 90mgKOH/g to obtain the target product.
Wherein the esterification and alcoholysis catalyst can be a compound of zinc, titanium or tin, such as zinc acetate, dibutyltin oxide and tetrabutyl titanate, and the dosage of the esterification and alcoholysis catalyst is 0.005-0.2 percent of the weight of all materials, and the proper dosage is 0.05-0.1 percent.
The polyisocyanate constituting the polyurethane binder may be selected from the group consisting of phenyl diisocyanate, toluene diisocyanate, xylene methane diisocyanate, ethylbenzene diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, polymethylene polyphenyl isocyanates (abbreviated as PAPI), and has an average functionality of 2.5 to 2.6.
The hydrogel dry powder used in the invention is a polymer with a three-dimensional network structure, can absorb a large amount of water in water to swell, and can continuously keep the original structure after swelling without being dissolved. All water-soluble or hydrophilic polymers can form hydrogel through certain chemical crosslinking or physical crosslinking. These polymers can be classified into two major categories, natural and synthetic, depending on their origin. The natural hydrophilic polymer includes polysaccharides (starch, cellulose, alginic acid, chitosan, etc.) and polypeptides (collagen, poly-L-lysine, poly-L-glutamic acid, etc.). The synthetic hydrophilic polymer includes acrylic acid and its derivatives (polyacrylic acid, polymethacrylic acid, polyacrylamide, poly-N-polyacrylamide, etc.).
According to a preferred embodiment of the invention, in the preparation method of the proppant, the aggregate is heated to 180-220 ℃ in the step 1), then the temperature is reduced, when the temperature is reduced to 180 +/-20 ℃, the transition layer resin containing the coupling agent is added, the stirring time is 40 +/-20 seconds, and the curing time is 90 +/-30 seconds when the curing agent is added for curing, so that the transition layer resin is completely cured and the resin film is not abraded; in the step 2), before and after the hydrogel dry powder is added, sulfonate polyester polyol and polyisocyanate which are components of the water-swellable adhesive are respectively added, the stirring time of the sulfonate polyester polyol is 40 +/-10 seconds, the stirring time of the hydrogel dry powder is 40 +/-10 seconds, and the stirring and curing time of the polyisocyanate is 120 +/-20 seconds. Therefore, the hydrogel dry powder can be uniformly coated on the outer surface of the interface transition layer, the sulfonate polyester polyol and the polyisocyanate are completely cured, the hydrogel dry powder cannot be abraded, and the production efficiency is improved. In addition, the temperature is increased and then reduced, the moisture and a small amount of impurities in the aggregate can be removed at high temperature, and then the temperature is reduced to meet the requirement, so that the strength of the coating can be enhanced.
The present invention will be described in further detail below by way of examples.
The following examples are provided to provide a better understanding of the present invention and are not intended to limit the invention to the best mode contemplated. The examples are not intended to limit the scope or content of this invention, and any product or method that comes within the teachings of this invention or combines these with other features of the prior art, which has the characteristics set forth in the claims, falls within the scope of this invention.
Sources of raw materials used in the examples:
thermoplastic phenolic resins are commercially available from Shandong Shengquan chemical industries, Inc. or Nantong Sumitomo electric Wood, bisphenol A type epoxy resins are commercially available from Baling petrochemical industries, Inc., and hydrogel dry powders are commercially available from A1 hydrogel dry powder of Beijing Huaruixiang science and technology, Inc. or K4 hydrogel dry powder of Yuqiquan chemical industries, Inc.
The specific techniques or conditions not specified in each example were carried out according to the conventional techniques or conditions described in the literature in the art. The reagents or instruments used are conventional commercial products which are not indicated by the manufacturer and are commercially available.
Example 1
Sulfonate polyester polyol synthesis example 1: adding 11.1 kg of sodium dimethyl isophthalate sulfonate, 18.7 kg of isophthalic acid, 15.9 kg of diethylene glycol, 27.0 kg of triethylene glycol and 50g of zinc acetate into a reaction kettle, introducing nitrogen for protection, heating to 120 ℃, stirring, heating to 140-160 ℃, keeping the temperature for one hour, gradually heating to 170 ℃, keeping the temperature at 170-175 ℃, cooling to 140 ℃ when the acid value is less than 90mgKOH/g and the reactants are completely clear and transparent, adding 22.2 kg of phthalic anhydride and 0.67 kg of trimethylolpropane, heating to 140-160 ℃, keeping the temperature for one hour, gradually heating to 190 ℃, controlling the internal temperature to be not more than 103 ℃ in the heating process, keeping the temperature at 190-200 ℃, and vacuumizing to reduce the acid value to below 1mgKOH/g when the acid value is less than 60mgKOH/g to obtain the sulfonate polyester polyol with the hydroxyl value of 46.2 mgKOH/g.
Example 2
Sulfonate polyester polyol synthesis example 2: adding 13.4 kg of sodium m-phthalate sulfonate, 14.8 kg of phthalic anhydride, 16.9 kg of diethylene glycol, 32.0 kg of tetraethylene glycol and 28 g of dibutyltin oxide into a reaction kettle, introducing nitrogen for protection, heating to 120 ℃, stirring, heating to 140-160 ℃, keeping the temperature for one hour, gradually heating to 170 ℃, keeping the temperature at 170-175 ℃, cooling to 160 ℃ when the acid value is less than 90mgKOH/g, adding 22.2 kg of phthalic anhydride and 2.6 kg of trimethylolpropane, heating to 140-160 ℃, keeping the temperature for one hour, gradually heating to 190 ℃, controlling the internal temperature to be not more than 103 ℃ in the heating process, keeping the temperature at 190-200 ℃, and vacuumizing to reduce the acid value to below 1mgKOH/g when the acid value is less than 60mgKOH/g to obtain the sulfonate polyester polyol with the hydroxyl value of 57.6 mgKOH/g.
Example 3
Sulfonate polyester polyol synthesis example 3: adding 22.2 kg of sodium dimethyl isophthalate sulfonate, 11.1 kg of phthalic anhydride, 33.75 kg of triethylene glycol, 45.0 kg of polyethylene glycol and 56 g of zinc acetate into a reaction kettle, introducing nitrogen for protection, heating to 120 ℃, stirring, heating to 140-160 ℃, keeping the temperature for one hour, gradually heating to 170-175 ℃, keeping the temperature at 170-175 ℃, cooling to 160 ℃ when the acid value is less than 90mgKOH/g, adding 22.2 kg of phthalic anhydride and 5.4 kg of trimethylolpropane, heating to 140-160 ℃, keeping the temperature for one hour, gradually heating to 190 ℃, controlling the internal temperature to be not more than 103 ℃ in the heating process, keeping the temperature at 190-200 ℃, and vacuumizing to reduce the acid value to 1mgKOH/g when the acid value is less than 60mgKOH/g to obtain sulfonate polyester polyol with the hydroxyl value of 52.1 mgKOH/g.
Example 4
Heating 3 kg of quartz sand with the particle size of 850/425 mu m (20/40 meshes) to 220 ℃, putting the quartz sand into a self-made sand mixer for stirring, cooling to 200 ℃, adding 45 g of epoxy resin and 0.3 g of gamma-glycidyl ether propyl trimethoxy silane, stirring for 40 seconds, adding 5.4 g of diaminodiphenylmethane, stirring and curing for 150 seconds; after the temperature is reduced to 140 ℃, 18.6 g of the sulfonate polyester polyol prepared in example 1 is added and stirred for 40 seconds, 60 g of hydrogel dry powder is added and stirred for 40 seconds, 5.4 g of toluene diisocyanate is added and stirred for solidification until the particles are completely dispersed, and the suspendable proppant is obtained after cooling and sieving.
Example 5 (comparative example)
Heating 3 kg of quartz sand with the particle size of 850/425 microns (20/40 meshes) to 220 ℃, putting the quartz sand into a self-made sand mixer for stirring, cooling to 140 ℃, adding 18.6 g of the sulfonated polyester polyol prepared in example 1, stirring for 40 seconds, adding 60 g of hydrogel dry powder, stirring for 40 seconds, adding 5.4 g of toluene diisocyanate, stirring and curing until the particles are completely dispersed, cooling and sieving to obtain the contrast proppant.
Example 6 (comparative example)
Heating 3 kg of quartz sand with the particle size of 850/425 microns (20/40 meshes) to 220 ℃, putting the quartz sand into a self-made sand mixer, stirring, cooling to 180 ℃, adding 18.6 g of phenolic resin, stirring for 40 seconds, adding 60 g of hydrogel dry powder, stirring for 40 seconds, adding 3.7 g of hexamethylenetetramine solution, stirring and curing until the particles are completely dispersed, cooling, and sieving to obtain the contrast proppant.
TABLE 1 comparison of results for examples 4, 5 and 6
Note: adding 20 g of proppant into a 150ml beaker, adding 100ml of water, and observing the expansion times and shelling phenomena of the proppant
Example 7
3 kg of a powder having a particle size of 850/425 μm (20)40 mesh) of low-density ceramic particles (produced by Yixin Gaokai ceramics Co., Ltd., Pingxiang city, volume density 1.35 g/cm)3Apparent density 2.38g/cm3) Heating to 220 ℃, putting into a self-made sand mixer, stirring, cooling to 200 ℃, adding 60 g of phenolic resin (the resin contains 1% of gamma-aminopropyltriethoxysilane) and stirring for 45 seconds, adding 27 g of hexamethylenetetramine aqueous solution (the mass ratio of hexamethylenetetramine to water is 1:2), and stirring and curing for 140 seconds; after the temperature is reduced to 140 ℃, 26.3 g of the sulfonate polyester polyol prepared in example 2 is added and stirred for 30 seconds, 75 g of hydrogel dry powder is added and stirred for 50 seconds, 3.8 g of polymethylene polyphenyl isocyanate (PM-200) is added and stirred and solidified until the particles are completely dispersed, and the suspensible proppant is obtained after cooling and sieving.
Example 8 (comparative example)
3 kg of low-density ceramsite with the particle size of 850/425 mu m (20/40 meshes) and the same as that in example 7 are heated to 220 ℃, then placed into a self-made sand mixer for stirring, cooled to 140 ℃, added with 26.3 g of the sulfonate polyester polyol prepared in example 2 and stirred for 40 seconds, added with 75 g of hydrogel dry powder and stirred for 50 seconds, added with 3.8 g of polymethylene polyphenyl isocyanate (PM-200) and stirred for solidification until the particles are completely dispersed, cooled and sieved to obtain the comparative proppant.
Example 9 (comparative example)
3 kg of low-density ceramsite with the particle size of 850/425 mu m (20/40 meshes) and the same as that in example 7 are heated to 220 ℃, then placed into a self-made sand mixer for stirring, cooled to 200 ℃, added with 26.8 g of epoxy resin and stirred for 50 seconds, added with 75 g of hydrogel dry powder and stirred for 50 seconds, added with 3.2 g of diaminodiphenylmethane and stirred for solidification until the particles are completely dispersed, cooled and sieved to obtain the contrast proppant.
TABLE 2 comparison of results for examples 7, 8 and 9
Note: adding 20 g of proppant into a 150ml beaker, adding 100ml of water, and observing the expansion times and shelling phenomena of the proppant
Example 10
3 kg of low-density ceramsite (Yixin Gaokai ceramics Co., Ltd., Pingxiang city, volume density 1.18 g/cm) with particle size of 425/212 μm (40/70 mesh)3Apparent density 2.23g/cm3) Heating to 230 ℃, putting into a self-made sand mixer for stirring, cooling to 210 ℃, adding 75 g of phenolic resin (containing 0.5% of gamma-aminopropyltriethoxysilane) and stirring for 50 seconds, adding 34 g of hexamethylenetetramine aqueous solution (the mass ratio of hexamethylenetetramine to water is 1:2), and stirring and curing for 120 seconds; after the temperature is reduced to 140 ℃, 26.5 g of the sulfonate polyester prepared in example 3 is added and stirred for 40 seconds, 75 g of hydrogel dry powder is added and stirred for 50 seconds, 3.5 g of polymethylene polyphenyl isocyanate (PM-200) is added and stirred and solidified until the particles are completely dispersed, and the suspensible proppant is obtained after cooling and sieving.
Example 11 (comparative example)
3 kg of low-density ceramsite with the particle size of 425/212 mu m (40/70 meshes) and the same size as in example 8 are heated to 220 ℃, then placed into a self-made sand mixer for stirring, cooled to 140 ℃, added with 26.5 g of the sulfonate polyester polyol prepared in example 3 and stirred for 40 seconds, added with 75 g of hydrogel dry powder and stirred for 50 seconds, added with 3.5 g of polymethylene polyphenyl isocyanate (PM-200) and stirred for solidification until the particles are completely dispersed, cooled and sieved to obtain the comparative proppant.
TABLE 3 comparison of the results of examples 10 and 11
Note: adding 20 g of proppant into a 150ml beaker, adding 100ml of water, and observing the expansion times and shelling phenomena of the proppant
Experiment for degrading hydrogel on suspensible proppant
Degradation at 70 ℃: each 30 g of the proppants of examples 4 to 11 was placed in a 150ml beaker, 100g of tap water containing 0.06 wt% of ammonium persulfate was added, and the mixture was placed in a constant temperature water bath at 70 ℃ for heat preservation, and after 4 hours, the hydrogel on the proppants was completely degraded.
Degradation at 50 ℃: each 30 g of the proppants of examples 4 to 11 was placed in a 150ml beaker, 100g of tap water containing 0.03 wt% ammonium persulfate and 0.03 wt% potassium periodate was added thereto, and the mixture was placed in a thermostatic water bath at 50 ℃ for heat preservation, and after 12 hours, the hydrogel on the proppants was completely degraded.
Claims (10)
1. The suspended proppant comprises proppant aggregate, an expansion layer and an interface transition layer between the aggregate and the expansion layer; the interface transition layer comprises epoxy resin and/or thermoplastic phenolic resin serving as interface transition layer resin and a coupling agent, wherein the coupling agent accounts for 0.5-2% of the weight of the interface transition layer resin; the expansion layer comprises a polyurethane adhesive and hydrogel dry powder, wherein the polyurethane adhesive accounts for 0.1-2% of the weight of the aggregate, and the hydrogel dry powder accounts for 0.1-4% of the weight of the aggregate;
the polyurethane adhesive consists of polyisocyanate and water-soluble sulfonate polyester polyol;
the water-soluble sulfonate polyester polyol is prepared by the following method: reacting sulfonate, dibasic acid and dihydric alcohol at 140-175 ℃ in the presence of an esterification and alcoholysis catalyst, adding dibasic acid and/or dibasic acid anhydride and trihydric alcohol to perform polycondensation reaction at 140-200 ℃ when reactants are clear and transparent and the acid value is less than 90mgKOH/g until the acid value is less than 1mgKOH/g and the hydroxyl value is 50-100 mgKOH/g, and obtaining a target product, wherein the molar ratio of the use amount of the sulfonate to the total use amount of the dibasic acid and/or dibasic acid anhydride is 1: 20-4, wherein the molar ratio of the trihydric alcohol to the dihydric alcohol is 1: 30-10, the molar ratio of the dibasic acid added for the first time to the dibasic acid and/or the dibasic acid anhydride added for the second time is 1: 0.8-5, and the molar ratio of the total usage amount of the dihydric alcohol and the trihydric alcohol to the dibasic acid and/or the dibasic acid anhydride is 1.05-1.3: 1.
2. The water-suspendable proppant of claim 1, wherein the interfacial transition layer comprises 0.1 to 4% by weight of the aggregate.
3. The suspendable aqueous proppant of claim 1, wherein the sulfonate salt used to prepare said water-soluble sulfonate polyester polyol is sodium isophthalate or sodium dimethyl isophthalate or a mixture thereof.
4. An aqueous suspendable proppant as set forth in claim 1,
the molar ratio of the usage amount of the sulfonate to the total usage amount of the dibasic acid and/or the dibasic acid anhydride is 1: 10-5, wherein the molar ratio of the trihydric alcohol to the dihydric alcohol is 1: 20-15, wherein the molar ratio of the dibasic acid added for the first time to the dibasic acid and/or the dibasic acid anhydride added for the second time is 1: 1-3.
5. An aqueous suspendable proppant as set forth in claim 4 wherein the molar ratio of first added diacid to second added diacid and/or diacid anhydride is 1: 2.
6. An aquatic suspendable proppant as set forth in one of claims 1 to 5, wherein said interfacial transition layer comprises an epoxy resin, and said curing agent is selected from the group consisting of alicyclic polyamines, aromatic polyamines, modified alicyclic polyamines and/or modified aromatic polyamines, and is used in an amount of 10 to 40% by weight based on the epoxy resin; or the interface transition layer comprises thermoplastic phenolic resin, the used curing agent is hexamethylenetetramine, and the curing agent accounts for 10-20% of the weight of the phenolic resin.
7. The suspendable proppant in water of claim 1, wherein said coupling agent is a silane coupling agent; the weight ratio of the coupling agent to the interfacial transition layer resin is 0.1-3: 100.
8. The water-suspendable proppant as set forth in claim 7, wherein said coupling agents are γ -aminopropyltriethoxysilane, N-bis (β -hydroxyethyl) - γ -aminopropyltrimethoxysilane, anilinomethylenetriethoxysilane, and γ -glycidoxypropyltrimethoxysilane, and the weight ratio of said coupling agents to the interfacial transition layer resin is 0.5 to 2: 100.
9. A method of making an in-water suspendable proppant as set forth in one of claims 1 to 8 comprising the steps of:
1) heating aggregate, adding a coupling agent-containing interface transition layer component under stirring to enable the interface transition layer to be coated on the aggregate, and then adding a curing agent to cure, wherein the coupling agent accounts for 0.5-2% of the weight of the interface transition layer;
2) adding water-swellable adhesive and hydrogel dry powder and stirring;
3) the material was cooled, crushed and sieved.
10. The preparation method according to claim 9, characterized in that the aggregate is heated to 180-220 ℃ in the step 1), then cooled, when the temperature is reduced to 180 +/-20 ℃, the interface transition layer resin containing the coupling agent is added, and the curing agent is added for curing; adding water-soluble sulfonate polyester polyol and polyisocyanate before and after adding the hydrogel dry powder in the step 2).
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