Ultra-light proppant

Abstract

Systems and methods for making and using proppant particles are provided. Exemplary proppant particles include a composite of a precipitated polymer matrix and a plant-based material, where the precipitated polymer matrix includes a thermoplastic material, and where the plant-based material includes microparticles.

Description

Priority Claim

[0001] This application claims priority to U.S. Patent Application No. 17 / 992,360, filed on November 22, 2022, the entire content of which is incorporated herein by reference. Technical Field

[0002] This disclosure relates to methods for producing ultra-lightweight proppants. Background Art

[0003] Well completion procedures for low-permeability hydrocarbon reservoirs, such as shale oil and shale gas fields, typically require hydraulic fracturing to create fractures that allow hydrocarbon flow. Hydraulic fracturing is initiated by pumping a fracturing fluid into the wellbore and increasing the pressure to a high enough level to cause fracturing of the subterranean formation. The fracturing fluid contains proppants that are used to keep the fractures open and allow flow through the induced fractures for hydrocarbon recovery. In the long term, the use of proppants provides high conductivity and increased well production.

[0004] Typically, proppants are spherical particles characterized by heat and pressure resistance, low cost, and a specific size distribution in the micron to millimeter range. The selection of proppants is based on the properties of the wellbore formation such as closure pressure and heat resistance. Materials used to prepare proppants include silica, ceramics, glass beads, nut shells, resin-coated sand, and bauxite. Based on composition, proppants can be prepared using methods such as crushing, screening, coating, or sintering.

[0005] Since proppants are resistant to high closure pressures, they typically have a high density, and density is generally related to mechanical crush resistance. Since the density of proppants is typically more than twice the density of water, proppants tend to precipitate out of the fracturing fluid, which reduces the efficiency of hydraulic fracturing. The fracturing fluid typically includes additives or viscosifiers to increase viscosity, thereby improving the transport of proppants into the well by keeping them suspended. However, this increases power consumption due to the increased load on the pump. In addition, residual materials from the viscosifiers may reduce the permeability of the reservoir rock to hydrocarbon flow. Summary of the Invention

[0006] One embodiment described herein provides a method of using a composite proppant. The method includes grinding plant material to form particles, dissolving a polymer in a solvent, and mixing the particles into the solvent. The solvent is injected into a microfluidic chip, and a polymer-precipitating phase is injected into the microfluidic chip. Emulsified solvent droplets are formed in the polymer-precipitating phase in the microfluidic chip, and the proppant particles are collected after polymer precipitation.

[0007] Another embodiment disclosed by the examples herein provides a proppant particle. The proppant particle includes a composite material of a precipitated polymer matrix and a plant-based material, wherein the precipitated polymer matrix includes a thermoplastic, and wherein the plant-based material includes microparticles. Brief Description of the Drawings

[0008] Figure 1 is a schematic diagram of forming proppant particles from an emulsion.

[0009] Figure 2 is a schematic diagram of a microfluidic system for forming proppant particles using a microfluidic chip.

[0010] Figure 3 is an alternative configuration of the microfluidic chip.

[0011] Figure 4 is a block diagram of a method of preparing proppant particles using a microfluidic system. Detailed Description

[0012] The embodiments described herein provide methods of using a microfluidic system for producing ultra-lightweight (ULW) proppants. Reducing the proppant density will reduce proppant settling, allow the use of lower viscosity fluids, minimize flood loss, and reduce the pumping rate, which reduces the risk of unwanted fracturing in the reservoir.

[0013] Various types of ULW proppants have been tested, including organic polymer proppants (ULW-1), reinforced composite materials composed of polymer-coated impregnated nut shells (ULW-2), and resin-coated porous ceramics (ULW-3), etc. A comparison of conventional proppants with these three types of ULW proppants is provided in Table 1. The research results show that plant-based fillers (e.g., composed of strength materials such as lignin, cellulose, and hemicellulose) maintain the mechanical strength of the proppants without increasing the density. In addition, since waste materials can be used, plant-based fillers will have a reduced environmental impact.

[0014] To prepare ULW proppants using plant-based fillers, the particles of the plant-based fillers are held or fixed in an attached state. Matrix polymers are an effective solution for holding the plant particles in place. Since the size of the proppants is important for efficacy, the method used to form the proppants should provide strong control. It is known that microfluidic systems provide precise adjustment and control of parameters during microsphere formation, and as a result, it ensures high precision in particle size during production.

[0015] Table 1: Comparison of the general properties of conventional proppants and ultra-light proppants

[0016]

[0017] *ULW-1 is an organic polymer proppant; ULW-2 is a reinforced composite material of polymer-coated nut shells; ULW-3 is a resin-coated porous ceramic.

[0018] Therefore, we aim to use a microfluidic system to produce ultra-lightweight proppants using plant-based fillers combined with matrix polymers.

[0019] Figure 1 Figure 100 is a schematic diagram of the formation of proppant particles from an emulsion. During the formation, a solvent 102 containing dissolved polymer 104 and plant-based filler 106 is mixed with a precipitation solvent 108 (such as an aqueous phase), which results in the removal 110 of the solvent phase 102 by diffusion and evaporation. During the removal of the solvent 102, the polymer 104 precipitates to form a matrix polymer 112, which results in the formation of a strong particle-polymer association 114, thereby forming a hardened proppant 116. Once the matrix polymer 112 is completely precipitated, the formed proppant 118 can be used (e.g., after drying).

[0020] In various embodiments, the plant-based filler 106 includes plants, recycled plants, wood, recycled wood, invasive plant species, recycled invasive plant species, recycled bio-based waste, bio-based waste, organic sludge, recycled organic sludge, grass, recycled grass, seeds, recycled seeds, wood chips or recycled wood chips, etc. The plant-based filler 106 may also include plant-based derivatives such as lignin, lignin derivatives, cellulose, cellulose derivatives, hemicellulose, hemicellulose derivatives, starch, starch derivatives, inulin, inulin derivatives, kraft lignin or kraft lignin derivatives, etc.

[0021] In various embodiments, an emulsion stabilizer is used to stabilize the emulsion of solvent 102 formed in precipitation solvent 108. The emulsion stabilizer is a surfactant, including fatty acids, amino alcohols, fatty alcohols, fatty mercaptans, polyethylene glycols, polypropylene glycols, polyvinyl alcohols, polysorbates, fatty acid esters of sorbitol, fatty acid esters of glycerol, fatty acid esters of polyhydroxy compounds, alkylphenol ethoxylates, alkyl polyglucosides (alkylpolysaccharides or alkyl polyglucosides), fatty alcohol ethoxylates, ethoxylated amines, fatty acid amides, cetrimonium bromide, octenidine dihydrochloride, didodecyldimethylammonium bromide, cetylpyridinium chloride, benzalkonium chloride, benzethonium chloride, dimethyldioctadecylammonium chloride, ammonium lauryl sulfate, sodium lauryl sulfate, ammonium dodecyl sulfate, sodium dodecyl sulfate, sodium lauryl ether sulfate, sodium myrethsulfate, dioctyl sodium sulfosuccinate, perfluorobutanesulfonate, alkyl-aryl ether phosphates, alkyl ether phosphates, alkyl aryl sulfonates, alkyl benzene sulfonates, alkyl sulfates, N-ethoxy sulfonates, sodium lauryl sulfate, alcohol propoxy sulfates, alkyl ethoxy sulfates, alpha-olefin sulfonates, alpha-olefin sulfates, branched alkyl benzenesulfonates, docusate sodium, ethoxy glycidylsulfonates, propoxyglycidyl sulfonate), alkyl ether sulfate, internal olefin sulfonate, sulfonated ethoxylated alcohol, sulfonated ethoxylated alkyl phenol, sodium petroleum sulfonate, alkyl alcohol propoxylated sulfate, alkyl phenol, monoglyceride, diglyceride, guar gum, rapeseed oil, lecithin, carrageenan or ammonium phosphatide, or derivatives thereof, etc.

[0022] In various embodiments, the matrix polymer 112 is a thermoplastic polymer, including poly(methyl methacrylate), polymethacrylate, poly(lactic-co-glycolic acid), polyester, polyethylene terephthalate, poly(styrene-isoprene), polybromostyrene, polyethylene, polyphenylene oxide, polyethersulfone, acrylonitrile butadiene styrene (acrylonitrile butadiene styrene terpolymer), polycarbonate, polyhydroxyalkanoate, polyhydroxybutyrate, polylactic acid, polyurethane, polyvinyl chloride, poly(methyl methacrylate)-based copolymer, polymethacrylate-based copolymer, poly(lactic-co-glycolic acid)-based copolymer, polyester-based copolymer, polyethylene terephthalate-based copolymer, polystyrene-based copolymer, poly(styrene-isoprene)-based copolymer, polybromostyrene-based copolymer, polyethylene-based copolymer, polyphenylene oxide-based copolymer, polyethersulfone-based copolymer, acrylonitrile butadiene styrene-based copolymer, polycarbonate-based copolymer, polyhydroxyalkanoate-based copolymer, polyhydroxybutyrate-based copolymer, polylactic acid-based copolymer, polyurethane-based copolymer, polyvinyl chloride-based copolymer, styrene-acrylate copolymer, polyamide, polyamide-based copolymer, polyether, polyether-based copolymer, polyimide, polyimide-based copolymer, polyolefin, polyolefin-based copolymer, polypropylene-polyethylene copolymer, ethylene-vinyl acetate copolymer, polyacrylic acid, polyacrylic acid-based copolymer, polyacrylate, polyacrylate-based copolymer, propylene-acrylate copolymer, propylene-methacrylate copolymer, oxidized polypropylene, oxidized polyethylene, propylene-ethylene oxide copolymer or acrylonitrile-butadiene-styrene copolymer, etc.

[0023] In various embodiments, the solvent 102 for the polymer 104 is an organic solvent, including dichloromethane, dichloroethane, acetone, methyl ethyl ketone, acetic acid, cyclopentane, ethyl acetate, carbon disulfide, N,N-dimethylformamide, ethanol, isopropanol, propanol, formaldehyde, chloroform, carbon tetrachloride, hexane, heptane, octane, benzene, toluene, acetonitrile, 1,4-dioxane, dimethyl sulfide, tetrahydrofuran or diethyl ether, etc.

[0024] Figure 2 is a schematic diagram of a microfluidic system 200 that uses a microfluidic chip 202 to form proppant particles 118. Items with the same number are as described with respect to Figure 1As described above, the microfluidic system 200 includes a pump 202 (such as an injection pump 204 or a gas-driven pump) and a microfluidic chip 206. In some embodiments, the microfluidic system 200 has a temperature control system to maintain conditions for production, such as a heater to increase the diffusion rate of the solvent 102 or to promote the evaporation of the solvent 102. Each pump 204 has a feed rate control unit. In some embodiments, at least one pump 204 has a mixer to incorporate particles of the plant-based filler 106. The operation of the pumps 202 can be synchronized to maintain a constant supply of components within the microfluidic chip 206.

[0025] As described herein, the plant-based filler 106 is ground and then sieved to control the particle size, form a uniform particle size, or both. The particle size can be determined based on the diameter of the channels 208 of the microfluidic chip 206. For example, if the channels 208 of the microfluidic chip have a diameter of about 500 μm, a particle size limit of about 400 μm can be selected to prevent clogging.

[0026] The solvent 102 including the polymer 104 and the plant-based filler 106 is injected into the channels 208. Nozzles at the ends of the channels 208 inject droplets of the solvent 102 (carrying the plant-based filler 106 and the polymer 104) into the flow of the precipitation solvent 108. As the solvent 102 is removed 110 from the droplets, the polymer 102 forms a matrix polymer 112 that houses the plant-based filler 106, thereby forming hardened proppant particles 116. Further precipitation forms the proppant 118, which exits the microfluidic chip 206 to the isolation unit 210. In the isolation unit, a capture container 212 is used to collect the proppant 118. From there, the proppant 118 can be dried before final use.

[0027] Figure 3 is an alternative configuration of the microfluidic chip 300 that can be used to form the proppant 118. Items with the same number are as described with respect to Figure 1 As described above. In this microfluidic chip 300, a third solvent system 302 can be introduced to improve the precipitation of the proppant 118, enhance control over the size of the proppant 118, etc. For example, the solvent 102 can include an organic solvent as described with respect to Figure 1 and the precipitation solvent 108 to initiate precipitation, while the third solvent system 302 includes an emulsion stabilizer to enhance the formation of the emulsion. In this configuration, any number of other solvent combinations can be used to control the precipitation of the proppant 118.

[0028] Figure 4FIG. 400 is a block diagram of a method four hundred (400) for preparing proppant particles using a microfluidic system. The method begins at block 402 where a plant-based material is ground to form micron-sized particles. The particles are then screened to provide a generally uniform size range. For example, the particles can be in the range of about 10 μm to about 2 mm, about 20 μm to about 1 mm, or about 50 μm to 500 μm. In some embodiments, the particles can be within 20% of the central value. For example, if the central value is about 100 μm, the particle size can be in the range of about 80 μm to about 120 μm. The micron-sized screened particles can undergo several grindings and screenings to achieve the target size and range. In various embodiments, the concentration of the plant-based filler 106 is between about 0% w / v (g / 100 mL) and about 35% w / v. For example, the concentration of the plant-based filler can be 1% w / v or 28% w / v. The optimal concentration of the plant-based filler in the proppant is about 5% to 15% w / v.

[0029] At block 404, a polymer is dissolved in a solvent phase. In some embodiments, the matrix polymer is prepared from a mixture of dissolved polymers, which can form a mechanically stronger alloy.

[0030] At block 406, a plant-based filler is added to the solvent. Mechanical stirring is used to disperse the plant-based filler to form a generally uniform suspension.

[0031] At block 408, an emulsion stabilizer is added to the solvent. In some embodiments, as described with respect to Figure 3 the emulsion stabilizer is added to a separate solvent. For example, the emulsion stabilizer can be added to a precipitation solvent, a third solvent, or both. In these embodiments, the plant-based filler can be added to the phase containing the polymer and stabilizer or only to the phase containing the polymer.

[0032] At block 410, these phases are then introduced into a microfluidic chip using a pump. Mixing can be performed within the microfluidic chip using miscible or immiscible phases. At the channel junctions of the microfluidic chip, such as at the nozzle, these phases are mixed.

[0033] At block 412, solvent droplets are formed in the precipitate phase within the microfluidic chip. Emulsified solvent droplets can form during the mixing of immiscible phases. As used herein, an emulsion is a fine dispersion of one liquid in another liquid in which it is not soluble or miscible. Emulsions include any number of droplet sizes, including submicron emulsified droplets, micron-sized emulsified droplets, and suspensions of larger-sized droplets. The emulsion can be a discontinuous oil phase in a continuous aqueous phase (O / W) or a discontinuous aqueous phase in a continuous oil phase (O / O). The emulsion can be even more complex, where the inner phase itself is a dispersion, such as an O / W / O-type emulsion. Precipitation of the polymer in the emulsion can occur in the aqueous phase, the oil phase, or the interfacial phase between the aqueous and oil phases, in more than one of the above phases, or in all of the above phases. For example, the solvent can diffuse out of the emulsified solvent droplets and the polymer can precipitate.

[0034] At block 414, the proppant is collected after precipitation. Prior to use, the proppant can be dried to remove any trace amounts of residual solvent, which can increase the hardness of the proppant.

[0035] The final proppant can be suspended in a fracturing fluid such as a water-based fracturing fluid. The fracturing fluid is injected into the reservoir under pressure to create fractures. When the fractures are created, the fracturing fluid carries the proppant into the fractures.

[0036] Embodiments

[0037] One embodiment described herein provides a method of using a composite proppant. The method includes grinding plant material to form particles, dissolving a polymer in a solvent, and mixing the particles into the solvent. The solvent is injected into a microfluidic chip and the polymer precipitate phase is injected into the microfluidic chip. Emulsified solvent droplets are formed in the polymer precipitate phase within the microfluidic chip, and the particulate proppant is collected after precipitation of the polymer.

[0038] In one aspect, the method includes mixing an emulsion stabilizer into the solvent prior to injecting the solvent into the microfluidic chip. In one aspect, the method includes mixing an emulsion stabilizer into the aqueous phase prior to injecting the aqueous phase into the microfluidic chip.

[0039] In one aspect, the plant material includes nut shells, wood, recycled wood, invasive plant species, recycled invasive plant species, recycled bio-based waste, bio-based waste, organic sludge, recycled organic sludge, grass, recycled grass, seeds, recycled seeds, wood chips or recycled wood chips or any combination thereof. In one aspect, the plant material includes lignin, lignin derivatives, cellulose, cellulose derivatives, hemicellulose, hemicellulose derivatives, starch, starch derivatives, inulin, inulin derivatives, kraft lignin or kraft lignin derivatives or any combination thereof.

[0040] In one aspect, the polymer comprises a thermoplastic polymer. In one aspect, the polymer comprises poly(methyl methacrylate), polymethacrylate, poly(lactic-co-glycolic acid), polyester, polyethylene terephthalate, poly(styrene-isoprene), polybromostyrene, polyethylene, polyphenylene ether, polyethersulfone, acrylonitrile butadiene styrene, polycarbonate, polyhydroxyalkanoate, polyhydroxybutyrate, polylactic acid, polyurethane, polyvinyl chloride, copolymers based on poly(methyl methacrylate), copolymers based on polymethacrylate, copolymers based on poly(lactic-co-glycolic acid), copolymers based on polyester, copolymers based on polyethylene terephthalate, copolymers based on polystyrene, copolymers based on poly(styrene-isoprene), copolymers based on polybromostyrene, copolymers based on polyethylene, copolymers based on polyphenylene ether, copolymers based on polyethersulfone, copolymers based on acrylonitrile butadiene styrene, copolymers based on polycarbonate, copolymers based on polyhydroxyalkanoate, copolymers based on polyhydroxybutyrate, copolymers based on polylactic acid, copolymers based on polyurethane, copolymers based on polyvinyl chloride, styrene-acrylate copolymer, polyamide, copolymers based on polyamide, polyether, copolymers based on polyether, polyimide, copolymers based on polyimide, polyolefin, copolymers based on polyolefin, polypropylene-polyethylene copolymer, ethylene-vinyl acetate copolymer, polyacrylic acid, copolymers based on polyacrylic acid, polyacrylate, copolymers based on polyacrylate, propylene-acrylate copolymer, propylene-methacrylate copolymer, oxidized polypropylene, oxidized polyethylene, propylene-ethylene oxide copolymer or acrylonitrile-butadiene-styrene copolymer or any combination thereof.

[0041] In one aspect, the solvent comprises dichloromethane, dichloroethane, acetone, methyl ethyl ketone, acetic acid, cyclopentane, ethyl acetate, carbon disulfide, N,N-dimethylformamide, ethanol, isopropanol, propanol, formaldehyde, chloroform, carbon tetrachloride, hexane, heptane, octane, benzene, toluene, acetonitrile, 1,4-dioxane, dimethyl sulfide, tetrahydrofuran or diethyl ether or a combination thereof.

[0042] In one aspect, an emulsion stabilizer is added to stabilize the emulsion. In one aspect, the emulsion stabilizer includes a surfactant. In one aspect, the emulsion stabilizer includes fatty acids, amino alcohols, fatty alcohols, fatty thiols, polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polysorbate, fatty acid esters of sorbitol, fatty acid esters of glycerol, fatty acid esters of polyhydroxy compounds, alkylphenol ethoxylates, alkyl glycosides, fatty alcohol ethoxylates, ethoxylated amines, fatty acid amides, cetrimonium bromide, octenidine dihydrochloride, dimethyldioctadecylammonium bromide, cetylpyridinium chloride, benzalkonium chloride, benzethonium chloride, dimethyldioctadecylammonium chloride, ammonium lauryl sulfate, sodium lauryl sulfate, ammonium dodecyl sulfate, sodium dodecyl sulfate, sodium lauryl ether sulfate, sodium myreth sulfate, sodium dioctyl sulfosuccinate, perfluorobutane sulfonate, alkyl-aryl ether phosphates, alkyl ether phosphates, alkyl aryl sulfonates, alkyl benzene sulfonates, alkyl sulfates, N-ethoxysulfonates, sodium lauryl sulfate, alcohol propoxysulfates, alkyl ethoxysulfates, alpha-olefin sulfonates, alpha-olefin sulfates, branched alkyl benzene sulfonates, sodium docusate, ethoxy glycidyl sulfonates, propoxy glycidyl sulfonates, alkyl ether sulfates, internal olefin sulfonates, sulfonated ethoxylated alcohols, sulfonated ethoxylated alkylphenols, sodium petroleum sulfonate, alkyl alcohol propoxysulfates, alkylphenols, monoglycerides, diglycerides, guar gum, rapeseed oil, lecithin, carrageenan or ammonium phospholipids, or their derivatives or any combination thereof.

[0043] In one aspect, the method includes drying the proppant.

[0044] In one aspect, the method includes suspending the proppant in a fracturing fluid and injecting the fracturing fluid into a formation to support the opened fractures.

[0045] Another embodiment disclosed by the examples herein provides a proppant particle. The proppant particle includes a composite of a precipitated polymer matrix and a plant-based material, wherein the precipitated polymer matrix includes a thermoplastic material and wherein the plant-based material includes microparticles.

[0046] In one aspect, the microparticles of the plant-based material are between about 10 μm and about 2 mm. In one aspect, the plant-based material includes nut shells, wood, recycled wood, invasive plant species, recycled invasive plant species, recycled bio-based waste, bio-based waste, organic sludge, recycled organic sludge, grass, recycled grass, seeds, recycled seeds, wood chips or recycled wood chips or any combination thereof. In one aspect, the plant-based material includes lignin, lignin derivatives, cellulose, cellulose derivatives, hemicellulose, hemicellulose derivatives, starch, starch derivatives, inulin, inulin derivatives, kraft lignin or kraft lignin derivatives or any combination thereof.

[0047] In one aspect, the thermoplastic material includes poly(methyl methacrylate), polymethacrylate, poly(lactic-co-glycolic acid), polyester, polyethylene terephthalate, poly(styrene-isoprene), polybromostyrene, polyethylene, polyphenylene ether, polyethersulfone, acrylonitrile butadiene styrene, polycarbonate, polyhydroxyalkanoate, polyhydroxybutyrate, polylactic acid, polyurethane, polyvinyl chloride, copolymers based on poly(methyl methacrylate), copolymers based on polymethacrylate, copolymers based on poly(lactic-co-glycolic acid), copolymers based on polyester, copolymers based on polyethylene terephthalate, copolymers based on polystyrene, copolymers based on poly(styrene-isoprene), copolymers based on polybromostyrene, copolymers based on polyethylene, copolymers based on polyphenylene ether, copolymers based on polyethersulfone, copolymers based on acrylonitrile butadiene styrene, copolymers based on polycarbonate, copolymers based on polyhydroxyalkanoate, copolymers based on polyhydroxybutyrate, copolymers based on polylactic acid, copolymers based on polyurethane, copolymers based on polyvinyl chloride, styrene-acrylate copolymer, polyamide, copolymers based on polyamide, polyether, copolymers based on polyether, polyimide, copolymers based on polyimide, polyolefin, copolymers based on polyolefin, polypropylene-polyethylene copolymer, ethylene-vinyl acetate copolymer, polyacrylic acid, copolymers based on polyacrylic acid, polyacrylate, copolymers based on polyacrylate, propylene-acrylate copolymer, propylene-methacrylate copolymer, oxidized polypropylene, oxidized polyethylene, propylene-ethylene oxide copolymer or acrylonitrile-butadiene-styrene copolymer or any combination thereof.

[0048] In one aspect, the precipitated polymer matrix comprises an emulsion stabilizer. In one aspect, the emulsion stabilizer comprises a surfactant. In one aspect, the emulsion stabilizer comprises fatty acids, amino alcohols, fatty alcohols, fatty thiols, polyethylene glycols, polypropylene glycols, polyvinyl alcohols, polysorbates, fatty acid esters of sorbitol, fatty acid esters of glycerol, fatty acid esters of polyhydroxy compounds, alkylphenol ethoxylates, alkyl glycosides, fatty alcohol ethoxylates, ethoxylated amines, fatty acid amides, cetrimonium bromide, octenidine dihydrochloride, didodecyldimethylammonium bromide, cetylpyridinium chloride, benzalkonium chloride, benzethonium chloride, dimethyldioctadecylammonium chloride, ammonium lauryl sulfate, sodium lauryl sulfate, ammonium dodecyl sulfate, sodium dodecyl sulfate, sodium lauryl ether sulfate, sodium myreth sulfate, sodium dioctyl sulfosuccinate, perfluorobutane sulfonate, alkyl-aryl ether phosphates, alkyl ether phosphates, alkyl aryl sulfonates, alkyl benzene sulfonates, alkyl sulfates, N-ethoxysulfonates, sodium lauryl sulfate, alcohol propoxysulfates, alkyl ethoxysulfates, alpha-olefin sulfonates, alpha-olefin sulfates, branched alkyl benzene sulfonates, sodium docusate, ethoxy glycidyl sulfonates, propoxy glycidyl sulfonates, alkyl ether sulfates, internal olefin sulfonates, sulfonated ethoxylated alcohols, sulfonated ethoxylated alkylphenols, sodium petroleum sulfonate, alkyl alcohol propoxylated sulfates, alkylphenols, monoglycerides, diglycerides, guar gum, rapeseed oil, lecithin, carrageenan or phosphatidylammonium, or derivatives thereof or any combination thereof.

[0049] Other embodiments are within the scope of the appended claims.

Claims

1. A method of using a composite proppant, the method comprises: grinding plant material to form particles; dissolving a polymer in a solvent; mixing the particles into the solvent; injecting the solvent into a microfluidic chip; injecting a polymer precipitation phase into the microfluidic chip; forming emulsified solvent droplets in the polymer precipitation phase in the microfluidic chip; and collecting proppant particles after the polymer precipitation.

2. The method according to claim 1, the method comprising mixing an emulsion stabilizer into the solvent before injecting into the microfluidic chip.

3. The method according to claim 1, the method comprising mixing an emulsion stabilizer into the aqueous phase before injecting into the microfluidic chip.

4. The method according to claim 1, wherein the plant material comprises nut shells, wood, recycled wood, invasive plant species, recycled invasive plant species, recycled bio-based waste, bio-based waste, organic sludge, recycled organic sludge, grass, recycled grass, seeds, recycled seeds, wood chips or recycled wood chips or any combination thereof.

5. The method according to claim 1, wherein the plant material comprises lignin, lignin derivatives, cellulose, cellulose derivatives, hemicellulose, hemicellulose derivatives, starch, starch derivatives, inulin, inulin derivatives, kraft lignin or kraft lignin derivatives or any combination thereof.

6. The method according to claim 1, wherein the polymer comprises a thermoplastic polymer.

7. The method according to claim 1, wherein the polymer comprises poly(methyl methacrylate), polymethacrylate, poly(lactic-co-glycolic acid), polyester, polyethylene terephthalate, poly(styrene-isoprene), polybromostyrene, polyethylene, polyphenylene ether, polyethersulfone, acrylonitrile butadiene styrene, polycarbonate, polyhydroxyalkanoate, polyhydroxybutyrate, polylactic acid, polyurethane, polyvinyl chloride, copolymer based on poly(methyl methacrylate), copolymer based on polymethacrylate, copolymer based on poly(lactic-co-glycolic acid), copolymer based on polyester, copolymer based on polyethylene terephthalate, copolymer based on polystyrene, copolymer based on poly(styrene-isoprene), copolymer based on polybromostyrene, copolymer based on polyethylene, copolymer based on polyphenylene ether, copolymer based on polyethersulfone, copolymer based on acrylonitrile butadiene styrene, copolymer based on polycarbonate, copolymer based on polyhydroxyalkanoate, copolymer based on polyhydroxybutyrate, copolymer based on polylactic acid, copolymer based on polyurethane, copolymer based on polyvinyl chloride, styrene-acrylate copolymer, polyamide, copolymer based on polyamide, polyether, copolymer based on polyether, polyimide, copolymer based on polyimide, polyolefin, copolymer based on polyolefin, polypropylene-polyethylene copolymer, ethylene-vinyl acetate copolymer, polyacrylic acid, copolymer based on polyacrylic acid, polyacrylate, copolymer based on polyacrylate, propylene-acrylate copolymer, propylene-methacrylate copolymer, oxidized polypropylene, oxidized polyethylene, propylene-ethylene oxide copolymer or acrylonitrile-butadiene-styrene copolymer or any combination thereof.

8. The method according to claim 1, wherein the solvent comprises dichloromethane, dichloroethane, acetone, methyl ethyl ketone, acetic acid, cyclopentane, ethyl acetate, carbon disulfide, N,N-dimethylformamide, ethanol, isopropanol, propanol, formaldehyde, chloroform, carbon tetrachloride, hexane, heptane, octane, benzene, toluene, acetonitrile, 1,4-dioxane, dimethyl sulfide, tetrahydrofuran or diethyl ether or a combination thereof.

9. The method according to claim 1, the method comprising adding an emulsion stabilizer to stabilize the emulsion.

10. The method according to claim 9, wherein the emulsion stabilizer comprises a surfactant.

11. The method according to claim 9, wherein the emulsion stabilizer comprises fatty acids, amino alcohols, fatty alcohols, fatty thiols, polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polysorbates, fatty acid esters of sorbitol, fatty acid esters of glycerol, fatty acid esters of polyhydroxy compounds, alkylphenol ethoxylates, alkyl glycosides, fatty alcohol ethoxylates, ethoxylated amines, fatty acid amides, cetrimonium bromide, octenidine dihydrochloride, didodecyldimethylammonium bromide, cetylpyridinium chloride, benzalkonium chloride, benzethonium chloride, dimethyldioctadecylammonium chloride, ammonium lauryl sulfate, sodium lauryl sulfate, ammonium dodecyl sulfate, sodium dodecyl sulfate, sodium lauryl ether sulfate, sodium myreth sulfate, sodium dioctyl sulfosuccinate, perfluorobutane sulfonate, alkyl-aryl ether phosphates, alkyl ether phosphates, alkyl aryl sulfonates, alkyl benzene sulfonates, alkyl sulfates, N-ethoxysulfonates, sodium lauryl sulfate, alcohol propoxysulfates, alkyl ethoxysulfates, alpha-olefin sulfonates, alpha-olefin sulfates, branched alkyl benzene sulfonates, sodium docusate, ethoxy glycidyl sulfonates, propoxy glycidyl sulfonates, alkyl ether sulfates, internal olefin sulfonates, sulfonated ethoxylated alcohols, sulfonated ethoxylated alkylphenols, sodium petroleum sulfonate, alkyl alcohol propoxylated sulfates, alkylphenols, monoglycerides, diglycerides, guar gum, rapeseed oil, lecithin, carrageenan or phosphatidylammonium, or their derivatives or any combination thereof.

12. The method according to claim 1, wherein the method comprises drying the proppant.

13. The method according to claim 1, the method comprises: suspending the proppant in a fracturing fluid; and injecting the fracturing fluid into a formation to support the opened fractures.

14. A proppant particle comprising a composite material of a precipitated polymer matrix and a plant-based material, wherein the precipitated polymer matrix comprises a thermoplastic material, and wherein the plant-based material comprises microparticles.

15. The proppant particle according to claim 14, wherein the microparticles of the plant-based material are between about 10 μm and about 2 mm.

16. The proppant particle according to claim 14, wherein the plant-based material comprises nut shells, wood, recycled wood, invasive plant species, recycled invasive plant species, recycled bio-based waste, bio-based waste, organic sludge, recycled organic sludge, grass, recycled grass, seeds, recycled seeds, wood chips or recycled wood chips or any combination thereof.

17. The proppant particle according to claim 14, wherein the plant-based material comprises lignin, lignin derivatives, cellulose, cellulose derivatives, hemicellulose, hemicellulose derivatives, starch, starch derivatives, inulin, inulin derivatives, lignosulfonate or lignosulfonate derivatives or any combination thereof.

18. The proppant particles of claim 14, wherein the thermoplastic material comprises poly(methyl methacrylate), polymethacrylate, poly(lactic-co-glycolic acid), polyester, polyethylene terephthalate, poly(styrene-isoprene), polybromostyrene, polyethylene, polyphenylene ether, polyethersulfone, acrylonitrile butadiene styrene, polycarbonate, polyhydroxyalkanoate, polyhydroxybutyrate, polylactic acid, polyurethane, polyvinyl chloride, copolymers based on poly(methyl methacrylate), copolymers based on polymethacrylate, copolymers based on poly(lactic-co-glycolic acid), copolymers based on polyester, copolymers based on polyethylene terephthalate, copolymers based on polystyrene, copolymers based on poly(styrene-isoprene), copolymers based on polybromostyrene, copolymers based on polyethylene, copolymers based on polyphenylene ether, copolymers based on polyethersulfone, copolymers based on acrylonitrile butadiene styrene, copolymers based on polycarbonate, copolymers based on polyhydroxyalkanoate, copolymers based on polyhydroxybutyrate, copolymers based on polylactic acid, copolymers based on polyurethane, copolymers based on polyvinyl chloride, styrene-acrylate copolymer, polyamide, copolymers based on polyamide, polyether, copolymers based on polyether, polyimide, copolymers based on polyimide, polyolefin, copolymers based on polyolefin, polypropylene-polyethylene copolymer, ethylene-vinyl acetate copolymer, polyacrylic acid, copolymers based on polyacrylic acid, polyacrylate, copolymers based on polyacrylate, propylene-acrylate copolymer, propylene-methacrylate copolymer, oxidized polypropylene, oxidized polyethylene, propylene-ethylene oxide copolymer or acrylonitrile-butadiene-styrene copolymer or any combination thereof.

19. The proppant particles of claim 14, wherein the precipitated polymer matrix comprises an emulsion stabilizer.

20. The proppant particles according to claim 19, wherein the emulsion stabilizer comprises a surfactant.

21. The proppant particle according to claim 19, wherein the emulsion stabilizer comprises fatty acids, amino alcohols, fatty alcohols, fatty thiols, polyethylene glycols, polypropylene glycols, polyvinyl alcohols, polysorbates, fatty acid esters of sorbitol, fatty acid esters of glycerol, fatty acid esters of polyhydroxy compounds, alkylphenol ethoxylates, alkyl glycosides, fatty alcohol ethoxylates, ethoxylated amines, fatty acid amides, cetrimonium bromide, octenidine dihydrochloride, didodecyldimethylammonium bromide, cetylpyridinium chloride, benzalkonium chloride, benzethonium chloride, dimethyldioctadecylammonium chloride, ammonium lauryl sulfate, sodium lauryl sulfate, ammonium dodecyl sulfate, sodium dodecyl sulfate, sodium lauryl ether sulfate, sodium myreth sulfate, sodium dioctyl sulfosuccinate, perfluorobutane sulfonate, alkyl-aryl ether phosphates, alkyl ether phosphates, alkyl aryl sulfonates, alkyl benzene sulfonates, alkyl sulfates, N-ethoxysulfonates, sodium lauryl sulfate, alcohol propoxysulfates, alkyl ethoxysulfates, alpha-olefin sulfonates, alpha-olefin sulfates, branched alkyl benzene sulfonates, sodium docusate, ethoxy glycidyl sulfonates, propoxy glycidyl sulfonates, alkyl ether sulfates, internal olefin sulfonates, sulfonated ethoxylated alcohols, sulfonated ethoxylated alkylphenols, sodium petroleum sulfonate, alkyl alcohol propoxylated sulfates, alkylphenols, monoglycerides, diglycerides, guar gum, rapeseed oil, lecithin, carrageenan or phosphatidylammonium, or derivatives thereof or any combination thereof.

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