Resin porous carbon microspheres and preparation method and reaction device thereof

Abstract

According to the preparation method of the resin porous carbon microspheres, the resin is used for preparing the porous carbon microspheres, the problems that the particle size distribution range of the resin porous carbon microspheres is wide, and the microspheres are prone to adhesion are effectively solved, and the porous carbon microspheres prepared through the method are concentrated in particle size distribution, free of adhesion and high in sphericity degree. The particle size of the microspheres can be controlled by adjusting process parameters, and the method is environment-friendly and simple in process; meanwhile, the invention also provides the resin porous carbon microspheres and a reaction device for the preparation method of the resin porous carbon microspheres.

Description

Technical Field

[0001] The invention relates to the technical field of porous carbon microspheres, in particular to resin porous carbon microspheres and a preparation method and a reaction device thereof. Background Art

[0002] Porous carbon microspheres are activated carbon microspheres with small particle size, low density, high specific surface area, and spherical structure. They have broad application prospects in potassium ion batteries, lithium ion batteries, catalysis, adsorption, electromagnetic wave absorption, etc. Pitch porous carbon microspheres are available, but the sphericity is poor and the specific surface area is difficult to control. The existing preparation methods of resin porous carbon microspheres have the following problems: First, CN202010939933.2 discloses a method for preparing porous carbon microspheres, which comprises mixing a resin and a curing agent into one, then adding deionized water, stirring at high speed to form an emulsion, then adding the emulsion droplets into silicone oil, stirring at high speed to form resin-encapsulated water droplets, heating to cure the resin to form resin-encapsulated water microcapsules, and then subjecting the microcapsules to high-temperature pyrolysis and carbonization, and finally obtaining porous carbon microspheres, but the microspheres are prone to adhesion; Second, some preparation methods require multiple rounds of pelletization, which results in many production steps and high costs.

[0003] In view of this, the inventor specially designed a resin porous carbon microsphere and its preparation method and reaction device, and this case was thus generated. Summary of the invention

[0004] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention proposes a method for preparing resin porous carbon microspheres. The porous carbon microspheres are prepared using resin, which can effectively solve the problems of wide particle size distribution range of resin porous carbon microspheres and easy adhesion between microspheres. The porous carbon microspheres obtained after the preparation by this method have a concentrated particle size distribution, the microspheres do not stick together, and the sphericity is high. By adjusting the process parameters, the particle size of the microspheres can also be controlled, and it is environmentally friendly and the process is simple.

[0005] The invention also provides a resin porous carbon microsphere.

[0006] The invention also provides a reaction device.

[0007] A method for preparing resin porous carbon microspheres provided by the present invention comprises the following steps in sequence: Step 1, dissolving the resin, curing agent, curing accelerator and fixing agent in a solvent, and mixing them evenly to obtain a resin solution containing the curing agent, curing accelerator and fixing agent with a certain solid content; Step 2, dissolving the surfactant in deionized water and placing it in a reaction kettle; Step 3, heating the deionized water containing the surfactant to boiling in a reaction kettle, and starting stirring; Step 4: atomize the resin solution containing the curing agent, curing accelerator and fixing agent into small droplets with a certain particle size through an atomizing device in the reactor, and send the small droplets into the boiling deionized water in the reactor by the downward airflow provided by the blower in the reactor; Step 5, the small droplets are stirred in boiling deionized water for a certain period of time, and a cross-linking reaction occurs to solidify to obtain solidified resin microspheres; Step 6, drying the solidified resin microspheres to obtain resin microsphere powder; Step 7, subjecting the resin microsphere powder to high temperature treatment in a high temperature treatment device under the protection of an inert gas for a certain period of time to obtain resin carbon microspheres; Step eight, activating the resin carbon microspheres to obtain resin porous carbon microspheres.

[0008] The preparation process of the present invention uses an atomizer in a reaction kettle to atomize a resin containing a curing agent, a curing accelerator, and a fixing agent into small droplets, which are then put into boiling hot water containing a surfactant and stirred in a suspended and dispersed state. The resin microspheres undergo a cross-linking reaction and solidify in the water, and then undergo subsequent drying, carbonization, and activation treatment to obtain resin porous carbon spheres. The preparation method provided by the present invention is simple, has low requirements on production equipment, has high production efficiency, is easy to industrialize, is environmentally friendly, and is safe and controllable.

[0009] In some embodiments of the present invention, the resin, curing agent, curing accelerator and fixing agent in step 1 are mixed in the following mass ratio: Resin: 100~120 parts; Curing agent: 2~20 parts; Curing accelerator: 6~15 parts; Fixative: 0~10 parts; The resin is a water-insoluble resin; the resin, curing agent, curing accelerator and fixing agent are dissolved in a solvent and mixed evenly to obtain a resin solution containing the curing agent, curing accelerator and fixing agent with a solid content of 5% to 80%.

[0010] In some embodiments of the present invention, in step 1, the resin is a resin capable of preparing a porous carbon material, the curing agent is a reagent that causes a cross-linking reaction in the resin, and the curing accelerator accelerates the curing rate of the resin.

[0011] In some embodiments of the present invention, the resin capable of preparing the porous carbon material comprises any one of phenolic resin, melamine resin and epoxy resin; In some embodiments of the present invention, the curing agent is any one of hexamethylenetetramine, melamine, paraformaldehyde, phenolic resin aniline, epoxy resin, low molecular weight polyisocyanate resin, triacetin, and diacetin, or a combination of any two or more thereof; In some embodiments of the present invention, the curing accelerator is any one of p-toluenesulfonic acid, benzenesulfonyl chloride, p-toluenesulfonyl chloride, ethyl sulfate, and petroleum sulfonic acid, or a combination of any two or more thereof; In some embodiments of the present invention, the fixing agent is any one of carbon nanotubes, carbon nanofibers, graphite flakes, and graphene, or a combination of any two or more thereof; In some embodiments of the present invention, the solvent is an alcohol solvent, which is any one of ethanol, methanol, propanol, and butanol, or a combination of any two or more thereof; In some embodiments of the present invention, the mixing method in step 1 includes manual stirring, mechanical stirring, high-speed dispersion and the like.

[0012] In some embodiments of the present invention, the surfactant in step 2 is any one of anionic surfactants, nonionic surfactants and organosilane surfactants, or a combination of any two or more thereof; the anionic surfactant is sodium dodecyl sulfate and / or sodium dodecyl sulfonate, the nonionic surfactant is Span 60 and / or Tween 80, and the organosilane surfactant is polyether-modified organopolysiloxane and / or water-soluble silicone oil DC-19.

[0013] In some embodiments of the present invention, the surfactant and deionized water in step 2 are mixed according to the following mass ratio: Deionized water: 100 parts; Surfactant: 1~30 parts.

[0014] In some embodiments of the present invention, the reaction kettle in step 2 is a device equipped with a heating and stirring device, and an atomizing device and a blower on the top.

[0015] In some embodiments of the present invention, the heating temperature in step three is 80° C. to 300° C., and the stirring frequency is 1 to 50 Hz.

[0016] In some embodiments of the present invention, the particle size of the small droplets in step 4 is 1 um to 100 um.

[0017] In some embodiments of the present invention, the atomization device in step 4 includes a two-fluid atomizer, a pressure atomizer, a centrifugal atomizer, etc.; the frequency of the blower is 1-50HZ; In some embodiments of the present invention, the stirring time in step 5 is 0.5h~12h; In some embodiments of the present invention, the curing in step 5 is resin cross-linking curing; In some embodiments of the present invention, the drying method in step 6 includes one or more of other drying methods such as normal pressure drying, reduced pressure drying, fluidized drying, spray drying, etc.; In some embodiments of the present invention, in step seven, the temperature of the high temperature treatment is: 500°C-1600°C, and the time of the high temperature treatment is: 2~24h; and the high temperature treatment equipment includes a box furnace, a tube furnace, a metal furnace, a roller kiln, etc.; the inert gas includes nitrogen, argon, argon / hydrogen mixed gas, etc.; In some embodiments of the present invention, the activation process in step eight includes physical activation or chemical activation; the physical activation includes water vapor activation or carbon dioxide activation; the activating agent used in the chemical activation is any one of KOH, KHCO3, NaHCO3, H3PO4, and ZnCl2.

[0018] The resin porous carbon microspheres provided by the present invention are prepared by a preparation method.

[0019] A reaction device provided by the present invention is mainly used in a method for preparing resin porous carbon microspheres. The reaction device includes a reactor with a cavity, a stirring paddle arranged in the cavity and driven by a stirring motor, an atomizer arranged outside the reactor and capable of spraying toward the cavity, an air supply port of a blower arranged on the reactor and used for supplying air into the cavity, an air outlet arranged on the reactor and used for exhausting air, and an outer shell arranged outside the reactor; a space is formed between the outside of the reactor and the outer shell, and a heating medium is arranged in the space.

[0020] In some embodiments of the present invention, a heating medium inlet and a heating medium outlet are provided on the outer shell; the atomizer is a two-fluid atomizer, a centrifugal atomizer or a pressure atomizer; the stirring motor is arranged directly above the reactor and the output end faces the inside of the cavity to drive the stirring paddle to rotate, and the atomizer and the blower are both arranged on the outside above the reactor; the heating medium is any one of steam, water, molten salt, heat transfer oil, etc., and a feed port is also opened at the top of the reactor, and a discharge port is opened at the bottom. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] The drawings described herein are used to provide further understanding of the present invention and constitute a part of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute improper limitations on the present invention.

[0022] in: Figure 1 is a scanning electron microscope photograph of the present invention; Figure 2This is a scanning electron microscope photograph of Comparative Example 1 of the present invention; Figure 3 It is a schematic diagram of the reaction device of the present invention.

[0023] In the diagram: 001, reactor; 10, feed inlet; 20, stirring paddle motor; 30, air outlet of blower; 40, atomizer; 50, air outlet of blower; 60, heating medium inlet; 70, outer shell; 80, heating medium outlet; 90, discharge port; 100, stirring paddle. DETAILED DESCRIPTION

[0024] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer and more understandable, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0025] The present invention provides a method for preparing resin porous carbon microspheres, which specifically comprises the following steps: Step 1), dissolving the resin, curing agent, curing accelerator and fixing agent in a solvent, and mixing them evenly to obtain a resin solution containing the curing agent, curing accelerator and fixing agent with a certain solid content; The resin is a resin that can be used to prepare porous carbon materials; the resin that can be used to prepare porous carbon materials is any one of phenolic resin, melamine resin, epoxy resin, etc., or a combination of any two or more thereof; the resins are all water-insoluble resins, preferably phenolic resin and epoxy resin; The curing agent is a reagent that can cause a cross-linking reaction of the resin, such as any one or a combination of any two or more of the curing agents such as hexamethylenetetramine, melamine, polyformaldehyde, phenolic resin aniline, epoxy resin, low molecular weight polyisocyanate resin, triacetin, diacetin, etc., preferably hexamethylenetetramine, melamine, and epoxy resin; The curing accelerator is any one or a combination of any two or more of the curing accelerators such as p-toluenesulfonic acid, benzenesulfonyl chloride, p-toluenesulfonyl chloride, ethyl sulfate and petroleum sulfonic acid, preferably toluenesulfonic acid and ethyl sulfate; The fixing agent is any one or a combination of any two or more carbon materials such as carbon nanotubes, carbon nanofibers, graphite flakes, and graphene; The solvent is mainly an environmentally friendly solvent, preferably any one or a combination of any two or more alcohol solvents such as methanol, ethanol, propanol, butanol, etc.; The certain solid content is 5% to 80%; The resin, curing agent, curing accelerator and fixing agent are mixed in the following mass ratio: Resin: 100~120 parts; Curing agent: 2~20 parts; Curing accelerator: 6~15 parts; Fixative: 0~10 parts; The mixing method is any one of manual stirring, stirring with a stirring paddle, and high-speed dispersion; Step 2), dissolving the surfactant in deionized water and placing it in a reaction kettle; The surfactant is one or more of anionic surfactants, nonionic surfactants and organosilane surfactants; the anionic surfactant is sodium dodecyl sulfate and / or sodium dodecyl sulfonate, the nonionic surfactant is Span 60 and / or Tween 80, and the organosilane surfactant is polyether-modified organopolysiloxane and / or water-soluble silicone oil DC-19, etc., preferably sodium dodecyl sulfate and Tween 80; The surfactant and deionized water are mixed according to the following mass ratio: Deionized water: 100 parts; Surfactant: 1~30 parts; The reactor is equipped with a heating and stirring device, and an atomizing device and a blower on the top; Step 3), heating the deionized water containing the surfactant to boiling in a reaction kettle, and starting stirring; The heating temperature is 80°C to 300°C, and the stirring frequency is 1 to 50 Hz; Step 4), atomizing the resin solution containing the curing agent, curing accelerator and fixing agent into small droplets with a certain particle size in an atomizing device in the reactor, and sending the small droplets into the boiling deionized water in the reactor by the downward airflow provided by the blower in the reactor; The atomizing device includes a two-fluid atomizer, a pressure atomizer, a centrifugal atomizer, etc.; the frequency of the blower is 1-50HZ; the two-fluid atomizer is preferred; the two-fluid atomizer can change the size of the resin microspheres by adjusting the atomization pressure; the atomization pressure range is 0.05~0.4Mpa; The particle size of the small droplets is a controllable size of 1um to 100um; Step 5), the small droplets are stirred in boiling deionized water for a certain period of time, and a cross-linking reaction occurs to solidify to obtain solidified resin microspheres; The stirring time is 0.5h~12h; The curing is resin cross-linking curing; Step 6), drying the solidified resin microspheres to obtain resin microsphere powder; The drying method includes one or more of normal pressure drying, reduced pressure drying, fluidized bed drying, spray drying and other drying methods, preferably spray drying; Step 7), subjecting the resin microsphere powder to high temperature treatment in a high temperature treatment device under the protection of an inert gas for a certain period of time to obtain resin carbon microspheres; The high temperature treatment equipment is any one of a box furnace, a tube furnace, a metal furnace, a roller kiln, etc., preferably a box furnace; The temperature treatment temperature is 500°C-1600°C; the inert gas is any one of nitrogen, argon, argon / hydrogen mixed gas, etc., preferably nitrogen and argon; The certain period of time is 2 to 24 hours; Step 8), activating the resin carbon microspheres to obtain resin porous carbon microspheres; The activation process adopts physical activation or chemical activation; the physical activation adopts any one of water vapor activation and carbon dioxide activation; the chemical activation includes using an activator such as KOH, KHCO3, NaHCO3, H3PO4 and ZnCl2, etc., preferably physical activation, more preferably water vapor activation; The following is further described by specific examples: Embodiment 1

[0026] An alcohol-soluble thermosetting phenolic resin is selected and dissolved in 100 parts of ethanol according to a weight ratio of 100 parts: 5 parts: 5 parts, and the alcohol-soluble thermosetting phenolic resin: curing agent: curing accelerator are stirred evenly to obtain an alcohol-soluble thermosetting phenolic resin solution A containing a curing agent and a curing accelerator with a solid content of 28.5%, wherein the curing agent is hexamethylenetetramine and the curing accelerator is p-toluenesulfonic acid.

[0027] Deionized water containing 1% of a surfactant was placed in the reactor, and stirring was started at a frequency of 5 Hz to make it dispersed evenly, and the temperature in the reactor was set to 120°C to make the deionized water boil. The surfactant was sodium dodecyl sulfate.

[0028] The blower of the reactor was turned on and the blower frequency was set to 10 Hz. The atomizer was turned on, where the atomizer was selected as a two-fluid atomizer, the atomization pressure was adjusted to 0.3 MPa, and solution A was pumped into the atomizer through a peristaltic pump to atomize it into small droplets. The small droplets were then sent into boiling deionized water containing 1% surfactant using the blower at the top of the reactor. After the atomization was completed, the temperature was maintained and stirring was continued for 1 hour, at which time the small droplets of phenolic resin were cross-linked and cured in the deionized water in the reactor.

[0029] The aqueous solution containing the completely cured phenolic resin microspheres is spray-dried and dehydrated, and the powder is collected to obtain the phenolic resin microspheres.

[0030] The dried phenolic resin microspheres were carbonized in a vacuum box furnace at 800° C. for 2 hours, and nitrogen was introduced for protection during the carbonization process to obtain phenolic resin carbon microspheres.

[0031] The carbonized phenolic resin carbon microspheres are activated by water vapor in an activation furnace to obtain phenolic resin porous carbon microspheres. Embodiment 2

[0032] An alcohol-soluble thermosetting epoxy resin is selected and dissolved in 1080 parts of propylene glycol in a weight ratio of 100 parts: 10 parts: 10 parts, and the mixture is mixed with a curing agent and a curing accelerator to obtain an alcohol-soluble thermosetting epoxy resin solution B containing a curing agent and a curing accelerator with a solid content of 10%, wherein the curing agent is polyamide and the curing accelerator is phenol.

[0033] Deionized water containing 2% of a surfactant was placed in the reactor, and stirring was started at a frequency of 5 Hz to make it dispersed evenly, and the temperature in the reactor was set to 150°C to make the deionized water boil. Tween 80 was selected as the surfactant.

[0034] Turn on the blower of the reactor and set the blower frequency to 10HZ. Turn on the atomizer, where the atomizer is selected as a two-fluid atomizer, adjust the atomization pressure to 0.1Mpa, and pump solution B into the atomizer through a peristaltic pump to atomize it into small droplets. Then use the blower on the top of the reactor to send the small droplets into boiling deionized water containing 2% surfactant. After the atomization is completed, maintain the temperature and continue stirring for 4 hours. At this time, the small droplets of epoxy resin are cross-linked and cured in the deionized water in the reactor.

[0035] The aqueous solution containing the completely cured epoxy resin microspheres is spray dried and dehydrated, and the powder is collected to obtain the epoxy resin microspheres.

[0036] The dried epoxy resin microspheres were carbonized in a vacuum box furnace at 900° C. for 2 hours, and nitrogen was introduced for protection during the carbonization process to obtain epoxy resin carbon microspheres.

[0037] The carbonized epoxy resin carbon microspheres are activated by water vapor in an activation furnace to obtain epoxy resin porous carbon microspheres. Embodiment 3

[0038] An alcohol-soluble thermosetting melamine resin is selected and dissolved in 460 parts of ethanol in a weight ratio of 100 parts: 10 parts: 5 parts: a curing agent: a curing accelerator, and stirred evenly to obtain an alcohol-soluble thermosetting melamine resin solution C containing a curing agent and a curing accelerator with a solid content of 20%, wherein the curing agent is phthalic anhydride and the curing accelerator is DMP-30 (2,4,6-tris(dimethylaminomethylene)phenol).

[0039] Deionized water containing 2% surfactant was placed in the reactor, and stirring was started at a frequency of 5 Hz to make it dispersed evenly, and the temperature in the reactor was set to 150°C to make the deionized water boil. The surfactant was a mixture of BD-3088 (an organic silane surfactant) and Tween 80 (the ratio of the two was 1:1).

[0040] Turn on the blower of the reactor and set the blower frequency to 10HZ. Turn on the atomizer, where the atomizer is selected as a two-fluid atomizer, adjust the atomization pressure to 0.25Mpa, and pump solution C into the atomizer through a peristaltic pump to atomize it into small droplets. Then use the blower on the top of the reactor to send the small droplets into boiling deionized water containing 2% surfactant. After the atomization is completed, maintain the temperature and continue stirring for 2 hours. At this time, the small droplets of melamine resin are cross-linked and cured in the deionized water in the reactor.

[0041] The aqueous solution containing the completely cured melamine resin microspheres is vacuum dried and dehydrated, and the powder is collected to obtain the melamine resin microspheres.

[0042] The dried melamine resin microspheres are carbonized at 1000° C. in a vacuum box furnace, and nitrogen is introduced for protection during the carbonization process to obtain melamine resin carbon microspheres.

[0043] The carbonized melamine resin carbon microspheres are activated by water vapor in an activation furnace to obtain melamine resin porous carbon microspheres. Embodiment 4

[0044] An alcohol-soluble thermosetting polyurethane was selected and dissolved in 268 parts of butanol according to a weight ratio of 100 parts: 10 parts: 5 parts: a curing agent: a curing accelerator, and stirred evenly to obtain an alcohol-soluble thermosetting polyurethane solution D containing a curing agent and a curing accelerator with a solid content of 30%, wherein the curing agent was hexamethylene diisocyanate and the curing accelerator was WL-710.

[0045] Deionized water containing 1% of a surfactant was placed in the reactor, and stirring was started at a frequency of 5 Hz to make it dispersed evenly, and the temperature in the reactor was set to 200°C to make the deionized water boil. The surfactant was sodium dodecylbenzene sulfonate.

[0046] The blower of the reactor was turned on and the blower frequency was set to 10 Hz. The atomizer was turned on, where the atomizer was selected as a two-fluid atomizer, the atomization pressure was adjusted to 0.15 MPa, and solution D was pumped into the atomizer through a peristaltic pump to atomize it into small droplets. The small droplets were then sent into boiling deionized water containing 1% surfactant using the blower at the top of the reactor. After the atomization was completed, the temperature was maintained and stirring was continued for 1 hour, at which time the small droplets of phenolic resin were cross-linked and cured in the deionized water in the reactor.

[0047] The aqueous solution containing the completely cured polyurethane microspheres is vacuum dried and dehydrated, and the powder is collected to obtain the polyurethane microspheres.

[0048] The dried phenolic resin microspheres were carbonized in a vacuum box furnace at 1000° C. for 2 hours, and nitrogen was introduced for protection during the carbonization process to obtain phenolic resin carbon microspheres.

[0049] The carbonized phenolic resin carbon microspheres are activated by water vapor in an activation furnace to obtain phenolic resin porous carbon microspheres. Embodiment 5

[0050] An alcohol-soluble thermoplastic phenolic resin is selected and dissolved in 268 parts of isopropanol according to a weight ratio of 100 parts: 10 parts: 5 parts: a curing agent: a curing accelerator, and stirred evenly to obtain an alcohol-soluble thermoplastic phenolic resin solution E containing a curing agent and a curing accelerator with a solid content of 30%, wherein the curing agent is selected as epoxy resin, and the curing accelerator is selected as ethyl sulfate.

[0051] Deionized water containing 1% of a surfactant was placed in the reactor, and stirring was started at a frequency of 5 Hz to make it dispersed evenly, and the temperature in the reactor was set to 200°C to make the deionized water boil. The surfactant was sodium dodecylbenzene sulfonate.

[0052] The blower of the reactor was turned on and the blower frequency was set to 10 Hz. The atomizer was turned on, where the atomizer was selected as a two-fluid atomizer, the atomization pressure was adjusted to 0.15 MPa, and solution E was pumped into the atomizer through a peristaltic pump to atomize it into small droplets. The small droplets were then sent into boiling deionized water containing 1% surfactant using the blower at the top of the reactor. After the atomization was completed, the temperature was maintained and stirring was continued for 1 hour, at which time the small droplets of phenolic resin were cross-linked and cured in the deionized water in the reactor.

[0053] The aqueous solution containing the completely cured phenolic resin microspheres is vacuum dried and dehydrated, and the powder is collected to obtain the phenolic resin microspheres.

[0054] The dried phenolic resin microspheres were carbonized in a vacuum box furnace at 1000° C. for 2 hours, and nitrogen was introduced for protection during the carbonization process to obtain phenolic resin carbon microspheres.

[0055] The carbonized phenolic resin carbon microspheres are activated by water vapor in an activation furnace to obtain phenolic resin porous carbon microspheres. Embodiment 6

[0056] An alcohol-soluble thermosetting phenolic resin is selected and dissolved in 460 parts of ethanol according to a weight ratio of 100 parts: 10 parts: 5 parts: 5 parts, and the mixture is stirred evenly to obtain an alcohol-soluble thermosetting phenolic resin solution F containing a curing agent, a curing accelerator and a fixing agent with a solid content of 20%, wherein the curing agent is melamine, the curing accelerator is ethyl sulfate, and the fixing agent is single-walled carbon nanotubes.

[0057] Deionized water containing 2% surfactant was placed in the reactor, and stirring was started at a frequency of 5 Hz to make it dispersed evenly, and the temperature in the reactor was set to 150°C to make the deionized water boil. The surfactant was a mixture of BD-3088 (an organic silane surfactant) and Tween 80 (the ratio of the two was 1:1).

[0058] The blower of the reactor was turned on and the blower frequency was set to 10 Hz. The atomizer was turned on, wherein the atomizer was selected as a two-fluid atomizer, the atomization pressure was adjusted to 0.25 MPa, and the solution F was pumped into the atomizer through a peristaltic pump to be atomized into small droplets. The small droplets were then sent into boiling deionized water containing 2% surfactant using the blower at the top of the reactor. After the atomization was completed, the temperature was maintained and stirring was continued for 2 hours, at which time the small droplets of phenolic resin were cross-linked and cured in the deionized water in the reactor.

[0059] The aqueous solution containing the completely cured phenolic resin microspheres is vacuum dried and dehydrated, and the powder is collected to obtain the phenolic resin microspheres.

[0060] The dried phenolic resin microspheres are carbonized at 1000° C. in a vacuum box furnace, and nitrogen is introduced for protection during the carbonization process to obtain phenolic resin carbon microspheres.

[0061] The carbonized phenolic resin carbon microspheres are activated by water vapor in an activation furnace to obtain phenolic resin porous carbon microspheres. Embodiment 7

[0062] All steps are the same as those in Example 6, except that the final activation step is chemical activation, that is, carbonized phenolic resin carbon microspheres and KOH are uniformly mixed and then gas activated in an activation furnace to obtain phenolic resin porous carbon microspheres.

[0063] Comparative Example 1 Thermoplastic phenolic resin, hexamethylenetetramine and methanol were heated to 80° C. in a reaction kettle at a ratio of 100:12:200 (mass ratio) and maintained for 1 hour, and all components were mixed by mechanical stirring.

[0064] Then, the mixed solution is decompressed to remove methanol to obtain a solid mixture of a curing agent and a thermoplastic phenolic resin. The solid mixture is crushed into particles of 1.0-0.59 mm as a raw material resin for spherical formation. The surfactant sodium dodecyl sulfate and water are added to the reactor at a ratio of 1:100 (mass ratio), stirred evenly, and then the raw material resin is added, and heated to 130°C under stirring at a frequency of 5HZ to obtain phenolic resin microspheres.

[0065] The obtained phenolic resin microspheres were carbonized in a vacuum box furnace at 800° C. for 2 hours, and nitrogen was introduced for protection during the carbonization process to obtain phenolic resin carbon microspheres.

[0066] The carbonized phenolic resin carbon microspheres are activated by water vapor in an activation furnace to obtain phenolic resin porous carbon microspheres.

[0067] The following table shows the use of Truth Optical Nanoparticle Size Analyzer LT3600 PLUS to detect the attached Figure 1 And attached Figure 2 Particle size data:

[0068] By attaching Figure 1 It can be seen that the particle size is consistent, there is no adhesion between particles, the sphericity is high, and the attachment Figure 2 It can be seen that the particle sizes are different, a large number of particles are adhered, and the sphericity is low, so the effect of the present invention is better.

[0069] In summary, the preparation process of the present invention uses an atomizer in a reactor to atomize the resin containing a curing agent, a curing accelerator, and a fixing agent into small droplets. The atomizer can be selected, such as using a two-fluid atomizer, by changing the compressed gas pressure and the feed speed, such as using a centrifugal atomizer, by changing the rotation speed of the centrifugal atomizer, such as adjusting the solid content of the phenolic resin solution, etc., the droplet size can be regulated to prepare resin microspheres of different particle sizes. After atomization, it enters boiling hot water containing a surfactant, and is stirred in a suspended and dispersed state. The resin microspheres undergo a cross-linking reaction and solidify in the water, and then undergo subsequent drying, carbonization, and activation treatment to obtain a resin porous carbon sphere with controllable size, narrow particle size distribution, and non-adhesiveness; the preparation method provided by the present invention is simple, and has low requirements on production equipment, high production efficiency, and is easy to industrialize, environmentally friendly, and safe and controllable.

[0070] It is worth noting that the raw materials and equipment used in the present invention, unless otherwise specified, are all commonly used raw materials and equipment in the field; the methods used in the present invention, unless otherwise specified, are all conventional methods in the field.

[0071] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0072] The present invention is described above by way of example in conjunction with the accompanying drawings. It is obvious that the specific implementation of the present invention is not limited to the above-mentioned method. As long as various non-substantial improvements are made using the method concept and technical solution of the present invention, or the concept and technical solution of the present invention are directly applied to other occasions without improvement, they are all within the protection scope of the present invention.

Claims

1. A method for preparing resin porous carbon microspheres, characterized in that: The following steps are included in sequence: Step 1, dissolving the resin, curing agent, curing accelerator and fixing agent in a solvent, and mixing them evenly to obtain a resin solution containing the curing agent, curing accelerator and fixing agent; Step 2, dissolving the surfactant in deionized water and placing it in a reaction kettle; Step 3, heating the deionized water containing the surfactant to boiling in a reaction kettle, and starting stirring; Step 4: atomize the resin solution containing the curing agent, curing accelerator and fixing agent into small droplets through an atomizing device in the reactor, and send the small droplets into the boiling deionized water in the reactor by the downward airflow provided by the blower in the reactor; Step 5, the small droplets are stirred in boiling deionized water for a certain period of time, and a cross-linking reaction occurs to solidify to obtain solidified resin microspheres; Step 6, drying the solidified resin microspheres to obtain resin microsphere powder; Step 7, subjecting the resin microsphere powder to high temperature treatment in a high temperature treatment device under the protection of an inert gas to obtain resin carbon microspheres; Step eight, activating the resin carbon microspheres to obtain resin porous carbon microspheres.

2. The method for preparing resin porous carbon microspheres according to claim 1, characterized in that: In step 1, the resin, curing agent, curing accelerator and fixing agent are mixed in the following mass ratio: Resin: 100~120 parts; Curing agent: 2~20 parts; Curing accelerator: 6~15 parts; Fixative: 0~10 parts; The resin is a water-insoluble resin; the resin, curing agent, curing accelerator and fixing agent are dissolved in a solvent and mixed evenly to obtain a resin solution containing the curing agent, curing accelerator and fixing agent with a solid content of 5% to 80%.

3. The method for preparing resin porous carbon microspheres according to claim 1, characterized in that: In step 1, the resin is a resin capable of preparing a porous carbon material, the curing agent is a reagent that causes a cross-linking reaction in the resin, and the curing accelerator accelerates the curing rate of the resin.

4. The method for preparing resin porous carbon microspheres according to claim 1, characterized in that: The surfactant in step 2 is any one of anionic surfactants, nonionic surfactants and organosilane surfactants, or a combination of any two or more thereof; the anionic surfactant is sodium dodecyl sulfate and / or sodium dodecyl sulfonate, the nonionic surfactant is Span 60 and / or Tween 80, and the organosilane surfactant is polyether-modified organopolysiloxane and / or water-soluble silicone oil DC-19.

5. The method for preparing resin porous carbon microspheres according to claim 1, characterized in that: In step 2, the surfactant and deionized water are mixed according to the following mass ratio: Deionized water: 100 parts; Surfactant: 1~30 parts.

6. The method for preparing resin porous carbon microspheres according to claim 1, characterized in that: In step three, the heating temperature is 80° C. to 300° C., and the stirring frequency is 1 to 50 Hz.

7. The method for preparing resin porous carbon microspheres according to claim 1, characterized in that: In step 4, the particle size of the small droplets is 1um~100um.

8. The method for preparing resin porous carbon microspheres according to claim 1, characterized in that: In step 7, the temperature of the high temperature treatment is: 500°C-1600°C, and the time of the high temperature treatment is: 2~24h; In step eight, the activation process includes physical activation or chemical activation; the physical activation includes water vapor activation or carbon dioxide activation; the activating agent used in the chemical activation is any one of KOH, KHCO3, NaHCO3, H3PO4, and ZnCl2.

9. A resin porous carbon microsphere, characterized in that: The preparation method according to any one of claims 1 to 8 is adopted.

10. A reaction device, characterized in that: A method for preparing resin porous carbon microspheres as described in any one of claims 1 to 8, the reaction device comprises a reactor with a cavity, a stirring paddle arranged in the cavity and driven by a motor, an atomizer arranged outside the reactor and capable of spraying toward the cavity, an air supply port of a blower arranged on the reactor and used for supplying air into the cavity, an air outlet arranged on the reactor and used for exhausting air, and an outer shell arranged outside the reactor; a space is formed between the outside of the reactor and the outer shell, and a heating medium is arranged in the space.

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