CN104386667A - Method for preparing dahurian larch-based resin carbon aerogel microspheres - Google Patents
Method for preparing dahurian larch-based resin carbon aerogel microspheres Download PDFInfo
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- CN104386667A CN104386667A CN201410612437.0A CN201410612437A CN104386667A CN 104386667 A CN104386667 A CN 104386667A CN 201410612437 A CN201410612437 A CN 201410612437A CN 104386667 A CN104386667 A CN 104386667A
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Abstract
The invention discloses a method for preparing dahurian larch-based resin carbon aerogel microspheres. The method is characterized by comprising the following steps: with dahurian larch chips as raw material and phenol as a liquefying agent, liquefying in an acid condition, and dissolving, neutralizing and filtering to obtain a dahurian larch liquefied product; reacting with a formaldehyde solution in an alkaline condition to generate stable thermosetting resin; pouring dahurian larch-based resin into a spray pyrolysis apparatus, forming light dahurian larch liquefied product resin microspheres by a spray calcination one-step method; and carbonizing to obtain carbon aerogel microspheres under the promoting and protecting conditions of nitrogen. The operation process has the main characteristics that due to adoption of biomass dahurian larch as the raw material, the raw material is abundant; resources are reutilized, and energy conservation and consumption reduction are achieved; the dahurian larch chips are decomposed by adopting a liquefaction method; the internal structure is relatively easy to regulate and control; a stable resin structure is generated by resin reaction and the reaction is simple and controllable; the dahurian larch-based resin carbon aerogel microspheres are prepared by using the independently developed spray calcination one-step method; the method has the advantages of low pollution, small time consumption and high yield, and can be effectively applied to preparation of capacitance carbon; and the application field of the carbon material is expanded.
Description
Art:
The present invention relates to biomass charcoal Material Field, particularly relate to a kind of preparation method of tamarack base resin carbon aerogel microball.
Background technology:
The preparation of Carbon Materials has more deep development, but preparation has the adjustable Novel carbon of desirable pattern, pore size and pore structure has become the focus that people pay close attention to.Up to the present, the Carbon Materials of many irregularly shaped, unordered pore textures is in the news, and in fact these materials greatly limit the practicality of Carbon Materials.In order to widen Carbon Materials in fractionation by adsorption, drug conveying, the application of the aspects such as gas selection and capacitor batteries, preparation has regular pattern, the Carbon Materials of regular pore texture has important researching value.
The feature that Carbon Aerogels not only has charcoal ball as a kind of existence form of charcoal ball also has Lightness, the features such as density is little, high conductivity.Early 1930s, utilizing sol-gel method and Supercritical Drying Technology to obtain Carbon Aerogels first, alcogel is placed in autoclave, carrying out drying higher than during ethanol stagnation point, obtaining silica aerogel.Late 1980s, American scientist prepares alkyd resin based organic aerogel first, and charing obtains charcoal-aero gel.This has initiative new development in aerogel material research, and aerogel material not only be extend to bios from the inorganic world by it, and extend to electrical conductor from the poor conductor of electricity, has started the Application Areas that aerogel is new.At home and abroad, have every year in a large number about the achievement in research of the aspect such as preparation, stuctures and properties of charcoal-aero gel and organic aerogel presoma thereof.Carbon Aerogels also receives extensive concern as a kind of aerogel of morphology controllable.Solution is completed, the orderly charcoal ball that utilized aerogel spray-drying process to prepare, by controlling macro-size and the mesoporous pore size of the ratio regulation and control carbon microspheres of resol and segmented copolymer by resol performed polymer and triblock copolymer F127 self-assembly one step.So far, the preparation of Carbon Aerogels forms phenolic aldehyde based sols for raw material with phenols and aldehydes polymerization, is prepared from through sol-gel, supercritical drying and carbonization process.But operation steps is too complicated, and dry technology is time-consuming, and cost is high again.However, researchist is making great efforts to explore always, seeks one and prepares, processes and shapingly can once to complete, convenient post-treatment, saves time and the preparation method of energy consumption.Ultrasonic spray pyrolysis, be by ultrasonic be mist by liquid conversion, be converted into rapidly micron order charcoal ball with the form of micron order small droplets by high temperature carbonization furnace, form Carbon Aerogels.Spray process not only can control the mode of appearance of microballoon, and controls the microcosmic nanostructure of microballoon, and in spray process, by adjustment stirring velocity, solution proportion etc. control outward appearance and the size of Carbon Aerogels; By adjustment reactant concn, temperature of reaction etc. control the microscopic appearance of Carbon Aerogels, nano particle diameter, nano aperture size etc.
In recent years, it is simple to operation that scholar explores a kind of technique, and energy-saving and cost-reducing one-step synthesis prepares the method for aerogel carbon microspheres.With high energy carbon precursor, with the Mono Chloro Acetic Acid aqueous solution, basic metal ester (CA), the mixing organic salt of dichloroacetic acid and sodium bicarbonate are catalyzer, and ion exchange resin and aliphatics mixing solutions are that raw material adopts ultrasonic spray pyrolysis to prepare porous charcoal ball.But the research preparing Carbon Aerogels with wood resin rarely has report.
European patent (WO12014025236) describes the preparation method of a kind of composition metal nanoparticle/carbon, and the spheroid of a kind of electrochemical appliance composition.Surface and the carbonization generation polymkeric substance of polymer/metallic nanoparticle is related to by thermal treatment, metal nanoparticle is in the polymer dispersed, synthesis composition metal nanoparticle/carbon ball.Lithium secondary battery composition metal nanoparticle/carbon ball prepared by this method can improve charge/discharge characteristics and life characteristics.But introduce metal in raw material, the raw material of environmental protection should be selected.
United States Patent (USP) (US2014255786A1) describe a kind of by spherical grinding tool and the blue dye-impregnated legal system of metal-dimethyl for charcoal ball.This method needs material cost higher, and metal environment Anti-Inactivation Stability is low, and reaction conditions is wayward.
Publication number has been the Introduction To Cn Patent of CN1013756253, and a kind of epoxy resin is raw material, in order to increase polymeric coating effect, by epoxy resin and solidifying agent mixing and stirring, eliminate foam and carry out being heating and curing with mould obtaining hollow carbon sphere/epoxy resin composite material.Hollow carbon sphere/epoxy resin composite material has the features such as lightweight, specific inductivity is low, thermal conductivity good, and dimensional stability, chemical stability are good.But the inadequate environmental protection of raw material, await developing a kind of biomass as raw material.
The Introduction To Cn Patent of publication number CN103848413A is a kind of under Ultrasonic Conditions, and dissolved polystyrene microballoon in water or organic solvent, adds carbon source and become suspension liquid and continual ultrasonic 0.5-6 hour; The method of high-temperature roasting prepares mesoporous carbon spheres material under an inert atmosphere.This method raw material and process costs high, operating procedure is complicated, and environmental protection not.
To be the Introduction To Cn Patent of CN103395773 a kind of with acetylene black salpeter solution for raw material for publication number, place it in a closed reactor, heated oxide generates the method for acetylene black and nitric acid vapor, prepares mean inside diameter 20-30nm, the hollow ball of average shell thickness 10-20nm.Preparation method's temperature of reaction is low, and the time is short, easy control of reaction conditions, and cheaper starting materials is conducive to large-scale commercial production, simultaneously hollow ball particle diameter and carbon shell thickness homogeneous, and there is good dispersiveness.But unique deficiency to be raw material comparatively large to environmental hazard, be difficult to recycle.
The micro-nano carbon ball preparation method of publication number a kind of kernel ion ball polyelectrolyte brush that has been the Introduction To Cn Patent of CN103709339A.Obtained by the micro-nano carbon ball radical polymerization loading the synthesis micro-nano carbon ball on azo acyl chlorides surface and the ion ball polyelectrolyte kernel of synthesis.Preparation method is simple, and feasibility is strong.Raw material and preparation process environmental protection, molecular weight is low, but working method is too accurate, and controllability is poor.
To be the Introduction To Cn Patent of CN103623779A a kind of is raw material with starch for publication number, uses high temperature hydro-thermal charring to prepare charcoal ball, spheroid regular appearance, have the efficient effect removing metal ion simultaneously.But this kind of inadequate lightweight of charcoal ball, limit its Application Areas.
To be the Introduction To Cn Patent of CN103623823 a kind of is raw material with native starch for publication number, dissolves the carbon ball of the many hydroxyls of pouring hot preparation.Raw material environmental protection, technique is simple, but this method is consuming time longer, and production efficiency is low.
In sum, current tradition prepares the method ubiquity of carbon microspheres, raw material not environmentally, complex process, the problems such as production cost is high, the present invention selects environment friendly biological matter to be raw material, make macromole become small molecules through liquefaction process, make pore structure controlled, utilize the equipment of independent research that one is walked and form lightweight tamarack liquefied substance resin microsphere, simplify response procedures, save the reaction times.
Summary of the invention:
The object of the present invention is to provide a kind of preparation method of tamarack base resin carbon aerogel microball.
In order to achieve the above object, the technical solution used in the present invention comprises: a kind of preparation method of tamarack base resin carbon aerogel microball, it is characterized in that: take larch sawdust as raw material, take phenol as liquefying agent, liquefy in acid condition, through dissolving, neutralization, the steps such as filtration obtain tamarack liquefied substance, in the basic conditions, react with formaldehyde solution and generate stable thermosetting resin, tamarack base resin is poured in spray pyrolysis instrument, combine with calcining furnace instrument through atomizer, one is walked and forms lightweight tamarack liquefied substance resin microsphere, under the promotion and protective condition of nitrogen, charing obtains Carbon Aerogels.The principal feature of this operating procedure is using biomass tamarack as raw material, abundant raw material, resource reutilization, energy-saving and cost-reducing; By liquifying method, Litter Decomposition pine sill bits, make its internal structure more easily regulate and control; Stable resin structure is generated again through resinifying reaction, simply controlled; Select the Spray calcination single stage method of independent research to prepare tamarack base resin carbon aerogel microball, pollute few, consuming time short, yield is high, effectively can be applied to and prepare electric capacity charcoal, has widened the Application Areas of Carbon Materials.
Advantage of the present invention is:
1, take larch sawdust as the utilization ratio that raw material improves biomass energy, raw materials cost is low, environmental protection.
2, the present invention changes traditional production technique, uses liquefaction process, the effective internal structure controlling timber.
3, select a kind of existence form of resin solution, make its stable existence in reaction process.
4, through spray pyrolysis, one is walked and forms lightweight tamarack resin microsphere.
5, under the promotion and protective condition of nitrogen, charing obtains Carbon Aerogels.
Figure of description:
Fig. 1 is the SEM figure of a kind of preparation method of tamarack base resin carbon aerogel microball.
Embodiment:
Below the invention process is described in further detail:
A kind of preparation method of tamarack based charcoal aerogel microballoon; it is characterized in that: take larch sawdust as raw material; take phenol as liquefying agent; liquefy in acid condition; through dissolving; neutralization; the steps such as filtration obtain tamarack liquefied substance; in the basic conditions, react with formaldehyde solution and generate stable thermosetting resin, tamarack base resin is poured in spray pyrolysis instrument; combine with calcining furnace instrument through atomizer; one is walked and forms lightweight tamarack liquefied substance resin microsphere, under the promotion and protective condition of nitrogen, charing obtains Carbon Aerogels.
Below, the present invention will be further detailed by embodiment, but it is not limited to any one or similar example of these embodiments.
Embodiment 1:
Get 10.0g larch sawdust, 30.0g phenol, the 1.0mL vitriol oil (98%), 2.0mL phosphoric acid (85%) 110 DEG C of back flow reaction 2h, after being cooled to room temperature, adding 80mL methyl alcohol, fully stirs, and after filtration washing, collects filtrate.Filtrate is neutralized to neutrality with sodium hydroxide, filters insolubless such as removing salt, collect filtrate 40 DEG C of underpressure distillation and remove methyl alcohol, obtain brown tamarack liquefied substance.90mL formaldehyde solution (37%) is added successively in flask, 3.0g NaOH, 10.0g P123,40 DEG C of reaction 20h, then add 10mL concentrated hydrochloric acid, regulate pH to be 0.5, continue reaction 8h, being cooled to room temperature after reaction terminates, through washing 100 DEG C of baking oven inner dryings, obtaining tamarack base resin mesophase spherule.
Utilize the equipment that the atomizer of independent research combines with calcining furnace; through spray pyrolysis, one is walked and forms lightweight tamarack liquefied substance microballoon, 700 DEG C of charings under the promotion and protective condition of nitrogen; be cooled to room temperature to take out, obtain Ye Songji resin carbon aerogel microball.
Embodiment 2:
Get 10.0g larch sawdust, 30.0g phenol, the 2.0mL vitriol oil (98%), 2.0mL phosphoric acid (85%) 120 DEG C of back flow reaction 2h, after being cooled to room temperature, adding 100mL methyl alcohol, fully stirs, and after filtration washing, collects filtrate.Filtrate is neutralized to neutrality with sodium hydroxide, filters insolubless such as removing salt, collect filtrate 40 DEG C of underpressure distillation and remove methyl alcohol, obtain brown tamarack liquefied substance.90mL formaldehyde solution (37%) is added successively in flask, 3.0g NaOH, 10.0g P123,40 DEG C of reaction 20h, then add 10mL concentrated hydrochloric acid, regulate pH to be 0.5, continue reaction 8h, being cooled to room temperature after reaction terminates, through washing 100 DEG C of baking oven inner dryings, obtaining tamarack base resin mesophase spherule.
Utilize the equipment that the atomizer of independent research combines with calcining furnace, through spray pyrolysis, one is walked and forms lightweight tamarack liquefied substance microballoon; 800 DEG C of charings under the promotion and protective condition of nitrogen; be cooled to room temperature to take out, obtain Ye Songji resin carbon aerogel microball, see accompanying drawing 1.
Claims (5)
1. the preparation method of a tamarack base resin carbon aerogel microball, it is characterized in that: take larch sawdust as raw material, take phenol as liquefying agent, liquefy in acid condition, through dissolving, neutralization, the steps such as filtration obtain tamarack liquefied substance, in the basic conditions, Heat of Formation solidity phenol resin solution is reacted with formaldehyde solution.Select atomizer to combine with calcining furnace instrument, through spray pyrolysis, one is walked and forms lightweight tamarack liquefied substance microballoon, under the promotion and protective condition of nitrogen, charing obtains Carbon Aerogels.
2., according to the preparation method of a kind of tamarack base resin carbon aerogel microball according to claim 1, it is characterized in that: select larch sawdust to be raw material, cost is low, aboundresources is renewable, simultaneously alternative part oil, the industrial chemicals such as coal, reduce environmental pollution, improve the ecological environment.
3. according to the preparation method of a kind of tamarack base resin carbon aerogel microball according to claim 1, it is characterized in that: liquefaction process decomposes wood internal structure, make its appearance structure controlled, timber liquefies in acid condition, sulfuric acid and phosphate mixture total amount are 7%-10%, prepare thermosetting resin in the basic conditions, the quality of sodium hydroxide is 6%-10%.
4., according to the preparation method of a kind of tamarack base resin carbon aerogel microball according to claim 1, it is characterized in that: tamarack base resinifying temperature of reaction is 30 ~ 50 DEG C, and the reaction times is 9 ~ 12h.
5., according to the preparation method of a kind of tamarack base resin carbon aerogel microball according to claim 1, it is characterized in that: quick burning, carbonize rapidly, calcining temperature is 700 ~ 800 DEG C.Calcination time is 1 ~ 4h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110371947A (en) * | 2019-06-21 | 2019-10-25 | 庞定根 | A kind of preparation method of middle micropore charcoal-aero gel |
| CN111961222A (en) * | 2020-07-15 | 2020-11-20 | 天津科技大学 | Method for preparing gel elastomer based on wood liquefied product and gel elastomer |
Citations (2)
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| CN101541674A (en) * | 2006-12-08 | 2009-09-23 | Lg化学株式会社 | Manufacturing methods of mesoporous carbon structure with spray drying or spray pyrolysis and composition thereof |
| CN103833003A (en) * | 2014-02-28 | 2014-06-04 | 东北林业大学 | Method for preparing larch based ordered mesoporous carbon by virtue of soft template |
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2014
- 2014-11-04 CN CN201410612437.0A patent/CN104386667A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101541674A (en) * | 2006-12-08 | 2009-09-23 | Lg化学株式会社 | Manufacturing methods of mesoporous carbon structure with spray drying or spray pyrolysis and composition thereof |
| CN103833003A (en) * | 2014-02-28 | 2014-06-04 | 东北林业大学 | Method for preparing larch based ordered mesoporous carbon by virtue of soft template |
Non-Patent Citations (2)
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| YAN YAN ET AL.: "One-step synthesis of ordered mesoporous carbonaceous spheres by an aerosol-assisted self-assembly", 《CHEM. COMMUN.》, 25 April 2007 (2007-04-25), pages 2867 - 2869 * |
| 赵鑫: "落叶松基多孔炭的形貌控制制备研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, no. 3, 15 March 2014 (2014-03-15) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110371947A (en) * | 2019-06-21 | 2019-10-25 | 庞定根 | A kind of preparation method of middle micropore charcoal-aero gel |
| CN111961222A (en) * | 2020-07-15 | 2020-11-20 | 天津科技大学 | Method for preparing gel elastomer based on wood liquefied product and gel elastomer |
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