CN101041430A - Preparation method of spherical charcoal-aero gel - Google Patents
Preparation method of spherical charcoal-aero gel Download PDFInfo
- Publication number
- CN101041430A CN101041430A CN 200710039795 CN200710039795A CN101041430A CN 101041430 A CN101041430 A CN 101041430A CN 200710039795 CN200710039795 CN 200710039795 CN 200710039795 A CN200710039795 A CN 200710039795A CN 101041430 A CN101041430 A CN 101041430A
- Authority
- CN
- China
- Prior art keywords
- spherical
- aerogel
- carbon aerogel
- spherical carbon
- gel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention discloses a preparing method of globular char gas gel, which comprises the following steps: making phenol- melamine-formaldehyde or water soluble phenol resin- melamine-formaldehyde as raw material; forming colloidal sols through pre-polymerization; adding into discontinuous phase with surface activator; forming floating system under the function of stirring; generating colloidal sols- gel transition at 60-85 deg.c; forming globular aquagel; proceeding organic solvent replace and hypercritical dry; getting organic aerogel; proceeding high temperature degradation; getting globular char gas gel; setting the specific surface area at 400-1000m2/g, bore diameter at 3-20 nanometer and ball calipers at 0.01-3 millimeter.
Description
Technical field
The present invention relates to a kind of preparation method who belongs to the spherical carbon aerogel.
Background technology
Charcoal-aero gel is a kind of carbonaceous porous material that is rich in the mesopore nanostructure, have good electrical conductivity, biocompatibility, corrosion-resistant, advantage such as height ratio strong, radioprotective and density are little, be with a wide range of applications in fields such as electronics, military project, medicine, environmental protection and chemical industry.
Existing charcoal-aero gel is single bulk more, mainly has the elasticity extreme difference and defective such as should not process.Limited the charcoal-aero gel application of (as ADSORPTION IN A FIXED BED, support of the catalyst and medical carrier etc.) in some aspects.Therefore, how to change the form that has charcoal-aero gel now and become the technical issues that need to address of the present invention.People such as Pekala in eighties of last century the mid-90 reported first prepare Resorcinol-formaldehyde spherical organic aerogel (Alviso CT by the polymerization of reversed-phase emulsion sol-gel, Pekala RW, GrossJ, Lu X, Caps R, Fricke J.Resorcinol-formaldehyde and carbon aerogel microspheres.Mater ResSoc Symp Proc 1996; 431:521-525.), but this method adopts the comparatively expensive Resorcinol of price as raw material, has limited its commercial application prospect.US.Pat.No 4997804 discloses a kind of method that adopts crosslinked polymer method of forming draft machine aerogel and charcoal-aero gel microballoon, but this method only prepares the less microballoon of sphere diameter, and sphericity is relatively poor.
Summary of the invention
The objective of the invention is to, a kind of cheap spherical carbon aerogel with good flowing property, low fluid resistance and superior release performance is provided, satisfy the application requiring of aspects such as ADSORPTION IN A FIXED BED, support of the catalyst and medical carrier.
The said spherical carbon aerogel of the present invention, it is made by the method that comprises the following steps:
(1) mixes in water by cheap reaction monomers, catalyzer and form the water-sol;
(2) water-sol glue is mixed with the organic solution of being made up of tensio-active agent and organic solvent, stir insulation 3 hours～24 hours in 60 ℃～85 ℃, got spherical hydrogel in aging 1-7 days room temperature (about 20 ℃)～85 ℃ again;
(3) replace water in the spherical hydrogel with organic solvent, obtain organic spherical gel;
(4) the organic spherical gel of supercritical drying, have under the condition of protection of inert gas, behind the organic spherical gel of Pintsch process drying target compound (spherical carbon aerogel);
The specific surface area of said spherical carbon aerogel is 400m
2/ g～1000m
2/ g, pore volume are 1.0m
3/ g～2m
3/ g, aperture are that 3nm～20nm and sphere diameter are 10 μ m～5mm;
Wherein, the mixture that said cheap reaction monomers is made up of phenol/melamine/formaldehyde, or the mixture of forming by water soluble phenol resin/melamine/formaldehyde; Described tensio-active agent is that a series of HLB values such as span 20 (SP20), sorbester p18 (SP60), sorbester p17 (SP80), half saponified polyvinyl acetate are one or more between 2-10; Described organic solvent can be selected one or more in the higher-boiling compound of hexanaphthene, ten fluorine hydrogen naphthalenes, paraffin oil, tetrafluoroethylene, trifluoro-ethylene, silicone oil, glycerol, hydro carbons.
And the spherical carbon aerogel sphere diameter size that makes reduces with the increase of surfactant concentrations, stirring velocity, and the microcosmos network structure of gel can be by changing the mol ratio control of each component that constitutes organogel.
The present invention is a reported first, has following advantage:
(1) widened the Application Areas of charcoal-aero gel.The spherical carbon aerogel also can be used as medical carrier, medical diagnosis agent, molecular sieve and lagging material etc. except that the electrode materials that can be used as monocell, low pressure " jelly roll " battery, ultracapacitor and fuel cell.
(2) adopt cheap raw material and shortened synthesis technique, especially generated time.
(3) utilize the hydrophilic characteristics of trimeric cyanamide in the raw material, can just can synthetic spherical carbon aerogel stabilizer pole, repeatable under the minute quantity Action of Surfactant.
(4) controllability of the sphere diameter of spherical carbon aerogel and microcosmos network structure.
Description of drawings
Fig. 1 tensio-active agent is a prepared spherical carbon aerogel SEM photo under the 0.1ml
Fig. 2 tensio-active agent is a prepared spherical carbon aerogel SEM photo under the 1ml
Fig. 3 tensio-active agent is a prepared spherical carbon aerogel SEM photo under the 10ml
Fig. 4 phenol, trimeric cyanamide and formaldehyde 1: 0.2: 3 in molar ratio, tensio-active agent are prepared spherical carbon aerogel SEM photo under the 10ml
Embodiment
Synthetic method of the present invention comprises the steps:
(1) each component that will constitute organogel is mixed formation colloidal sol monomer, carries out prepolymerization 0～10h under proper temperature.
(2) preparation contains the organic solvent of finite concentration tensio-active agent.This organic solvent of 10～50 times of sol volume is added in the reactor, be warming up to 60 ℃～85 ℃, stir with 50～400 rev/mins speed, add the colloidal sol of proper volume after prepolymerization, constant temperature and constant speed stir 3～24h.Under ℃ temperature of room temperature～85, further wear out and promptly make spherical hydrogel.
(3) with the water in the organic solvent replacing water gel, obtain organogel.
(4) organogel is placed autoclave and fill it up with sherwood oil, 240～300 ℃ of super critical conditions, 4.5～12Mpa dry 1～3 hour down perhaps makes drying medium with carbonic acid gas, 31～100 ℃ of super critical conditions, 7.5～20Mpa made the spherical organic aerogel down in dry 7～90 hours.
(5) under nitrogen or argon shield,, make the spherical carbon aerogel 600～1200 ℃ of cracking 1～5 hour.
Aforesaid organogel raw material can be trimeric cyanamide-formaldehyde systems, phenolic aldehyde-trimeric cyanamide-formaldehyde resin system.
Aforesaid tensio-active agent can select a series of HLB values such as span 20 (SP20), sorbester p18 (SP60), sorbester p17 (SP80), half saponified polyvinyl acetate to be between 2-10 one or more.。
Aforesaid organic solvent can be selected one or more in the higher-boiling compound of hexanaphthene, ten fluorine hydrogen naphthalenes, paraffin oil, tetrafluoroethylene, trifluoro-ethylene, silicone oil, glycerol, hydro carbons.
Supercritical drying that present method is used and charring are the technology commonly used in the existing chemical field.Charing is to carry out in low speed circulating fluidized bed.
The invention will be further described below by embodiment, and its purpose only is better to understand content of the present invention and unrestricted protection scope of the present invention.
Embodiment one
Phenol, trimeric cyanamide and formaldehyde 1: 0.4: 3 are in molar ratio mixed, add the catalyst n aOH of reactant total mass 1%, adding a certain amount of deionized water then, to make the reactant total concn be 18g/100ml, in 85 ℃ of reactions 5 hours.Get this reaction solution of 20ml then and pour in the 500ml hexanaphthene that contains 0.1mlSpan80, under 67 ℃, stir 4h with the 400rpm stirring velocity.Stop to stir the back and continue heating 72 hours, centrifugation obtains hydrogel sphere.Moisture content with in the acetone displacement gel makes spherical ketone gel.The ketone gel is placed autoclave and fills it up with sherwood oil, be warming up to 250 ℃, and to keep the still internal pressure be 8Mpa, supercritical drying 3h, naturally cooling after the slow release of constant temperature makes the spherical organic aerogel then; The gained aerogel is put into high-temperature cracking furnace, under nitrogen protection, be warmed up to 800 ℃ and constant temperature 3h and obtain the spherical carbon aerogel with 5 ℃/min.Its BET specific surface area is 690m
2/ g, pore volume are 1.43m
3/ g, mean pore size is 9nm, and average ball diameter is 1.205mm, and sphericity is 96, and intensity is 94wt%, true density is 0.29g/cm
3, its SEM Electronic Speculum picture is seen Fig. 1.Pore structure by ASAP absorption instrument according to the spherical carbon aerogel at low temperatures (77K) adsorption isothermal line of nitrogen is recorded, average ball diameter adopts Ma Erwen laser size distribution instrument to record, sphericity is the minor semi-axis of spherical carbon aerogel and the ratio of semi-major axis, intensity records according to Chinese national standard GB7702.3-87, and true density is to press mercury density.
Embodiment two
Phenol, trimeric cyanamide and formaldehyde 1: 0.2: 3 are in molar ratio mixed, add the catalyst n aOH of reactant total mass 1%, adding a certain amount of deionized water then, to make the reactant total concn be 18g/100ml, in 85 ℃ of reactions 5 hours.Get this reaction solution of 20ml then and pour in the 500ml hexanaphthene that contains 0.1mlSpan80, under 67 ℃, stir 4h with the 400rpm stirring velocity.Stop to stir the back and continue heating 72 hours, centrifugation obtains hydrogel sphere.Moisture content with in the acetone displacement gel makes spherical ketone gel.The ketone gel is placed autoclave and fills it up with sherwood oil, be warming up to 250 ℃, and to keep the still internal pressure be 8Mpa, supercritical drying 3h, naturally cooling after the slow release of constant temperature makes the spherical organic aerogel then; The gained aerogel is put into high-temperature cracking furnace, be warmed up to 800 ℃ and constant temperature 3h with 5 ℃/min and obtain the spherical carbon aerogel under nitrogen protection, its SEM figure sees Fig. 1.The BET specific surface area of this spherical carbon aerogel is 550m
2/ g, pore volume are 1.02m
3/ g, mean pore size is 9.12nm, and average ball diameter is 0.187mm, and sphericity is 94, and intensity is 98wt%, true density is 0.61g/cm
3
Embodiment three
Phenol, trimeric cyanamide and formaldehyde 1: 0.4: 3 are in molar ratio mixed, add the catalyst n aOH of reactant total mass 1%, adding a certain amount of deionized water then, to make the reactant total concn be 18g/100ml, in 85 ℃ of reactions 5 hours.Get this reaction solution of 20ml then and pour in the 500ml hexanaphthene that contains 1mlSpan80, under 67 ℃, stir 4h with the 400rpm stirring velocity.Stop to stir the back and continue heating 72 hours, centrifugation obtains hydrogel sphere.Moisture content with in the acetone displacement gel makes spherical ketone gel.The ketone gel is placed autoclave and fills it up with sherwood oil, be warming up to 250 ℃, and to keep the still internal pressure be 8Mpa, supercritical drying 3h, naturally cooling after the slow release of constant temperature makes the spherical organic aerogel then; The gained aerogel is put into high-temperature cracking furnace, be warmed up to 800 ℃ and constant temperature 3h with 5 ℃/min and obtain the spherical carbon aerogel under nitrogen protection, its SEM figure sees Fig. 2.The BET specific surface area of this spherical carbon aerogel is 640m
2/ g, pore volume are 1.80m
3/ g, mean pore size is 7nm, and average ball diameter is 0.093mm, and sphericity is 94, and intensity is 93wt%, true density is 0.54g/cm
3
Embodiment four
Phenol, trimeric cyanamide and formaldehyde 1: 0.2: 3 are in molar ratio mixed, add the catalyst n aOH of reactant total mass 1%, adding a certain amount of deionized water then, to make the reactant total concn be 18g/100ml, in 85 ℃ of reactions 5 hours.Get this reaction solution of 20ml then and pour in the 500ml hexanaphthene that contains 1mlSpan80, under 67 ℃, stir 4h with the 400rpm stirring velocity.Stop to stir the back and continue heating 72 hours, centrifugation obtains hydrogel sphere.Moisture content with in the acetone displacement gel makes spherical ketone gel.The ketone gel is placed autoclave and fills it up with sherwood oil, be warming up to 250 ℃, and to keep the still internal pressure be 8Mpa, supercritical drying 3h, naturally cooling after the slow release of constant temperature makes the spherical organic aerogel then; The gained aerogel is put into high-temperature cracking furnace, under nitrogen protection, be warmed up to 800 ℃ and constant temperature 3h and obtain the spherical carbon aerogel with 5 ℃/min.The BET specific surface area of this ball-type charcoal-aero gel is 670m
2/ g, pore volume are 1.95m
3/ g, mean pore size is 7nm, and average ball diameter is 0.097mm, and sphericity is 98, and intensity is 96wt%, true density is 0.64g/cm
3
Embodiment five
Phenol, trimeric cyanamide and formaldehyde 1: 0.4: 3 are in molar ratio mixed, add the catalyst n aOH of reactant total mass 1%, adding a certain amount of deionized water then, to make the reactant total concn be 18g/100ml, in 85 ℃ of reactions 5 hours.Get this reaction solution of 20ml then and pour in the 500ml hexanaphthene that contains 10mlSpan80, under 67 ℃, stir 4h with the 400rpm stirring velocity.Stop to stir the back and continue heating 72 hours, centrifugation obtains hydrogel sphere.Moisture content with in the acetone displacement gel makes spherical ketone gel.The ketone gel is placed autoclave and fills it up with sherwood oil, be warming up to 250 ℃, and to keep the still internal pressure be 8Mpa, supercritical drying 3h, naturally cooling after the slow release of constant temperature makes the spherical organic aerogel then; The gained aerogel is put into high-temperature cracking furnace, be warmed up to 800 ℃ and constant temperature 3h with 5 ℃/min and obtain the spherical carbon aerogel under nitrogen protection, its SEM figure sees Fig. 3.The BET specific surface area of this ball-type charcoal-aero gel is 689m
2/ g, pore volume are 1.91m
3/ g, mean pore size is 5.2nm, and average ball diameter is 0.023mm, and sphericity is 99, and intensity is 96wt%, true density is 0.69g/cm
3
Embodiment six
Phenol, trimeric cyanamide and formaldehyde 1: 0.2: 3 are in molar ratio mixed, add the catalyst n aOH of reactant total mass 1%, adding a certain amount of deionized water then, to make the reactant total concn be 18g/100ml, in 85 ℃ of reactions 5 hours.Get this reaction solution of 20ml then and pour in the 500ml hexanaphthene that contains 10mlSpan80, under 67 ℃, stir 4h with the 400rpm stirring velocity.Stop to stir the back and continue heating 72 hours, centrifugation obtains hydrogel sphere.Moisture content with in the methyl alcohol displacement gel makes spherical alcogel.Alcogel is placed autoclave and fills it up with sherwood oil, be warming up to 250 ℃, and to keep the still internal pressure be 8Mpa, supercritical drying 3h, naturally cooling after the slow release of constant temperature makes the spherical organic aerogel then; The gained aerogel is put into high-temperature cracking furnace, under nitrogen protection, is warmed up to 800 ℃ and constant temperature 3h and obtains the spherical carbon aerogel with 5 ℃/min,, its SEM figure sees Fig. 4.The BET specific surface area of this spherical carbon aerogel is 540m
2/ g, pore volume are 1.08m
3/ g, mean pore size is 5.3nm, and average ball diameter is 0.021mm, and sphericity is 92, and intensity is 93wt%, true density is 0.67g/cm
3
Embodiment seven
Phenol, trimeric cyanamide and formaldehyde 1: 0.4: 3 are in molar ratio mixed, add the catalyst n aOH of reactant total mass 1%, adding a certain amount of deionized water then, to make the reactant total concn be 18g/100ml, in 85 ℃ of reactions 5 hours.Get this reaction solution of 20ml then and pour in the 500ml hexanaphthene that contains 1mlSpan80, under 67 ℃, stir 4h with the 600rpm stirring velocity.Stop to stir the back and continue heating 72 hours, centrifugation obtains hydrogel sphere.Moisture content with in the methyl alcohol displacement gel makes spherical alcogel.Alcogel is placed autoclave and fills it up with sherwood oil, be warming up to 250 ℃, and to keep the still internal pressure be 8Mpa, supercritical drying 3h, naturally cooling after the slow release of constant temperature makes the spherical organic aerogel then; The gained aerogel is put into high-temperature cracking furnace, under nitrogen protection, be warmed up to 800 ℃ and constant temperature 3h and obtain the spherical carbon aerogel with 5 ℃/min.The BET specific surface area of this spherical carbon aerogel is 640m
2/ g, pore volume are 1.08m
3/ g, mean pore size is 5.3nm, and average ball diameter is 0.051mm, and sphericity is 92, and intensity is 93wt%, true density is 0.67g/cm
3
Embodiment eight
Phenol, trimeric cyanamide and formaldehyde 1: 0.4: 3 are in molar ratio mixed, add the catalyst n aOH of reactant total mass 1%, adding a certain amount of deionized water then, to make the reactant total concn be 15g/100ml, in 85 ℃ of reactions 5 hours.Get this reaction solution of 20ml then and pour in the 500ml hexanaphthene that contains 1mlSpan80, under 67 ℃, stir 4h with the 400rpm stirring velocity.Stop to stir the back and continue heating 72 hours, centrifugation obtains hydrogel sphere.Moisture content with in the methyl alcohol displacement gel makes spherical alcogel.Alcogel is placed autoclave and fills it up with sherwood oil, be warming up to 250 ℃, and to keep the still internal pressure be 8Mpa, supercritical drying 3h, naturally cooling after the slow release of constant temperature makes the spherical organic aerogel then; The gained aerogel is put into high-temperature cracking furnace, under nitrogen protection, be warmed up to 800 ℃ and constant temperature 3h and obtain the spherical carbon aerogel with 5 ℃/min.The BET specific surface area of this spherical carbon aerogel is 740m
2/ g, pore volume are 1.58m
3/ g, mean pore size is 8.3nm, and average ball diameter is 0.062mm, and sphericity is 94, and intensity is 94wt%, true density is 0.53g/cm
3
Embodiment nine
Phenol, trimeric cyanamide and formaldehyde 1: 0.4: 3 are in molar ratio mixed, add the catalyst n aOH of reactant total mass 1%, adding a certain amount of deionized water then, to make the reactant total concn be 18g/100ml, in 85 ℃ of reactions 5 hours.Get this reaction solution of 20ml then and pour in the 500ml hexanaphthene that contains 1mlSpan60, under 67 ℃, stir 4h with the 400rpm stirring velocity.Stop to stir the back and continue heating 72 hours, centrifugation obtains hydrogel sphere.Moisture content with in the methyl alcohol displacement gel makes spherical alcogel.Alcogel is placed autoclave and fills it up with sherwood oil, be warming up to 250 ℃, and to keep the still internal pressure be 8Mpa, supercritical drying 3h, naturally cooling after the slow release of constant temperature makes the spherical organic aerogel then; The gained aerogel is put into high-temperature cracking furnace, under nitrogen protection, be warmed up to 800 ℃ and constant temperature 3h and obtain the spherical carbon aerogel with 5 ℃/min.The BET specific surface area of this spherical carbon aerogel is 540m
2/ g, pore volume are 1.18m
3/ g, mean pore size is 5.3nm, and average ball diameter is 0.067mm, and sphericity is 84, and intensity is 93wt%, true density is 0.63g/cm
3
Embodiment ten
Phenol, trimeric cyanamide and formaldehyde 1: 0.4: 3 are in molar ratio mixed, add the catalyst n aOH of reactant total mass 1%, adding a certain amount of deionized water then, to make the reactant total concn be 18g/100ml, in 85 ℃ of reactions 5 hours.Get this reaction solution of 20ml then and pour in the 500ml hexanaphthene that contains 1mlSpan20, under 67 ℃, stir 4h with the 400rpm stirring velocity.Stop to stir the back and continue heating 72 hours, centrifugation obtains hydrogel sphere.Moisture content with in the methyl alcohol displacement gel makes spherical alcogel.Alcogel is placed autoclave and fills it up with sherwood oil, be warming up to 250 ℃, and to keep the still internal pressure be 8Mpa, supercritical drying 3h, naturally cooling after the slow release of constant temperature makes the spherical organic aerogel then; The gained aerogel is put into high-temperature cracking furnace, under nitrogen protection, be warmed up to 800 ℃ and constant temperature 3h and obtain the spherical carbon aerogel with 5 ℃/min.The BET specific surface area of this spherical carbon aerogel is 543m
2/ g, pore volume are 1.13m
3/ g, mean pore size is 5.6nm, and average ball diameter is 0.077mm, and sphericity is 78, and intensity is 82wt%, true density is 0.69g/cm
3
Embodiment 11
Phenol, trimeric cyanamide and formaldehyde 1: 0.4: 3 are in molar ratio mixed, add the catalyst n aOH of reactant total mass 1%, adding a certain amount of deionized water then, to make the reactant total concn be 18g/100ml, in 85 ℃ of reactions 5 hours.Get this reaction solution of 20ml then and pour in the 500ml paraffin oil that contains 1mlSpan80, under 85 ℃, stir 4h with the 400rpm stirring velocity.Stop to stir the back and continue heating 72 hours, centrifugation obtains hydrogel sphere.Moisture content with in the methyl alcohol displacement gel makes spherical alcogel.Alcogel is placed autoclave and fills it up with sherwood oil, be warming up to 250 ℃, and to keep the still internal pressure be 8Mpa, supercritical drying 3h, naturally cooling after the slow release of constant temperature makes the spherical organic aerogel then; The gained aerogel is put into high-temperature cracking furnace, under nitrogen protection, be warmed up to 800 ℃ and constant temperature 3h and obtain the spherical carbon aerogel with 5 ℃/min.The BET specific surface area of this spherical carbon aerogel is 443m
2/ g, pore volume are 0.53m
3/ g, mean pore size is 4.1nm, and average ball diameter is 0.074mm, and sphericity is 87, and intensity is 94wt%, true density is 0.71g/cm
3
Embodiment 12
Phenol, trimeric cyanamide and formaldehyde 1: 0.4: 3 are in molar ratio mixed, add the catalyst n aOH of reactant total mass 1%, adding a certain amount of deionized water then, to make the reactant total concn be 18g/100ml, in 85 ℃ of reactions 5 hours.Get this reaction solution of 20ml then and pour in the 500ml silicone oil that contains 1mlSpan80, under 85 ℃, stir 4h with the 400rpm stirring velocity.Stop to stir the back and continue heating 72 hours, centrifugation obtains hydrogel sphere.Moisture content with in the methyl alcohol displacement gel makes spherical alcogel.Alcogel is placed autoclave and fills it up with sherwood oil, be warming up to 250 ℃, and to keep the still internal pressure be 8Mpa, supercritical drying 3h, naturally cooling after the slow release of constant temperature makes the spherical organic aerogel then; The gained aerogel is put into high-temperature cracking furnace, under nitrogen protection, be warmed up to 800 ℃ and constant temperature 3h and obtain the spherical carbon aerogel with 5 ℃/min.The BET specific surface area of this spherical carbon aerogel is 465m
2/ g, pore volume are 0.63m
3/ g, mean pore size is 3.9nm, and average ball diameter is 0.068mm, and sphericity is 91, and intensity is 85wt%, true density is 0.69g/cm
3
Embodiment 13
The water soluble phenol resin of 3g 50wt.%, the 0.3g trimeric cyanamide, 4.5g 37% formaldehyde, 5g 0.01M sodium carbonate solution, 12g distilled water mix and are incorporated in 85 times ℃ of prepolymerization 5h.Configuration contains the hexanaphthene of the 500ml of 1vol%SP80, joins then in the round-bottomed flask, is warming up to 70 ℃, stirs with 400 rev/mins speed, adds the colloidal sol aqueous solution, and constant temperature and constant speed stir 6h.Further aging 6h promptly makes spherical hydrogel under 70 ℃ of temperature.Take out bead, toluene wash 3 times, acetone displacement 3 times.With sherwood oil as drying medium, dry 3h under 240 ℃, 6Mpa; The gained aerogel is put into high-temperature cracking furnace, under nitrogen protection, be warmed up to 800 ℃ and constant temperature 3h and obtain the ball-type charcoal-aero gel with 5 ℃/min.The BET specific surface area of this ball-type charcoal-aero gel is 830m
2/ g, pore volume are 1.82m
3/ g, mean pore size is 7nm, and average ball diameter is 0.15mm, and sphericity is 96, and intensity is 94wt%, true density is 0.49g/cm
3
Embodiment 14
The water soluble phenol resin of 3g 50wt.%, the 0.3g trimeric cyanamide, 4.5g 37% formaldehyde, 5g 0.01M sodium carbonate solution, 12g distilled water mix and are incorporated in 85 times ℃ of prepolymerization 5h.Configuration contains the hexanaphthene of the 500ml of 3vol%SP80, joins then in the round-bottomed flask, is warming up to 70 ℃, stirs with 400 rev/mins speed, adds the colloidal sol aqueous solution, and constant temperature and constant speed stir 6h.Further aging 6h promptly makes spherical hydrogel under 70 ℃ of temperature.Take out bead, toluene wash 3 times, acetone displacement 3 times.With sherwood oil as drying medium, dry 3h under 240 ℃, 6Mpa; The gained aerogel is put into high-temperature cracking furnace, under nitrogen protection, be warmed up to 800 ℃ and constant temperature 3h and obtain the ball-type charcoal-aero gel with 5 ℃/min.The BET specific surface area of this ball-type charcoal-aero gel is 983m
2/ g, pore volume are 2.82m
3/ g, mean pore size is 7nm, and average ball diameter is 0.015mm, and sphericity is 97, and intensity is 96wt%, true density is 0.54g/cm
3
The water soluble phenol resin of 3g 50wt.%, the 0.3g trimeric cyanamide, 4.5g 37% formaldehyde, 5g 0.01M sodium carbonate solution, 12g distilled water mix and are incorporated in 85 times ℃ of prepolymerization 5h.Configuration contains the paraffin oil of the 500ml of 3vol%SP80, joins then in the round-bottomed flask, is warming up to 85 ℃, stirs with 400 rev/mins speed, adds the colloidal sol aqueous solution, and constant temperature and constant speed stir 6h.Further aging 6h promptly makes spherical hydrogel under 70 ℃ of temperature.Take out bead, toluene wash 3 times, acetone displacement 3 times.With sherwood oil as drying medium, dry 3h under 240 ℃, 6Mpa; The gained aerogel is put into high-temperature cracking furnace, under nitrogen protection, be warmed up to 800 ℃ and constant temperature 3h and obtain the ball-type charcoal-aero gel with 5 ℃/min.The BET specific surface area of this ball-type charcoal-aero gel is 763m
2/ g, pore volume are 1.92m
3/ g, mean pore size is 7.3nm, and average ball diameter is 0.018mm, and sphericity is 99, and intensity is 93wt%, true density is 0.65g/cm
3
Claims (7)
1. the preparation method of a spherical carbon aerogel is characterized in that the preparation method comprises the steps:
(1) each component that will constitute organogel is mixed formation colloidal sol monomer, carries out prepolymerization 0～10h under proper temperature.
(2) preparation contains the organic solvent of 0.01～5vol% tensio-active agent (with the solvent volume ratio).This organic solvent of 10～50 times of sol volume is added in reactor, be warming up to room temperature～85 ℃, stir with 50～800 rev/mins speed, add the colloidal sol of proper volume after prepolymerization, constant temperature and constant speed stir 3～24h.Under 60～85 ℃ of temperature, further wear out and promptly make spherical hydrogel.
(3) with the water in the organic solvent replacing water gel, obtain organogel.
(4) organogel is placed autoclave and fill it up with sherwood oil, 240～300 ℃ of super critical conditions, 4.5～12Mpa dry 1～3 hour down perhaps makes drying medium with carbonic acid gas, 31～100 ℃ of super critical conditions, 7.5～20Mpa made the spherical organic aerogel down in dry 7～90 hours.
(5) under nitrogen or argon shield,, make the spherical carbon aerogel 600～1200 ℃ of cracking 1～5 hour.
2. spherical carbon aerogel as claimed in claim 1 close the preparation method, it is characterized in that the organogel raw material is phenol-carbamide or resol-carbamide.
3. the synthetic method of a kind of spherical carbon aerogel as claimed in claim 1 is characterized in that proper temperature is 0～85 ℃
4. the synthetic method of spherical carbon aerogel as claimed in claim 1 is characterized in that employed tensio-active agent can select a series of HLB values such as span 20 (SP20), sorbester p18 (SP60), sorbester p17 (SP80), half saponified polyvinyl acetate to be between 2-10 one or more.
5. as described in the claim 1 (2), it is characterized in that employed organic solvent can select one or more in the higher-boiling compound of hexanaphthene, ten fluorine hydrogen naphthalenes, paraffin oil, tetrafluoroethylene, trifluoro-ethylene, silicone oil, kerosene, glycerol, hydro carbons.
6. as described in the claim 1 (3), it is characterized in that employed organic solvent is methyl alcohol, ethanol, propyl alcohol and acetone etc.
7. the synthetic method of spherical carbon aerogel as claimed in claim 1 is characterized in that used supercritical drying and charring are the technology commonly used in the existing chemical field.Charing is to carry out in low speed circulating fluidized bed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710039795 CN101041430A (en) | 2007-04-23 | 2007-04-23 | Preparation method of spherical charcoal-aero gel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710039795 CN101041430A (en) | 2007-04-23 | 2007-04-23 | Preparation method of spherical charcoal-aero gel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101041430A true CN101041430A (en) | 2007-09-26 |
Family
ID=38807261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200710039795 Pending CN101041430A (en) | 2007-04-23 | 2007-04-23 | Preparation method of spherical charcoal-aero gel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101041430A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102091595A (en) * | 2011-01-12 | 2011-06-15 | 华东理工大学 | Method for preparing spherical carbon aerogel with specific absorbability for low density lipoprotein |
| CN102302917A (en) * | 2011-07-18 | 2012-01-04 | 南京工业大学 | Preparation method of bulk C-Al2O3 composite aerogel |
| CN102323317A (en) * | 2011-05-26 | 2012-01-18 | 北京工业大学 | Preparation method of immobilized enzyme electrode using ZrP-CA as carrier |
| CN102423668A (en) * | 2011-09-09 | 2012-04-25 | 中国人民解放军国防科学技术大学 | Preparation method of phenolic resin base carbon aerogel |
| CN102513041A (en) * | 2011-12-26 | 2012-06-27 | 南京工业大学 | Method for preparing high-strength and high-temperature-resistance carbon-supported Al2O3-Al4C3 composite blocky aerogel |
| CN101823705B (en) * | 2009-03-04 | 2012-08-01 | 南京大学 | Method for preparing high-surface-area nitrogenous mesoporous carbon material |
| CN103633340A (en) * | 2013-12-17 | 2014-03-12 | 哈尔滨工业大学 | Modified expanded graphite based composite material bipolar plate and preparation method thereof |
| CN101910058B (en) * | 2008-01-17 | 2014-06-18 | 赢创炭黑有限公司 | Carbon aerogels, process for their preparation and their use |
| CN104170023A (en) * | 2012-03-06 | 2014-11-26 | 东洋油墨Sc控股株式会社 | Conductive fine particles, method for manufacturing same, conductive resin composition, conductive sheet, and electromagnetic shielding sheet |
| CN104446330A (en) * | 2014-12-23 | 2015-03-25 | 中物院成都科学技术发展中心 | Preparation method of ultrahigh-specific-surface-area nitrogen-doped carbon aerogel |
| CN104707662A (en) * | 2015-02-13 | 2015-06-17 | 南京航空航天大学 | Phenolic organic aerogel-doped catalyst and preparation method thereof |
| CN110697677A (en) * | 2018-07-10 | 2020-01-17 | 中国石油大学(北京) | Hollow carbon microsphere and preparation method thereof |
| CN110937589A (en) * | 2019-12-11 | 2020-03-31 | 福州大学 | Method for preparing and regulating high-nitrogen-doped porous carbon high internal phase emulsion template |
| CN112063387A (en) * | 2020-09-21 | 2020-12-11 | 武汉大学 | Lignosulfonate-phenolic resin-based carbon aerogel microsphere and preparation method and application thereof |
| CN112892483A (en) * | 2021-01-29 | 2021-06-04 | 武汉大学 | Nitrogen-doped carbon aerogel nano-microsphere as well as preparation method and application thereof |
-
2007
- 2007-04-23 CN CN 200710039795 patent/CN101041430A/en active Pending
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101910058B (en) * | 2008-01-17 | 2014-06-18 | 赢创炭黑有限公司 | Carbon aerogels, process for their preparation and their use |
| CN101823705B (en) * | 2009-03-04 | 2012-08-01 | 南京大学 | Method for preparing high-surface-area nitrogenous mesoporous carbon material |
| CN102091595B (en) * | 2011-01-12 | 2012-11-07 | 华东理工大学 | Method for preparing spherical carbon aerogel with specific absorbability for low density lipoprotein |
| CN102091595A (en) * | 2011-01-12 | 2011-06-15 | 华东理工大学 | Method for preparing spherical carbon aerogel with specific absorbability for low density lipoprotein |
| CN102323317A (en) * | 2011-05-26 | 2012-01-18 | 北京工业大学 | Preparation method of immobilized enzyme electrode using ZrP-CA as carrier |
| CN102323317B (en) * | 2011-05-26 | 2014-02-26 | 北京工业大学 | Preparation method of immobilized enzyme electrode using ZrP-CA as carrier |
| CN102302917A (en) * | 2011-07-18 | 2012-01-04 | 南京工业大学 | Preparation method of bulk C-Al2O3 composite aerogel |
| CN102302917B (en) * | 2011-07-18 | 2013-09-04 | 南京工业大学 | Preparation method of bulk C-Al2O3 composite aerogel |
| CN102423668A (en) * | 2011-09-09 | 2012-04-25 | 中国人民解放军国防科学技术大学 | Preparation method of phenolic resin base carbon aerogel |
| CN102513041B (en) * | 2011-12-26 | 2014-09-03 | 南京工业大学 | Method for preparing high-strength and high-temperature-resistance carbon-supported Al2O3-Al4C3 composite blocky aerogel |
| CN102513041A (en) * | 2011-12-26 | 2012-06-27 | 南京工业大学 | Method for preparing high-strength and high-temperature-resistance carbon-supported Al2O3-Al4C3 composite blocky aerogel |
| CN104170023A (en) * | 2012-03-06 | 2014-11-26 | 东洋油墨Sc控股株式会社 | Conductive fine particles, method for manufacturing same, conductive resin composition, conductive sheet, and electromagnetic shielding sheet |
| CN104170023B (en) * | 2012-03-06 | 2016-12-28 | 东洋油墨Sc控股株式会社 | Electrically conductive microparticle and manufacture method, electroconductive resin constituent, conductive sheet and electromagnetic shielding sheet |
| CN103633340A (en) * | 2013-12-17 | 2014-03-12 | 哈尔滨工业大学 | Modified expanded graphite based composite material bipolar plate and preparation method thereof |
| CN104446330A (en) * | 2014-12-23 | 2015-03-25 | 中物院成都科学技术发展中心 | Preparation method of ultrahigh-specific-surface-area nitrogen-doped carbon aerogel |
| CN104446330B (en) * | 2014-12-23 | 2016-08-31 | 中物院成都科学技术发展中心 | A kind of preparation method of superhigh specific surface area nitrating carbon aerogels |
| CN104707662A (en) * | 2015-02-13 | 2015-06-17 | 南京航空航天大学 | Phenolic organic aerogel-doped catalyst and preparation method thereof |
| CN110697677A (en) * | 2018-07-10 | 2020-01-17 | 中国石油大学(北京) | Hollow carbon microsphere and preparation method thereof |
| CN110697677B (en) * | 2018-07-10 | 2021-03-05 | 中国石油大学(北京) | Hollow carbon microsphere and preparation method thereof |
| CN110937589A (en) * | 2019-12-11 | 2020-03-31 | 福州大学 | Method for preparing and regulating high-nitrogen-doped porous carbon high internal phase emulsion template |
| CN110937589B (en) * | 2019-12-11 | 2022-10-25 | 福州大学 | High internal phase emulsion template method for preparing and regulating high-nitrogen-doped porous carbon |
| CN112063387A (en) * | 2020-09-21 | 2020-12-11 | 武汉大学 | Lignosulfonate-phenolic resin-based carbon aerogel microsphere and preparation method and application thereof |
| CN112892483A (en) * | 2021-01-29 | 2021-06-04 | 武汉大学 | Nitrogen-doped carbon aerogel nano-microsphere as well as preparation method and application thereof |
| CN112892483B (en) * | 2021-01-29 | 2022-04-19 | 武汉大学 | Nitrogen-doped carbon aerogel nano-microsphere as well as preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101041430A (en) | Preparation method of spherical charcoal-aero gel | |
| CN1191195C (en) | Pyrolyzed hard carbon material, preparation and its applications | |
| Tong et al. | Lignin-derived electrode materials for supercapacitor applications: progress and perspectives | |
| JP6665121B2 (en) | Novel method for sol-gel polymerization in solvent-free and preparation of variable carbon structures derived from sol-gel polymerization | |
| Liang et al. | Facile synthesis of highly porous carbon from rice husk | |
| Antonietti et al. | Carbon aerogels and monoliths: control of porosity and nanoarchitecture via sol–gel routes | |
| KR101998848B1 (en) | Preparation of polymeric resins and carbon materials | |
| Titirici et al. | Chemistry and materials options of sustainable carbon materials made by hydrothermal carbonization | |
| JP6505020B2 (en) | Preparation of polymer resin and carbon material | |
| CN103947017B (en) | For the carbon lead blend in mixed tensor storage device | |
| Li et al. | Synthesis and adsorption properties of colloid-imprinted carbons with surface and volume mesoporosity | |
| KR100932979B1 (en) | Hollow capsule structure and manufacturing method thereof | |
| CN109385254B (en) | Graphene elastic polymer phase-change composite material and preparation method thereof | |
| Hao et al. | Three-dimensional hierarchical porous carbon with high oxygen content derived from organic waste liquid with superior electric double layer performance | |
| JP2021512190A (en) | How to prepare carbon material | |
| CN102092708B (en) | Method for preparing phenol-formaldehyde carbon aerogel in low alkali | |
| CN1281486C (en) | Preparation of polymer based carbon balls | |
| CN102352003A (en) | Preparation method of phenolic resin microballoons and method for preparing phenolic resin-based carbon spheres by use of preparation method | |
| Xue et al. | Synthesis of hierarchically porous carbon with tailored porosity and electrical conductivity derived from hard–soft carbon precursors for enhanced capacitive performance | |
| Díez et al. | Dense (non-hollow) carbon nanospheres: synthesis and electrochemical energy applications | |
| CN107720747B (en) | Preparation method of mesoporous-asphalt-based spherical activated carbon | |
| CN1923679A (en) | Charcoal aerogel | |
| Wang et al. | Lignin‐derived carbon materials for catalysis and electrochemical energy storage | |
| Liu et al. | Carbon nanosphere synthesis and applications for rechargeable batteries | |
| JP7132258B2 (en) | A novel method for solvent-free sol-gel polymerization and fabrication of variable carbon structures derived from sol-gel polymerization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| DD01 | Delivery of document by public notice |
Addressee: Zhang Rui Document name: Notification of before Expiration of Request of Examination as to Substance |
|
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20070926 |