CN106006633B - A kind of preparation method of the porous carbon material of three-dimensional macro self supporting structure - Google Patents
A kind of preparation method of the porous carbon material of three-dimensional macro self supporting structure Download PDFInfo
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- CN106006633B CN106006633B CN201610315894.2A CN201610315894A CN106006633B CN 106006633 B CN106006633 B CN 106006633B CN 201610315894 A CN201610315894 A CN 201610315894A CN 106006633 B CN106006633 B CN 106006633B
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
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Abstract
The invention belongs to porous material technical fields, and in particular to be a kind of preparation method of the porous carbon material of three-dimensional macro self supporting structure.Including：Polyvinylpyrrolidone（PVP）The preparation of solution, vacuum lyophilization obtains the PVP presomas of porous structure, above-mentioned 150 200 DEG C of presoma constant temperature is stablized into 12 48h again, again porous charcoal is obtained through 600 1000 DEG C of high temperature cabonizations, last KOH and above-mentioned porous charcoal are mixed according to certain mass ratio, 800 DEG C of 1 2h of activation, obtain integrating micropore, mesoporous and macropore porous carbon material.This method has advanced optimized the method for preparing porous carbon material, and preparation process is easy to operate, and yield is high, and green non-pollution, the porous carbon material pore structure of preparation is orderly, has high specific surface area and up to 90% porosity.
Description
Technical field
The invention belongs to porous material technical fields, and in particular to be a kind of porous carbon of three-dimensional macro self supporting structure
The preparation method of material.
Background technology
With the development of science and technology, the problem of environmental pollution getting worse brought in industrial production and in life, industry
The noxious materials such as acid, alkali, cadmium, mercury, arsenic, benzene, organic dyestuff in sewage can flow into body of groundwater by the osmosis of soil
System, poisons aquatile with poison, influences the drinking water source of people.So the processing to trade effluent is particularly important.At present, water pollution
Processing can be divided into chemical decomposition method and physisorphtion, wherein chemical decomposition method, i.e., by such as macromolecule one kind substance point in sewage
Xie Chengshui and some other small molecule, it is obvious that this processing mode of most cases inevitably causes the secondary of water body
Pollution.And the method for physical absorption avoids the presence of secondary pollution well.Research and development with good adsorption functional material into
For the research hotspot of nearly more than ten years, porous carbon material has been concerned as a kind of novel charcoal material.
At present, porous charcoal is lived mainly using coal tar, pitch, oil, biomass, polymer as raw material by physical chemistry
It is prepared by change method, mixed with polymers carbonizatin method, organic gel method and template.Porous carbon material can be divided into greatly according to its pore size
Hole（>50nm）, mesoporous (2 ~ 50nm) and micropore (<2nm), wherein microcellular structure can be divided into atomic hole again（<0.7nm）And ultramicropore
（0.7~2nm）, special pore size distribution structure makes it have high-specific surface area, high porosity, good permeability, green non-poisonous
The advantages that, it is widely used in the fields such as adsorbing separation, catalyst carrier, energy storage and biomaterial for medical purpose, in the suction of discarded dyestuff
It is attached use it is especially prominent.
Invention content
The technical problems to be solved by the invention are to provide a kind of preparation method of porous carbon material, and this method combines freezing
Seasoning, high temperature cabonization method and chemical activation method are made with self supporting structure, high-specific surface area, low density porous structure
Charcoal can be used as repeating adsorption and separation material, catalyst carrier etc..
The present invention includes：
(1) preparation of precursor solution and the vacuum drying of PVP
PVP and water magnetic agitation 12h by a certain percentage, are in orientation, quick insertion in centrifuge tube by PVP aqueous solutions
In liquid nitrogen, and Minton dryer is moved into rapidly, vacuum degree is kept to obtain pore structure queueing discipline less than 50Pa, dry 36h
PVP predecessors.
（2）The stabilization process of predecessor
Above-mentioned 150--200 DEG C of air environment of predecessor is stablized into 12--48h；
（3）PVP carbonisations
The material stably obtained is subjected to high temperature cabonization 4h, obtains preliminary porous carbon material；
（4）The activation process of porous charcoal
By KOH and above-mentioned porous charcoal according to mass ratio 4:1 mixing, 800 DEG C of activation 1--2h are to get target product.
The step（1）Middle magnetic agitation 12h, it is therefore intended that ensure that raw material is sufficiently mixed, be in loaded in centrifuge tube later
Quickly, orientation is inserted into liquid nitrogen, it is therefore intended that the porous structure of formation rule distribution.
The step（1）Middle vacuum drying is no less than 36h, it is therefore an objective to be eliminated as much as moisture.
The step（2）Middle constant temperature stabilizes to：150--200 DEG C, air environment drying 12--48h, Temperature fall.
The step（3）It is middle by predecessor in tube furnace to being carbonized, carbonisation is divided into 2 parts, first part, by
Room temperature is increased to 360 DEG C, and keeps 4h, second part, and in the environment of nitrogen is as protection gas, 600 DEG C are risen to by 360 DEG C --
1000 DEG C, and keep 4h, rear Temperature fall, it is 2 DEG C/min that heating rate is controllable in whole process -- 10 DEG C/min, tentatively
Obtain porous carbon material.
The step（4）It is middle by the above-mentioned charcoal porous material arrived and KOH according to mass ratio 1:4 weigh, and grind KOH, make
Porous charcoal is embedded in KOH wherein, in graphite crucible, moves into tube furnace, activation burning process is carried out under nitrogen environment：First by room temperature
400 DEG C are warming up to, keeps 30min, then be warming up to 800 DEG C, keeps 1--2h, heating rate is 5 DEG C/min in the process.Naturally it drops
It warms to room temperature.
The step（4）It is middle that sample is moved into 80 DEG C of water-bath 30min in deionized water, then cleaned repeatedly directly through deionized water
To neutrality, 60 DEG C of dryings.
Advantageous effect
（1）Porous charcoal obtained by the present invention is in three-dimensional self supporting structure.
（2）The features such as porous charcoal obtained by the present invention has high specific surface area, and density is small, and property is stablized, can be used as
Sorbing material, catalyst carrier etc..
（3）The present invention is more to change by concentration, carburizing temperature, heating rate and the soak time for changing PVP aqueous solutions
The appearance structure of hole charcoal.
（4）Preparation process of the present invention is simple, easily operated, environmentally safe.
Description of the drawings
Fig. 1 is the process route chart for preparing porous carbon material；
Fig. 2 is the XRD diagram of the porous carbon material of the present invention；
Fig. 3 is different (A.B.C) for PVP concentration in the present invention, and carburizing temperature difference (D.E.F) is different with heating rate
(G.H.I) the SEM figures of three groups of porous charcoals of gained；
Fig. 4 is the infrared spectrum of porous charcoal prepared by embodiment 1 in the present invention；
The physical absorption curve of porous charcoal that Fig. 5 is prepared for embodiment 1 in the present invention, specific surface area 1846cm3/g；
Fig. 6 is the graph of pore diameter distribution of porous charcoal prepared by embodiment 1 in the present invention；
Fig. 7 is absorption figure of the porous charcoal to MO, MB and RB of the preparation of embodiment 1 in the present invention.
Specific embodiment
With reference to specific embodiment, the present invention is furture elucidated.
Embodiment 1
（1）The preparation of precursor solution and the freeze-drying of PVP
Weigh a certain amount of PVP to mix by mass fraction 10wt% with water, magnetic agitation 12h, by PVP aqueous solutions be in be mounted in from
In heart pipe, in orientation, quick insertion liquid nitrogen, and Minton dryer is moved into rapidly, vacuum degree is kept to be less than 50Pa, dry 36h,
Obtain the PVP predecessors of pore structure queueing discipline.
（2）The stabilization process of predecessor
Above-mentioned 150 DEG C of air environments of predecessor are stablized for 24 hours；
（3）PVP carbonisations
PVP is placed in tube furnace, 360 DEG C are increased to, and keep 4h by room temperature, nitrogen is filled with as protection gas, by 360
DEG C 1000 DEG C are risen to, and keep 4h, Temperature fall, heating rate in whole process
5 DEG C/min, tentatively obtain porous carbon material.
（4）The activation process of porous charcoal
By porous carbon material and KOH according to mass ratio 1:4 weigh, and grind KOH, porous charcoal are made to be embedded in KOH wherein, in stone
Black crucible moves into tube furnace, under nitrogen environment, first by room temperature to 400 DEG C, keeps 30min, then be warming up to 800 DEG C, keeps
1h, in the process heating rate do not become 5 DEG C/min.It is naturally cooling to room temperature.
Embodiment 2
（1）The preparation of precursor solution and the freeze-drying of PVP
Weigh a certain amount of PVP to mix by mass fraction 10wt% with water, magnetic agitation 12h, by PVP aqueous solutions be in be mounted in from
In heart pipe, in orientation, quick insertion liquid nitrogen, and Minton dryer is moved into rapidly, vacuum degree is kept to be less than 50Pa, dry 36h,
Obtain the PVP predecessors of pore structure queueing discipline.
（2）The stabilization process of predecessor
Above-mentioned 150 DEG C of air environments of predecessor are stablized for 24 hours；
（3）PVP carbonisations
PVP is placed in tube furnace, 360 DEG C are increased to, and keep 4h by room temperature, nitrogen is filled with as protection gas, by 360
DEG C 800 DEG C are risen to, and keep 4h, Temperature fall, heating rate in whole process
5 DEG C/min, tentatively obtain porous carbon material.
（4）The activation process of porous charcoal
By porous carbon material and KOH according to mass ratio 1:4 weigh, and grind KOH, porous charcoal are made to be embedded in KOH wherein, in stone
Black crucible moves into tube furnace, under nitrogen environment, first by room temperature to 400 DEG C, keeps 30min, then be warming up to 800 DEG C, keeps
1h, in the process heating rate do not become 5 DEG C/min.It is naturally cooling to room temperature.
Embodiment 3
（1）The preparation of precursor solution and the freeze-drying of PVP
Weigh a certain amount of PVP to mix by mass fraction 10wt% with water, magnetic agitation 12h, by PVP aqueous solutions be in be mounted in from
In heart pipe, in orientation, quick insertion liquid nitrogen, and Minton dryer is moved into rapidly, vacuum degree is kept to be less than 50Pa, dry 36h,
Obtain the PVP predecessors of pore structure queueing discipline.
（2）The stabilization process of predecessor
Above-mentioned 150 DEG C of air environments of predecessor are stablized for 24 hours；
（3）PVP carbonisations
PVP is placed in tube furnace, 360 DEG C are increased to, and keep 4h by room temperature, nitrogen is filled with as protection gas, by 360
DEG C 600 DEG C are risen to, and keep 4h, Temperature fall, heating rate in whole process
5 DEG C/min, tentatively obtain porous carbon material.
（4）The activation process of porous charcoal
By porous carbon material and KOH according to mass ratio 1:4 weigh, and grind KOH, porous charcoal are made to be embedded in KOH wherein, in stone
Black crucible moves into tube furnace, under nitrogen environment, first by room temperature to 400 DEG C, keeps 30min, then be warming up to 800 DEG C, keeps
1h, in the process heating rate do not become 5 DEG C/min.It is naturally cooling to room temperature.
Embodiment 4
（1）The preparation of precursor solution and the freeze-drying of PVP
Weigh a certain amount of PVP to mix by mass fraction 15wt% with water, magnetic agitation 12h, by PVP aqueous solutions be in be mounted in from
In heart pipe, in orientation, quick insertion liquid nitrogen, and Minton dryer is moved into rapidly, vacuum degree is kept to be less than 50Pa, dry 36h,
Obtain the PVP predecessors of pore structure queueing discipline.
（2）The stabilization process of predecessor
Above-mentioned 150 DEG C of air environments of predecessor are stablized for 24 hours；
（3）PVP carbonisations
PVP is placed in tube furnace, 360 DEG C are increased to, and keep 4h by room temperature, nitrogen is filled with as protection gas, by 360
DEG C 800 DEG C are risen to, and keep 4h, Temperature fall, heating rate in whole process
5 DEG C/min, tentatively obtain porous carbon material.
（4）The activation process of porous charcoal
By porous carbon material and KOH according to mass ratio 1:4 weigh, and grind KOH, porous charcoal are made to be embedded in KOH wherein, in stone
Black crucible moves into tube furnace, under nitrogen environment, first by room temperature to 400 DEG C, keeps 30min, then be warming up to 800 DEG C, keeps
1h, in the process heating rate do not become 5 DEG C/min.It is naturally cooling to room temperature.
Embodiment 5
（1）The preparation of precursor solution and the freeze-drying of PVP
It weighs a certain amount of PVP to mix by mass fraction 5wt% with water, magnetic agitation 12h, is in mounted in centrifugation by PVP aqueous solutions
Guan Zhong is oriented, in quick insertion liquid nitrogen, and is moved into Minton dryer rapidly, and vacuum degree is kept to be obtained less than 50Pa, dry 36h
To the PVP predecessors of pore structure queueing discipline.
（2）The stabilization process of predecessor
Above-mentioned 150 DEG C of air environments of predecessor are stablized for 24 hours；
（3）PVP carbonisations
PVP is placed in tube furnace, 360 DEG C are increased to, and keep 4h by room temperature, nitrogen is filled with as protection gas, by 360
DEG C 800 DEG C are risen to, and keep 4h, Temperature fall, 5 DEG C/min of heating rate in whole process tentatively obtains porous carbon material.
（4）The activation process of porous charcoal
By porous carbon material and KOH according to mass ratio 1:4 weigh, and grind KOH, porous charcoal are made to be embedded in KOH wherein, in stone
Black crucible moves into tube furnace, under nitrogen environment, first by room temperature to 400 DEG C, keeps 30min, then be warming up to 800 DEG C, keeps
1h, in the process heating rate do not become 5 DEG C/min.It is naturally cooling to room temperature.
Embodiment 6
（1）The preparation of precursor solution and the freeze-drying of PVP
Weigh a certain amount of PVP to mix by mass fraction 10wt% with water, magnetic agitation 12h, by PVP aqueous solutions be in be mounted in from
In heart pipe, in orientation, quick insertion liquid nitrogen, and Minton dryer is moved into rapidly, vacuum degree is kept to be less than 50Pa, dry 36h,
Obtain the PVP predecessors of pore structure queueing discipline.
（2）The stabilization process of predecessor
Above-mentioned 150 DEG C of air environments of predecessor are stablized for 24 hours；
（3）PVP carbonisations
PVP is placed in tube furnace, 360 DEG C are increased to, and keep 4h by room temperature, nitrogen is filled with as protection gas, by 360
DEG C 800 DEG C are risen to, and keep 4h, Temperature fall, heating rate in whole process
5 DEG C/min, tentatively obtain porous carbon material.
（4）The activation process of porous charcoal
By porous carbon material and KOH according to mass ratio 1:4 weigh, and grind KOH, porous charcoal are made to be embedded in KOH wherein, in stone
Black crucible moves into tube furnace, under nitrogen environment, first by room temperature to 400 DEG C, keeps 30min, then be warming up to 800 DEG C, keeps
1.5h, in the process heating rate do not become 5 DEG C/min.It is naturally cooling to room temperature.
Claims (1)
1. a kind of preparation method of the porous carbon material of three-dimensional macro self supporting structure, it is characterized in that being as follows：
(1) preparation of precursor solution and the vacuum drying of PVP
PVP and water magnetic agitation 12h by a certain percentage, are in orientation, quick insertion liquid nitrogen in centrifuge tube by PVP aqueous solutions
In, and Minton dryer is moved into rapidly, vacuum degree is kept to obtain the PVP of pore structure queueing discipline less than 50Pa, dry 36h
Predecessor；
（2）The stabilization process of predecessor
Above-mentioned 150--200 DEG C of air environment of predecessor is stablized into 12--48h；
（3）PVP carbonisations
By predecessor in tube furnace to being carbonized, carbonisation is divided into 2 parts, and first part is increased to 360 DEG C by room temperature,
And 4h is kept, and in the environment of nitrogen is as protection gas, 600 DEG C are risen to by 360 DEG C for second part -- and 1000 DEG C, and 4h is kept,
Temperature fall afterwards, it is 2 DEG C/min that heating rate is controllable in whole process -- 10 DEG C/min, tentatively obtain porous carbon material；
（4）The activation process of porous charcoal
By the above-mentioned charcoal porous material arrived and KOH according to mass ratio 1:4 weigh, and grind KOH, porous charcoal is made to be embedded in KOH wherein,
In in graphite crucible, tube furnace is moved into, activation burning process is carried out under nitrogen environment：First by room temperature to 400 DEG C, keep
30min, then 800 DEG C are warming up to, 1--2h is kept, heating rate is 5 DEG C/min in the process, is naturally cooling to room temperature, will drop to room
The sample of temperature moves into 80 DEG C of water-bath 30min in deionized water, then is cleaned repeatedly up to neutral through deionized water, 60 DEG C of dryings, i.e.,
Obtain target product.
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| CN110396215B (en) * | 2019-07-22 | 2021-02-09 | 北京航空航天大学 | Directional porous structure and preparation method thereof |
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| CN104693474A (en) * | 2013-12-06 | 2015-06-10 | 上海交通大学 | Preparation method for three-dimensional porous material |
| CN105050949A (en) * | 2012-11-26 | 2015-11-11 | 佐治亚-太平洋化工品有限公司 | Preparation of polymeric resins and carbon materials |
| WO2016018192A1 (en) * | 2014-07-29 | 2016-02-04 | Agency For Science, Technology And Research | Method of preparing a porous carbon material |
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| CN105050949A (en) * | 2012-11-26 | 2015-11-11 | 佐治亚-太平洋化工品有限公司 | Preparation of polymeric resins and carbon materials |
| CN104693474A (en) * | 2013-12-06 | 2015-06-10 | 上海交通大学 | Preparation method for three-dimensional porous material |
| WO2016018192A1 (en) * | 2014-07-29 | 2016-02-04 | Agency For Science, Technology And Research | Method of preparing a porous carbon material |
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