CN101717085B - Activated carbon microspheres and preparation method thereof - Google Patents
Activated carbon microspheres and preparation method thereof Download PDFInfo
- Publication number
- CN101717085B CN101717085B CN200910241779A CN200910241779A CN101717085B CN 101717085 B CN101717085 B CN 101717085B CN 200910241779 A CN200910241779 A CN 200910241779A CN 200910241779 A CN200910241779 A CN 200910241779A CN 101717085 B CN101717085 B CN 101717085B
- Authority
- CN
- China
- Prior art keywords
- carbon
- active
- microball
- nano
- weight
- 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.)
- Expired - Fee Related
Links
Images
Abstract
The invention relates to activated carbon microspheres and a preparation method thereof. The diameter of the activated carbon microspheres is between 10 and 40 nm, the BET specific surface area is between 2,500 and 3,600m<2>/g, the total pore volume is between 2.5 and 3.2cm<3>/g, the mescopore pore volume is between 1.6 and 2.2cm<3>/g, and an average pore size is between 2.8 and 3.1nm. The preparation method for the activated carbon microspheres comprises the steps of: firstly, performing pre-oxidation on a mixture of coal tar pitch and an annexing agent; secondly, activating the mixture by using a strong basic compound; thirdly, cleaning by using a detergent; finally, drying to obtain the activated carbon microspheres.
Description
[technical field]
The invention belongs to a micron carbon material technical field.More specifically, the present invention relates to a kind of active-carbon-microball, also relate to the preparation method of said active-carbon-microball.
[background technology]
People know that existing active carbon material has a large amount of holes, high specific surface area; Also have various active functional group on its surface, have good catalytic activity, moreover; Chemicalstability is also fine; Physical strength is also very high, can use repeatedly, and these excellent characteristics make existing active carbon material become the high-quality sorbent material that a kind of common people of enjoying pay close attention to.Activated carbon has just obtained application at aspects such as food, pharmaceutically decolouring, gas defence and taste removals very early; And As time goes on, they are applied to industrial technology fields such as industry, national defence, medical and health, chemical industry, environmental protection more and more widely as fine sorbent material and support of the catalyst.But; Develop rapidly along with industrial technology; Therefore the actual requirement of key areas such as the more and more incompatibility environmental protection of performance of existing active carbon material, medicine, electrical condenser is badly in need of improving their performance, for example increases specific surface area, improves rate of adsorption and efficient.In order to improve the absorption property of activated carbon, people have done number of research projects.For example Osaka, Japan gas company is a raw material with the mesophase pitch microballoon, is acvator with KOH, makes specific surface area up to 3000～4600 activated carbon with high specific surface area microballoon.T.Kasuh, G.Morino have described use KOH and have prepared super-active carbon through the chemical activation effect in US 5 143 889 (1992), its specific surface area surpasses 4000m
2/ g, and these super-active carbon mainly are made up of micropore, it is very narrow that the aperture of this type active carbon with high specific surface area material distributes usually, and the micropore pore volume accounts for about 90%, and the content of mesopore (diameter is greater than the hole of 2nm) and macropore (diameter is greater than the hole of 50nm) is very little.Because mesopore not only can be used as the passage that adsorbate gets into micropore, and they itself can be adsorbed a large amount of adsorbates, and therefore, they have very important significance in adsorption applications.General active carbon material is along with the increase of mesopore content, and specific surface area then can reduce, and therefore is difficult to obtain to have the mesothyrid active carbon material of high-specific surface area.Yet using strongly alkaline compound in recent years is the maximum progress that the activated carbon field is obtained as the high-specific surface area active carbon material of acvator preparation.For example Shen Cengmin, Xue Ruisheng be in " the plain technology of charcoal ", and 5 (2001), the middle use KOH that reported carries out chemical activation to the mesopore microballoon, prepares activation mesopore microballoon, and its total pore volume can reach 2.45cm
3/ g, specific surface area reaches 3128m
2/ g, and mesopore content reaches 56.1-65.7%.Therefore; Adopt the mesothyrid powdered activated carbon of the high-specific surface area of this technology preparation; Should satisfy many industries; For example ultracapacitor, pharmacy, support of the catalyst etc. are to the requirement of this type material, so this mesothyrid activated carbon has boundless prospect in the field that relates to adsorption technologies such as methane.Yet they also seem not enough at absorption hydrogen, carbonic acid gas etc., and for example loading capacity is also not high, and rate of adsorption is also slow.Therefore, the inventor has accomplished the present invention finally through lot of experiments.
[summary of the invention]
[technical problem that will solve]
The purpose of this invention is to provide a kind of active-carbon-microball.
Another object of the present invention provides a kind of preparation method of said active-carbon-microball.
[technical scheme]
The present invention realizes through following technical proposals.
The present invention relates to a kind of active-carbon-microball.
This active-carbon-microball is by containing the carbosphere of forming in the above decolorizing carbon sill of 90.0 weight % of said active-carbon-microball gross weight, and its diameter is 10-40 μ m, and the BET specific surface area is 2500-3600m
2/ g, total hole pore volume 2.5-3.2cm
3/ g, mesopore volume 1.6-2.2cm
3/ g, mean pore size 2.8-3.1nm.
Preferably, this active-carbon-microball is the above decolorizing carbon sill of 93.0 weight % that contains in said active-carbon-microball gross weight, and its diameter is 15-35 μ m, and the BET specific surface area is 2600-3500m
2/ g, total hole pore volume 2.6-3.0cm
3/ g, mesopore volume 1.8-2.0cm
3/ g, mean pore size 2.8-3.0nm.
The present invention relates to the preparation method of said active-carbon-microball.
The step of this method is following:
A, according to coal-tar pitch weight meter; Add the additive that 10-30 weight % is selected from nano-ceramic powder, MOX, silicon-dioxide or carbonate toward said coal-tar pitch; Mixing the back carried out under temperature 300-400 ℃ preoxidation 1.0-3.0 hour in air; Under inert atmosphere, kept constant temperature 0.8-2.0 hour down then at temperature 400-600 ℃
B, let step A) product that obtains with in said product weight 300-900 weight % strongly alkaline compound activator mix; In activation furnace, under protection of inert gas, be heated to 750 ℃-900 ℃ then; Under this temperature, kept 0.5-1.5 hour again, obtain a kind of activation products;
The activation products that C, step B obtain use sanitising agent to clean, and carry out drying then, can make described active-carbon-microball material like this.
A preferred embodiment of the invention, described coal-tar pitch granularity is the 200-400 order.
According to another kind of preferred implementation of the present invention, described nano-ceramic powder is one or more nano-ceramic powders that are selected from nano zircite, silicon nitride crystal whisker, nanometer silicon carbide, nano titanium carbide, nano yttrium oxide, nano-silicon nitride, Nano titanium nitride, nano aluminum nitride or nano-zirconium carbide.
According to another kind of preferred implementation of the present invention, described MOX is that one or more are selected from aluminum oxide, Natural manganese dioxide, red stone, iron protoxide or zirconic MOX.
According to another kind of preferred implementation of the present invention, described carbonate is one or more carbonate that are selected from lime carbonate, yellow soda ash, magnesiumcarbonate, salt of wormwood, Calcium hydrogen carbonate, sodium hydrogencarbonate, Magnesium hydrogen carbonate or saleratus.
According to another kind of preferred implementation of the present invention, described inert atmosphere is the inert atmosphere of nitrogen, argon gas or nitrogen and ar mixture.
According to another kind of preferred implementation of the present invention, described acvator is one or more acvators that are selected from KOH, NaOH, LiOH, KOH/NaOH, KOH/LiOH or NaOH/LiOH mixture.
According to another kind of preferred implementation of the present invention, described sanitising agent is one or more sanitising agents that are selected from zero(ppm) water, ethanol, acetone or ether.
The present invention will be described in detail belows.
The present invention relates to a kind of active-carbon-microball.
This active-carbon-microball is by containing the carbosphere of forming in the above decolorizing carbon sill of 90.0 weight % of said active-carbon-microball gross weight, and outside the de-carbon, this active-carbon-microball also contains oxygen element and activator metal ion.
The diameter of said active-carbon-microball is 10-40 μ m, and the BET specific surface area is 2500-3600m
2/ g, total hole pore volume 2.5-3.2cm
3/ g, mesopore volume 1.6-2.2cm
3/ g, mean pore size 2.8-3.1nm.
On meaning of the present invention; Described active-carbon-microball should be appreciated that it is to have high BET specific surface area, high total hole pore volume, high mesopore volume and a suitable carbosphere in aperture, for example the diameter of described active-carbon-microball greater than 10 μ m, BET specific surface area greater than 2500m
2/ g, total hole pore volume are greater than 2.5cm
3/ g, mesopore volume is greater than 1.6cm
3/ g, mean pore size is greater than the carbosphere of 2.8nm.
The BET specific surface area of active-carbon-microball of the present invention, total hole pore volume, mesopore volume and mean pore size are to adopt following method to measure: adopt the automatic absorption appearance of selling in the market; According to the volumetry principle with nitrogen as adsorbate; Under liquid nitrogen temperature, adsorb; Adopt the BET method to calculate the BET specific surface area by the adsorption isothermal line that records; By relative pressure is that 0.98 o'clock nitrogen adsorptive value is converted into the liquid nitrogen volume and obtains total hole pore volume, adopts the Dubinin-Astakhov method to calculate the micropore pore volume, and total hole pore volume deducts the micropore pore volume and obtains mesopore volume; By the pore size distribution of density function Theoretical Calculation active-carbon-microball, calculate mean pore size by this pore size distribution again.Active-carbon-microball diameter of the present invention is measured with sem.
In the present invention, said micropore is the hole of bore dia less than 2nm; Described mesopore is a bore dia greater than 2nm and again less than the hole of 50nm.
Lot of experiments proves, described active-carbon-microball has only and satisfies above-mentioned basic product parameter, and they are to adsorptive capacity, kinetics of adsorption and the physical strength of hydrogen and carbonic acid gas, the requirement that regenerability can satisfy actual industrial enforcement.
For example, if the BET specific surface area less than 2000m
2/ g, the absorption property of sample can be very poor; Greater than 4000m
2/ g, then sample mainly is made up of micropore, and the aperture can be very little, is unfavorable for the absorption of gas.
If total hole pore volume of this active-carbon-microball is less than 2.5cm
3/ g or greater than 3.2cm
3/ g, then to the absorption meeting variation of gas molecule, the ability of stored-gas weakens.
If the mean pore size of this active-carbon-microball is less than 2.8nm or greater than 3.1nm, then because aperture too small or excessive causes molecule to be difficult to get into material, perhaps molecule gets in material too easily.
Therefore, the active-carbon-microball that just has an above-mentioned performance perameter is only preferred active-carbon-microball of the present invention.
Preferably, this active-carbon-microball is by containing the carbosphere of forming in the above decolorizing carbon sill of 93.0 weight % of said active-carbon-microball gross weight, and its diameter is 15-35 μ m, and the BET specific surface area is 2600-3500m
2/ g, total hole pore volume 2.6-3.0cm
3/ g, mesopore volume 1.8-2.0cm
3/ g, mean pore size 2.8-3.0nm.
More preferably, this active-carbon-microball is the above decolorizing carbon sill of 93.5 weight % that contains in said active-carbon-microball gross weight, and its diameter is 16-32 μ m, and the BET specific surface area is 2800-3000m
2/ g, total hole pore volume 2.6-2.8cm
3/ g, mesopore volume 1.8-2.0cm
3/ g, mean pore size 2.8-3.0nm.
The invention still further relates to the preparation method of said active-carbon-microball.
The step of this method is following:
A, according to coal-tar pitch weight meter; Add the additive that 10-30 weight % is selected from nano-ceramic powder, MOX, silicon-dioxide or carbonate toward said coal-tar pitch; Mixing the back carried out under temperature 300-400 ℃ preoxidation 1.0-3.0 hour in air; Under inert atmosphere, kept constant temperature 0.8-2.0 hour down then at temperature 400-600 ℃.
Coal-tar pitch is the pitch of being processed into through distillation again by the coal tar that the dry distillation of coal obtains, and at room temperature is black fragility block, and is glossy, easy firing during fusion.
The coal-tar pitch that the present invention uses should National standard GB/T2290-94, is product sold in the market.At first, should use at normally used in the art kibbler coal drop coal is pulverized.Then, the coal-tar pitch of pulverizing re-uses common standard sieve and sieves, and gets granularity 200-400 purpose coal-tar pitch and is used for preparation of the present invention.
For the present invention, described coal-tar pitch granularity is not crucial for embodiment of the present invention, and its granularity also can be used less than 200 orders or greater than 400 orders, but the product productive rate is had certain influence.
In the present invention, described additive should be appreciated that it is a kind of material that can help the pitch balling-up, and therefore, every material with this performance can be as additive of the present invention.
Preferably, according to coal-tar pitch weight meter, the amount of said additive is 300-900 weight %, more preferably 500-800 weight %, most preferably 500-700 weight %.
Described additive is selected from nano-ceramic powder, MOX or carbonate.
In the present invention, described nano-ceramic powder is the ceramic powder of mean particle size less than 50nm.
According to another kind of preferred implementation of the present invention, described nano-ceramic powder is one or more nano-ceramic powders that are selected from nano zircite, silicon nitride crystal whisker, nanometer silicon carbide, nano titanium carbide, nano yttrium oxide, nano-silicon nitride, Nano titanium nitride, nano aluminum nitride or nano-zirconium carbide.These nano-ceramic powders all are product solds on market at present; For example nano zircite be Shanghai color reputation nanosecond science and technology company with the trade(brand)name product sold, nano titanium carbide is a Hefei Kai Er nanosecond science and technology Development Co., Ltd with the trade(brand)name product sold etc.
According to another kind of preferred implementation of the present invention, described MOX is that one or more are selected from aluminum oxide, Natural manganese dioxide, red stone, iron protoxide or zirconic MOX.Described oxide compound all is a product sold on market at present.Usually, the granularity of said oxide compound is the 200-300 order.It is not crucial especially that said granularity is implemented for the present invention, and the oxide compound that exceeds this size range also can use, but product productive rate and performance are had certain influence.
According to another kind of preferred implementation of the present invention, described carbonate is one or more carbonate that are selected from lime carbonate, yellow soda ash, magnesiumcarbonate, salt of wormwood, Calcium hydrogen carbonate, sodium hydrogencarbonate, Magnesium hydrogen carbonate or saleratus.Described carbonate all is product sold on market at present.Usually, the granularity of said oxide compound is the 200-300 order.Said granularity implements there is not special influence for the present invention, and the oxide compound that exceeds this size range also can use, but just can influence speed of response.
, preferably in air, under temperature 320-380 ℃, carried out preoxidation 1.2-2.8 hour with after additive mixes at said coal-tar pitch.More preferably, under temperature 340-360 ℃, carried out preoxidation 1.5-2.5 hour.Most preferably, under temperature 340-360 ℃, carried out preoxidation 1.8-2.2 hour.
Said mixture after the preoxidation again under inert atmosphere, kept constant temperature 0.8-2.0 hour down at temperature 400-600 ℃.Preferably, kept constant temperature 1.0-1.8 hour down, more preferably kept constant temperature 1.2-1.6 hour down, most preferably kept constant temperature 1.2-1.6 hour down at temperature 480-520 ℃ at temperature 450-550 ℃ at temperature 420-580 ℃.
In the present invention, described inert atmosphere is the inert atmosphere of nitrogen, argon gas or nitrogen and ar mixture.Preferably, described inert atmosphere is nitrogen or argon gas.More preferably, described inert atmosphere is a nitrogen.
Implementing the employed equipment of this step is normally used in the art equipment, and this equipment can more accurate ground controlled temperature, for example the precision of controlled temperature be ± 2 ℃.This equipment can also be realized sealing, and the atmosphere that remains in the entire reaction course can not change because of leakage.
B, let step A) product (being the preoxidation bitumen product) that obtains with in said product weight 300-900 weight % strongly alkaline compound activator mix; In activation furnace, under protection of inert gas, be heated to 750 ℃-900 ℃ then; Under this temperature, kept 0.5-1.5 hour again, obtain a kind of activation products.
In the present invention, described activation should be appreciated that it is that a kind of preoxidation coal-tar pitch that can make reaches the method with certain adsorption activity, and coal-tar pitch has higher specific surface area like this.
Described acvator should be appreciated that be a kind of can the alkaline material of etching bituminous, therefore, every material with this performance can be as acvator of the present invention.
For example, preferably one or more are selected from the acvator of KOH, NaOH, LiOH, KOH/NaOH, KOH/LiOH or NaOH/LiOH mixture to described acvator.
More preferably be selected from KOH, NaOH, LiOH, KOH/NaOH or KOH/LiOH mixture.
Most preferably be selected from KOH, NaOH or KOH/NaOH mixture.
In step (B), in preoxidation pitch weight, the 300-900 weight % of the preferably preoxidation bitumen product of amount of said strongly alkaline compound acvator more preferably is 500-800 weight %, most preferably is 500-700 weight %.
In the present invention, if the amount of said strongly alkaline compound acvator is lower than 300 weight %, the specific surface area that sample then can occur is low excessively; If be higher than 900 weight %, the specific surface area that sample then can occur is low excessively.
In the present invention, the granularity of said strongly alkaline compound acvator is not crucial, and is big or too little so long as not too.
In the present invention, can use normally used in the art corrosion-resistant mixing equipment that said preoxidation bitumen product is mixed with said strongly alkaline compound acvator.Described corrosion-resistant mixing equipment for example is a nickel crucible.
Then in activation furnace, carry out activation after preoxidation bitumen product and the said strongly alkaline compound activator mix.
In the present invention, described activation furnace should be appreciated that it is a kind ofly can let said strongly alkaline compound acvator make steps A) obtain preoxidation pitch activatory equipment, for example, the crucible electrical resistance furnace equipment of producing in Beijing Electric Stove Factory that people in the art know.
Said preoxidation bitumen product and strongly alkaline compound activating mixtures preferably are heated to 750 ℃-900 ℃ under protection of inert gas, under this temperature, kept 0.5-1.5 hour again.
More preferably be heated to 800 ℃-900 ℃, under this temperature, kept 0.8-1.2 hour again.
Most preferably be heated to 850 ℃-900 ℃, under this temperature, kept 1.0-1.2 hour again.
Here, described inert atmosphere is the inert atmosphere of nitrogen, argon gas or nitrogen and ar mixture.Preferably, described inert atmosphere is nitrogen or argon gas.More preferably, described inert atmosphere is a nitrogen.
The activation products that C, step B obtain use sanitising agent to clean, and carry out drying then, can make described active-carbon-microball material like this.
In the present invention, said cleaning is to use sanitising agent to remove the impurity that said activation products exist.
Preferably one or more are selected from the sanitising agent of zero(ppm) water, ethanol, acetone or ether to described sanitising agent.
More preferably be zero(ppm) water, ethanol or ether.
Most preferably be zero(ppm) water or ethanol.
Activation products need be carried out drying treatment after cleaning.So-called drying is to remove the sanitising agent or the small amount of moisture that possibly exist in the activation products.
Withering temperature need be selected according to the sanitising agent kind of using, and this selection is that the technician in present technique field knows.
Carrying out the employed equipment of drying treatment is the normally used drying plant in present technique field, for example vacuum drying oven, air blast thermostatic drying chamber.
Adopt the product needed of the inventive method preparation to analyze the absorption property evaluation.
Use the S-4700 scanning electronic microscope observation of Japanese Hitachi company to adopt the product appearance of the inventive method preparation.
(40kv 40mA), uses CuK to use the Japanese Rigaku D/MAX2500 VB2+/PC of company type X-ray diffractometer of science
αGamma ray source scans at 0 °-5 ° and 5 °-90 °, analyzes the structure of the product that adopts the inventive method preparation.
Use the ASAP-2010 type analysis instrument of U.S. Micromeritics company, detect the BET specific surface area of the product that adopts the inventive method preparation, total hole pore volume, mesopore volume and mean pore size.
The intelligent analyser for gravity of IGA-003 type of use Britain Hiden company detects the absorption property of the product that adopts the inventive method preparation.
Adopt the active-carbon-microball of the inventive method preparation to can be used as the adsorption technology field that sorbent material is used for gases such as hydrogen and carbonic acid gas, can be used for technical fields such as ultracapacitor, pharmacy, support of the catalyst
[beneficial effect]
Sample of the present invention not only has high specific surface area and mesopore content, and has the good adsorption ability; The preparation technology of this invention is simple, is prone to row, environmental protection, can not produce poisonous, deleterious material and gas, and cost is low; Can be applicable to the electrode materials of energy storage material and ultracapacitor.
[description of drawings]
Fig. 1 is the electron scanning micrograph of active-carbon-microball before the activation
Fig. 2 is the electron scanning micrograph of active-carbon-microball after the activation
[embodiment]
Embodiment 1: the preparation method of active-carbon-microball of the present invention.
Preparation process is following:
A, the QM-1SP planetary ball mill disintegrating apparatus that uses Nanjing Univ. Instrument Factory to produce are pulverized 200 orders with the coal-tar pitch of National standard GB/T2290-94; Take by weighing comminuted coal pitch 100 grams; Add 18 gram nanometer zirconium oxide ceramic flour additive agents toward said coal-tar pitch, in the air dry oven of packing into after mixing with glass rod, in air, under 350 ℃ of temperature, carried out preoxidation 1.8 hours; Then under nitrogen atmosphere; Keep constant temperature 1.2 hours down for 480 ℃ in temperature, naturally cool to room temperature again, obtain 109.8 gram preoxidation products; Use Hitachi S-4700 scanning electronic microscope observation result to list in Fig. 1, this figure shows that this preoxidation product is spherical basically.
B, let step A) product that obtains with in said product weight 500 weight % sodium hydroxide activator mix; In vertical activation furnace, under the nitrogen gas protection, be heated to 820 ℃ then; Under this temperature, kept 1.0 hours again; Obtain a kind of activation products, use Hitachi S-4700 scanning electronic microscope observation result to list in Fig. 2, this figure shows that this activation products are elliposoidal basically.
Activation products that C, step B obtain use zero(ppm) water to clean twice, under 85 ℃ of-0.1PMa and temperature, carry out drying at vacuum drying oven then, make active-carbon-microball material of the present invention like this.
The active-carbon-microball material that present embodiment obtains uses equipment and the instrument in present specification, described to analyze, and its analytical results is listed in the table 1.
Embodiment 2: the preparation method of active-carbon-microball of the present invention.
According to implementing with the same manner of embodiment 1, difference is only to be to use nano titanium carbide ceramics powder additive.
The active-carbon-microball material that present embodiment obtains also uses equipment and the instrument in present specification, described to analyze, and its analytical results is listed in the table 1.
Embodiment 3: the preparation method of active-carbon-microball of the present invention.
According to implementing with the same manner of embodiment 1, difference is only to be to use the nano-si 3 n 4 ceramics flour additive agent.
The active-carbon-microball material that present embodiment obtains also uses equipment and the instrument in present specification, described to analyze, and its analytical results is listed in the table 1.
Embodiment 4: the preparation method of active-carbon-microball of the present invention.
According to implementing with the same manner of embodiment 1, difference is only to be to use nano-zirconium carbide ceramics powder additive.
The active-carbon-microball material that present embodiment obtains also uses equipment and the instrument in present specification, described to analyze, and its analytical results is listed in the table 1.
Embodiment 5: the preparation method of active-carbon-microball of the present invention.
According to implementing with the same manner of embodiment 1, difference is only to be to use lime carbonate carbonate additive.
The active-carbon-microball material that present embodiment obtains also uses equipment and the instrument in present specification, described to analyze, and its analytical results is listed in the table 1.
Embodiment 6: the preparation method of active-carbon-microball of the present invention.
According to implementing with the same manner of embodiment 1, difference is only to be to use silica additive.
The active-carbon-microball material that present embodiment obtains also uses equipment and the instrument in present specification, described to analyze, and its analytical results is listed in the table 1.
Embodiment 7: the preparation method of active-carbon-microball of the present invention.
According to implementing with the same manner of embodiment 1, difference is only to be to use the Natural manganese dioxide additive.
The active-carbon-microball material that present embodiment obtains also uses equipment and the instrument in present specification, described to analyze, and its analytical results is listed in the table 1.
Embodiment 8: the preparation method of active-carbon-microball of the present invention.
According to implementing with the same manner of embodiment 1, difference is only to be to use the iron protoxide additive.
The active-carbon-microball material that present embodiment obtains also uses equipment and the instrument in present specification, described to analyze, and its analytical results is listed in the table 1.
The comparative example 1
According to implementing with the same manner of embodiment 1, difference is not use any additives.
The active-carbon-microball material that present embodiment obtains also uses equipment and the instrument in present specification, described to analyze, and its analytical results is listed in the table 1.
Table 1
Can find out by table 1: add the BET that additive makes sample, pore volume, mesopore volume, mean pore sizes etc. all are significantly improved.The difference of additive, the performance of sample is also different.According to the difference of demand, can select different additives.
Embodiment 9: the preparation method of active-carbon-microball of the present invention.
Preparation process is following:
A, the QM-1SP planetary ball mill disintegrating apparatus that uses Nanjing Univ. Instrument Factory to produce are pulverized 200 orders with the coal-tar pitch of National standard GB/T2290-94; Take by weighing comminuted coal pitch 100 grams; Add 14 gram Natural manganese dioxide additives toward said coal-tar pitch, in the convection oven equipment of packing into after mixing with glass rod, in air, under 360 ℃ of temperature, carried out preoxidation 1.5 hours; Then under argon gas atmosphere; Keep constant temperature 1.6 hours down for 520 ℃ in temperature, naturally cool to room temperature again, obtain 109.6 gram preoxidation products.
B, let step A) product that obtains with in said product weight 600 weight % sodium hydroxide activator mix, in vertical activation furnace, be heated to 800 ℃ down then in the nitrogen gas protection, maintenance 1.2 hours under this temperature again obtains a kind of activation products;
Activation products that C, step B obtain use absolute ethyl alcohol to clean twice, under 85 ℃ of-0.1PMa and temperature, carry out drying at vacuum drying oven then, make active-carbon-microball material of the present invention like this.
The active-carbon-microball material that present embodiment obtains uses equipment and the instrument in present specification, described to analyze, and its analytical results is listed in the table 2.
Embodiment 10: the preparation method of active-carbon-microball of the present invention.
Preparation process is following:
A, the QM-1SP planetary ball mill disintegrating apparatus that uses Nanjing Univ. Instrument Factory to produce are pulverized 300 orders with the coal-tar pitch of National standard GB/T2290-94; Take by weighing comminuted coal pitch 100 grams; Add 20 gram Natural manganese dioxide additives toward said coal-tar pitch, in the air dry oven equipment of packing into after mixing with glass rod, in air, under 320 ℃ of temperature, carried out preoxidation 2.5 hours; Then under argon gas atmosphere; Keep constant temperature 1.8 hours down for 550 ℃ in temperature, naturally cool to room temperature again, obtain 109.8 gram preoxidation products.
B, let step A) product that obtains with in said product weight 500 weight % sodium hydroxide activator mix, in vertical activation furnace, be heated to 850 ℃ down then in the nitrogen gas protection, maintenance 0.8 hour under this temperature again obtains a kind of activation products;
Activation products that C, step B obtain use absolute ethyl alcohol to clean twice, under 85 ℃ of-0.1PMa and temperature, carry out drying at vacuum drying oven then, make active-carbon-microball material of the present invention like this.
The active-carbon-microball material that present embodiment obtains uses equipment and the instrument in present specification, described to analyze, and its analytical results is listed in the table 2.
Embodiment 11: the preparation method of active-carbon-microball of the present invention.
Preparation process is following:
A, the QM-1SP planetary ball mill disintegrating apparatus that uses Nanjing Univ. Instrument Factory to produce are pulverized 400 orders with the coal-tar pitch of National standard GB/T2290-94; Take by weighing comminuted coal pitch 100 grams; Add 30 gram Natural manganese dioxide additives toward said coal-tar pitch, in the air dry oven equipment of packing into after mixing with glass rod, in air, under 400 ℃ of temperature, carried out preoxidation 1.0 hours; Then under argon gas atmosphere; Keep constant temperature 0.8 hour down for 600 ℃ in temperature, naturally cool to room temperature again, obtain 109.5 gram preoxidation products.
B, let step A) product that obtains with in said product weight 700 weight % sodium hydroxide activator mix, in vertical activation furnace, be heated to 750 ℃ down then in the nitrogen gas protection, maintenance 1.5 hours under this temperature again obtains a kind of activation products;
Activation products that C, step B obtain use absolute ethyl alcohol to clean twice, under 85 ℃ of-0.1PMa and temperature, carry out drying at vacuum drying oven then, make active-carbon-microball material of the present invention like this.
The active-carbon-microball material that present embodiment obtains uses equipment and the instrument in present specification, described to analyze, and its analytical results is listed in the table 2.
Embodiment 12: the preparation method of active-carbon-microball of the present invention.
Preparation process is following:
A, the QM-1SP planetary ball mill disintegrating apparatus that uses Nanjing Univ. Instrument Factory to produce are pulverized 250 orders with the coal-tar pitch of National standard GB/T2290-94; Take by weighing comminuted coal pitch 100 grams; Add 10 gram Natural manganese dioxide additives toward said coal-tar pitch, in the air dry oven equipment of packing into after mixing with glass rod, in air, under 300 ℃ of temperature, carried out preoxidation 3.0 hours; Then under argon gas atmosphere; Keep constant temperature 2.0 hours down for 400 ℃ in temperature, naturally cool to room temperature again, obtain 109.8 gram preoxidation products.
B, let step A) product that obtains with in said product weight 800 weight % sodium hydroxide activator mix, in vertical activation furnace, be heated to 900 ℃ down then in the nitrogen gas protection, maintenance 0.5 hour under this temperature again obtains a kind of activation products;
Activation products that C, step B obtain use ether to clean twice, under 85 ℃ of-0.1PMa and temperature, carry out drying at vacuum drying oven then, make active-carbon-microball material of the present invention like this.
The active-carbon-microball material that present embodiment obtains uses equipment and the instrument in present specification, described to analyze, and its analytical results is listed in the table 2.
The comparative example 2:
According to implementing with the same manner of embodiment 8, difference is not use any additives.
The active-carbon-microball material that present embodiment obtains also uses equipment and the instrument in present specification, described to analyze, and its analytical results is listed in the table 2.
Table 2
Can find out by table 2: add additive the sample various aspects of performance is got a promotion, different activated temperature and soak time, all influential to the performance of sample each side.Therefore, choosing suitable additive and suitable activation condition is key of the present invention.
Claims (6)
1. an active-carbon-microball is characterized in that this active-carbon-microball by containing the carbosphere of forming in the above decolorizing carbon sill of 90.0 weight % of said active-carbon-microball gross weight, and its diameter is 10-40nm, and the BET specific surface area is 2500-3600m
2/ g, total hole pore volume 2.5-3.2cm
3/ g, mesopore volume 1.6-2.2cm
3/ g, mean pore size 2.8-3.1nm.
2. according to the said active-carbon-microball of claim 1, it is characterized in that this active-carbon-microball is the above decolorizing carbon sill of 93.0 weight % that contains in said active-carbon-microball gross weight, its diameter is 15-35nm, and the BET specific surface area is 2600-3500m
2/ g, total hole pore volume 2.6-3.0cm
3/ g, mesopore volume 1.8-2.0cm
3/ g, mean pore size 2.8-3.0nm.
3. according to the preparation method of claim 1 or 2 said active-carbon-microballs, it is characterized in that the step of this method is following:
A, according to coal-tar pitch weight meter; Add the additive that 10-30 weight % is selected from nano-ceramic powder, MOX, silicon-dioxide or carbonate toward said coal-tar pitch; Mixing the back carried out under temperature 300-400 ℃ preoxidation 1.0-3.0 hour in air; Under inert atmosphere, kept constant temperature 0.8-2.0 hour down then at temperature 400-600 ℃;
The granularity of said coal-tar pitch is the 200-400 order;
Described nano-ceramic powder is one or more nano-ceramic powders that are selected from nano zircite, nanometer silicon carbide, nano titanium carbide, nano yttrium oxide, nano-silicon nitride, Nano titanium nitride, nano aluminum nitride or nano-zirconium carbide;
Described MOX is that one or more are selected from aluminum oxide, Natural manganese dioxide, red stone, iron protoxide or zirconic MOX;
Described carbonate is one or more carbonate that are selected from lime carbonate, yellow soda ash, magnesiumcarbonate, salt of wormwood, Calcium hydrogen carbonate, sodium hydrogencarbonate, Magnesium hydrogen carbonate or saleratus;
B, let step A) product that obtains with in said product weight 300-900 weight % strongly alkaline compound activator mix; In activation furnace, under protection of inert gas, be heated to 750 ℃-900 ℃ then; Under this temperature, kept 0.5-1.5 hour again, obtain a kind of activation products;
The activation products that C, step B obtain use sanitising agent to clean, and carry out drying then, can make described active-carbon-microball material like this.
4. preparation method according to claim 3 is characterized in that described inert atmosphere is the inert atmosphere of nitrogen, argon gas or nitrogen and ar mixture.
5. preparation method according to claim 3 is characterized in that described acvator is one or more acvators that are selected from KOH, NaOH, LiOH and composition thereof.
6. preparation method according to claim 3 is characterized in that described sanitising agent is one or more sanitising agents that are selected from zero(ppm) water, ethanol, acetone or ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910241779A CN101717085B (en) | 2009-12-07 | 2009-12-07 | Activated carbon microspheres and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910241779A CN101717085B (en) | 2009-12-07 | 2009-12-07 | Activated carbon microspheres and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101717085A CN101717085A (en) | 2010-06-02 |
| CN101717085B true CN101717085B (en) | 2012-09-05 |
Family
ID=42431734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910241779A Expired - Fee Related CN101717085B (en) | 2009-12-07 | 2009-12-07 | Activated carbon microspheres and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101717085B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102031171A (en) * | 2011-01-04 | 2011-04-27 | 北京化工大学 | Method for removing carbon dioxide in natural gas by utilizing novel high specific surface active carbon material |
| CN102431992B (en) * | 2011-09-22 | 2013-07-24 | 安徽工业大学 | Method for preparing porous carbon material by using magnesium oxide template in cooperation with activation of potassium hydroxide |
| CN102491320B (en) * | 2011-11-28 | 2013-06-05 | 福州大学 | Pitch-based active carbon with superhigh specific surface area and preparation method thereof |
| CN102838105B (en) * | 2012-09-11 | 2014-03-12 | 安徽工业大学 | Preparation method of grading porous carbon material |
| TWI511923B (en) * | 2013-09-26 | 2015-12-11 | China Steel Corp | Activated carbon microspheres with high specific surface area for electrode sheet and capacitor and method of manufacturing the same |
| CN103474253B (en) * | 2013-09-30 | 2016-01-06 | 武汉理工大学 | Based on function of surface functional group porous carbon microsphere electrode material and preparation method thereof, its ultracapacitor and preparation method |
| CN103996833A (en) * | 2014-06-12 | 2014-08-20 | 上海第二工业大学 | Modified hard carbon microsphere negative material for lithium ion battery and preparation method of material |
| CN104944425A (en) * | 2015-07-02 | 2015-09-30 | 神华集团有限责任公司 | Preparation method of active carbon |
| CN106986340A (en) * | 2017-04-20 | 2017-07-28 | 神华集团有限责任公司 | Super-activated carbon, and preparation method thereof |
| CN108163854A (en) * | 2017-12-25 | 2018-06-15 | 河南师范大学 | For the universality preparation method of the porous C catalyst of organic pollutants in water body degradation |
| KR102113719B1 (en) * | 2018-08-31 | 2020-05-21 | 주식회사 티씨케이 | Activated carbon and its manufacturing method |
| CN110465267B (en) * | 2019-07-08 | 2022-08-19 | 天津大学 | Method for preparing nitrogen-sulfur-rich porous adsorbent material from oil sand asphaltene and application |
| CN111920968B (en) * | 2020-08-26 | 2023-04-07 | 成都纽瑞特医疗科技股份有限公司 | Visual radioactive carbon microsphere and preparation method and application thereof |
| CN113604843B (en) * | 2021-07-02 | 2023-04-21 | 北京化工大学 | Low-load Pt/C catalyst hydrogen diffusion anode and preparation method and application thereof |
| CN113731361A (en) * | 2021-09-06 | 2021-12-03 | 山西华青环保股份有限公司 | Preparation method of magnesium oxide loaded activated carbon |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB699470A (en) * | 1950-08-10 | 1953-11-11 | Standard Oil Dev Co | Improvements in or relating to the production of microspherical carbon particles |
| CN85102191A (en) * | 1985-04-01 | 1986-08-06 | 中国科学院成都有机化学研究所 | Microspheroidal gac and preparation method |
| CN1250024A (en) * | 1998-10-07 | 2000-04-12 | 中国科学院山西煤炭化学研究所 | Preparation of middle-pore asphalt-base globular active carbon |
| CN101081698A (en) * | 2006-09-15 | 2007-12-05 | 天津大学 | Preparation method of active meson-phase charcoal micro-balloon with high-ratio surface area and high mesoporosity |
| CN101143720A (en) * | 2006-09-29 | 2008-03-19 | 北京化工大学 | Active carbon micro-sphere absorption material and preparation method thereof |
-
2009
- 2009-12-07 CN CN200910241779A patent/CN101717085B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB699470A (en) * | 1950-08-10 | 1953-11-11 | Standard Oil Dev Co | Improvements in or relating to the production of microspherical carbon particles |
| CN85102191A (en) * | 1985-04-01 | 1986-08-06 | 中国科学院成都有机化学研究所 | Microspheroidal gac and preparation method |
| CN1250024A (en) * | 1998-10-07 | 2000-04-12 | 中国科学院山西煤炭化学研究所 | Preparation of middle-pore asphalt-base globular active carbon |
| CN101081698A (en) * | 2006-09-15 | 2007-12-05 | 天津大学 | Preparation method of active meson-phase charcoal micro-balloon with high-ratio surface area and high mesoporosity |
| CN101143720A (en) * | 2006-09-29 | 2008-03-19 | 北京化工大学 | Active carbon micro-sphere absorption material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 刘皓等.高比表面积中间相沥青基活性炭微球的制备.《科学技术与工程》.2009,第9卷(第3期), * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101717085A (en) | 2010-06-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101717085B (en) | Activated carbon microspheres and preparation method thereof | |
| Tseng | Physical and chemical properties and adsorption type of activated carbon prepared from plum kernels by NaOH activation | |
| Liou | Evolution of chemistry and morphology during the carbonization and combustion of rice husk | |
| Liou | Preparation and characterization of nano-structured silica from rice husk | |
| Martinez et al. | Preparation and characteristics of activated carbon from olive stones and walnut shells | |
| Wu et al. | Preparation and characteristics of medicinal activated carbon powders by CO2 activation of peanut shells | |
| CN110064367A (en) | A kind of biomass-based activated carbon microballon and its preparation method and application | |
| CN108483444A (en) | A kind of preparation method of the multiporous biological carbon composite of alpha-FeOOH nano-rod load | |
| CN105536660B (en) | A kind of preparation method of nano-silver loaded oil-tea camellia husks pyrolysis carbosphere | |
| CN109809403A (en) | A kind of preparation method and application of the biogas residue matrix activated carbon with high absorption property | |
| CN105833850B (en) | A kind of method that Fe/C compound porous structure materials are prepared with limonite | |
| CN110813233A (en) | Method for adsorbing heavy metal ions in soil by coconut shell charcoal | |
| Hao et al. | Preparation and characterization of porous ceramics with low-grade diatomite and oyster shell | |
| CN110316734A (en) | A kind of industrial silicon production carbonaceous reducing agent pelletizing and preparation method thereof | |
| CN105817212B (en) | A kind of method for preparing Fe/C compound porous structure materials with deposition siderite | |
| CN115400729B (en) | Method for preparing magnetic biochar by using titanium gypsum | |
| CN102863025A (en) | Preparation method of piece-shaped tungsten disulfide nanometer lubricating oil additive | |
| CN102432326A (en) | Porous carbon-titanium dioxide compound material and preparation method thereof | |
| CN109368632A (en) | Graphitized carbon material and preparation method thereof | |
| PANHWAR et al. | Utilization of biomass (Rice straw) to produce activated charcoal through single stage pyrolysis process. | |
| CN109192524B (en) | Preparation method of activated carbon-graphene composite porous material | |
| CN108686664B (en) | Application method of multifunctional metal catalyst in biomass catalytic pyrolysis process | |
| Kan et al. | Molten salt synthesis of porous chromium carbide/carbon biomorphic ceramics for Pb2+ removal from water | |
| CN102839033A (en) | Biomass fuel passivation method and application of passivation products in iron ore sintering | |
| Hu et al. | Li4SiO4 pellets templated by rice husk for cyclic CO2 capture: Insight into the modification mechanism |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120905 Termination date: 20151207 |
|
| EXPY | Termination of patent right or utility model |