CN105016338A - Activated carbon microsphere and preparation method thereof - Google Patents
Activated carbon microsphere and preparation method thereof Download PDFInfo
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- CN105016338A CN105016338A CN201510449937.1A CN201510449937A CN105016338A CN 105016338 A CN105016338 A CN 105016338A CN 201510449937 A CN201510449937 A CN 201510449937A CN 105016338 A CN105016338 A CN 105016338A
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- activated carbon
- carbon microballon
- preparation
- phosphoric acid
- microballon
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Abstract
The invention discloses a preparation method of an activated carbon microsphere. The preparation method comprises the steps of dissolving resorcinol, hexamethylene tetramine and boric acid according to the mass ratio of 10:(1-8):(1-8), and reacting in a sealed environment with the temperature of 80-180 DEG C for 4-12 hours; drying the reaction product, and grinding to obtain boron-containing organic microsphere powder; adding the boron-containing organic microsphere powder and phosphoric acid into a proper amount of deionized water according to the mass ratio of 1:(1-6), drying after sufficiently mixing, then, activating at the temperature of 400-700 DEG C for 1 hour, and washing an activator by using a hydrochloric acid solution and deionized water to obtain an activated carbon microsphere containing boron phosphate; soaking the activated carbon microsphere containing boron phosphate by using a caustic alkali solution to remove boron phosphate, filtering and washing until the filtrate is neutral; and finally, drying to obtain the activated carbon microsphere. The invention also provides the activated carbon microsphere obtained by using the method.
Description
Technical field
The present invention relates to a kind of activated carbon microballon and preparation method thereof, particularly a kind of have activated carbon microballon of high-ratio surface sum height pore volume activity and preparation method thereof.
Background technology
Activated carbon microballon has the features such as good fluidity, packing density is high, stable chemical nature, physical strength are high, specific surface area is large, pore texture is abundant, has broad application prospects in fields such as absorption and energy storage.
In prior art, generally with phenol or Resorcinol and formaldehyde or hexamethylenetetramine for raw material, prepare micron order resin balls by hydrothermal method, suspension condensation methods, then through charing and the described activated carbon microballon of activation preparation.In reactivation process, with carbonic acid gas or water vapour for activated media carries out the physically activated spherical morphology that can ensure activated carbon microballon.But the specific surface area of the activated carbon microballon obtained is larger, and yield is lower, physical strength is also lower.Higher specific surface area and higher yield can be obtained for activator carries out chemical activation with potassium hydroxide or zinc chloride.But, due to the deep-etching effect of potassium hydroxide and zinc chloride activation agent, the sphericity of activated carbon microballon is easy to be destroyed, and easy etching apparatus.
Summary of the invention
The invention provides a kind of activated carbon microballon and preparation method thereof, can effectively solve the problem.
A preparation method for activated carbon microballon, comprises the steps:
Resorcinol, hexamethylenetetramine and boric acid are dissolved in appropriate first solvent 10:1 ~ 8:1 ~ 8 in mass ratio, and 80 ~ 180 DEG C of reactions under closed environment;
Reaction product is dried, grinds, obtain the organic micro-spheres powder of boracic;
The organic micro-spheres powder of boracic and phosphoric acid are added to appropriate second solvent and fully mix post-drying in 1:1 ~ 6 in mass ratio, then activates at 400 ~ 700 DEG C of temperature, and wash activator, obtain the activated carbon microballon of phosphoric acid boron;
Soak the activated carbon microballon of phosphoric acid boron with eccysis borophosphoric acid with caustic solution, filtering and washing to filtrate is neutrality, finally dries, obtains described activated carbon microballon.
Further, described first solvent and the second solvent are deionized water.
Further, at 400 ~ 700 DEG C of temperature, activate 1 hour, and with hydrochloric acid soln and deionized water wash activator, wherein, hydrochloric acid soln is the hydrochloric acid soln of 1M ~ 5M.
Further, the temperature rise rate of described reactivation process is 3 ~ 5 DEG C/min.
Further, described reactivation process is carried out in rare gas element.
Further, described caustic alkali is sodium hydroxide, potassium hydroxide or the mixture of the two.
Further, described caustic solution is the caustic solution of 1 ~ 5M.
The activated carbon microballon that above-mentioned preparation method obtains, wherein, specific surface area 1400 ~ 3000 m of described activated carbon microballon
2/ g, total pore volume is 0.4 ~ 1.7 m
3/ g.
Further, the diameter of described activated carbon microballon is 1 ~ 20 μm.
A kind of activated carbon microballon provided by the invention and preparation method thereof, by the polyreaction of boric acid with Resorcinol and hexamethylenetetramine is combined, obtain the organic micro-spheres powder of boracic, in phosphoric acid activation process subsequently, the hard template of the borophosphoric acid simultaneously utilizing the chemical activation effect of phosphoric acid and reactivation process situ to generate is used for the specific surface area of carbon microspheres and pore volume and then the activated carbon microballon that acquisition physical strength is high.
Accompanying drawing explanation
The schema preparing activated carbon microballon that Fig. 1 provides for the embodiment of the present invention.
Fig. 2 is the stereoscan photograph of the activated carbon microballon obtained by the present embodiment 1.
Fig. 3 is the X ray diffracting spectrum of activated carbon microballon before and after alkali cleaning obtained by the present embodiment 1.
Fig. 4 is the nitrogen adsorption/desorption curve of the activated carbon microballon obtained by the present embodiment 1.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.Be understandable that, specific embodiment described herein is only for explaining the present invention, but not limitation of the invention.It also should be noted that, for convenience of description, illustrate only part related to the present invention in accompanying drawing but not entire infrastructure.
Please refer to Fig. 1, a kind of preparation method of activated carbon microballon, comprises the steps:
S1, is dissolved in appropriate first solvent 10:1 ~ 8:1 ~ 8 in mass ratio by Resorcinol, hexamethylenetetramine and boric acid, and under closed environment 80 ~ 180 DEG C reaction 4 ~ 12h;
S2, dries reaction product, grinds, obtain the organic micro-spheres powder of boracic;
S3, in mass ratio by the organic micro-spheres powder of boracic and phosphoric acid is added to appropriate second solvent and fully mixes post-drying in 1:1 ~ 6, then activate at 400 ~ 700 DEG C of temperature, and with hydrochloric acid soln and deionized water wash activator, obtain the activated carbon microballon of phosphoric acid boron;
S4, soaks the activated carbon microballon of phosphoric acid boron with eccysis borophosphoric acid with caustic solution, and filtering and washing to filtrate is neutrality, finally dries, obtains described activated carbon microballon.
In step sl, after described Resorcinol, hexamethylenetetramine and boric acid can being dissolved in appropriate first solvent, be transferred in stainless steel cauldron airtight, and to control temperature of reaction be 80 ~ 180 DEG C, hydro-thermal reaction 4 ~ 12h.Described first solvent can dissolve above-mentioned solute for deionized water etc. and the solvent do not reacted with above-mentioned solute.
In step s3, described hydrochloric acid soln can be the hydrochloric acid soln of 1M ~ 5M.Described reactivation process is chemical activation, and its temperature rise rate can be 3 ~ 5 DEG C/min, and reactivation process can be carried out in rare gas element.Described second solvent can be deionized water etc.Preferably, described activation temperature can be 500 ~ 600 DEG C of temperature.
In step s3, described caustic solution can be the caustic solution of 1 ~ 5M, and described caustic alkali is preferably sodium hydroxide, potassium hydroxide or the mixture of the two.Preferred, the organic micro-spheres powder of described boracic and phosphoric acid 1:4 ~ 1:5 in mass ratio.Experiment proves, when the organic micro-spheres powder of described boracic and phosphoric acid in mass ratio 1:4 ~ 1:5 can obtain very high specific surface area and total pore volume.
The preparation method that the embodiment of the present invention provides, there is following beneficial effect: by the polyreaction of boric acid with Resorcinol and hexamethylenetetramine being combined, obtain the organic micro-spheres powder of boracic, in phosphoric acid activation process subsequently, the hard template of the borophosphoric acid simultaneously utilizing the chemical activation effect of phosphoric acid and reactivation process situ to generate is used for the specific surface area of carbon microspheres and pore volume and then the activated carbon microballon that acquisition physical strength is high.
By the activated carbon microballon that aforesaid method obtains, wherein, the diameter of described activated carbon microballon is 1 ~ 20 μm, specific surface area 1400 ~ 3000 m
2/ g, the total pore volume of described activated carbon microballon is 0.4 ~ 1.7 m
3/ g.
Embodiment 1:
By Resorcinol, hexamethylenetetramine and boric acid in mass ratio 10:4.2:4 be dissolved in appropriate amount of deionized water, be then transferred in stainless steel cauldron, airtight and at 140 DEG C of hydro-thermal reaction 4h; Reaction product directly dried, grinding, acquires boracic organic micro-spheres powder; By organic micro-spheres powder and phosphoric acid in mass ratio 1:3 be added to appropriate amount of deionized water and fully mix post-drying, then 600 DEG C of chemical activations 1 hour, by 2M aqueous hydrochloric acid and deionized water wash activation products, obtain the activated carbon microballon of phosphoric acid boron; Soaked by the activated carbon microballon 2M sodium hydroxide solution of phosphoric acid boron obtained, eccysis borophosphoric acid, then filters, and is neutral repeatedly, dries, namely obtain activated carbon microballon with deionized water wash to filtrate.
Please refer to Fig. 2, Fig. 2 is the stereoscan photograph of the activated carbon microballon obtained by the present embodiment.As we can see from the figure, the diameter of described activated carbon microballon is at about 1 ~ 20 μm, and sphericity is better.Fig. 3 is the X ray diffracting spectrum of activated carbon microballon before and after alkali cleaning obtained by the present embodiment, proves that caustic scrubbing step effectively eliminates borophosphoric acid.Fig. 4 is the nitrogen adsorption/desorption curve of the activated carbon microballon obtained by the present embodiment.As calculated, prepared activated carbon microballon its specific surface area before alkali cleaning is 1361 m
2/ g, total pore volume is 0.552 cm
3/ g; After alkali cleaning, specific surface area reaches 1820 m
2/ g, total pore volume reaches 0.998 cm
3/ g.
Embodiment 2:
The present embodiment is substantially the same manner as Example 1, and difference is, activation temperature is 500 DEG C.The activated carbon microballon obtained its specific surface area and total pore volume after alkali cleaning are respectively 1717 m
2/ g and 0.912 cm
3/ g.
Embodiment 3:
The present embodiment is substantially the same manner as Example 1, and difference is, the mass ratio of machine microballoon powder and phosphoric acid is 1:4.The activated carbon microballon obtained its specific surface area and total pore volume after alkali cleaning are respectively 2730 m
2/ g and 1.53 cm
3/ g.
Embodiment 4:
The present embodiment is substantially the same manner as Example 1, and difference is, the mass ratio of organic micro-spheres powder and phosphoric acid is 1:5.The activated carbon microballon obtained its specific surface area and total pore volume after alkali cleaning are respectively 2954 m
2/ g and 1.81 cm
3/ g.
Note, above are only preferred embodiment of the present invention and institute's application technology principle.Skilled person in the art will appreciate that and the invention is not restricted to specific embodiment described here, various obvious change can be carried out for a person skilled in the art, readjust and substitute and can not protection scope of the present invention be departed from.Therefore, although be described in further detail invention has been by above embodiment, the present invention is not limited only to above embodiment, when not departing from the present invention's design, can also comprise other Equivalent embodiments more, and scope of the present invention is determined by appended right.
Claims (10)
1. a preparation method for activated carbon microballon, is characterized in that, comprises the steps:
Resorcinol, hexamethylenetetramine and boric acid are dissolved in the first solvent 10:1 ~ 8:1 ~ 8 in mass ratio, and 80 ~ 180 DEG C of reactions under closed environment;
Reaction product is dried, grinds, obtain the organic micro-spheres powder of boracic;
The organic micro-spheres powder of boracic and phosphoric acid are added to the second solvent and fully mix post-drying in 1:1 ~ 6 in mass ratio, then activates at 400 ~ 700 DEG C of temperature, and wash activator, obtain the activated carbon microballon of phosphoric acid boron;
Soak the activated carbon microballon of phosphoric acid boron with eccysis borophosphoric acid with caustic solution, filtering and washing to filtrate is neutrality, finally dries, obtains described activated carbon microballon.
2. the preparation method of activated carbon microballon according to claim 1, is characterized in that, described first solvent and the second solvent are deionized water.
3. the preparation method of activated carbon microballon according to claim 1, is characterized in that, describedly activates at 400 ~ 700 DEG C of temperature, and the step of washing activator comprises:
At 400 ~ 700 DEG C of temperature, activate 1 hour, and with hydrochloric acid soln and deionized water wash activator, wherein, hydrochloric acid soln is the hydrochloric acid soln of 1M ~ 5M.
4. the preparation method of activated carbon microballon according to claim 1, is characterized in that, the temperature rise rate of described reactivation process is 3 ~ 5 DEG C/min.
5. the preparation method of activated carbon microballon according to claim 1, is characterized in that, described reactivation process is carried out in rare gas element.
6. the preparation method of activated carbon microballon according to claim 1, is characterized in that, described caustic alkali is sodium hydroxide, potassium hydroxide or the mixture of the two.
7. the preparation method of activated carbon microballon according to claim 1, is characterized in that, described caustic solution is the caustic solution of 1 ~ 5M.
8. the preparation method of activated carbon microballon according to claim 1, is characterized in that, the organic micro-spheres powder of described boracic and phosphoric acid are 1:4 ~ 1:5 in mass ratio.
9. an activated carbon microballon for the preparation method acquisition of basis as described in any one of claim 1-7, is characterized in that, specific surface area 1400 ~ 3000 m of described activated carbon microballon
2/ g, total pore volume is 0.4 ~ 1.7 m
3/ g.
10. a basis activated carbon microballon as claimed in claim 8, is characterized in that, the diameter of described activated carbon microballon is 1 ~ 20 μm.
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| CN201510449937.1A CN105016338B (en) | 2015-07-28 | 2015-07-28 | Activated carbon microsphere and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153082A (en) * | 2011-04-25 | 2011-08-17 | 福建省将乐县乐洪活性炭有限公司 | Method for preparing wood activated carbon by phosphoric acid method |
| CN102774836A (en) * | 2012-07-18 | 2012-11-14 | 太仓市联林活性炭厂 | Process for preparing sawdust activated carbon by boric acid catalysis |
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2015
- 2015-07-28 CN CN201510449937.1A patent/CN105016338B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153082A (en) * | 2011-04-25 | 2011-08-17 | 福建省将乐县乐洪活性炭有限公司 | Method for preparing wood activated carbon by phosphoric acid method |
| CN102774836A (en) * | 2012-07-18 | 2012-11-14 | 太仓市联林活性炭厂 | Process for preparing sawdust activated carbon by boric acid catalysis |
Non-Patent Citations (1)
| Title |
|---|
| JOWITA LUDWINOWICZ ET AL.: "Effect of activating agents on the development of microporosity in polymeric-based carbon for CO2 adsorption", 《CARBON》 * |
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Granted publication date: 20170322 Termination date: 20200728 |