CN110064367A - A kind of biomass-based activated carbon microballon and its preparation method and application - Google Patents
A kind of biomass-based activated carbon microballon and its preparation method and application Download PDFInfo
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- CN110064367A CN110064367A CN201910359643.8A CN201910359643A CN110064367A CN 110064367 A CN110064367 A CN 110064367A CN 201910359643 A CN201910359643 A CN 201910359643A CN 110064367 A CN110064367 A CN 110064367A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
The invention discloses a kind of biomass-based activated carbon microballons and its preparation method and application.Preparation method the following steps are included: abandoned biomass powder is mixed with plurality of reagents and be stirred well at room temperature uniformly, obtain suspension；Suspension is transferred in reaction kettle after hydro-thermal, hydro-thermal carbon ball is obtained；The presoma of charcoal is obtained after water washing, drying after hydro-thermal carbon ball is cooling；The presoma of charcoal and nitrogenous object, activator are mixed in a certain proportion after grinding through roasting, washing, drying, the biomass-based activated carbon microballon is made, specific surface area is up to 1349.17~1685.68m2/g.The present invention is cheap with raw material, formula is simple, preparation condition is mild, product pattern spherical in shape and obtained activated carbon microballon are at room temperature to CO2With excellent absorption property and stable circular regeneration absorption property, preferable CO2/N2The advantages that adsorptive selectivity.
Description
Technical field
The invention belongs to CO2Absorbent fields, and in particular to a kind of biomass-based activated carbon microballon and preparation method thereof and
Using.
Background technique
Biomass is the animal and plant resource of certain accumulation and the general name from animals and plants waste, is unique on the earth
The renewable carbon energy, be known as " conventional fossil fuel substitute ", about produce 6,600,000,000 tons every year, wherein most agriculture is given up quilt
Burning disposal, utilization rate are extremely low.It is the maximum CO in the whole world with the thermal power plant that combustion of fossil fuel generates electricity2Emission source accounts for about
CO2The 35% of total release.After fuel combustion, precombustion and burning in three kinds of carbon catching methods, from the flue gas after burning
Middle capture CO2It is simplest method.Flue gas (200 DEG C of T <) after burning is mainly CO2And N2Mixture, but because of CO2
Divide it is lower cause its separating difficulty very big, in some sense, it has also become restrict 21 century world energy-saving and emission-reduction pattern weight
Big science problem.Therefore, to low temperature CO2It adsorbed, recycled with highly important strategic importance.
Hydro-thermal charring (HTC) refers in the pressure vessel of sealing, using biomass as raw material, takes water as a solvent and reacts
Medium, in the process for synthesizing rich carbon product under pressure and 150~375 DEG C of reaction temperature.With traditional thermochemical study method
It compares, HTC temperature is low, and raw material is not limited by moisture content, and energy consumption is few, CO2Burst size is few, has become a kind of efficient biology
Matter preprocessing means and biomass full constituent method for transformation；And hydro-thermal charcoal oxygen-containing functional group is abundant, surface chemical property is adjustable, hot
It is worth (HHV) height, is obtained in fields such as adsorption of metal ions, the preparation of porous carbon material, solid acid catalyst and clean energy resourcies
Some progress (Wu Yanjiao, Li Wei, Wu Qiong, wait the preparation of hydro-thermal charcoal, property and apply [J] chemical progress, and 2015,28
(1):121-130.).CN106629661A discloses the technique that a kind of bagasse prepares Nano carbon balls, and bagasse is placed in sulphur
In the mixed solution of acid, phosphoric acid and water, make the cellulose and hemicellulose dissolution in bagasse, and the solvent filter is filtered
Liquid, filtrate dissolve out bagasse small molecular sugar when hydro-thermal reaction, and small molecular sugar solution hydro-thermal method is recycled to prepare carbon ball.
This method simple process, raw material sources are extensive, but two kinds of acid solutions are used in preparation process, unfriendly to environment.
CN102219204A discloses a kind of preparation method of biomass-based colloidal carbon, and with diluted acid, concentrated acid, hydrolysed corn stalk is obtained respectively
The sugar acid solution of xylose and glucose is obtained, the charing of sugar acid solution in-situ polycondensation is prepared using xylose or glucose as presoma
Colloidal carbon sphere.This method salvage value is high, but operating process is more complex.
Traditional hydro-thermal method preparation carbon ball generally can use small molecule biomass such as sucrose, glucose etc. for carbon source, such as
Sevilla Marta et al. (Marta Sevilla, Antonio B.Fuertes.Chemical and structural
properties of carbonaceous products obtained by hydrothermal carbonization of
Saccharides [J] .Chemistry-A European Journal, 2009,15,4195-4203) by three kinds of different sugar
Hydro-thermal prepares micron order carbon ball to class (glucose, sucrose, starch) respectively.But to be rich in the agriculture of lignin, high crystalline cellulose
Industry abandoned biomass (core, shell, skin, bar) is raw material, prepares spherical biological Carbon Materials through mild hydro-thermal method and at home and abroad rarely has
Report.Based on this, it can be used for room temperature CO using abandoned biomass as raw material preparation2The carbon micron-spheres of trapping just have extremely strong
Competitiveness, and it is expected to the cheap load matrix as multiple material.
Summary of the invention
The primary purpose of the present invention is that providing a kind of preparation method of biomass-based activated carbon microballon.
The technical problems to be solved by the present invention are: providing, a kind of preparation condition is relatively mild, raw material is cheap and performance is good
The preparation method of good biomass-based spherical activated charcoal, prepared adsorbent is at room temperature to main greenhouse gas CO2Have
Excellent absorption property, stable circular regeneration absorption property.
Another object of the present invention is to provide the biomass-based activated carbon microballons that above-mentioned preparation method obtains.
A further object of the present invention is to provide the applications of above-mentioned biomass-based activated carbon microballon.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method of biomass-based activated carbon microballon, comprising the following steps:
Firstly, the abandoned biomass powder of 20-100 mesh is mixed with plurality of reagents and is stirred well at room temperature
It is even, obtain suspension；Suspension is transferred in reaction kettle after hydro-thermal, hydro-thermal carbon ball is obtained；Through washing after hydro-thermal carbon ball is cooling
Wash, dry after obtain the presoma of charcoal；The presoma of charcoal and nitrogenous object, activator are mixed in a certain proportion after grinding through roasting
It burns, washing, drying, the biomass-based activated carbon microballon is made；The plurality of reagents is ammonium persulfate, sulfuric acid and water.
The abandoned biomass powder is green shell powder, pineapple peels and chips meal, melon seed cases powder, walnut shell powder, coconut inner casing powder
At least one of；It is by by least one of green shell, pineapple peel, melon seed cases, walnut shell, coconut inner casing, through washing
Only, dry, be made after broken and screening.
The dosage of the abandoned biomass powder and plurality of reagents is respectively as follows: abandoned biomass powder=1~2 mass parts,
Ammonium persulfate=1~2 mass parts, sulfuric acid=0.5~1 parts by volume, water=40~60 parts by volume.
0.5~the 1h of mixing time, revolving speed 600r/min.
The h 2 so 4 concentration range is 95.0-98.0%.
The process conditions of the hydro-thermal are as follows: after reacting 16~20h at 120 DEG C, 230 DEG C are warming up to from 120 DEG C, 230
It is reacted for 24 hours at DEG C.
The nitrogenous object is chitosan；The activator is one or both of potassium oxalate, potassium tartrate；The charcoal
Presoma, nitrogenous object, activator level are respectively as follows: presoma=1~1.5 mass parts of charcoal, and nitrogenous object=1~3 mass parts is living
Agent=3~4.5 mass parts.
The process conditions of the roasting: N2Or static roasting under inert gas atmosphere, 700~800 DEG C of maturing temperature, roasting
Time 2h.
First in 200 DEG C of heat preservation 1h before the roasting.
The biomass-based activated carbon microballon, it is characterized in that can be straight by abandoned biomass powder by simple hydro-thermal method
It connects obtained hydro-thermal carbosphere, and remains to retain most of carbosphere after high-temperature roasting activation (partial size is 3 ± 1 μm).
The biomass-based activated carbon microballon, specific surface area are 1349.17~1685.68m2/g。
The biomass-based activated carbon microballon can be used for CO absorption2。
The biomass-based activated carbon microballon, at normal temperatures and pressures to CO2Adsorbance be 3.86~4.09mmol/g.
Gained activated carbon microballon adsorbent CO absorption2Afterwards, then at different temperature de-adsorption cycle regenerates.
The biomass-based activated carbon microballon, at normal temperatures and pressures to CO2/N2Adsorptive selectivity up to 10.71~
14.37。
1 mass parts in the present invention: 1 parts by volume=1g/ml.
The present invention has following major advantage compared with prior art:
(1) it selects waste biomass mass shell a variety of cheap and easy to get and nontoxic as carbon source, there is certain universality；
It selects mild potassium tartrate or potassium oxalate as activator, the absorption of active carbon can be greatly improved on the basis of reducing energy consumption
Performance；
(2) hydro-thermal carbosphere is made using the ammonium persulfate auxiliary hydro-thermal reaction with strong oxidizing property, then through high-temperature roasting
Activated carbon microballon adsorbent is obtained, spherical morphology can not only be retained, and the absorption property of active carbon can be enhanced；In ammonium persulfate
Strong oxidizing property and sulfuric acid the common booster action of acidity under, macromolecular substances such as cellulose, lignin etc. can resolve into small
Molecule solable matter such as glucose, small-molecule substance can assemble under thermal and hydric environment to be formed spheric granules (Holger V.Lutze,Klaudiusz Grübel,et al.Chemistry of
persulfates in water and wastewater treatment:a review[J].Chemical
Engineering Journal,2017,330,44-62)。
(3) activated carbon microballon obtained by is at room temperature to CO2With excellent absorption property and stable circular regeneration
Absorption property, preferable CO2/N2The advantages that adsorptive selectivity: the preparation biomass-based activated carbon microballon (partial size is about 3 ±
1 μm) at normal temperatures and pressures to CO2Adsorbance up to 3.86~4.09mmol/g；At normal temperatures and pressures to CO2/N2Absorption choosing
Selecting property is up to 10.71~14.37；Its specific surface area is up to 1349.17~1685.68m2/g。
(4) the biomass-based activated carbon microballon prepared by can be regenerated at a lower temperature (by CO absorption2Sample afterwards is in beauty
In 200 on the II 3020 type Sorption Analyzer degasser of first generation TriStar of Micro meritics instrument company, state production
DEG C, deaerate under vacuum condition 4h, regeneration tests can be completed), and there is excellent circular regeneration absorption property.
Detailed description of the invention
In Fig. 1, a, b, c, d, e are respectively the scanning electron microscope (SEM) photograph of biomass-based activated carbon microballon prepared by Examples 1 to 5
Piece.
Fig. 2 is the X-ray diffractogram of biomass-based activated carbon microballon prepared by embodiment 1.
In Fig. 3, a, b are respectively the N of biomass-based activated carbon microballon prepared by Examples 1 to 52Adsorption-desorption curve.
In Fig. 4, a, b are respectively the pore distribution curve of biomass-based activated carbon microballon prepared by Examples 1 to 5.
Fig. 5 is biomass-based activated carbon microballon prepared by Examples 1 to 5 at normal temperatures and pressures to CO2Adsorption curve.
Fig. 6 is biomass-based activated carbon microballon prepared by embodiment 1 at normal temperatures and pressures to CO2Circulation absorption column
Figure.
In Fig. 7, a, b are respectively biomass-based activated carbon microballon prepared by embodiment 1 at normal temperatures and pressures to CO2And N2
Adsorption curve, at normal temperatures and pressures to CO2/N2The initial slope measurement chart of adsorption curve.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.Sulfuric acid concentration ranges used in the embodiment of the present invention are 95.0-98.0%.In the test of the embodiment of the present invention, room temperature,
The actual range of room temperature is 20-25 DEG C.
Embodiment 1:
Firstly, will successively be cleaned, the pineapple peel after 100 DEG C of drying for 24 hours is at powder to 20-100 mesh；Take 1g pineapple peels and chips meal,
0.5mL sulfuric acid, 1g ammonium persulfate, 40mL distilled water stir 0.5h at room temperature and obtain suspension；Suspension is transferred to liner
After keeping the temperature 16h at 120 DEG C in the reaction kettle of polytetrafluoroethylene (PTFE), 230 DEG C are warming up to from 120 DEG C, keeps the temperature for 24 hours, obtains at 230 DEG C
To hydro-thermal carbosphere product；
Secondly, by hydro-thermal carbosphere product be placed at room temperature cool down after through distill water washing, 110 DEG C of dry 12h, obtain charcoal
Presoma；By the presoma of charcoal and chitosan, potassium tartrate with the mass ratio mixed grinding of 1:2:3, it is all transferred to crucible
In, it is placed in N2The lower 200 DEG C of heat preservations 1h of (50ml/min) atmosphere, and it is warming up to 800 DEG C of charings (heating rate is 5 DEG C/min) 2h,
Obtain carbide；It is given birth to after carbide is washed repeatedly through 1mol/L hydrochloric acid and distilled water to neutral, dry (80 DEG C, 12h)
Substance base globe activated char, at normal temperatures and pressures to CO2Adsorbance be 4.06mmol/g (see Fig. 1 curve), it is normal in room temperature
Pressure is to CO2/N2Selectivity 11.02.
Embodiment 2:
Firstly, will successively be cleaned, green shell after 100 DEG C of drying for 24 hours is at powder to 20-100 mesh；Take green shell of 2g
Powder, 1mL sulfuric acid, 2g ammonium persulfate, 60mL distilled water stir 1h at room temperature and obtain suspension；Suspension is transferred to liner to gather
After keeping the temperature 18h at 120 DEG C in the reaction kettle of tetrafluoroethene, 230 DEG C are warming up to from 120 DEG C, keeps the temperature for 24 hours, obtains at 230 DEG C
Hydro-thermal carbosphere product；
Secondly, by hydro-thermal carbosphere product be placed at room temperature cool down after through distill water washing, 110 DEG C of dry 12h, obtain charcoal
Presoma；By the presoma of charcoal and chitosan, potassium tartrate with the mass ratio mixed grinding of 1:1:3, it is all transferred to crucible
In, it is placed in N2The lower 200 DEG C of heat preservations 1h of (50ml/min) atmosphere, and it is warming up to 750 DEG C of charings (heating rate is 5 DEG C/min) 2h,
Obtain carbide；It is given birth to after carbide is washed repeatedly through 1mol/L hydrochloric acid and distilled water to neutral, dry (80 DEG C, 12h)
Substance base globe activated char, at normal temperatures and pressures to CO2Adsorbance be 3.86mmol/g (see Fig. 1 curve), it is normal in room temperature
Pressure is to CO2/N2Selectivity be 10.71.
Embodiment 3:
Firstly, will successively be cleaned, the melon seed cases after 100 DEG C of drying for 24 hours are at powder to 20-100 mesh；Take 2g melon seed cases powder,
1mL sulfuric acid, 2g ammonium persulfate, 40mL distilled water stir 0.5h at room temperature and obtain suspension；Suspension is transferred to liner to gather
After keeping the temperature 20h at 120 DEG C in the reaction kettle of tetrafluoroethene, 230 DEG C are warming up to from 120 DEG C, keeps the temperature for 24 hours, obtains at 230 DEG C
Hydro-thermal carbosphere product；
Secondly, by hydro-thermal carbosphere product be placed at room temperature cool down after through distill water washing, 110 DEG C of dry 12h, obtain charcoal
Presoma；By the presoma of charcoal and chitosan, potassium oxalate with the mass ratio mixed grinding of 1.5:1.5:4.5, all it is transferred to
In crucible, it is placed in N2The lower 200 DEG C of heat preservations 1h of (50ml/min) atmosphere, and it is warming up to 700 DEG C of charings (heating rate is 5 DEG C/min)
2h obtains carbide；It is obtained after carbide is washed repeatedly through 1mol/L hydrochloric acid and distilled water to neutral, dry (80 DEG C, 12h)
Biomass-based spherical activated charcoal, at normal temperatures and pressures to CO2Adsorbance be 3.86mmol/g (see Fig. 1 curve), in room temperature
To CO under normal pressure2/N2Selectivity be 11.04.
Embodiment 4:
Firstly, will successively be cleaned, the walnut shell after 100 DEG C of drying for 24 hours is at powder to 20-100 mesh；Take 2g walnut shell powder,
1mL sulfuric acid, 2g ammonium persulfate, 40mL distilled water stir 0.5h at room temperature and obtain suspension；Suspension is transferred to liner to gather
After keeping the temperature 16h at 120 DEG C in the reaction kettle of tetrafluoroethene, 230 DEG C are warming up to from 120 DEG C, keeps the temperature for 24 hours, obtains at 230 DEG C
Hydro-thermal carbosphere product；
Secondly, by hydro-thermal carbosphere product be placed at room temperature cool down after through distill water washing, 110 DEG C of dry 12h, obtain charcoal
Presoma；By the presoma of charcoal and chitosan, potassium tartrate with the mass ratio mixed grinding of 1.5:3:4.5, all it is transferred to
In crucible, it is placed in N2The lower 200 DEG C of heat preservations 1h of (50ml/min) atmosphere, and it is warming up to 750 DEG C of charings (heating rate is 5 DEG C/min)
2h obtains carbide；It is obtained after carbide is washed repeatedly through 1mol/L hydrochloric acid and distilled water to neutral, dry (80 DEG C, 12h)
Biomass-based spherical activated charcoal, at normal temperatures and pressures to CO2Adsorbance be 4.00mmol/g (see Fig. 1 curve), in room temperature
To CO under normal pressure2/N2Selectivity be 12.17.
Embodiment 5:
Firstly, will successively be cleaned, the coconut inner casing after 100 DEG C of drying for 24 hours is at powder to 20-100 mesh；Take 2g coconut inner casing
Powder, 1mL sulfuric acid, 2g ammonium persulfate, 40mL distilled water stir 0.5h at room temperature and obtain suspension；Suspension is transferred to liner
After keeping the temperature 16h at 120 DEG C in the reaction kettle of polytetrafluoroethylene (PTFE), 230 DEG C are warming up to from 120 DEG C, keeps the temperature for 24 hours, obtains at 230 DEG C
To hydro-thermal carbosphere product；
Secondly, by hydro-thermal carbosphere product be placed at room temperature cool down after through distill water washing, 110 DEG C of dry 12h, obtain charcoal
Presoma；By the presoma of charcoal and chitosan, potassium oxalate with the mass ratio mixed grinding of 1:1:3, all it is transferred in crucible,
It is placed in N2The lower 200 DEG C of heat preservations 1h of (50ml/min) atmosphere, and it is warming up to 800 DEG C of charings (heating rate is 5 DEG C/min) 2h, it obtains
Carbide；Biomass is obtained after carbide is washed repeatedly through 1mol/L hydrochloric acid and distilled water to neutral, dry (80 DEG C, 12h)
Base globe activated char, at normal temperatures and pressures to CO2Adsorbance be 4.09mmol/g (see Fig. 1 curve), at normal temperatures and pressures
To CO2/N2Selectivity be 14.37.
Comparative example 1:
In order to probe into whether ammonium persulfate auxiliary hydro-thermal treatment method can effectively improve biomass-based spheric active Carbon Materials
At room temperature to CO2Adsorption capacity, design control experiment under preferable experiment condition (embodiment 1):
Firstly, will successively be cleaned, the pineapple peel after 100 DEG C of drying for 24 hours is at powder to 20-100 mesh；Take 1g pineapple peels and chips meal,
40mL distilled water stirs 0.5h at room temperature and obtains suspension；Suspension is transferred in the reaction kettle of inner liner polytetrafluoroethylene
After keeping the temperature 16h at 120 DEG C, 230 DEG C are warming up to from 120 DEG C, is kept the temperature at 230 DEG C for 24 hours, obtains hydrothermal product；
Secondly, by hydrothermal product be placed at room temperature cool down after through distill water washing, 110 DEG C of dry 12h, obtain the forerunner of charcoal
Body；By the presoma of charcoal and chitosan, potassium tartrate with the mass ratio mixed grinding of 1:2:3, all it is transferred in crucible, is placed in
N2The lower 200 DEG C of heat preservations 1h of (50ml/min) atmosphere, and it is warming up to 800 DEG C of charings (heating rate is 5 DEG C/min) 2h, it is carbonized
Object；Biomass-based work is obtained after carbide is washed repeatedly through 1mol/L hydrochloric acid and distilled water to neutral, dry (80 DEG C, 12h)
Property charcoal, at normal temperatures and pressures to CO2Adsorbance be 3.57mmol/g.
Sample is inhaled using II 3020 type of TriStar that U.S. Micro meritics instrument company produces in above-described embodiment
Fufen analyzer comparison surface area and hole are analyzed, and total specific surface area is measured using BET method, and total pore volume is in relative pressure (P/
P0) be calculated for 0~0.995 by the adsorbance of liquid nitrogen；Sample is at normal temperatures and pressures to CO2And N2Adsorbance be using beauty
II 3020 type Sorption Analyzer of the TriStar test of Micro meritics instrument company, state production, CO2/N2Selectivity pass through
CO2And N2The initial slope of adsorption curve is calculated with Henry's law；The microstructure of sample surfaces is using Japan Electronics strain
The JSM-IT300 type scanning electron microscope test of formula commercial firm production；The phase structure of sample uses Brooker AXS company, Germany
D8Advance type X-ray diffractometer detection.
Scanning electron microscope diagram piece (the figure of biomass-based activated carbon microballon prepared by according to embodiments of the present invention 1~5
1) product of all embodiments known to is the spheric granules that partial size is about 3 ± 1 μm.
The production known to the X-ray diffractogram (Fig. 2) of biomass-based activated carbon microballon prepared by according to embodiments of the present invention 1
Object is amorphous carbon.
The analysis such as the specific surface area of the sample of Examples 1 to 5 and pore structure, design parameter are shown in Table 1.It can be seen by table 1
Out, the total specific surface area with higher of biomass-based activated carbon microballon prepared by according to embodiments of the present invention 1~5 and total pore volume
Product, highest is respectively up to 1685.68m2/g、0.3533cm3/ g, and CO2The diameter of molecule is 0.33nm, therefore prepared by the present invention
Active carbon to CO2The absorption of gas plays a very important role.
The N of biomass-based activated carbon microballon prepared by according to embodiments of the present invention 1~52Absorption --- desorption curve (figure
3) and known to pore distribution curve (Fig. 4) it shows typical microcellular structure.In conjunction with Main Texture nature parameters and CO in table 12
The variation tendency of adsorbance can speculate that the physical factors such as specific surface area and the pore structure of sample may play decision to absorption property and make
With.
By the sample of Examples 1 to 5 through CO absorption2Afterwards in the production of Micro meritics instrument company, the U.S.
Deaerate under 200 DEG C, vacuum condition 4h on II 3020 type Sorption Analyzer degasser of TriStar.Then by the sample after degassing
Product carry out circulation absorption experiment respectively, recycle 10 times, room temperature CO2Adsorbance is still up to 3.54~3.59mmol/g, absorption
Amount is respectively 87.2%, 86.3%, 87.0%, 87.3%, the 87.8% of initial adsorption amount, shows excellent circular regeneration
It uses ability (see Fig. 6).
The CO of biomass-based activated carbon microballon at normal temperatures and pressures prepared by according to embodiments of the present invention 12And N2Absorption is bent
Line (Fig. 7), low-down N is shown at 25 DEG C, under the conditions of 1bar2Adsorbance, value are only 0.6525mmol/g, this shows
The sample can be used for selective absorption CO in flue gas2。CO2/N2Selectivity be to pass through CO2And N2Adsorption curve it is initial
Slope is calculated with Henry's law, and specific method is shown in Fig. 7, and the selectivity being thus calculated is 11.02.According to the present invention
Biomass-based activated carbon microballon is at normal temperatures and pressures to CO prepared by Examples 1 to 52/N2Adsorptive selectivity design parameter see
Table 1.
In above-described embodiment, former occupation can be usedMultifunctional crusher carries out solution product before the activation after drying
It crushes, smashed product is 20-100 mesh.
The Main Texture nature parameters of biomass-based activated carbon microballon prepared by 1 Examples 1 to 5 of table, in normal temperature and pressure
Under CO2Adsorbance, N2Adsorbance and CO2/N2Adsorptive selectivity
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of biomass-based activated carbon microballon, which comprises the following steps:
Firstly, abandoned biomass powder is mixed with plurality of reagents and is stirred well at room temperature uniformly, suspension is obtained；It will
Suspension is transferred in reaction kettle after hydro-thermal, obtains hydro-thermal carbon ball；Charcoal is obtained after water washing, drying after hydro-thermal carbon ball is cooling
Presoma；, through roasting, washing, drying, it will be made described biomass-based after the presoma of charcoal and nitrogenous object, activator mixed grinding
Activated carbon microballon；The plurality of reagents is ammonium persulfate, sulfuric acid and water.
2. a kind of preparation method of biomass-based activated carbon microballon according to claim 1, which is characterized in that described discarded
Powdered biomass is at least one of green shell powder, pineapple peels and chips meal, melon seed cases powder, walnut shell powder, coconut inner casing powder.
3. a kind of preparation method of biomass-based activated carbon microballon according to claim 1, which is characterized in that described discarded
The dosage of powdered biomass and plurality of reagents is respectively as follows: abandoned biomass powder=1~2 mass parts, ammonium persulfate=1~2 matter
Measure part, sulfuric acid=0.5~1 parts by volume, water=40~60 parts by volume.
4. a kind of preparation method of biomass-based activated carbon microballon according to claim 1, which is characterized in that the hydro-thermal
Process conditions are as follows: at 120 DEG C react 16~20h after, be warming up to 230 DEG C from 120 DEG C, reacted for 24 hours at 230 DEG C.
5. a kind of preparation method of biomass-based activated carbon microballon according to claim 1, which is characterized in that described nitrogenous
Object is chitosan；The activator is one or both of potassium oxalate, potassium tartrate；The presoma of the charcoal, nitrogenous object, work
Agent dosage is respectively as follows: presoma=1~1.5 mass parts of charcoal, nitrogenous object=1~3 mass parts, activator=3~4.5 mass
Part.
6. a kind of preparation method of biomass-based activated carbon microballon according to claim 1, which is characterized in that the roasting
Process conditions: N2Or static roasting under inert gas atmosphere, 700~800 DEG C of maturing temperature, calcining time 2h.
7. the biomass-based activated carbon microballon as made from preparation method described in any one of claims 1-6.
8. biomass-based activated carbon microballon according to claim 7, which is characterized in that the biomass-based activated carbon microballon
Specific surface area is 1349.17~1685.68m2/g。
9. biomass-based activated carbon microballon is in CO absorption described in claim 7 or 82In application.
10. application according to claim 9, which is characterized in that the biomass-based activated carbon microballon is in normal temperature and pressure
Under to CO2Adsorbance be 3.86~4.09mmol/g, at normal temperatures and pressures to CO2/N2Adsorptive selectivity up to 10.71~
14.37。
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