CN109231204A - A kind of method of biomass substep activation preparation porous charcoal - Google Patents
A kind of method of biomass substep activation preparation porous charcoal Download PDFInfo
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- CN109231204A CN109231204A CN201811147626.XA CN201811147626A CN109231204A CN 109231204 A CN109231204 A CN 109231204A CN 201811147626 A CN201811147626 A CN 201811147626A CN 109231204 A CN109231204 A CN 109231204A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
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Abstract
The invention discloses a kind of methods of biomass substep activation preparation porous charcoal, preparation process is as follows: after biomass is crushed drying, it is activated under indifferent gas part after evenly mixing with activator, activator is reacted with biomass fermentation life-stylize, preliminarily form the charcoal with certain porosity, charcoal is impregnated uniformly again with activator and is mixed, make activator well into the hole to charcoal, activator with good dispersion effective rate of utilization during re-activation greatly improves, charcoal skeleton can sufficiently be etched, generate a large amount of micropore and mesoporous, so that the porous carbon material with flourishing pore structure can also be formed even if using a small amount of activator, it is being catalyzed, absorption, the fields such as energy storage are all with a wide range of applications, porous carbon material is prepared to realize biomass greenization, facilitate Promote biomass higher value application process.
Description
Technical field
The present invention relates to biomass economy fields, and in particular to a kind of method of biomass substep activation preparation porous charcoal.
Background technique
With fossil fuel peter out and its caused by the environmental problem that gets worse, develop renewable resources and have become
For current extremely urgent task.Biomass is unique renewable carbon source in nature, and it is huge with content, environment is friendly
The series of advantages such as good, carbon negative emission, thus Bio-energy Development is a current hot research topic.Biomass passes through simple
Heat treatment (such as be pyrolyzed) biological carbon materials can be obtained, but since the charcoal porosity being directly pyrolyzed not enough is sent out
It reaches, is difficult higher value application.Charcoal must be thus activated, to form the porous charcoal with flourishing pore structure
Material then can be widely applied to the electrode material of ion battery and supercapacitor, the carbon-based material of catalyst and gas
The fields such as isolated adsorbent have the very big market space.
Currently, KOH, K2CO3、ZnCl2、H3PO4、KHCO3The common activator of porous carbon material is prepared etc. being, although they
Charcoal can be etched and form flourishing pore structure, but it in activation process, additional amount is big, usually biomass quality
1-4 times, a large amount of activator can cause serious corrosion to equipment, cause to be difficult to be widely applied.
Thus, it needs to find a kind of environmentally protective method, prepares the porous carbon material with flourishing pore structure, with full
The domestic wilderness demand of foot.
Summary of the invention
For disadvantages described above and Improvement requirement, the present invention is directed to propose a kind of side of biomass substep activation preparation porous charcoal
Method, biomass generate the charcoal of part pore structure by once activation, and activator can be sufficiently uniformly when re-activation
It is distributed in hole, and then activator and charcoal carry out secondary abundant priming reaction, generates a large amount of micropore and mesoporous, thus
Only adding a small amount of activator can be obtained the porous carbon material of hole prosperity.The method of the present invention significantly reduces the use of activator
Amount, has but obtained the more flourishing porous carbon materials of porosity.
To achieve the above object, the present invention provides a kind of methods of biomass substep activation preparation porous charcoal, including such as
Lower step:
S1: it after biomass solid wastes to be crushed to the particle less than 60 mesh, is dried；
S2: the biomass solid wastes in step S1 are passed through into the side of dipping with activator 50:1~5:1 in mass ratio
Formula is sufficiently mixed, and is then evaporated moisture content therein, is obtained uniformly mixed sample after dry；
S3: the sample in step S2 is subjected to priming reaction, activator and biomass solid under nitrogen or argon atmosphere
Priming reaction occurs for the active component in waste, forms the charcoal with certain pore structure
S4: the charcoal that step S3 is obtained carries out pickling, then with excessive deionized water filtration and washing to filtrate at
Neutrality, the charcoal once activated after dry；
S5: the charcoal that step S4 is obtained is carried out with activator used in step S2 by impregnation method sufficiently mixed again
After conjunction, it is evaporated moisture content and drying sample, the amount of activator and the activator in step S2 are identical in quality, again in nitrogen or argon gas
Sufficient priming reaction is carried out under atmosphere, since activator can be well into the life formed to after once activating in dipping process
In the hole of object charcoal, so that finely dispersed activator sufficiently etches carbon skeleton, a large amount of micropore and mesoporous is generated, to be formed
Charcoal with flourishing pore structure.
S6: the charcoal that step S5 is obtained carries out the operation of step S4, finally obtains porous carbon material.
The principle of the above inventive concept of the present invention is: for biomass in an activation process, activator and biomass are discarded
Active material reaction in object, preliminarily forms the charcoal with certain porosity, living in the dipping process again of charcoal
Agent can well into the hole for once activating formation to biomass, make activator have full and uniform dispersibility, from
And during the re-activation of charcoal, activator utilization rate greatly improves, and can sufficiently etch charcoal skeleton, generates a large amount of
Micropore and mesoporous, so that the porous carbon material with flourishing pore structure can also be formed even if using a small amount of activator, it is more
Hole carbon material is all with a wide range of applications in fields such as catalysis, absorption, energy storage, to realize the high-valued benefit of biomass
With.
When preparing porous activated carbon as raw material using activator and biomass, it is common practice to a large amount of that activity is added
Agent, the additional amount of activating agent can achieve the purpose of abundant reaming, and the universal amount for perceiving as activating agent is The more the better, preparation
Porous charcoal porosity is more flourishing.But excessive activator can badly damaged equipment.The above inventive concept of the invention seems
Only increase the number of activation, still, breach the cognition of the prior art, be not activation dosage it is The more the better, but
" having many meals but little food at eath " type is needed, the hole preliminarily formed after activating for the first time is made full use of, work at second and later
In change further, more sufficiently, it is more effective, more fully etch charcoal skeleton, it is final to obtain the more flourishing porous carbon of porosity
Material.It can be obtained same or higher porosity using only the activator of the prior art 2%~10% according to the method for the present invention
Porous carbon material.
Further, the biomass in the step S1 is one of bamboo scraps, peanut shell, rice husk, straw or a variety of, is done
Dry temperature is 100 DEG C~150 DEG C, and drying time is 10h~30h.
Further, activator is selected from KOH, K in the step S22CO3、ZnCl2、H3PO4、KHCO3One of or it is more
Kind, the temperature for evaporating moisture content is 50-80 DEG C, and the temperature of dry mixed sample is 100 DEG C~150 DEG C, drying time be 10h~
30h。
Further, the flow of the argon gas in the step S3 or nitrogen is 50mL/min~500mL/min, activation temperature
It is 700 DEG C~900 DEG C, the reaction time is 30~90min.
Further, the acid solution in the step S4 is hydrochloric acid solution, and concentration is 0.05~2mol/L, dry charcoal
Temperature be 100 DEG C~150 DEG C, drying time be 10h~30h.
Further, the evaporation moisture content temperature in the step S5 and drying sample temperature are identical as the step S2.
Further, the flow of the argon gas in the step S5 or nitrogen, activation temperature and reaction time and the step
S3 is identical.
Further, the concentration of hydrochloric acid solution in the step S6 and drying temperature are identical as the step S4.
Further, the step S5 and step S6 can be recycled repeatedly, to obtain the porous charcoal of more high porosity
Material.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
(1) in method of the invention, porous carbon material is prepared using biomass castoff substep activation, passes through biomass one
In secondary activation process, activator is reacted with the active material in biomass castoff, preliminarily forms the life with certain porosity
Object charcoal；In the dipping process again of charcoal, in the fully dispersed hole to charcoal of activator, thus the two of charcoal
In secondary activation process, activator can sufficiently etch charcoal skeleton, generate a large amount of micropore and mesoporous, so that being formed has flourishing hole
The porous carbon material of gap structure.
(2) in method of the invention, by substep activation method, to improve the utilization rate of activator, thus living with a step
Change mode is compared, and in the case where obtaining close porosity, the additive amount of activator can be greatly decreased, to reduce activation
Corrosion of the activator to equipment in the process is conducive to produce porous carbon material on a large scale.According to the prior art, activator adds
Dosage is 1-4 times of biomass quality, and according to the method for the present invention, the additive amount of activator is the 1/50-1/5 of biomass quality.
(3) in method of the invention, the hole of porous charcoal can be regulated and controled by adjusting activation number of substep activation etc.
Structure and the additive amount of activator etc. are solved and were activated while realizing the porous charcoal quality for guaranteeing flourishing pore structure
Corrosive harm in journey is a kind of environmentally protective porous charcoal preparation method.
Detailed description of the invention
Fig. 1 is the flow diagram of present invention method.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, not
For limiting the present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below that
Not constituting conflict between this can be combined with each other.
The present invention provides a kind of methods of biomass substep activation preparation porous charcoal, specifically comprise the following steps:
(1) it after biomass solid wastes being crushed to the particle less than 60 mesh, is dried；
(2) biomass solid wastes in step (1) are passed through into the side of dipping with activator 50:1~5:1 in mass ratio
Formula is sufficiently mixed, and is then evaporated moisture content therein, is obtained uniformly mixed sample after dry；
(3) sample in step (2) is subjected to priming reaction, activator and biomass solid under nitrogen or argon atmosphere
Priming reaction occurs for the active component in waste, forms the charcoal with certain pore structure
(4) charcoal obtained step (3) carries out pickling, then with excessive deionized water filtration and washing to filtrate at
Neutrality, the charcoal once activated after dry；
(5) charcoal for obtaining step (4) is carried out with activator used in step (2) by impregnation method abundant again
After mixing, be evaporated moisture content and drying sample, the amount of activator and the activator in step (2) are identical in quality, again in nitrogen or
Sufficient priming reaction is carried out under argon atmosphere, since activator can be formed in dipping process well into after once activating
Charcoal hole in, so that finely dispersed activator sufficiently etches carbon skeleton, generate a large amount of micropore and mesoporous, thus
Form the charcoal with flourishing pore structure.
(6) charcoal for obtaining step (5) carries out the operation of step (4), finally obtains porous carbon material.
Wherein, the biomass in the step (1) is one of bamboo scraps, peanut shell, rice husk, straw or a variety of, drying
Temperature is 100 DEG C~150 DEG C, and drying time is 10h~30h.
Activator in step (2) is selected from KOH, K2CO3、ZnCl2、H3PO4、KHCO3One of or it is a variety of, evaporate moisture content
Temperature be 50-80 DEG C, the temperature of dry mixed sample is 100 DEG C~150 DEG C, and drying time is 10h~30h.
The flow of argon gas or nitrogen in step (3) is 50mL/min~500mL/min, and activation temperature is 700 DEG C~900
DEG C, the reaction time is 30~90min.
Acid solution in step (4) is hydrochloric acid solution, and concentration is 0.05~2mol/L, and the temperature of dry charcoal is 100
DEG C~150 DEG C, drying time is 10h~30h.
Evaporation moisture content temperature and drying sample temperature in step (5) is identical as the step S2；The stream of argon gas or nitrogen
Amount, activation temperature and reaction time are identical as the step S3.
Concentration of hydrochloric acid solution and drying temperature in step (6) is identical as the step S4.
Step (5) and step (6) can be recycled repeatedly, to obtain the porous carbon material of more high porosity.
The principle of the above inventive concept of the present invention is: for biomass in an activation process, activator and biomass are discarded
Active material reaction in object, preliminarily forms the charcoal with certain porosity, living in the dipping process again of charcoal
Agent can be dispersed well well into having, activator in the hole for once activating formation to biomass, thus
During the re-activation of charcoal, activator utilization rate is greatly improved, and can sufficiently be etched charcoal skeleton, be generated a large amount of micropore
With it is mesoporous, so that the porous carbon material with flourishing pore structure can also be formed even if using a small amount of activator, urging
The fields such as change, absorption, energy storage are all with a wide range of applications, to realize the higher value application of biomass.
For more detailed description the method for the present invention, further illustrated below with reference to specific embodiment
Embodiment 1
The method that the embodiment of the present invention illustrates a kind of biomass substep activation preparation porous charcoal, the method specifically include as
Lower step:
S1: bamboo scraps are crushed and screened less than 60 mesh, after being put into 105 DEG C of oven dryings for 24 hours, obtain activation raw material；
S2: the bamboo scraps in step S1 are sufficiently mixed for 24 hours with KOH activator 20:1 in mass ratio by impregnation method, then
Moisture content is evaporated at a temperature of 60 DEG C, however is placed in drying in 105 DEG C of baking ovens and for 24 hours, obtains uniformly mixed biomass samples；
S3: being 45mm using diameter, and length is that the fixed bed reactors of 60mm are activated, and reactor is heated to
After 800 DEG C of activation temperature, the uniformly mixed biomass samples in~2g step S2 are rapidly feeding in the middle part of reactor, when activation
Between be 60min, react biomass with activator, argon flow 200mL/min；
S4: charcoal obtained in step S3 is subjected to pickling, then concentration of hydrochloric acid solution 1mol/L is gone with excessive
Ionized water filtration and washing, at neutrality, dries the charcoal once activated afterwards for 24 hours to filtrate at 105 DEG C；
S5: the charcoal that step S4 is obtained is mixed for 24 hours with KOH impregnation method again, and KOH mass is about 0.1g,
Moisture content is evaporated at a temperature of 60 DEG C, however is placed in 105 DEG C of baking ovens after drying for 24 hours, priming reaction 60min, charcoal at 800 DEG C
It is sufficiently reacted with activator, argon flow 200mL/min；
S6: charcoal obtained in step S5 is subjected to pickling, then concentration of hydrochloric acid solution 1mol/L is gone with excessive
Ionized water filtration and washing is to filtrate at neutrality, and drying obtains porous carbon material afterwards for 24 hours at 105 DEG C.
Obtained porous carbon material has flourishing pore structure, and specific surface area reaches 1260m2/g。
Embodiment 2
The present embodiment is same as Example 1, activator K2CO3。
Obtained porous carbon material has flourishing pore structure, and specific surface area reaches 1050m2/g。
Embodiment 3
The present embodiment is same as Example 1, and only activator is ZnCl2。
Obtained porous carbon material has flourishing pore structure, and specific surface area reaches 1190m2/g。
Embodiment 4
The present embodiment is same as Example 1, and only activator is H3PO4。
Obtained porous carbon material has flourishing pore structure, and specific surface area reaches 920m2/g。
Embodiment 5
The present embodiment is same as Example 1, and only activator is KHCO3。
Obtained porous carbon material has flourishing pore structure, and specific surface area reaches 950m2/g。
Embodiment 6
S1: bamboo scraps are crushed and screened less than 60 mesh, after being put into 105 DEG C of oven dryings for 24 hours, obtain activation raw material；
S2: the bamboo scraps in step S1 are sufficiently mixed for 24 hours with KOH activator 50:1 in mass ratio by impregnation method, then
Moisture content is evaporated at a temperature of 60 DEG C, however is placed in drying in 105 DEG C of baking ovens and for 24 hours, obtains uniformly mixed biomass samples；
S3: being 45mm using diameter, and length is that the fixed bed reactors of 60mm are activated, and reactor is heated to
After 800 DEG C of activation temperature, the uniformly mixed biomass samples in~2g step S2 are rapidly feeding in the middle part of reactor, when activation
Between be 60min, react biomass with activator, argon flow 200mL/min；
S4: charcoal obtained in step S3 is subjected to pickling, then concentration of hydrochloric acid solution 1mol/L is gone with excessive
Ionized water filtration and washing, at neutrality, dries the charcoal once activated afterwards for 24 hours to filtrate at 105 DEG C；
S5: the charcoal that step S4 is obtained is mixed for 24 hours with KOH impregnation method again, and KOH mass is~0.04g, 60
Moisture content is evaporated at a temperature of DEG C, however be placed in 105 DEG C of baking ovens it is dry for 24 hours after, the priming reaction 60min at 800 DEG C, charcoal with
Activator sufficiently reacts, argon flow 200mL/min；
S6: charcoal obtained in step S5 is subjected to pickling, then concentration of hydrochloric acid solution 1mol/L is gone with excessive
Ionized water filtration and washing is to filtrate at neutrality, and drying obtains porous carbon material afterwards for 24 hours at 105 DEG C.
Obtained porous carbon material has flourishing pore structure, and specific surface area reaches 760m2/g。
Embodiment 7
S1: bamboo scraps are crushed and screened less than 60 mesh, after being put into 105 DEG C of oven dryings for 24 hours, obtain activation raw material；
S2: the bamboo scraps in step S1 are sufficiently mixed for 24 hours with KOH activator 5:1 in mass ratio by impregnation method, then
Moisture content is evaporated at a temperature of 60 DEG C, however is placed in drying in 105 DEG C of baking ovens and for 24 hours, is obtained uniformly mixed biomass samples；
S3: being 45mm using diameter, and length is that the fixed bed reactors of 60mm are activated, and reactor is heated to
After 800 DEG C of activation temperature, the uniformly mixed biomass samples in~2g step S2 are rapidly feeding in the middle part of reactor, when activation
Between be 60min, react biomass with activator, argon flow 200mL/min；
S4: charcoal obtained in step S3 is subjected to pickling, then concentration of hydrochloric acid solution 1mol/L is gone with excessive
Ionized water filtration and washing, at neutrality, dries the charcoal once activated afterwards for 24 hours to filtrate at 105 DEG C；
S5: the charcoal that step S4 is obtained is mixed for 24 hours with KOH impregnation method again, and KOH mass is~0.3g, 60
Moisture content is evaporated at a temperature of DEG C, however be placed in 105 DEG C of baking ovens it is dry for 24 hours after, the priming reaction 60min at 800 DEG C, charcoal with
Activator sufficiently reacts, argon flow 200mL/min；
S6: charcoal obtained in step S5 is subjected to pickling, then concentration of hydrochloric acid solution 1mol/L is gone with excessive
Ionized water filtration and washing is to filtrate at neutrality, and drying obtains porous carbon material afterwards for 24 hours at 105 DEG C.
Obtained porous carbon material has flourishing pore structure, and specific surface area reaches 3060m2/g。
Embodiment 8
S1: peanut shell is crushed and screened less than 60 mesh, after being put into 105 DEG C of oven dryings for 24 hours, obtains activation raw material；
S2: the bamboo scraps in step S1 are sufficiently mixed for 24 hours with KOH activator 10:1 in mass ratio by impregnation method, then
Moisture content is evaporated at a temperature of 60 DEG C, however is placed in drying in 105 DEG C of baking ovens and for 24 hours, obtains uniformly mixed biomass samples；
S3: being 45mm using diameter, and length is that the fixed bed reactors of 60mm are activated, and reactor is heated to
After 800 DEG C of activation temperature, the uniformly mixed biomass samples in~2g step S2 are rapidly feeding in the middle part of reactor, when activation
Between be 60min, react biomass with activator, argon flow 200mL/min；
S4: charcoal obtained in step S3 is subjected to pickling, then concentration of hydrochloric acid solution 1mol/L is gone with excessive
Ionized water filtration and washing, at neutrality, dries the charcoal once activated afterwards for 24 hours to filtrate at 105 DEG C；
S5: the charcoal that step S4 is obtained is mixed for 24 hours with KOH impregnation method again, and KOH mass is~0.2g, 60
Moisture content is evaporated at a temperature of DEG C, however be placed in 105 DEG C of baking ovens it is dry for 24 hours after, the priming reaction 60min at 800 DEG C, charcoal with
Activator sufficiently reacts, argon flow 200mL/min；
S6: charcoal obtained in step S5 is subjected to pickling, then concentration of hydrochloric acid solution 1mol/L is gone with excessive
Ionized water filtration and washing is to filtrate at neutrality, and drying obtains porous carbon material afterwards for 24 hours at 105 DEG C.
Obtained porous carbon material has flourishing pore structure, and specific surface area reaches 1690m2/g。
Embodiment 9
The present embodiment is same as Example 8, and only activation temperature is 700 DEG C, activation time 90min.
Obtained porous carbon material has flourishing pore structure, and specific surface area reaches 1550m2/g。
Embodiment 10
The present embodiment is same as Example 8, and only activation temperature is 900 DEG C, activation time 30min.
Obtained porous carbon material has flourishing pore structure, and specific surface area reaches 1730m2/g。
Embodiment 11
S1: rice husk is crushed and screened less than 60 mesh, after being put into 100 DEG C of oven drying 30h, obtains activation raw material；
S2: the bamboo scraps in step S1 are sufficiently mixed for 24 hours with KOH activator 10:1 in mass ratio by impregnation method, then
Moisture content is evaporated at a temperature of 60 DEG C, however is placed in 100 DEG C of baking ovens dry 30h, obtains uniformly mixed biomass samples；
S3: being 45mm using diameter, and length is that the fixed bed reactors of 60mm are activated, and reactor is heated to
After 800 DEG C of activation temperature, the uniformly mixed biomass samples in~2g step S2 are rapidly feeding in the middle part of reactor, when activation
Between be 60min, react biomass with activator, argon flow 200mL/min；
S4: charcoal obtained in step S3 is subjected to pickling, then concentration of hydrochloric acid solution 1mol/L is gone with excessive
Ionized water filtration and washing, at neutrality, dries the charcoal once activated after 30h to filtrate at 100 DEG C；
S5: the charcoal that step S4 is obtained is mixed for 24 hours with KOH impregnation method again, and KOH mass is~0.2g, 60
Moisture content is evaporated at a temperature of DEG C, however after being placed in 100 DEG C of baking ovens dry 30h, the priming reaction 60min at 800 DEG C, charcoal with
Activator sufficiently reacts, argon flow 200mL/min；
S6: charcoal obtained in step S5 is subjected to pickling, then concentration of hydrochloric acid solution 1mol/L is gone with excessive
Ionized water filtration and washing, at neutrality, obtains porous carbon material after dry 30h at 100 DEG C to filtrate.
Obtained porous carbon material has flourishing pore structure, and specific surface area reaches 1660m2/g。
Embodiment 12
S1: straw is crushed and screened less than 60 mesh, after being put into 150 DEG C of oven drying 10h, obtains activation raw material；
S2: the bamboo scraps in step S1 are sufficiently mixed for 24 hours with KOH activator 10:1 in mass ratio by impregnation method, then
Moisture content is evaporated at a temperature of 60 DEG C, however is placed in 150 DEG C of baking ovens dry 10h, obtains uniformly mixed biomass samples；
S3: being 45mm using diameter, and length is that the fixed bed reactors of 60mm are activated, and reactor is heated to
After 800 DEG C of activation temperature, the uniformly mixed biomass samples in~2g step S2 are rapidly feeding in the middle part of reactor, when activation
Between be 60min, react biomass with activator, argon flow 200mL/min；
S4: charcoal obtained in step S3 is subjected to pickling, then concentration of hydrochloric acid solution 1mol/L is gone with excessive
Ionized water filtration and washing, at neutrality, dries the charcoal once activated after 10h to filtrate at 150 DEG C；
S5: the charcoal that step S4 is obtained is mixed for 24 hours with KOH impregnation method again, and KOH mass is~0.2g, 60
Moisture content is evaporated at a temperature of DEG C, however after being placed in 150 DEG C of baking ovens dry 10h, the priming reaction 60min at 800 DEG C, charcoal with
Activator sufficiently reacts, argon flow 200mL/min；
S6: charcoal obtained in step S5 is subjected to pickling, then concentration of hydrochloric acid solution 1mol/L is gone with excessive
Ionized water filtration and washing, at neutrality, obtains porous carbon material after dry 10h at 150 DEG C to filtrate.
Obtained porous carbon material has flourishing pore structure, and specific surface area reaches 1630m2/g。
Embodiment 13
S1: bamboo scraps are crushed and screened less than 60 mesh, after being put into 105 DEG C of oven dryings for 24 hours, obtain activation raw material；
S2: the bamboo scraps in step S1 are sufficiently mixed for 24 hours with KOH activator 10:1 in mass ratio by impregnation method, then
Moisture content is evaporated at a temperature of 80 DEG C, however is placed in drying in 105 DEG C of baking ovens and for 24 hours, obtains uniformly mixed biomass samples；
S3: being 45mm using diameter, and length is that the fixed bed reactors of 60mm are activated, and reactor is heated to
After 800 DEG C of activation temperature, the uniformly mixed biomass samples in~2g step S2 are rapidly feeding in the middle part of reactor, when activation
Between be 60min, react biomass with activator, nitrogen flow 500mL/min；
S4: charcoal obtained in step S3 is subjected to pickling, then concentration of hydrochloric acid solution 2mol/L is gone with excessive
Ionized water filtration and washing, at neutrality, dries the charcoal once activated afterwards for 24 hours to filtrate at 105 DEG C；
S5: the charcoal that step S4 is obtained is mixed for 24 hours with KOH impregnation method again, and KOH mass is~0.2g, 80
Moisture content is evaporated at a temperature of DEG C, however be placed in 105 DEG C of baking ovens it is dry for 24 hours after, the priming reaction 60min at 800 DEG C, charcoal with
Activator sufficiently reacts, nitrogen flow 500mL/min；
S6: charcoal obtained in step S5 is subjected to pickling, then concentration of hydrochloric acid solution 2mol/L is gone with excessive
Ionized water filtration and washing is to filtrate at neutrality, and drying obtains porous carbon material afterwards for 24 hours at 105 DEG C.
Obtained porous carbon material has flourishing pore structure, and specific surface area reaches 1450m2/g。
Embodiment 14
S1: bamboo scraps are crushed and screened less than 60 mesh, after being put into 105 DEG C of oven dryings for 24 hours, obtain activation raw material；
S2: the bamboo scraps in step S1 are sufficiently mixed for 24 hours with KOH activator 10:1 in mass ratio by impregnation method, then
Moisture content is evaporated at 50 °C, however is placed in drying in 105 DEG C of baking ovens and for 24 hours, is obtained uniformly mixed biomass samples；
S3: being 45mm using diameter, and length is that the fixed bed reactors of 60mm are activated, and reactor is heated to
After 800 DEG C of activation temperature, the uniformly mixed biomass samples in~2g step S2 are rapidly feeding in the middle part of reactor, when activation
Between be 60min, react biomass with activator, nitrogen flow 50mL/min；
S4: charcoal obtained in step S3 is subjected to pickling, concentration of hydrochloric acid solution 0.5mol/L, then with excessive
Deionized water filtration and washing, at neutrality, dries the charcoal once activated afterwards for 24 hours to filtrate at 105 DEG C；
S5: the charcoal that step S4 is obtained is mixed for 24 hours with KOH impregnation method again, and KOH mass is~0.2g, 50
Moisture content is evaporated at a temperature of DEG C, however be placed in 105 DEG C of baking ovens it is dry for 24 hours after, the priming reaction 60min at 800 DEG C, charcoal with
Activator sufficiently reacts, nitrogen flow 50mL/min；
S6: charcoal obtained in step S5 is subjected to pickling, concentration of hydrochloric acid solution 0.5mol/L, then with excessive
Deionized water filtration and washing is to filtrate at neutrality, and drying obtains porous carbon material afterwards for 24 hours at 105 DEG C.
Obtained porous carbon material has flourishing pore structure, and specific surface area reaches 1980m2/g。
The porous carbon material of the method for the present invention preparation can be used as catalyst, adsorbent or/and electrode material and be applied.Than
Such as, carbon-supported catalysts are used to prepare, CO absorption is used for2、SOx、NOxEqual sour gas are used to prepare supercapacitor or battery
Electrode etc..
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (9)
1. a kind of method of biomass substep activation preparation porous charcoal, which comprises the steps of:
S1: it after biomass solid wastes to be crushed to the particle less than 60 mesh, is dried；
S2: by step S1 biomass solid wastes and activator 50:1~5:1 in mass ratio by way of dipping into
Row is sufficiently mixed, and is then evaporated moisture content therein, is obtained uniformly mixed sample after dry；
S3: the sample in step S2 is subjected to priming reaction under nitrogen or argon atmosphere, activator and biomass solid are discarded
Priming reaction occurs for the active component in object, forms the charcoal with certain pore structure；
S4: the charcoal that step S3 is obtained carries out pickling, then with excessive deionized water filtration and washing to filtrate at neutrality,
The charcoal once activated after drying；
S5: the charcoal once activated that step S4 is obtained is carried out with activator used in step S2 by impregnation method again
After being sufficiently mixed, it is evaporated moisture content and drying sample, the amount of activator and the activator in step S2 are identical in quality, again in nitrogen
Or sufficient priming reaction is carried out under argon atmosphere, since activator can be well into the shape to after once activating in dipping process
At charcoal hole in, so that finely dispersed activator further can sufficiently etch carbon skeleton, generate a large amount of
Micropore and mesoporous, to form the charcoal with flourishing pore structure；
S6: the charcoal that step S5 is obtained carries out the operation of step S4, finally obtains the more flourishing porous carbon material of hole.
2. a kind of method of biomass substep activation preparation porous charcoal according to claim 1, which is characterized in that the step
Biomass in rapid S1 is one of bamboo scraps, peanut shell, rice husk, straw or a variety of, and drying temperature is 100 DEG C~150 DEG C, is done
The dry time is 10h~30h.
3. a kind of method of biomass substep activation preparation porous charcoal according to claim 2, which is characterized in that the step
Activator is KOH, K in rapid S22CO3、ZnCl2、H3PO4、KHCO3One of or it is a variety of, evaporate moisture content temperature be 50 DEG C~
80 DEG C, the temperature of dry mixed sample is 100 DEG C~150 DEG C, and drying time is 10h~30h.
4. a kind of method of biomass substep activation preparation porous charcoal according to claim 3, which is characterized in that the step
The flow of argon gas or nitrogen in rapid S3 is 50mL/min~500mL/min, and activation temperature is 700 DEG C~900 DEG C, the reaction time
For 30~90min.
5. a kind of method of biomass substep activation preparation porous charcoal according to claim 4, which is characterized in that the step
Pickling is carried out using hydrochloric acid solution in rapid S4, concentration of hydrochloric acid solution is 0.05~2mol/L, and the temperature of dry charcoal is 100 DEG C
~150 DEG C, drying time is 10h~30h.
6. a kind of method of biomass substep activation preparation porous charcoal according to claim 5, which is characterized in that the step
Evaporation moisture content temperature and drying sample temperature in rapid S5 is identical as the step S2.
7. a kind of method of biomass substep activation preparation porous charcoal according to claim 6, which is characterized in that the step
The flow of argon gas or nitrogen in rapid S5, activation temperature and reaction time are identical as the step S3.
8. a kind of method of biomass substep activation preparation porous charcoal according to claim 7, which is characterized in that the step
Concentration of hydrochloric acid solution and drying temperature in rapid S6 is identical as the step S4.
9. a kind of method of biomass substep activation preparation porous charcoal according to claim 8, which is characterized in that repeatedly weight
Multiple step S5 and step S6, to obtain the porous carbon material of more high porosity.
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| CN110683540A (en) * | 2019-10-25 | 2020-01-14 | 四川大学 | Nitrogen-rich hierarchical pore biomass charcoal and application thereof |
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| CN114538408A (en) * | 2020-11-24 | 2022-05-27 | 中国科学院广州能源研究所 | Method for preparing high electrocatalytic activity biochar through micro-aerobic pyrolysis |
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