CN109879281A - A kind of preparation method and product of biomass-based porous charcoal - Google Patents
A kind of preparation method and product of biomass-based porous charcoal Download PDFInfo
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Abstract
The invention belongs to biomass utilization fields, and disclose the preparation method and product of a kind of biomass-based porous charcoal.This method includes after S1 mixes biological particles with potassium salt or Organic Sodium Salt, and heat drying obtains porous charcoal predecessor；Porous charcoal predecessor is carried out heating pyrolysis charring by S2 under an inert atmosphere, is then kept the temperature；Mixture is carried out pickling by S3, after removing alkali metal salt, then obtains biomass-based porous charcoal after dry at neutrality with excessive deionized water filtration and washing to filtrate.The invention also discloses corresponding products.The present invention is by adjusting preparation condition, catalyzing and carbonizing is carried out to biomass using activator, the biomass carbonated coking of activator catalysis comes into full contact with coke granule and the further obtained biomass-based porous charcoal with high-specific surface area of activation generation micropore, method is simple, it is a kind of sustainable preparation method of green, all there is wide applicability for different carbohydrates and lignocellulose-like biomass raw material.
Description
Technical field
The invention belongs to biomass energy utilization technologies fields, more particularly, to a kind of preparation of biomass-based porous charcoal
Method and product.
Background technique
Biomass is the unique cleaning renewable resource containing charcoal, the fossil energies such as petroleum, coal can be replaced to give birth to for electric power
Production, Carbon Materials preparation etc..Exploitation biomass energy is conducive to optimize China's energy supply structure, alleviates increasingly serious environment and asks
Topic.
Biomass-based porous charcoal using long-standing, early in Han dynasty, China period, people are raw material through smoldering using timber
Made of charcoal just have been supplied in the moisture absorption, decoloration etc..Nowadays biomass-based porous charcoal is even more the hole knot for relying on it flourishing
Structure, higher stability, easily adulterates the features such as load at good thermal conductivity, in adsorbing separation, energy storage, catalysis
The fields such as conversion suffer from broad application prospect.
The microcellular structure of porous charcoal is most important in adsorbing separation, energy storage field, has flourishing micropore hole for preparation
The biomass-based porous charcoal of gap generally requires to carry out high-temperature activation processing to predecessor.Activation method is broadly divided into physically activated
Two class of method and chemical activation method, wherein chemical activation method has better activation effect and higher charcoal yield.Traditional chemistry
Activator such as KOH, ZnCl2Although having excellent activation effect, due to the spies such as highly corrosive, high toxicity, environment be unfriendly
Property is unfavorable for their sustainable large-scale use.
In the prior art, the two-step carbonization method that potassium, sodium, the oxalates of ammonium and bicarbonate are activator is generallyd use to prepare
Biomass-based multi-stage porous charcoal, these activators are nontoxic, corrosion-free, environmental-friendly, new selection provided for chemical activation method, such as
It is prepared for biomass-based grading-hole charcoal through one-step method using saleratus as activator, when the generation of hole is mainly due to 200 DEG C
The physical expansion and decompose the high-temperature activation effect for generating potassium carbonate that saleratus decomposes.
But in the prior art, on the one hand more demanding to the raw material of biomass, generally require the cellulose of raw material to contain
Amount can reach preferable effect 20% or more, on the other hand, the biomass-based multi-stage porous charcoal obtained in the prior art
Preparation process is complicated, and the specific surface area of acquired product is small.Therefore, it is urgent to provide a kind of new wider array of technologies of applicability
Scheme, specific surface area is prepared with simpler process bigger, the higher biomass-based multi-stage porous charcoal of micropore accounting.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, a kind of preparation method of biomass-based porous charcoal is provided,
It carries out catalyzing and carbonizing to biomass by adjusting preparation condition, using activator, and catalysis biomass charing coking comes into full contact with
Coke granule and further activation generate micropore and the biomass-based porous charcoal with high-specific surface area are made, and method is simple, is one
The sustainable preparation method of kind green all has extensive be applicable in for different carbohydrates and lignocellulose-like biomass raw material
Property.
To achieve the above object, the invention proposes a kind of preparation methods of biomass-based porous charcoal, which is characterized in that packet
Include following steps,
After S1 is mixed smashed biological particles with potassium salt or Organic Sodium Salt according to certain mass ratio, add
Heated drying obtains porous charcoal predecessor；
Porous charcoal predecessor obtained in step S1 is carried out heating pyrolysis charring by S2 under an inert atmosphere, is then kept the temperature,
Obtain the mixture of charcoal and alkali metal salt；
The mixture of charcoal obtained in step S2 and alkali metal salt is carried out pickling by S3, after removing alkali metal salt, so
Biomass-based porous charcoal is obtained after dry at neutrality with excessive deionized water filtration and washing to filtrate afterwards.
Further, in step S1, the mass ratio of the biological particles and potassium salt or Organic Sodium Salt be 1:0.5~
1:4, it is preferred that the mass ratio of the biological particles and potassium salt or Organic Sodium Salt is 1:1~1:2.
Further, in step S1, the material grains and potassium salt or Organic Sodium Salt using direct mechanical mixture or
The mode of solvent auxiliary mechanical mixture is mixed.
Further, in the mode of solvent auxiliary mechanical mixture, in the material grains and potassium salt or need to have
Mixed solvent is added in the mixture of machine sodium salt, the mixed solvent is ethyl alcohol or water, it is preferred that the mixed solvent is second
Alcohol；The mass ratio of the mixed solvent and the material grains is 0.2:1~1:1, it is preferred that the mixed solvent and the object
The mass ratio of matter particle is 0.5:1.
Further, the potassium salt is potassium oxalate, potassium formate, potassium acetate, potassium citrate, potassium tartrate, potassium lactate
At least one of；The Organic Sodium Salt is sodium oxalate, in sodium formate, sodium acetate, sodium citrate, sodium tartrate, sodium lactate
It is at least one.
Further, in step S2, the reaction temperature of the pyrolysis charring is 700 DEG C~1000 DEG C, it is preferred that the heat
The reaction temperature of solution charing is 800 DEG C；
Heating rate during the pyrolysis charring is 5 DEG C/min~100 DEG C/min, it is preferred that the pyrolysis charring
Heating rate in the process is 10 DEG C/min~15 DEG C/min.
Further, in step S2, the inert atmosphere is argon atmosphere or nitrogen atmosphere.
Further, in step S3, the temperature of the drying is 60 DEG C~100 DEG C, it is preferred that the time of the drying is
80 DEG C, drying time is 2h~12h, it is preferred that the time of the drying is 7h.
Other side according to the invention, additionally provide it is a kind of should prepare with the aforedescribed process it is biomass-based more
Hole charcoal product.
Further, the micropore accounting of the biomass-based porous charcoal product is not less than 50%.
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) present invention utilizes the lower fusing point of organic potassium (sodium) salt and stronger catalytic pyrolysis characteristic, makes biomass pyrolytic
Temperature shifts to an earlier date, and promotes biomass coking and discharges gas, the organic potassium melted at the same time (sodium) ionic liquid infiltration biology
Matter is burnt internal, and further catalysis biomass pyrolysis to mould the channel design goed deep into inside particle, makes priming reaction
Ground is more abundant, while by adjusting preparation condition, so that activator and biomass carry out catalyzing and carbonizing, come into full contact with coke
Grain and further activation generate micropore and the biomass-based porous charcoal with high specific surface area are made, and prepared is biomass-based more
Hole charcoal specific surface area is up to 1700m2/ g, method is simple, is a kind of sustainable preparation method of green, for different carbohydrate and
Lignocellulose-like biomass raw material all has wide applicability, this method simple process and low cost.
(2) mass ratio of biological particles of the present invention and potassium salt or Organic Sodium Salt is 1:0.5~1:4, it is preferred that institute
The mass ratio for stating biological particles and potassium salt or Organic Sodium Salt is 1:1~1:2, and then in lower activator additive amount
Under, higher activation effect can be reached, effectively reduce the dosage and the discharge of possible potassium of potassium.
(3) material grains of the present invention and potassium salt or Organic Sodium Salt are mechanical mixed using direct mechanical mixture or solvent auxiliary
The mode of conjunction is mixed, and in turn, selected organic potassium (sodium) salt activator can be sufficiently distributed in inside particle, passes through depth
Enter inside particle and radiate out two paths construction micropore and mesoporous, so as to by adjusting heating rate and activator
Additive amount realizes effective regulation to pore structure (micropore and mesoporous ratio).
(4) potassium salt be potassium oxalate, potassium formate, potassium acetate, potassium citrate, potassium tartrate, in potassium lactate extremely
Few one kind；The Organic Sodium Salt is sodium oxalate, sodium formate, sodium acetate, sodium citrate, sodium tartrate, at least one in sodium lactate
Kind, selected organic potassium (sodium) salt is used as activator, can melt under lower temperature (150 DEG C~350 DEG C) and with compared with
The stronger catalytic pyrolysis effect of inorganic alkaline metal salt, generates stomata by bubbing product, enables the activator of melting
Under the conditions of optimum proportioning deeper into ground in conjunction with biomass, so that it is anti-that carbon skeleton etching can more efficiently occur at high temperature
It answers, the biomass-based porous charcoal with flourishing hole has been obtained by simple step charring and post-processing, for any one
Kind carbohydrate or lignocellulose-like biomass all show excellent activation effect, have good raw material universality.
(5) present invention carries out matching design by the process condition carbonized to biomass pyrolytic, to realize biomass in work
Property agent under the action of to porous charcoal product Efficient Conversion, reaction temperature be 700 DEG C~1000 DEG C under the conditions of, biomass char
Homolysis and radical reaction occur for organic potassium (sodium) salt of grain surface infiltration, and partially moulding in particle surface deposition has certainization
Learn the carbon skeleton of structure.Priming reaction will be occurred with biomass char by decomposing the inorganic base metal oxide generated or carbonate, be led to
It crosses and gos deep into inside particle and radiate out two kinds of path configuration micropores and mesoporous, so that the product obtained has higher ratio
(biomass-based porous charcoal specific surface area is up to 1700m for surface area2/ g) and micropore accounting (micropore accounting is not less than 50%).
(6) for the micropore accounting for the biomass-based porous charcoal product that the present invention obtains not less than 50%, specific surface area is reachable
1700m2/ g, before flourishing pore structure is suffered from and is widely applied in fields such as adsorbing separation, energy storage, catalyzed conversions
Scape.
Detailed description of the invention
Fig. 1 is a kind of process of the preparation method of biomass-based porous charcoal constructed by preferred embodiment according to the invention
Figure；
Fig. 2 is the SEM figure of the biomass-based porous carbon material prepared according to the embodiment of the present invention 1；
Fig. 3 is the TEM figure of the biomass-based porous carbon material prepared according to the embodiment of the present invention 1；
Fig. 4 be according to the embodiment of the present invention 1 prepare biomass-based porous carbon material isothermal nitrogen adsorption desorption curve and
Accumulate pore-size distribution；
Fig. 5 is the SEM figure of the biomass-based porous carbon material prepared according to the embodiment of the present invention 2
Fig. 6 is the TEM figure of the biomass-based porous carbon material prepared according to the embodiment of the present invention 2
Fig. 7 be according to the embodiment of the present invention 2 prepare biomass-based porous carbon material isothermal nitrogen adsorption desorption curve and
Accumulate pore-size distribution；
Fig. 8 is the SEM figure of the biomass-based porous carbon material prepared according to the embodiment of the present invention 3；
Fig. 9 is the TEM figure of the biomass-based porous carbon material prepared according to the embodiment of the present invention 3；
Figure 10 is to apply the isothermal nitrogen adsorption desorption curve of the biomass-based porous carbon material of the preparation of example 3 according to the present invention and tire out
Product pore-size distribution；
Figure 11 is the SEM figure of the biomass-based porous carbon material prepared according to the embodiment of the present invention 4；
Figure 12 be according to the embodiment of the present invention 4 prepare biomass-based porous carbon material isothermal nitrogen adsorption desorption curve and
Accumulate pore-size distribution；
Figure 13 be according to the embodiment of the present invention 5 prepare biomass-based porous carbon material isothermal nitrogen adsorption desorption curve and
Accumulate pore-size distribution；
Figure 14 be according to the embodiment of the present invention 6 prepare biomass-based porous carbon material isothermal nitrogen adsorption desorption curve and
Accumulate pore-size distribution；
Figure 15 be according to the embodiment of the present invention 7 prepare biomass-based porous carbon material isothermal nitrogen adsorption desorption curve and
Accumulate pore-size distribution；
Figure 16 be according to the embodiment of the present invention 8 prepare biomass-based porous carbon material isothermal nitrogen adsorption desorption curve and
Accumulate pore-size distribution；
Figure 17 be according to the embodiment of the present invention 9 prepare biomass-based porous carbon material isothermal nitrogen adsorption desorption curve and
Accumulate pore-size distribution.
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 the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
As shown in Figure 1, being a kind of preparation side of biomass-based porous charcoal constructed by preferred embodiment according to the invention
The flow chart of method, comprising the following steps:
Biomass powder is broken to the biological particles less than 40 mesh by S1；Wherein, the biomass be saccharide biomass and/or
Lignocellulose-like biomass
S2 mixes biological particles obtained in step S1 with potassium salt or Organic Sodium Salt according to certain mass ratio
It is dry after conjunction, obtain porous charcoal predecessor；Wherein, the mass ratio of the biological particles and potassium salt or Organic Sodium Salt is
1:0.5~1:4, it is preferred that the mass ratio of the biological particles and potassium salt or Organic Sodium Salt is 1:1~1:2.The object
Matter particle is mixed by the way of direct mechanical mixture or solvent auxiliary mechanical mixture with potassium salt or Organic Sodium Salt.?
In the mode of the solvent auxiliary mechanical mixture, it need to add in the material grains and the mixture of potassium salt or Organic Sodium Salt
Add mixed solvent, the mixed solvent is ethyl alcohol or water, it is preferred that the mixed solvent is ethyl alcohol；The mixed solvent and institute
The mass ratio for stating material grains is 0.2:1~1:1, it is preferred that the mass ratio of the mixed solvent and the material grains is
0.5:1。
Porous charcoal predecessor obtained in step S2 is carried out heating pyrolysis charring by S3 under an inert atmosphere, is then kept the temperature,
Obtain the mixture of charcoal and alkali metal salt；Wherein, the reaction temperature of the pyrolysis charring is 700 DEG C~1000 DEG C, preferably
, the reaction temperature of the pyrolysis charring is 800 DEG C；Heating rate during the pyrolysis charring is 5 DEG C/min~100
DEG C/min, it is preferred that the heating rate during the pyrolysis charring is 10 DEG C/min~15 DEG C/min.The inert atmosphere is
Argon atmosphere or nitrogen atmosphere.
The mixture of charcoal obtained in step S2 and alkali metal salt is carried out pickling by S4, after removing alkali metal salt, so
Biomass-based porous charcoal is obtained after dry at neutrality with excessive deionized water filtration and washing to filtrate afterwards.Wherein, described dry
Dry temperature is 60 DEG C~100 DEG C, it is preferred that the time of the drying is 80 DEG C, and drying time is 2h~12h, it is preferred that institute
Stating the dry time is 7h.
Wherein, the potassium salt is potassium oxalate, in potassium formate, potassium acetate, potassium citrate, potassium tartrate, potassium lactate
It is at least one；The Organic Sodium Salt be sodium oxalate, sodium formate, sodium acetate, sodium citrate, sodium tartrate, in sodium lactate at least
It is a kind of.
The present invention utilizes the lower fusing point of organic potassium (sodium) salt and stronger catalytic pyrolysis characteristic, makes biomass pyrolytic temperature
In advance, promote biomass coking and discharge gas, the organic potassium melted at the same time (sodium) ionic liquid infiltrates biomass char
It is internal.Inside burnt particle, organic potassium (sodium) salt can the pyrolysis of further catalysis biomass, go deep into inside particle to mould
Channel design keeps priming reaction spot more abundant.There are bubble holes in the biomass char that the precipitation of gas will lead to viscoelastic state,
Also it can make glassy state biomass char breakage of particles, generate smaller particle.Temperature is decomposed as temperature is increased to organic potassium (sodium) salt
Homolysis and radical reaction occur for organic potassium (sodium) salt of degree, the infiltration of biomass char particle surface, partially deposit in particle surface
Mould the carbon skeleton with certain chemical structure.Decomposing the inorganic base metal oxide generated or carbonate will send out with biomass char
Life-stylize reaction, by going deep into inside particle and radiating out two kinds of path configuration micropores and mesoporous.It is adjusted so as to pass through
It saves heating rate and activator additive amount and effective regulation is realized to pore structure (microporous mesoporous ratio), have verified that micropore accounting tune
Range is controlled between 68%~94%.
By adjusting preparation condition, can be prepared using this method with high-specific surface area and the adjustable biology of micropore accounting
Matter base porous carbon material.
The present invention is further illustrated below in conjunction with specific embodiments.
Embodiment 1, raw material are main components cellulose in lignocellulose-like biomass.,
0.5g microcrystalline cellulose and 0.5g potassium acetate are weighed, 0.5mL dehydrated alcohol is added and mixes to thick slurry shape, is transferred to just
In beautiful crucible, one step of middle progress is dry in vertical heater and a step inert atmosphere is calcined, temperature program are as follows: 5min is risen to by room temperature
100 DEG C, after keeping 30min, 800 DEG C are risen to the heating rate of 10 DEG C/min and keeps the temperature 2h, after natural cooling, obtains biology
Carbon semiproduct.Gained charcoal is cleaned with deionized water to neutrality after 1M salt acid elution 6h, dry 10h under the conditions of 80 DEG C
After obtain biomass-based porous charcoal, actual yield is about 14.1% (on the basis of material quality).Its scanning electron microscope (SEM) photograph such as Fig. 2 institute
Show, it is seen that micron-sized etching duct is deep into inside particle.Its transmission electron microscope picture is as shown in Figure 3, it is seen that nanoscale etching
Duct is in particle and has micropore abundant.Its isothermal nitrogen adsorption desorption curve and accumulation pore-size distribution such as Fig. 4 in
(a) and shown in (b), it is seen that its hole is mainly made of micropore, and has certain mesoporous, parameter of pore structure being calculated
It is shown in Table 1, it is seen that its specific surface area has reached 1768.8m2/g。
Embodiment 2, raw material are main sugar components xylan in lignocellulose-like biomass.
The xylan and 0.5g potassium acetate that 0.5g is extracted from hair beech are weighed, 0.2mL dehydrated alcohol is added and mixes to thick
Pulpous state is transferred in corundum crucible, and one step of middle progress is dry in vertical heater and a step inert atmosphere is calcined, temperature program are as follows:
5min rises to 700 DEG C by room temperature, after keeping 30min, rises to 800 DEG C with the heating rate of 10 DEG C/min and keeps the temperature 2h, to nature
After cooling, biological carbon semiproduct is obtained.Gained charcoal is cleaned with deionized water to neutrality, after 1M salt acid elution 6h 100
Biomass-based porous charcoal is obtained after dry 2h under the conditions of DEG C, actual yield is about 4% (on the basis of material quality).It scans electricity
Mirror figure is as shown in Figure 5, it is seen that due to the macroporous structure for the thin layer composition that gas release overhangs, thickness is less than 100nm.It is transmitted
Electron microscope is as shown in Figure 6, it is seen that nanoscale etches duct in particle, and has microcellular structure abundant.Its nitrogen
Isothermal adsorption desorption curve and (a) and (b) that accumulates in pore-size distribution such as Fig. 7 are shown, it is seen that and its hole is mainly made of micropore, and
With more abundant mesoporous, the parameter of pore structure being calculated is shown in Table 1.
Embodiment 3, raw material are main component lignin in lignocellulose-like biomass.
0.5g alkali lignin and 0.5g potassium acetate are weighed, 0.2mL dehydrated alcohol is added and mixes to thick slurry shape, is transferred to corundum earthenware
In crucible, one step of middle progress is dry in vertical heater and a step inert atmosphere is calcined, temperature program are as follows: 5min rises to 100 by room temperature
DEG C, after keeping 30min, 1000 DEG C are risen to the heating rate of 10 DEG C/min and keeps the temperature 2h, after natural cooling, obtains charcoal
Semi-finished product.Gained charcoal is cleaned with deionized water to neutrality after 1M salt acid elution 6h, under the conditions of 50 DEG C after dry 12h
Biomass-based porous charcoal is obtained, actual yield is about 39.1% (on the basis of material quality).Its scanning electron microscope (SEM) photograph such as Fig. 8 institute
Show, it is seen that the crack as caused by gas release, the pit-hole and deeply internal hole that activator etches.Its transmission electron microscope picture
As shown in Figure 9, it is seen that enrich uniform microcellular structure.Its isothermal nitrogen adsorption desorption curve and accumulation pore-size distribution such as Figure 10 in
(a) and shown in (b), it is seen that its hole is mainly made of micropore, and has a small amount of mesoporous, parameter of pore structure being calculated
It is shown in Table 1.
Embodiment 4, raw material are typical wood cellulose series biomass bamboo.
The bamboo scraps and 0.5g potassium acetate for weighing the mesh of 0.5g60~80 are added 0.5mL dehydrated alcohol and mix to thick slurry shape, transfer
Into corundum crucible, one step of middle progress is dry in vertical heater and a step inert atmosphere is calcined, temperature program are as follows: 5min is by room temperature
100 DEG C are risen to, after keeping 30min, 800 DEG C is risen to the heating rate of 10 DEG C/min and keeps the temperature 2h, after natural cooling, obtain
Biological carbon semiproduct.Gained charcoal is cleaned with deionized water to neutrality after 1M salt acid elution 6h, dry under the conditions of 60 DEG C
Biomass-based porous charcoal is obtained after 8h, actual yield is about 21.5% (on the basis of material quality).Its scanning electron microscope (SEM) photograph is as schemed
Shown in 11, it is seen that the pit hole of etching and go deep into the micron order duct inside particle, and the nano-lamellar structure to extend out.Its
Isothermal nitrogen adsorption desorption curve and (a) and (b) that accumulates in pore-size distribution such as Figure 12 are shown, it is seen that its hole is mainly by micropore structure
At, and there is on a small quantity mesoporous, the parameter of pore structure being calculated is shown in Table 1, it is seen that its specific surface area has reached 1668.3m2/
g。
Embodiment 5, raw material are bamboo, using different activation temperatures.
The bamboo scraps and 0.5g potassium acetate for weighing 60~80 mesh of 0.5g are added 0.5mL dehydrated alcohol and mix to thick slurry shape, turn
It moves on in corundum crucible, one step of middle progress is dry in vertical heater and a step inert atmosphere is calcined, temperature program are as follows: 5min is by room
Temperature rise is to 100 DEG C, after keeping 30min, rises to final temperature with the heating rate of 10 DEG C/min, 800 DEG C and keeps the temperature 2h, to natural cooling
Afterwards, biological carbon semiproduct is obtained.Gained charcoal is cleaned to neutrality with deionized water, is obtained after drying after 1M salt acid elution 6h
To biomass-based porous charcoal, actual yield is shown in Table 2 (on the basis of material qualities).Its isothermal nitrogen adsorption desorption curve and accumulation hole
Shown in diameter is distributed as shown in (a) and (b) in Figure 13, it is seen that its hole is mainly made of micropore, the pore structure being calculated
Parameter is shown in Table 2.With the raising of activation temperature, specific surface area and pore volume first increases and then decreases, micropore are gradually expanded to be mesoporous,
Micropore volume decline, mesoporous ratio improve.
Embodiment 6, raw material are bamboo, using different potassium acetate additive amounts.
The bamboo scraps and potassium acetate of 60~80 mesh of 1.5g are weighed, the two mass ratio is respectively 1:0.5,1:1,1:2,1:4, is added
Enter 0.5mL dehydrated alcohol to mix to thick slurry shape, be transferred in corundum crucible, one step of middle progress is dry in vertical heater and a step is lazy
Property atmosphere calcining, rise to 800 DEG C with the heating rate of 10 DEG C/min and keep the temperature 2h, after natural cooling, obtain charcoal half at
Product.Gained charcoal is cleaned to neutrality with deionized water after 1M salt acid elution 6h, biomass-based porous charcoal is obtained after drying,
Actual yield is shown in Table 2 (on the basis of material qualities).Its isothermal nitrogen adsorption desorption curve and accumulation pore-size distribution such as Figure 14 in
(a) and shown in (b), it is seen that its hole is mainly made of micropore, and the parameter of pore structure being calculated is shown in Table 2.With potassium acetate
The raising of ratio, specific surface area and pore volume have obtained certain raising, but ratio is more than that it is smaller to promote amplitude after 1.This
Outside, the raising of potassium acetate ratio produces more mesoporous.
Embodiment 7, raw material are bamboo, using different heating rates.
The bamboo scraps and 1g potassium acetate for weighing 60~80 mesh of 0.5g are added 0.5mL dehydrated alcohol and mix to thick slurry shape, transfer
Into corundum crucible, one step of middle progress is dry in vertical heater and a step inert atmosphere is calcined, with 5 DEG C/min, 10 DEG C/min, 15
DEG C/heating rate of min rises to 800 DEG C and keeps the temperature 2h, after natural cooling, obtain biological carbon semiproduct.Gained charcoal warp
After 1M salt acid elution 6h, cleaned with deionized water to neutrality, obtain biomass-based porous charcoal after drying, actual yield be shown in Table 2 (with
On the basis of material quality).Its isothermal nitrogen adsorption desorption curve and (a) and (b) that accumulates in pore-size distribution such as Figure 15 are shown, it is seen that
Its hole is mainly made of micropore, and the parameter of pore structure being calculated is shown in Table 2.With the raising of heating rate, pore volume has
Biggish raising, when heating rate is increased to 15 DEG C/min, mesoporous ratio is greatly improved, this is mesoporous micropore ratio
The regulation of example provides possibility.
Embodiment 8, raw material are bamboo, use potassium citrate for activator.
The bamboo scraps and 0.5g potassium citrate for weighing 60~80 mesh of 0.5g are added 0.5mL deionized water and mix to thick slurry shape,
Be transferred in corundum crucible, one step of middle progress is dry in vertical heater and step inert atmosphere calcining, temperature program are as follows: 5min by
Room temperature rises to 100 DEG C, after keeping 30min, rises to 800 DEG C with the heating rate of 10 DEG C/min and keeps the temperature 2h, after natural cooling,
Obtain biological carbon semiproduct.Gained charcoal is cleaned to neutrality with deionized water, is given birth to after drying after 1M salt acid elution 6h
Substance base porous charcoal, actual yield are about 24.6% (on the basis of material quality).Its isothermal nitrogen adsorption desorption curve and accumulation
Pore-size distribution is as described in (a) and (b) in Figure 16, it is seen that its hole is mainly made of micropore, and has a small amount of mesoporous, is calculated
To parameter of pore structure be shown in Table 3, it is seen that its specific surface area has reached 1567.9m2/g。
Embodiment 9, raw material are cellulose, use sodium acetate for activator.
The bamboo scraps and 0.5g sodium acetate for weighing 60~80 mesh of 0.5g are added 0.5mL deionized water and mix to thick slurry shape, turn
It moves on in corundum crucible, one step of middle progress is dry in vertical heater and a step inert atmosphere is calcined, temperature program are as follows: 5min is by room
Temperature rise after keeping 30min, rises to 800 DEG C with the heating rate of 10 DEG C/min and keeps the temperature 2h, after natural cooling, obtain to 100 DEG C
To biological carbon semiproduct.Gained charcoal is cleaned to neutrality with deionized water after 1M salt acid elution 6h, obtains biology after drying
Matter base porous charcoal, actual yield are about 21.4% (on the basis of material quality).Its isothermal nitrogen adsorption desorption curve and accumulation hole
Diameter distribution is as shown in (a) and (b) in Figure 17, it is seen that its hole is made of micropore, mesoporous, macropore, is typical classification hole
Structure, macropore are mainly derived from sodium acetate and decompose the hard template effect for generating sodium carbonate, and the parameter of pore structure being calculated is shown in
Table 4, it is seen that its specific surface area is 652m2/ g, micropore accounting are only 56.3%.
Table 1
Micropore accounting *: it is calculated by t-plot method；Micropore accounting * *: it is calculated by QSDFT method.
Table 2
Micropore accounting *: it is calculated by t-plot method；Micropore accounting * *: it is calculated by QSDFT method.
Table 3
Micropore accounting *: it is calculated by t-plot method；Micropore accounting * *: it is calculated by QSDFT method.
Table 4
Micropore accounting *: it is calculated by t-plot method；Micropore accounting * *: it is calculated by QSDFT method.
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 (10)
1. a kind of preparation method of biomass-based porous charcoal, which is characterized in that include the following steps,
After S1 is mixed smashed biological particles with potassium salt or Organic Sodium Salt according to certain mass ratio, heating is dry
It is dry, obtain porous charcoal predecessor；
Porous charcoal predecessor obtained in step S1 is carried out heating pyrolysis charring by S2 under an inert atmosphere, is then kept the temperature, and is obtained
The mixture of charcoal and alkali metal salt；
The mixture of charcoal obtained in step S2 and alkali metal salt is carried out pickling by S3, after removing alkali metal salt, with excess
Deionized water filtration and washing to filtrate at neutrality, obtain biomass-based porous charcoal after dry.
2. preparation method according to claim 1, which is characterized in that in step S1, the biological particles and organic potassium
The mass ratio of salt or Organic Sodium Salt is 1:0.5~1:4, it is preferred that the biological particles and potassium salt or Organic Sodium Salt
Mass ratio is 1:1~1:2.
3. preparation method according to claim 1 or 2, which is characterized in that in step S1, the biological particles with it is organic
Sylvite or Organic Sodium Salt are mixed by the way of direct mechanical mixture or solvent auxiliary mechanical mixture.
4. preparation method according to claim 3, which is characterized in that in the mode of the solvent auxiliary mechanical mixture, need
Add mixed solvent in the mixture of the material grains and potassium salt or Organic Sodium Salt, the mixed solvent be ethyl alcohol or
Water, it is preferred that the mixed solvent is ethyl alcohol；The mass ratio of the mixed solvent and the material grains is 0.2:1~1:1,
Preferably, the mass ratio of the mixed solvent and the material grains is 0.5:1.
5. preparation method according to claim 1-4, which is characterized in that the potassium salt is potassium oxalate, first
At least one of sour potassium, potassium acetate, potassium citrate, potassium tartrate, potassium lactate；The Organic Sodium Salt be sodium oxalate, sodium formate,
At least one of sodium acetate, sodium citrate, sodium tartrate, sodium lactate.
6. preparation method according to claim 1-5, which is characterized in that in step S2, the pyrolysis charring
Reaction temperature is 700 DEG C~1000 DEG C, it is preferred that the reaction temperature of the pyrolysis charring is 800 DEG C；The pyrolysis charring process
In heating rate be 5 DEG C/min~100 DEG C/min, it is preferred that heating rate during the pyrolysis charring is 10 DEG C/
Min~15 DEG C/min.
7. preparation method according to claim 1-6, which is characterized in that in step S2, the inert atmosphere is
Argon atmosphere or nitrogen atmosphere.
8. preparation method according to claim 1-7, which is characterized in that in step S3, the temperature of the drying
It is 60 DEG C~100 DEG C, it is preferred that the time of the drying is 80 DEG C, and drying time is 2h~12h, it is preferred that the drying
Time is 7h.
9. the biomass-based porous charcoal product that a kind of the method according to claim 1 prepares.
10. biomass-based porous charcoal product according to claim 9, which is characterized in that the biomass-based porous charcoal produces
The micropore accounting of product is not less than 50%.
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