CN108773844A - A kind of method that micro-calcium addition catalytic activation prepares coal base porous carbon materials - Google Patents
A kind of method that micro-calcium addition catalytic activation prepares coal base porous carbon materials Download PDFInfo
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- CN108773844A CN108773844A CN201811039564.0A CN201811039564A CN108773844A CN 108773844 A CN108773844 A CN 108773844A CN 201811039564 A CN201811039564 A CN 201811039564A CN 108773844 A CN108773844 A CN 108773844A
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
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- C01B32/336—Preparation characterised by gaseous activating agents
Abstract
A kind of method that micro-calcium addition catalytic activation prepares coal base porous carbon materials, is related to a kind of preparation method of porous carbon materials.Purpose is to solve the problems, such as that physically activated obtained porous carbon materials pore structure is undeveloped big with required activator level in chemical activation preparation process in traditional coal base porous carbon materials preparation method.The present invention is using coal as raw material, pass through the ball milling mixing process of micro organic or inorganic calcium source and coal, calcium source is set to be distributed in matrix of coal, by catalyst activation procedure and the removal process of calcareous material, obtain coal base porous carbon materials, the hole combo and Pore genesis of coal base porous carbon, obtain micro-pore carbon material and grading-hole carbon material as obtained by calcium source and content regulation and control.The coal base grading-hole carbon ratio surface area of gained is up to 1535m2/ g, Kong Rong is up to 1.66cm3/g.The present invention is suitable for depth and regulates and controls porous carbon materials pore structure, has application prospect in gas molecule, liquid phase molecule absorption and super capacitor energy-storage field.
Description
Technical field
The present invention relates to a kind of preparation methods of porous carbon materials.
Background technology
Porous active carbon material is since porous active carbon material is due to its physicochemical structure stabilization, hole and surface chemistry
It is easy to regulation and control, advantages of environment protection, important application is presented in fields such as absorption, catalysis and electrochemical energy storages.According to structure
The adsorption storage performance of effect mechanism, porous carbon materials depends on its pore structure and target substance (such as gas molecule, liquid phase point
Son) molecular dimension matching relationship.In general, microcellular structure is conducive to the absorption of gas molecules, and central hole structure helps
In the absorption and storage of liquid phase molecule.The porous carbon materials developed include microporous carbon, ordered mesopore carbon and grading-hole carbon etc.,
Preparation method is related to physical/chemical activation method, template, self-assembling method and hydrothermal carbonization method etc..
Currently, the complexity of the raw material sources of the preparation process of high-performance porous carbon materials, cost and preparation process is still
It is the key that limit its large-scale production.Using coal or biomass as the physical/chemical activating process of raw material have it is at low cost, can work
The advantage of industry metaplasia production.However, traditional physically or chemically activation, which prepares coal base porous carbon process, has following two aspect：
(1) with CO2Or the physically activated method cost porous carbon materials hole knot that is relatively low, but being prepared that vapor is activated media
Structure is undeveloped, and mostly microcellular structure, and 1000m is usually less than using the specific surface area that BET method characterizes2/g；(2) chemistry is living
Change method is by chemical activating agent KOH, H3PO4、K2CO3Or ZnCl2Mixing with carbonaceous presoma is carbonized altogether realizes pore-creating, but is
Obtain flourishing pore structure, it is often necessary to consume a large amount of chemical activating agent, the dosage of activator is carbonaceous forerunner's weight
3~4 times or so, therefore manufacturing cost is higher, and activation products are needed to consume and be remained in a large amount of acid and water removal activated carbon
Activating substance, to increase the difficulty of technology difficulty and environmental protection.Therefore, for above-mentioned physics, chemical activation processes
The problem of preparing porous active carbon material, Development of Novel low cost, environmental-friendly high-performance porous carbon preparation method for material are extremely
It closes important.
Invention content
The invention solves the porous active carbons that in traditional coal base porous carbon materials preparation method, physically activated method obtains
The undeveloped problem big with activator level needed for chemical activation method of material pore structure proposes a kind of micro-calcium addition catalysis
The method that activation prepares coal base porous carbon materials.
The method that micro-calcium addition catalytic activation of the present invention prepares coal base porous carbon materials carries out according to the following steps：
One, raw material refines
Coal raw material is crushed, is ground and is sieved successively, obtains refinement coal dust；
The grain size of the refinement coal dust is the mesh of 40 mesh~200；
The coal raw material is one or more mixtures in any proportion in lignite, bituminous coal, ub-bituminous coal or anthracite；
Two, ball milling mixing
Refinement coal dust is mixed with calcium source, ball milling 1h~8h obtains mixture；
The drum's speed of rotation when ball milling is 100r/min~500r/min, and ball grinder material is agate or stainless steel；
The calcium source is anhydrous calcium chloride, calcium sulfate, calcium hydroxide, calcium carbonate, calcium nitrate, calcium formate, calcium acetate, lemon
One or more mixtures in any proportion in sour calcium, calcium gluconate；
The mass ratio of the refinement coal dust and calcium constituent in calcium source is 1：(0.001~0.05)；
Three, high-temperature activation
Mixture in step 2 is placed in atmosphere furnace, atmosphere furnace is warming up to 700 DEG C~1000 DEG C and keeps the temperature 0.5h
~10h, room temperature is down to after heat preservation naturally by atmosphere furnace, obtains activation products；
The heating rate of the atmosphere furnace is 0.1 DEG C/min~15 DEG C/min；
Atmosphere in the atmosphere furnace is CO2With the mixed atmosphere or vapor and inert gas group of inert gas composition
At mixed atmosphere；The CO2With CO in the mixed atmosphere of inert gas composition2With the volume ratio of inert gas be (0.1~
10)：1；The vapor and inert gas composition mixed atmosphere in the volume ratio of vapor and inert gas be (0.1~
10)：1；The inert gas is high pure nitrogen or high-purity argon gas；
Four, activation products are cleaned
Activation products are carried out to pickling processes 2~3 times and washing process 2~3 times successively, the activation after clean is produced
Object；
The pickle used when the pickling processes is dilute hydrochloric acid or nitric acid, a concentration of 0.01mol/ of the pickle of use
L~1mol/L；
Five, dry
Processing is dried to get to coal base porous carbon materials in activation products after cleaning；
The temperature of the drying process is 60 DEG C~200 DEG C, and the time is 5h~12h.
It the principle of the invention and has the beneficial effect that：
The present invention provides a kind of method preparing high porosity coal base porous carbon materials by adding micro calcium source.Specifically
For：Using coal as raw material, catalyst is used as by micro organic calcium source or inorganic calcium source, the ball milling mixing of calcium source and coal makes calcium
Source is evenly distributed in the skeleton structure of coal, by high-temperature activation process and the removal process of calcareous material, obtains hole prosperity
Microporous carbon or micropore, the grading-hole carbon that coexists of mesoporous and macropore.Compared with prior art, the advantage of the method for the present invention exists
In：
One, the present invention uses lignite, bituminous coal, ub-bituminous coal or anthracite for carbon source, and the source of carbon source is wide and of low cost；It is logical
It crosses and adds micro calcium source and coal ball milling mixing and activation process prepares porous carbon materials, wherein micro calcium source plays catalysis CO2With
Matrix of coal activates pore forming process, to make the coal base porous carbon materials of acquisition have flourishing hole.Compared to traditional physics
Activating process can change the distribution of pores and combo of gained porous carbon by regulating and controlling the type and content of calcium source, it is only necessary to few
The pickling or washing of amount can remove remaining calcium substratess matter；It is used in the present invention to add compared to traditional chemical activating process
Add the dosage of agent (calcium source) far below additive (such as KOH, H in conventional chemical activation process3PO4、K2CO3Or ZnCl2) dosage, greatly
Manufacturing cost is reduced greatly, is easy to amplification production；
Two, traditional coal base porous carbon materials preparation process usually requires pre- carbonization treatment to obtain having preliminary hole structure
The carbonized stock of frame, then carbonized stock is mixed with activator, and obtain active carbon material by high-temperature activation process.The present invention is direct
Pass through coal dust and micro calcium source ball milling mixing and activating process, you can the coal based activated carbon for obtaining hole prosperity eliminates coal
Charcoal pretreating process reduces technology difficulty, and the coal adaptability of the method for the present invention is wide, is suitable for lignite, ub-bituminous coal, bituminous coal
And one or more Mixture Density Networks in anthracite；
Three, the H that high-temperature activation process of the present invention introduces2O or CO2Be conducive to hole with the mixed atmosphere of inert gas composition
Development, the H of introducing2O diffusivitys and reactivity are stronger, work as H2When O is as activation phenomenon, middle macroporous structure is contributed to develop；It introduces
CO2Micropore can be promoted to develop；On the contrary, only with N2Or Ar is then unfavorable for pore structure development, the present invention as reaction gas
In, the reaction temperature of matrix of coal and activation phenomenon is generally at 700~1000 DEG C, with the raising of activation temperature, matrix of coal and work
The reactivity for changing atmosphere improves, and may advantageously facilitate pore structure development.Through nitrogen absorption under low temperature analysis shows, method energy of the invention
The porous carbon materials of the different pore structures enough obtained, including microporous carbon or grading-hole carbon.The grading-hole carbon ratio of gained of the invention
Surface area is up to 1535m2/ g, Kong Rong is up to 1.66cm3/g；It is gentle in electrochemical energy storage such as electric double layer super capacitance electrode material
Body absorption, liquid phase adsorption field have application potential.
Description of the drawings
Fig. 1 is the TEM figures for the coal base porous carbon materials that embodiment 1 is prepared；
Fig. 2 is the Nitrogen adsorption isotherm for the coal base porous carbon materials that embodiment 1 obtains；
Fig. 3 is the TEM figures for the coal base porous carbon materials that embodiment 2 is prepared；
Fig. 4 is the Nitrogen adsorption isotherm for coal Quito hole active carbon material that embodiment 2 obtains；
Fig. 5 is the TEM figures for the coal base porous carbon materials that embodiment 3 is prepared；
Fig. 6 is the Nitrogen adsorption isotherm for the coal base porous carbon materials that embodiment 3 obtains；
Fig. 7 is the Nitrogen adsorption isotherm for the coal base porous carbon materials that embodiment 4 obtains；
Fig. 8 is the Nitrogen adsorption isotherm for the coal base porous carbon materials that comparative example obtains.
Specific implementation mode：
Technical solution of the present invention is not limited to act specific implementation mode set forth below, further includes between each specific implementation mode
Arbitrary reasonable combination.
Specific implementation mode one：Present embodiment micro-calcium addition catalytic activation prepare the methods of coal base porous carbon materials by
Following steps carry out：
One, raw material refines
Coal raw material is crushed, is ground and is sieved successively, obtains refinement coal dust；
The grain size of the refinement coal dust is the mesh of 40 mesh~200；
Two, ball milling mixing
Refinement coal dust is mixed with calcium source, ball milling 1h~8h obtains mixture；
The calcium source is anhydrous calcium chloride, calcium sulfate, calcium hydroxide, calcium carbonate, calcium nitrate, calcium formate, calcium acetate, lemon
One or more mixtures in any proportion in sour calcium, calcium gluconate；
The mass ratio of the refinement coal dust and calcium constituent in calcium source is 1：(0.001~0.05)；
Three, high-temperature activation
Mixture in step 2 is placed in atmosphere furnace, atmosphere furnace is warming up to 700 DEG C~1000 DEG C and keeps the temperature 0.5h
~10h, room temperature is down to after heat preservation naturally by atmosphere furnace, obtains activation products；
Atmosphere in the atmosphere furnace is CO2With the mixed atmosphere or vapor and inert gas group of inert gas composition
At mixed atmosphere；
Four, activation products are cleaned
Activation products are carried out to pickling processes 2~3 times and washing process 2~3 times successively, the activation after clean is produced
Object；
Five, dry
Processing is dried to get to coal base porous carbon materials in activation products after cleaning.
It present embodiment principle and has the beneficial effect that：
Present embodiment provides a kind of method preparing high porosity coal base porous carbon materials by adding micro calcium source.Tool
Body is：Using coal as raw material, catalyst is used as by micro organic calcium source or inorganic calcium source, the ball milling mixing of calcium source and coal makes
Calcium source is evenly distributed in the skeleton structure of coal, by high-temperature activation process and the removal process of calcareous material, obtains hole hair
The grading-hole carbon that microporous carbon or micropore, mesoporous and the macropore reached coexists.Compared with prior art, present embodiment method is excellent
Gesture is：
One, present embodiment uses lignite, bituminous coal, ub-bituminous coal or anthracite for carbon source, and the source of carbon source is wide and at low cost
It is honest and clean；Porous carbon materials are prepared with coal ball milling mixing and activation process, wherein micro calcium source plays catalysis by adding micro calcium source
CO2Pore forming process is activated with matrix of coal, to make the coal base porous carbon materials of acquisition that there is flourishing hole.Compared to traditional
Physically activated technique can change the distribution of pores and combo of gained porous carbon by regulating and controlling the type and content of calcium source, it is only necessary to
Want a small amount of pickling or washing that can remove remaining calcium substratess matter；Compared to traditional chemical activating process, present embodiment
The dosage of middle additive therefor (calcium source) is far below additive (such as KOH, H in conventional chemical activation process3PO4、K2CO3Or ZnCl2)
Dosage, greatly reduce manufacturing cost, be easy to amplification production；
Two, traditional coal base porous carbon materials preparation process usually requires pre- carbonization treatment to obtain having preliminary hole structure
The carbonized stock of frame, then carbonized stock is mixed with activator, and obtain active carbon material by high-temperature activation process.Present embodiment
Directly pass through coal dust and micro calcium source ball milling mixing and activating process, you can the coal based activated carbon for obtaining hole prosperity saves
Coal pretreating process, reduces technology difficulty, and the coal adaptability of present embodiment method is wide, is suitable for lignite, secondary
One or more Mixture Density Networks in bituminous coal, bituminous coal and anthracite；
Three, the H that present embodiment high-temperature activation process introduces2O or CO2Be conducive to the mixed atmosphere of inert gas composition
Pore development, the H of introducing2O diffusivitys and reactivity are stronger, work as H2When O is as activation phenomenon, middle macroporous structure is contributed to develop；
The CO of introducing2Micropore can be promoted to develop；On the contrary, only with N2Or Ar is then unfavorable for pore structure development as reaction gas, this
In embodiment, the reaction temperature of matrix of coal and activation phenomenon is generally at 700~1000 DEG C, with the raising of activation temperature, coal
Matrix and the reactivity of activation phenomenon improve, and may advantageously facilitate pore structure development.Through nitrogen absorption under low temperature analysis shows, this implementation
The porous carbon materials for the different pore structures that the method for mode can obtain, including microporous carbon or grading-hole carbon.Present embodiment
The grading-hole carbon ratio surface area of gained is up to 1535m2/ g, Kong Rong is up to 1.66cm3/g；It is super in electrochemical energy storage such as electric double layer
Capacitance electrode material and gas absorption, liquid phase adsorption field have application potential.
Specific implementation mode two：The present embodiment is different from the first embodiment in that：Coal raw material described in step 1 is
One or more mixtures in any proportion in lignite, bituminous coal, ub-bituminous coal or anthracite.Other steps and parameter with it is specific
Embodiment one is identical.
Specific implementation mode three：The present embodiment is different from the first and the second embodiment in that：Ball milling described in step 2
When drum's speed of rotation be 100r/min~500r/min, ball grinder material be agate or stainless steel.Other steps and parameter with
Specific implementation mode one or two is identical.
Specific implementation mode four：Unlike one of present embodiment and specific implementation mode one to three：Described in step 3
The heating rate of atmosphere furnace is 0.1 DEG C/min~15 DEG C/min.Other steps and one of parameter and specific implementation mode one to three
It is identical.
Specific implementation mode five：Unlike one of present embodiment and specific implementation mode one to four：Described in step 3
CO2With CO in the mixed atmosphere of inert gas composition2Volume ratio with inert gas is (0.1~10)：1.Other steps and parameter
It is identical as one of specific implementation mode one to four.
Specific implementation mode six：Unlike one of present embodiment and specific implementation mode one to five：Described in step 3
The volume ratio of vapor and inert gas is (0.1~10) in the mixed atmosphere of vapor and inert gas composition：1.Other steps
Rapid and parameter is identical as one of specific implementation mode one to five.
Specific implementation mode seven：Unlike one of present embodiment and specific implementation mode one to six：Described in step 3
Inert gas is high pure nitrogen or high-purity argon gas.Other steps and parameter are identical as one of specific implementation mode one to six.
Specific implementation mode eight：Unlike one of present embodiment and specific implementation mode one to seven：Described in step 4
The pickle used when pickling processes is dilute hydrochloric acid or nitric acid.Other steps and one of parameter and specific implementation mode one to seven phase
Together.
Specific implementation mode nine：Present embodiment is unlike specific implementation mode eight：The acid used described in step 4
A concentration of 0.01mol/L~1mol/L of washing lotion.Other steps and parameter are identical as specific implementation mode eight.
Specific implementation mode ten：Unlike one of present embodiment and specific implementation mode one to nine：Described in step 5
The temperature of drying process is 60 DEG C~200 DEG C, and the time is 5h~12h.Other steps and parameter and specific implementation mode one to nine
One of it is identical.
Beneficial effects of the present invention are verified using following embodiment：
Embodiment 1：
The method that the present embodiment micro-calcium addition catalytic activation prepares coal base porous carbon materials carries out according to the following steps：
One, raw material refines
The accurate eastern coal dusts of 3g are crushed, are ground and are sieved successively, obtain refinement coal dust；
The grain size of the refinement coal dust is the mesh of 80 mesh~100；
Two, ball milling mixing
Refinement coal dust is mixed with calcium source, ball milling 4h obtains mixture；
The drum's speed of rotation when ball milling is 300r/min, and ball grinder material is agate；
The calcium source is calcium acetate；
The mass ratio of the refinement coal dust and calcium constituent in calcium source is 1:0.01；
Three, high-temperature activation
Mixture in step 2 is placed in atmosphere furnace, atmosphere furnace is warming up to 900 DEG C and keeps the temperature 10h, heat preservation terminates
Atmosphere furnace is down to room temperature naturally afterwards, obtains activation products；
The heating rate of the atmosphere furnace is 10 DEG C/min；
Atmosphere in the atmosphere furnace is CO2With the mixed atmosphere of inert gas composition；
The CO2With CO in the mixed atmosphere of inert gas composition2Volume ratio with inert gas is 2:3；The indifferent gas
Body is high pure nitrogen；
Four, activation products are cleaned
Activation products are carried out to pickling processes 3 times and washing process 3 times, the activation products after being cleaned successively；
The pickle used when the pickling processes is dilute hydrochloric acid, a concentration of 0.5mol/L of the pickle of use；
Five, dry
Processing is dried to get to coal base porous carbon materials in activation products after cleaning；
The temperature of the drying process is 100 DEG C, time 8h.
Fig. 1 is the TEM figures for the coal base porous carbon materials that embodiment 1 is prepared, from TEM it can be seen that made porous carbon
Micropore and central hole structure is distributed in material surface；Fig. 2 is the N2 adsorption isothermal for coal Quito hole active carbon material that embodiment 1 obtains
Line；The specific surface area that Fig. 2 can calculate the porous active carbon material that embodiment 1 obtains is up to 1535m2/ g, Kong Rongwei
1.66cm3/g。
Embodiment 2：
The method that the present embodiment micro-calcium addition catalytic activation prepares coal base porous carbon materials carries out according to the following steps：
One, raw material refines
The accurate eastern coal dusts of 3g are crushed, are ground and are sieved successively, obtain refinement coal dust；
The grain size of the refinement coal dust is the mesh of 80 mesh~100；
Two, ball milling mixing
Refinement coal dust is mixed with calcium source, ball milling 4h obtains mixture；
The drum's speed of rotation when ball milling is 300r/min, and ball grinder material is agate；
The calcium source is anhydrous calcium chloride；
The mass ratio of the refinement coal dust and calcium constituent in calcium source is 1:0.01；
Three, high-temperature activation
Mixture in step 2 is placed in atmosphere furnace, atmosphere furnace is warming up to 900 DEG C and keeps the temperature 1h, after heat preservation
Atmosphere furnace is down to room temperature naturally, obtains activation products；
The heating rate of the atmosphere furnace is 10 DEG C/min；
Atmosphere in the atmosphere furnace is CO2With the mixed atmosphere of inert gas composition；
The CO2With CO in the mixed atmosphere of inert gas composition2Volume ratio with inert gas is 2:3；The indifferent gas
Body is high pure nitrogen；
Four, activation products are cleaned
Activation products are carried out to pickling processes 3 times and washing process 3 times, the activation products after being cleaned successively；
The pickle used when the pickling processes is dilute hydrochloric acid, a concentration of 0.5mol/L of the pickle of use；
Five, dry
Processing is dried to get to coal base porous carbon materials in activation products after cleaning；
The temperature of the drying process is 100 DEG C, time 8h.
Fig. 3 is the TEM figures for the coal base porous carbon materials that embodiment 2 is prepared；Fig. 3 can be seen that the present embodiment obtained
Porous carbon materials have micropore and central hole structure simultaneously；Fig. 4 is the N2 adsorption for coal Quito hole active carbon material that embodiment 2 obtains
Thermoisopleth；The specific surface area that Fig. 4 can calculate the porous active carbon material that embodiment 2 obtains is up to 936m2/ g, Kong Rongwei
1.31cm3/g。
Embodiment 3：
The method that the present embodiment micro-calcium addition catalytic activation prepares coal base porous carbon materials carries out according to the following steps：
One, raw material refines
The accurate eastern coal dusts of 3g are crushed, are ground and are sieved successively, obtain refinement coal dust；
The grain size of the refinement coal dust is the mesh of 80 mesh~100；
Two, ball milling mixing
Refinement coal dust is mixed with calcium source, ball milling 4h obtains mixture；
The drum's speed of rotation when ball milling is 300r/min, and ball grinder material is agate；
The calcium source is calcium sulfate；
The mass ratio of the refinement coal dust and calcium constituent in calcium source is 1:0.01；
Three, high-temperature activation
Mixture in step 2 is placed in atmosphere furnace, atmosphere furnace is warming up to 900 DEG C and keeps the temperature 1h, after heat preservation
Atmosphere furnace is down to room temperature naturally, obtains activation products；
The heating rate of the atmosphere furnace is 10 DEG C/min；
Atmosphere in the atmosphere furnace is CO2With the mixed atmosphere of inert gas composition；
The CO2With CO in the mixed atmosphere of inert gas composition2Volume ratio with inert gas is 2:3；The indifferent gas
Body is high pure nitrogen；
Four, activation products are cleaned
Activation products are carried out to pickling processes 3 times and washing process 3 times, the activation products after being cleaned successively；
The pickle used when the pickling processes is dilute hydrochloric acid, a concentration of 0.5mol/L of the pickle of use；
Five, dry
Processing is dried to get to coal base porous carbon materials in activation products after cleaning；
The temperature of the drying process is 100 DEG C, time 8h.
Fig. 5 is the TEM figures for the coal base porous carbon materials that embodiment 3 is prepared；Fig. 5 can be seen that the present embodiment obtained
Porous carbon materials surface relative smooth, no apparent hole occur, for typical unformed micropore carbon structure；Fig. 6 obtains for embodiment 3
The Nitrogen adsorption isotherm of the coal Quito hole active carbon material arrived；Fig. 6 can calculate the porous active carbon material that embodiment 2 obtains
Specific surface area be 764m2/ g, Kong Rongwei 0.59cm3/g.Have obviously compared to embodiment 1 and 2 gained grading-hole carbon material of example
It is different.This explanation adds the type of calcium source by change, can adjust the pore structure of prepared coal base porous carbon.The reason is that not
It is different with the reactivity of the catalytic activation of calcium source, the development of macropore during the calcium source with higher catalytic activity can promote.
Embodiment 4：
The method that the present embodiment micro-calcium addition catalytic activation prepares coal base porous carbon materials carries out according to the following steps：
One, raw material refines
The accurate eastern coal dusts of 3g are crushed, are ground and are sieved successively, obtain refinement coal dust；
The grain size of the refinement coal dust is the mesh of 80 mesh~100；
Two, ball milling mixing
Refinement coal dust is mixed with calcium source, ball milling 4h obtains mixture；
The drum's speed of rotation when ball milling is 300r/min, and ball grinder material is agate；
The calcium source is anhydrous calcium chloride；
The mass ratio of the refinement coal dust and calcium constituent in calcium source is 1:0.005；
Three, high-temperature activation
Mixture in step 2 is placed in atmosphere furnace, atmosphere furnace is warming up to 900 DEG C and keeps the temperature 1h, after heat preservation
Atmosphere furnace is down to room temperature naturally, obtains activation products；
The heating rate of the atmosphere furnace is 10 DEG C/min；
Atmosphere in the atmosphere furnace is CO2With the mixed atmosphere of inert gas composition；
The CO2With CO in the mixed atmosphere of inert gas composition2Volume ratio with inert gas is 2:3；The indifferent gas
Body is high pure nitrogen；
Four, activation products are cleaned
Activation products are carried out to pickling processes 3 times and washing process 3 times, the activation products after being cleaned successively；
The pickle used when the pickling processes is dilute hydrochloric acid, a concentration of 0.5mol/L of the pickle of use；
Five, dry
Processing is dried to get to coal base porous carbon materials in activation products after cleaning；
The temperature of the drying process is 100 DEG C, time 8h.
Fig. 7 is the Nitrogen adsorption isotherm for coal Quito hole active carbon material that embodiment 4 obtains；Fig. 7 can calculate implementation
The specific surface area for the porous active carbon material that example 2 obtains is 970m2/ g, Kong Rongwei 0.69cm3/g.Compared to 2 gained classification of example
Hole carbon material has significantly different, and the porous carbon materials obtained by this example are based on micropore.This explanation adds calcium source by change
Content can adjust the pore structure of prepared coal base porous carbon.The reason is that with the increase of calcium source additive amount, to CO2With coal
Catalytic activity enhancing, the development of macropore in promotion.
Comparative example：
The method of this comparative example coal base porous carbon materials carries out according to the following steps：
One, raw material refines
The accurate eastern coal dusts of 3g are crushed, are ground and are sieved successively, obtain refinement coal dust；
The grain size of the refinement coal dust is the mesh of 80 mesh~100；
Two, high-temperature activation
Refinement coal dust in step 1 is placed in atmosphere furnace, atmosphere furnace is warming up to 900 DEG C and keeps the temperature 1h, heat preservation terminates
Atmosphere furnace is down to room temperature naturally afterwards, obtains activation products；
The heating rate of the atmosphere furnace is 10 DEG C/min；
Atmosphere in the atmosphere furnace is CO2With the mixed atmosphere of inert gas composition；
The CO2With CO in the mixed atmosphere of inert gas composition2Volume ratio with inert gas is 2:3；The indifferent gas
Body is high pure nitrogen；
Three, activation products are cleaned
Activation products are carried out to pickling processes 3 times and washing process 3 times, the activation products after being cleaned successively；
The pickle used when the pickling processes is dilute hydrochloric acid, a concentration of 0.5mol/L of the pickle of use；
Four, dry
Processing is dried to get to coal base porous carbon materials in activation products after cleaning；
The temperature of the drying process is 100 DEG C, time 8h.
Fig. 8 is the Nitrogen adsorption isotherm for coal Quito hole active carbon material that comparative example obtains；Nitrogen absorption under low temperature test result
Show：The specific surface area of coal Quito hole active carbon material and hole, which are held, obtained by comparative example only has 511m2/ g and 0.31cm3/ g, is far below
Coal Quito hole active carbon material obtained by Examples 1 to 4, micropore or middle macropore can be promoted by directly demonstrating the micro calcium source of addition
Development.
Claims (10)
1. a kind of method that micro-calcium addition catalytic activation prepares coal base porous carbon materials, it is characterised in that：This method is by following
Step carries out：
One, raw material refines
Coal raw material is crushed, is ground and is sieved successively, obtains refinement coal dust；
The grain size of the refinement coal dust is the mesh of 40 mesh~200；
Two, ball milling mixing
Refinement coal dust is mixed with calcium source, ball milling 1h~8h obtains mixture；
The calcium source is anhydrous calcium chloride, calcium sulfate, calcium hydroxide, calcium carbonate, calcium nitrate, calcium formate, calcium acetate, citric acid
One or more mixtures in any proportion in calcium, calcium gluconate；
The mass ratio of the refinement coal dust and calcium constituent in calcium source is 1：(0.001~0.05)；
Three, high-temperature activation
Mixture in step 2 is placed in atmosphere furnace, by atmosphere furnace be warming up to 700 DEG C~1000 DEG C and keep the temperature 0.5h~
Atmosphere furnace is down to room temperature by 10h naturally after heat preservation, obtains activation products；
Atmosphere in the atmosphere furnace is CO2With the mixed atmosphere or vapor of inert gas composition and mixing for inert gas composition
Close atmosphere；
Four, activation products are cleaned
Activation products are carried out to pickling processes 2~3 times and washing process 2~3 times, the activation products after being cleaned successively；
Five, dry
Processing is dried to get to coal base porous carbon materials in activation products after cleaning.
2. the method that micro-calcium addition catalytic activation according to claim 1 prepares coal base porous carbon materials, feature exist
In：Coal raw material described in step 1 is one or more mixing in any proportion in lignite, bituminous coal, ub-bituminous coal or anthracite
Object.
3. the method that micro-calcium addition catalytic activation according to claim 1 or 2 prepares coal base porous carbon materials, feature
It is：Drum's speed of rotation described in step 2 when ball milling is 100r/min~500r/min, and ball grinder material is agate or stainless
Steel.
4. the method that micro-calcium addition catalytic activation according to claim 3 prepares coal base porous carbon materials, feature exist
In：The heating rate of atmosphere furnace described in step 3 is 0.1 DEG C/min~15 DEG C/min.
5. the method that micro-calcium addition catalytic activation according to claim 1,2 or 4 prepares coal base porous carbon materials, special
Sign is：CO described in step 32With CO in the mixed atmosphere of inert gas composition2With the volume ratio of inert gas be (0.1~
10)：1.
6. the method that micro-calcium addition catalytic activation according to claim 5 prepares coal base porous carbon materials, feature exist
In：Vapor described in step 3 and inert gas composition mixed atmosphere in the volume ratio of vapor and inert gas be (0.1~
10)：1.
7. the method that micro-calcium addition catalytic activation according to claim 6 prepares coal base porous carbon materials, feature exist
In：Inert gas described in step 3 is high pure nitrogen or high-purity argon gas.
8. the method that micro-calcium addition catalytic activation according to claim 7 prepares coal base porous carbon materials, feature exist
In：The pickle used when pickling processes described in step 4 is dilute hydrochloric acid or nitric acid.
9. the method that micro-calcium addition catalytic activation according to claim 8 prepares coal base porous carbon materials, feature exist
In：A concentration of 0.01mol/L~1mol/L of the pickle used described in step 4.
10. the method that micro-calcium addition catalytic activation according to claim 9 prepares coal base porous carbon materials, feature exist
In：The temperature being dried described in step 5 is 60 DEG C~200 DEG C, and the time is 5h~12h.
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| CN109835900A (en) * | 2019-03-21 | 2019-06-04 | 哈尔滨工业大学 | A kind of preparation method of the coal base porous carbon based on potassium carbonate cyclic activation and the preparation method of biomass-based porous carbon |
| CN110550629A (en) * | 2019-09-24 | 2019-12-10 | 册亨县魅宝活性炭有限公司 | Production process for increasing adsorption pore diameter of wood physical method activated carbon |
| CN110745824A (en) * | 2019-11-21 | 2020-02-04 | 哈尔滨工业大学 | Method for regulating and controlling coal-based porous carbon pore matching based on trace potassium source catalytic activation |
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| CN111617737A (en) * | 2019-02-27 | 2020-09-04 | 河北工业大学 | Hierarchical porous carbon material and preparation method and application thereof |
| CN109835900A (en) * | 2019-03-21 | 2019-06-04 | 哈尔滨工业大学 | A kind of preparation method of the coal base porous carbon based on potassium carbonate cyclic activation and the preparation method of biomass-based porous carbon |
| CN110550629A (en) * | 2019-09-24 | 2019-12-10 | 册亨县魅宝活性炭有限公司 | Production process for increasing adsorption pore diameter of wood physical method activated carbon |
| CN110745824A (en) * | 2019-11-21 | 2020-02-04 | 哈尔滨工业大学 | Method for regulating and controlling coal-based porous carbon pore matching based on trace potassium source catalytic activation |
| CN111763097A (en) * | 2020-07-14 | 2020-10-13 | 淄博钛金窑炉科技有限公司 | Method for preparing porous ceramic by using coal gangue |
| CN111763097B (en) * | 2020-07-14 | 2022-08-26 | 淄博钛金窑炉科技有限公司 | Method for preparing porous ceramic by using coal gangue |
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