CN110368897A - A kind of nitrogenous porous charcoal of coal-tar base superhigh specific surface area and its preparation method and application - Google Patents
A kind of nitrogenous porous charcoal of coal-tar base superhigh specific surface area and its preparation method and application Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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Abstract
The invention discloses a kind of nitrogenous porous charcoals of coal-tar base superhigh specific surface area and its preparation method and application, belong to Absorbent field；It using coal tar as carbon source, calcium oxide is template in porous carbon preparation process of the invention, potassium hydroxide is activator preparation porous charcoal, and carries out ethylenediamine dipping to its surface and be modified；Gained porous charcoal has more than 2000m2The specific surface area of/g, surface are rich in nitrogen-containing functional group, can adsorb to the acid dyes in waste water；Operating cost of the present invention is low, easy to operate, stable, and achieve efficiently removal dyestuff purpose, it can be achieved that low cost under waste water from dyestuff advanced treating and qualified discharge.
Description
Technical field
The invention belongs to technical field of porous carbon material preparation, and in particular to a kind of coal-tar base superhigh specific surface area is nitrogenous
Porous charcoal and its preparation method and application.
Background technique
In DYE PRODUCTION and use process, about 10%~20% dyestuff is gone out with discharge of wastewater.Some dyestuffs
It can be entered in human body by food chain, lead to cell carcinogenic, teratogenesis, therefore waste water from dyestuff brings danger to environment and human health
Evil.The processing common method of waste water from dyestuff has physical method, chemical method and bioanalysis both at home and abroad.Absorption method is due to easy to operate, energy
Compared with the excellent performance for handling pollutant under temperate condition, it is used widely in waste water from dyestuff improvement.Adsorbent is then to inhale
The core of attached technology.Active carbon has many advantages, such as that flourishing pore structure, huge specific surface area, functional group abundant make because of it
It is most widely used for adsorbent in water treatment procedure.However since dye molecule size is larger, it is difficult to enter active carbon
Celled portion, therefore microporous activated carbon is bad to the adsorption effect of dyestuff.
Summary of the invention
One of the objects of the present invention is to provide a kind of nitrogenous porous charcoals of coal-tar base superhigh specific surface area, with superelevation
Specific surface area, surface also contains there are many nitrogen-containing functional group.
The second object of the present invention is to provide a kind of preparation method of nitrogenous porous charcoal of coal-tar base superhigh specific surface area.
The third object of the present invention is to provide a kind of nitrogenous porous charcoal of coal-tar base superhigh specific surface area in Dye Adsorption
The application of aspect, the nitrogenous porous charcoal of coal-tar base superhigh specific surface area is as adsorbent, in multilayer absorption method absorption waste liquid
Dyestuff, adsorption effect are good.
To reach above-mentioned technical purpose, The technical solution adopted by the invention is as follows:
Technical solution one:
A kind of nitrogenous porous charcoal of coal-tar base superhigh specific surface area, micropore, aperture and mesoporous rich in；Its surface
Contain nitrogen-containing functional group；Its specific surface area is more than 2000m2/g。
As a further improvement of the present invention, the nitrogen-containing functional group is C-N-C, N- (C)3With C-N-H.
Technical solution two:
A kind of preparation method of the nitrogenous porous charcoal of coal-tar base superhigh specific surface area, using coal tar as carbon source, calcium oxide
For template, potassium hydroxide is that activator is prepared into coal-tar base porous carbon, and it is modified then to carry out dipping with ethylenediamine to obtain the final product.
As a further improvement of the present invention, the mass ratio of the coal tar and calcium oxide be 1:1~1:3, coal tar with
The mass ratio of potassium hydroxide is 1:1~1:5.
As a further improvement of the present invention, the amount ratio of ethylenediamine and coal-tar base porous carbon is 0.5~1:2.
As a further improvement of the present invention, preparation method includes the following steps:
(1) coal tar, calcium oxide and potassium hydroxide are weighed respectively, is placed in grinder and grinds, and are sufficiently mixed material
To reactant；
(2) resulting reactant is put into crucible, then crucible is put into tube furnace, be slowly uniformly passed through nitrogen,
To drain air therein, 850 DEG C~900 DEG C are slowly uniformly heating to, constant temperature cools down after keeping 55-65min, is down to room temperature
Afterwards, power supply and nitrogen to be closed, crucible is taken out, takes out product, grinding, pickling is placed on magnetic stirring apparatus and stands after mixing evenly,
It is washed to neutrality, drying is sieved up to coal-tar base porous carbon；Preferably, leading to nitrogen flow rate is 6mL/min；Ventilation 30min be
The air in device can be drained；Heating rate is preferably controlled in 5 DEG C/min, the preferred 60min of thermostatic hold-time in temperature-rise period；
The preferred 2M dilute hydrochloric acid of acid cleaning process；The magnetic agitation time preferably for 24 hours, is then allowed to stand 6h；Drying process preferably 110 DEG C of freeze-day with constant temperature
Dry in case, drying time is preferably for 24 hours.
(3) coal-tar base porous carbon is mixed with ethylenediamine solution, filters after mixing evenly, washes, is dried to obtain coal tar
The nitrogenous porous charcoal of oil base superhigh specific surface area.
Technical solution three:
Application of the above-mentioned nitrogenous porous charcoal of coal-tar base superhigh specific surface area in terms of adsorbing dyestuff, the coal-tar base are super
The nitrogenous porous charcoal of high-specific surface area is used as adsorbent.
As a further improvement of the present invention, the dyestuff is that acid dyes is Congo red and acid dyes is pinkish red.
As a further improvement of the present invention, the nitrogenous porous carbon adsorbent of coal-tar base superhigh specific surface area is to the Congo
Red and acid fuchsin saturated extent of adsorption respectively reaches 3500mg/g and 2500mg/g.
Compared with prior art, the present invention has following technical effect that
Coal tar is a kind of complex mixture of the hydrocarbon of high aromaticity, and the overwhelming majority is for band side chain or without side
The heterocyclic compound of the polycyclic of chain, fused ring compound and oxygen-containing, sulphur, nitrogen, and contain a small amount of aliphatic hydrocarbon, cycloalkane and unsaturation
Hydrocarbon is also entrained with coal dust, burnt dirt and pyrolytic carbon.The coal tar just recycled is also containing 5% or so dissolved with plurality of inorganic salt and its
The moisture of his impurity.High temperature coal-tar contains 10,000 multiple compounds, can be divided into neutral hydro carbons, acid phenol by chemical property
The pyridine of class and alkalinity, quinolines.1819, British Jia Deng (Garden) and Blanc moral (Brand) were in coal tar
In have found naphthalene, this is first compound found in coal tar.It is later mainly scientist and the phase of Britain and Germany
After have found anthracene, phenol, aniline, quinoline, pyridine, pyrene andDeng.480 kinds of compounds are identified by 1972, content accounts for altogether
The 55% of coal tar oil quality, wherein 174 kinds of neutral compound, 63 kinds of acid compound, 113 kinds of alkali compounds, remaining is thick
Ring and oxygen-containing, sulphur heterocyclic compound.
The present invention is using coal tar as carbon source, and one side abundance is cheap, is on the other hand due to changing in coal tar
It is abundant to close species, using it as functional group rich in porous carbon materials made from carbon source, wherein there are many functional groups can
So that porous carbon has the absorption for being significantly better than normal activated carbon and handles the performance of waste water；The nitrogen-containing functional group tool wherein contained
There is alkalinity, energy is effective and acid dyes forms chemisorption, and excellent absorption property, isothermal are especially shown to acid dyes
Adsorption experiment show the nitrogenous porous charcoal of the coal-tar base to Congo red highest adsorbance be 3500mg/g, to acid fuchsin most
High adsorption capacity is 2500mg/g.In Dye Adsorption field, the adsorbance of the adsorbent is very high.In addition, type is abundant in coal tar
Compound different reactions can occur in activation process, to form different size of pore structure, make porous carbon materials
With aperture type abundant and aperture quantity, to make specific surface of the nitrogenous porous carbon materials being prepared with superelevation
Product, has advanced optimized its absorption property.
The present invention can stablize and enrich the kind of coal-tar base activated carbon surface nitrogen-containing functional group using ethylenediamine as modifying agent
Class and quantity, to further improve the absorption property of the nitrogenous porous carbon materials of coal-tar base.
The nitrogenous porous carbon materials of coal-tar base of the invention are mainly used in the absorption of acid dyes, for having adsorbed
The porous charcoal of dyestuff, using multilayer adsorption method.Under the premise of not changing porous carbon structure, increases adsorbent and show porose benefit
With rate, total adsorbance of adsorbent is increased, relative to regeneration techniques, more economical environmental protection has adsorbed dyestuff for processing
Adsorbent, provide new approaches.
Detailed description of the invention
It in order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, below will be to institute in embodiment
Attached drawing to be used is needed to be briefly described, it should be apparent that, the accompanying drawings in the following description is only some implementations of the invention
Example, for those of ordinary skill in the art, without creative efforts, can also obtain according to these attached drawings
Obtain other attached drawings.
Fig. 1 is the scanning figure of the nitrogenous porous charcoal of coal-tar base prepared by embodiment 1；
Fig. 2 is the transmission plot of the nitrogenous porous charcoal of coal-tar base prepared by embodiment 1；
Fig. 3 is the full spectrogram of the nitrogenous porous charcoal XPS of coal-tar base prepared by embodiment 1；
Fig. 4 is the Nls orbit analysis of the nitrogenous porous charcoal of coal-tar base prepared by embodiment 1；
Fig. 5 is adsorption isotherm experiment result (single layer of the nitrogenous porous charcoal of coal-tar base to acid dyes of the preparation of embodiment 1
Absorption).
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Technical solution one:
A kind of nitrogenous porous charcoal of coal-tar base superhigh specific surface area, micropore, aperture and mesoporous rich in；Its surface
Contain nitrogen-containing functional group；Its specific surface area is more than 2000m2/g。
As a further improvement of the present invention, the nitrogen-containing functional group is C-N-C, N- (C)3With C-N-H.
Technical solution two:
A kind of preparation method of the nitrogenous porous charcoal of coal-tar base superhigh specific surface area, using coal tar as carbon source, calcium oxide
For template, potassium hydroxide is that activator is prepared into coal-tar base porous carbon, and it is modified then to carry out dipping with ethylenediamine to obtain the final product.
As a further improvement of the present invention, the mass ratio of the coal tar and calcium oxide be 1:1~1:3, coal tar with
The mass ratio of potassium hydroxide is 1:1~1:5.
As a further improvement of the present invention, the amount ratio of ethylenediamine and coal-tar base porous carbon is 0.5~1:2.
As a further improvement of the present invention, preparation method includes the following steps:
(1) coal tar, calcium oxide and potassium hydroxide are weighed respectively, is placed in grinder and grinds, and are sufficiently mixed material
To reactant；
(2) resulting reactant is put into crucible, then crucible is put into tube furnace, be slowly uniformly passed through nitrogen,
To drain air therein, 850 DEG C~900 DEG C are slowly uniformly heating to, constant temperature cools down after keeping 55-65min, is down to room temperature
Afterwards, power supply and nitrogen to be closed, crucible is taken out, takes out product, grinding, pickling is placed on magnetic stirring apparatus and stands after mixing evenly,
It is washed to neutrality, drying is sieved up to coal-tar base porous carbon；Preferably, leading to nitrogen flow rate is 6mL/min；Ventilation 30min be
The air in device can be drained；Heating rate is preferably controlled in 5 DEG C/min, the preferred 60min of thermostatic hold-time in temperature-rise period；
The preferred 2M dilute hydrochloric acid of acid cleaning process；The magnetic agitation time preferably for 24 hours, is then allowed to stand 6h；Drying process preferably 110 DEG C of freeze-day with constant temperature
Dry in case, drying time is preferably for 24 hours.
(3) coal-tar base porous carbon is mixed with ethylenediamine solution, filters after mixing evenly, washes, is dried to obtain coal tar
The nitrogenous porous charcoal of oil base superhigh specific surface area.
Technical solution three:
Application of the above-mentioned nitrogenous porous charcoal of coal-tar base superhigh specific surface area in terms of adsorbing dyestuff, the coal-tar base are super
The nitrogenous porous charcoal of high-specific surface area is used as adsorbent.
As a further improvement of the present invention, it is adsorbed, is included the following steps: with multilayer absorption method
(1) first layer adsorbs: adsorbent puts into the acid dyes congo red water that initial concentration is 100-800mg/L
In, at room temperature, sufficient standing, adsorbent dosage is 0.125g/L；
(2) second layer adsorbs: after the adsorbent that first layer is adsorbed Congo red saturation is dry, investment initial concentration is 100-
In the basic dye methylene blue dye water of 450mg/L, at room temperature, 36h is stood, adsorbent injected volume is 0.25g/L；
(3) third layer is adsorbed: after the adsorbent drying of second layer absorption methylene blue saturation, investment initial concentration is
In the acid dyes congo red water of 100-800mg/L, at room temperature, 36h is stood, the injected volume of adsorbent is
0.2g/L。
As a further improvement of the present invention, the nitrogenous porous carbon adsorbent of coal-tar base superhigh specific surface area is to the Congo
The saturated extent of adsorption of red and acid fuchsin monolayer adsorption respectively reaches 3500mg/g and 2500mg/g.
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to the accompanying drawings and examples
The present invention is described in further detail.
Embodiment 1:
The present embodiment provides a kind of nitrogenous porous charcoal of coal-tar base superhigh specific surface area for Dye Adsorption, the porous charcoals
Using coal tar as carbon source, calcium oxide is template, and potassium hydroxide is to carry out ethylenediamine dipping after prepared by activator to its surface and be modified
It forms.Specific step is as follows:
Step 1: weighing 5g coal tar, 10g calcium oxide and 20g potassium hydroxide respectively, be placed in grinder and grind, make material
It is sufficiently mixed to obtain reactant；
Step 2: resulting reactant is put into crucible, then crucible is put into tube furnace, it is logical with the flow velocity of 6mL/min
Enter nitrogen, after ventilation 30min drains the air in device, 900 DEG C is warming up to the heating rate of 5 DEG C/min, after constant temperature 60min
Cooling closes power supply and nitrogen when tube furnace is down to room temperature, takes out crucible, obtained product is taken out, grinding, with 2M salt
Pickling is placed on magnetic stirring apparatus and stirs for 24 hours, stands 6h, is washed to neutrality, in 110 DEG C of air dry oven with distillation
Dry rear for 24 hours, sieving obtains coal-tar base porous charcoal；
Step 3: take 2g coal-tar base porous charcoal to mix with the solution of 100ml ethylenediamine containing 1g, after continuously stirring 24 hours,
It filters, wash, being dried to obtain nitrogenous porous charcoal.
Porous charcoal manufactured in the present embodiment is porous structure, is seen rich in a large amount of large micropore and small mesoporous, shape characteristic
Scanning figure, transmission plot, respectively Fig. 1, Fig. 2, as seen from Figure 1, Figure 2, by the synergistic effect of template and potassium hydroxide, the charcoal coal tar
The pattern of oil base porous charcoal is irregular vesica shape, has cellular structure abundant, is conducive to the absorption of dyestuff.
Porous charcoal manufactured in the present embodiment is that porous structure is rich in large micropore and small mesoporous, with 3H-2000PM1 porous carbon
Expect that specific surface area and Porosimetry carry out specific surface area measurement and analysis, the porous carbon materials that detection obtains the present embodiment compare table
Area is 2310m2/g。
XPS analysis is carried out to porous charcoal manufactured in the present embodiment, as a result as shown in figure 3, as can be seen that the adsorbent in figure
In main carbon containing, two kinds of elements of oxygen, in addition to this also contain a small amount of nitrogen.
Nls orbit analysis is carried out to porous charcoal manufactured in the present embodiment, as a result as shown in Figure 4.From fig. 4, it can be seen that Nls
Most of presence in the form of C-N-C (398.3eV) and 3 (400.5eV) form of C- (N) exist, on a small quantity with C-N-H (401.8eV)
Form exist.
Adsorption isotherm experiment is carried out to the nitrogenous porous charcoal of the present embodiment, as a result as shown in figure 5, as seen from the figure, this is porous
Charcoal is up to 3500mg/g to Congo red saturation balance adsorbance, is also up to the saturation balance adsorbance of acid fuchsin
2500mg/g.Adsorbance quickly increases at the beginning with the increase of equilibrium concentration, and then adsorbance variation is slow.
Influence for verifying activation temperature to porous carbon structure, is arranged embodiment 2-4.
Embodiment 2:
The present embodiment provides a kind of nitrogenous porous charcoal of coal-tar base superhigh specific surface area for Dye Adsorption, the porous charcoals
Using coal tar as carbon source, calcium oxide is template, and potassium hydroxide is to carry out ethylenediamine dipping after prepared by activator to its surface and be modified
It forms.Specific step is as follows:
Step 1: weighing 5g coal tar, 10g calcium oxide and 20g potassium hydroxide respectively, be placed in grinder and grind, make material
It is sufficiently mixed to obtain reactant；
Step 2: resulting reactant is put into crucible, then crucible is put into tube furnace, it is logical with the flow velocity of 6mL/min
Enter nitrogen, after ventilation 30min drains the air in device, 850 DEG C is warming up to the heating rate of 5 DEG C/min, after constant temperature 60min
Cooling closes power supply and nitrogen when tube furnace is down to room temperature, takes out crucible, obtained product is taken out, grinding, with 2M salt
Pickling is placed on magnetic stirring apparatus and stirs for 24 hours, stands 6h, is washed to neutrality, in 110 DEG C of air dry oven with distillation
Dry rear for 24 hours, sieving obtains coal-tar base porous charcoal；
Step 3: take 2g coal-tar base porous charcoal to mix with the solution of 100ml ethylenediamine containing 1g, after continuously stirring 24 hours,
It filters, wash, being dried to obtain nitrogenous porous charcoal.
Embodiment 3
The present embodiment provides a kind of nitrogenous porous charcoal of coal-tar base superhigh specific surface area for Dye Adsorption, the porous charcoals
Using coal tar as carbon source, calcium oxide is template, and potassium hydroxide is to carry out ethylenediamine dipping after prepared by activator to its surface and be modified
It forms.Specific step is as follows:
Step 1: weighing 5g coal tar, 10g calcium oxide and 20g potassium hydroxide respectively, be placed in grinder and grind, make material
It is sufficiently mixed to obtain reactant；
Step 2: resulting reactant is put into crucible, then crucible is put into tube furnace, it is logical with the flow velocity of 6mL/min
Enter nitrogen, after ventilation 30min drains the air in device, 870 DEG C is warming up to the heating rate of 5 DEG C/min, after constant temperature 60min
Cooling closes power supply and nitrogen when tube furnace is down to room temperature, takes out crucible, obtained product is taken out, grinding, with 2M salt
Pickling is placed on magnetic stirring apparatus and stirs for 24 hours, stands 6h, is washed to neutrality, in 110 DEG C of air dry oven with distillation
Dry rear for 24 hours, sieving obtains coal-tar base porous charcoal；
Step 3: take 2g coal-tar base porous charcoal to mix with the solution of 100ml ethylenediamine containing 1g, after continuously stirring 24 hours,
It filters, wash, being dried to obtain nitrogenous porous charcoal.
The nitrogenous porous carbon that embodiment 2-3 is prepared is analyzed respectively, embodiment 2-3 is prepared nitrogenous more
Hole carbon material is rich in large micropore and small mesoporous, is compared with 3H-2000PM1 porous carbon materials specific surface area and Porosimetry
Surface area measurement and analysis, the porous carbon materials specific surface area that detection obtains embodiment 2 is 2180m2/g；Embodiment 3 it is porous
Carbon material specific surface area is 2240m2/g。
Embodiment 4
The present embodiment and the difference of embodiment 1 are only that: activation temperature is 950 DEG C, remaining step and parameter are the same as implementation
Example 1, the nitrogenous porous carbon that the present embodiment is prepared are analyzed, this is equally rich in large micropore and small mesoporous for discovery, still
Specific surface area measurement and analysis are carried out with 3H-2000PM1 porous carbon materials specific surface area and Porosimetry, detection is implemented
The porous carbon materials specific surface area of example 2 is 1790m2/ g, it may be possible to lead to partial hole structure collapses institute since activation temperature is excessively high
It causes.
Influence for verifying ethylenediamine dosage to porous carbon materials nitrogen-containing functional group, is arranged embodiment 5-9.
Embodiment 5
The present embodiment provides a kind of nitrogenous porous charcoal of coal-tar base superhigh specific surface area for Dye Adsorption, the porous charcoals
Using coal tar as carbon source, calcium oxide is template, and potassium hydroxide is to carry out ethylenediamine dipping after prepared by activator to its surface and be modified
It forms.Specific step is as follows:
Step 1: weighing 5g coal tar, 10g calcium oxide and 20g potassium hydroxide respectively, be placed in grinder and grind, make material
It is sufficiently mixed to obtain reactant；
Step 2: resulting reactant is put into crucible, then crucible is put into tube furnace, it is logical with the flow velocity of 6mL/min
Enter nitrogen, after ventilation 30min drains the air in device, 900 DEG C is warming up to the heating rate of 5 DEG C/min, after constant temperature 60min
Cooling closes power supply and nitrogen when tube furnace is down to room temperature, takes out crucible, obtained product is taken out, grinding, with 2M salt
Pickling is placed on magnetic stirring apparatus and stirs for 24 hours, stands 6h, is washed to neutrality, in 110 DEG C of air dry oven with distillation
Dry rear for 24 hours, sieving obtains coal-tar base porous charcoal；
Step 3: taking 2g coal-tar base porous charcoal to mix with the solution of 100ml ethylenediamine containing 0.5g, continuously stir 24 hours
Afterwards, it filters, wash, being dried to obtain nitrogenous porous charcoal.
Embodiment 6
The difference of the present embodiment and embodiment 5 is only that step 3.
Step 3: taking 2g coal-tar base porous charcoal to mix with the solution of 100ml ethylenediamine containing 0.7g, continuously stir 24 hours
Afterwards, it filters, wash, being dried to obtain nitrogenous porous charcoal.
Embodiment 7
The difference of the present embodiment and embodiment 5 is only that step 3.
Step 3: take 2g coal-tar base porous charcoal to mix with the solution of 100ml ethylenediamine containing 2g, after continuously stirring 24 hours,
It filters, wash, being dried to obtain nitrogenous porous charcoal.
Embodiment 8
The difference of the present embodiment and embodiment 5 is only that step 3.
Step 3: taking 2g coal-tar base porous charcoal to mix with the solution of 150ml ethylenediamine containing 10g, continuously stir 24 hours
Afterwards, it filters, wash, being dried to obtain nitrogenous porous charcoal.
Embodiment 9
The difference of the present embodiment and embodiment 5 is only that step 3.
Step 3: taking 2g coal-tar base porous charcoal to mix with the solution of 200ml ethylenediamine containing 20g, continuously stir 24 hours
Afterwards, it filters, wash, being dried to obtain nitrogenous porous charcoal.
XPS analysis is carried out to the porous charcoal of embodiment 5-9 preparation, the results show that main in the porous charcoal of embodiment 5-9 preparation
Carbon containing, two kinds of elements of oxygen are wanted, a small amount of nitrogen is in addition to this also contained.
Nls orbit analysis is carried out to the porous charcoal of embodiment 5-9 preparation, the results show that Nls is most of with C-N-C
(398.3eV) form exists and 3 (400.5eV) form of C- (N) exists, and exists on a small quantity in the form of C-N-H (401.8eV), but
It is that the type and quantity of nitrogen-containing functional group are basically unchanged afterwards as the increase of ethylenediamine dosage first increases, when porous charcoal and ethylenediamine
Mass ratio after 1:5, nitrogen-containing functional group quantity starts in slow reduction trend, the porous charcoal that wherein prepared by embodiment 7
Middle nitrogen-containing functional group quantity is most, and type is also most abundant.
Comparative example 1
The difference of this comparative example and embodiment 1 is only that impregnate without ethylenediamine and be modified.
Comparative example 2
Ethylenediamine of this comparative example by normal activated carbon by step (3) in embodiment 1, which impregnates, to be modified.
Reference examples 1
Using active porous carbon as blank control example.
Effect example 1:
By nitrogenous porous carbon that embodiment 1-9 is prepared, comparative example the 1-2 porous carbon materials being prepared and blank pair
Active carbon in as usual carries out the Congo red adsorption treatment of acid dyes as adsorbent, is carried out using multilayer absorption method, step
It is as follows:
(1) first layer adsorbs: adsorbent is put into the acid dyes congo red water that initial concentration is 700mg/L,
At room temperature, sufficient standing, adsorbent dosage are 0.125g/L；
(2) second layer adsorbs: continuous to be added in step (1) after the adsorbent that first layer is adsorbed Congo red saturation is dry
In processed waste water from dyestuff, at room temperature, 36h is stood, adsorbent injected volume is 0.25g/L；
(3) third layer is adsorbed: after the adsorbent drying after the second layer is adsorbed, putting into step (2) processed dyestuff
In waste water, at room temperature, 36h is stood, the injected volume of adsorbent is 0.2g/L.
Absorption result is shown in Table 1.
Table 1
| First layer adsorbance | Second layer adsorbance | Third layer adsorbance | Total adsorbance | |
| Embodiment 1 | 3815 | 931 | 1001 | 5747 |
| Embodiment 2 | 3391 | 882 | 742 | 5015 |
| Embodiment 3 | 3443 | 901 | 858 | 5202 |
| Embodiment 4 | 2490 | 394 | 402 | 3286 |
| Embodiment 5 | 3520 | 839 | 895 | 5254 |
| Embodiment 6 | 3501 | 918 | 902 | 5321 |
| Embodiment 7 | 3899 | 935 | 1059 | 5893 |
| Embodiment 8 | 3845 | 923 | 989 | 5757 |
| Embodiment 9 | 3830 | 903 | 969 | 5702 |
| Comparative example 1 | 2467 | 506 | 689 | 3662 |
| Comparative example 2 | 2339 | 358 | 202 | 2899 |
| Reference examples 1 | 1893 | 305 | 189 | 2387 |
Effect example 2:
By nitrogenous porous carbon that embodiment 1-9 is prepared, comparative example the 1-2 porous carbon materials being prepared and blank pair
Active carbon in as usual carries out the adsorption treatment of acid dyes magenta as adsorbent, is carried out using multilayer absorption method, step is such as
Under: (1) first layer adsorb: adsorbent is put into the acid dyes congo red water that initial concentration is 600mg/L, in room temperature
Under the conditions of, sufficient standing, adsorbent dosage is 0.125g/L；
(2) second layer adsorbs: continuous to be added in step (1) after the adsorbent that first layer is adsorbed Congo red saturation is dry
In processed waste water from dyestuff, at room temperature, 36h is stood, adsorbent injected volume is 0.25g/L；
(3) third layer is adsorbed: after the adsorbent drying after the second layer is adsorbed, putting into step (2) processed dyestuff
In waste water, at room temperature, 36h is stood, the injected volume of adsorbent is 0.2g/L.
Absorption result is shown in Table 2.
Table 2
| First layer adsorbance | Second layer adsorbance | Third layer adsorbance | Total adsorbance | |
| Embodiment 1 | 2530 | 635 | 426 | 3591 |
| Embodiment 2 | 2469 | 623 | 408 | 3500 |
| Embodiment 3 | 2498 | 626 | 398 | 3522 |
| Embodiment 4 | 1563 | 206 | 132 | 1901 |
| Embodiment 5 | 2432 | 602 | 401 | 3435 |
| Embodiment 6 | 2451 | 623 | 431 | 3505 |
| Embodiment 7 | 2559 | 634 | 451 | 3644 |
| Embodiment 8 | 2542 | 626 | 442 | 3610 |
| Embodiment 9 | 2501 | 603 | 423 | 3527 |
| Comparative example 1 | 1653 | 295 | 167 | 2115 |
| Comparative example 2 | 1569 | 263 | 124 | 1956 |
| Reference examples 1 | 1035 | 186 | 95 | 1316 |
By table 1-2 it is found that nitrogenous porous carbon materials prepared by the present invention have good effect to the absorption of dyestuff, hence it is evident that
Better than normal activated carbon；In addition, nitrogenous porous carbon materials prepared by the present invention may also pass through multiple utilization, suction is substantially increased
Attached dose of utilization rate.
Embodiment described above is only that preferred embodiment of the invention is described, and is not carried out to the scope of the present invention
It limits, without departing from the spirit of the design of the present invention, those of ordinary skill in the art make technical solution of the present invention
Various changes and improvements, should all fall into claims of the present invention determine protection scope in.
Claims (9)
1. a kind of nitrogenous porous charcoal of coal-tar base superhigh specific surface area, which is characterized in that its micropore rich in, aperture and in
Hole；Contain nitrogen-containing functional group in its surface；Its specific surface area is more than 2000m2/g。
2. a kind of nitrogenous porous charcoal of coal-tar base superhigh specific surface area according to claim 1, which is characterized in that described to contain
Nitrogen functional group is C-N-C, N- (C)3With C-N-H.
3. a kind of preparation method of the nitrogenous porous charcoal of coal-tar base superhigh specific surface area as claimed in claim 1 or 2, feature
Be:, using coal tar as carbon source, calcium oxide is template for it, and potassium hydroxide is that activator is prepared into coal-tar base porous carbon, then
It is modified to carry out dipping with ethylenediamine to obtain the final product.
4. the preparation method of the nitrogenous porous charcoal of coal-tar base superhigh specific surface area according to claim 3, which is characterized in that
The mass ratio of the coal tar and calcium oxide is 1:1~1:3, the mass ratio of coal tar and potassium hydroxide is 1:1~1:5.
5. the preparation method of the nitrogenous porous charcoal of coal-tar base superhigh specific surface area according to claim 4, which is characterized in that
The mass ratio of porous charcoal and ethylenediamine is 1:10~4:1.
6. according to the preparation method of the described in any item nitrogenous porous charcoals of coal-tar base superhigh specific surface area of claim 3-5,
It is characterized in that, includes the following steps:
(1) coal tar, calcium oxide and potassium hydroxide are weighed respectively, is placed in grinder and grinds, and material is made to be sufficiently mixed to obtain instead
Answer object；
(2) resulting reactant is put into crucible, then crucible is put into tube furnace, be slowly uniformly passed through nitrogen, with row
Air therein to the greatest extent is slowly uniformly heating to 850 DEG C~900 DEG C, and constant temperature cools down after keeping 55-65min, is cooled to room temperature, and closes
Power supply and nitrogen are closed, crucible is taken out, takes out product, grinding, pickling is placed on magnetic stirring apparatus and stands after mixing evenly, washes
To neutrality, drying is sieved up to coal-tar base porous carbon；
(3) coal-tar base porous carbon is mixed with ethylenediamine solution, filters after mixing evenly, washes, is dried to obtain coal-tar base
The nitrogenous porous charcoal of superhigh specific surface area.
7. the nitrogenous porous charcoal of coal-tar base superhigh specific surface area as described in any one of claims 1-3 is in terms of adsorbing dyestuff
Using, which is characterized in that the nitrogenous porous charcoal of coal-tar base superhigh specific surface area is used as adsorbent.
8. the use as claimed in claim 7, which is characterized in that the dyestuff is that acid dyes is Congo red and acid dyes product
It is red.
9. application as claimed in claim 7 or 8, which is characterized in that the nitrogenous porous charcoal of coal-tar base superhigh specific surface area
Adsorbent respectively reaches 3500mg/g and 2500mg/g to the saturated extent of adsorption of Congo red and acid fuchsin monolayer adsorption.
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