CN110339812A - Modification biological charcoal and its application in absorption VOCs - Google Patents
Modification biological charcoal and its application in absorption VOCs Download PDFInfo
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- CN110339812A CN110339812A CN201910616272.7A CN201910616272A CN110339812A CN 110339812 A CN110339812 A CN 110339812A CN 201910616272 A CN201910616272 A CN 201910616272A CN 110339812 A CN110339812 A CN 110339812A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—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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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—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
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
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- B01D2257/708—Volatile organic compounds V.O.C.'s
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- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a kind of modification biological charcoal and its applications in absorption VOCs, belong to environmental pollution processing technology field.The present invention provides a kind of high yield pulp1, high-specific surface area, high porosities, and have the modification biological charcoal of high adsorption capacity to VOCs: carbon precursor being mixed with nitrogenous phosphate, is pre-oxidized；After pre-oxidation, carry out carbonization reaction, then through acid elution to obtain the final product.The present invention is pre-oxidized using air or oxygen, selects abandoned biomass cheap and easy to get as carbon precursor, uses safe non-corrosive nitrogenous phosphate as in-situ activation nitrating agent, pre-oxidizing conditions are optimized simultaneously, greatly increase the yield of charcoal, and effectively improve its specific surface area, porosity and itrogen content of getter with nitrogen doped, the charcoal greatly promotes the adsorption capacity of the VOCs such as toluene, maximum saturation adsorbance is up to 438mg/g, and there is good capacity of resisting impact load, there is excellent application value.
Description
Technical field
The invention belongs to environmental pollution processing technology fields, and in particular to a kind of to pre-oxidize modified life obtained using air
Object charcoal and its application in absorption VOCs.
Background technique
From petrochemical industry, sewage treatment facility to coating furniture industry, the discharge of volatile organic compounds (VOCs) comes
Source is very extensive.VOCs not only to ecological environment and human health all constitute grave danger or secondary organic aerosol and
An important factor for important as precursors object of Tropospheric ozone is the serious haze weather in China and ozone pollution formation.At VOCs
Numerous technologies of reason are such as catalyzed burning, biofiltration, absorption, plasma, absorption method high, cost of investment with its removal efficiency
The advantages that low, Yi Zaisheng is considered as most promising VOCs control method.In terms of adsorbent, some economically feasibles, environment
Friendly agricultural or industrial source plant base biomass castoff, such as rice husk, stalk, sawdust, vinasse, have very big potentiality to become
Synthesize the raw material presoma of various functional carbon-supported catalysts.For example, containing 220g/kg starch and 117g/kg in maize alcohol stillage
Fiber is expected to become the strong biological carbon precursor of preparation adsorption capacity.
However, often there is specific surface area using the Carbon Materials that the abandoned biomass such as vinasse are pyrolyzed preparation in an inert atmosphere
Lowly, the problems such as porosity is poor, as Cao et al. (Environmental Science&Technology 2016,50 (23),
Rice straw, pig manure and sludge 12957-12965.) are warming up to charcoal specific surface area that 500 DEG C are prepared only under nitrogen atmosphere
For 41.5,10.1 and 4.83m2/ g, due to specific surface area and pollutant the adsorbance often correlation of charcoal, these
The adsorbance of charcoal is lower, can not all promote and apply.Therefore, it needs to promote its ratio using activator in the preparation of charcoal
Surface area and porosity, common activator such as potassium hydroxide, zinc chloride etc. can effectively be promoted charcoal specific surface area and
Porosity, but safety problem and secondary pollution problem are easily caused, and the charcoal yield prepared is very low, it is unable to high level money
Source.Phosphoric acid salt activator can increase the yield of charcoal, Zhou et al. (RSCAdvances 2018,8 (53),
30171-30179.) carbonized jointly using ammonium phosphate etc. as activator with vinasse, can by yield from about 20% promoted to
45% or more, specific surface area reaches 480.7m2/ g, total pore volume reach 0.291cm3/ g reaches the saturated extent of adsorption of toluene
296.4mg/g, but its charcoal conversion ratio and porosity are still lower, are not able to satisfy the requirement of industrial application.
Pre-oxidation, using more in Carbon fibe, active carbon from coal, is demonstrated to as preprocess method before a kind of charing
Specific surface area, the porosity of material after enough effectively promotion charings.CN1935642A discloses a kind of petroleum coke pre-oxidation treatment
The method of carbon molecular sieve can be conducive to subsequent charing and activation process after carrying out impregnation to petroleum coke powder using oxidant
The formation and development of middle pore structure, but its oxidant is H2O2、HNO3And H2SO4The mixture of equal strong oxidizers, operated
Not only there is security risk in journey, it is also possible to which the corrosion for causing equipment, the active carbon specific surface area highest finally obtained also can only
Reach 82m2/g。
Summary of the invention
First technical problem to be solved by this invention is to provide a kind of high yield pulp1, high-specific surface area, high porosity, and
There is the modification biological charcoal of high adsorption capacity to VOCs.
The technical proposal adopted by the invention to solve the above technical problems is that a kind of modification biological charcoal is provided, by following
Method is prepared:
A, it by after biomass material drying, crushes, sieving, obtains carbon precursor；
B, carbon precursor is uniformly mixed with nitrogenous phosphate, under inert gas shielding, is warming up to Pre oxidation, then
It is passed through oxidizing gas, is pre-oxidized；
C, it after pre-oxidation, under inert gas shielding, is warming up to carbonization temperature and is carbonized, after charing, obtain charcoal
Compound；
D, carbide is mixed with inorganic acid, is boiled, be washed out to neutrality, dry to get modification biological charcoal.
Wherein, in modification biological charcoal described above, in step A, the temperature of the drying is 60~105 DEG C, and the time is
12~36h.
Wherein, in modification biological charcoal described above, in step A, the mesh number of the sieving is 100~200 mesh.
Wherein, in modification biological charcoal described above, in step B, the nitrogenous phosphate is ammonium phosphate, urea phosphate, gathers
At least one of ammonium phosphate, melamine phosphate.
Wherein, in modification biological charcoal described above, in step B, the carbon precursor phosphatic mixes matter with nitrogenous
Amount is than being 1~4:1.
Wherein, in modification biological charcoal described above, in step B, the rate for being warming up to Pre oxidation is 5~10
℃/min。
Wherein, in modification biological charcoal described above, in step B, the temperature of the pre-oxidation is 150~400 DEG C.
Wherein, in modification biological charcoal described above, in step B, the time of the pre-oxidation is 0.5~3h.
Wherein, in modification biological charcoal described above, in step B, the oxidizing gas is air or oxygen.
Wherein, it in modification biological charcoal described above, in step B, when oxidizing gas is air, is controlled in pre-oxidation
Air mass flow is 60~300mL/min.
Wherein, it in modification biological charcoal described above, in step B, when oxidizing gas is oxygen, is controlled in pre-oxidation
Oxygen flow is 12~60mL/min.
Wherein, in modification biological charcoal described above, in step C, the rate for being warming up to carbonization temperature is 5~10
DEG C/min, carbonization temperature is 500~900 DEG C, and carbonization time is 0.5~3h.
Wherein, in modification biological charcoal described above, in step D, the inorganic acid is hydrochloric acid or nitric acid solution；Wherein,
The volumetric concentration of hydrochloric acid is 5%~20%；Nitric acid mass concentration is 5%~20%.
Wherein, in modification biological charcoal described above, in step D, the mixed proportion of carbide and inorganic acid is 5~15g/
100mL。
Wherein, in modification biological charcoal described above, in step D, the time boiled is 10~30min.
Modification biological charcoal specific surface area is up to 820.8m prepared by the present invention2/ g, total pore volume is up to 0.473cm3/ g, it is micro-
Kong Kongrong is up to 0.233cm3/ g, nitrogen content are had excellent performance up to 5.66%, are had to volatile organic compounds such as toluene
Efficient adsorption capacity, therefore the application the present invention also provides modification biological charcoal described above in absorption VOCs.
Wherein, modification biological charcoal described above is in the application in absorption VOCs, and the modification biological charcoal is to toluene
Maximum saturation adsorbance is 438mg/g.
Beneficial effects of the present invention:
The present invention uses convenient and safe air or oxygen pre-oxidation for pretreatment mode, selects discarded life cheap and easy to get
Substance as carbon precursor, use safe non-corrosive nitrogenous phosphate as in-situ activation nitrating agent, while to pre-oxidation
Condition optimizes, and greatly increases the yield of charcoal, and effectively improves its specific surface area, porosity and itrogen content of getter with nitrogen doped, the biology
Charcoal greatly promotes the adsorption capacity of the VOCs such as toluene, to toluene maximum saturation adsorbance up to 438mg/g, and has good
Capacity of resisting impact load has excellent application value.
Detailed description of the invention
Fig. 1 is not pre-oxidize charcoal S and pre-oxidation modification biological charcoal SP (350/120/2) in embodiment 1 to toluene
Adsorption breakthrough curve.
Fig. 2 is not pre-oxidize charcoal W and pre-oxidation modification biological charcoal WP (350/120/3) in embodiment 2 to toluene
Adsorption breakthrough curve.
Fig. 3 is the nitrogenous official for not pre-oxidizing charcoal H in embodiment 3 and pre-oxidizing modification biological charcoal HP (250/240/1)
XPS swarming can be rolled into a ball.
Specific embodiment
Specifically, modification biological charcoal, is prepared by following methods:
A, it by after biomass material drying, crushes, sieving, obtains carbon precursor；
B, carbon precursor is uniformly mixed with nitrogenous phosphate, under inert gas shielding, is warming up to Pre oxidation, then
It is passed through oxidizing gas, is pre-oxidized；
C, it after pre-oxidation, under inert gas shielding, is warming up to carbonization temperature and is carbonized, after charing, obtain charcoal
Compound；
D, carbide is mixed with inorganic acid, is boiled, be washed out to neutrality, dry to get modification biological charcoal.
Biomass material of the present invention is from a wealth of sources, such as vinasse, coconut husk, walnut shell, stalk, sawdust, animal excreta
Just, sludge etc., generally there are also moisture for these biomass materials, therefore first by its 60~105 DEG C dry 12~36h in the present invention.
In order to make subsequent mixing more uniformly, to make pre-oxidation, carbonization reaction etc. more evenly, thoroughly, by the material powder after drying
It is broken, and cross 100~200 meshes.
In step B of the present invention, carbon precursor is uniformly mixed with nitrogenous phosphate, during pre-oxidation, air or
Oxygen can promote oxygen-containing functional group to increase in biological surface, and oxygen-containing functional group can be preferably crosslinked with nitrogenous phosphate
Reaction, forms cyclized structure, and this cyclized structure can have better thermostabilization in the high temperature carbonization under subsequent nitrogen atmosphere
Property, to increase charcoal yield；Still further aspect, oxygen-containing functional group understand ablated formation hole again in subsequent carbonization reaction,
To increase the porosity of charcoal.Wherein, nitrogenous phosphate is ammonium phosphate, in urea phosphate, ammonium polyphosphate, melamine phosphate
At least one；And carbon precursor and nitrogenous phosphatic mixing mass ratio are controlled as 1~4:1.
When to avoid pre-oxidation, system internal oxidition atmosphere is uneven, and material pre-oxidation is uneven, in step B of the present invention
It is first warming up to Pre oxidation under inert gas protection, then is passed through oxidizing gas.It is tested, control is warming up to pre-oxidation temperature
The rate of degree is 5~10 DEG C/min, and the temperature of pre-oxidation is 150~400 DEG C, and the time of pre-oxidation is 0.5~3h, can significantly be mentioned
High charcoal yield and performance；The effect that charcoal performance is not promoted when temperature is too low, and charcoal if temperature is too high
Yield can decline.
In step B of the present invention, air or oxygen can be used and pre-oxidized, when oxidizing gas is air, control is empty
Throughput is 60~300mL/min；When oxidizing gas is oxygen, control oxygen flow is 12~60mL/min；Control oxygen
The property changed gas flow, avoids the excessive ablation for leading to charcoal of flow, influences charcoal yield and modification biological charcoal performance.
After pre-oxidation, oxidizing gas is excluded, carries out carbonization reaction under inert gas protection, control is warming up to
The rate of carbonization temperature is 5~10 DEG C/min, and carbonization temperature is 500~900 DEG C, and carbonization time is 0.5~3h.
In step D of the present invention, carbide is mixed with inorganic acid, carries out pickling primarily to removing the ash content inside carbon removal
The impurity such as heavy metal, while convenient for being washed to neutrality；In the present invention, the mixed proportion for controlling carbide and acid solution is 5
~15g/100mL, the time boiled are 10~30min.Hydrochloric acid or nitric acid can be used in inorganic acid；Wherein, the volumetric concentration of hydrochloric acid
It is 5%~20%；Nitric acid mass concentration is 5%~20%.
Modification biological charcoal specific surface area is up to 820.8m prepared by the present invention2/ g, Kong Rong is up to 0.473cm3/ g, micropore
Kong Rong is up to 0.233cm3/ g, nitrogen content are had excellent performance up to 5.66%, have efficient adsorption energy to VOCs such as toluene
Power, therefore the application the present invention also provides modification biological charcoal described above in absorption VOCs, and the modification biological charcoal pair
The maximum saturation adsorbance of toluene is up to 438mg/g.
Below by embodiment, invention is further described in detail, but does not therefore limit the scope of the present invention
Among the embodiment described range.
Embodiment 1
Vinasse are placed in baking oven, under the conditions of 105 DEG C after drying for 24 hours, vinasse after drying are crushed with high speed disintegrator,
200 meshes are crossed, carbon precursor is obtained；Carbon precursor and ammonium phosphate 1:1 ratio in mass ratio are uniformly mixed, 20g aggregate sample is taken
Product are put into tube furnace in quartz boat, after leading to the nitrogen venting air of half an hour, with the heating rate of 10 DEG C/min in nitrogen atmosphere
350 DEG C of Pre oxidation required for (120mL/min) is warming up under enclosing, is switched to air by nitrogen for air inlet, and adjust sky
Throughput is 120mL/min, keeps 2h at such a temperature.
After pre-oxidizing, air inlet is switched to nitrogen by air, after air displacement is complete, is warming up to 600 DEG C of charing temperature
Degree, keeps 1h, cooled to room temperature obtains carbide at such a temperature；Carbide and HCl (1+9) are pressed into 10g/100mL ratio
20min is boiled after example mixing, neutrality is washed to distillation, is subsequently placed in 105 DEG C of air dry oven, postposition that drying to constant weight
It is cooling in drier, after being cooled to room temperature, weighing, grinding are taken out, obtains modification biological charcoal (number: SP (350/120/2)),
It is put into spare in drier.
In addition, the sample without air pre-oxidation also in preparing in addition to pre-oxidation, i.e. charcoal forerunner under the same conditions
Body directly carbonizes after mixing with ammonium phosphate, obtains the charcoal (number: S) without pre-oxidation.
The specific surface area that gained modification biological charcoal (number: SP (350/120/2)) is pre-oxidized through air is 762.9m2/ g,
Kong Rongwei 0.444cm3/ g, wherein Micropore volume is 0.271cm3/ g, modification biological charcoal yield are 55.5%；Without pre-oxidation
The specific surface area of charcoal (number: S) is 480.7m2/ g, Kong Rongwei 0.291cm3/ g, wherein Micropore volume is 0.202cm3/ g,
Charcoal yield is 53.1%；It can be seen that the physical property of charcoal is greatly improved after pre-oxidizing, have
Huge specific surface area, porosity abundant and higher yield, promote the process of abandoned biomass recycling.
It adsorbs toluene simulation test: being packed into modification biological charcoal SP (350/120/ into two adsorption columns (diameter 1cm) respectively
And charcoal S, bed height 2cm 2)；It adjusting nitrogen and toluene flux carries out distribution, setting toluene inlet concentration is 600ppm,
It keeps 60min to stablize air inlet, toluene gas is passed through adsorption column, record exit concentration every 10min.
(ordinate is toluene to breakthrough curve such as Fig. 1 of modification biological charcoal SP (350/120/2) and charcoal S absorption toluene
The ratio of exit concentration and inlet concentration) shown in, the numerical value by curve represents adsorption penetration capacity.As shown in Figure 1, (350/ SP
120/2) the adsorption penetration capacity of toluene is greatly promoted, it is possible thereby to infer, the specific surface area that increases after pre-oxidation and
Porosity can increase the adsorption site, storage space and transmission speed of toluene.
Embodiment 2
Sawdust is placed in baking oven, under the conditions of 105 DEG C after dry 12h, sawdust after drying is crushed with high speed disintegrator,
It sieves with 100 mesh sieve, obtains carbon precursor；Carbon precursor and urea phosphate 1:1 ratio in mass ratio are uniformly mixed, 20g aggregate sample is taken
Product are put into tube furnace in quartz boat, after leading to the nitrogen venting air of half an hour, with the heating rate of 5 DEG C/min in nitrogen atmosphere
350 DEG C of Pre oxidation required for (120mL/min) is warming up under enclosing, is switched to air by nitrogen for air inlet, and adjust sky
Throughput is 120mL/min, keeps 3h at such a temperature.
After pre-oxidizing, air inlet is switched to nitrogen by air, after air displacement is complete, is warming up to 900 DEG C of charing temperature
Degree, keeps 1h, cooled to room temperature obtains carbide at such a temperature；Carbide and HCl (1+9) are pressed into 15g/100mL ratio
15min is boiled after example mixing, neutrality is washed to distillation, is subsequently placed in 105 DEG C of air dry oven, after drying to constant weight,
It is placed in cooling in drier, after being cooled to room temperature, weighing, grinding is taken out, obtains modification biological charcoal (number: WP (350/120/
3) it), is put into spare in drier.
In addition, the sample without pre-oxidation is also in preparing in addition to pre-oxidation under the same conditions, i.e., carbon precursor with
It is directly carbonized after urea phosphate mixing, obtains the charcoal (number: W) without pre-oxidation.
Specific surface area through pre-oxidation gained modification biological charcoal (number: WP (350/120/3)) is 820.8m2/ g, Kong Rong
For 0.473cm3/ g, wherein Micropore volume is 0.233cm3/ g, charcoal yield are 47.7%；Charcoal without pre-oxidation (is compiled
Number: specific surface area W) is 499.5m2/ g, Kong Rongwei 0.329cm3/ g, wherein Micropore volume is 0.242cm3/ g, charcoal obtain
Rate is 33.1%；It can be seen that the physical property of charcoal is greatly improved after pre-oxidizing, have huge ratio
Surface area, porosity abundant and higher yield, wherein pre-oxidation can be such that cellulose in sawdust is sufficiently cyclized with phosphate
Stable gradient-structure is formed, so that sample after pre-oxidation be made still to keep higher yield at high temperature.
It adsorbs toluene simulation test: being packed into modification biological charcoal WP (350/120/ into two adsorption columns (diameter 1cm) respectively
And charcoal W, bed height 2cm 3)；It adjusting nitrogen and toluene flux carries out distribution, setting toluene inlet concentration is 600ppm,
60min is kept, toluene gas is passed through adsorption column, records exit concentration every 10min.
The breakthrough curve of modification biological charcoal WP (350/120/3) and charcoal W absorption toluene is as shown in Fig. 2, by curve
Numerical value represents adsorption penetration capacity.As shown in Figure 2, WP (350/120/3) greatly promotes the adsorption penetration capacity of toluene, thus
It is inferred that the specific surface area and porosity increased after pre-oxidation can increase the adsorption site, storage space and biography of toluene
Defeated speed.
Embodiment 3
Stalk is placed in baking oven, under the conditions of 105 DEG C after drying for 24 hours, stalk after drying is crushed with high speed disintegrator,
200 meshes are crossed, carbon precursor is obtained；Carbon precursor and ammonium phosphate 1:1 ratio in mass ratio are uniformly mixed, 20g aggregate sample is taken
Product are put into tube furnace in quartz boat, after leading to the nitrogen venting air of half an hour, with the heating rate of 10 DEG C/min in nitrogen atmosphere
250 DEG C of Pre oxidation required for (120mL/min) is warming up under enclosing, is switched to air by nitrogen for air inlet, and adjust sky
Throughput is 240mL/min, keeps 1h at such a temperature.
After pre-oxidizing, air inlet is switched to nitrogen by air, after air displacement is complete, is warming up to 600 DEG C of charing temperature
Degree, keeps 2h, cooled to room temperature obtains carbide at such a temperature；Carbide and HCl (1+9) are pressed into 5g/100mL ratio
10min is boiled after example mixing, neutrality is washed to distillation, is subsequently placed in 105 DEG C of air dry oven, postposition that drying to constant weight
It is cooling in drier, after being cooled to room temperature, weighing, grinding are taken out, obtains modification biological charcoal (number: HP (250/240/1)),
It is put into spare in drier.
In addition, the sample without pre-oxidation is also in preparing in addition to pre-oxidation under the same conditions, i.e., carbon precursor with
It is directly carbonized after ammonium phosphate mixing, obtains the charcoal (number: H) without pre-oxidation.
Modification biological charcoal (number: HP (250/240/1)) nitrogen content by pre-oxidation is 5.66%, and without pre-oxidation
Charcoal (number: H) nitrogen content be 4.16%, it is known that during pre-oxidation, ammonium phosphate decomposes the ammonia generated can
It preferably reacts with charcoal, to increase nitrogen content while increasing porosity.Wherein, nitrogenous function in two kinds of charcoals
The type of group is shown in Fig. 3 respectively, is all class pyridine nitrogen by the type of nitrogen functional group is identical in two kinds of samples it can be seen from xps energy spectrum
(N-6,398.1-398.8eV), class pyrroles's nitrogen (N-5,400.0-400.1eV), protonation pyridine nitrogen (N-Q, 401.0-
401.2eV) and pyrrolones nitrogen (N-X, 402.5-402.8eV)；Wherein, after pre-oxidation, N-6 content declines from 30.29%
52.77%, N-Q and N-X content is increased to from 47.36% to 20.26%, N-5 content slightly to rise, illustrate nitrogen-containing group by
It is gradually converted into more firm structure nitrogen, further increases the nonpolarity of charcoal, so as to increase from another point of view pair
The absorption property of toluene.
Embodiment 4
Coconut husk is placed in baking oven, under the conditions of 105 DEG C after drying for 24 hours, coconut husk after drying is crushed with high speed disintegrator,
200 meshes are crossed, carbon precursor is obtained；Carbon precursor and urea phosphate 2:1 ratio in mass ratio are uniformly mixed, 20g aggregate sample is taken
Product are put into tube furnace in quartz boat, after leading to the nitrogen venting air of half an hour, with the heating rate of 10 DEG C/min in nitrogen atmosphere
400 DEG C of Pre oxidation required for (120mL/min) is warming up under enclosing, is switched to air by nitrogen for air inlet, and adjust sky
Throughput is 120mL/min, keeps 3h at such a temperature.
After pre-oxidizing, air inlet is switched to nitrogen by air, after air displacement is complete, is warming up to 700 DEG C of charing temperature
Degree, keeps 1h, cooled to room temperature obtains carbide at such a temperature；Carbide and HCl (1+9) are pressed into 10g/100mL ratio
20min is boiled after example mixing, neutrality is washed to distillation, is subsequently placed in 110 DEG C of air dry oven, postposition that drying to constant weight
It is cooling in drier, after being cooled to room temperature, weighing, grinding are taken out, obtains modification biological charcoal (number: CP (400/120/3)),
It is put into spare in drier.
To modification biological charcoal (number: CP (400/120/3)) is packed into adsorption column (diameter 1cm), bed height 2cm remembers
Quality is recorded, nitrogen is adjusted and toluene flux carries out distribution, different toluene inlet concentrations is set, 60min is kept, by toluene gas
It is passed through adsorption column, exit concentration is recorded every 10min, the results are shown in Table 1；Wherein TbAnd QbDistribution represents time of break-through and penetrates suction
Attached capacity, TsAnd QsRespectively represent saturation time of break-through and saturated adsorption capacity.
As shown in Table 1, with the increase of imported toluene concentration, modification biological charcoal CP (400/12/3) penetrates suction to toluene
Attached capacity and saturated adsorption capacity are all gradually increasing, it was demonstrated that the anti-load impact ability of pre-oxidation charcoal, wherein pre-oxidation
Charcoal meets Freundlich model to the absorption isotherm of toluene, and calculating highest adsorbance is 437.8mg/g, significantly high
In the prior art, it was demonstrated that the positive correlation influence that the chemical property and physical property promoted after pre-oxidation adsorb toluene.
Adsorption capacity of the 1 pre-oxidised samples CP (400/120/3) of table to different toluene inlet concentrations
Claims (10)
1. modification biological charcoal, it is characterised in that: be prepared by following methods:
A, it by after biomass material drying, crushes, sieving, obtains carbon precursor；
B, carbon precursor is uniformly mixed with nitrogenous phosphate, under inert gas shielding, is warming up to Pre oxidation, then passes to
Oxidizing gas is pre-oxidized；
C, it after pre-oxidation, under inert gas shielding, is warming up to carbonization temperature and is carbonized, after charing, obtain carbide；
D, carbide is mixed with inorganic acid, is boiled, be washed out to neutrality, dry to get modification biological charcoal.
2. modification biological charcoal according to claim 1, it is characterised in that: in step A, at least meet following one:
The temperature of the drying is 60~105 DEG C, and the time is 12~36h；
The mesh number of the sieving is 100~200 mesh.
3. modification biological charcoal according to claim 1, it is characterised in that: in step B, the nitrogenous phosphate is phosphoric acid
At least one of ammonium, urea phosphate, ammonium polyphosphate, melamine phosphate；The carbon precursor phosphatic is mixed with nitrogenous
Mass ratio is 1~4:1.
4. modification biological charcoal according to claim 1, it is characterised in that: in step B, at least meet following one:
The rate for being warming up to Pre oxidation is 5~10 DEG C/min；
The temperature of the pre-oxidation is 150~400 DEG C；
The time of the pre-oxidation is 0.5~3h.
5. modification biological charcoal according to claim 1, it is characterised in that: in step B, the oxidizing gas be air or
Oxygen；When oxidizing gas is air, control air mass flow is 60~300mL/min in pre-oxidation；When oxidizing gas is
It is 12~60mL/min that oxygen flow is controlled when oxygen, in pre-oxidation.
6. modification biological charcoal according to claim 1, it is characterised in that: in step C, the speed for being warming up to carbonization temperature
Rate is 5~10 DEG C/min, and carbonization temperature is 500~900 DEG C, and carbonization time is 0.5~3h.
7. modification biological charcoal according to claim 1, it is characterised in that: in step D, the inorganic acid is hydrochloric acid or nitre
Acid；Wherein, the volumetric concentration of hydrochloric acid is 5%~20%；Nitric acid mass concentration is 5%~20%.
8. modification biological charcoal according to claim 1, it is characterised in that: in step D, the mixing ratio of carbide and inorganic acid
Example is 5~15g/100mL；The time boiled is 10~30min.
9. application of the modification biological charcoal according to any one of claims 1 to 8 in absorption VOCs.
10. application of the modification biological charcoal according to claim 9 in absorption VOCs, it is characterised in that: described modified raw
Object charcoal is 438mg/g to the maximum saturation adsorbance of toluene.
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