CN110508274A - Modification biological charcoal low-temperature denitration catalyst and its application - Google Patents
Modification biological charcoal low-temperature denitration catalyst and its application Download PDFInfo
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Abstract
The invention discloses a kind of modification biological charcoal low-temperature denitration catalyst and its applications, belong to air contaminant treatment and environmental functional field of charcoal material.The present invention is to solve the technical problem that existing denitrating catalyst low-temperature denitration rate is low, preparation method is complicated, at high cost, provides a kind of modification biological charcoal low-temperature denitration catalyst, is made by following methods: charcoal being carried out pre-oxidation treatment, obtains high-area carbon；The ultrasonic immersing in metal salt solution by high-area carbon, after drying, then under oxidizing atmosphere low temperature calcination to get.The present invention passes through oxidizing atmosphere pre-oxidation-metal salt solution ultrasonic immersing-low-temperature oxidation atmosphere calcining, significantly improve the denitration performance of modification biological charcoal denitrating catalyst, making it, (100-200 DEG C) activity is more preferable under cryogenic, and denitrification rate is up to 99%.
Description
Technical field
The invention belongs to air contaminant treatment and environmental functional Carbon Materials technical fields, and in particular to a kind of modification biological charcoal
Low-temperature denitration catalyst and its application.
Background technique
Industrial smoke is the important sources of China's flue gas emission, using coal as the boiler of fuel or thermal power plant and with iron
Ore is a large amount of pollution flue gases of the annual discharge such as steel plant of raw material.Nitrogen oxides (NO in flue gasX) gray haze, ozone can be caused
Many environmental problems such as pollution, are the main sources of atmosphere pollution.The discharge of effectively control NOx is the important of control atmosphere pollution
Project.Selective catalytic reduction (SCR) is one of current most effective gas denitrifying technology, specifically with NH3Deng as reduction
NOx is selectively reduced into N under certain temperature and catalyst action by agent2And H2O, since its operating process is simple, denitration effect
The features such as rate is high, it has also become the research hotspot in domestic and international denitrating flue gas field.In recent years, vanadium titanium oxide is industrially generallyd use
It is denitrating catalyst, the NOx in flue gas is reduced to N at a temperature of 300~450 DEG C2.However, for effectively avoid flying dust and its
Abrasion, blocking and poisoning effect of its component to catalyst, denitrating catalyst are typically placed in after dust-removing desulfurating apparatus, at this time
Flue-gas temperature is usually at 100~150 DEG C, it is therefore desirable to by flue gas to progress denitration after 300 DEG C or more, energy consumption be caused to mention
It is high.In order to avoid flue gas reheating leads to the increase of processing cost, it is low that exploitation high efficient cryogenic denitration catalyst material has become solution
The task of top priority of warm denitration technology problem.
Currently, the research of low-temperature denitration catalyst is concentrated mainly on metal oxide (such as Mn, Ce, V, Fe, Cu both at home and abroad
Deng), wherein Mn oxide such as MnO, MnO2、Mn2O3、Mn3O4、Mn5O8Deng abundant because its multivalent state redox cycle is reacted
Acidic site and active oxygen, excellent low-temperature catalytic activity, and cheap receives significant attention.In addition, Mn is loaded
The dispersion degree of active component can be improved on to carrier, increase specific surface area, further increase catalyst activity.Relative to
TiO2、Al2O3、SiO2Equal carriers, porous charcoal such as charcoal, active carbon, activated carbon fibre etc. have from a wealth of sources, ecological hold
The advantages such as continuous, low in cost, at the same its porous structure can for the load and the diffusions of reactant gas molecules of active component, absorption,
Reaction provides place, and its active site of surface functional group abundant as catalyzed conversion, enables it can be in lower temperature
Under (80~150 DEG C) show good catalytic activity, be particularly suitable for the carrier as low-temperature SCR catalyst.Therefore, it is more to carry manganese
Hole Pd/carbon catalyst is a kind of low-temperature denitration catalyst of great application prospect.
CN107115868A discloses a kind of low temperature SCR denitration catalyst and preparation method thereof based on active carbon: will too
Western anthracite, Taiyuan Fugu coal, Guilin lignite are mixed in a certain ratio uniformly after crushing, and binder is added and forms to obtain cylinder
Honeycomb moulding mixture green body；Honeycomb moulding mixture green body after drying is placed in incinerator, first it is warming up to 240 under nitrogen atmosphere~
250℃；Then blowing air aoxidizes 6h；Then lead to nitrogen temperature to 650~700 DEG C, carbonization reaction 1h, it is continuously heating to 900~
950℃；And then change logical CO2Priming reaction 2h, then be cooled to room temperature under nitrogen protection, obtain charcoal base honeycomb structure carrier；Again
After carrier at room temperature ultrasonic immersing concentrated nitric acid 1h, washing is placed in baking oven to neutrality is dried；By the carrier leaching after drying
It steeps in Ce (NO3)3、Fe(NO3)3、Cu(NO3)2With Mn (NO3)2In the mixed solution of solution, it is warming up to 600 under nitrogen protection~
700 DEG C of calcination 3h are to get low-temperature denitration catalyst.The invention catalyst preparation process is complicated, and the denitrification rate at 150 DEG C is only
Have 84%.
CN106000415A disclose a kind of denitrating catalyst with and preparation method thereof and preparation system, by by Carbon Materials
Radioactivation is carried out using microwave in atmosphere of inert gases after impregnating in liquor zinci chloridi, modified raw material of wood-charcoal is obtained after drying
Material, then dried after being impregnated in manganese salt and cobalt salt mixed solution, finally calcine in an inert atmosphere.Catalyst in the invention is not
Only preparation process is complicated, and zinc chloride can hydrolyze generation volatility HCl during heating, seriously pollute environment.
Therefore, it is simple, safe to find a kind of preparation method, the strong and cheap low-temperature denitration catalyst of catalytic capability has
It is significant.
Summary of the invention
That the technical problem to be solved by the present invention is to existing denitrating catalyst low-temperature denitration rates is low, preparation method is complicated, cost
High technical problem.
The technical proposal adopted by the invention to solve the above technical problems is that providing a kind of modification biological charcoal low-temperature denitration
Catalyst is prepared by following methods:
A, charcoal is subjected to pre-oxidation treatment in the case where aoxidizing atmosphere, obtains high-area carbon；
B, the ultrasonic immersing in metal salt solution by high-area carbon, is then dried；
C, the low temperature calcination in the case where aoxidizing atmosphere of the material after drying, obtains modification biological charcoal denitrating catalyst.
Wherein, the modification biological charcoal denitrating catalyst, in step A, the oxidation atmosphere is air or oxygen；When for
When air, control air mass flow is 100~300mL/min；When for oxygen, control oxygen flow is 20~60mL/min.
Wherein, the modification biological charcoal denitrating catalyst, in step A, when pre-oxidation treatment, controlled at 300~
400 DEG C, the time is 0.5~4h.
Wherein, the modification biological charcoal denitrating catalyst, in step A, the charcoal is coconut husk charcoal, charcoal, peanut
At least one of shell charcoal, walnut shell charcoal, straw charcoal or bamboo charcoal.
Wherein, the modification biological charcoal denitrating catalyst, in step A, the charcoal is particle size range in 5~20 mesh
Particle.
Wherein, the modification biological charcoal denitrating catalyst, in step B, the metal salt solution is manganese nitrate solution, second
Sour manganese solution, carbonic acid manganese solution or manganese chloride solution, mass concentration are 1%~20%.
Preferably, the modification biological charcoal denitrating catalyst, in step B, the metal salt solution is manganese nitrate solution.
Wherein, the modification biological charcoal denitrating catalyst, in step B, the high-area carbon and metal salt solution mass body
Product is than being 1~20g:1~60mL.
Wherein, the modification biological charcoal denitrating catalyst, in step B, the time of the ultrasound is 0.5~3h.
Wherein, the modification biological charcoal denitrating catalyst, in step B, the temperature of the drying is 100~140 DEG C, when
Between for 6~for 24 hours.
Wherein, the modification biological charcoal denitrating catalyst, in step C, the oxidation atmosphere is air or oxygen；When for
When air, control air mass flow is 100~300mL/min；When for oxygen, control oxygen flow is 20~60mL/min.
Wherein, the modification biological charcoal denitrating catalyst, in step C, the temperature of the low temperature calcination is 200~300
DEG C, the time is 0.5~3h.
Modification biological charcoal denitrating catalyst provided by the invention has excellent low-temperature denitration activity, is in operating temperature
At 100~200 DEG C, denitrification rate is up to 99%.
The utility model has the advantages that
The present invention uses pre-oxidation treatment charcoal, the oxidation removal for the property of can choose lignin charcoal therein, to change
The pore structure of kind Carbon Materials, is conducive to the entrance and dispersion of active component during impregnation, promotes more active sites
Point exposure, is conducive to the absorption and activation of reactant molecule, to promote the progress of denitration reaction.Moreover it is possible on its surface
Modified grafting oxygen-containing functional group and acid point, can significantly improve its denitration performance.
The present invention using charcoal metal salt solution dipping after, then under oxidizing atmosphere direct low temperature calcination method.It is low
Temperature processing, can the effectively save energy；Meanwhile calcining is more advantageous to the formation of high oxidation state manganese oxide under oxidizing atmosphere atmosphere,
Its denitration performance can be improved significantly.
The present invention passes through pre-oxidation-metal salt solution ultrasonic immersing-low-temperature oxidation atmosphere calcining, gained modification biological charcoal
Denitrating catalyst is in denitration application, and activity is more preferable under the conditions of low temperature (100-200 DEG C), can be substantially reduced in application process
Energy consumption, and denitrification rate is up to 99%.
Modification biological charcoal denitration catalyst carrier of the present invention belongs to waste resource recovery recycling, warp using charcoal as raw material
Feasibility of helping is high；And it is preparation method mild condition, easy to operate, it is a kind of environmentally friendly system that nonstaining property by-product, which generates,
Preparation Method.
Detailed description of the invention
Fig. 1 is 1 gained modification biological charcoal denitrating catalyst SCR denitration effect picture of embodiment.
Fig. 2 is 2 gained modification biological charcoal denitrating catalyst SCR denitration effect picture of embodiment.
Fig. 3 is 3 gained modification biological charcoal denitrating catalyst of embodiment and 1~6 denitrating catalyst SCR denitration effect of comparative example
Figure.
Fig. 4 is 3 gained modification biological charcoal denitrating catalyst of embodiment and 7 denitrating catalyst SCR denitration effect picture of comparative example.
Specific embodiment
Specifically, modification biological charcoal low-temperature denitration catalyst, is prepared by following methods:
A, charcoal is subjected to pre-oxidation treatment in the case where aoxidizing atmosphere, obtains high-area carbon；
B, the ultrasonic immersing in metal salt solution by high-area carbon, is then dried；
C, the low temperature calcination in the case where aoxidizing atmosphere of the material after drying, obtains modification biological charcoal denitrating catalyst.
To realize that waste resource recovery recycles, coconut husk charcoal, charcoal, peanut shell charcoal, walnut shell charcoal, stalk is can be used in the present invention
Charcoal, bamboo charcoal etc. are as biological carbon feedstock；Charcoal particle size range is controlled in the particle of 5~20 mesh.It is preferred that using particle size range 6
The charcoal particle of~10 mesh.
The present invention carries out pre-oxidation treatment to charcoal first, selectively oxidation removal lignin charcoal therein, thus
Improve the pore structure of Carbon Materials.By being decomposed under oxidizing atmosphere to charcoal and reduced gravity situations are analyzed, when for air
When, control air mass flow is 100~300mL/min；When for oxygen, control oxygen flow is 20~60mL/min, control temperature
Degree is 300~400 DEG C, and the time is 0.5~4h, is pre-oxidized, is conducive to the dispersion of active component during impregnation, is promoted
Into the exposure of more active sites, be conducive to the absorption and activation of reactant molecule, to promote the progress of denitration reaction.This
Outside, in the modified grafting oxygen-containing functional group in its surface, its denitration performance can be significantly improved.Temperature is relatively low or higher, is unfavorable for
The improvement of pore structure.
In step B of the present invention, metal salt solution is that manganese nitrate solution, acetic acid manganese solution, carbonic acid manganese solution or manganese chloride are molten
Liquid, mass concentration are 1%~20%, and controlling high-area carbon with metal salt solution mass volume ratio is 1~20g:1~60mL,
The load capacity of metal manganese salt in modification biological charcoal denitrating catalyst can be controlled 1~10%, be conducive in subsequent low temperature at this time
The Mn oxide that high-valence state is formed in calcining, improves low-temperature denitration ability；It is preferred that using manganese nitrate solution.
For the benefit of manganese is loaded on high-area carbon, in step B, using ultrasonic treatment, generally requires 0.5~3h of ultrasound；It is super
After sound, material 100~140 DEG C dry 6~for 24 hours.
High-area carbon after Supported Manganese is carried out low temperature calcination by the present invention under oxidizing atmosphere.When using air, control is empty
Throughput is 100~300mL/min；When using oxygen, control oxygen flow is 20~60mL/min.Controlling calcination temperature is
200~300 DEG C, the time is 0.5~3h, and in the case where aoxidizing atmosphere, calcining is more advantageous to the formation of high oxidation state manganese oxide, and makes to urge
What is combined between agent and carrier is stronger, to significantly improve its denitration performance, energy is also effectively reduced simultaneously in low-temperature process
Consumption.
Modification biological charcoal denitrating catalyst provided by the invention has excellent low-temperature denitration activity, is in operating temperature
At 100~200 DEG C, denitrification rate is up to 99%.
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
Coconut husk charcoal is ground to 6-10 mesh particle size range particle, in the case where air mass flow is 150mL/min, 300 DEG C are forged
2h is burnt, high-area carbon is obtained；10g high-area carbon is immersed in the Mn (NO that 20mL mass concentration is 6.5% at normal temperature3)2In solution, ultrasound
It is dried at 105 DEG C after processing 1h, drying time 12h；4h is finally calcined at air atmosphere, 250 DEG C, air mass flow is
150mL/min obtains modification biological charcoal denitrating catalyst.
Denitrating flue gas performance evaluation, the flue gas of laboratory simulation are carried out using above-mentioned gained modification biological charcoal denitrating catalyst
Atmospheric condition: 5%O2、400ppm NO、NH3: NO=1.1:1, N2As carrier gas, air speed 2000h-1, reaction temperature 150
DEG C, NO conversion ratio is shown in Fig. 1.
Embodiment 2
Coconut husk charcoal is ground to 6-10 mesh particle size range particle, in the case where air mass flow is 150mL/min, 400 DEG C are forged
2h is burnt, obtain high-area carbon；10g high-area carbon is immersed in the Mn (NO that 20mL mass concentration is 9.8% at normal temperature3)2In solution, ultrasound
It is dried at 105 DEG C after processing 0.5h, drying time 12h；2h is finally calcined at air atmosphere, 300 DEG C, air mass flow is
150mL/min obtains modification biological charcoal denitrating catalyst.
Denitrating flue gas performance evaluation, the flue gas of laboratory simulation are carried out using above-mentioned gained modification biological charcoal denitrating catalyst
Atmospheric condition: 5%O2、400ppm NO、NH3: NO=1.1:1, N2As carrier gas, air speed 4000h-1, reaction temperature 150
DEG C, NO conversion ratio is shown in Fig. 2.
Embodiment 3
Coconut husk charcoal is ground to 6-10 mesh particle size range particle, in the case where air mass flow is 150mL/min, 380 DEG C are forged
2h is burnt, high-area carbon is obtained；10g high-area carbon is immersed in the Mn (NO that 20mL mass concentration is 13% at normal temperature3)2In solution, at ultrasound
It is dried at 105 DEG C after reason 0.5h, drying time 12h；2h is finally calcined at air atmosphere, 250 DEG C, air mass flow is
150mL/min obtains modification biological charcoal denitrating catalyst.
Denitrating flue gas performance evaluation, the flue gas of laboratory simulation are carried out using above-mentioned gained modification biological charcoal denitrating catalyst
Atmospheric condition: 5%O2、400ppm NO、NH3: NO=1.1:1, N2As carrier gas, air speed 6000h-1, reaction temperature 150
DEG C, NO conversion ratio is shown in Fig. 3.
Comparative example 1
Coconut husk charcoal is ground to 6-10 mesh particle size range particle, in the case where nitrogen flow is 150mL/min, 380 DEG C are forged
2h is burnt, high-area carbon is obtained；10g high-area carbon is immersed in the Mn (NO that 20mL mass concentration is 13% at normal temperature3)2In solution, at ultrasound
It is dried at 105 DEG C after reason 0.5h, drying time 12h；2h is finally calcined at air atmosphere, 250 DEG C, air mass flow is
150mL/min obtains charcoal denitrating catalyst.
Denitrating flue gas performance evaluation is carried out using above-mentioned gained denitrating catalyst, the flue gas atmospheric condition of laboratory simulation:
5%O2、400ppm NO、NH3: NO=1.1:1, N2As carrier gas, air speed 6000h-1, reaction temperature is 150 DEG C, NO conversion
Rate is shown in Fig. 3.
Comparative example 2
Coconut husk charcoal is ground to 6-10 mesh particle size range particle, in the case where nitrogen flow is 150mL/min, 380 DEG C are forged
2h is burnt, high-area carbon is obtained；10g high-area carbon is immersed in the Mn (NO that 20mL mass concentration is 13% at normal temperature3)2In solution, at ultrasound
It is dried at 105 DEG C after reason 0.5h, drying time 12h；2h is finally calcined at nitrogen atmosphere, 250 DEG C, nitrogen flow is
150mL/min obtains charcoal denitrating catalyst.
Denitrating flue gas performance evaluation is carried out using above-mentioned gained denitrating catalyst, the flue gas atmospheric condition of laboratory simulation:
5%O2、400ppmNO、NH3: NO=1.1:1, N2As carrier gas, air speed 6000h-1, reaction temperature is 150 DEG C, NO conversion
Rate is shown in Fig. 3.
Comparative example 3
Coconut husk charcoal is ground to 6-10 mesh particle size range particle, in the case where air mass flow is 150mL/min, 380 DEG C are forged
2h is burnt, high-area carbon is obtained；10g high-area carbon is immersed in the Mn (NO that 20mL mass concentration is 13% at normal temperature3)2In solution, at ultrasound
It is dried at 105 DEG C after reason 0.5h, drying time 12h；2h is finally calcined at nitrogen atmosphere, 250 DEG C, nitrogen flow is
150mL/min obtains charcoal denitrating catalyst.
Denitrating flue gas performance evaluation is carried out using above-mentioned gained denitrating catalyst, the flue gas atmospheric condition of laboratory simulation:
5%O2、400ppmNO、NH3: NO=1.1:1, N2As carrier gas, air speed 6000h-1, reaction temperature is 150 DEG C, NO conversion
Rate is shown in Fig. 3.
Comparative example 4
Coconut husk charcoal is ground to 6-10 mesh particle size range particle, 10g charcoal is immersed in 20mL mass at normal temperature
Mn (the NO that concentration is 13%3)2In solution, dried at 105 DEG C after being ultrasonically treated 0.5h, drying time 12h；Finally in sky
Atmosphere is enclosed, and 2h is calcined at 250 DEG C, and air mass flow 150mL/min obtains charcoal denitrating catalyst.
Denitrating flue gas performance evaluation is carried out using above-mentioned gained denitrating catalyst, the flue gas atmospheric condition of laboratory simulation:
5%O2、400ppmNO、NH3: NO=1.1:1, N2As carrier gas, air speed 6000h-1, reaction temperature is 150 DEG C, NO conversion
Rate is shown in Fig. 3.
Comparative example 5
Coconut husk charcoal is ground to 6-10 mesh particle size range particle, 10g charcoal is immersed in 20mL mass at normal temperature
Mn (the NO that concentration is 13%3)2In solution, dried at 105 DEG C after being ultrasonically treated 0.5h, drying time 12h；Finally in nitrogen
Atmosphere is enclosed, and 2h is calcined at 250 DEG C, and nitrogen flow 150mL/min obtains charcoal denitrating catalyst.
Denitrating flue gas performance evaluation is carried out using above-mentioned gained denitrating catalyst.The flue gas atmospheric condition of laboratory simulation:
5%O2、400ppmNO、NH3: NO=1.1:1, N2As carrier gas, air speed 6000h-1, reaction temperature is 150 DEG C, NO conversion
Rate is shown in Fig. 3.
Comparative example 6
Coconut husk charcoal is ground to 6-10 mesh particle size range particle, carries out denitrating flue gas performance evaluation.Laboratory simulation
Flue gas atmospheric condition: 5%O2、400ppm NO、NH3: NO=1.1:1, N2As carrier gas, air speed 6000h-1, reaction temperature
Degree is 150 DEG C, and NO conversion ratio is shown in Fig. 3.
Comparative example 7
Coconut husk charcoal is ground to 6-10 mesh particle size range particle, 10g charcoal is immersed in 20mL mass at normal temperature
Mn (the NO that concentration is 13%3)2In solution, dried at 105 DEG C after being ultrasonically treated 0.5h, drying time 12h；Finally in nitrogen
Atmosphere is enclosed, and 2h is calcined at 450 DEG C, and nitrogen flow 150mL/min obtains charcoal denitrating catalyst.Denitration catalyst is prepared
Agent carries out denitrating flue gas performance evaluation.
The flue gas atmospheric condition of laboratory simulation: 5%O2、400ppmNO、NH3: NO=1.1:1, N2It is empty as carrier gas
Speed is 6000h-1, reaction temperature is 150 DEG C, and NO conversion ratio is shown in Fig. 4.
As can be seen from figs. 3 and 4 the present invention is using impregnating metal saline solution again after air pre-oxidation treatment, last air calcination
The catalyst of preparation has best denitration performance, and denitrification rate is compared to comparative example 1~7 up to 97%, and of the invention changes
Property charcoal denitrating catalyst catalytic activity is obviously improved.
Claims (10)
1. modification biological charcoal low-temperature denitration catalyst, it is characterised in that: be prepared by following methods:
A, charcoal is subjected to pre-oxidation treatment in the case where aoxidizing atmosphere, obtains high-area carbon；
B, the ultrasonic immersing in metal salt solution by high-area carbon, is then dried；
C, the low temperature calcination in the case where aoxidizing atmosphere of the material after drying, obtains modification biological charcoal denitrating catalyst.
2. modification biological charcoal denitrating catalyst according to claim 1, it is characterised in that: in step A, the oxidation atmosphere
For air or oxygen；When for air, control air mass flow is 100~300mL/min；When for oxygen, oxygen flow is controlled
For 20~60mL/min.
3. modification biological charcoal denitrating catalyst according to claim 1 or 2, it is characterised in that: in step A, at pre-oxidation
When reason, controlled at 300~400 DEG C, the time is 0.5~4h.
4. modification biological charcoal denitrating catalyst according to claim 1, it is characterised in that: in step A, the charcoal is
At least one of coconut husk charcoal, charcoal, peanut shell charcoal, walnut shell charcoal, straw charcoal or bamboo charcoal；The charcoal is that particle size range exists
The particle of 5~20 mesh.
5. modification biological charcoal denitrating catalyst according to claim 1, it is characterised in that: in step B, the metal salt is molten
Liquid is manganese nitrate solution, acetic acid manganese solution, carbonic acid manganese solution or manganese chloride solution, and mass concentration is 1%~20%；It is preferred that
, the metal salt solution is manganese nitrate solution.
6. modification biological charcoal denitrating catalyst according to claim 1, it is characterised in that: in step B, the high-area carbon with
Metal salt solution mass volume ratio is 1~20g:1~60mL.
7. modification biological charcoal denitrating catalyst according to claim 1, it is characterised in that: in step B, at least meet following
One:
The time of the ultrasound is 0.5~3h；
The temperature of the drying be 100~140 DEG C, the time be 6~for 24 hours.
8. modification biological charcoal denitrating catalyst according to claim 1, it is characterised in that: in step C, the oxidation atmosphere
For air or oxygen；When for air, control air mass flow is 100~300mL/min；When for oxygen, oxygen flow is controlled
For 20~60mL/min.
9. modification biological charcoal denitrating catalyst according to claim 1 or 8, it is characterised in that: in step C, the low temperature
The temperature of calcining is 200~300 DEG C, and the time is 0.5~3h.
10. application of the modification biological charcoal denitrating catalyst according to any one of claims 1 to 9 in low-temperature denitration of flue gas,
Be characterized in that: denitration temperature is 100~200 DEG C.
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