CN103566928B - For the NACF and preparation method thereof of the load manganese dioxide of NO_x removal under room temperature - Google Patents
For the NACF and preparation method thereof of the load manganese dioxide of NO_x removal under room temperature Download PDFInfo
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- CN103566928B CN103566928B CN201310542796.9A CN201310542796A CN103566928B CN 103566928 B CN103566928 B CN 103566928B CN 201310542796 A CN201310542796 A CN 201310542796A CN 103566928 B CN103566928 B CN 103566928B
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Abstract
The invention discloses NACF of a kind of load manganese dioxide and preparation method thereof, it is carrier with NACF that object is to provide a kind of, load manganese dioxide makes catalyst, manganese dioxide and NACF are acted synergistically, there is the ability at room temperature can carrying out catalytic oxidation to the NO of low concentration, and then NOx is removed further, its preparation method is for be immersed in the certain density bivalent manganese aqueous solution by NACF, then certain density potassium permanganate solution is dripped, potassium permanganate and bivalent manganese generation redox reaction, in the manganese dioxide surface that is deposited on NACF generated and micropore, the i.e. NACF of obtained load manganese dioxide, the NACF of the load manganese dioxide prepared by the present invention is at room temperature had NOx and stronger removes ability.
Description
Technical field
The invention belongs to the preparation method of a kind of new material and this material, relate to NACF of the load manganese dioxide for NO_x removal under room temperature and preparation method thereof.
Background technology
One of air-polluting main component based on the nitrogen oxide (NOx) of nitric oxide and nitrogen dioxide, form one of Heavy environmental pollution problem major reasons such as acid rain, photochemical fog and gray haze, the serious threat mankind and vegeto-animal health.Therefore, the improvement of nitrogen oxide is very urgent.At present, the method for NO_x removal can be divided into on-catalytic method and the large class of catalysis method two.The former comprises absorption process, absorption method etc., has that equipment is huge, cost is high, secondary pollution problems.The latter's catalysis method mainly contains catalytic reduction and catalytic oxidation, for the catalyst in catalysis method, there is the problem of poor activity, although some noble metal activity are higher, noble metal is expensive, resource scarcity, and can only at far above the temperature of room temperature effectively.
At present, can be used in the catalyst material mainly material with carbon element of catalytic oxidation NO under room temperature, comprise active carbon, NACF, porous charcoal nanofiber etc.Chinese patent ZL201110396801.0 reports porous charcoal nanofiber prepared by method of electrostatic spinning at room temperature to the removal effect that the NO of low concentration has had.But because carbon nanofibers preparation cost is high, be difficult to large-scale application.And active carbon is owing to being graininess, mounting design difficulty is existed for the improvement of NOx in air, the problems such as efficiency is low.Integrated comparative gets up, and in this several Carbon Materials, what be hopeful large-scale application most is NACF, and this has benefited from it and has larger specific area, fiber condition and moderate preparation cost.
Pitch-based activated carbon fiber is used for removing of room temperature low concentration of NO by us, and discovery can by NO catalytic oxidation (Journal of Chemical Industry and Engineering, 2011,62 (2): 369-373), but Catalytic Oxygen rate is on the low side.For improving its catalytic oxidation activity further, strengthen that ability is removed to NOx, need on NACF supported catalyst.
Summary of the invention
In order to improve the catalytic oxidation efficiency to low concentration of NO under NACF room temperature further, the present invention adopts coprecipitation load manganese dioxide on NACF, utilize manganese dioxide abundance, cheap, safety non-toxic, there is the advantages such as higher catalytic activity, the NACF of preparation load manganese dioxide, low concentration of NO in air is adsorbed and catalytic oxidation, and and then removes.
To achieve these goals, the technical solution used in the present invention is:
Have the catalyst of NACF as low concentration of NO of manganese dioxide using load, utilize the concerted catalysis effect of NACF and manganese dioxide, the NO of low concentration under room temperature being carried out catalytic oxidation is NO
2, then remove further.
Present invention also offers described for removing the preparation method of the NACF of the load manganese dioxide of NOx in air, utilizing chemical coprecipitation technique, by manganese dioxide load on NACF.
For removing a NACF for the load manganese dioxide of low concentration of NO x in air under room temperature, take NACF as carrier, the manganese dioxide of load quality mark 0.001-5%.
Described NACF is polyacrylonitrile-radical, viscose base, asphaltic base or phenolic aldehyde base, and specific area is 500-2000m
2/ g.
The mass fraction of described manganese dioxide is 0.6%, 1.8%, 2.6%, 3.6% or 4.3%.
A preparation method for the NACF of described load manganese dioxide, take NACF as carrier, utilizes coprecipitation, comprise the following steps:
Step one, the manganous salt aqueous solution of compound concentration to be the potassium permanganate solution of 0.005-0.05mol/L and concentration be 0.005-0.05mol/L;
Step 2, is immersed in the manganous salt aqueous solution by NACF, under agitation drip the liquor potassic permanganate of the identical amount of same concentrations under state, continue stirring and make the abundant load of product after dripping after dipping certain hour;
Step 3, is filtered dry the NACF in step 2, makes it dry at being placed in 90-120 DEG C;
Step 4, is placed in nitrogen atmosphere stove by the NACF obtained in step 3, rises to 200-300 DEG C from room temperature, cools to room temperature with the furnace after being then incubated a period of time.
Coprecipitation in described step one manganous salt used is the water-soluble manganese salts such as manganese nitrate, manganese sulfate or manganese acetate.
In described step 2, dip time is at least 10 minutes
In described step 4, temperature retention time is at least 1 hour.
Compared with prior art, the NACF of the load manganese dioxide prepared by the present invention is at room temperature had NOx and stronger removes ability, can make NO Catalytic Oxygen rate more than 27%, reach as high as 31%.
Accompanying drawing explanation
NACF ESEM (SEM) figure of Fig. 1 load manganese dioxide.
Relation on Fig. 2 NACF between manganese dioxide load amount and NO Catalytic Oxygen rate.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is further elaborated.When not departing from the above-mentioned thought of the present invention, the various replacement made according to ordinary skill knowledge and customary means or change, all within the scope of the present invention.
Embodiment one
For the preparation method of the NACF of the load manganese dioxide of room temperature NO_x removal, utilize coprecipitation load manganese dioxide on NACF, comprise the following steps:
Step one, compound concentration is manganese nitrate solution and the 0.005mol/L liquor potassic permanganate of 0.005mol/L;
Specific area is 700m by step 2
2the pitch-based activated carbon fiber of/g is immersed in the manganese nitrate solution that step one is equipped with, and drips the liquor potassic permanganate in step one, continue to stir 90min after dripping after 1h under stirring;
Step 3, is filtered dry the NACF in step 2, dry 4h at being placed in 90 DEG C;
Step 4, is placed in nitrogen atmosphere stove by the NACF obtained in step 3, rises to 200 DEG C from room temperature, cools to room temperature with the furnace after being then incubated 4h.
Obtain the NACF of load 0.6% manganese dioxide.
Embodiment two
For the preparation method of the NACF of the load manganese dioxide of room temperature NO_x removal, utilize coprecipitation load manganese dioxide on NACF, comprise the following steps:
Step one, compound concentration is manganese sulfate solution and the 0.01mol/L liquor potassic permanganate of 0.01mol/L;
Specific area is 700m by step 2
2/ g polyacrylonitrile radical active carbon fiber is immersed in the manganese sulfate solution that step one is equipped with, and drips the liquor potassic permanganate in step one after 1.5h under stirring, continues to stir 120min after dripping;
Step 3, takes out the active carbon fibre Wesy in step 2 and is filtered dry, dry 4h at being placed in 110 DEG C;
Step 4, is placed in nitrogen atmosphere stove by the NACF obtained in step 3, rises to 300 DEG C from room temperature, cools to room temperature with the furnace after being then incubated 2h.
Obtain the NACF of load 1.8% manganese dioxide.
Embodiment three
For the preparation method of the NACF of the load manganese dioxide of room temperature NO_x removal, utilize coprecipitation load manganese dioxide on NACF, comprise the following steps:
Step one, compound concentration is manganese acetate solution and the 0.02mol/L liquor potassic permanganate of 0.02mol/L;
Specific area is 1000m by step 2
2the pitch-based activated carbon fiber of/g is immersed in the manganese acetate solution that step one is equipped with, and drips rapidly the liquor potassic permanganate in step one with vigorous stirring, continue to stir 120min after dripping after 2h;
Step 3, takes out the NACF in step 2, dry 1h at being placed in 120 DEG C;
Step 4, is placed in nitrogen atmosphere stove by the NACF obtained in step 3, rises to 300 DEG C from room temperature, cools to room temperature with the furnace after being then incubated 3h.
Obtain the NACF of load 2.6% manganese dioxide.
Embodiment four
For the preparation method of the NACF of the load manganese dioxide of room temperature NO_x removal, utilize coprecipitation load manganese dioxide on NACF, comprise the following steps:
Step one, compound concentration is manganese nitrate solution and the 0.03mol/L liquor potassic permanganate of 0.03mol/L;
Specific area is 2000m by step 2
2the resin-based NACF of/g is immersed in the manganese nitrate solution that step one is equipped with, and drips rapidly the liquor potassic permanganate in step one with vigorous stirring, continue to stir 120min after dripping after 2h;
Step 3, takes out the active carbon fibre Wesy in step 2, dry 1h at being placed in 120 DEG C;
Step 4, is placed in nitrogen atmosphere stove by the NACF obtained in step 3, rises to 300 DEG C from room temperature, cools to room temperature with the furnace after being then incubated 2h.
Obtain the NACF of load 3.6% manganese dioxide.
Embodiment five
For the preparation method of the NACF of the load manganese dioxide of room temperature NO_x removal, utilize coprecipitation load manganese dioxide on NACF, comprise the following steps:
Step one, compound concentration is manganese nitrate solution and the 0.04mol/L liquor potassic permanganate of 0.04mol/L;
Specific area is 1500m by step 2
2the pitch-based activated carbon fiber of/g is immersed in the manganese nitrate solution that step one is equipped with, and drips rapidly the liquor potassic permanganate in step one with vigorous stirring, continue to stir 120min after dripping after 2.5h;
Step 3, takes out the NACF in step 2, dry 4h at being placed in 110 DEG C;
Step 4, is placed in nitrogen atmosphere stove by the NACF obtained in step 3, rises to 300 DEG C from room temperature, cools to room temperature with the furnace after being then incubated 2h.
Obtain the NACF of load 4.3% manganese dioxide, its form as shown in Figure 1.
Utilize said method to obtain the NACF of load manganese dioxide, at room temperature have low concentration of NO x and stronger remove ability.
The NACF catalytic oxidation NO method of testing of load manganese dioxide was as follows: by composite active carbon fibre at 120 DEG C dry 12 hours, with removing moisture wherein and the material of other absorption, the fiber taking a certain amount of (0.05 ~ 0.20g) is inserted in fixed bed.Fixed bed diameter is 11mm, and packed height is 15 ~ 50mm.Low concentration of NO gas is by NO Standard Gases, O
2, N
2three kinds of gases are formulated, and its flow is controlled by mass flowmenter and regulates, and gaseous mixture total flow is 100 ~ 200SCCM.Through flowmeter Hou tri-road, gas enters mixed gas tank, after mixed gas tank mixes, enter fixed bed carry out NO catalytic oxidation, the temperature of fixed bed is controlled by water-bath, and reacted gas enters nitrogen-oxide analyzer, (Thermo42i type) and carries out concentration determination.
Be 1500m by specific area
2the manganese dioxide of load difference amount on the pitch-based activated carbon fiber of/g, (test condition is relation between test NO Catalytic Oxygen rate and carrying capacity: NO concentration is 50ppm, reaction temperature is 30 DEG C, test amount of samples is 0.100g, packed height 6mm, gas flow rate is 200mL/min), acquired results is as shown in Figure 2.Can find out, when load 3-4.5% manganese dioxide, NO Catalytic Oxygen rate, more than 27%, reaches as high as 31%.
Claims (4)
1. the preparation method of the NACF of a load manganese dioxide, the NACF of described load manganese dioxide removes low concentration of NO x in air under room temperature, take NACF as carrier, the manganese dioxide of load quality mark 0.001-5%, it is characterized in that, utilize coprecipitation, comprise the following steps:
Step one, the manganous salt aqueous solution of compound concentration to be the potassium permanganate solution of 0.005-0.05mol/L and concentration be 0.005-0.05mol/L;
Step 2, is immersed in the manganous salt aqueous solution by NACF, under agitation drip the liquor potassic permanganate of the identical amount of same concentrations under state, continue stirring and make the abundant load of product after dripping after dipping certain hour;
Step 3, is filtered dry the NACF in step 2, makes it dry at being placed in 90-120 DEG C;
Step 4, is placed in nitrogen atmosphere stove by the NACF obtained in step 3, rises to 200-300 DEG C from room temperature, cools to room temperature with the furnace after being then incubated a period of time.
2. preparation method according to claim 1, is characterized in that, the manganous salt used of the coprecipitation in described step one is manganese nitrate, manganese sulfate or manganese acetate water-soluble manganese salt.
3. preparation method according to claim 1, is characterized in that, in described step 2, dip time is at least 10 minutes.
4. preparation method according to claim 1, is characterized in that, in described step 4, temperature retention time is at least 1 hour.
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