CN109772374A - Fluorine is grafted supported porous charcoal base catalysis material of manganese and preparation method thereof and its application in low temperature water resistant denitration - Google Patents
Fluorine is grafted supported porous charcoal base catalysis material of manganese and preparation method thereof and its application in low temperature water resistant denitration Download PDFInfo
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Abstract
The invention discloses a kind of fluorine grafting supported porous charcoal base catalysis material of manganese and preparation method thereof and its applications in low temperature water resistant denitration, belong to environmental protection, porous carbon material technical field.The present invention provides a kind of low cost, high waterproof, high activity low-temperature denitration fluorination C catalyst, contains C:30%~75%, O:1%~15%, F:20%~55%, Mn:0.01%~5%.Present invention introduces the Mn elements having to fluorination reaction efficient catalytic, carry out fluorine grafting process can in room temperature or low temperature, and the fluorine grafted porous charcoal base catalysis material of F content 20%~55% is made, it has the characteristics that high hydrophobic, high abrasion, high resistance to corrosion, it can be applied to low-temperature selective catalytic reduction denitration (SCR), denitrification rate solves the defect that current SCR catalyst causes denitration efficiency low because of water-resistance difference up to 100%.
Description
Technical field
The invention belongs to environmental protections, porous carbon material technical field, and in particular to a kind of fluorine grafting supported porous charcoal of manganese
Base catalysis material and its preparation method and application.
Background technique
2017, China's energy consumption accounted for the 23.2% of the whole world, and energy-consuming increment accounts for the 33.6% of the whole world, occupied complete
Ball is the first.In China's energy consumption structure, coal accounting is up to 60.4%, and consumption of coal can generate a large amount of pernicious gases, especially
It is nitrogen oxides, and 2017, China's nitrogen oxides whole year total emission volumn was still up to 13,260,000 tons, causes photochemical fog, ash
Many environmental problems such as haze, ozone pollution seriously affect ecology and environment.NOx is considered as one of primary pollutant in atmosphere,
Efficiently control being emitted in control atmosphere pollution in occupation of particularly important position for NOx.
Nitrogen oxides control technology mainly has low-NO_x combustion technology and gas denitrifying technology.Currently, low-NO_x combustion technology is remote
Existing discharge standard is not achieved, denitrating flue gas is the nitrogen oxides control method generallyd use.Gas denitrifying technology includes selection
Property non-catalytic reduction (SNCR) and selective catalytic reduction (SCR).Wherein, SCR is that the mainstream of effectively control NOx emission at present is de-
One of nitre technology.The position arranged in entire flue gas purification system according to Benitration reactor can be classified as three kinds: (1)
HD-SCR (high dust SCR): after reactor is arranged in economizer by such technique, air preheater and deduster it
Before.The advantage of this arrangement is that the flue-gas temperature into reactor is up to 300~500 DEG C, meets vanadium titanium catalyst
(V2O5/TiO2) active temperature demand.But the shortcomings that technique, is, since catalyst is in high cloud of dust gas, so easily
Poisoning and deactivation limits its industrial application.(2) LD-SCR (low dust SCR): the technique is to be arranged in Benitration reactor
After deduster, before desulfurizing tower.The advantages of this technique, resides in reduced abrasion and toxic action of the dust to catalyst, but
It is the disadvantage is that flue-gas temperature still can make to urge already below the active demand and sulfur dioxide in flue gas of vanadium titanium catalyst at this time
Agent poisoning.(3) TE-SCR (tail end SCR): reactor is placed in the end of entire purification system by the technique, and advantage is
Greatly reduce the toxic action of dust and sulfur dioxide to catalyst, the disadvantage is that flue-gas temperature is too low (80~150 DEG C), Wu Fada
To the reactivity temperature requirements (350~450 DEG C) of such as traditional vanadium series catalyst of general commercial catalyst.Therefore, low temperature is developed
Denitrating catalyst is of great significance to SCR technology popularization.
Currently, both at home and abroad focus mostly on the research of low-temperature SCR catalyst in transition metal such as Mn, Ce, Fe, Cu etc., wherein
Mn oxide due to it is abundant appraise at the current rate, cheap, excellent catalytic performance receives the especially more concern of scholar.Manganese is aoxidized
Object, which loads on carrier, can be improved the dispersion degree of active component, increases specific surface area, and then improve the activity of catalyst.It is porous
Carbon Materials specific surface area is huge, surface functional group is abundant, the adsorbable NH of acidic functionality3, the adsorbable NO of basic functionalityx, non-
Often be suitable for carrier as SCR catalyst, and with molecular sieve, TiO2Etc. comparing, porous carbon material Surface Physical Chemistry property
Regulation is easy, it can be achieved that low-temperature denitration of flue gas (80~150 DEG C).
But vapor, about 5~20% are typically contained in most of industrial smokes.Such as: petrochemical industry catalytic cracker cigarette
Water vapour content is 10% or so in gas；Water vapour content is 5~15% in steel industry sintering device flue gas；Cement industry cement
Water vapour content is 20% or so in kiln exhaust gas.Although Mn oxide has excellent catalytic performance, but its activity is also vulnerable to H2O
The influence of effect.When using the catalysis material denitration of porous charcoal base, since the hydrophily of porous carbon material is very strong, H2O with react
Object (NO or NH3) there are competitive Adsorption, H on a catalyst2O is easier to be adsorbed and occupy active point, H2O is to NOxAnd NH3It
Between be catalyzed the inhibiting effect of reaction, cause porous charcoal base catalyst poisoning to inactivate.So when there is vapor in flue gas, it is porous
Carbon base catalyst denitration efficiency sharply declines, and seriously limits its large-scale industrial application.
Therefore, it is living to develop novel low cost, high waterproof, height for the hydrophobicity for enhancing porous charcoal base catalysis material surface
Property low-temperature denitration catalyst, is porous charcoal base SCR catalyst industrial application urgent need to solve the problem.
Fluorine is the strongest element of nonmetal character, and this give fluorine material many excellent properties and function.It is fluorinated carbon materials
Expect the п key by breaking carbon-coating, forms C-F key in conjunction with carbon atom, bond energy reaches 485kJ/mol, bigger than the bond energy of c h bond
75kJ/mol, stability are very high.In addition, single fluorine atom substitution shows as hydrophily, but polyfluoro atom is replaced, due to adding
Cooperation, which is used, shows as strong hydrophobicity, and replaces quantity increase performance more significant with fluorine atom.After fluorine content increases, material has
Excellent hydrophobicity, wearability, corrosion resistance etc..But fluorination porous carbon material is applied to SCR low-temperature denitration and is not yet appeared in the newspapers
Road.
Surface fluorination is to prepare fluorine grafting Carbon Materials most simple effective method.Surface fluorination carbon material type is more, from
Fluorographite has been obtained to fluorinated fullerene, fluorination single-walled carbon nanotube, fluorination multi-walled carbon nanotube, fluorinated graphene etc.
The fluorination Carbon Materials of a variety of different structures and different physicochemical properties, but by the directly fluorinated report in porous carbon based material surface
It is less.CN102382366A discloses a kind of preparation method for being fluorinated charcoal, by carbon material in -25 DEG C of -100 DEG C of reaction 10min-48h
The fluorocarbons of modifying super hydrophobicity is made, although the reaction carries out at low temperature, due to carbon material steady chemical structure, under low temperature
It is difficult to directly introduce fluorine on the carbon material, causes the fluorination charcoal fluorine content lower；CN106941178A although fluorocarbons obtained
Content must react 6~24 hours, hot conditions up to 40% or more in 400~700 DEG C of high temperature, 100~500KPa of high pressure
There are high-temperature oxydation, burnings etc. to lead to porous carbon material reduced performance and operating safety risks, and fluorocarbons obtained is main
Applied to lithium battery.Therefore, how to prepare the fluorocarbons of high fluorine content under mild conditions is the fluorinated difficulty of charcoal material surface
Point.
In conclusion it is badly in need of a kind of method of fluorocarbons that can prepare high fluorine content under mild conditions at present, and
Enable to be fluorinated charcoal efficient catalytic reduction denitration in cold aqueous steam ambient.
Summary of the invention
The invention solves first technical problem be to provide a kind of low cost, high waterproof, high activity low-temperature denitration
It is fluorinated C catalyst.
The technical proposal adopted by the invention to solve the above technical problems is that providing a kind of fluorine grafting supported porous charcoal of manganese
Base catalysis material, the element containing following mass percentage: C:30%~75%, O:1%~15%, F:20%~
55%, Mn:0.01%~5%.
The above-mentioned fluorine grafting supported porous charcoal base catalysis material of manganese provided by the invention have excellent hydrophobicity, wearability,
The performances such as corrosion resistance can be applied during in low temperature (≤150 DEG C), water resistant is catalytic-reduction denitrified, and denitration effect is significant, denitrification rate
Up to 85% or more, and highest denitrification rate is up to 100%, solves in low-temperature flue gas when having vapor, porous carbon base catalyst
The technical issues of denitration efficiency sharply declines.
The invention solves second technical problem be the fluorocarbons for how preparing high fluorine content under mild conditions.
The technical proposal adopted by the invention to solve the above technical problems is that providing a kind of fluorine grafting supported porous charcoal of manganese
The preparation method of base catalysis material comprising following steps:
The supported porous charcoal base catalysis material of manganese is in the environment of fluoro-gas, under the conditions of 20~150 DEG C and 100~500Kpa
Reaction 1~be grafted the supported porous charcoal base catalysis material of manganese for 24 hours to get fluorine.
Wherein, in the preparation method of the fluorine described above grafting supported porous charcoal base catalysis material of manganese, the manganese load is more
The mass percentage content of Mn is 0.01~10% in the charcoal base catalysis material of hole.
Preferably, in the preparation method of the fluorine described above grafting supported porous charcoal base catalysis material of manganese, the manganese load
The mass percentage content of porous charcoal base catalysis material Mn is 5~10%.
Further, in the preparation method of the fluorine described above grafting supported porous charcoal base catalysis material of manganese, the manganese is negative
Carry porous charcoal base catalysis material obtained by following manner: commercially available product, impregnated using manganese salt solution porous carbon based material be made.
Further, described to make in the preparation method of the fluorine described above grafting supported porous charcoal base catalysis material of manganese
The concrete operations of porous carbon based material are impregnated with manganese salt solution are as follows: porous carbon based material first uses concentrated nitric acid to pre-oxidize, and then exists
It impregnates in manganese salt solution, finally roasts, obtain the supported porous carbon based material of manganese.
Wherein, in the preparation method of the fluorine described above grafting supported porous charcoal base catalysis material of manganese, the porous charcoal base
Material is at least one of activated coke, active carbon, activated carbon fibre, mesoporous carbon, carbon molecular sieve.
Wherein, in the preparation method of the fluorine described above grafting supported porous charcoal base catalysis material of manganese, the porous charcoal base
The mass volume ratio of material and concentrated nitric acid is 1~20g:10~60mL.
Wherein, in the preparation method of the fluorine described above grafting supported porous charcoal base catalysis material of manganese, the concentrated nitric acid
Mass concentration is 20~60%.
Wherein, in the preparation method of the fluorine described above grafting supported porous charcoal base catalysis material of manganese, the manganese salt solution
For manganese nitrate solution, manganese sulfate solution, carbonic acid manganese solution or manganese chloride solution, mass concentration is 10%~60%.
Preferably, in the preparation method of the fluorine described above grafting supported porous charcoal base catalysis material of manganese, the manganese salt is molten
Liquid is manganese nitrate solution.
Wherein, in the preparation method of the fluorine described above grafting supported porous charcoal base catalysis material of manganese, the pre-oxidation
Time is 1~4h, and temperature is 50~100 DEG C.
Wherein, in the preparation method of the fluorine grafting supported porous charcoal base catalysis material of manganese described above, the dipping when
Between be 6~12h.
Wherein, in the preparation method of the fluorine described above grafting supported porous charcoal base catalysis material of manganese, the temperature of the roasting
Degree is 250~550 DEG C, and the time is 1~6h.
Wherein, in the preparation method of the fluorine described above grafting supported porous charcoal base catalysis material of manganese, when molten using manganese salt
When liquid impregnates porous carbon based material, the mass volume ratio of the porous carbon based material and manganese salt solution is 1~20g:10~60mL.
In order to guarantee sufficiently to remove the foreign gas in reaction vessel, fluorination effect is improved, fluorine described above is grafted manganese
In the preparation method of supported porous charcoal base catalysis material, the environment of the fluoro-gas is obtained by following operation: to reaction vessel
It vacuumizes and (its vacuum degree is made to be at least up to -0.01Mpa) or inert gas replacement (is passed through inert gas to reaction vessel, and will
Gas extraction in reaction vessel makes number of operations of the pressure lower than 100pa) in reaction vessel not less than 3 times, then will contain
Fluorine gas (before fluoro-gas is passed through reaction vessel, can first be dried) is passed through reaction vessel；The fluoro-gas by purity not
At least one of borontrifluoride carbon, boron trifluoride or phosphorus trifluoride less than 98% are prepared with inert gas and are obtained, wherein institute
The volume accounting for stating at least one of borontrifluoride carbon, boron trifluoride or phosphorus trifluoride is 5~20%, and the inert gas is nitrogen
At least one of gas, argon gas, helium or carbon dioxide.
The fluorine grafting supported porous charcoal base catalysis material of manganese that the above method provided by the invention is prepared has excellent
The performances such as hydrophobicity, wearability, corrosion resistance can be applied during water resistant is catalytic-reduction denitrified in low-temperature flue gas (≤150 DEG C), be taken off
Nitre significant effect, denitrification rate is up to 85% or more, and highest denitrification rate up to 100%, solving has vapor in low-temperature flue gas
When, the technical issues of porous carbon base catalyst denitration efficiency sharply declines.
Beneficial effects of the present invention:
The present invention is introduced in fluorine grafting process with the Mn element to fluorination reaction efficient catalytic, makes fluorine grafting process can
Carried out in room temperature or low temperature, can to avoid in manganese Metal valence transition caused by high-temperature fluorination and fluorine grafting process because of height
Temperature oxidation, burning etc. lead to porous charcoal base catalysis material reduced performance and operating safety risks；And the fluorine grafted porous charcoal of preparation
Base catalysis material fluorine content is high, more than 20%；The fluorine grafted porous charcoal base catalysis material of preparation has high hydrophobic, high abrasion, height
The features such as against corrosion, can be applied to low-temperature selective catalytic reduction denitration (SCR), and denitrification rate solves current commercialization up to 100%
The defect that SCR catalyst causes denitration efficiency low because of water-resistance difference.Preparation method of the present invention is simple, low in cost, condition temperature
It is grafted that the supported porous charcoal base catalysis material fluorine content of manganese is high, stability is high with, fluorine, is suitable for large-scale serial production application.
Detailed description of the invention
Fig. 1 is the low temperature water resistant SCR denitration effect of 1 manganese load type active carbon fluorine of embodiment of the present invention grafting front and back, denitration item
Part: 90 DEG C of reaction temperature, NO initial concentration 115mg/Nm3, air speed 4000h-1, water vapour content 10%.
Fig. 2 is that manganese load type active carbon is containing 10% vapor and is being free of water vapor conditions before 1 fluorine of the embodiment of the present invention is grafted
Under SCR denitration effect, other denitration conditions: 90 DEG C of reaction temperature, NO initial concentration 115mg/Nm3, air speed 4000h-1。
Fig. 3 is the SEM spectrum that 1 fluorine of the embodiment of the present invention is grafted the supported porous charcoal base catalysis material of manganese.
Fig. 4 is the EDS map that 1 fluorine of the embodiment of the present invention is grafted the supported porous charcoal base catalysis material of manganese.
Specific embodiment
Specifically, a kind of fluorine is grafted the supported porous charcoal base catalysis material of manganese, the element containing following mass percentage:
C:30%~75%, O:1%~15%, F:20%~55%, Mn:0.01%~5%.
Experiment discovery, simple introduces Mn metal on porous carbon based material, although can improve to a certain extent porous
The denitration performance of carbon based material, but under the conditions of existing for the low-temperature flue gas vapor, the modified porous charcoal base of these Mn is catalyzed material
The denitration efficiency of material can still decline.
Simultaneously as carbon material steady chemical structure, is difficult to directly using conventional method in carbon material in a mild condition
It is upper to introduce a large amount of fluorine.The reacting using manganese catalysis carbon and fluorine of the invention, can make fluorination reaction compared under temperate condition
It carries out, to obtain the fluorination Carbon Materials of high fluorine content；On the other hand, manganese is carried in porous carbon based material also can be improved it
The denitration reaction activity of SCR catalyst, improves its low-temperature denitration performance.
The above-mentioned fluorine grafting supported porous charcoal base catalysis material of manganese provided by the invention have excellent hydrophobicity, wearability,
The performances such as corrosion resistance can be applied in low-temperature flue gas water resistant catalytic denitration, and denitration effect is significant, denitrification rate up to 85% with
On, and denitrification rate reaches as high as 100%, solves in low-temperature flue gas when having vapor, porous carbon base catalyst denitration efficiency
The technical issues of sharply declining.
The elemental composition and initial feed (porous charcoal base of the fluorine grafting supported porous charcoal base catalysis material of manganese provided by the invention
Material or the supported porous carbon based material of manganese) it is related, when containing the elements such as Si in initial feed, fluorine is grafted the supported porous charcoal base of manganese
It can also contain in catalysis material: Si:0.1~5wt% etc..
By the way that manganese to be carried in porous carbon based material, the fluorine realized under room temperature or cryogenic conditions was grafted the present invention
Journey, therefore the above-mentioned fluorine grafting supported porous charcoal base catalysis material of manganese can be used following methods and be prepared: the supported porous charcoal base of manganese
Material reacts 1 in the environment of fluoro-gas, under the conditions of 20~150 DEG C and 100~500Kpa~and it is negative to get fluorine grafting manganese for 24 hours
Carry porous charcoal base catalysis material.
The present invention is introduced in fluorine grafting process with the Mn element to fluorination reaction efficient catalytic, makes fluorine grafting process
It can carry out, be avoided in manganese Metal valence transition caused by high-temperature fluorination and fluorine grafting process because of height in room temperature or low temperature
Temperature oxidation, burning etc. lead to porous charcoal base catalysis material reduced performance and operating safety risks；And the fluorine grafted porous prepared
Charcoal base catalysis material fluorine content is high, more than 20%.
In the present invention, the supported porous carbon based material of manganese can be obtained by following manner: commercially available product, using manganese salt solution impregnate it is more
Hole carbon based material is made；The mass percentage content of Mn is 0.01~10% in the supported porous charcoal base catalysis material of manganese；For
Fluorine content in the raising fluorine grafting supported porous charcoal base catalysis material of manganese, it is preferred that Mn in the supported porous charcoal base catalysis material of manganese
Mass percentage content be 5~10%.
The porous carbon based material of initial raw material of the invention is activated coke, active carbon, activated carbon fibre, mesoporous carbon, charcoal molecule
At least one of sieve, it is in order to be conducive to that Mn is metal-doped in porous carbon based material, use first mass concentration for 20~
60% concentrated nitric acid pre-oxidizes 1~4h to it at 50~100 DEG C, and the mass volume ratio for controlling porous carbon based material and concentrated nitric acid is
1~20g:10~60mL.
The concrete operations described above that porous carbon based material is impregnated using manganese salt solution are as follows: porous carbon based material first uses dense
Nitric acid pre-oxidation, pre-oxidation terminates, and takes out porous carbon based material, can be 5-6 or can not be washed with solution ph is washed to,
It is baked to, is then impregnated in manganese salt solution, finally roasted in inert atmosphere, obtain the supported porous charcoal base catalysis material of manganese
Material.
When preparing the supported porous charcoal base catalysis material of manganese, the manganese salt solution is manganese nitrate solution, manganese sulfate solution, carbonic acid
Manganese solution or manganese chloride solution, mass concentration are 10%~60%；Preferably manganese nitrate solution.
To guarantee dipping effect, and doping of the metal in porous carbon based material is controlled, is impregnated when using manganese salt solution
When porous carbon based material, the mass volume ratio of the porous carbon based material and manganese salt solution is 1~20g:10~60mL；When dipping
Between be 6~12h.
Wherein, in the preparation method of the fluorine described above grafting supported porous charcoal base catalysis material of manganese, the temperature of the roasting
Degree is 250~550 DEG C, and the time is 1~6h.
In order to guarantee sufficiently to remove the foreign gas in reaction vessel, fluorination effect is improved, fluorine described above is grafted manganese
In the preparation method of supported porous charcoal base catalysis material, the environment of the fluoro-gas is obtained by following operation: to reaction vessel
It vacuumizes and (its vacuum degree is made to be at least up to -0.01Mpa) or inert gas replacement (is passed through inert gas to reaction vessel, and will
Gas extraction in reaction vessel makes number of operations of the pressure lower than 100pa) in reaction vessel not less than 3 times, then will contain
Fluorine gas (before fluoro-gas is passed through reaction vessel, can first be dried) is passed through reaction vessel；The fluoro-gas by purity not
At least one of borontrifluoride carbon, boron trifluoride or phosphorus trifluoride less than 98% are prepared with inert gas and are obtained, wherein institute
The volume accounting for stating at least one of borontrifluoride carbon, boron trifluoride or phosphorus trifluoride is 5~20%, and the inert gas is nitrogen
At least one of gas, argon gas, helium or carbon dioxide.
The fluorine grafting supported porous charcoal base catalysis material of manganese that the above method provided by the invention is prepared has excellent
The performances such as hydrophobicity, wearability, corrosion resistance can be applied in low temperature water resistant catalytic denitration, and denitration effect is significant, denitrification rate
Up to 85% or more, and denitrification rate reaches as high as 100%, solves in flue gas porous carbon base catalyst denitration when having vapor
The technical issues of efficiency sharply declines.
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
The denitration multiporous carbon based material that the present embodiment is selected is that (purchase is in the limited public affairs of Shanxi Xinhua active carbon for commercial activated carbons
Department), the mass percent of essential element are as follows: C 68.50%, O 6.92%.The above-mentioned active carbon of 20g is utilized into 20% nitric acid
1h is pre-oxidized at 80 DEG C, after then impregnating 6h at room temperature in 50% manganese nitrate solution of 30mL, is forged for 250 DEG C in Muffle furnace
3h is burnt, the manganese load type active carbon that Mn content is 3.94% is obtained；Then, manganese load type active carbon is put into fluorizating apparatus, to fluorine
Change equipment to be vacuumized, so that its vacuum degree is reached 10kpa, then three times with nitrogen displacement；It is passed through the mixed of phosphorus trifluoride and nitrogen
Gas is closed, wherein phosphorus trifluoride accounts for volume ratio 10%, reacts for 24 hours under conditions of 130 DEG C, 300Kpa, and fluorine grafting can be obtained
Denitration activity charcoal, the mass percent of essential element are as follows: F 30.05%, C 53.08%, O 9.10%, Mn 1.0%
(table 1).
Front and back denitration activity charcoal is grafted in 90 DEG C of reaction temperature, NO initial concentration 115mg/Nm using above-mentioned fluorine3, air speed
4000h-1, vapor volume content 10% is lower carries out denitrating flue gas test, as shown in Figure 1, fluorine be grafted before denitration activity charcoal denitration
Rate is 30%, and denitration activity charcoal denitrification rate is 100% after fluorine grafting.
The constituent content (wt%) of 1 the present embodiment manganese load type active carbon fluorine of table grafting front and back
| C | O | F | Mn | Ce | Fe | Ca | Si | Al | |
| Before grafting | 68.50 | 6.92 | 0 | 3.94 | 5.10 | 4.16 | 3.76 | 4.78 | 2.84 |
| After grafting | 53.08 | 9.10 | 30.05 | 1.00 | 2.31 | 1.76 | 2.07 | 0.51 | 0.12 |
Comparative example 1
The denitration multiporous carbon based material that the present embodiment is selected is that (purchase is in the limited public affairs of Shanxi Xinhua active carbon for commercial activated carbons
Department), it is 68.50%, O 6.92% that the mass percent of essential element, which is respectively as follows: C,.The above-mentioned active carbon of 20g is utilized 20%
Nitric acid pre-oxidizes 1h at 80 DEG C, after then impregnating 6h at room temperature in 50% manganese nitrate solution of 30mL, 250 in Muffle furnace
DEG C calcining 3h, obtain Mn content be 3.94% manganese load type active carbon.
Using above-mentioned manganese load type active carbon in 90 DEG C of reaction temperature, NO initial concentration 115mg/Nm3, air speed 4000h-1Under into
The test of row denitrating flue gas, as shown in Fig. 2, denitration activity charcoal denitrification rate is 100% when anhydrous steam in flue gas, and water in flue gas
Denitration activity charcoal denitrification rate is only 30% when vapor volume content is 10%.
Embodiment 2
The denitration multiporous carbon based material that the present embodiment is selected is that business (is bought in Inner Mongol Tai Xi coal collection with denitrification activated coke
Xingtai coalification Co., Ltd, group), it is 76%, O 16.2% that the mass percent of essential element, which is respectively as follows: C, and Mn is
2.5%, Si 5.3%.
20g above-mentioned material is put into fluorizating apparatus, then fluorizating apparatus is vacuumized, reaches its vacuum degree
10kpa, then three times with nitrogen displacement；It is passed through the mixed gas of borontrifluoride carbon and nitrogen, wherein borontrifluoride carbon accounts for volume ratio 10%,
1h is reacted under conditions of 20 DEG C, 100Kpa, fluorine grafting denitrification activated coke can be obtained, the mass percent of element includes: F
For 20.5%, C 64.5%, O 12.2%, Mn 0.5%, Si 2.3%.
Using above-mentioned fluorine grafting denitrification activated coke in 100 DEG C, the NO initial concentration of 90ppm, air speed 5000h-1, volume content
Denitrating flue gas test, denitrification rate 85% are carried out under 10% vapor.
Embodiment 3
The denitration multiporous carbon based material that the present embodiment is selected is that laboratory makes activated carbon fiber, the quality of essential element by oneself
Percentage are as follows: C 75.8%, O 7%, Mn 10%, Si 4.2%.
20g above-mentioned material is put into fluorizating apparatus, then fluorizating apparatus is vacuumized, reaches its vacuum degree
10kpa, then replaced five times with nitrogen.It is passed through the mixed gas of borontrifluoride carbon and nitrogen, wherein borontrifluoride carbon accounts for volume ratio 10%,
It is reacted for 24 hours under conditions of 150 DEG C, 500Kpa, fluorine grafting denitration activity carbon fiber, the mass percent of element can be obtained
Include: F be 53.6%, C 32.6%, O 8.5%, Mn 1.8%, Si 2.1%.
Using above-mentioned fluorine grafting denitration activity carbon fiber in 90 DEG C, the NO initial concentration of 100ppm, air speed 4000h-1, volume
Denitrating flue gas test, denitrification rate 100% are carried out under the vapor of content 10%.
Embodiment 4
The denitration multiporous carbon based material that the present embodiment is selected is that (purchase is in Inner Mongol Tai Xi coal group Xingtai for commercial activated carbons
Coalification Co., Ltd), the mass percent of essential element are as follows: C 78.9%, O 16%, Si 5.1%.
The above-mentioned active carbon of 20g is pre-oxidized into 1h using 20% nitric acid at 80 DEG C, it is then molten in 50% manganese nitrate of 30mL
After impregnating 6h at room temperature in liquid, 250 DEG C of calcining 3h in Muffle furnace obtain the manganese load type active carbon that Mn content is 2.3%；So
Afterwards, manganese load type active carbon is put into fluorizating apparatus, fluorizating apparatus is vacuumized, so that its vacuum degree is reached 10kpa, then use
Nitrogen is replaced three times；Be passed through the mixed gas of boron trifluoride and nitrogen, wherein boron trifluoride accounts for volume ratio 10%, 150 DEG C,
It is reacted under conditions of 300Kpa for 24 hours, fluorine grafting denitration activity charcoal can be obtained, the mass percent of element includes: that F is
20.8%, C 66.4%, O 10%, Mn 0.8%, Si 2.0%.
Using above-mentioned fluorine grafting denitration activity charcoal in 90 DEG C, the NO initial concentration of 90ppm, air speed 5000h-1, volume content
Denitrating flue gas test, denitrification rate 87% are carried out under 10% vapor.
Embodiment 5
The denitration multiporous carbon based material that the present embodiment is selected is that laboratory makes mesoporous carbon, the quality percentage of essential element by oneself
It is 79%, O 13%, Si 4.6% than being respectively as follows: C.
It weighs the above-mentioned mesoporous carbon of 20g and pre-oxidizes 3h at 80 DEG C using 30% nitric acid, then in 50% nitre of 30mL
After impregnating 6h at room temperature in sour manganese solution, 500 DEG C of calcining 3h in Muffle furnace obtain the loaded mesoporous charcoal of manganese that Mn content is 4%；
Then, the loaded mesoporous charcoal of manganese is put into fluorizating apparatus, fluorizating apparatus is vacuumized, its vacuum degree is made to reach 10kpa, then
It is replaced five times with argon gas；Be passed through the mixed gas of borontrifluoride carbon and nitrogen, wherein borontrifluoride carbon accounts for volume ratio 10%, 80 DEG C,
10h is reacted under conditions of 300Kpa, fluorine grafting denitration mesoporous carbon can be obtained, the mass percent of element includes: that F is
24.2%, C 61.5%, O 9.5%, Mn 1.1%, Si 1.6%.
Using above-mentioned fluorine grafting denitration mesoporous carbon in 100 DEG C, the NO initial concentration of 90ppm, air speed 5000h-1, volume content
Denitrating flue gas test, denitrification rate 89% are carried out under 10% vapor.
Embodiment 6
The denitration multiporous carbon based material that the present embodiment is selected is that laboratory makes carbon molecular sieve, the quality hundred of essential element by oneself
Divide ratio are as follows: C 80%, O 12%, Si 3.0%.
It weighs the above-mentioned carbon molecular sieve of 20g and pre-oxidizes 3h at 80 DEG C using 30% nitric acid, then the 50% of 50mL
After impregnating 10h at room temperature in manganese nitrate solution, 500 DEG C of calcining 5h in Muffle furnace obtain the manganese load carbon point that Mn content is 8%
Son sieve；Then, manganese load carbon molecular sieve is put into fluorizating apparatus, fluorizating apparatus is vacuumized, its vacuum degree is reached
10kpa, then replaced five times with nitrogen；It is passed through the mixed gas of phosphorus trifluoride and helium, wherein phosphorus trifluoride accounts for volume ratio 10%,
It is reacted for 24 hours under conditions of 25 DEG C, 100Kpa, fluorine grafting denitration carbon molecular sieve, the mass percent packet of element can be obtained
It includes: F 35%, C 52.4%, O 7.2%, Mn 2.6%, Si 1.0%.
Using above-mentioned fluorine grafting denitration carbon molecular sieve in 100 DEG C, the NO initial concentration of 90ppm, air speed 4000h-1, volume contains
Denitrating flue gas test, denitrification rate 100% are carried out under the vapor of amount 10%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. fluorine is grafted the supported porous charcoal base catalysis material of manganese, it is characterised in that: the element containing following mass percentage: C:
30%~75%, O:1%~15%, F:20%~55%, Mn:0.01%~5%.
2. application of the fluorine grafting supported porous charcoal base catalysis material of manganese described in claim 1 in low temperature water resistant denitration.
3. the preparation method of the fluorine described in claim 1 grafting supported porous charcoal base catalysis material of manganese, it is characterised in that: including with
Lower step: the supported porous charcoal base catalysis material of manganese is in the environment of fluoro-gas, under the conditions of 20~150 DEG C and 100~500Kpa
Reaction, end of reaction are grafted the supported porous charcoal base catalysis material of manganese to get fluorine.
4. the preparation method of the fluorine grafting supported porous charcoal base catalysis material of manganese according to claim 3, it is characterised in that: institute
State reaction time be 1~for 24 hours.
5. the preparation method of the fluorine grafting supported porous charcoal base catalysis material of manganese according to claim 3, it is characterised in that: institute
Stating Mn mass percentage content in the supported porous charcoal base catalysis material of manganese is 0.01~10%；Preferably 5~10%.
6. the preparation method of the fluorine grafting supported porous charcoal base catalysis material of manganese according to claim 5, it is characterised in that: institute
State the supported porous charcoal base catalysis material of manganese to be obtained by following manner: commercially available product impregnates porous carbon based material system using manganese salt solution
?.
7. the preparation method of the fluorine grafting supported porous charcoal base catalysis material of manganese according to claim 6, it is characterised in that: institute
State the concrete operations that porous carbon based material is impregnated using manganese salt solution are as follows: porous carbon based material first uses concentrated nitric acid to pre-oxidize, so
It impregnates in manganese salt solution, finally roasts afterwards, obtain the supported porous charcoal base catalysis material of manganese.
8. the preparation method of the fluorine grafting supported porous charcoal base catalysis material of manganese according to claim 7, it is characterised in that: extremely
Meet following one less:
The porous carbon based material is at least one of activated coke, active carbon, activated carbon fibre, mesoporous carbon, carbon molecular sieve；
The mass volume ratio of the porous carbon based material and concentrated nitric acid is 1~20g:10~60mL；
The mass concentration of the concentrated nitric acid is 20~60%；
The manganese salt solution is that manganese nitrate solution, manganese sulfate solution, carbonic acid manganese solution or manganese chloride solution, mass concentration are
10%~60%；Preferably manganese nitrate solution；
The time of the pre-oxidation is 1~4h, and temperature is 50~100 DEG C；
The time of the dipping is 6~12h；
The temperature of the roasting is 250~550 DEG C, and the time is 1~6h.
When impregnating porous carbon based material using manganese salt solution, the mass volume ratio of the porous carbon based material and manganese salt solution is
1~20g:10~60mL.
9. the preparation method of the fluorine grafting supported porous charcoal base catalysis material of manganese according to claim 4, it is characterised in that: institute
The environment for stating fluoro-gas is obtained by following operation: vacuumizing to reaction vessel or the number of operations of inert gas replacement is not less than
3 times, fluoro-gas is then passed through reaction vessel；Borontrifluoride carbon, borontrifluoride of the fluoro-gas by purity not less than 98%
At least one of boron or phosphorus trifluoride are prepared with inert gas and are obtained, wherein the borontrifluoride carbon, boron trifluoride or three
The volume accounting for being fluorinated at least one of phosphorus is 5~20%, and the inert gas is in nitrogen, argon gas, helium or carbon dioxide
At least one.
10. the preparation method of the described in any item fluorine grafting supported porous charcoal base catalysis materials of manganese of claim 3~9 prepares gained
Fluorine is grafted application of the supported porous charcoal base catalysis material of manganese in low temperature water resistant denitration.
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| CN102382366A (en) * | 2011-08-19 | 2012-03-21 | 瓮福（集团）有限责任公司 | Fluorocarbon-modified super-hydrophobic material and preparation method thereof |
| CN107115868A (en) * | 2016-02-24 | 2017-09-01 | 无锡中强电碳有限公司 | A kind of low temperature SCR denitration catalyst based on activated carbon and preparation method thereof |
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| CN109092325A (en) * | 2018-09-11 | 2018-12-28 | 东北大学 | A kind of catalyst and the preparation method and application thereof for low-temperature denitration of flue gas |
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| CN102382366A (en) * | 2011-08-19 | 2012-03-21 | 瓮福（集团）有限责任公司 | Fluorocarbon-modified super-hydrophobic material and preparation method thereof |
| CN107115868A (en) * | 2016-02-24 | 2017-09-01 | 无锡中强电碳有限公司 | A kind of low temperature SCR denitration catalyst based on activated carbon and preparation method thereof |
| CN108579731A (en) * | 2018-04-28 | 2018-09-28 | 盐城东博环保科技有限公司 | A kind of preparation method of low-temperature denitration carbon-supported catalysts |
| CN109092325A (en) * | 2018-09-11 | 2018-12-28 | 东北大学 | A kind of catalyst and the preparation method and application thereof for low-temperature denitration of flue gas |
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