CN107570142A - Low-temperature denitration catalyst and preparation method thereof - Google Patents
Low-temperature denitration catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN107570142A CN107570142A CN201710773182.XA CN201710773182A CN107570142A CN 107570142 A CN107570142 A CN 107570142A CN 201710773182 A CN201710773182 A CN 201710773182A CN 107570142 A CN107570142 A CN 107570142A
- Authority
- CN
- China
- Prior art keywords
- low
- denitration catalyst
- nitrogen
- temperature denitration
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The present invention is that its preparation method includes on a kind of low-temperature denitration catalyst and preparation method thereof：1) graphene oxide and nitrogen substance are disperseed in water, heating, cleaning filtering, obtains nitrogen-doped graphene；2) by transition metal salt formation metal front liquid solution soluble in water；3) titanium dioxide is mixed with the nitrogen-doped graphene, immersed in described metallic precursor solution, addition precipitant mix is uniform, heating, filtering drying, obtains catalyst powder；4) by described catalyst powder under a shielding gas, it is calcined, obtains low-temperature denitration catalyst.The low-temperature denitration catalyst of the present invention has good denitration effect under cryogenic, and can effectively resist sulfur dioxide.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method thereof, more particularly to a kind of low-temperature denitration catalyst and its preparation
Method.
Background technology
In NOx removal technology, SCR (SCR) is the denitrating flue gas skill being most widely used in the world
Art, its denitration rate can reach 85-99%.In recent years, researcher is directed to the NH that exploitation is applied under cryogenic conditions3- SCR skills
Art, because after catalyst system directly being configured at into dedusting and desulfurizer, so just without to existing boiler system
System carries out big transformation, and feasibility spatially and economically is all higher.Mn bases catalyst can be in 80-220 DEG C of low temperature bar
Good NH is shown under part3- SCR denitration activity, but catalyst is unstable, easy SO2Poisoning, life-span are difficult to ensure.Graphene
With excellent performance, such as high carrier mobility, huge specific surface area, stable chemical property, by graphene
It is modified, increases the avtive spot on surface, it is expected not only provide larger load space for active material, and help
Carried out in denitration reaction.
The content of the invention
It is a primary object of the present invention to, there is provided a kind of new low-temperature denitration catalyst and preparation method thereof, to be solved
Technical problem certainly is to make have good denitration effect under its cryogenic conditions, and can resist sulfur dioxide, so as to more
Suitable for practicality.
The object of the invention to solve the technical problems is realized using following technical scheme.Itd is proposed according to the present invention
A kind of low-temperature denitration catalyst preparation method, it includes：
1) graphene oxide and nitrogen substance are disperseed in water, heating, cleaning filtering, obtains nitrogen-doped graphene；
2) by transition metal salt formation metal front liquid solution soluble in water；
3) titanium dioxide is mixed with the nitrogen-doped graphene, immersed in described metallic precursor solution, add precipitation
Agent is well mixed, and heating, filtering drying, obtains catalyst powder；
4) by described catalyst powder under a shielding gas, it is calcined, obtains low-temperature denitration catalyst.
The object of the invention to solve the technical problems can be also applied to the following technical measures to achieve further.
Preferably, the preparation method of foregoing low-temperature denitration catalyst, wherein described nitrogen substance be urea, ammoniacal liquor,
At least one of hydrazine hydrate, methylamine, dimethylamine, ethamine, diethylamine, propylamine and butylamine.
Preferably, graphene oxide in the preparation method of foregoing low-temperature denitration catalyst, wherein step 1) with it is nitrogenous
The mass ratio of material is 1:10-100.
Preferably, the heating-up temperature in the preparation method of foregoing low-temperature denitration catalyst, wherein step 1) is 100-200
DEG C, heat time 5-48h.
Preferably, the preparation method of foregoing low-temperature denitration catalyst, wherein described transition metal salt is manganese salt, vanadium
At least one of salt, tungsten salt, molybdenum salt, cerium salt and molysite；
Wherein, described manganese salt is at least one of manganese sulfate, manganese acetate, manganese carbonate and manganese nitrate；
Described vanadic salts is at least one of sodium metavanadate, ammonium metavanadate and potassium metavanadate；
Described tungsten salt is at least one in ammonium tungstate, ammonium paratungstate, nitric acid tungsten, tungsten chloride and sulfuric acid tungsten；
Described molybdenum salt is at least one in ammonium molybdate, ammonium dimolybdate, ammonium tetramolybdate, nitric acid molybdenum, molybdenum chloride and molybdenum trisulfate
Kind；
Described cerium salt is at least one of cerous chlorate, cerous nitrate, ammonium ceric nitrate and cerous sulfate；
Described molysite is at least one of ferric nitrate, iron chloride and ferric sulfate.
Preferably, the preparation method of foregoing low-temperature denitration catalyst, wherein described titanium dioxide and nitrogen-doped graphene
Weight ratio be 20-50:1.
Preferably, the preparation method of foregoing low-temperature denitration catalyst, wherein it is described the step of 3) in precipitating reagent be ammonia
Water, regulation pH are 9-11；Heating-up temperature is 120-200 DEG C, heat time 1-12h；Drying temperature is 60-120 DEG C, during drying
Between be 3-10h.
Preferably, the preparation method of foregoing low-temperature denitration catalyst, wherein it is described the step of 4) in protective gas be
Nitrogen or argon gas；Sintering temperature is 350-500 DEG C, roasting time 3-10h.
The object of the invention to solve the technical problems is also realized using following technical scheme.Itd is proposed according to the present invention
A kind of low-temperature denitration catalyst, be prepared by foregoing method；Its active component is made up of transition metal oxide；Carrier
For nitrogen-doped graphene and titanium dioxide；Transition metal in transition metal oxide be in manganese, vanadium, tungsten, molybdenum, cerium and iron at least
It is a kind of.
The object of the invention to solve the technical problems can be also applied to the following technical measures to achieve further.
Preferably, foregoing low-temperature denitration catalyst, wherein described transition metal oxide accounts for low-temperature denitration catalyst
Mass fraction be 1.5-48%.
The object of the invention to solve the technical problems is also realized using following technical scheme.Itd is proposed according to the present invention
A kind of denitration method for flue gas, selective catalytic reduction reaction, described selectivity are carried out with foregoing low-temperature denitration catalyst
The temperature of catalytic reduction reaction is 80-180 DEG C.
By above-mentioned technical proposal, low-temperature denitration catalyst of the present invention and preparation method thereof at least has following advantages：This
Using nitrogen-doped graphene and titanium dioxide collectively as carrier, nitrogen, which can be penetrated into the carbon lattice of graphene, forms stable contain for invention
Nitrogen functional group, the alkali bit number of points of carrier surface is added, increases NO and SO2Deng the adsorbance of sour gas, NO is promoted
Reduction, avoid SO2Poison the activated centre of catalyst.Not only there is good denitration effect under cryogenic, and it is right
Anti- sulfur dioxide has good effect.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be practiced according to the content of specification, described in detail below with presently preferred embodiments of the present invention as after.
Embodiment
Further to illustrate the present invention to reach the technological means and effect that predetermined goal of the invention is taken, below in conjunction with
Preferred embodiment, to according to low-temperature denitration catalyst proposed by the present invention and preparation method thereof its embodiment, structure, spy
Sign and its effect, describe in detail as after.In the following description, what different " embodiment " or " embodiment " referred to is not necessarily same
One embodiment.In addition, the special characteristic, structure or feature in one or more embodiments can be combined by any suitable form.
A kind of preparation method for low-temperature denitration catalyst that one embodiment of the present of invention proposes, it includes：
1) graphene oxide and nitrogen substance are disperseed in water, 100-200 DEG C of heating 5-48h, cleaning filtering, obtains nitrogen
Doped graphene；Wherein, the mass ratio of graphene oxide and nitrogen substance is 1:10-100, nitrogen substance are urea, ammoniacal liquor, water
Close at least one of hydrazine, methylamine, dimethylamine, ethamine, diethylamine, propylamine and butylamine.
2) by transition metal salt formation metal front liquid solution soluble in water；
Wherein, transition metal salt is at least one of manganese salt, vanadic salts, tungsten salt, molybdenum salt, cerium salt and molysite；
The combination of transition metal salt can be any of manganese salt and cerium salt, molysite；Mole of Ce elements and Mn elements
Than for 0.01-1, the mol ratio of Fe elements and Mn elements is 0.01-1；
Wherein, described manganese salt is at least one of manganese sulfate, manganese acetate, manganese carbonate and manganese nitrate；
Vanadic salts is at least one of sodium metavanadate, ammonium metavanadate and potassium metavanadate；
Molysite is at least one of ferric nitrate, iron chloride and ferric sulfate.
The combination of transition metal salt can also be any of vanadic salts and molybdenum salt, tungsten salt；
Molybdenum salt is at least one of ammonium molybdate, ammonium dimolybdate, ammonium tetramolybdate, nitric acid molybdenum, molybdenum chloride and molybdenum trisulfate；
Cerium salt is at least one of cerous chlorate, cerous nitrate, ammonium ceric nitrate and cerous sulfate；
Tungsten salt is at least one in ammonium tungstate, ammonium paratungstate, nitric acid tungsten, tungsten chloride and sulfuric acid tungsten.
3) by titanium dioxide and the nitrogen-doped graphene by weight 20-50：1 mixing, immerses described metallic precursor
In solution, it is 9-11 to add precipitating reagent regulation pH, is well mixed, 120-200 DEG C of heating 1-12h, filtering, 60-120 DEG C of drying 3-
10h, obtain catalyst powder；
4) by described catalyst powder under a shielding gas, 350-500 DEG C of roasting 3-10h, low-temperature denitration catalysis is obtained
Agent；Protective gas is nitrogen or argon gas.
A kind of low-temperature denitration catalyst that one embodiment of the present of invention proposes, is prepared by foregoing method；It is lived
Property component is made up of transition metal oxide；Carrier is nitrogen-doped graphene and titanium dioxide；Transition in transition metal oxide
Metal is at least one of manganese, vanadium, tungsten, molybdenum, cerium and iron.
The combination of filtering metal oxide can be Mn oxide (MnOx) and cerium oxide (CeOx), ferriferous oxide
(FeOxAt least one of)；The mass fraction that Mn element quality accounts for low-temperature denitration catalyst is 1.5%-15%, Ce elements with
The mol ratio of Mn elements is 0.01-1, and the mol ratio of Fe elements and Mn elements is 0.01-1；The quality of Ce elements and Fe elements point
Number can not be 0% simultaneously.MnOx、CeOx、FeOxAt least one of quality account for the mass fraction of low-temperature denitration catalyst
1.5%-50%
The combination of transition metal oxide can be barium oxide (V2O5) and tungsten oxide (WO3), molybdenum oxide (MoO3)
At least one of；V2O5Quality to account for the mass fraction of low-temperature denitration catalyst be 1.5%-4%, WO3Quality account for low temperature and take off
The mass fraction of denox catalyst is 0%-10%, MoO3The mass fraction for accounting for low-temperature denitration catalyst is 0%-10%, WO3With
MoO3Mass fraction can not simultaneously be 0%.
A kind of denitration method for flue gas that one embodiment of the present of invention proposes, is selected with foregoing low-temperature denitration catalyst
Selecting property catalytic reduction reaction, the temperature of described selective catalytic reduction reaction is 80-180 DEG C, and denitration rate is more than 80%.
Embodiment 1
A kind of preparation method for low-temperature denitration catalyst that one embodiment of the present of invention proposes, it includes：
1) 12g urea is added in 2g/L graphene oxides aqueous dispersions 200mL, 160 DEG C is placed in reactor, stops after 5h
Heating, cleaned after cooling and be filtrated to get nitrogen-doped graphene；
2) deionized water 200mL is heated, adds 0.7g ammonium metavanadates, add 500 μ L monoethanolamines and treat that ammonium metavanadate is molten
Xie Hou, 1.1g Ammonium Molybdate Tetrahydrates are added, dissolve and be well mixed, obtain metal front liquid solution；
3) titanium dioxide 20g, nitrogen-doped graphene 0.4g are added into metal front liquid solution；1mL ammoniacal liquor is added dropwise, with
After be placed in 150 DEG C, 5h in reactor, after taking-up filtration washing dry, obtain catalyst powder；
4) under conditions of high pure nitrogen, catalyst powder is calcined 3h at 450 DEG C, obtains low-temperature denitration catalyst.
A kind of low-temperature denitration catalyst that one embodiment of the present of invention proposes, is prepared by the method for embodiment 1；Its
Active component is by V2O5And Mo03Composition；Carrier is nitrogen-doped graphene and titanium dioxide.
Embodiment 2
A kind of preparation method for low-temperature denitration catalyst that one embodiment of the present of invention proposes, it includes：
1) 12g urea is added in 2g/L graphene oxides aqueous dispersions 200mL, 160 DEG C is placed in reactor, stops after 5h
Heating, cleaned after cooling and be filtrated to get nitrogen-doped graphene；
2) deionized water 200mL is heated, adds 0.7g ammonium metavanadates, add 500 μ L monoethanolamines and treat that ammonium metavanadate is molten
Xie Hou, 1.1g ammonium metatungstates are added, dissolve and be well mixed, obtain metal front liquid solution；
3) titanium dioxide 20g, nitrogen-doped graphene 0.4g are added into metal front liquid solution, 1mL ammoniacal liquor is added dropwise, with
After be placed in 150 DEG C, 5h in reactor, after taking-up filtration washing dry, obtain catalyst powder；
4) under conditions of high pure nitrogen, catalyst powder is calcined 3h at 450 DEG C, obtains low-temperature denitration catalyst.
A kind of low-temperature denitration catalyst that one embodiment of the present of invention proposes, is prepared by the method for embodiment 2；Its
Active component is by V2O5And W03Composition；Carrier is nitrogen-doped graphene and titanium dioxide.
Embodiment 3
A kind of preparation method for low-temperature denitration catalyst that one embodiment of the present of invention proposes, it includes：
1) 12g urea is added in 2g/L graphene oxides aqueous dispersions 200mL, 160 DEG C is placed in reactor, stops after 5h
Heating, cleaned after cooling and be filtrated to get nitrogen-doped graphene；
2) deionized water 200mL is heated, adds 1.0g ammonium metavanadates, add 500 μ L monoethanolamines and treat that ammonium metavanadate is molten
Xie Hou, 1.4g Ammonium Molybdate Tetrahydrates are added, dissolve and be well mixed, obtain metal front liquid solution；
3) titanium dioxide 20g, nitrogen-doped graphene 0.4g are added into metal front liquid solution, 1mL ammoniacal liquor is added dropwise, with
After be placed in 150 DEG C, 5h in reactor, after taking-up filtration washing dry, obtain catalyst powder；
4) under conditions of high pure nitrogen, catalyst powder is calcined 3h at 450 DEG C, obtains low-temperature denitration catalyst.
A kind of low-temperature denitration catalyst that one embodiment of the present of invention proposes, is prepared by the method for embodiment 3；Its
Active component is by V2O5And Mo03Composition；Carrier is nitrogen-doped graphene and titanium dioxide.
Embodiment 4
A kind of preparation method for low-temperature denitration catalyst that one embodiment of the present of invention proposes, it includes：
1) 12g urea is added in 2g/L graphene oxides aqueous dispersions 200mL, 160 DEG C is placed in reactor, stops after 5h
Heating, cleaned after cooling and be filtrated to get nitrogen-doped graphene；
2) deionized water 200mL is heated, adds 1.0g ammonium metavanadates, add 500 μ L monoethanolamines and treat that ammonium metavanadate is molten
Xie Hou, 1.3g ammonium metatungstates are added, dissolve and be well mixed, obtain metal front liquid solution；
3) titanium dioxide 20g, nitrogen-doped graphene 0.4g are added into metal front liquid solution.1mL ammoniacal liquor is added dropwise, with
After be placed in 150 DEG C, 5h in reactor, after taking-up filtration washing dry, obtain catalyst powder；
4) under conditions of high pure nitrogen, catalyst powder is calcined 3h at 450 DEG C, obtains low-temperature denitration catalyst.
A kind of low-temperature denitration catalyst that one embodiment of the present of invention proposes, is prepared by the method for embodiment 4；Its
Active component is by V2O5And W03Composition；Carrier is nitrogen-doped graphene and titanium dioxide.
Embodiment 5
A kind of preparation method for low-temperature denitration catalyst that one embodiment of the present of invention proposes, it includes：
1) 30g urea is added in 2g/L graphene oxides aqueous dispersions 500mL, 160 DEG C is placed in reactor, stops after 5h
Heating, cleaned after cooling and be filtrated to get nitrogen-doped graphene；
2) deionized water 200mL is heated, adds 1.0g ammonium metavanadates, add 500 μ L monoethanolamines and treat that ammonium metavanadate is molten
Xie Hou, 1.4g Ammonium Molybdate Tetrahydrates are added, dissolve and be well mixed, obtain metal front liquid solution；
3) titanium dioxide 20g, nitrogen-doped graphene 1.0g are added into metal front liquid solution.1mL ammoniacal liquor is added dropwise, with
After be placed in 150 DEG C, 5h in reactor, filtration washing dries to obtain catalyst powder after taking-up；
3) under conditions of high pure nitrogen, catalyst powder is calcined 3h at 450 DEG C, obtains low-temperature denitration catalyst.
A kind of low-temperature denitration catalyst that one embodiment of the present of invention proposes, is prepared by the method for embodiment 5；Its
Active component is by V2O5And Mo03Composition；Carrier is nitrogen-doped graphene and titanium dioxide.
Comparative example 1
A kind of preparation method for low-temperature denitration catalyst that the comparative example of the present invention proposes, it includes：
1) deionized water 200mL is heated, adds 0.7g ammonium metavanadates, add 500 μ L monoethanolamines and treat that ammonium metavanadate is molten
Xie Hou, 1.1g ammonium metatungstates are added, obtain metal front liquid solution；
2) titanium dioxide 20g is added into metal front liquid solution.1mL ammoniacal liquor is added dropwise, is subsequently placed at 150 in reactor
DEG C, 5h, after taking-up filtration washing dry, obtain catalyst powder.
3) under conditions of high pure nitrogen, catalyst powder is calcined 3h at 450 DEG C, obtains low-temperature denitration catalyst.
A kind of low-temperature denitration catalyst that the comparative example of the present invention proposes, is prepared by the method for comparative example 1；Its
Active component is by V2O5And W03Composition；Carrier is titanium dioxide.
Embodiment 6
A kind of preparation method for low-temperature denitration catalyst that one embodiment of the present of invention proposes, it includes：
1) 12g urea is added in 2g/L graphene oxides aqueous dispersions 200mL, 160 DEG C is placed in reactor, stops after 5h
Heating, cleaned after cooling and be filtrated to get nitrogen-doped graphene；
2) deionized water 200mL is heated, adds the manganese nitrate that 4.8g mass fractions are 50%, add 4.7g six and be hydrated
Cerous nitrate, dissolve and be well mixed, obtain metal front liquid solution；
3) titanium dioxide 20g, nitrogen-doped graphene 0.4g are added into metal front liquid solution；1mL ammoniacal liquor is added dropwise, with
After be placed in 150 DEG C, 5h in reactor, after taking-up filtration washing dry, obtain catalyst powder
4) under conditions of high pure nitrogen, catalyst powder is calcined 3h at 450 DEG C, obtains low-temperature denitration catalyst.
A kind of low-temperature denitration catalyst that one embodiment of the present of invention proposes, is prepared by the method for embodiment 6；Its
Active component is by MnOxAnd Ce0xComposition；Carrier is nitrogen-doped graphene and titanium dioxide.
Embodiment 7
A kind of preparation method for low-temperature denitration catalyst that one embodiment of the present of invention proposes, it includes：
1) 12g urea is added in 2g/L graphene oxides aqueous dispersions 200mL, 160 DEG C is placed in reactor, stops after 5h
Heating, cleaned after cooling and be filtrated to get nitrogen-doped graphene；
2) deionized water is heated, adds the manganese nitrate that 4.8g mass fractions are 50%, add 3.8g iron chloride, dissolve
And be well mixed, obtain metal front liquid solution；
3) titanium dioxide 20g, nitrogen-doped graphene 0.4g are added into metal front liquid solution.1mL ammoniacal liquor is added dropwise, with
After be placed in 150 DEG C, 5h in reactor, after taking-up filtration washing dry, obtain catalyst powder；
4) under conditions of high pure nitrogen, catalyst powder is calcined 3h at 450 DEG C, obtains low-temperature denitration catalyst.
A kind of low-temperature denitration catalyst that one embodiment of the present of invention proposes, is prepared by the method for embodiment 7；Its
Active component is by MnOxAnd Fe0xComposition；Carrier is nitrogen-doped graphene and titanium dioxide.
Embodiment 8
A kind of preparation method for low-temperature denitration catalyst that one embodiment of the present of invention proposes, it includes：
1) 12g urea is added in 2g/L graphene oxides aqueous dispersions 200mL, 160 DEG C is placed in reactor, stops after 5h
Heating, cleaned after cooling and be filtrated to get nitrogen-doped graphene；
2) deionized water 200mL is heated, adds the manganese nitrate that 2.2g mass fractions are 50%, add 2.3g six and be hydrated
Cerous nitrate, dissolve and be well mixed, obtain metal front liquid solution；
3) titanium dioxide 20g, nitrogen-doped graphene 0.4g are added into metal front liquid solution, 1mL ammoniacal liquor is added dropwise, with
After be placed in 150 DEG C, 5h in reactor, after taking-up filtration washing dry, obtain catalyst powder；
4) under conditions of high pure nitrogen, catalyst powder is calcined 3h at 450 DEG C, obtains low-temperature denitration catalyst.
A kind of low-temperature denitration catalyst that one embodiment of the present of invention proposes, is prepared by the method for embodiment 8；Its
Active component is by MnOxAnd Ce0xComposition；Carrier is nitrogen-doped graphene and titanium dioxide.
Embodiment 9
A kind of preparation method for low-temperature denitration catalyst that one embodiment of the present of invention proposes, it includes：
1) 12g urea is added in 2g/L graphene oxides aqueous dispersions 200mL, 160 DEG C is placed in reactor, stops after 5h
Heating, cleaned after cooling and be filtrated to get nitrogen-doped graphene；
2) deionized water is heated, adds the manganese nitrate that 2.2g mass fractions are 50%, add 1.7g iron chloride, dissolve
And be well mixed, obtain metal front liquid solution；
3) titanium dioxide 20g, nitrogen-doped graphene 0.4g are added into metal front liquid solution, 1mL ammoniacal liquor is added dropwise, with
After be placed in 150 DEG C, 5h in reactor, after taking-up filtration washing dry, obtain catalyst powder；
4) under conditions of high pure nitrogen, catalyst powder is calcined 3h at 450 DEG C, obtains low-temperature denitration catalyst.
A kind of low-temperature denitration catalyst that one embodiment of the present of invention proposes, is prepared by the method for embodiment 9；Its
Active component is by MnOxAnd Fe0xComposition；Carrier is nitrogen-doped graphene and titanium dioxide.
Embodiment 10
A kind of preparation method for low-temperature denitration catalyst that one embodiment of the present of invention proposes, it includes：
1) 30g urea is added in 2g/L graphene oxides aqueous dispersions 500mL, 160 DEG C is placed in reactor, stops after 5h
Heating, cleaned after cooling and be filtrated to get nitrogen-doped graphene；
2) deionized water 200mL is heated, adds the manganese nitrate that 4.8g mass fractions are 50%, add 4.7g six and be hydrated
Cerous nitrate, dissolve and be well mixed, obtain metal front liquid solution；
3) titanium dioxide 20g, nitrogen-doped graphene 1.0g are added into metal front liquid solution；1mL ammonia is added dropwise
Water, 150 DEG C, 5h in reactor are subsequently placed at, filtration washing is dried after taking-up, obtains catalyst powder；
4) under conditions of high pure nitrogen, catalyst powder is calcined 3h at 450 DEG C, obtains low-temperature denitration catalyst.
A kind of low-temperature denitration catalyst that one embodiment of the present of invention proposes, is prepared by the method for embodiment 10；
Its active component is by MnOxAnd Ce0xComposition；Carrier is nitrogen-doped graphene and titanium dioxide.
Comparative example 2
A kind of preparation method for low-temperature denitration catalyst that the comparative example of the present invention proposes, it includes：
1) deionized water 200mL is heated, adds 4.8g manganese nitrates, add the nitric hydrate ceriums of 4.7g six, dissolve and mix
Close uniformly, obtain metal front liquid solution；
2) titanium dioxide 20g is added into metal front liquid solution.1mL ammoniacal liquor is added dropwise, is subsequently placed at 150 in reactor
DEG C, 5h, after taking-up filtration washing dry, obtain catalyst powder.
3) under conditions of high pure nitrogen, catalyst powder is calcined 3h at 450 DEG C, obtains low-temperature denitration catalyst.
A kind of low-temperature denitration catalyst that the comparative example of the present invention proposes, is prepared by the method for comparative example 2；Its
Active component is by MnOxAnd Ce0xComposition；Carrier is titanium dioxide.
A kind of denitration method for flue gas that one embodiment of the present of invention proposes, with the low of embodiment 1-10 and comparative example 1-2
Warm denitrating catalyst carries out selective catalytic reduction reaction, and reaction condition and Activity Results are shown in Table 1.
Catalyst performance evaluation：Activity experiment is carried out on self-control catalyst test platform, catalyst volume 10ml, ammonia
Nitrogen ratio is 1:1, O2 concentration is 6% (V/V), GHSV (gas space velocity per hour)=20000h-1 flue gas, determines 100 respectively
DEG C, the NO conversion ratios of 120 DEG C, 150 DEG C, 180 DEG C etc. 4 temperature spots.When temperature of reactor is stabilized to a certain temperature spot, start
Simulated flue gas is passed through, after reacting 10min, uses the NO in gas before and after flue gas analyzer (Testo350, Germany) measure reaction
Concentration, each temperature spot test constantly time are 15min, are averaged, and NO conversion ratios, i.e. denitration rate are calculated according to formula 1.
NO conversion ratios=[(NOin-NOout)/NOin] × 100% (formula 1)
The low-temperature denitration catalyst reaction test Activity Results of table 1
The above described is only a preferred embodiment of the present invention, any formal limitation not is made to the present invention, according to
Any simple modification, equivalent change and modification made according to the technical spirit of the present invention to above example, still falls within this hair
In the range of bright technical scheme.
Claims (10)
1. a kind of preparation method of low-temperature denitration catalyst, it is characterised in that it includes：
1) graphene oxide and nitrogen substance are disperseed in water, heating, cleaning filtering, obtains nitrogen-doped graphene；
2) by transition metal salt formation metal front liquid solution soluble in water；
3) titanium dioxide is mixed with the nitrogen-doped graphene, immersed in described metallic precursor solution, added precipitating reagent and mix
Close uniformly, heating, filtering drying, obtain catalyst powder；
4) by described catalyst powder under a shielding gas, it is calcined, obtains low-temperature denitration catalyst.
2. the preparation method of low-temperature denitration catalyst according to claim 1, it is characterised in that described nitrogen substance is
At least one of urea, ammoniacal liquor, hydrazine hydrate, methylamine, dimethylamine, ethamine, diethylamine, propylamine and butylamine.
3. the preparation method of low-temperature denitration catalyst according to claim 1, it is characterised in that the oxidation stone in step 1)
The mass ratio of black alkene and nitrogen substance is 1:10-100；Described heating-up temperature is 100-200 DEG C, heat time 5-48h.
4. the preparation method of low-temperature denitration catalyst according to claim 1, it is characterised in that described transition metal salt
For at least one of manganese salt, vanadic salts, tungsten salt, molybdenum salt, cerium salt and molysite；
Wherein, described manganese salt is at least one of manganese sulfate, manganese acetate, manganese carbonate and manganese nitrate；
Described vanadic salts is at least one of sodium metavanadate, ammonium metavanadate and potassium metavanadate；
Described tungsten salt is at least one in ammonium tungstate, ammonium paratungstate, nitric acid tungsten, tungsten chloride and sulfuric acid tungsten；
Described molybdenum salt is at least one of ammonium molybdate, ammonium dimolybdate, ammonium tetramolybdate, nitric acid molybdenum, molybdenum chloride and molybdenum trisulfate；
Described cerium salt is at least one of cerous chlorate, cerous nitrate, ammonium ceric nitrate and cerous sulfate；
Described molysite is at least one of ferric nitrate, iron chloride and ferric sulfate.
5. the preparation method of low-temperature denitration catalyst according to claim 1, it is characterised in that described titanium dioxide and nitrogen
The weight ratio of doped graphene is 20-50:1.
6. the preparation method of low-temperature denitration catalyst according to claim 1, it is characterised in that in described step 3)
Precipitating reagent is ammoniacal liquor, and regulation pH is 9-11；Heating-up temperature is 120-200 DEG C, heat time 1-12h；Drying temperature is 60-
120 DEG C, drying time 3-10h.
7. the preparation method of low-temperature denitration catalyst according to claim 1, it is characterised in that in described step 4)
Protective gas is nitrogen or argon gas；Sintering temperature is 350-500 DEG C, roasting time 3-10h.
8. a kind of low-temperature denitration catalyst, it is characterised in that be prepared by the method described in claim any one of 1-7；Its
Active component is made up of transition metal oxide；Carrier is nitrogen-doped graphene and titanium dioxide；Mistake in transition metal oxide
Metal is crossed as at least one of manganese, vanadium, tungsten, molybdenum, cerium and iron.
9. low-temperature denitration catalyst according to claim 8, it is characterised in that described transition metal oxide accounts for low temperature
The mass fraction of denitrating catalyst is 1.5-48%.
10. a kind of denitration method for flue gas, it is characterised in that entered with the low-temperature denitration catalyst described in claim any one of 8-9
Row selective catalytic reduction reaction, the temperature of described selective catalytic reduction reaction is 80-180 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710773182.XA CN107570142B (en) | 2017-08-31 | 2017-08-31 | Low-temperature denitration catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710773182.XA CN107570142B (en) | 2017-08-31 | 2017-08-31 | Low-temperature denitration catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107570142A true CN107570142A (en) | 2018-01-12 |
| CN107570142B CN107570142B (en) | 2019-08-23 |
Family
ID=61030761
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710773182.XA Active CN107570142B (en) | 2017-08-31 | 2017-08-31 | Low-temperature denitration catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107570142B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108380225A (en) * | 2018-02-07 | 2018-08-10 | 齐齐哈尔大学 | A kind of synthetic method of the anti-inactivation denitrating catalyst of efficient cryogenic |
| CN108927145A (en) * | 2018-06-11 | 2018-12-04 | 白茹 | A kind of preparation method of catalyst for denitrating flue gas |
| CN109433188A (en) * | 2018-12-11 | 2019-03-08 | 四川大学 | The preparation method and method of denitration of a kind of denitrating catalyst, denitrating catalyst |
| CN110354846A (en) * | 2019-07-31 | 2019-10-22 | 上海应用技术大学 | A kind of preparation method of manganese cerium dopping graphene low temperature SCR denitration catalyst |
| CN110961138A (en) * | 2019-12-25 | 2020-04-07 | 福州大学 | Nitrogen-doped graphene grown in situ by self-assembled denitration sulfur-resistant catalyst and preparation method thereof |
| CN111841614A (en) * | 2020-08-18 | 2020-10-30 | 福州大学 | Nitrogen-boron-codoped graphene composite denitration sulfur-resistant catalyst and preparation method thereof |
| CN111939959A (en) * | 2020-08-18 | 2020-11-17 | 福州大学 | Nitrogen-sulfur co-doped graphene composite material loaded with ternary efficient denitration sulfur-resistant catalyst and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104190409A (en) * | 2014-08-19 | 2014-12-10 | 南京师范大学 | Graphene-loaded titanium-based core-shell-structured low-temperature SCR sulfur-resisting catalyst and preparation method thereof |
| CN105413674A (en) * | 2015-11-30 | 2016-03-23 | 安徽省元琛环保科技有限公司 | Preparation method of denitration catalyst carrier with graphene |
| CN107029704A (en) * | 2017-05-19 | 2017-08-11 | 四川大学 | Catalyst and preparation method thereof, the method for removing nitrogen oxides |
-
2017
- 2017-08-31 CN CN201710773182.XA patent/CN107570142B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104190409A (en) * | 2014-08-19 | 2014-12-10 | 南京师范大学 | Graphene-loaded titanium-based core-shell-structured low-temperature SCR sulfur-resisting catalyst and preparation method thereof |
| CN105413674A (en) * | 2015-11-30 | 2016-03-23 | 安徽省元琛环保科技有限公司 | Preparation method of denitration catalyst carrier with graphene |
| CN107029704A (en) * | 2017-05-19 | 2017-08-11 | 四川大学 | Catalyst and preparation method thereof, the method for removing nitrogen oxides |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108380225A (en) * | 2018-02-07 | 2018-08-10 | 齐齐哈尔大学 | A kind of synthetic method of the anti-inactivation denitrating catalyst of efficient cryogenic |
| CN108380225B (en) * | 2018-02-07 | 2022-11-29 | 齐齐哈尔大学 | Synthetic method of low-temperature efficient deactivation-resistant denitration catalyst |
| CN108927145A (en) * | 2018-06-11 | 2018-12-04 | 白茹 | A kind of preparation method of catalyst for denitrating flue gas |
| CN108927145B (en) * | 2018-06-11 | 2021-06-25 | 安徽佳环重工机械有限公司 | Preparation method of flue gas denitration catalyst |
| CN109433188A (en) * | 2018-12-11 | 2019-03-08 | 四川大学 | The preparation method and method of denitration of a kind of denitrating catalyst, denitrating catalyst |
| CN109433188B (en) * | 2018-12-11 | 2021-09-14 | 四川大学 | Denitration catalyst, preparation method of denitration catalyst and denitration method |
| CN110354846A (en) * | 2019-07-31 | 2019-10-22 | 上海应用技术大学 | A kind of preparation method of manganese cerium dopping graphene low temperature SCR denitration catalyst |
| CN110961138A (en) * | 2019-12-25 | 2020-04-07 | 福州大学 | Nitrogen-doped graphene grown in situ by self-assembled denitration sulfur-resistant catalyst and preparation method thereof |
| CN111841614A (en) * | 2020-08-18 | 2020-10-30 | 福州大学 | Nitrogen-boron-codoped graphene composite denitration sulfur-resistant catalyst and preparation method thereof |
| CN111939959A (en) * | 2020-08-18 | 2020-11-17 | 福州大学 | Nitrogen-sulfur co-doped graphene composite material loaded with ternary efficient denitration sulfur-resistant catalyst and preparation method thereof |
| CN111841614B (en) * | 2020-08-18 | 2021-10-29 | 福州大学 | Nitrogen-boron-codoped graphene composite denitration sulfur-resistant catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107570142B (en) | 2019-08-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107570142B (en) | Low-temperature denitration catalyst and preparation method thereof | |
| CN111229212B (en) | CO-SCR denitration catalyst, preparation method and application | |
| CN105727985B (en) | Honeycomb monolith low-temperature denitration catalyst and preparation method thereof | |
| CN105618032B (en) | Support type manganese-based low-temperature denitration catalyst and preparation method thereof | |
| CN103055848B (en) | Rare-earth doped low-temperature denitration catalyst and preparation method thereof | |
| CN103638942B (en) | SCR (selective catalytic reduction) catalyst for denitrating low-temperature smoke of cement kiln and preparation method thereof | |
| CN1917955B (en) | Exhaust gas catalyst | |
| CN106475129B (en) | Using hexagonal boron nitride as the preparation method of the composite oxides denitrating catalyst of carrier | |
| CN104307564B (en) | A kind of Cu-SAPO-34 catalyst of auxiliary agent doping and its preparation method and application | |
| CN105080566A (en) | Flue gas denitrification powder catalyst as well as preparation method and application thereof | |
| EP2922633B1 (en) | Process for the preparation of mixed metal oxide ammoxidation catalysts | |
| CN102764643A (en) | Vanadium-titanium oxide catalyst, and preparation method and application thereof | |
| CN102000572B (en) | Method for preparing denitration catalyst by performing selective catalytic reduction on CuMgAl composite oxide | |
| CN105363430B (en) | Titania oxide supported vanadic acid cerium zirconium denitrating catalyst, preparation method and application | |
| CN103894182A (en) | Flue gas denitrification catalyst with wide activity temperature interval as well as preparation method thereof | |
| CN102631921A (en) | Nitric acid exhaust gas denitration catalyst and preparation method thereof | |
| CN103111280A (en) | Transition metal doped cerium-zirconium solid solution high-air-speed denitrification catalyst and preparation method thereof | |
| CN107008327A (en) | A kind of low temperature sulfuric-resisting hydrogen ammonium SCR denitration and its preparation method and application | |
| CN102513095B (en) | Medium temperature denitration catalyst with carbon-based material loaded with cerium tungsten and preparation method of medium temperature denitration catalyst | |
| CN106582874A (en) | High temperature resistant phosphotungstic acid adsorbed iron-based oxide catalyst and preparation method thereof | |
| CN106513005A (en) | A preparing method of an iron-based composite oxide catalyst | |
| CN112844366A (en) | Multiple poisoning resistant NH3-SCR catalyst and method for producing the same | |
| CN109331837A (en) | A kind of catalyst of catalytic wet air oxidation processing furans waste water | |
| CN105727965B (en) | A kind of copper zirconium cerium and titanium compound oxide catalyst and its preparation method for denitrating flue gas | |
| CN106362733A (en) | High-temperature resistant manganite catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |