CN102000585A - Denitration catalyst and preparation method thereof - Google Patents
Denitration catalyst and preparation method thereof Download PDFInfo
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- CN102000585A CN102000585A CN2010102542497A CN201010254249A CN102000585A CN 102000585 A CN102000585 A CN 102000585A CN 2010102542497 A CN2010102542497 A CN 2010102542497A CN 201010254249 A CN201010254249 A CN 201010254249A CN 102000585 A CN102000585 A CN 102000585A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 33
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000010883 coal ash Substances 0.000 claims abstract description 28
- 239000004575 stone Substances 0.000 claims abstract description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 8
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 67
- WZUKKIPWIPZMAS-UHFFFAOYSA-K Ammonium alum Chemical compound [NH4+].O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O WZUKKIPWIPZMAS-UHFFFAOYSA-K 0.000 claims description 62
- 150000003839 salts Chemical class 0.000 claims description 55
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 33
- 238000001914 filtration Methods 0.000 claims description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- 238000002425 crystallisation Methods 0.000 claims description 29
- 230000008025 crystallization Effects 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 26
- 235000021110 pickles Nutrition 0.000 claims description 24
- 229910052742 iron Inorganic materials 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 238000005470 impregnation Methods 0.000 claims description 14
- 244000025254 Cannabis sativa Species 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000003245 coal Substances 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 11
- -1 iron ion Chemical class 0.000 claims description 11
- 238000002386 leaching Methods 0.000 claims description 11
- 235000006408 oxalic acid Nutrition 0.000 claims description 11
- 238000001953 recrystallisation Methods 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 239000004411 aluminium Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 5
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 20
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 16
- 239000003546 flue gas Substances 0.000 abstract description 16
- 238000013461 design Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 3
- 238000003915 air pollution Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 23
- 238000000227 grinding Methods 0.000 description 18
- 239000002893 slag Substances 0.000 description 18
- 238000005516 engineering process Methods 0.000 description 13
- 238000006424 Flood reaction Methods 0.000 description 10
- 229910010413 TiO 2 Inorganic materials 0.000 description 9
- 238000013019 agitation Methods 0.000 description 9
- 239000000284 extract Substances 0.000 description 9
- 238000002803 maceration Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 150000003681 vanadium Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- JMTJYLISOWJQAT-UHFFFAOYSA-N [Zr].[V].[Ti] Chemical compound [Zr].[V].[Ti] JMTJYLISOWJQAT-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to a denitration catalyst and a preparation method thereof, in particular to a flue gas selective catalytic reduction denitration catalyst prepared by utilizing stone coal ash and a preparation method thereof, belonging to the field of environmental-friendly catalytic materials used for air pollution. The denitration catalyst comprises a carrier and an active component, wherein the carrier is anatase type nanometer titanium dioxide; and the active component is a mixed metal oxide of vanadium, aluminum and ferrum. The invention has the advantages of reasonable component design, high active degree, difficult ineffectiveness, low price, stability, reliability, reasonable process design, energy saving, environmental protection, low cost and stable product quality.
Description
Technical field
The present invention relates to a kind of denitrating catalyst and preparation method thereof, belong to the environment protection catalytic material field of using in the atmosphere pollution, specifically a kind of flue gas selective catalytic reduction denitrating catalyst that utilizes the stone coal ash preparation and preparation method thereof.
Background technology
Nitrogen oxide (NO
x) be one of generally acknowledged main atmosphere pollution in countries in the world.It damages the ozone layer, and forms acid rain and photochemical fog, influence ecological environment, and harm humans health, nitrogen oxide reduction of discharging at present has been subjected to people and has paid close attention to greatly.Advantages such as catalytic activity, selectivity and heat endurance are widely used in the denitrating flue gas engineering both domestic and external selective catalytic reduction (SCR) gas denitrifying technology because of it has preferably, also become the mainstream technology of coal-fired flue gas denitration.Because activity of such catalysts has determined the denitration efficiency of SCR flue gas denitrification system largely, therefore active good catalyst becomes the key of SCR gas denitrifying technology.Simultaneously, because catalyst activity composition addition is big and cost an arm and a leg, therefore how to develop the hot issue that efficient, cheap SCR catalyst for denitrating flue gas has become domestic and international denitrating flue gas field.
The patent of the relevant SCR catalyst for denitrating flue gas of having applied for at present has multiple, and from disclosed patent as can be seen, carrier and active component that all kinds of SCR catalyst for denitrating flue gas use have nothing in common with each other.Can be divided into vanadium class catalyst and non-vanadium class catalyst two big classes according to the catalyst main active.Vanadium class catalyst such as patent (CN101284229) are that drying, roasting were prepared from again after titanium-base ceramics was flooded titanium zirconium vanadium complex sol.Patent (CN101352679) is to adopt step impregnation method, is carrier with ceramic honey comb, metallic plate, glass corrugated plating, and active component is V
2O
5, WO
3And ZrO
2, one or more that add rare earth metals such as an amount of Pr, Nd simultaneously are co-catalyst component.
Non-vanadium class catalyst is to be main active with other transition metal or rare-earth oxide, as patent (CN101507920) is that employing chromium and cerium are key component, realize active constituent loading by coprecipitation or infusion process, make low-temperature denitration catalyst through calcination again.Patent (CN101234345) is after Al-base ceramic is flooded aluminium colloidal sol drying and roasting and prepares aluminum oxide coating layer, floods cerium salt again and the doped metal salt composite solution prepares the active catalytic components coating.
Though the SCR catalyst for denitrating flue gas of existing catalyst preparation technology preparation can obtain higher denitration activity, but, make that the cost of catalyst is high owing to all be the technology that adopts active component corresponding finished raw material after suitable proportioning, to prepare complex catalyst precursor liquid and then generate catalyst; Simultaneously, the existing SCR catalyst for denitrating flue gas is relatively more responsive to the moisture in the flue gas and sulfur dioxide, and when moisture and content of sulfur dioxide were higher, denitration activity descended.Therefore, when guaranteeing the catalyst denitration activity, how to reduce the Preparation of catalysts cost and improve its stability, become the significant problem that solution is needed in China denitrating flue gas field badly.
Summary of the invention
Technical problem to be solved by this invention provides that a kind of component is reasonable in design, level of activity is high, be difficult for losing efficacy, cheap, reliable and stable denitrating catalyst.
Another technical problem to be solved by this invention provide a kind of technological design rationally, the preparation method of the denitrating catalyst of low, the constant product quality of energy-conserving and environment-protective, cost.
It is this denitrating catalyst that the present invention solves the problems of the technologies described above the technical scheme that is adopted, and it consists of: carrier and active component are formed, and described carrier is an anatase-type nanometer titanium dioxide, and described active component is the mixed-metal oxides of vanadium, aluminium, iron.
As preferably, the mass percent of anatase-type nanometer titanium dioxide of the present invention is 80～97.5% of a gross weight, and the mass percent of the mixed-metal oxides of described vanadium, aluminium, iron is 2.5～20% of a gross weight.
As preferably, the mixed-metal oxides of vanadium of the present invention, aluminium, iron, wherein V
2O
5Mass percent be 0.5～6% of gross weight, Al
2O
3Mass percent be 1～8% of gross weight, Fe
2O
3Mass percent be 1～6% of gross weight.
The present invention solves the problems of the technologies described above the preparation method that the technical scheme that is adopted still is a kind of denitrating catalyst, and preparation process is:
A, stone coal ash is dropped into coal pulverizer be finely ground to granularity≤200 μ m, obtain the powdery stone coal ash.
B, the powdery stone coal ash joined stir acidleach in the sulfuric acid solution, leaching time is 2～4 hours, and the solid-liquid weight ratio is 1:2～4, after the filtration pickle liquor.
C, in pickle liquor, add excessive (NH
4)
2SO
4, its consumption is control Al
3+And NH
4 +Mol ratio be 1:5～8, at the uniform velocity stir in the adition process, pickle liquor is cooled to room temperature, be 2～4 hours cool time, the ammonia-alum crystalline deposit, filtration obtains thick ammonia-alum and contains vanadium mother liquid, obtains smart ammonia-alum after adopting reduction-recrystallization method secondary crystallization to remove wherein impurity such as iron ion thick ammonia-alum.
D, heating contain vanadium mother liquid to separating out the intermediate salt crystal, and more after filtration, obtain intermediate salt after the washing, the filtrate reclaim sulfuric acid is reused.
E, preparation mass concentration are 5～10% oxalic acid solution, add intermediate salt then, and the solid-liquid weight ratio is 1:5～20, is to stir under 50～60 ℃ of conditions to dissolve fully until intermediate salt in temperature, forms grass green solution.
F, with grass green solution spend the night leave standstill after, add Powdered dried anatase-type nanometer titanium dioxide, under stirring condition at the uniform velocity, flood 3～6 hours after, the white slurry that obtains was put into the ultrasonic cleaner ultrasonic immersing 2～4 hours, obtained impregnation product.
G, with after impregnation product drying, the roasting, make denitrating catalyst.
As preferably, the sulfuric acid volumetric concentration among the step b of the present invention is 40～50%, and the acidleach temperature is 100～120 ℃.
As preferably, heating contains vanadium mother liquid to 120～150 ℃, 2～4 hours retention times in the steps d of the present invention.The intermediate salt main component of separating out in the solution is the sulfate of vanadium, aluminium, iron.
As preferably, the dipping among the step f of the present invention, the solid-liquid volume ratio of dipping is 1:1～2.
As preferably, the drying in the step g of the present invention is to carry out in air dry oven, and baking temperature is 110 ℃, and be 4～8 hours drying time.
As preferably, the roasting in the step g of the present invention is to be to carry out under 350～450 ℃ of conditions in temperature, and roasting time is 3～6 hours.
The present invention compares with existing technology, has the following advantages and characteristics:
1, the stone coal ash process for extracting vanadium is combined with SCR catalyst for denitrating flue gas preparation technology, technology is simple, and is workable, is fit to scale and uses.
2, can carry out comprehensive reutilization to the metal in the stone coal ash, consumption of raw materials is low, has good benefits in environment.
3, when guaranteeing that prepared catalyst has efficient denitration activity, greatly reduced the cost of catalyst.
4, in the use, denitration activity descends few, steady quality, and the life-span is long.
The specific embodiment
The present invention is described in further detail below in conjunction with embodiment, and following examples are explanation of the invention and the present invention is not limited to following examples.
Embodiment 1: present embodiment with the lower part preparation method of denitrating catalyst has been described:
1, material slag fine grinding
Stone coal ash is dropped into coal pulverizer be finely ground to granularity≤200 μ m.
2, material slag acidleach
It is to stir acidleach in 40% the sulfuric acid solution that stone coal ash after the fine grinding is joined volumetric concentration, and the acidleach temperature is 110 ℃, leaching time 3 hours, the solid-liquid weight ratio is 1:3, after the filtration pickle liquor.
3, ammonia-alum crystallization
In pickle liquor, add excessive (NH
4)
2SO
4, its consumption is control Al
3+And NH
4 +Mol ratio be 1:5, at the uniform velocity stir in the adition process.Use running water that solution is cooled to room temperature, be 2 hours cool time.The ammonia-alum crystalline deposit can get thick ammonia-alum after filtration, and filtrate being contains vanadium mother liquid.Employing reduction-recrystallization method is removed the impurity such as iron ion in the thick ammonia-alum again, can obtain smart ammonia-alum through secondary crystallization.
4, intermediate salt crystallization
What obtain after the heating ammonia-alum filters contains vanadium mother liquid to 120 ℃, and the time is 4 hours, separates out the intermediate salt crystal in the solution, obtains intermediate salt after the washing after filtration again.
5, the preparation of activity component impregnation liquid
The preparation mass concentration is 10% oxalic acid solution, adds intermediate salt then, and the solid-liquid weight ratio is 1:15, adds thermal agitation and dissolve fully until intermediate salt under 60 ℃ of conditions, forms grass green solution.
6, the load of active component
After maceration extract spends the night and leaves standstill, toward wherein adding anatase type nano TiO
2Powder floods, and the solid-liquid volume ratio is 1:1.2, and the time is 4 hours.Then resulting white slurry is put into heavily ultrasonic immersing 2 hours of ultrasonic cleaner.
7, dry, roasting
The drying case is dry 5 hours again.Dried catalyst is put into Muffle furnace, and high-temperature roasting is 4 hours under 400 ℃ of conditions, promptly makes final denitrating catalyst.
Embodiment 2: present embodiment with the lower part preparation method of denitrating catalyst has been described:
1, material slag fine grinding
Stone coal ash is dropped into coal pulverizer be finely ground to granularity≤200 μ m.
2, material slag acidleach
It is to stir acidleach in 50% the sulfuric acid that stone coal ash after the fine grinding is joined volumetric concentration, and the acidleach temperature is 120 ℃, leaching time 4 hours, the solid-liquid weight ratio is 1:4, after the filtration pickle liquor.
3, ammonia-alum crystallization
In pickle liquor, add excessive (NH
4)
2SO
4, its consumption is control Al
3+And NH
4 +Mol ratio be 1:7.At the uniform velocity stir in the adition process, use running water solution to be cooled to room temperature, 3 hours cool times.The ammonia-alum crystalline deposit can get thick ammonia-alum after filtration, and filtrate being contains vanadium mother liquid.Employing reduction-recrystallization method is removed the impurity such as iron ion in the thick ammonia-alum again, can obtain smart ammonia-alum through secondary crystallization.
4, intermediate salt crystallization
What obtain after the heating ammonia-alum filters contains vanadium mother liquid to 150 ℃, and the time is 3 hours, separates out the intermediate salt crystal in the solution, obtains intermediate salt after the washing after filtration again.
5, the preparation of activity component impregnation liquid
The preparation mass concentration is 10% oxalic acid solution, adds intermediate salt then, and the solid-liquid weight ratio is 1:20, adds thermal agitation and dissolve fully until intermediate salt under 50 ℃ of conditions, forms grass green solution.
6, the load of active component
After maceration extract spends the night and leaves standstill, toward wherein adding anatase type nano TiO
2Powder floods, and the solid-liquid volume ratio is 1:1.5, and the time is 4 hours.Then resulting white slurry was put into the supersonic wave cleaning machine ultrasonic immersing 2 hours.
7, dry, roasting
The drying case is dry 6 hours again.Dried catalyst is put into Muffle furnace, and high-temperature roasting is 3 hours under 450 ℃ of conditions, promptly makes final denitrating catalyst.
Embodiment 3: present embodiment with the lower part preparation method of denitrating catalyst has been described:
1, material slag fine grinding
Stone coal ash is dropped into coal pulverizer be finely ground to granularity≤200 μ m.
2, material slag acidleach
It is to stir acidleach in 42% the sulfuric acid solution that stone coal ash after the fine grinding is joined volumetric concentration, and the acidleach temperature is 100 ℃, leaching time 3 hours, the solid-liquid weight ratio is 1:3, after the filtration pickle liquor.
3, ammonia-alum crystallization
In pickle liquor, add excessive (NH
4)
2SO
4, its consumption is control Al
3+And NH
4 +Mol ratio be 1:6, at the uniform velocity stir in the adition process.Use running water that solution is cooled to room temperature, be 2 hours cool time.The ammonia-alum crystalline deposit can get thick ammonia-alum after filtration, and filtrate being contains vanadium mother liquid.Employing reduction-recrystallization method is removed the impurity such as iron ion in the thick ammonia-alum again, can obtain smart ammonia-alum through secondary crystallization.
4, intermediate salt crystallization
What obtain after the heating ammonia-alum filters contains vanadium mother liquid to 150 ℃, and the time is 2 hours, separates out the intermediate salt crystal in the solution, obtains intermediate salt after the washing after filtration again.
5, the preparation of activity component impregnation liquid
The preparation mass concentration is 8% oxalic acid solution, adds intermediate salt then, and the solid-liquid weight ratio is 1:16, adds thermal agitation and dissolve fully until intermediate salt under 60 ℃ of conditions, forms grass green solution.
6, the load of active component
After maceration extract spends the night and leaves standstill, toward wherein adding anatase type nano TiO
2Powder floods, and the solid-liquid volume ratio is 1:1.3, and the time is 4 hours.Then resulting white slurry is put into heavily ultrasonic immersing 2 hours of ultrasonic cleaner.
7, dry, roasting
The drying case is dry 4 hours again.Dried catalyst is put into Muffle furnace, and high-temperature roasting is 3 hours under 380 ℃ of conditions, promptly makes final denitrating catalyst.
Embodiment 4: present embodiment with the lower part preparation method of denitrating catalyst has been described:
1, material slag fine grinding
Stone coal ash is dropped into coal pulverizer be finely ground to granularity≤200 μ m.
2, material slag acidleach
It is to stir acidleach in 46% the sulfuric acid solution that stone coal ash after the fine grinding is joined volumetric concentration, and the acidleach temperature is 115 ℃, leaching time 4 hours, the solid-liquid weight ratio is 1:2, after the filtration pickle liquor.
3, ammonia-alum crystallization
In pickle liquor, add excessive (NH
4)
2SO
4, its consumption is control Al
3+And NH
4 +Mol ratio be 1:7, at the uniform velocity stir in the adition process.Use running water that solution is cooled to room temperature, be 3 hours cool time.The ammonia-alum crystalline deposit can get thick ammonia-alum after filtration, and filtrate being contains vanadium mother liquid.Employing reduction-recrystallization method is removed the impurity such as iron ion in the thick ammonia-alum again, can obtain smart ammonia-alum through secondary crystallization.
4, intermediate salt crystallization
What obtain after the heating ammonia-alum filters contains vanadium mother liquid to 140 ℃, and the time is 2 hours, separates out the intermediate salt crystal in the solution, obtains intermediate salt after the washing after filtration again.
5, the preparation of activity component impregnation liquid
The preparation mass concentration is 7% oxalic acid solution, adds intermediate salt then, and the solid-liquid weight ratio is 1:12, adds thermal agitation and dissolve fully until intermediate salt under 50 ℃ of conditions, forms grass green solution.
6, the load of active component
After maceration extract spends the night and leaves standstill, toward wherein adding anatase type nano TiO
2Powder floods, and the solid-liquid volume ratio is 1:1.4, and the time is 5 hours.Then resulting white slurry is put into heavily ultrasonic immersing 3 hours of ultrasonic cleaner.
7, dry, roasting
The drying case is dry 5 hours again.Dried catalyst is put into Muffle furnace, and high-temperature roasting is 4 hours under 450 ℃ of conditions, promptly makes final denitrating catalyst.
Embodiment 5: present embodiment with the lower part preparation method of denitrating catalyst has been described:
1, material slag fine grinding
Stone coal ash is dropped into coal pulverizer be finely ground to granularity≤200 μ m.
2, material slag acidleach
It is to stir acidleach in 50% the sulfuric acid solution that stone coal ash after the fine grinding is joined volumetric concentration, and the acidleach temperature is 120 ℃, leaching time 3 hours, the solid-liquid weight ratio is 1:3, after the filtration pickle liquor.
3, ammonia-alum crystallization
In pickle liquor, add excessive (NH
4)
2SO
4, its consumption is control Al
3+And NH
4 +Mol ratio be 1:5, at the uniform velocity stir in the adition process.Use running water that solution is cooled to room temperature, be 3 hours cool time.The ammonia-alum crystalline deposit can get thick ammonia-alum after filtration, and filtrate being contains vanadium mother liquid.Employing reduction-recrystallization method is removed the impurity such as iron ion in the thick ammonia-alum again, can obtain smart ammonia-alum through secondary crystallization.
4, intermediate salt crystallization
What obtain after the heating ammonia-alum filters contains vanadium mother liquid to 130 ℃, and the time is 3 hours, separates out the intermediate salt crystal in the solution, obtains intermediate salt after the washing after filtration again.
5, the preparation of activity component impregnation liquid
The preparation mass concentration is 6% oxalic acid solution, adds intermediate salt then, and the solid-liquid weight ratio is 1:7, adds thermal agitation and dissolve fully until intermediate salt under 55 ℃ of conditions, forms grass green solution.
6, the load of active component
After maceration extract spends the night and leaves standstill, toward wherein adding anatase type nano TiO
2Powder floods, and the solid-liquid volume ratio is 1:1.8, and the time is 6 hours.Then resulting white slurry is put into heavily ultrasonic immersing 3 hours of ultrasonic cleaner.
7, dry, roasting
The drying case is dry 7 hours again.Dried catalyst is put into Muffle furnace, and high-temperature roasting is 5 hours under 350 ℃ of conditions, promptly makes final denitrating catalyst.
Embodiment 6: present embodiment with the lower part preparation method of denitrating catalyst has been described:
1, material slag fine grinding
Stone coal ash is dropped into coal pulverizer be finely ground to granularity≤200 μ m.
2, material slag acidleach
It is to stir acidleach in 48% the sulfuric acid solution that stone coal ash after the fine grinding is joined volumetric concentration, and the acidleach temperature is 118 ℃, leaching time 3 hours, the solid-liquid weight ratio is 1:4, after the filtration pickle liquor.
3, ammonia-alum crystallization
In pickle liquor, add excessive (NH
4)
2SO
4, its consumption is control Al
3+And NH
4 +Mol ratio be 1:6, at the uniform velocity stir in the adition process.Use running water that solution is cooled to room temperature, be 4 hours cool time.The ammonia-alum crystalline deposit can get thick ammonia-alum after filtration, and filtrate being contains vanadium mother liquid.Employing reduction-recrystallization method is removed the impurity such as iron ion in the thick ammonia-alum again, can obtain smart ammonia-alum through secondary crystallization.
4, intermediate salt crystallization
What obtain after the heating ammonia-alum filters contains vanadium mother liquid to 135 ℃, and the time is 3 hours, separates out the intermediate salt crystal in the solution, obtains intermediate salt after the washing after filtration again.
5, the preparation of activity component impregnation liquid
The preparation mass concentration is 7% oxalic acid solution, adds intermediate salt then, and the solid-liquid weight ratio is 1:11, adds thermal agitation and dissolve fully until intermediate salt under 58 ℃ of conditions, forms grass green solution.
6, the load of active component
After maceration extract spends the night and leaves standstill, toward wherein adding anatase type nano TiO
2Powder floods, and the solid-liquid volume ratio is 1:1.5, and the time is 3 hours.Then resulting white slurry is put into heavily ultrasonic immersing 4 hours of ultrasonic cleaner.
7, dry, roasting
The drying case is dry 6 hours again.Dried catalyst is put into Muffle furnace, and high-temperature roasting is 4 hours under 370 ℃ of conditions, promptly makes final denitrating catalyst.
Embodiment 7: present embodiment with the lower part preparation method of denitrating catalyst has been described:
1, material slag fine grinding
Stone coal ash is dropped into coal pulverizer be finely ground to granularity≤200 μ m.
2, material slag acidleach
It is to stir acidleach in 44% the sulfuric acid solution that stone coal ash after the fine grinding is joined volumetric concentration, and the acidleach temperature is 116 ℃, leaching time 3 hours, the solid-liquid weight ratio is 1:4, after the filtration pickle liquor.
3, ammonia-alum crystallization
In pickle liquor, add excessive (NH
4)
2SO
4, its consumption is control Al
3+And NH
4 +Mol ratio be 1:8, at the uniform velocity stir in the adition process.Use running water that solution is cooled to room temperature, be 3 hours cool time.The ammonia-alum crystalline deposit can get thick ammonia-alum after filtration, and filtrate being contains vanadium mother liquid.Employing reduction-recrystallization method is removed the impurity such as iron ion in the thick ammonia-alum again, can obtain smart ammonia-alum through secondary crystallization.
4, intermediate salt crystallization
What obtain after the heating ammonia-alum filters contains vanadium mother liquid to 145 ℃, and the time is 3 hours, separates out the intermediate salt crystal in the solution, obtains intermediate salt after the washing after filtration again.
5, the preparation of activity component impregnation liquid
The preparation mass concentration is 9% oxalic acid solution, adds intermediate salt then, and the solid-liquid weight ratio is 1:18, adds thermal agitation and dissolve fully until intermediate salt under 60 ℃ of conditions, forms grass green solution.
6, the load of active component
After maceration extract spends the night and leaves standstill, toward wherein adding anatase type nano TiO
2Powder floods, and the solid-liquid volume ratio is 1:1, and the time is 3 hours.Then resulting white slurry is put into heavily ultrasonic immersing 2 hours of ultrasonic cleaner.
7, dry, roasting
The drying case is dry 6 hours again.Dried catalyst is put into Muffle furnace, and high-temperature roasting is 6 hours under 420 ℃ of conditions, promptly makes final denitrating catalyst.
Embodiment 8: present embodiment with the lower part preparation method of denitrating catalyst has been described:
1, material slag fine grinding
Stone coal ash is dropped into coal pulverizer be finely ground to granularity≤200 μ m.
2, material slag acidleach
It is to stir acidleach in 45% the sulfuric acid solution that stone coal ash after the fine grinding is joined volumetric concentration, and the acidleach temperature is 105 ℃, leaching time 2 hours, the solid-liquid weight ratio is 1:2, after the filtration pickle liquor.
3, ammonia-alum crystallization
In pickle liquor, add excessive (NH
4)
2SO
4, its consumption is control Al
3+And NH
4 +Mol ratio be 1:7, at the uniform velocity stir in the adition process.Use running water that solution is cooled to room temperature, be 4 hours cool time.The ammonia-alum crystalline deposit can get thick ammonia-alum after filtration, and filtrate being contains vanadium mother liquid.Employing reduction-recrystallization method is removed the impurity such as iron ion in the thick ammonia-alum again, can obtain smart ammonia-alum through secondary crystallization.
4, intermediate salt crystallization
What obtain after the heating ammonia-alum filters contains vanadium mother liquid to 125 ℃, and the time is 4 hours, separates out the intermediate salt crystal in the solution, obtains intermediate salt after the washing after filtration again.
5, the preparation of activity component impregnation liquid
The preparation mass concentration is 5% oxalic acid solution, adds intermediate salt then, and the solid-liquid weight ratio is 1:5, adds thermal agitation and dissolve fully until intermediate salt under 52 ℃ of conditions, forms grass green solution.
6, the load of active component
After maceration extract spends the night and leaves standstill, toward wherein adding anatase type nano TiO
2Powder floods, and the solid-liquid volume ratio is 1:2, and the time is 4 hours.Then resulting white slurry is put into heavily ultrasonic immersing 3 hours of ultrasonic cleaner.
7, dry, roasting
The drying case is dry 8 hours again.Dried catalyst is put into Muffle furnace, and high-temperature roasting is 3 hours under 430 ℃ of conditions, promptly makes final denitrating catalyst.
Embodiment 9: present embodiment with the lower part preparation method of denitrating catalyst has been described:
1, material slag fine grinding
Stone coal ash is dropped into coal pulverizer be finely ground to granularity≤200 μ m.
2, material slag acidleach
It is to stir acidleach in 47% the sulfuric acid solution that stone coal ash after the fine grinding is joined volumetric concentration, and the acidleach temperature is 110 ℃, leaching time 4 hours, the solid-liquid weight ratio is 1:3, after the filtration pickle liquor.
3, ammonia-alum crystallization
In pickle liquor, add excessive (NH
4)
2SO
4, its consumption is control Al
3+And NH
4 +Mol ratio be 1:6, at the uniform velocity stir in the adition process.Use running water that solution is cooled to room temperature, be 3 hours cool time.The ammonia-alum crystalline deposit can get thick ammonia-alum after filtration, and filtrate being contains vanadium mother liquid.Employing reduction-recrystallization method is removed the impurity such as iron ion in the thick ammonia-alum again, can obtain smart ammonia-alum through secondary crystallization.
4, intermediate salt crystallization
What obtain after the heating ammonia-alum filters contains vanadium mother liquid to 130 ℃, and the time is 3 hours, separates out the intermediate salt crystal in the solution, obtains intermediate salt after the washing after filtration again.
5, the preparation of activity component impregnation liquid
The preparation mass concentration is 8% oxalic acid solution, adds intermediate salt then, and the solid-liquid weight ratio is 1:12, adds thermal agitation and dissolve fully until intermediate salt under 55 ℃ of conditions, forms grass green solution.
6, the load of active component
After maceration extract spends the night and leaves standstill, toward wherein adding anatase type nano TiO
2Powder floods, and the solid-liquid volume ratio is 1:1.3, and the time is 5 hours.Then resulting white slurry is put into heavily ultrasonic immersing 4 hours of ultrasonic cleaner.
7, dry, roasting
The drying case is dry 4 hours again.Dried catalyst is put into Muffle furnace, and high-temperature roasting is 4 hours under 360 ℃ of conditions, promptly makes final denitrating catalyst.
Following table has illustrated the composition of resultant denitrating catalyst among the embodiment 1-9: (unit is weight percentage)
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| Anatase-type nanometer titanium dioxide | 95 | 86 | 92 | 90 | 80 | 87 | 97.5 | 82 | 92 |
| V 2O 5 | 0.8 | 4 | 2 | 5 | 6 | 4 | 0.5 | 5.5 | 1.5 |
| Al 2O 3 | 1.5 | 5 | 4.5 | 3 | 8 | 3.5 | 1 | 7 | 2 |
| Fe 2O 3 | 2.7 | 5 | 1.5 | 2 | 6 | 5.5 | 1 | 5.5 | 4.5 |
Catalyst denitration activity test case:
Catalyst prepared among the embodiment 2 pulverized sieve, obtain granularity and be the catalyst granules between 30～60 orders, get this catalyst granules 3 ml and put into the catalyst activity evaluating apparatus, activity rating carries out in internal diameter is the quartz tube reactor of 10 mm; Simulated flue gas consists of 500 ppm NO, 5% O
2, NH
3/ NO
xBe 1, N
2Be balance gas, air speed is 24000 h
-1In the time of 400 ℃, NO
xRemoval efficiency be 95%.
Moisture and sulfur dioxide are to catalyst denitration activity test case
Catalyst prepared among the embodiment 2 pulverized sieve, obtain granularity and be the catalyst granules between 30～60 orders, get this catalyst granules 3 ml and put into the catalyst activity evaluating apparatus, activity rating carries out in internal diameter is the quartz tube reactor of 10 mm; Simulated flue gas consists of 500 ppm NO, 5% O before adding moisture and sulfur dioxide
2, N
2Be balance gas, air speed is 24000 h
-1400 ℃ of reaction temperatures, NH
3/ NO
xBe 1.The catalyst of preparation has good anti-moisture and anti-sulfur poisonous performance.
In addition, need to prove, the specific embodiment described in this specification, its prescription, title that technology is named etc. can be different.Allly conceive equivalence or the simple change that described structure, feature and principle are done, be included in the protection domain of patent of the present invention according to patent of the present invention.The technical staff of the technical field of the invention can make various modifications or replenishes or adopt similar mode to substitute described specific embodiment; only otherwise depart from structure of the present invention or surmount the defined scope of these claims, all should belong to protection scope of the present invention.
Though the present invention with embodiment openly as above; but it is not in order to limit protection scope of the present invention; any technical staff who is familiar with this technology, change and the retouching done in not breaking away from design of the present invention and scope all should belong to protection scope of the present invention.
Claims (9)
1. denitrating catalyst, it is characterized in that: it consists of: carrier and active component are formed, and described carrier is an anatase-type nanometer titanium dioxide, and described active component is the mixed-metal oxides of vanadium, aluminium, iron.
2. denitrating catalyst according to claim 1, it is characterized in that: the mass percent of described anatase-type nanometer titanium dioxide is 80～97.5% of a gross weight, and the mass percent of the mixed-metal oxides of described vanadium, aluminium, iron is 2.5～20% of a gross weight.
3. denitrating catalyst according to claim 2 is characterized in that: the mixed-metal oxides of described vanadium, aluminium, iron, wherein V
2O
5Mass percent be 0.5～6% of gross weight, Al
2O
3Mass percent be 1～8% of gross weight, Fe
2O
3Mass percent be 1～6% of gross weight.
4. denitrating catalyst according to claim 1, its preparation method is:
A, stone coal ash is dropped into coal pulverizer be finely ground to granularity≤200 μ m, obtain the powdery stone coal ash;
B, the powdery stone coal ash joined stir acidleach in the sulfuric acid solution, leaching time is 2～4 hours, and the solid-liquid weight ratio is 1:2～4, after the filtration pickle liquor;
C, in pickle liquor, add excessive (NH
4)
2SO
4, its consumption is control Al
3+And NH
4 +Mol ratio be 1:5～8, at the uniform velocity stir in the adition process, pickle liquor is cooled to room temperature, be 2～4 hours cool time, the ammonia-alum crystalline deposit, filtration obtains thick ammonia-alum and contains vanadium mother liquid, obtains smart ammonia-alum after adopting reduction-recrystallization method secondary crystallization to remove wherein impurity such as iron ion thick ammonia-alum;
D, heating contain vanadium mother liquid to separating out the intermediate salt crystal, and more after filtration, obtain intermediate salt after the washing, the filtrate reclaim sulfuric acid is reused;
E, preparation mass concentration are 5～10% oxalic acid solution, add intermediate salt then, and the solid-liquid weight ratio is 1:5～20, is to stir under 50～60 ℃ of conditions to dissolve fully until intermediate salt in temperature, forms grass green solution;
F, with grass green solution spend the night leave standstill after, add Powdered dried anatase-type nanometer titanium dioxide, under stirring condition at the uniform velocity, flood 3～6 hours after, the white slurry that obtains was put into the ultrasonic cleaner ultrasonic immersing 2～4 hours, obtained impregnation product;
G, with after impregnation product drying, the roasting, make denitrating catalyst.
5. the preparation method of denitrating catalyst according to claim 4, it is characterized in that: the sulfuric acid volumetric concentration among the described described step b is 40～50%, the acidleach temperature is 100～120 ℃.
6. the preparation method of denitrating catalyst according to claim 4 is characterized in that: heating contains vanadium mother liquid to 120～150 ℃, 2～4 hours retention times in the described described steps d.
7. the preparation method of denitrating catalyst according to claim 4, it is characterized in that: the dipping among the described step f, the solid-liquid volume ratio of dipping is 1:1～2.
8. the preparation method of denitrating catalyst according to claim 4, it is characterized in that: the drying in the described step g is to carry out in air dry oven, and baking temperature is 110 ℃, and be 4～8 hours drying time.
9. the preparation method of denitrating catalyst according to claim 4 is characterized in that: the roasting in the described step g is to be to carry out under 350～450 ℃ of conditions in temperature, and roasting time is 3～6 hours.
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| CN102921404A (en) * | 2012-09-11 | 2013-02-13 | 河南佰利联化学股份有限公司 | Preparation method of titanium-tungsten composite powder for denitrification catalyst |
| CN103506121A (en) * | 2013-07-22 | 2014-01-15 | 大连理工大学 | Low-temperature denitration catalyst with iron loaded on carbon nanotube and preparation method thereof |
| CN104959145A (en) * | 2015-06-24 | 2015-10-07 | 方耀 | Solid catalyst used for denitration of coal-fired flue gas |
| CN106513008A (en) * | 2016-10-18 | 2017-03-22 | 佛山慧创正元新材料科技有限公司 | Catalyst for removing NOx and preparation method therefor |
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| CN102716753A (en) * | 2012-06-08 | 2012-10-10 | 华电电力科学研究院 | Catalyst for low-temperature selective catalytic reduction of nitric oxide and preparation method of catalyst |
| CN102716753B (en) * | 2012-06-08 | 2015-06-17 | 华电电力科学研究院 | Catalyst for low-temperature selective catalytic reduction of nitric oxide and preparation method of catalyst |
| CN102921404A (en) * | 2012-09-11 | 2013-02-13 | 河南佰利联化学股份有限公司 | Preparation method of titanium-tungsten composite powder for denitrification catalyst |
| CN102921404B (en) * | 2012-09-11 | 2014-06-04 | 河南佰利联化学股份有限公司 | Preparation method of titanium-tungsten composite powder for denitrification catalyst |
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| CN104959145A (en) * | 2015-06-24 | 2015-10-07 | 方耀 | Solid catalyst used for denitration of coal-fired flue gas |
| CN106513008A (en) * | 2016-10-18 | 2017-03-22 | 佛山慧创正元新材料科技有限公司 | Catalyst for removing NOx and preparation method therefor |
| CN107519862A (en) * | 2017-08-23 | 2017-12-29 | 北京工业大学 | A kind of method that ferro-silicon slag prepares medium temperature denitration catalyst material |
| CN107519862B (en) * | 2017-08-23 | 2020-02-04 | 北京工业大学 | Method for preparing medium-temperature denitration catalytic material from ferrosilicon slag |
| CN109351358A (en) * | 2018-10-18 | 2019-02-19 | 中国科学院城市环境研究所 | A kind of transition metal oxide composite catalyst and its preparation method and use |
| CN113929199A (en) * | 2021-10-26 | 2022-01-14 | 伊犁新天煤化工有限责任公司 | Method for reducing chemical oxygen demand of coal gasification wastewater by utilizing coal gasification ash |
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