CN103127930A - High-activity nano-grade flue gas denitrification catalyst and low-temperature liquid-phase preparation method thereof - Google Patents
High-activity nano-grade flue gas denitrification catalyst and low-temperature liquid-phase preparation method thereof Download PDFInfo
- Publication number
- CN103127930A CN103127930A CN2013100794321A CN201310079432A CN103127930A CN 103127930 A CN103127930 A CN 103127930A CN 2013100794321 A CN2013100794321 A CN 2013100794321A CN 201310079432 A CN201310079432 A CN 201310079432A CN 103127930 A CN103127930 A CN 103127930A
- Authority
- CN
- China
- Prior art keywords
- solution
- catalyst
- flue gas
- mol ratio
- coo
- 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 invention provides a high-activity nano-grade flue gas denitrification catalyst for removing nitric oxides in fuel gas under a low temperature condition, and a low-temperature liquid-phase preparation method of the high-activity nano-grade flue gas denitrification catalyst. The method does not relate to high-temperature roasting; and the prepared catalyst exists in a manner of a lot of amorphous state mixed oxides, and the activity is obviously improved. The high-activity nano-grade flue gas denitrification catalyst can be widely applied to selective catalytic reduction reaction of the fuel gas under an SO2-free or low-concentration SO2 environment of the fuel gas, so as to reduce the nitric oxides in the fuel gas into N2 and H2O. The catalyst takes a Ti oxide as a main component and is at least loaded with Mn-Ce-M-Ti-Ox of compound oxides of active components Mn and Ce, wherein M represents one or more elements of Fe, Co, Cu, Cr, Zr, Al and V; and the mol ratio of the elements is as follows: Ti: Mn: Ce: M is equal to 1: (0.005-1): (0.005-1): (0-0.3).
Description
Technical field
The present invention relates to a kind of low-temperature SCR catalyst for the flue gas NO_x removal and preparation method thereof, particularly avoid using high-temperature calcination process effectively to improve specific surface area of catalyst and reduced the catalyst degree of crystallization in the preparation process of low-temperature SCR catalyst, catalyst is existed with a large amount of amorphous state mixed oxide forms, effectively increased the density of catalyst surface active point position.
Background technology
At present, utilize ammonia NH
3As reducing agent, SCR (SCR) NO_x removal technology is most widely used gas denitrifying technology.NH
3, NO and O
2Redox reaction occurs under catalyst action generate N
2And H
2O。The catalyst of its application is mainly V
2O
5/ TiO
2Series, it has very high catalytic activity, needs to introduce high-temperature calcination process in the process of preparation, increases industrial energy consumption, simultaneously, easily destroys the microstructure of catalyst due to roasting process, and the activity of catalyst has been produced certain influence.
Summary of the invention
The object of the invention is to be provided for removing under low temperature (100-180 ℃) condition the selective catalysis (SCR) of nitrogen oxides in effluent.
Another object of the present invention is to provide the preparation method of this catalyst, and the method does not relate to high-temperature roasting, and the catalyst for preparing exists with a large amount of amorphous state mixed oxide forms, and activity obviously improves.Can be widely used in flue gas without SO
2, or low concentration SO
2Flue gas selective catalytic reduction reaction under environment becomes N with the reduction of nitrogen oxide in flue gas
2And H
2O。
The objective of the invention is to realize by following measures:
High-activity nano level catalyst for denitrating flue gas, this catalyst are take the Ti oxide as main component, and load has the Mn-Ce-M-Ti-O of active component Mn, Ce composite oxides at least
x, wherein M represents one or more elements in Fe, Co, Cu, Cr, Zr, Al, V, the mol ratio of each element is Ti:Mn:Ce:M=1:(0.005 ~ 1): (0.005 ~ 1): (0 ~ 0.3).
The preparation method of above-mentioned catalyst, concrete steps are:
(1) slowly add alkaline solution in the aqueous solution of precursor inorganic titanium salt, be precipitated thing, and filtration washing obtains solid; OH in Ti element and alkaline solution in inorganic titanium salt
-Mol ratio be 4:1;
(2) use concentration 20-90% nitric acid with gained dissolution of solid in step (1), form solution; HNO wherein
3With the mol ratio of Ti in solid be 4:1;
(3) get potassium permanganate KMnO
4With manganese acetate Mn (CH
3COO)
2Be added to the water separately respectively, electromagnetic agitation forms solution, at Mn (CH to dissolving fully
3COO)
2Add cerous nitrate solution in solution, after stirring, then with KMnO
4Solution slowly adds, and under the stirring condition of 120～150r/min, slowly adds step (2) gained solution, then reacts 6-10h, slowly splashes into alkaline solution and keep pH 7-9 in the process of reaction; Wherein add the mol ratio 1:(0.005 of Ti:Mn:Ce in material～1): (0.005～1), the molal quantity of Mn are potassium permanganate KMnO
4With manganese acetate Mn (CH
3COO)
2The molal quantity sum, potassium permanganate KMnO
4With manganese acetate Mn (CH
3COO)
2Mol ratio is 2:3;
(4) the described sediment of step (3) washes with water, and it is neutral that vacuum filtration to filtrate is, then obtains catalyst after sediment is put into drying box 102-120 ℃ (the embodiment temperature reaches) oven dry.
3, the preparation method of catalyst according to claim 2, wherein, after slowly adding step (2) gained solution in step (3), then splash into soluble M salting liquid participation reaction, the mol ratio 1:(0 of M～0.3 in wherein said Ti and soluble M salting liquid).
Wherein, described in step (1), the aqueous solution of the inorganic titanium salt of precursor is selected salt titanium sulfate, titanyl sulfate, titanium tetrachloride or titanium trichloride aqueous solution.
Wherein, the alkaline solution described in step (1) and step (3) is selected one or more in ammoniacal liquor, sal volatile, ammonium bicarbonate soln, sodium hydroxide solution, sodium carbonate liquor, sodium bicarbonate solution.
Wherein, described soluble M salting liquid is selected one or more in copper nitrate solution, iron nitrate solution, zirconium nitrate solution, cobalt nitrate solution, ammonium metavanadate solution, chromium nitrate solution or aluminum nitrate solution.
The present invention has following advantage compared to existing technology:
The Mn-Ce-M-TiO of the present invention's preparation (embodiment 1)
xCatalyst adopts ESEM (SEM) analysis at surface topography, can find that it is the particle of 0.1-0.3 μ m that catalyst agglomeration becomes diameter.Adopt transmission electron microscope (TEM) further to observe the pattern of catalyst primary, can find out, the metal oxide that low temperature liquid polymerization process is prepared is that diameter is at the particle of 3-50nm.
The catalyst of the inventive method preparation effectively reduces particle scale and the degree of crystallization of catalyst, nano level particle scale is conducive to fully contacting of reacting gas and catalyst surface active point position, lower particle degree of crystallization is conducive to increase catalyst surface active point position, improves catalytic reaction activity.
In this catalyst, the crystal formation that exists of main active component Mn is unformed, and the active sites of catalytic reaction can be provided, can be to reactant NO and the NH of flue-gas denitrification
3Adsorb, and react on contiguous acid sites.MnOx can impel redox reaction to begin 100 ℃ of left and right to occur, and obtains good effect in the time of 120-200 ℃.And because there are a large amount of dissimilar oxides in Mn, as MnO, MnO
2, Mn
2O
3And Mn
3O
4Deng, various oxides can transform mutually, wherein contain a large amount of active oxygens, make MnOx complete the circulation of catalysis in catalytic process.
Ce in catalyst of the present invention is as co-catalyst, and Main Function is to promote NO to NO
2Change, improve the SCR reactivity, the Ce electronics that can also increase in catalytic reaction shifts in addition, and with it as storing preferably the oxygen agent, strengthen the oxygen cycle of catalyst, the continuing of assurance catalytic reaction carries out.
The catalyst preparation process that the present invention adopts can improve the composite attribute of manganese, these two kinds of elements of cerium and titanium oxide, has improved decentralization and the bond strength of active component.
Method for preparing catalyst of the present invention has reduced catalyst and has prepared required temperature, avoided the high-temperature firing more than 300 ℃ in the preparation process, done like this mainly containing following two advantages: 1, avoid the minimizing of catalyst surface area in high-temperature sintering process on the impact of catalyst activity; 2, effectively reduce the inner degree of crystallization of catalyst, effectively improve the density of catalyst surface active point position.
The catalyst of the present invention preparation has reduced the manufacturing temperature of SCR catalyst, makes in SCR technique, with NH
3During for reducing agent, can just can obtain very high NO clearance in the time of 80-120 ℃.
In addition, adding of some transition metals played obvious synergism to catalyst.As the water resistant ability that can improve catalyst adding of Fe; Cu adds the activity that can improve catalyst; Adding of Zr, V can suppress SO
2Poisoning effect; Adding of Co can strengthen catalyst to the oxidability of NO, promotes the activity and selectivity of catalyst.
The specific embodiment
Concentration related in following examples is all measured except special instruction is arranged by weight.
Embodiment 1
(1) 200 gram titanium sulfate crystal are dissolved in 500ml water, dropwise add 20% ammoniacal liquor 200ml, obtain white Ti (OH)
4Precipitation is filtered, washed with water to precipitation after precipitation is complete,, removes Ti (OH)
4Sulfate ion in white precipitate.
(2) be that 40% nitric acid 350ml dissolves above-mentioned white precipitate fully with concentration, obtain solution;
(3) get 3.1 gram potassium permanganate KMnO
4With 4.2 gram manganese acetate Mn (CH
3COO)
2Join separately respectively in 200ml water, electromagnetic agitation forms solution to dissolving fully.Cerous nitrate crystal 10.8 grams are dissolved in 150ml water, add Mn (CH
3COO)
2In solution, after stirring, then with KMnO
4Solution slowly adds, and under 120r/min speed stirring condition, slowly adds step (2) gained solution, and reaction 8h slowly splashes into 5% ammoniacal liquor maintenance pH 7-9 in the process of reaction, finally form sediment;
(4) the gained sediment is filtered, to neutral, dry under 105 ℃ with deionized water rinsing, can obtain required catalyst;
This catalyst is used for the SCR method denitration of flue gas, flue gas GHSV (per hour gas space velocity)=40000h
-1, O
2Volumetric concentration 3%, denitrfying agent NH
3Press NO:NH
3=1(mol ratio) add, during 120 ℃ of reaction temperatures, catalytic efficiency 95.8% left and right.Adopt transmission electron microscope (TEM) further to observe the pattern of catalyst primary, in catalyst, particle size is 3-50nm.
Embodiment 2
(1) 80 gram titanyl sulfates are dissolved in 500ml water, dropwise add 20% ammoniacal liquor 200ml, obtain white Ti (OH)
4Precipitation after precipitation is complete, is filtered, is washed with water, removes sulfate ion.Be that 20% nitric acid 350ml dissolves white precipitate fully with concentration;
(2) get 3.1 gram potassium permanganate KMnO
4With 4.2 gram manganese acetate Mn (CH
3COO)
2Join separately respectively in 200ml water, electromagnetic agitation forms solution to dissolving fully.Cerous nitrate crystal 10.8 grams are dissolved in 150ml water, add Mn (CH
3COO)
2In solution, after stirring, with KMnO
4Solution slowly adds, and under 120r/min speed stirring condition, slowly adds step (1) gained solution, and reaction 8h slowly splashes into 5% ammoniacal liquor maintenance pH 7-9 in the process of reaction, finally form sediment;
(3) the gained sediment is filtered, to neutral, dry under 105 ℃ with deionized water rinsing, can obtain required catalyst;
This catalyst is used for the SCR method denitration of flue gas, flue gas GHSV (per hour gas space velocity)=30000h
-1, O
2Volumetric concentration 3%, denitrfying agent NH
3Press NO:NH
3=1(mol ratio) add, during 100 ℃ of reaction temperatures, catalytic efficiency 95.8% left and right.Adopt transmission electron microscope (TEM) further to observe the pattern of catalyst primary, in catalyst, particle size is 3-50nm.
Embodiment 3
(1) 95 gram titanium tetrachlorides are dissolved in (ice-water bath) in 500ml water, dropwise add 10% ammoniacal liquor 200ml, obtain white Ti (OH)
4Precipitation after precipitation is complete, is filtered, is washed, and removes chlorion.Be that 20% nitric acid 350ml dissolves white precipitate fully with concentration;
(2) get 3.1 gram potassium permanganate KMnO
4With 4.2 gram manganese acetate Mn (CH
3COO)
2Join separately respectively in 200ml water, electromagnetic agitation forms solution to dissolving fully.Cerous nitrate crystal 10.8 grams are dissolved in 150ml water, add Mn (CH
3COO)
2In solution, after stirring, with KMnO
4Solution slowly adds, and under 130r/min speed stirring condition, slowly adds (1) gained solution, and reaction 8h slowly splashes into 5% ammoniacal liquor maintenance pH 7-9 in the process of reaction, finally form sediment;
(3) the gained sediment is filtered, to neutral, dry under 110 ℃ with deionized water rinsing, can obtain required catalyst;
This catalyst is used for the SCR method denitration of flue gas, flue gas GHSV (per hour gas space velocity)=30000h
-1, O
2Volumetric concentration 3%, denitrfying agent NH
3Press NO:NH
3=1(mol ratio) add, during 120 ℃ of reaction temperatures, catalytic efficiency 90% left and right.Adopt transmission electron microscope (TEM) further to observe the pattern of catalyst primary, in catalyst, particle size is 3-50nm.
Embodiment 4
(1) 76.7 gram titanium trichlorides are dissolved in (ice-water bath) in 500ml water, dropwise add 10% ammoniacal liquor 200ml, obtain white Ti (OH)
4Precipitation after precipitation is complete, is filtered, is washed, and removes chlorion.Be that 40% nitric acid 350ml dissolves white precipitate fully with concentration;
(2) get 3.1 gram potassium permanganate KMnO
4With 4.2 gram manganese acetate Mn (CH
3COO)
2Join separately respectively in 200ml water, electromagnetic agitation forms solution to dissolving fully.Cerous nitrate crystal 10.8 grams are dissolved in 150ml water, add Mn (CH
3COO)
2In solution, after stirring, with KMnO
4Solution slowly adds, and under 120r/min speed stirring condition, slowly adds (1) gained solution, and reaction 8h slowly splashes into 5% ammoniacal liquor maintenance pH 7-9 in the process of reaction, finally form sediment;
(3) the gained sediment is filtered, to neutral, dry under 110 ℃ with deionized water rinsing, can obtain required catalyst;
This catalyst is used for the SCR method denitration of flue gas, flue gas GHSV (per hour gas space velocity)=30000h
-1, O
2Volumetric concentration 3%, denitrfying agent NH
3Press NO:NH
3=1(mol ratio) add, during 100 ℃ of reaction temperatures, catalytic efficiency 90.4% left and right.Adopt transmission electron microscope (TEM) further to observe the pattern of catalyst primary, in catalyst, particle size is 3-50nm.
Embodiment 5
(1) 200 gram titanium sulfate crystal are dissolved in 500ml water, dropwise adding concentration is that 10% ammoniacal liquor+concentration is 10% sal volatile, obtains white Ti (OH)
4Precipitation after precipitation is complete, is filtered, is washed, and removes sulfate ion.Be that 40% nitric acid 350ml dissolves white precipitate fully with concentration;
(2) get 3.1 gram potassium permanganate KMnO
4With 4.2 gram manganese acetate Mn (CH
3COO)
2Join separately respectively in 200ml water, electromagnetic agitation forms solution to dissolving fully.Cerous nitrate crystal 10.8 grams are dissolved in 150ml water, add Mn (CH
3COO)
2In solution, after stirring, with KMnO
4Solution slowly adds, and under 130r/min speed stirring condition, slowly adds (1) gained solution, and reaction 8h slowly splashes into 5% ammoniacal liquor maintenance pH 7-9 in the process of reaction, finally form sediment;
(3) the gained sediment is filtered, to neutral, dry under 110 ℃ with deionized water rinsing, can obtain required catalyst;
This catalyst is used for the SCR method denitration of flue gas, flue gas GHSV (per hour gas space velocity)=30000h
-1, O
2Volumetric concentration 3%, denitrfying agent NH
3Press NO:NH
3=1(mol ratio) add, during 120 ℃ of reaction temperatures, catalytic efficiency 94.5% left and right.Adopt transmission electron microscope (TEM) further to observe the pattern of catalyst primary, in catalyst, particle size is 3-50nm.
Embodiment 6
(1) 200 gram titanium sulfate crystal are dissolved in 500ml water, dropwise add 1% sodium hydroxide solution, obtain white Ti (OH) 4 precipitations, after precipitation is complete, filter, wash, remove sulfate ion.Be that 40% nitric acid 350ml dissolves white precipitate fully with concentration;
(2) get 3.1 gram potassium permanganate KMnO
4With 4.2 gram manganese acetate Mn (CH
3COO)
2Join separately respectively in 200ml water, electromagnetic agitation forms solution to dissolving fully.Cerous nitrate crystal 10.8 grams are dissolved in 150ml water, add Mn (CH
3COO)
2In solution, after stirring, with KMnO
4Solution slowly adds, and under 120r/min speed stirring condition, slowly adds (1) gained solution, and reaction 8h slowly splashes into 5% ammoniacal liquor maintenance pH 7-9 in the process of reaction, finally form sediment;
(3) the gained sediment is filtered, to neutral, dry under 110 ℃ with deionized water rinsing, can obtain required catalyst;
This catalyst is used for the SCR method denitration of flue gas, flue gas GHSV (per hour gas space velocity)=30000h
-1, O
2Volumetric concentration 3%, denitrfying agent NH
3Press NO:NH
3=1(mol ratio) add, during 120 ℃ of reaction temperatures, catalytic efficiency 84% left and right.Adopt transmission electron microscope (TEM) further to observe the pattern of catalyst primary, in catalyst, particle size is 3-50nm.
Embodiment 7
(1) 80 gram titanyl sulfates are dissolved in 500ml water, dropwise add 20% ammoniacal liquor 200ml, obtain white Ti (OH)
4Precipitation after precipitation is complete, is filtered, is washed, and removes sulfate ion.Be that 40% nitric acid 350ml dissolves white precipitate fully with concentration;
(2) get 3.1 gram potassium permanganate KMnO
4With 4.2 gram manganese acetate Mn (CH
3COO)
2Join separately respectively in 200ml water, electromagnetic agitation forms solution to dissolving fully.After being dissolved in 150ml water, cerous nitrate 10.8 grams add Mn (CH
3COO)
2In solution, after stirring, with KMnO
4Solution slowly adds, and under 120r/min speed stirring condition, slowly adds step (1) gained solution, 3.6 gram copper nitrates are dissolved in 100ml water, splash into mixed solution, reaction 8h, slowly splash into 5% ammoniacal liquor maintenance pH 7-9 in the process of reaction, finally form sediment;
(3) the gained sediment is filtered, to neutral, dry under 110 ℃ with deionized water rinsing, can obtain required catalyst;
This catalyst is used for the SCR method denitration of flue gas, flue gas GHSV (per hour gas space velocity)=30000h
-1, O
2Volumetric concentration 3%, denitrfying agent NH
3Press NO:NH
3=1(mol ratio) add, during 120 ℃ of reaction temperatures, catalytic efficiency 89.2% left and right.Adopt transmission electron microscope (TEM) further to observe the pattern of catalyst primary, in catalyst, particle size is 3-50nm.
Embodiment 8
(1) 80 gram titanyl sulfates are dissolved in 500ml water, dropwise add 20% ammoniacal liquor 200ml, obtain white Ti (OH)
4Precipitation after precipitation is complete, is filtered, is washed, and removes sulfate ion.Be that 40% nitric acid 350ml dissolves white precipitate fully with concentration;
(2) get 3.1 gram potassium permanganate KMnO
4With 4.2 gram manganese acetate Mn (CH
3COO)
2Join separately respectively in 200ml water, electromagnetic agitation forms solution to dissolving fully.After being dissolved in 150ml water, cerous nitrate 10.8 grams add Mn (CH
3COO)
2In solution, after stirring, under 120r/min speed stirring condition, with KMnO
4Solution slowly adds, and slowly adds step (1) gained solution, and 1.74 gram ammonium metavanadates are dissolved in 100ml water, splashes into mixed solution, and reaction 8h slowly splashes into 5% ammoniacal liquor maintenance pH 7-9 in the process of reaction, finally form sediment;
(3) the gained sediment is filtered, to neutral, dry under 110 ℃ with deionized water rinsing, can obtain required catalyst;
This catalyst is used for the SCR method denitration of flue gas, flue gas GHSV (per hour gas space velocity)=30000h
-1, O
2Volumetric concentration 3%, denitrfying agent NH
3Press NO:NH
3=1(mol ratio) add, during 120 ℃ of reaction temperatures, catalytic efficiency 90% left and right.Adopt transmission electron microscope (TEM) further to observe the pattern of catalyst primary, in catalyst, particle size is 3-50nm.
Embodiment 9
(1) 80 gram titanyl sulfates are dissolved in 500ml water, dropwise add 20% ammoniacal liquor 200ml, obtain white Ti (OH)
4Precipitation after precipitation is complete, is filtered, is washed, and removes sulfate ion.Be that 40% nitric acid 350ml dissolves white precipitate fully with concentration;
(2) get 3.1 gram potassium permanganate KMnO
4With 4.2 gram manganese acetate Mn (CH
3COO)
2Join separately respectively in 200ml water, electromagnetic agitation forms solution to dissolving fully.Cerous nitrate 10.8 grams are dissolved in 150ml water add Mn (CH
3COO)
2In solution, after stirring, KMnO
4Solution slowly adds, and under the strong agitation condition, slowly adds step (1) gained solution, 6.2 gram ferric nitrates are dissolved in 150ml water, splash into mixed solution, reaction 8h, slowly splash into 5% ammoniacal liquor maintenance pH 7-9 in the process of reaction, finally form sediment;
(3) the gained sediment is filtered, to neutral, dry under 110 ℃ with deionized water rinsing, can obtain required catalyst;
This catalyst is used for the SCR method denitration of flue gas, flue gas GHSV (per hour gas space velocity)=30000h
-1, O
2Volumetric concentration 3%, denitrfying agent NH
3Press NO:NH
3=1(mol ratio) add, during 120 ℃ of reaction temperatures, catalytic efficiency 98% left and right.Adopt transmission electron microscope (TEM) further to observe the pattern of catalyst primary, in catalyst, particle size is 3-50nm.
Embodiment 10
(1) 80 gram titanyl sulfates are dissolved in 500ml water, dropwise add 20% ammoniacal liquor 200ml, obtain white Ti (OH)
4Precipitation after precipitation is complete, is filtered, is washed, and removes sulfate ion.Be that 40% nitric acid 350ml dissolves white precipitate fully with concentration;
(2) get 3.1 gram potassium permanganate KMnO
4With 4.2 gram manganese acetate Mn (CH
3COO)
2Join separately respectively in 200ml water, electromagnetic agitation forms solution to dissolving fully.Cerous nitrate 10.8 grams are dissolved in 150ml water add Mn (CH
3COO)
2In solution, after stirring, KMnO
4Solution slowly adds, and under 120r/min speed strong agitation condition, slowly adds step (1) gained solution, 5.1 gram zirconium nitrates are dissolved in 150ml water, splash into mixed solution, reaction 8h, slowly splash into 5% ammoniacal liquor and keep pH greater than 7 in the process of reaction, finally form sediment;
(3) the gained sediment is filtered, to neutral, dry under 110 ℃ with deionized water rinsing, can obtain required catalyst;
This catalyst is used for the SCR method denitration of flue gas, flue gas GHSV (per hour gas space velocity)=30000h
-1, O
2Volumetric concentration 3%, denitrfying agent NH
3Press NO:NH
3=1(mol ratio) add, during 120 ℃ of reaction temperatures, catalytic efficiency 94% left and right.Adopt transmission electron microscope (TEM) further to observe the pattern of catalyst primary, in catalyst, particle size is 3-50nm.
Embodiment 11
(1) 80 gram titanyl sulfates are dissolved in 500ml water, dropwise add 20% ammoniacal liquor 200ml, obtain white Ti (OH)
4Precipitation after precipitation is complete, is filtered, is washed, and removes sulfate ion.Be that 40% nitric acid 350ml dissolves white precipitate fully with concentration;
(2) get 3.1 gram potassium permanganate KMnO
4With 4.2 gram manganese acetate Mn (CH
3COO)
2Join separately respectively in 200ml water, electromagnetic agitation forms solution to dissolving fully.Cerous nitrate 10.8 grams are dissolved in 150ml water add Mn (CH
3COO)
2In solution, after stirring, KMnO
4Solution slowly adds, and under 120r/min speed strong agitation condition, slowly adds step (1) gained solution, 4.5 gram cobalt nitrates are dissolved in 100ml water, splash into mixed solution, reaction 8h, slowly splash into 5% ammoniacal liquor maintenance pH 7-9 in the process of reaction, finally form sediment;
(3) the gained sediment is filtered, to neutral, dry under 105 ℃ with deionized water rinsing, can obtain required catalyst;
This catalyst is used for the SCR method denitration of flue gas, flue gas GHSV (per hour gas space velocity)=30000h
-1, O
2Volumetric concentration 3%, denitrfying agent NH
3Press NO:NH
3=1(mol ratio) add, during 120 ℃ of reaction temperatures, catalytic efficiency 96.5% left and right.Adopt transmission electron microscope (TEM) further to observe the pattern of catalyst primary, in catalyst, particle size is 3-50nm.
Embodiment 12
(1) 80 gram titanyl sulfates are dissolved in 500ml water, dropwise add 20% ammoniacal liquor 200ml, obtain white Ti (OH)
4Precipitation after precipitation is complete, is filtered, is washed, and removes sulfate ion.Be that 40% nitric acid 350ml dissolves white precipitate fully with concentration;
(2) get 3.1 gram potassium permanganate KMnO
4With 4.2 gram manganese acetate Mn (CH
3COO)
2Join separately respectively in 200ml water, electromagnetic agitation forms solution to dissolving fully.Cerous nitrate 10.8 grams are dissolved in 150ml water add Mn (CH
3COO)
2In solution, after stirring, KMnO
4Solution slowly adds, and under 120r/min speed strong agitation condition, slowly adds step (1) gained solution, 5.1 gram chromic nitrates are dissolved in 150ml water, splash into mixed solution, reaction 8h, slowly splash into 5% ammoniacal liquor and keep pH greater than 7 in the process of reaction, finally form sediment;
(3) the gained sediment is filtered, to neutral, dry under 105 ℃ with deionized water rinsing, can obtain required catalyst;
This catalyst is used for the SCR method denitration of flue gas, flue gas GHSV (per hour gas space velocity)=30000h
-1, O
2Volumetric concentration 3%, denitrfying agent NH
3Press NO:NH
3=1(mol ratio) add, during 120 ℃ of reaction temperatures, catalytic efficiency 92% left and right.Adopt transmission electron microscope (TEM) further to observe the pattern of catalyst primary, in catalyst, particle size is 3-50nm.
Embodiment 13
(1) 80 gram titanyl sulfates are dissolved in 500ml water, dropwise add 20% ammoniacal liquor 200ml, obtain white Ti (OH)
4Precipitation after precipitation is complete, is filtered, is washed, and removes sulfate ion.Be that 40% nitric acid 350ml dissolves white precipitate fully with concentration;
(2) get 3.1 gram potassium permanganate KMnO
4With 4.2 gram manganese acetate Mn (CH
3COO)
2Join separately respectively in 200ml water, electromagnetic agitation forms solution to dissolving fully.Cerous nitrate 10.8 grams are dissolved in 150ml water add Mn (CH
3COO)
2In solution, after stirring, KMnO
4Solution slowly adds, under 120r/min speed strong agitation condition, slowly add step (1) gained solution, 3.5 gram aluminum nitrates are dissolved in 100ml water, splash into mixed solution, reaction 8h slowly splashes into 1% sodium hydroxide solution maintenance pH 7-9 in the process of reaction, finally form sediment;
(3) the gained sediment is filtered, to neutral, dry under 105 ℃ with deionized water rinsing, can obtain required catalyst;
This catalyst is used for the SCR method denitration of flue gas, flue gas GHSV (per hour gas space velocity)=30000h
-1, O
2Volumetric concentration 3%, denitrfying agent NH
3Press NO:NH
3=1(mol ratio) add, during 120 ℃ of reaction temperatures, catalytic efficiency 85.4% left and right.Adopt transmission electron microscope (TEM) further to observe the pattern of catalyst primary, in catalyst, particle size is 3-50nm.
Embodiment 14
(1) 80 gram titanyl sulfates are dissolved in 500ml water, dropwise add 20% ammoniacal liquor 200ml, obtain white Ti (OH)
4Precipitation after precipitation is complete, is filtered, is washed, and removes sulfate ion.Be that 40% nitric acid 350ml dissolves white precipitate fully with concentration;
(2) get 3.1 gram potassium permanganate KMnO
4With 4.2 gram manganese acetate Mn (CH
3COO)
2Join separately respectively in 200ml water, electromagnetic agitation forms solution to dissolving fully.Cerous nitrate 10.8 grams are dissolved in 150ml water, then add Mn (CH
3COO)
2In solution, after stirring, KMnO
4Solution slowly adds, under 120r/min speed strong agitation condition, slowly add step (1) gained solution, 5.1 gram zirconium nitrates and 3.4 gram ferric nitrates are dissolved in 100ml water, splash into mixed solution, reaction 8h slowly splashes into 5% sodium bicarbonate solution maintenance pH 8 in the process of reaction, finally form sediment;
(3) the gained sediment is filtered, to neutral, dry under 105 ℃ with deionized water rinsing, can obtain required catalyst;
This catalyst is used for the SCR method denitration of flue gas, flue gas GHSV (per hour gas space velocity)=30000h
-1, O
2Volumetric concentration 3%, denitrfying agent NH
3Press NO:NH
3=1(mol ratio) add, during 120 ℃ of reaction temperatures, catalytic efficiency 87.6% left and right.Adopt transmission electron microscope (TEM) further to observe the pattern of catalyst primary, in catalyst, particle size is 3-50nm.
Can be drawn by above each embodiment, the good catalyst activity of the present invention's preparation, catalytic efficiency is high.
Claims (6)
1. high-activity nano level catalyst for denitrating flue gas, this catalyst is take the Ti oxide as main component, and load has the Mn-Ce-M-Ti-O of active component Mn, Ce composite oxides at least
x, wherein M represents one or more elements in Fe, Co, Cu, Cr, Zr, Al, V, the mol ratio of each element is Ti:Mn:Ce:M=1:(0.005 ~ 1): (0.005 ~ 1): (0 ~ 0.3).
2. the preparation method of the described catalyst of claim 1, concrete steps are:
(1) slowly add alkaline solution in the aqueous solution of precursor inorganic titanium salt, be precipitated thing, and filtration washing obtains solid; OH in Ti element and alkaline solution in inorganic titanium salt
-Mol ratio be 4:1;
(2) use concentration 20-90% nitric acid with gained dissolution of solid in step (1), form solution; HNO wherein
3With the mol ratio of Ti in solid be 4:1;
(3) get potassium permanganate KMnO
4With manganese acetate Mn (CH
3COO)
2Be added to the water separately respectively, electromagnetic agitation forms solution, at Mn (CH to dissolving fully
3COO)
2Add cerous nitrate solution in solution, after stirring, then with KMnO
4Solution slowly adds, and under the stirring condition of 120～150r/min, slowly adds step (2) gained solution, then reacts 6-10h, slowly splashes into alkaline solution and keep pH 7-9 in the process of reaction; Wherein add the mol ratio 1:(0.005 of Ti:Mn:Ce in material～1): (0.005～1), the molal quantity of Mn are potassium permanganate KMnO
4With manganese acetate Mn (CH
3COO)
2The molal quantity sum, potassium permanganate KMnO
4With manganese acetate Mn (CH
3COO)
2Mol ratio is 2:3;
(4) the described sediment of step (3) washes with water, and it is neutral that vacuum filtration to filtrate is, then obtain catalyst after sediment is put into drying box 102-120 ℃ oven dry.
3. the preparation method of catalyst according to claim 2 wherein, after adding step (2) gained solution in step (3), then splashes into the soluble M salting liquid and participates in reaction, the mol ratio 1:(0 of M～0.3 in wherein said Ti and soluble M salting liquid).
4. the preparation method of according to claim 2 or 3 described catalyst, wherein, described in step (1), the aqueous solution of the inorganic titanium salt of precursor is selected the aqueous solution of salt titanium sulfate, titanyl sulfate, titanium tetrachloride or titanium trichloride.
5. the preparation method of according to claim 2 or 3 described catalyst, wherein, the alkaline solution described in step (1) and step (3) is selected one or more in ammoniacal liquor, sal volatile, ammonium bicarbonate soln, sodium hydroxide solution, sodium carbonate liquor, sodium bicarbonate solution.
6. the preparation method of according to claim 2 or 3 described catalyst, wherein, described soluble M salting liquid is selected one or more in copper nitrate solution, iron nitrate solution, zirconium nitrate solution, cobalt nitrate solution, ammonium metavanadate solution, chromium nitrate solution or aluminum nitrate solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310079432.1A CN103127930B (en) | 2013-03-13 | 2013-03-13 | High-activity nano-grade flue gas denitrification catalyst and low-temperature liquid-phase preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310079432.1A CN103127930B (en) | 2013-03-13 | 2013-03-13 | High-activity nano-grade flue gas denitrification catalyst and low-temperature liquid-phase preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103127930A true CN103127930A (en) | 2013-06-05 |
| CN103127930B CN103127930B (en) | 2015-05-06 |
Family
ID=48488757
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310079432.1A Active CN103127930B (en) | 2013-03-13 | 2013-03-13 | High-activity nano-grade flue gas denitrification catalyst and low-temperature liquid-phase preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103127930B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104785246A (en) * | 2015-04-13 | 2015-07-22 | 国电环境保护研究院 | Manganese-cerium supported low-temperature SCR catalyst preparation method based on metatitanic acid material |
| CN105056923A (en) * | 2015-08-17 | 2015-11-18 | 成都金鑫天蓝科技有限公司 | Anti-water and anti-sulfur denitration catalyst, preparation method and application thereof |
| JP2016022437A (en) * | 2014-07-22 | 2016-02-08 | トヨタ自動車株式会社 | Catalyst for exhaust gas purification |
| CN105948140A (en) * | 2016-06-12 | 2016-09-21 | 上海大学 | Preparation method of semiconductor-carried manganese cobalt composite oxide nanometer material |
| CN106824174A (en) * | 2017-03-22 | 2017-06-13 | 无锡威孚环保催化剂有限公司 | A kind of coccoid catalyst of high-efficient purification nitrogen oxides and preparation method thereof |
| CN108855044A (en) * | 2018-04-18 | 2018-11-23 | 浙江工业大学 | Preparation method of vanadium-tungsten catalyst |
| CN109289330A (en) * | 2018-11-14 | 2019-02-01 | 北京建筑材料科学研究总院有限公司 | A kind of sheet stock and its manufacturing method integrating dust removal by filtration and catalytic denitration |
| CN110026182A (en) * | 2019-05-20 | 2019-07-19 | 中国人民大学 | Low-temperature denitration catalyst and its preparation and application in high sulfur resistive |
| CN110935441A (en) * | 2019-11-12 | 2020-03-31 | 湖南省尤利威科技有限公司 | Titanium-based composite catalytic net for efficiently degrading formaldehyde and preparation method thereof |
| CN112337477A (en) * | 2020-11-10 | 2021-02-09 | 黑河学院 | Preparation and application of high-performance Fe, Ce, Mn and Ti four-component catalyst |
| CN112619661A (en) * | 2019-09-24 | 2021-04-09 | 大唐环境产业集团股份有限公司 | Preparation method of carrier-free catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102008956A (en) * | 2010-12-27 | 2011-04-13 | 国电科学技术研究院 | Preparation method of low-temperature selective catalytic reduction (SCR) catalyst by removing NOx from flue gas |
| CN102114424A (en) * | 2010-12-29 | 2011-07-06 | 国电科学技术研究院 | Low-temperature smoke denitration SCR (silicon controlled rectifier) catalyst and preparation method |
| CN102935361A (en) * | 2012-11-09 | 2013-02-20 | 国电环境保护研究院 | MnOx-TiO2 composite oxide with rutile TiO2 serving as matrix |
-
2013
- 2013-03-13 CN CN201310079432.1A patent/CN103127930B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102008956A (en) * | 2010-12-27 | 2011-04-13 | 国电科学技术研究院 | Preparation method of low-temperature selective catalytic reduction (SCR) catalyst by removing NOx from flue gas |
| CN102114424A (en) * | 2010-12-29 | 2011-07-06 | 国电科学技术研究院 | Low-temperature smoke denitration SCR (silicon controlled rectifier) catalyst and preparation method |
| CN102935361A (en) * | 2012-11-09 | 2013-02-20 | 国电环境保护研究院 | MnOx-TiO2 composite oxide with rutile TiO2 serving as matrix |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016022437A (en) * | 2014-07-22 | 2016-02-08 | トヨタ自動車株式会社 | Catalyst for exhaust gas purification |
| CN104785246B (en) * | 2015-04-13 | 2017-06-23 | 国电环境保护研究院 | Manganese cerium support type low-temperature SCR catalyst preparation method based on titanyl hydroxide starting material |
| CN104785246A (en) * | 2015-04-13 | 2015-07-22 | 国电环境保护研究院 | Manganese-cerium supported low-temperature SCR catalyst preparation method based on metatitanic acid material |
| CN105056923A (en) * | 2015-08-17 | 2015-11-18 | 成都金鑫天蓝科技有限公司 | Anti-water and anti-sulfur denitration catalyst, preparation method and application thereof |
| CN105056923B (en) * | 2015-08-17 | 2018-11-09 | 成都金鑫天蓝科技有限公司 | A kind of water resistant sulfur resistive type denitrating catalyst, preparation method and its usage |
| CN105948140A (en) * | 2016-06-12 | 2016-09-21 | 上海大学 | Preparation method of semiconductor-carried manganese cobalt composite oxide nanometer material |
| CN106824174A (en) * | 2017-03-22 | 2017-06-13 | 无锡威孚环保催化剂有限公司 | A kind of coccoid catalyst of high-efficient purification nitrogen oxides and preparation method thereof |
| CN108855044A (en) * | 2018-04-18 | 2018-11-23 | 浙江工业大学 | Preparation method of vanadium-tungsten catalyst |
| CN108855044B (en) * | 2018-04-18 | 2021-06-08 | 浙江工业大学 | Preparation method of vanadium-tungsten catalyst |
| CN109289330A (en) * | 2018-11-14 | 2019-02-01 | 北京建筑材料科学研究总院有限公司 | A kind of sheet stock and its manufacturing method integrating dust removal by filtration and catalytic denitration |
| CN110026182A (en) * | 2019-05-20 | 2019-07-19 | 中国人民大学 | Low-temperature denitration catalyst and its preparation and application in high sulfur resistive |
| CN112619661A (en) * | 2019-09-24 | 2021-04-09 | 大唐环境产业集团股份有限公司 | Preparation method of carrier-free catalyst |
| CN110935441A (en) * | 2019-11-12 | 2020-03-31 | 湖南省尤利威科技有限公司 | Titanium-based composite catalytic net for efficiently degrading formaldehyde and preparation method thereof |
| CN110935441B (en) * | 2019-11-12 | 2022-07-29 | 湖南省尤利威科技有限公司 | Titanium-based composite catalytic net for efficiently degrading formaldehyde and preparation method thereof |
| CN112337477A (en) * | 2020-11-10 | 2021-02-09 | 黑河学院 | Preparation and application of high-performance Fe, Ce, Mn and Ti four-component catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103127930B (en) | 2015-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103127930B (en) | High-activity nano-grade flue gas denitrification catalyst and low-temperature liquid-phase preparation method thereof | |
| CN104492446B (en) | A kind of catalyst and preparation method for ammonia selective reducing nitrogen oxide | |
| CN103433034B (en) | Activated coke Supported Manganese cerium composite oxides low-temperature SCR catalyst and preparation method thereof | |
| CN111229212B (en) | CO-SCR denitration catalyst, preparation method and application | |
| CN102008956B (en) | Preparation method of low-temperature selective catalytic reduction (SCR) catalyst by removing NOx from flue gas | |
| CN102151543B (en) | Preparation method, product and application of catalytic activity nano particle loaded absorbent | |
| CN105080566A (en) | Flue gas denitrification powder catalyst as well as preparation method and application thereof | |
| CN101352681A (en) | Low-temperature SCR catalyst using nitrogen-dopped activated carbon as carrier and preparation technique thereof | |
| WO2017181570A1 (en) | Alkali (alkaline earth) metal-resistant, sulfur-resistant, and water-resistant denitrification catalyst, and manufacturing method and application thereof | |
| CN105013474B (en) | The preparation method of metal oxide denitrating catalyst with orderly hierarchical porous structure | |
| CN102114424A (en) | Low-temperature smoke denitration SCR (silicon controlled rectifier) catalyst and preparation method | |
| CN106166487A (en) | A kind of quaternary composite oxides low-temperature SCR catalyst and preparation method thereof | |
| CN102000572B (en) | Method for preparing denitration catalyst by performing selective catalytic reduction on CuMgAl composite oxide | |
| CN104492425A (en) | Catalyst for ammonia selective reduction of nitrogen oxide and preparation method of catalyst | |
| CN105854560A (en) | Flue gas desulfurization and denitration method | |
| CN107376896A (en) | A kind of cerium tungsten titanium composite oxide SCR denitration and preparation method thereof | |
| Yang et al. | Low temperature denitrification and mercury removal of Mn/TiO2-based catalysts: A review of activities, mechanisms, and deactivation | |
| CN101028596B (en) | Production of oxide nitrogen oxidation catalyst | |
| CN103894186B (en) | A kind of acid-dissolved titanium slag prepares the method for manganese titanium system low-temperature denitration catalysis material | |
| CN105148927B (en) | A kind of water resistant sulfur resistive type denitrating flue gas powder catalyst, preparation method and its usage | |
| CN109331837A (en) | A kind of catalyst of catalytic wet air oxidation processing furans waste water | |
| CN104368329B (en) | A kind of cerium niobium zirconium mixed oxide catalyst, preparation method and its usage | |
| CN106111123A (en) | A kind of support type manganio composite oxides selective denitrification catalyst containing tourmaline | |
| CN102698709A (en) | Method for treating flue gas containing nitrogen oxide | |
| CN109012703B (en) | Method for preparing iron-sulfur-titanium-based high-temperature NH3-SCR denitration catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 210031 Pudong Road, Pukou District, Jiangsu, No. 10, No. Patentee after: National Electric Environmental Protection Research Institute Co., Ltd. Address before: 210031 Pudong Road, Pukou District, Jiangsu, No. 10, No. Patentee before: State Power Environmental Protection Research Institute |