CN1817448A - Selective catalytic reducing NOx catalyst based on MnOx/TiO2 system at low-temperature and production thereof - Google Patents
Selective catalytic reducing NOx catalyst based on MnOx/TiO2 system at low-temperature and production thereof Download PDFInfo
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- CN1817448A CN1817448A CN 200610049762 CN200610049762A CN1817448A CN 1817448 A CN1817448 A CN 1817448A CN 200610049762 CN200610049762 CN 200610049762 CN 200610049762 A CN200610049762 A CN 200610049762A CN 1817448 A CN1817448 A CN 1817448A
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- transition metal
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract description 8
- 229910016978 MnOx Inorganic materials 0.000 title abstract description 4
- 230000003197 catalytic effect Effects 0.000 title description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910001868 water Inorganic materials 0.000 claims abstract description 44
- 239000002253 acid Substances 0.000 claims abstract description 14
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000011572 manganese Substances 0.000 claims description 64
- 239000010936 titanium Substances 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 26
- 239000002994 raw material Substances 0.000 claims description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 22
- 238000003980 solgel method Methods 0.000 claims description 22
- 229910052719 titanium Inorganic materials 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 229910052723 transition metal Inorganic materials 0.000 claims description 20
- 150000003624 transition metals Chemical class 0.000 claims description 20
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 17
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 12
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 12
- 239000007848 Bronsted acid Substances 0.000 claims description 11
- 150000001298 alcohols Chemical class 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 25
- -1 alkoxy compound Chemical class 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract 2
- 238000001354 calcination Methods 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 230000007704 transition Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 34
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 27
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 21
- 239000003546 flue gas Substances 0.000 description 21
- 239000000203 mixture Substances 0.000 description 17
- 239000007789 gas Substances 0.000 description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 14
- 229910017604 nitric acid Inorganic materials 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000000607 poisoning effect Effects 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 231100000572 poisoning Toxicity 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical group [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- Catalysts (AREA)
Abstract
A catalyst based on MnOx/TiO2 system for low-temp selective catalytic reduction of NOx is proportionally prepared from alkoxy compound of Ti, alcohol solvent, water, protonic acid, soluble salt of Mn and the soluble salt of transition element through proportional mixing, stirring until sol becomes gel, drying, grinding and high-temp calcining.
Description
Technical field
The present invention relates to a kind of catalyst of in the air pollution control technique field, using, specifically relate to a kind of with the sol-gel process preparation based on MnO
x/ TiO
2The low-temperature selective catalytic reduction NO of system
xCatalyst.
Background technology
Through years of researches and practice, use NH
3SCR method denitrating flue gas as reducing agent reaches its maturity, and the SCR catalyst of commercial Application is mainly V
2O
5-WO
3/ TiO
2(V
2O
5-MoO
3/ TiO
2), the operating temperature range of this type of catalyst roughly between 300～400 ℃, places before the desulfation dust-extraction device.In the practical application, this type of catalyst has anti-SO
2Ability is strong, the advantage of stable operation.
But because the higher operating temperature that industrial catalyst requires, the SCR denitrification apparatus must place before the desulfation dust-extraction device, at this moment flue dust and SO in the flue gas
2Concentration higher, though the superior performance of industrial catalyst still causes catalyst poisoning easily, at present among the SCR of commercial Application, prime cost still comes from the replacing of catalyst; As for fear of catalyst poisoning and denitrification apparatus is placed after the desulfurization and dedusting, for reaching the desired active temperature scope of industrial catalyst, the flue gas of lower temperature after the desulfurization must be heated, the heat energy of consumption also will increase the denitration cost greatly.In sum, the bottleneck that reduces the cost of SCR denitration at present is the operating temperature range of industrial catalyst, therefore, develop a kind of low-temperature denitration catalyst, can carry out denitrating flue gas under the flue-gas temperature after desulfurization and dedusting, can reduce cost greatly, prospect be arranged for the industrialization utmost point of denitration.
Though for low temperature catalyst certain report is arranged at present, the overwhelming majority still is in the experimental study stage.Reduce the required temperature of reaction, must reduce the activation energy of reaction, increase the reaction active site of catalyst surface; In addition, because desulfurization still has part SO later
2Exist, in long-term contact, still can produce poisoning effect catalyst.Therefore how to increase reactivity, reduce SO
2Murder by poisoning extremely important.
At present all carry out Preparation of Catalyst based on infusion process for the research of catalyst, this kind preparation method must depend on existing TiO
2Carrier, and the distribution performance of MnOx limits to some extent: people such as Qi (Gongshin Qi, Ralph T.Yang, Low-temperature selective catalytic reduction ofNO with NH3 over iron and manganese oxides supported on titania, AppliedCatalysis B:Environmental 44 (2003) 217-225) use infusion process that Mn is loaded on TiO
2On, find that in the load capacity of Mn 10% when following, catalytic efficiency increases along with the increase of the load capacity of Mn, but load capacity being when reaching on 10%, catalytic efficiency is but along with the load capacity increase of Mn and descend.Through detecting, find that load capacity at Mn is greater than 10% after, the MnO of original unformed shape
xBe converted into crystal MnO
x, crystal MnO
xTo NO
xRemoval there is no facilitation, therefore, use catalyst prepared MnO
xBad dispersibility, cause in the catalyst surperficial sintering and active site to reduce.Therefore how avoiding agglomeration when increasing the active material load capacity, also is to need improved emphasis.
Summary of the invention
In catalytic reaction, the activation of free electron is very important, must find a kind of active material, can provide electronics at low temperatures.The valence electron of transition metal is configured as half full state, moves to O easily
2And NH
3On, thereby impelled the generation of reacting.As element M n, valency layer electron configuration is 3d
54s
2, tetravalence Mn is configured as d
3, the electron configuration of divalence Mn is d
5, the electronics on the d track is in half full state, and the good condition that provides of reaction is provided.So MnO
xAs catalyst, can impel to be reflected to begin about 100 ℃ to take place, and in the time of 120-200 ℃, obtain good effect.And because a large amount of different oxide types of its existence of Mn, as MnO, MnO
2, Mn
2O
3, Mn
3O
4And Mn
5O
8Can transform mutually along with the different of temperature Deng, various oxides, a large amount of free O that wherein contain make MnO
xIn catalytic process, finished the circulation of catalysis.
Aspect carrier, SO
2When occupying the catalyst activity position, at first occupy TiO
2On active sites, protected the performance of active material effectively, and at TiO
2The surface can only form more weak and reversible sulfate.Therefore, SO is arranged in system
2Under the reaction condition that exists, with TiO
2As the catalyst of carrier, its surface only the part or reversibly by sulphation.Use sharp titanium phase TiO
2This catalyst carrier with " activation " performance can reduce SO greatly
2Toxicity to catalyst.Therefore with MnO
xLoad to TiO
2On be a feasible approach, can mutually promote, obtain the long catalyst of catalytic efficiency height, life-span.
In sum, the invention provides a kind of with MnO
x/ TiO
2Be primary structure, with the low-temperature selective catalytic reduction NO of sol-gel process as preparation method's preparation
xCatalyst.By adjusting sol formulation, preparation and drying condition, sintering temperature, increase MnO
xIn the degree of scatter of carrier surface, in the active sites that increases catalyst surface simultaneously, reduce the sintering degree.Then, containing transition metal in catalyst increases the utilization of O between lattice, breaks through the temperature bottleneck, is implemented in NO under the low temperature condition
xRemove.
A kind of based on MnO
x/ TiO
2The low-temperature selective catalytic reduction NO of system
xCatalyst, alkyl oxide, alcohols solvent, water, the soluble-salt of manganese, Bronsted acid with titanium are raw material, and wherein: the volume ratio of the alkyl oxide of titanium, alcohols solvent, water, Bronsted acid is: the alkyl oxide of titanium: alcohols solvent: water: Bronsted acid is 1: (1～2): (0.05～0.5): (0.01～0.5); The addition of the soluble-salt of manganese contains the molar ratio computing of Ti element with the alkyl oxide of Mn element and titanium, and its value is that Mn: Ti is 0.01～1.
Described low-temperature selective catalytic reduction NO
xThe soluble-salt that also can add transition metal in the raw material of catalyst, the addition of the soluble-salt of transition metal contains the molar ratio computing of Ti element with the alkyl oxide of the transition metal that contains and titanium, and its value is: transition metal: Ti is 0.001～0.4.
The alkyl oxide of described titanium is a kind of in metatitanic acid n-propyl, purity titanium tetraethoxide, tetrabutyl titanate, isopropyl titanate preferably.
The soluble-salt of described manganese is a kind of in manganese sulfate, manganese nitrate, manganese chloride preferably.
The transition metal of the soluble-salt of described transition metal is preferably iron, chromium element.
Above-mentioned Preparation of catalysts method: adopt sol-gel process, with the soluble-salt of the soluble-salt of the alkyl oxide of titanium, alcohols solvent, water, manganese, Bronsted acid, transition metal according to the above ratio addition mix, treat colloidal sol be converted into dry behind the gel, grind, and under 200～600 ℃, carry out roasting, obtain catalyst.
Wherein Mn is as the catalytic active component in the catalyst, and its main existence form is MnO
2, can provide the active sites of catalytic reaction, to reactant NO and NH
3Adsorb, and on contiguous acid sites, react.
Ti is as the carrier of catalyst activity component, mainly with TiO
2Form exist, the existence of Ti is similarly NO and NH3 provides certain adsorption potential, has increased the possibility of reactant in catalyst surface absorption, simultaneously TiO
2Existence become the target position of sulfate and sulphite deposition, protected the Mn active sites in the catalyst effectively, strengthened the sulfur resistance of catalyst, prolonged the service life of catalyst;
In addition, also have the oxide of some transition metal in the catalyst, it mainly act as the electronics that increases in the catalytic reaction and shifts, and with it as storing the oxygen agent preferably, the oxygen recoverability of enhancing catalyst;
In present technique, owing to adopt sol-gel process to prepare catalyst, make in the process that colloid changes, to be in contact with one another fully between each component, and mutually combine, change, can form MnO
x-MO
x/ TiO
2(M is a transition metal) conglomerate in conjunction with closely, is easier to the utilization of oxygen between the transfer of electronics and lattice between each component.
At first from catalytic effect, in the scope that said components is formed, in 80～250 ℃ scope, the highest catalytic efficiency can be near 100%, wherein MnOx (0.4)-Fe (0.01)/TiO2 in the time of 120 ℃, can reach the treatment effeciency to NO more than 90%, and existing commercial Application technology can not be carried out NO at all and be removed in this temperature range.
Aspect the crystal formation of catalyst, when the load capacity of Mn is hanged down, detect less than MnO substantially in the catalyst
x, and TiO
2Be that form with sharp titanium exists, and when the load capacity of Mn increases, the TiO in the catalyst
2Degree of crystallinity is more and more littler, and MnO
xDegree of crystallinity slowly increase, but tangible MnO does not appear
xCrystal, wherein the minority crystal of Chu Xianing is many with MnO
2Form exist, reach after 0.4 in the load capacity of Mn, a large amount of MnO is just arranged
2Crystal forms.As mentioned above, the MnO of crystal attitude
xTo not effect of catalysis, therefore, the catalyst in the present technique can keep MnO when the high capacity amount of Mn
xUnformed shape, can when many active sites is provided, keep the favourable crystal formation of active component, catalytic performance is greatly improved.
Aspect the influence of SO2, SO is arranged in system
2When existing, the removal efficiency of NO is slightly reduced, but work as SO
2After removing, the clearance of NO has been got back to previous level substantially, therefore, catalyst of the present invention is to SO
2Murder by poisoning comparatively insensitive.
The catalyst of the present invention preparation has reduced the operating temperature of SCR, makes in SCR technology, and when being reducing agent with NH3, can be at 150 ℃ to be issued to high NO clearance.
The specific embodiment
Embodiment 1:
Adopting sol-gel process, is raw material with tetrabutyl titanate, ethanol, water, Mn (NO3) 2, acetic acid, and the volume ratio of each component is as follows, tetrabutyl titanate: ethanol: water: acetic acid=1: 1.5: 0.5: 0.5, and Mn (NO
3)
2Addition be Mn: Ti=0.4, mix, treat colloidal sol be converted into dry behind the gel, grind, and under 200～600 ℃, carry out roasting, obtain catalyst.
Use and handle NO: NH3=1, O
2Concentration=3%, GHSV (per hour gas space velocity)=30000h
-1SCR method denitrating flue gas, when reaction temperature was 100 ℃, catalytic efficiency was about 50%, when reaction temperature was 150 ℃, catalytic efficiency was more than 90%.
Embodiment 2:
Adopting sol-gel process, is raw material with isopropyl titanate, ethanol, water, Mn (NO3) 2, acetic acid, and the volume ratio of each component is as follows, isopropyl titanate: ethanol: water: acetic acid=1: 1.65: 0.4: 0.5, and Mn (NO
3)
2Addition be Mn: Ti=0.4, mix, treat colloidal sol be converted into dry behind the gel, grind, and under 200～600 ℃, carry out roasting, obtain catalyst.
Use and handle NO: NH3=1, O
2Concentration=3%, GHSV (per hour gas space velocity)=30000h
-1SCR method denitrating flue gas, when reaction temperature was 100 ℃, catalytic efficiency was about 50%, when reaction temperature was 150 ℃, catalytic efficiency was more than 90%.
Embodiment 3:
Adopt sol-gel process, with purity titanium tetraethoxide, ethanol, water, MnCl
2, hydrochloric acid is raw material, the volume ratio of each component is as follows, purity titanium tetraethoxide: ethanol: water: acetic acid=1: 1.85: 0.08: 0.03, MnCl
2Addition be Mn: Ti=0.3, mix, treat colloidal sol be converted into dry behind the gel, grind, and under 200～600 ℃, carry out roasting, obtain catalyst.
Use and handle NO: NH3=1, O
2Concentration=3%, GHSV (per hour gas space velocity)=30000h
-1SCR method denitrating flue gas, when reaction temperature was 120 ℃, catalytic efficiency was about 50%, in the time of 200 ℃, can reach more than 90%.
Embodiment 4:
Adopting sol-gel process, is raw material with purity titanium tetraethoxide, methyl alcohol, water, MnCl2, acetic acid, and the volume ratio of each component is as follows, purity titanium tetraethoxide: methyl alcohol: water: acetic acid=1: 1.85: 0.4: 0.5, and MnCl
2Addition be Mn: Ti=0.4, mix, treat colloidal sol be converted into dry behind the gel, grind, and under 200～600 ℃, carry out roasting, obtain catalyst.
Use and handle NO: NH3=1, O
2Concentration=3%, GHSV (per hour gas space velocity)=30000h
-1SCR method denitrating flue gas, when reaction temperature was 120 ℃, catalytic efficiency was about 50%, when reaction temperature was 165 ℃, catalytic efficiency was more than 90%.
Embodiment 5:
Adopt sol-gel process, with purity titanium tetraethoxide, ethanol, water, Mn (NO3) 2, nitric acid is raw material, the volume ratio of each component is as follows, purity titanium tetraethoxide: ethanol: water: nitric acid=1: 1.65: 0.05: 0.07, the addition of Mn (NO3) 2 is Mn: Ti=0.6, mixes, treat colloidal sol be converted into dry behind the gel, grind, and under 200～600 ℃, carry out roasting, obtain catalyst.
Use and handle NO: NH3=1, O2 concentration=3%, GHSV (per hour gas space velocity)=30000h
-1SCR method denitrating flue gas, when reaction temperature was 120 ℃, catalytic efficiency was about 50%, when reaction temperature was 170 ℃, catalytic efficiency was more than 90%.
Embodiment 6:
Adopt sol-gel process, with isopropyl titanate, ethanol, water, MnSO
4, sulfuric acid is raw material, the volume ratio of each component is as follows, isopropyl titanate: ethanol: water: sulfuric acid=1: 1.85: 0.4: 0.05, MnSO
4Addition be Mn: Ti=0.4, mix, treat colloidal sol be converted into dry behind the gel, grind, and under 200～600 ℃, carry out roasting, obtain catalyst.
Use and handle NO: NH3=1, O
2Concentration=3%, GHSV (per hour gas space velocity)=30000h
-1SCR method denitrating flue gas, when reaction temperature was 150 ℃, catalytic efficiency was about 50%, when reaction temperature was 190 ℃, catalytic efficiency was more than 90%.
Embodiment 7:
Adopt sol-gel process, with tetrabutyl titanate, propyl alcohol, water, Mn (NO3)
2, nitric acid is raw material, the volume ratio of each component is as follows, tetrabutyl titanate: propyl alcohol: water: nitric acid=1: 1.5: 0.08: 0.07, Mn (NO3)
2Addition be Mn: Ti=0.4, mix, treat colloidal sol be converted into dry behind the gel, grind, and under 200～600 ℃, carry out roasting, obtain catalyst.
Use and handle NO: NH3=1, O
2Concentration=3%, GHSV (per hour gas space velocity)=30000h
-1SCR method denitrating flue gas, when reaction temperature was 150 ℃, catalytic efficiency was about 50%, when reaction temperature was 190 ℃, catalytic efficiency was more than 90%.
Embodiment 8:
Adopt sol-gel process, with metatitanic acid n-propyl, propyl alcohol, water, Mn (NO
3)
2, nitric acid is raw material, metatitanic acid n-propyl: propyl alcohol: water: the volume ratio of nitric acid=1: 1.85: 0.06: 0.02, Mn (NO
3)
2Addition be: Mn: Ti=0.1, mix, treat colloidal sol be converted into dry behind the gel, grind, and under 200～600 ℃, carry out roasting, obtain catalyst.
Use and handle NO: NH3=1, O
2Concentration=3%, GHSV (per hour gas space velocity)=30000h
-1SCR method denitrating flue gas, when reaction temperature was 180 ℃, catalytic efficiency was about 50%.
Embodiment 9:
Adopt sol-gel process, with isopropyl titanate, propyl alcohol, water, Mn (NO3) 2, FeCl3, hydrochloric acid is raw material, the volume ratio of each component is as follows, isopropyl titanate: propyl alcohol: water: hydrochloric acid=1: 1.5: 0.5: 0.05, Fe: Mn: Ti=0.005: 0.4: 1, mix, treat colloidal sol be converted into dry behind the gel, grind, and under 200～600 ℃, carry out roasting, obtain catalyst.
Use and handle NO: NH3=1, O
2Concentration=3%, GHSV (per hour gas space velocity)=30000h
-1SCR method denitrating flue gas, reaction temperature is about 95 ℃, catalytic efficiency can reach 50%, when reaction temperature during at 150 ℃, catalytic efficiency can reach 90%.
Embodiment 10:
Adopt sol-gel process, with tetrabutyl titanate, butanols, water, Mn (NO
3)
2, acetic acid is raw material, tetrabutyl titanate: butanols: water: the volume ratio of acetic acid=1: 1.85: 0.06: 0.5, Mn (NO
3)
2Addition be: Mn: Ti=0.05, mix, treat colloidal sol be converted into dry behind the gel, grind, and under 200～600 ℃, carry out roasting, obtain catalyst.
Use and handle NO: NH3=1, O
2Concentration=3%, GHSV (per hour gas space velocity)=30000h
-1SCR method denitrating flue gas, when reaction temperature was 180 ℃, catalytic efficiency was about 30%.
Embodiment 11:
Adopt sol-gel process, with metatitanic acid n-propyl, propyl alcohol, water, Mn (NO3) 2, Fe (NO3) 3, nitric acid is raw material, the volume ratio of each component is as follows, metatitanic acid n-propyl: propyl alcohol: water: nitric acid=1: 1.5: 0.5: 0.05, Fe: Mn: Ti=0.01: 0.4: 1, mix, treat colloidal sol be converted into dry behind the gel, grind, and under 200～600 ℃, carry out roasting, obtain catalyst.
Use and handle NO: NH3=1, O
2Concentration=3%, GHSV (per hour gas space velocity)=30000h
-1SCR method denitrating flue gas, reaction temperature is about 80 ℃, catalytic efficiency can reach 50%, when reaction temperature during at 120 ℃, catalytic efficiency can reach 90%.
Embodiment 12:
Use sol-gel process, with tetrabutyl titanate, butanols, water, MnCl2, FeCl3, hydrochloric acid is raw material, the volume ratio of each component is as follows, tetrabutyl titanate: butanols: water: hydrochloric acid=1: 1.75: 0.5: 0.03, Fe: Mn: Ti=0.05: 0.4: 1, mix, treat colloidal sol be converted into dry behind the gel, grind, and under 200～600 ℃, carry out roasting, obtain catalyst.
Use and handle NO: NH3=1, O
2Concentration=3%, GHSV (per hour gas space velocity)=30000h
-1SCR method denitrating flue gas, reaction temperature is about 100 ℃, catalytic efficiency can reach 50%, when reaction temperature during at 150 ℃, catalytic efficiency can reach 90%.
Embodiment 13:
Adopt sol-gel process, with tetrabutyl titanate, ethanol, water, MnSO4, Fe
2(SO
4)
3, 1 sulfuric acid is raw material, the volume ratio of each component is as follows, tetrabutyl titanate: ethanol: water: sulfuric acid=1: 1.85: 0.06: 0.08, Fe: Mn: Ti=0.1: 0.4: 1, mix, treat colloidal sol be converted into dry behind the gel, grind, and under 200～600 ℃, carry out roasting, obtain catalyst.
Use and handle NO: NH3=1, O
2Concentration=3%, GHSV (per hour gas space velocity)=30000h
-1SCR method denitrating flue gas, reaction temperature is about 90 ℃, catalytic efficiency can reach 50%, when reaction temperature during at 135 ℃, catalytic efficiency can reach 90%.
Embodiment 14:
Adopt sol-gel process, with metatitanic acid n-propyl, propyl alcohol, water, Mn (NO3) 2, Cr (NO3) 3, nitric acid is raw material, the volume ratio of each component is as follows, metatitanic acid n-propyl: propyl alcohol: water: nitric acid=1: 1.5: 0.5: 0.05, Cr: Mn: Ti=0.01: 0.4: 1, mix, treat colloidal sol be converted into dry behind the gel, grind, and under 200～600 ℃, carry out roasting, obtain catalyst.
Use and handle NO: NH3=1, O
2Concentration=3%, GHSV (per hour gas space velocity)=30000h
-1SCR method denitrating flue gas, reaction temperature is about 85 ℃, catalytic efficiency can reach 50%, when reaction temperature during at 129 ℃, catalytic efficiency can reach 90%.
Embodiment 15:
Adopt sol-gel process, with metatitanic acid n-propyl, propyl alcohol, water, Mn (NO3) 2, Cu (NO3) 2, nitric acid is raw material, the volume ratio of each component is as follows, metatitanic acid n-propyl: propyl alcohol: water: nitric acid=1: 1.5: 0.5: 0.05, Cu: Mn: Ti=0.01: 0.4: 1, mix, treat colloidal sol be converted into dry behind the gel, grind, and under 200～600 ℃, carry out roasting, obtain catalyst.
Use and handle NO: NH3=1, O
2Concentration=3%, GHSV (per hour gas space velocity)=30000h
-1SCR method denitrating flue gas, reaction temperature is about 90 ℃, catalytic efficiency can reach 50%, when reaction temperature during at 138 ℃, catalytic efficiency can reach 90%.
Embodiment 16:
Adopt sol-gel process, with metatitanic acid n-propyl, propyl alcohol, water, Mn (NO3) 2, Ni (NO3) 2, nitric acid is raw material, the volume ratio of each component is as follows, metatitanic acid n-propyl: propyl alcohol: water: nitric acid=1: 1.5: 0.5: 0.05, Ni: Mn: Ti=0.01: 0.4: 1, mix, treat colloidal sol be converted into dry behind the gel, grind, and under 200～600 ℃, carry out roasting, obtain catalyst.
Use and handle NO: NH3=1, O
2Concentration=3%, GHSV (per hour gas space velocity)=30000h
-1SCR method denitrating flue gas, reaction temperature is about 99 ℃, catalytic efficiency can reach 50%, when reaction temperature during at 145 ℃, catalytic efficiency can reach 90%.
Claims (7)
1. one kind based on MnO
x/ TiO
2The low-temperature selective catalytic reduction NO of system
xCatalyst, alkyl oxide, alcohols solvent, water, the soluble-salt of manganese, Bronsted acid with titanium are raw material, and it consists of: the volume ratio of the alkyl oxide of titanium, alcohols solvent, water, Bronsted acid is: the alkyl oxide of titanium: alcohols solvent: water: Bronsted acid is 1: (1～2): (0.05～0.5): (0.01～0.5); The addition of the soluble-salt of manganese contains the molar ratio computing of Ti element with the alkyl oxide of Mn element and titanium, and its value is that Mn: Ti is 0.01～1.
2. low-temperature selective catalytic reduction NO according to claim 1
xCatalyst is characterized in that: described low-temperature selective catalytic reduction NO
xThe soluble-salt that also can add transition metal in the raw material of catalyst, the addition of the soluble-salt of transition metal contains the molar ratio computing of Ti element with the alkyl oxide of the transition metal that contains and titanium, and its value is: transition metal: Ti is 0.001～0.4.
3. low-temperature selective catalytic reduction NO according to claim 1 and 2
xCatalyst is characterized in that: the alkyl oxide of described titanium is selected from a kind of in metatitanic acid n-propyl, purity titanium tetraethoxide, tetrabutyl titanate, the isopropyl titanate.
4. low-temperature selective catalytic reduction NO according to claim 1 and 2
xCatalyst is characterized in that: the soluble-salt of described manganese is selected from a kind of in manganese sulfate, manganese nitrate, the manganese chloride.
5. low-temperature selective catalytic reduction NO according to claim 2
xCatalyst is characterized in that: a kind of in the soluble-salt of described transition metal in transition metal chosen from Fe, the chromium element.。
6. low-temperature selective catalytic reduction NO according to claim 1
xThe Preparation of catalysts method, comprise: adopt sol-gel process, with alkyl oxide, alcohols solvent, water, the Bronsted acid of raw material titanium be by volume: the alkyl oxide of titanium, alcohols solvent, water, Bronsted acid are 1: (1～2): (0.05～0.5): (0.01～0.5) adds, the addition of the soluble-salt of raw material manganese contains the molar ratio computing of Ti element with the alkyl oxide of Mn element and titanium, its value is that Mn: Ti is 0.01～1, mix, treat colloidal sol be converted into dry behind the gel, grind, and under 200～600 ℃, carry out roasting, obtain catalyst.
7. preparation method according to claim 6, comprise: adopt sol-gel process, alkyl oxide with the raw material titanium, alcohols solvent, water, Bronsted acid is by volume: the alkyl oxide of titanium, alcohols solvent, water, Bronsted acid is 1: (1～2): (0.05～0.5): (0.01～0.5) adds, the addition of the soluble-salt of raw material manganese contains the molar ratio computing of Ti element with the alkyl oxide of Mn element and titanium, its value is that Mn: Ti is 0.01～1, the addition of the soluble-salt of raw material transition metal contains the molar ratio computing of Ti element with the alkyl oxide of the transition metal that contains and titanium, and its value is: transition metal: Ti is 0.001～0.4; Mix, treat colloidal sol be converted into dry behind the gel, grind, and under 200～600 ℃, carry out roasting, obtain catalyst.
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