CN100998939A - MnOx/ZrO2-TiO2 low temperature selective catalytic reduction NOx catalyst possessing anti SO2 performance and its preparation technology - Google Patents
MnOx/ZrO2-TiO2 low temperature selective catalytic reduction NOx catalyst possessing anti SO2 performance and its preparation technology Download PDFInfo
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- CN100998939A CN100998939A CN 200710066668 CN200710066668A CN100998939A CN 100998939 A CN100998939 A CN 100998939A CN 200710066668 CN200710066668 CN 200710066668 CN 200710066668 A CN200710066668 A CN 200710066668A CN 100998939 A CN100998939 A CN 100998939A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000010531 catalytic reduction reaction Methods 0.000 title claims abstract description 7
- 229910016978 MnOx Inorganic materials 0.000 title 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title 1
- 239000010936 titanium Substances 0.000 claims abstract description 53
- 239000011572 manganese Substances 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 16
- 238000003980 solgel method Methods 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000007848 Bronsted acid Substances 0.000 claims description 9
- 150000001298 alcohols Chemical class 0.000 claims description 9
- 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 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 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 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 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
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 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
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 25
- 230000000607 poisoning effect Effects 0.000 abstract description 7
- 231100000572 poisoning Toxicity 0.000 abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract 2
- 238000000227 grinding Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- -1 titanium alkoxide Chemical class 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 15
- 239000003546 flue gas Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- 229910007926 ZrCl Inorganic materials 0.000 description 8
- 239000011149 active material Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000008021 deposition 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
- 230000003993 interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种具有抗SO2性能的MnOx/ZrO2－TiO2低温选择性催化还原NOx催化剂，原料组成为：钛的烷氧化合物、醇类溶剂、水、质子酸的体积比为1∶(1～2)∶(0.05～0.5)∶(0.01～0.5)；锰的可溶性盐的加入量为Mn∶Ti摩尔比为0.05～1，锆的可溶性盐的加入量Zr∶Ti摩尔比为0.05～5。本发明还公开了该催化剂的制备方法，采用溶胶－凝胶法，按比例加入上述原料，混合，待溶胶转化为凝胶后干燥、研磨，高温下焙烧而得。本发明制备的催化剂，降低了SCR的操作温度，在SCR工艺中，以NH3为还原剂时，在150℃以下达到90％以上的NO去除率，并且加入SO2后，仍具有较高的催化效率，并且SO2对催化剂的毒害具有可恢复性。The invention discloses a MnO x /ZrO 2 -TiO 2 low-temperature selective catalytic reduction NO x catalyst with anti-SO 2 performance. The raw material is composed of the volume ratio of titanium alkoxide, alcohol solvent, water, and protonic acid It is 1: (1～2): (0.05～0.5): (0.01～0.5); the addition amount of manganese soluble salt is Mn: Ti molar ratio is 0.05～1, the addition amount of zirconium soluble salt Zr: Ti mole The ratio is 0.05-5. The invention also discloses a preparation method of the catalyst, which is obtained by adding the above-mentioned raw materials in proportion by adopting a sol-gel method, mixing, drying, grinding and roasting at high temperature after the sol is converted into a gel. The catalyst prepared by the present invention reduces the operating temperature of SCR. In the SCR process, when NH is used as a reducing agent, the NO removal rate of more than 90% can be achieved below 150 ° C, and after adding SO 2 , it still has a higher Catalytic efficiency, and the poisoning of the catalyst by SO 2 is recoverable.
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 have sulfur resistance based on MnO
x/ ZrO
2-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.
SO
2Harm for catalyst mainly comes from SO
2Deposition at catalyst surface.Main mode has two kinds: 1. and NH
3Reaction generates ammonium sulfite or ammonium sulfate and is deposited on catalyst surface, covering catalyst original activity point position; 2.SO
2Active component reaction with in the catalyst directly generates metal sulfate or metal sulphite, makes the catalyst activity component lose original activity.Though for low temperature catalyst certain report is arranged at present, the overwhelming majority still is in the experimental study stage.Because desulfurization still has part SO later
2Exist, in long-term contact, still can produce poisoning effect catalyst.Therefore how to reduce SO
2Murder by poisoning extremely important.
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.
ZrO
2It is the fine semi-conducting material of a kind of heat endurance.Have specific surface acidity, alkalescence and OR characteristic on its surface.As a kind of semi-conducting material, it more easily produces the electron hole and interacts with active material simultaneously.Work as ZrO
2And TiO
2In conjunction with as carrier the time, can replace the position of Ti in original lattice, form ZrTiO
4At this moment, will form new acidity and basicity on the carrier.SO
2When occupying catalyst, these acid sites can attract SO
2, form and occupy target position, protect the active sites of active material effectively, and because the adding of Zr has changed the bond energy of crystal, SO
2At ZrTiO
4The surface can only form more weak and reversible sulfate; In addition, ZrO
2Can interact with active material, form metal solid solution, thereby make SO
2Be difficult to generate metal sulfate and metal sulphite with the active material reaction.
Therefore, use ZrO
2-TiO
2This catalyst carrier can reduce SO greatly
2Toxicity to catalyst.Therefore with MnO
xLoad to ZrO
2-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/ ZrO
2-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, improve the formation of crystal and the distribution of active site, in the active sites that increases catalyst surface simultaneously, form SO
2The target position of attacking reduces SO
2Deposition.Remove NO being implemented under the low temperature condition
xThe time, increase catalyst to SO
2Mithridatism.
A kind of have an anti-SO
2The MnO of performance
x/ ZrO
2-TiO
2Low-temperature selective catalytic reduction NO
xCatalyst, alkyl oxide, alcohols solvent, water, the soluble-salt of zirconium, 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 0.05～1; The addition of the soluble-salt of zirconium contains the molar ratio computing of Ti element with the alkyl oxide of Zr element and titanium, and its value is that Zr: Ti is 0.05～5.
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.
The soluble-salt of described manganese is selected from a kind of in manganese sulfate, manganese nitrate, the manganese chloride.
The soluble-salt of described zirconium is selected from a kind of in zirconium nitrate, zirconium chloride, the zirconium oxychloride.。
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, zr element 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 unformed shape, MnO
2Or and ZrO
2Solid solution, can provide the active sites of catalytic reaction, to reactant NO and NH
3Adsorb, and on contiguous acid sites, react.
ZrO
2-TiO
2As the carrier of catalyst activity component, mainly with ZrO
2, TiO
2And ZrTiO
4Form have ZrO
2-TiO
2Existence become the target position of sulfate and sulphite deposition, protected the Mn active sites in the catalyst effectively, and ZrO
2Form solid solution with the active material interaction, make active material be difficult for and SO
2In conjunction with generating metal sulfate or metal sulphite.Strengthen the sulfur resistance of catalyst, prolonged the service life of 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/ ZrO
2-TiO
2Conglomerate in conjunction with closely, is easy to the utilization of oxygen between the transfer of electronics and lattice between each component, and effective guard catalyst active sites simultaneously adds the anti-SO of powerful catalyst
2Performance.
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 Mn (0.4)/Zr (0.1)-TiO
2, in the time of 120 ℃, can reach the treatment effeciency more than 90%, and existing commercial Application technology can not be carried out NO at all and be removed in this temperature range to NO.
At SO
2Influence the aspect, 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, with Mn (0.4)/Zr (1)-TiO
2Be example, the SO of 150ppm is arranged in system
2When existing, in the time of 120 ℃, catalytic efficiency is still more than 75%, and in the time of 150 ℃, catalytic efficiency can reach 85%.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, with NH
3During for reducing agent, can 150 ℃ being issued to high NO clearance, and in system, contain SO
2The time, still possess higher catalytic efficiency, and SO
2Murder by poisoning to it has restorability.
The specific embodiment
Embodiment 1:
Adopt sol-gel process, with tetrabutyl titanate, ethanol, water, Mn (NO
3)
2, ZrOCl
2, acetic acid is raw material, the volume ratio of each component is as follows, tetrabutyl titanate: ethanol: water: acetic acid=1: 1.5: 0.5: 0.5, Mn (NO
3)
2Addition be Mn: Ti=0.4, ZrOCl
2Addition be: Zr: Ti=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: NH
3=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 90%, added the S0 of 150ppm
2After, catalytic efficiency is 75%.
Embodiment 2:
Adopt sol-gel process, with purity titanium tetraethoxide, ethanol, water, Mn (NO
3)
2, ZrCl
4, 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, Mn: Ti=0.4, ZrCl
4Addition be: Zr: Ti=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: NH
3=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 90%, added the SO of 150ppm
2After, catalytic efficiency is 72%.
Embodiment 3:
Adopt sol-gel process, with metatitanic acid n-propyl, propyl alcohol, water, Mn (NO
3)
2, Zr (NO
3)
4, 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=0.4, Zr (NO
3)
4Addition be: Zr: Ti=0.5, 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: NH
3=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 80%, added the SO of 150ppm
2After, catalytic efficiency is 65%.
Embodiment 4:
Adopt sol-gel process, with purity titanium tetraethoxide, ethanol, water, MnCl
2, ZrCl
4, 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=0.4, ZrCl
4Addition be: Zr: Ti=0.8, 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: NH
3=1, O
2Concentration=3%, GHSV (per hour gas space velocity)=30000h
-1SCR method denitrating flue gas, when reaction temperature was 190 ℃, catalytic efficiency was about 90%, added the SO of 150ppm
2After, catalytic efficiency is 70%.
Embodiment 5:
Adopt sol-gel process, with purity titanium tetraethoxide, methyl alcohol, water, MnCl
2, Zr (NO
3)
4, acetic acid is raw material, the volume ratio of each component is as follows, purity titanium tetraethoxide: methyl alcohol: water: acetic acid=1: 1.85: 0.4: 0.5, MnCl
2Addition be Mm: Ti=0.4, Zr (NO
3)
4Addition be: Zr: Ti=2, 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: NH
3=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%, added the SO of 150ppm
2After, catalytic efficiency is 35%.
Embodiment 6:
Adopt sol-gel process, with purity titanium tetraethoxide, ethanol, water, Mn (NO
3)
2, ZrCl
4, 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, Mn: Ti=0.8, ZrCl
4Addition be: Zr: Ti=1.5, 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: NH
3=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 80%, added the SO of 150ppm
2After, catalytic efficiency is 57%.
Embodiment 7:
Adopt sol-gel process, with metatitanic acid n-propyl, propyl alcohol, water, MnCl
4Zr (NO
3)
4, 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, Zr (NO
3)
4Addition be: Zr: Ti=0.8, 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: NH
3=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%, added the SO of 150ppm
2After, catalytic efficiency is 41%.
Embodiment 8:
Adopt sol-gel process, with isopropyl titanate, ethanol, water, Mn (NO
3)
2, Zr (NO
3)
4, acetic acid is raw material, the volume ratio of each component is as follows, isopropyl titanate: ethanol: water: acetic acid=1: 1.65: 0.4: 0.5, Mn (NO
3)
2Addition be Mn: Ti=0.4, Zr (NO
3)
4Addition be: Zr: 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: NH
3=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 80%, added the SO of 150ppm
2After, catalytic efficiency is 60%.
Embodiment 9:
Adopt sol-gel process, with isopropyl titanate, ethanol, water, MnSO
4, ZrCl
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, ZrCl
4Addition be: Zr: Ti=5, 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: NH
3=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 80%, added the SO of 150ppm
2After, catalytic efficiency is 60%.
Embodiment 10:
Adopt sol-gel process, with tetrabutyl titanate, propyl alcohol, water, Mn (NO
3)
2, Zr (NO
3)
4, 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 (NO
3)
2Addition be Mn: Ti=0.4, Zr (NO
3)
4Addition be: Zr: Ti=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: NH
3=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 90%, added the SO of 150ppm
2After, catalytic efficiency is 75%.
Claims (5)
1, a kind of have an anti-SO
2The MnO of performance
x/ ZrO
2-TiO
2Low-temperature selective catalytic reduction NO
xCatalyst, alkyl oxide, alcohols solvent, water, the soluble-salt of manganese, the soluble-salt of zirconium, 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 0.05～1 for Mn:Ti; The addition of the soluble-salt of zirconium contains the molar ratio computing of Ti element with the alkyl oxide of Zr element and titanium, and its value is 0.05～5 for Zr:Ti.
2, catalyst according to claim 1 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.
3, catalyst according to claim 1 is characterized in that: the soluble-salt of described manganese is selected from a kind of in manganese sulfate, manganese nitrate, the manganese chloride.
4, catalyst according to claim 1 is characterized in that: the soluble-salt of described zirconium is selected from a kind of in zirconium nitrate, zirconium chloride, the zirconium oxychloride.
5, Preparation of catalysts method according to claim 1, 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 0.05～1 for Mn:Ti, the addition of the soluble-salt of raw material zirconium contains the molar ratio computing of Ti element with the alkyl oxide of Zr element and titanium, its value is 0.05～5 for Zr:Ti, mix, it is dry to treat that colloidal sol is converted into behind the gel, grind, and under 200～600 ℃, carry out roasting, obtain catalyst.
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| CNB2007100666686A CN100490968C (en) | 2007-01-10 | 2007-01-10 | MnOx/ZrO2-TiO2 Catalyst for Selective Catalytic Reduction of NOx at Low Temperature with Anti-SO2 Performance and Its Preparation Process |
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