CN101947443B - Cellular Mn-Ti-based catalyst for low-temperature selective catalytic reduction denitration reaction and preparation method and using method - Google Patents
Cellular Mn-Ti-based catalyst for low-temperature selective catalytic reduction denitration reaction and preparation method and using method Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 127
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000010531 catalytic reduction reaction Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 26
- 230000001413 cellular effect Effects 0.000 title description 13
- 239000000843 powder Substances 0.000 claims abstract description 18
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 239000010936 titanium Substances 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 10
- 229940071125 manganese acetate Drugs 0.000 claims description 10
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 10
- 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 10
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 8
- 239000012018 catalyst precursor Substances 0.000 claims description 8
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 claims description 8
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 8
- 229960001471 sodium selenite Drugs 0.000 claims description 8
- 235000015921 sodium selenite Nutrition 0.000 claims description 8
- 239000011781 sodium selenite Substances 0.000 claims description 8
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229920000058 polyacrylate Polymers 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 6
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- JRLDUDBQNVFTCA-UHFFFAOYSA-N antimony(3+);trinitrate Chemical compound [Sb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JRLDUDBQNVFTCA-UHFFFAOYSA-N 0.000 claims 2
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- -1 polytetrafluoroethylene Polymers 0.000 claims 1
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- 230000000694 effects Effects 0.000 abstract description 15
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- 239000003546 flue gas Substances 0.000 abstract description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
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- 239000000314 lubricant Substances 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 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 description 7
- WBJXZTQXFVDYIZ-UHFFFAOYSA-N [Sb].[N+](=O)(O)[O-] Chemical compound [Sb].[N+](=O)(O)[O-] WBJXZTQXFVDYIZ-UHFFFAOYSA-N 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910016978 MnOx Inorganic materials 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 4
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- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
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- 238000001354 calcination Methods 0.000 description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
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- 229910052720 vanadium Inorganic materials 0.000 description 3
- 241001466460 Alveolata Species 0.000 description 2
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 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 description 2
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
本发明公开了一种用于低温选择性催化还原脱硝反应的蜂窝状Mn-Ti基催化剂及制备和使用方法。以摩尔百分含量计催化剂的组分为：TiO2：40～60％；MnO2：5～16％；Mn2O3：3～7％；Mn3O4：2～4％；CeO2：2～8％；V2O5：1～3％；Se：0.5～1％；Sb：0.5～1％；Bi：0.15～1.5％。制备方法为：首先采用水热法制备Mn-Ti催化剂粉体，然后通过挤压成型和浸渍等工艺后制备改性的蜂窝状Mn-Ti基催化剂，提高了催化剂的低温SCR活性和抗硫中毒能力。并且，采用本发明方法制备的催化剂具有很高的机械强度，活性物质分散性好，不易烧结。本发明制备的催化剂可应用于烟气低温SCR脱硝反应，直接布置于除尘甚至脱硫装置之后，能够大大降低传统SCR工艺的操作温度和运行成本，在100℃左右即有很高的氮氧化物去除率。The invention discloses a honeycomb Mn-Ti-based catalyst for low-temperature selective catalytic reduction and denitrification reaction, as well as preparation and use methods. The components of the catalyst in terms of mole percentage are: TiO 2 : 40-60%; MnO 2 : 5-16%; Mn 2 O 3 : 3-7%; Mn 3 O 4 : 2-4%; CeO 2 V 2 O 5 : 1-3%; Se: 0.5-1%; Sb: 0.5-1%; Bi: 0.15-1.5%. The preparation method is as follows: firstly, the Mn-Ti catalyst powder is prepared by the hydrothermal method, and then the modified honeycomb Mn-Ti-based catalyst is prepared by extrusion molding and impregnation, which improves the low-temperature SCR activity and sulfur poisoning resistance of the catalyst ability. Moreover, the catalyst prepared by the method of the invention has high mechanical strength, good dispersion of active substances and is not easy to sinter. The catalyst prepared by the invention can be applied to low-temperature SCR denitrification reaction of flue gas, and it can be directly arranged after dust removal or even desulfurization device, which can greatly reduce the operating temperature and operating cost of the traditional SCR process, and has high nitrogen oxide removal at about 100°C Rate.
Description
Technical field
The present invention relates to catalyst, relate in particular to a kind of cellular Mn-Ti catalyst based and preparation and using method that is used for the low-temperature selective catalytic reduction denitration reaction.
Background technology
NO at stationary source (coal-burning power plant, Industrial Boiler etc.) discharging
X, with NH
3For the SCR technology (SCR) of reducing agent is that research is maximum, most widely used at present, also be the most effective flue gas NO
XRemove technology.Using the most ripe catalyst at present is V
2O
5/ TiO
2Perhaps at V
2O
5/ TiO
2Carry out the catalyst of modification on the basis, its major advantage shows high activity and high antisulphuric ability, but this type of catalyst just has greater activity when operating temperature is higher than 350 ℃, therefore the SCR reactor can only be arranged between economizer and the deduster.But do not reserve the denitration space mostly in this position in the existing boiler, brought very big difficulty therefore for the commercial Application of SCR technology; The dust that contains high concentration in the flue gas of this external this process section also contains materials such as alkali metal, arsenic and mercury in the dust, can produce very strong erosion and poisoning effect to catalyst, influences its life-span.And the expense of catalyst accounts for the nearly 40% of whole SCR technology cost, so life of catalyst is directly determining the operating cost of SCR system.
For these reasons, many in recent years scholar's suggestions is arranged in the SCR reactor after dedusting or even the desulfurizer.For avoiding the repeating heating, save operation and boiler improvement cost of flue gas, research and development has active SCR catalyst and has important economy and practical significance under cryogenic conditions, also obtain many research workers' attention in the world.The research of relevant low-temperature SCR catalyst is at present mainly concentrated both ways: (1) develops low-temperature SCR catalyst active component efficiently at different active materials such as Mn, Cu, Fe, Cr, metal oxides such as Mo, V; (2) above-mentioned various high-efficiency activated components are cooperated different carrier mass, as active carbon material, TiO
2, activated alumina and metal ion molecular sieve ZSM-5 etc. prepare have high-specific surface area, the whole low-temperature SCR catalyst of high thermal stability.
Research is at present used comparatively widely, and low-temperature SCR catalyst mainly contains MnOx/TiO
2, MnOx-CeO
2And V
2O
5/ AC etc. are at low temperatures to NO
xHigher removal is arranged.People such as G.Qi (G.Qi, R.T.Yang, Low-temperature selective catalytic reduction of NO with NH
3Over iron andmanganese oxides supported on titania.Appl.Catal.B:Environmental, 44 (2003) 217-225) use infusion process that Mn is carried on TiO
2On, find that the MnOx of finely disseminated unformed shape has good catalytic activity, when the load capacity of Mn greater than 10% the time, the MnOx of original unformed shape is converted into crystal MnOx, the SCR activity reduces greatly; People such as G.Qi have also prepared MnOx-CeO by the precipitation method
2Composite oxides (G.Qi, R.T.Yang, R.Chang, MnOx-CeO
2Mixed oxidesprepared by co-precipitation for selective catalytic reduction of NO with NH
3At lowtemperatures.Appl.Catal.B:Environmental, 51 (2004) 93-106.), catalyst activity is the highest when the mol ratio of Mn/ (Mn+Ce) is 0.4, can reach 95% NO clearance at 150 ℃; People such as Z.P.Zhu (Z.P.Zhu, Z.Y.Liu, S.J.Liu, H.X.Niu, A novel carbon-supported vanadiumoxide catalyst for NO reduction with NH
3At low temperature.Appl.Catal.B:Environmental, 23 (1999) L229-L233.) be equipped with V by the pore volume impregnation legal system
2O
5/ AC catalyst finds to work as V
2O
5Load capacity when being 1-5%, V
2O
5/ AC has showed very high SCR activity at 180-250 ℃.
MnO
xBe carried on TiO
2Go up and obtained extensive studies as low-temperature SCR catalyst, can further improve activity of such catalysts if on the catalyst of the type, add appropriate ingredients, make multiple catalyst activity component that cooperative effect can take place, thereby further reduce reaction activity and reduce reaction temperature, improving pollutants removal rate will have very important significance.In addition, although the low-temperature SCR system is positioned over after desulfurization and/or the dust arrester, sulfur in smoke is not removed fully, still can contain the remaining SO of low concentration in the flue gas of this process section
2, many results of study show, in the low-temperature SCR reaction, and SO
2Existence can make catalysqt deactivation, reduce denitration efficiency greatly, can the anti-sulphur that therefore improves low-temperature SCR catalyst be its key point that realize industrial applications.
In sum, be necessary at present active down raising of low-temperature SCR catalyst low temperature and sulfur resistance improvement are goed deep into and systematic research.At last, if the catalyst of research will be realized industrial applications also must cooperate suitable material with these active components, prepare cellular monoblock type SCR catalyst, to have less bed resistance, bigger geometric proportion surface area and higher mechanical strength and heat endurance.Therefore must study the preparation process of honeycombed catalyst, screen suitable binding agent and definite optimum amount, optimize some technological parameters in the extrusion modling process, make that the cellular integer catalyzer active component for preparing at last is evenly distributed, duct and abundant, active high, the long service life of specific area.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of cellular Mn-Ti catalyst based and preparation and using method that is used for the low-temperature selective catalytic reduction denitration reaction is provided.Improve catalyst based low-temperature SCR activity of cellular Mn-Ti and sulfur poisoning-resistant ability by adjusting and control catalyst precarsor mother liquor prescription, co-catalyst active component and subsequent preparation technology.
A kind of catalyst based component in the molar content catalyst of cellular Mn-Ti that is used for the low-temperature selective catalytic reduction denitration reaction is:
(1) TiO
2Content accounts for 40～60% of catalyst total content;
(2) Mn oxide: MnO
2Content accounts for 5～16% of catalyst total content
Mn
2O
3Content accounts for 3～7% of catalyst total content
Mn
3O
4Content accounts for 2～4% of catalyst total content;
(3) co-catalyst: CeO
2Content accounts for 2～8% of catalyst total content;
V
2O
5Content accounts for 1～3% of catalyst total content;
The Se oxide content accounts for 0.5～1% of catalyst total content;
The Sb oxide content accounts for 0.5～1% of catalyst total content;
The Bi oxide content accounts for 0.15～1.5% of catalyst total content;
The catalyst based component in the molar content catalyst of cellular Mn-Ti that another kind is used for the low-temperature selective catalytic reduction denitration reaction is:
(1) TiO
2Content accounts for 40～60% of catalyst total content;
(2) Mn oxide: MnO
2Content accounts for 5～16% of catalyst total content
Mn
2O
3Content accounts for 3～7% of catalyst total content
Mn
3O
4Content accounts for 2～4% of catalyst total content;
(3) co-catalyst: CeO
2Content accounts for 2～7% of catalyst total content;
V
2O
5Content accounts for 1～3% of catalyst total content;
The Se oxide content accounts for 0.5～1% of catalyst total content;
The Sb oxide content accounts for 0.5～1% of catalyst total content;
The Bi oxide content accounts for 0.05～0.5% of catalyst total content;
The P oxide content accounts for 0.05～0.5% of catalyst total content;
The Si oxide content accounts for 0.05～0.5% of catalyst total content.
The preparation method's that a kind of cellular Mn-Ti that is used for low-temperature selective catalytic reduction denitration reaction is catalyst based step is as follows:
(1) with the alkyl oxide of titanium, ethanol, water according to mol ratio 1: (1～10): (0.2～5) mixes the soluble-salt that the back adds manganese, pour into after the stirring in the teflon-lined autoclave, 120 ℃ of following hydro-thermal reactions 12 hours, afterwards with the suspension in the reactor through centrifugal, filter, oven dry, obtain solid powdery Mn-Ti catalyst;
(2) get 1000g solid powdery Mn-Ti catalyst, add 5-10g expanding agent, 5-10mL lubricant, 500-1000mL molding adhesive and 3-8g reinforcing agent material therein and after fully mediating, re-use mould and be squeezed into regular block with alveolate texture, standby after drying, the roasting;
(3) will be immersed in the precursor solution that contains cerous nitrate, ammonium metavanadate, sodium selenite, nitric acid antimony and bismuth nitrate 6 hours by the honeycombed catalyst precursor that step (2) obtain, Ce in the precursor solution: V: Se: Sb: Bi mol ratio=(2～8): (1～3): (0.5～1): (0.5～1): (0.05～0.5): (0.05～0.5), following dry 4 hours at 110 ℃ afterwards, activate 4 hours down at 500 ℃ at last, it is catalyst based to obtain integral honeycomb shape Mn-Ti.
The step that another kind is used for the catalyst based preparation method of the cellular Mn-Ti of low-temperature selective catalytic reduction denitration reaction is as follows:
(1) with the alkyl oxide of titanium, ethanol, water according to mol ratio 1: (1～10): (0.2～5) mixes the soluble-salt that the back adds manganese, pour into after the stirring in the teflon-lined autoclave, 120 ℃ of following hydro-thermal reactions 12 hours, afterwards with the suspension in the reactor through centrifugal, filter, oven dry, obtain solid powdery Mn-Ti catalyst;
(2) get 1000g solid powdery Mn-Ti catalyst, add 5-10g expanding agent, 5-10mL lubricant, 500-1000mL molding adhesive and 3-8g reinforcing agent material therein and after fully mediating, re-use mould and be squeezed into regular block with alveolate texture, standby after drying, the roasting;
(3) will be immersed in the precursor solution that contains cerous nitrate, ammonium metavanadate, sodium selenite, nitric acid antimony, bismuth nitrate, ammonium borate and silester 6 hours by the honeycombed catalyst precursor that step (2) obtain, Ce in the precursor solution: V: Se: Sb: Bi: P: Si mol ratio=(2～7): (1～3): (0.5～1): (0.5～1): (0.15～1.5): (0.05～0.5): (0.05～0.5), following dry 4 hours at 110 ℃ afterwards, activate 4 hours down at 500 ℃ at last, it is catalyst based to obtain integral honeycomb shape Mn-Ti.
The alkyl oxide of described titanium is tetrabutyl titanate or isopropyl titanate.The soluble-salt of described manganese is manganese nitrate or manganese acetate.Described expanding agent is one or more in active carbon, starch, poly-oxireme, the polyethylene glycol.Described lubricant is one or more of glycerine, polyacrylate, and molding adhesive is one or more in titanium tetrachloride aqueous solution, polyacrylamide, the titanium glue.Described reinforcing agent is one or more in shaft-like glass fibre, carbon fiber, the calcium sulfate.
The catalyst based using method of cellular Mn-Ti that is used for the low-temperature selective catalytic reduction denitration reaction is at the SCR reactor with catalyst filling, reactor is arranged in after flue gas ash removal or the desulfurizer, be used for removing the flue gas nitrogen oxide, the reaction temperature of reactor is 80～150 ℃, and the operation air speed is 3000～30000h
-1
In the catalyst of the present invention, the main active component that Mn and Ti are.Their main effect is the active sites that catalytic reaction can be provided, to reactant NO and NH
3Adsorb, and on contiguous acid sites, react; Ce is main co-catalyst component, and its effect is to promote NO to NO
2Change, improve the SCR reactivity, the Ce electronics that can also increase in the catalytic reaction shifts in addition, and with it as storing the oxygen agent preferably, strengthen the oxygen cycle of catalyst, the continuing of assurance catalytic reaction carries out; The main effect of materials such as V, Se and Sb is to reduce the stability of sulphur ammonium salt at catalyst surface, quickens the decomposition of sulphur ammonium salt, thereby reduces its deposition in the catalyst duct and the sulfur poisoning-resistant ability of obstruction raising catalyst.
The present invention adopts hydro-thermal method to come the synthetic catalyst powder to be because the catalyst powder of this method preparation is one step completed in liquid phase, do not need subsequent crystallization heat treatment, thereby avoided owing to hard aggregation, crystal grain that later stage heat treatment produces powder shortcoming such as grow up voluntarily, the powder of this method preparation has purity height, crystal grain component and advantage such as form is controlled, the reunion degree is light.
The present invention uses expanding agent in preparation honeycombed catalyst process be in order to produce hole in catalyst inside in calcination process, to improve specific surface area of catalyst and pore volume, improve the pore structure of catalyst, improving the diffusivity of gas in catalyst inside; Making with lubricator is the bonding of wet feed group and mould or contact-making surface in the kneading process; The effect of molding adhesive is that its meeting and water form jelly, can form adhesive membrane in the catalyst powder surface in the kneading process, catalyst powder is kneaded together, improve interparticle adhesion strength, adhesive meeting decomposition in calcination process can not remain in catalyst surface influences its activity, and the catalyst that obtain this moment has had reasonable mechanical strength; Because TiO
2Catalyst based mechanical strength is relatively poor, adds the mechanical strength that reinforcing agent can improve the SCR catalyst in the shaping of catalyst process.
Compared with the prior art the catalyst of the inventive method preparation has following advantage: the catalyst of the present invention's preparation has very high catalytic activity, active material good dispersion, not easy-sintering; This catalyst has sulfur poisoning-resistant ability preferably, has long service life; The honeycombed catalyst of the present invention's preparation has higher specific surface area and good pore passage structure in addition, also has very strong mechanical strength.This catalyst is applied to operating temperature and the operating cost that flue gas low-temperature SCR denitration reaction can reduce traditional SCR technology greatly, can reach the NO clearance more than 80% about 100 ℃.
The specific embodiment
Embodiment 1
Preparation of Catalyst: with tetrabutyl titanate, ethanol, water and manganese nitrate are raw material, each material molar ratio is 1: 5: 1: 0.4, each component stirs after fully mixing fast, stir and pour in the teflon-lined autoclave after two hours, under 120 ℃, put into the Muffle furnace hydro-thermal reaction 12 hours, afterwards the suspension in the reactor is put into centrifuge and carry out high speed centrifugation, take out supernatant liquor after the centrifugal end, use ethanol to clean, centrifugal once more after the cleaning, filter, afterwards milky substance is put into drying in oven and promptly obtained solid powdery Mn-Ti catalyst.
Get the catalyst powder of the above-mentioned preparation of 1000g, the poly-oxireme of adding 10g, 10mL glycerine, 600mL titanium tetrachloride aqueous solution (contain TiO
260g), the shaft-like glass fibre of 5g, in kneader, mediated 40 minutes under the room temperature, in vacuum-extruder, be squeezed into cellular Mn-Ti based catalyst precursors then, 100 ℃ dry 5 hours down, 400 ℃ calcining is standby after 4 hours down.
Get the honeycombed catalyst precursor of the above-mentioned preparation of 1000g, immerse (Ce: V: Se: Sb: Bi mol ratio=2: 3: 0.5: 1: 0.15) in the precursor solution that 400mL is made up of cerous nitrate, ammonium metavanadate, sodium selenite, nitric acid antimony and bismuth nitrate under the room temperature, flood after 6 hours and take out, drying is 4 hours under 110 ℃, activate 4 hours down at 500 ℃ at last, it is catalyst based to obtain integral honeycomb shape Mn-Ti.
The catalyst that obtains is used for the low temperature SCR denitration reaction, and reaction condition the results are shown in Table 1 with active.
Embodiment 2
Step by embodiment 1 is prepared, and just makes molding adhesive into 800mL titanium sol solution, and with Ce: V: Se: Sb in the precursor solution: the Bi mol ratio changes 8: 1: 1 into: 0.5: 1.5.Other reagent, addition and operation are all by embodiment 1, and the catalyst that obtains is used for the low temperature SCR denitration reaction, and reaction condition the results are shown in Table 1 with active.
Embodiment 3
Step by embodiment 1 is prepared, just when preparation powder catalyst, change manganese nitrate into manganese acetate, lubricant makes the 7mL polyacrylate into, and reinforcing agent makes the 5g carbon fiber into, and with Ce: V: Se: Sb in the precursor solution: the Bi mol ratio changes 5: 2: 0.7 into: 0.6: 0.5.Other reagent, addition and operation are all by embodiment 1, and the catalyst that obtains is used for the low temperature SCR denitration reaction, and reaction condition the results are shown in Table 1 with active.
Embodiment 4
Step by embodiment 1 is prepared, just when preparation powder catalyst, change tetrabutyl titanate into isopropyl titanate, expanding agent changes 7g starch into, lubricant makes the 5mL polyacrylate into, molding adhesive makes the 500mL polyacrylamide into, reinforcing agent makes the 8g carbon fiber into, and with Ce: V: Se: Sb in the precursor solution: the Bi mol ratio changes 4: 3: 0.8 into: 0.8: 0.8.Other reagent, addition and operation are all by embodiment 1, and the catalyst that obtains is used for the low temperature SCR denitration reaction, and reaction condition the results are shown in Table 1 with active.
Embodiment 5
Step by embodiment 1 is prepared, just when preparation powder catalyst, change tetrabutyl titanate into isopropyl titanate, isopropyl titanate, ethanol, each material molar ratio of water and manganese nitrate changes 1: 6: 0.8 into: 0.5, expanding agent changes 10g starch into, and reinforcing agent changes 3g calcium sulfate into, and with Ce: V: Se: Sb in the precursor solution: the Bi mol ratio changes 6: 1: 1 into: 0.5: 0.15.Other reagent, addition and operation are all by embodiment 1, and the catalyst that obtains is used for the low temperature SCR denitration reaction, and reaction condition the results are shown in Table 1 with active.
Embodiment 6
Step by embodiment 1 is prepared, just when preparation powder catalyst, change tetrabutyl titanate into isopropyl titanate, isopropyl titanate, ethanol, each material molar ratio of water and manganese nitrate changes 1: 8: 3 into: 0.5, expanding agent changes the 7g polyethylene glycol into, and lubricant changes the 8mL polyacrylate into, and reinforcing agent changes the 7g carbon fiber into.Other reagent, addition and operation are all by embodiment 1, and the catalyst that obtains is used for the low temperature SCR denitration reaction, and reaction condition the results are shown in Table 1 with active.
Embodiment 7
Step by embodiment 1 is prepared, just when preparation powder catalyst, change manganese nitrate into manganese acetate, tetrabutyl titanate, ethanol, each material molar ratio of water and manganese acetate changes 1: 3: 2 into: 0.6, expanding agent changes the 5g active carbon into, and lubricant changes the 6mL polyacrylate into, and reinforcing agent changes the 8g carbon fiber into.Other reagent, addition and operation are all by embodiment 1, and the catalyst that obtains is used for the low temperature SCR denitration reaction, and reaction condition the results are shown in Table 1 with active.
Embodiment 8
Step by embodiment 1 is prepared, just when preparation powder catalyst, change manganese nitrate into manganese acetate, tetrabutyl titanate, ethanol, each material molar ratio of water and manganese acetate changes 1: 5: 5 into: 1, expanding agent changes the 10g active carbon into, and molding adhesive changes 800mL titanium glue into, and reinforcing agent changes 7g calcium sulfate into.With Ce: V: Se: Sb in the precursor solution: the Bi mol ratio changes 3: 2: 0.6 into: 0.6: 0.65.Other reagent, addition and operation are all by embodiment 1, and the catalyst that obtains is used for the low temperature SCR denitration reaction, and reaction condition the results are shown in Table 1 with active.
Embodiment 9
Step by embodiment 1 is prepared, just when preparation powder catalyst, change manganese nitrate into manganese acetate, tetrabutyl titanate, ethanol, each material molar ratio of water and manganese acetate changes 1: 10: 3 into: 0.4, expanding agent changes active carbon and each 5g of poly-oxireme into, and molding adhesive changes the 600mL polyacrylamide into.With Ce: V: Se: Sb in the precursor solution: the Bi mol ratio changes 8: 1: 0.8 into: 0.8: 1.Other reagent, addition and operation are all by embodiment 1, and the catalyst that obtains is used for the low temperature SCR denitration reaction, and reaction condition the results are shown in Table 1 with active.
Embodiment 10
Step by embodiment 1 is prepared, and just with Ce: V: Se: Sb in the precursor solution: the Bi mol ratio changes 7: 3: 0.5 into: 0.5: 0.15.Other reagent, addition and operation are all by embodiment 1, and the catalyst that obtains is used for the low temperature SCR denitration reaction, and reaction condition the results are shown in Table 1 with active.
Embodiment 11
Step by embodiment 1 is prepared, and just changes expanding agent into active carbon 3g, poly-oxireme 6g, and molding adhesive changes 1000mL titanium glue into, and reinforcing agent changes 8g calcium sulfate into.Change precursor solution into be made up of cerous nitrate, ammonium metavanadate, sodium selenite, nitric acid antimony, bismuth nitrate, ammonium borate and silester mixed solution, Ce in the solution: V: Se: Sb: Bi: P: the Si mol ratio is 2: 3: 0.5: 1: 0.05: 0.5: 0.05.Other reagent, addition and operation are all by embodiment 1, and the catalyst that obtains is used for the low temperature SCR denitration reaction, and reaction condition the results are shown in Table 1 with active.
Embodiment 12
Step by embodiment 1 is prepared, and just changes tetrabutyl titanate into isopropyl titanate, and lubricant changes the 8mL polyacrylamide into.Change precursor solution into be made up of cerous nitrate, ammonium metavanadate, sodium selenite, nitric acid antimony, bismuth nitrate, ammonium borate and silester mixed solution, Ce in the solution: V: Se: Sb: Bi: P: the Si mol ratio is 7: 1: 1: 0.5: 0.05: 0.5: 0.05.Other reagent, addition and operation are all by embodiment 1, and the catalyst that obtains is used for the low temperature SCR denitration reaction, and reaction condition the results are shown in Table 1 with active.
Embodiment 13
Step by embodiment 1 is prepared, and just changes manganese nitrate into manganese acetate, and expanding agent changes 8g starch into.Change precursor solution into be made up of cerous nitrate, ammonium metavanadate, sodium selenite, nitric acid antimony, bismuth nitrate, ammonium borate and silester mixed solution, Ce in the solution: V: Se: Sb: Bi: P: the Si mol ratio is 4: 2: 0.6: 0.6: 0.3: 0.3: 0.3.Other reagent, addition and operation are all by embodiment 1, and the catalyst that obtains is used for the low temperature SCR denitration reaction, and reaction condition the results are shown in Table 1 with active.
Table 1
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