CN102941083B - Medium/low-temperature core-shell denitration catalyst and preparation method and application thereof - Google Patents
Medium/low-temperature core-shell denitration catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a medium/low-temperature core-shell denitration catalyst and a preparation method and application thereof, belonging to the technical field of air pollution control. Main raw materials consist of a titanium-based nano tube, soluble salt of cerium and soluble salt of manganese, wherein a carrier shell of the catalyst is formed by the titanium-based nano tube, and an active nanoparticle core is formed by oxides of cerium and manganese. The molar ratio of the total amount of cerium and manganese to the amount of titanium is (0.02-0.12):1, the molar ratio of cerium to manganese is more than 0.5 or less than 0.25, and when the molar ratio of cerium to manganese is between 0.25 and 0.5, the catalyst has good activity in a medium-temperature zone, a low-temperature zone and a medium/low-temperature zone. The preparation method comprises the steps of soaking the titanium-based nano tube in an organic solvent, adding the soluble salt of cerium and the soluble salt of manganese, impregnating, drying and roasting, thereby obtaining the medium/low-temperature core-shell denitration catalyst. The catalyst has broad application prospects in treatment of waste gases with high contents of solid toxic components, such as exhaust gas of industrial furnaces, flue gas of power plants using biomass fuels and the like.
Description
Technical field
The present invention relates to technical field of air pollution control, be specifically related to medium/low-temperature core-shell denitration catalyst and preparation method thereof and application in one.
Background technology
Nitrogen oxide fixed discharge source, based on coal-burning boiler, glass kiln and cement furnace etc., is the key object that China's nitrogen oxide controls.SCR (SCR) denitration technology is most widely used in world wide, that occupation rate of market is the highest, operation is the most reliable and the most stable gas denitrifying technology.
Current most of SCR denitration device selects V
2o
5-WO
3/ TiO
2or V
2o
5-MoO
3/ TiO
2catalyst, this kind of catalytic component based on vanadium has active high, selective good advantage, but also have active temperature windows narrower (focusing mostly at 300 ~ 450 DEG C), easily because of the solid-state toxic poisoning such as potassium, calcium, sodium, magnesium, lead, the shortcomings such as poisonous solid waste (vanadium is poisonous) can be produced, limit its applying in treating tail gas fields such as cement kiln, glass furnace, biomass fuel power plant.Therefore, for the various defects of catalytic component based on vanadium, the novel non-catalytic component based on vanadium that exploitation has middle low temperature active is focus both domestic and external always.
In numerous novel non-vanadium base in low temperature catalyst, Mn oxide (Chinese patent 201010223099.3), cerium oxide (Chinese patent 200610165430.4) and ferriferous oxide (Chinese patent 200810112624.7) most study, be also expected most.But these catalyst exist easily because of shortcomings such as solid-state toxic poisoning or poor selectivity such as alkali metal/alkaline-earth metal in flue gas.
Have both at home and abroad at present and patent discloses various types of denitrating catalyst and preparation technology in a large number, but extremely lack the denitrating catalyst simultaneously possessing low temperature active in strong selectivity, strong anti-poisoning performance and excellence.
Summary of the invention
Primary and foremost purpose of the present invention is that the shortcoming overcoming prior art is with not enough, a kind of middle medium/low-temperature core-shell denitration catalyst with strong selectivity, strong anti-Poisoning, function admirable is provided, be applicable to the denitration of various stationary source, the waste gas pollution control and treatment particularly suitable high to solid-state poisonous component content such as industrial furnace tail gas (as cement kiln, glass furnace etc.) and biomass fuel power-plant flue gas (comprising waste incineration and generating electricity).
Another object of the present invention is to the preparation method that above-mentioned middle medium/low-temperature core-shell denitration catalyst is provided.
Another object of the present invention is the application providing above-mentioned middle medium/low-temperature core-shell denitration catalyst.
Object of the present invention is achieved through the following technical solutions:
Medium/low-temperature core-shell denitration catalyst in one, comprises carrier shell and active nano ion kernel; Described carrier shell is titanium-based nano pipe, and described active nano ion kernel is the oxide of cerium and the oxide (its structural representation as shown in Figure 1) of manganese; The oxide of described cerium and the oxide of manganese generate after the soluble-salt roasting by the soluble-salt of cerium and manganese.
The internal diameter of described titanium-based nano pipe is preferably 2 ~ 25nm, is one or more the combination in titanate nanotube, hydrogen titanate radical nanopipe or titania nanotube, obtains by hydro-thermal method or anodizing.
The soluble-salt of described cerium is preferably at least one in cerous nitrate, ammonium ceric nitrate, cerous sulfate, Cericammoniumsulfate and cerous acetate etc.
The soluble-salt of described manganese is preferably at least one in manganese nitrate, manganese carbonate, manganese acetate and manganese sulfate etc.
The soluble-salt of described cerium and the soluble-salt consumption of manganese calculate according to the mol ratio of titanium elements in Ce elements and manganese element and titanium-based nano pipe, and the mol ratio of Ce elements and manganese element sum of the two and titanium elements is preferably 0.02 ~ 1.2:1.
The cerium manganese element mol ratio of the soluble-salt of described cerium and the soluble-salt of manganese is preferably: middle warm area type > 0.5, low temperature zone type < 0.25, wide warm area type >=0.25 and≤0.5.Wherein the temperature range of middle warm area type is about 200 ~ 450 DEG C, and low temperature zone type temperature range is about 80 ~ 200 DEG C, and wide warm area type temperature range is about 120 ~ 420 DEG C.
The preparation method of above-mentioned middle medium/low-temperature core-shell denitration catalyst, comprises the steps:
(1) pretreatment of titanium-based nano pipe: titanium-based nano pipe is soaked more than 6 hours with organic solvent.
(2) preparation of medium/low-temperature core-shell denitration catalyst in: get a certain amount of pretreated titanium-based nano pipe, add the soluble salt solutions of cerium and the soluble salt solutions of manganese, the mol ratio of Ce elements and manganese element sum of the two and titanium elements is controlled at 0.02 ~ 1.2:1, and require to control cerium manganese element mol ratio according to warm area, flood 4 ~ 16 hours, then in 30 ~ 90 DEG C of oven dry, with temperature-programmed mode roasting 2 ~ 6 hours, obtain middle medium/low-temperature core-shell denitration catalyst.
Organic solvent described in step (1) is preferably acetone, ethanol or dimethylbenzene etc.
Immersion described in step (1) preferably soaks 6 ~ 36 hours at normal temperatures.
Dipping described in step (2) is preferably stirring at normal temperature dipping.
Temperature programming described in step (2) is preferably warming up to 300 ~ 460 DEG C with 5 ~ 25 DEG C/min.
The application of above-mentioned middle medium/low-temperature core-shell denitration catalyst in denitration.
Activity, the selective and heat endurance of medium/low-temperature core-shell denitration catalyst in can being improved further by interpolation co-catalyst and middle medium/low-temperature core-shell denitration catalyst coupling.
Described co-catalyst is preferably at least one in iron oxide, tungsten oxide and molybdenum oxide.
The principle that middle medium/low-temperature core-shell denitration catalyst provided by the invention is successfully prepared is: generally speaking, internal diameter is that the titanium-based nano pipe of 2 ~ 25nm has superpower capillary absorption ability, it is inner that solution spontaneously can enter titanium-based nano pipeline under capillary action, and be enriched in pipe in dry run.Therefore, if maintain the stability of titanium-based nano pipe tubular morphology, and ensure enough times of contact, it is inner that the soluble salt solutions of cerium and the soluble salt solutions of manganese just can enter titanium-based nano pipe, the soluble-salt of cerium and the soluble salts deposit of manganese are at pipe interior after drying, generate the oxide of cerium and the oxide of manganese after roasting.Organic solvent immersion treatment effectively can improve the decentralization between titanium-based nano pipe individuality, avoids the reunion between titanium-based nano pipe individuality, is conducive to the carrying out of capillary absorption process.Titanium-based nano pipe forms by nanometer sheet is curling, and high-temperature process, by the energy balance of the system of destruction, causes tubular structure to destroy, therefore needs sintering temperature to be strict controlled in less than 460 DEG C.
Middle medium/low-temperature core-shell denitration catalyst provided by the invention has the principle that is active and strong selectivity of low-temperature denitration in excellence: in nano core-shell system, due to special confinement effect and quantum effect, the growth of active nanoparticles suffers restraints, its size diminishes, contribute to generating more Donna rice grain defect and Lacking oxygen, this is significant to the raising of catalytic activity.In confinement space, the interaction between active nanoparticles and titanium-based nano pipe strengthens rapidly, and the catalytic reduction characteristic of active particle is by modulation, and its catalytic activity strengthens, and the selective of reaction also effectively strengthens.Visible, once the oxide of cerium and manganese enter titanium-based nano pipe pipe in confinement space, its catalytic activity and selectively all will effectively to strengthen.
Middle medium/low-temperature core-shell denitration catalyst provided by the invention has strong anti-toxic principle: solid-state noxious material completely cuts off outside tube wall by the tube wall of titanium-based nano pipe, make it cannot contact the active nanoparticles being positioned at pipe interior, avoid the toxic action of poisonous substance to active nanoparticles.In addition, partial-titanium based nanotube has stronger ion-exchange capacity, can be fixed between wall layers by the poisonous component of ionic state by ion-exchange, stops it to poison active nanoparticles.
The present invention has following advantage and effect relative to prior art:
(1) excellent anti-poisoning capability.Compared with various traditional graininess denitrating catalyst, middle medium/low-temperature core-shell denitration catalyst provided by the invention has excellent resistance to common solid-state noxious material in the flue gases such as potassium, sodium, magnesium, calcium, arsenic, lead, has broad application prospects in the waste gas pollution control and treatment that the solid-state poisonous component content such as industrial furnace tail gas (as cement kiln, glass furnace etc.) and biomass fuel power-plant flue gas (comprising waste incineration and generating electricity) are high.
(2) good selective.Compared with the identical active constituent catalyst reported with open source information, middle medium/low-temperature core-shell denitration catalyst provided by the invention is better selective, laughing gas (N when less than 300 DEG C in catalytic reaction
2o) content is extremely low.
(3) middle medium/low-temperature core-shell denitration catalyst preparation method provided by the invention is simply effective.By organic solvent immersion treatment titanium-based nano pipe, control bake out temperature, control roasting process and temperature, achieve maintenance titanium-based nano pipe tubular structure and stablize and active particle be distributed in the object of titanium-based nano pipeline inside.
Accompanying drawing explanation
Fig. 1 is the structure chart of middle medium/low-temperature core-shell denitration catalyst.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
The pretreatment of titanium-based nano pipe: titanium-based nano pipe is the hydrogen titanate radical nanopipe that highly basic hydro-thermal method obtains, and internal diameter is 3 ~ 5nm, and external diameter is 7 ~ 15nm, and length is 50 ~ 300nm; Titanium-based nano pipe is inserted soak at room temperature 12h in excessive propanone solution, for subsequent use after suction filtration.
The preparation of the hud typed denitrating catalyst of wide temperature: get the pretreated hydrogen titanate radical nanopipe of 2g, toward wherein adding manganese nitrate solution, the 0.7583g cerous nitrate (by the water-soluble solution of 50mL) that 2.5mL mass fraction is 50%, dipping 12h is stirred under normal temperature, then dry at 60 DEG C, obtain the hud typed denitrating catalyst of wide temperature with 5 DEG C of ramp to 400 per minute DEG C roasting 2h.
The activity of catalyst and selectivity test: the catalyst prepared by 0.5g is put into fixed bed reactors and carried out activity and selectivity test, test reaction temperature is 80 ~ 450 DEG C, air speed is about 100000h
-1, simulated flue gas is by N
2, O
2, NO and NH
3composition, wherein NO 700ppm, NH
3700ppm, O
23 ~ 5%(percent by volume), N
2for carrier gas.When reaction temperature is 140 ~ 370 DEG C, NO conversion ratio is stabilized in more than 85%, when reaction temperature is lower than 300 DEG C, and N
2the growing amount of O is less than 10ppm.
The anticalcium poisoning performance test of catalyst: load 0.31g calcium nitrate in the catalyst prepared to 3g by dry pigmentation, after 400 DEG C of calcination 3h, test activity again, when reaction temperature is 140 ~ 370 DEG C, NO conversion ratio is stabilized in more than 80%, when reaction temperature is lower than 300 DEG C, N
2the growing amount of O is less than 10ppm.
Embodiment 2
The pretreatment of titanium-based nano pipe: titanium-based nano pipe is the sodium titanate nanotubes that highly basic hydro-thermal method obtains, and internal diameter is 3 ~ 5nm, and external diameter is 7 ~ 15nm, and length is 50 ~ 300nm; Titanium-based nano pipe is inserted soak at room temperature 12h in excessive amount of ethanol solution, for subsequent use after suction filtration.
The preparation of medium/low-temperature core-shell denitration catalyst: get the pretreated sodium titanate nanotubes of 2g, toward wherein adding manganese nitrate solution, the 0.06g ammonium ceric nitrate (by the water-soluble solution of 50mL) that 2.5mL mass fraction is 50%, dipping 4h is stirred under normal temperature, then dry at 60 DEG C, obtain medium/low-temperature core-shell denitration catalyst with 10 DEG C of ramp to 400 per minute DEG C roasting 4h.
The activity of catalyst and selectivity test: the catalyst prepared by 0.5g is put into fixed bed reactors and carried out activity and selectivity test, test reaction temperature is 80 ~ 450 DEG C, air speed is about 100000h
-1, simulated flue gas is by N
2, O
2, NO and NH
3composition, wherein NO 700ppm, NH
3700ppm, O
23 ~ 5%(percent by volume), N
2for carrier gas.When reaction temperature is 100 ~ 200 DEG C, NO conversion ratio is stabilized in more than 85%, N
2the growing amount of O is less than 10ppm.
Resistant to potassium poisoning performance is tested: load 0.14g potassium nitrate in the catalyst prepared to 3g by infusion process, after 400 DEG C of calcination 4h, test activity again, when reaction temperature is 100 ~ 250 DEG C, NO conversion ratio is stabilized in more than 80%, N
2the growing amount of O is less than 10ppm.
Embodiment 3
The pretreatment of titanium-based nano pipe: titanium-based nano pipe is the sodium titanate nanotubes that highly basic hydro-thermal method obtains, and internal diameter is 3 ~ 5nm, and external diameter is 7 ~ 15nm, and length is 50 ~ 300nm; Titanium-based nano pipe is inserted soak at room temperature 6h in excessive xylene solution, for subsequent use after suction filtration.
The preparation of the hud typed denitrating catalyst of middle temperature: get the pretreated sodium titanate nanotubes of 2g, toward wherein adding 0.12g manganese sulfate (by the water-soluble solution of 25mL), 0.51g cerous sulfate (by the water-soluble solution of 25mL), dipping 16h is stirred under normal temperature, then dry at 80 DEG C, obtain the hud typed denitrating catalyst of middle temperature with 15 DEG C of ramp to 450 per minute DEG C roasting 5h.
The activity of catalyst and selectivity test: the catalyst prepared by 0.5g is put into fixed bed reactors and carried out activity and selectivity test, test reaction temperature is 80 ~ 450 DEG C, air speed is about 100000h
-1, simulated flue gas is by N
2, O
2, NO and NH
3composition, wherein NO 700ppm, NH
3700ppm, O
23 ~ 5%(percent by volume), N
2for carrier gas.When reaction temperature is 220 ~ 450 DEG C, NO conversion ratio is stabilized in more than 85%, when reaction temperature is lower than 430 DEG C, and N
2the growing amount of O is less than 10ppm.
Anti-sodium poisoning performance test: load 0.11g sodium nitrate in the catalyst prepared to 3g by infusion process, after 450 DEG C of calcination 4h, test activity again, when reaction temperature is 220 ~ 450 DEG C, NO conversion ratio is stabilized in more than 80%, when reaction temperature is lower than 430 DEG C, N
2the growing amount of O is less than 10ppm.
Embodiment 4
The pretreatment of titanium-based nano pipe: titanium-based nano pipe is the titania nanotube that anodizing obtains, and internal diameter is about 20nm, and length is 1 ~ 7 micron; Titanium-based nano pipe is inserted soak at room temperature 24h in excessive amount of ethanol solution, for subsequent use after suction filtration.
The preparation of the hud typed denitrating catalyst of wide temperature: get the pretreated titania nanotube of 2g, dipping 16h is stirred under wherein adding 0.5g manganese carbonate (by the water-soluble solution of 25mL), 1.197g Cericammoniumsulfate (by the water-soluble solution of 25mL) normal temperature, add 2.37g wolframic acid ammonia and 1.23g ferrous sulfate again, dipping 4h is stirred under normal temperature, then dry at 90 DEG C, obtain the hud typed denitrating catalyst of wide temperature with 25 DEG C of ramp to 450 per minute DEG C roasting 6h.
The activity of catalyst and selectivity test: the catalyst prepared by 0.5g is put into fixed bed reactors and carried out activity and selectivity test, test reaction temperature is 80 ~ 450 DEG C, air speed is about 100000h
-1, simulated flue gas is by N
2, O
2, NO and NH
3composition, wherein NO 700ppm, NH
3700ppm, O
23 ~ 5%(percent by volume), N
2for carrier gas.When reaction temperature is 120 ~ 420 DEG C, NO conversion ratio is stabilized in more than 85%, when reaction temperature is lower than 310 DEG C, and N
2the growing amount of O is less than 5ppm.
Anti-magnesium poisoning performance test: load 0.2g magnesium nitrate in the catalyst prepared to 3g by dry pigmentation, after 450 DEG C of calcination 4h, test activity again, when reaction temperature is 150 ~ 350 DEG C, NO conversion ratio is stabilized in more than 80%, when reaction temperature is lower than 310 DEG C, N
2the growing amount of O is less than 5ppm.
Embodiment 5
The pretreatment of titanium-based nano pipe: titanium-based nano pipe is the titania nanotube that anodizing obtains, and internal diameter is about 20nm, and length is 1 ~ 7 micron; Titanium-based nano pipe is inserted in excessive propanone solution and under normal temperature, soaks 24h, for subsequent use after suction filtration.
The preparation of the hud typed denitrating catalyst of middle temperature: get the pretreated titania nanotube of 3.046g, toward wherein adding manganese nitrate solution, the 0.27g cerous nitrate (by the water-soluble solution of 50mL) that 0.05mL mass fraction is 50%, dipping 12h is stirred under normal temperature, then dry at 80 DEG C, obtain the hud typed denitrating catalyst of middle temperature with 10 DEG C of ramp to 300 per minute DEG C roasting 5h.
The activity of catalyst and selectivity test: the catalyst prepared by 0.5g is put into fixed bed reactors and carried out activity and selectivity test, test reaction temperature is 80 ~ 450 DEG C, air speed is about 100000h
-1, simulated flue gas is by N
2, O
2, NO and NH
3composition, wherein NO 700ppm, NH
3700ppm, O
23 ~ 5%(percent by volume), N
2for carrier gas.When reaction temperature is 230 ~ 430 DEG C, NO conversion ratio is stabilized in more than 85%, when reaction temperature is lower than 400 DEG C, and N
2the growing amount of O is less than 10ppm.
Resistance to leaded fuel is tested: load 0.41g lead acetate in warm hud typed denitrating catalyst in being prepared to 3g by dry pigmentation, after 400 DEG C of calcination 3h, test activity again, when reaction temperature is 230 ~ 430 DEG C, NO conversion ratio is stabilized in more than 80%, when reaction temperature is lower than 400 DEG C, N
2the growing amount of O is less than 10ppm.
Embodiment 6
The pretreatment of titanium-based nano pipe: titanium-based nano pipe is the hydrogen titanate radical nanopipe that highly basic hydro-thermal method obtains, and internal diameter is 3 ~ 5nm, and external diameter is 7 ~ 15nm, and length is 50 ~ 300nm; Titanium-based nano pipe is inserted in excessive xylene solution and soaks 12h, for subsequent use after suction filtration.
The preparation of the hud typed denitrating catalyst of middle temperature: get the pretreated hydrogen titanate radical nanopipe of 2g, toward wherein adding 1.2g manganese acetate (by the water-soluble solution of 20mL), 0.3g ammonium ceric nitrate (by the water-soluble solution of 15mL), 0.3g cerous acetate (by the water-soluble solution of 15mL), dipping 12h is stirred under normal temperature, add 1.5g ammonium molybdate again, dipping 4h is stirred under normal temperature, then dry at 80 DEG C, obtain the hud typed denitrating catalyst of wide temperature with 15 DEG C of ramp to 350 per minute DEG C roasting 4h.
The activity of catalyst and selectivity test: the catalyst prepared by 0.5g is put into fixed bed reactors and carried out activity and selectivity test, test reaction temperature is 80 ~ 450 DEG C, air speed is about 100000h
-1, simulated flue gas is by N
2, O
2, NO and NH
3composition, wherein NO 700ppm, NH
3700ppm, O
23 ~ 5%(percent by volume), N
2for carrier gas.When reaction temperature is 120 ~ 400 DEG C, NO conversion ratio is stabilized in more than 85%, when reaction temperature is lower than 360 DEG C, and N
2the growing amount of O is less than 5ppm.
Anti-sodium poisoning performance test: load 0.11g sodium nitrate in the catalyst prepared to 3g by infusion process, after 350 DEG C of calcination 4h, test activity again, when reaction temperature is 120 ~ 400 DEG C, NO conversion ratio is stabilized in more than 85%, when reaction temperature is lower than 360 DEG C, N
2the growing amount of O is less than 5ppm.
Embodiment 7
The pretreatment of titanium-based nano pipe: titanium-based nano pipe is the potassium titanate nanotube that highly basic hydro-thermal method obtains, and internal diameter is 3 ~ 5nm, and external diameter is 7 ~ 15nm, and length is 50 ~ 300nm; Titanium-based nano pipe is inserted soak at room temperature 36h in excessive amount of ethanol solution, for subsequent use after suction filtration.
The preparation of medium/low-temperature core-shell denitration catalyst: get the pretreated titanium nanotube of 2g, toward wherein adding manganese nitrate solution, 3.12g manganese carbonate (by the water-soluble solution of 17mL), the 0.06g cerous nitrate (by the water-soluble solution of 25mL) that 8mL mass fraction is 50%, dipping 12h is stirred under normal temperature, then dry at 30 DEG C, obtain medium/low-temperature core-shell denitration catalyst with 10 DEG C of ramp to 400 per minute DEG C roasting 6h.
The activity of catalyst and selectivity test: the catalyst prepared by 0.5g is put into fixed bed reactors and carried out activity and selectivity test, test reaction temperature is 80 ~ 450 DEG C, air speed is about 100000h
-1, simulated flue gas is by N
2, O
2, NO and NH
3composition, wherein NO 700ppm, NH
3700ppm, O
23 ~ 5%(percent by volume), N
2for carrier gas.When reaction temperature is 80 ~ 200 DEG C, NO conversion ratio is stabilized in more than 85%, N
2the growing amount of O is less than 10ppm.
Resistant to potassium poisoning performance is tested: load 0.14g potassium nitrate in the catalyst prepared to 3g by dry pigmentation, after 400 DEG C of calcination 4h, test activity again, when reaction temperature is 80 ~ 200 DEG C, NO conversion ratio is stabilized in more than 80%, N
2the growing amount of O is less than 10ppm.
In above-described embodiment the molal quantity of titanium, cerium, manganese element and corresponding mol ratio as shown in table 1:
The molal quantity of table 1. titanium, cerium, manganese element and corresponding mol ratio
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (6)
1. a medium/low-temperature core-shell denitration catalyst in, is characterized in that comprising carrier shell and active nanoparticles kernel; Described carrier shell is titanium-based nano pipe, and described active nanoparticles kernel is the oxide of cerium and the oxide of manganese; The oxide of described cerium and the oxide of manganese generate after the soluble-salt roasting by the soluble-salt of cerium and manganese; The cerium manganese element mol ratio of the soluble-salt of described cerium and the soluble-salt of manganese is: middle warm area type > 0.5, low temperature zone type < 0.25, wide warm area type >=0.25 and≤0.5; Wherein, the temperature range of middle warm area type is 200 ~ 450 DEG C, and low temperature zone type temperature range is 80 ~ 200 DEG C, and wide warm area type temperature range is 120 ~ 420 DEG C; The internal diameter of described titanium-based nano pipe is 2 ~ 25nm.
2. middle medium/low-temperature core-shell denitration catalyst according to claim 1, is characterized in that:
Described titanium-based nano pipe is one or more the combination in titanate nanotube, hydrogen titanate radical nanopipe or titania nanotube.
3. middle medium/low-temperature core-shell denitration catalyst according to claim 1, is characterized in that:
The soluble-salt of described cerium is at least one in cerous nitrate, ammonium ceric nitrate, cerous sulfate, Cericammoniumsulfate and cerous acetate;
The soluble-salt of described manganese is at least one in manganese nitrate, manganese carbonate, manganese acetate and manganese sulfate.
4. middle medium/low-temperature core-shell denitration catalyst according to claim 1, it is characterized in that: the soluble-salt of described cerium and the soluble-salt consumption of manganese calculate according to the mol ratio of titanium elements in Ce elements and manganese element and titanium-based nano pipe, and the mol ratio of Ce elements and manganese element sum of the two and titanium elements is 0.02 ~ 0.12:1.
5. the preparation method of the middle medium/low-temperature core-shell denitration catalyst described in any one of Claims 1 to 4, is characterized in that comprising the steps:
(1) pretreatment of titanium-based nano pipe: titanium-based nano pipe is soaked more than 6 hours with organic solvent;
(2) preparation of medium/low-temperature core-shell denitration catalyst in: get a certain amount of pretreated titanium-based nano pipe, add the soluble salt solutions of cerium and the soluble salt solutions of manganese, the mol ratio of Ce elements and manganese element sum of the two and titanium elements is controlled at 0.02 ~ 0.12:1, and require to control cerium manganese element mol ratio according to warm area, flood 4 ~ 16 hours, then in 30 ~ 90 DEG C of oven dry, with temperature-programmed mode roasting 2 ~ 6 hours, obtain middle medium/low-temperature core-shell denitration catalyst.
6. the preparation method of middle medium/low-temperature core-shell denitration catalyst according to claim 5, is characterized in that:
Organic solvent described in step (1) is acetone, ethanol or dimethylbenzene;
Immersion described in step (1) is for soak 6 ~ 36 hours at normal temperatures;
Dipping described in step (2) is stirring at normal temperature dipping;
Temperature programming described in step (2) is for be warming up to 300 ~ 460 DEG C with 5 ~ 25 DEG C/min.
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