CN102941083A - 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 the air pollution control technique field, be specifically related to hud typed denitrating catalyst of a kind of middle low temperature and preparation method thereof and application.
Background technology
Nitrogen oxide fixed discharge source is the key object of China's nitrogen oxide control take coal-burning boiler, glass kiln and cement furnace etc. as main.SCR (SCR) denitration technology is gas denitrifying technology most widely used in the world wide, that occupation rate of market is the highest, operation is the most reliable and the most stable.
Most SCR denitrification apparatus is selected V
2O
5-WO
3/ TiO
2Or V
2O
5-MoO
3/ TiO
2Catalyst, this class catalytic component based on vanadium has advantages of active high, selective good, but also have active temperature windows narrower (focusing mostly at 300～450 ℃), easily because of the solid-state toxic poisoning such as potassium, calcium, sodium, magnesium, lead, can produce the shortcoming such as poisonous solid waste (vanadium is poisonous), limited its applying in treating tail gas fields such as cement kiln, glass furnace, biomass fuel power plant.Therefore, for the various defectives 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 the low temperature catalyst, Mn oxide (Chinese patent 201010223099.3), cerium oxide (Chinese patent 200610165430.4) and ferriferous oxide (Chinese patent 200810112624.7) most study also are expected most in numerous novel non-vanadium bases.Yet these catalyst exist easily because of shortcomings such as the solid-state toxic poisoning such as alkali metal/alkaline-earth metal in the flue gas or poor selectivity.
Existing a large amount of patents disclose various types of denitrating catalysts and preparation technology both at home and abroad at present, but extremely lack the denitrating catalyst that possesses simultaneously low temperature active in strong selectivity, strong anti-poisoning performance and the excellence.
Summary of the invention
Primary and foremost purpose of the present invention is to overcome the shortcoming of prior art with not enough, a kind of hud typed denitrating catalyst of middle low temperature with strong selectivity, strong anti-Poisoning, function admirable is provided, be applicable to the denitration of various stationary sources, to high waste gas pollution control and treatment particularly suitables of solid-state poisonous component content such as industrial furnace tail gas (such 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 provide the preparation method of the hud typed denitrating catalyst of above-mentioned middle low temperature.
A further object of the present invention is to provide the application of the hud typed denitrating catalyst of above-mentioned middle low temperature.
Purpose of the present invention is achieved through the following technical solutions:
The hud typed denitrating catalyst of a kind of middle low temperature comprises carrier shell and active nano ion kernel; Described carrier shell is the titanium-based nano pipe, and described active nano ion kernel is the oxide of cerium and the oxide of manganese (its structural representation as shown in Figure 1); The oxide of described cerium and the oxide of manganese are to 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, and one or more the combination in titanate nanotube, hydrogen titanate radical nanopipe or the titania nanotube can make by hydro-thermal method or anodizing.
The soluble-salt of described cerium is preferably at least a in cerous nitrate, ammonium ceric nitrate, cerous sulfate, Cericammoniumsulfate and the cerous acetate etc.
The soluble-salt of described manganese is preferably at least a in manganese nitrate, manganese carbonate, manganese acetate and the manganese sulfate etc.
The soluble-salt consumption of the soluble-salt of described cerium and manganese calculates according to the mol ratio of titanium elements in Ce elements and manganese element and the 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 space 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 ℃, and low-temperature space type temperature range is about 80～200 ℃, and wide warm area type temperature range is about 120～420 ℃.
The preparation method of the hud typed denitrating catalyst of above-mentioned middle low temperature comprises the steps:
(1) preliminary treatment of titanium-based nano pipe: soak the titanium-based nano pipe more than 6 hours with organic solvent.
(2) preparation of the hud typed denitrating catalyst of low temperature in: get a certain amount of pretreated titanium-based nano pipe, the soluble-salt solution that adds cerium and the soluble-salt solution 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 according to warm area requirement control cerium manganese element mol ratio, flooded 4～16 hours, then in 30～90 ℃ of oven dry, with temperature-programmed mode roasting 2～6 hours, obtain the hud typed denitrating catalyst of middle low temperature.
Organic solvent described in the step (1) is preferably acetone, ethanol or dimethylbenzene etc.
Immersion described in the step (1) is preferably soaks 6～36 hours at normal temperatures.
Dipping described in the step (2) is preferably the stirring at normal temperature dipping.
Temperature programming described in the step (2) is preferably with 5～25 ℃/min and is warming up to 300～460 ℃.
The application of the hud typed denitrating catalyst of above-mentioned middle low temperature in denitration.
By add co-catalyst and the hud typed denitrating catalyst coupling of middle low temperature can further improve in the activity, selectively and heat endurance of the hud typed denitrating catalyst of low temperature.
Described co-catalyst is preferably at least a in iron oxide, tungsten oxide and the molybdenum oxide.
The principle that the hud typed denitrating catalyst of middle low temperature provided by the invention successfully prepares is: generally speaking, internal diameter is that the titanium-based nano pipe of 2～25nm has superpower capillary absorption ability, solution can spontaneously enter the titanium-based nano pipeline under capillary action inner, and is enriched in the pipe in dry run.Therefore, if keep the stability of titanium-based nano pipe tubulose pattern, and guarantee enough times of contact, it is inner that the soluble-salt solution of cerium and the soluble-salt solution of manganese just can enter the titanium-based nano pipe, the soluble-salt of the soluble-salt of cerium and manganese is deposited on pipe interior after drying, generates the oxide of cerium and the oxide of manganese after roasting.But the decentralization between organic solvent immersion treatment Effective Raise titanium-based nano pipe individuality is avoided the reunion between titanium-based nano pipe individuality, is conducive to the carrying out of capillary absorption process.The titanium-based nano pipe forms by nanometer sheet is curling, and high-temperature process will be destroyed the energy balance of system, causes tubular structure to destroy, and therefore needs sintering temperature is strict controlled in below 460 ℃.
The hud typed denitrating catalyst of middle low temperature provided by the invention has the principle active and strong selectivity of low-temperature denitration in the excellence: in the nano core-shell system, because special confinement effect and quantum effect, the growth of active nano particle suffers restraints, its size decreases, help to generate more Donna rice grain defective and oxygen room, this raising to catalytic activity is significant.In confinement space, the interaction between active nano particle and titanium-based nano pipe strengthens rapidly, and the catalytic reduction characteristic of active particle is by modulation, and its catalytic activity strengthens, the selectively also effectively enhancing of reaction.As seen, in case the oxide of cerium and manganese enters confinement space in the pipe of titanium-based nano pipe, its catalytic activity and selectively all will effectively strengthening.
The hud typed denitrating catalyst of middle low temperature provided by the invention has strong anti-toxic principle: the tube wall of titanium-based nano pipe completely cuts off solid-state noxious material outside tube wall, make it can't contact the active nano particle that is positioned at pipe interior, avoided the toxic action of poisonous substance to the active nano particle.In addition, the partial-titanium based nanotube has stronger ion-exchange capacity, the poisonous component of ionic state can be fixed between wall layers by ion-exchange, stops it to poison the active nano particle.
The present invention has following advantage and effect with respect to prior art:
(1) excellent anti-poisoning capability.Compare with various traditional graininess denitrating catalysts, the hud typed denitrating catalyst of middle low temperature 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 high waste gas pollution control and treatment of the solid-state poisonous component content such as industrial furnace tail gas (such as cement kiln, glass furnace etc.) and biomass fuel power-plant flue gas (comprising waste incineration and generating electricity).
(2) good selective.Compare with the identical active constituent catalyst of open source information report, the hud typed denitrating catalyst of middle low temperature provided by the invention is selectively better, laughing gas (N below 300 ℃ time the in the catalytic reaction
2O) content is extremely low.
(3) the hud typed denitrating catalyst preparation method of middle low temperature 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, realized keeping the purpose that titanium-based nano pipeline inside is stablized and active particle is distributed in to titanium-based nano pipe tubular structure.
Description of drawings
Fig. 1 is the structure chart of the hud typed denitrating catalyst of middle low temperature.
The specific embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited to this.
Embodiment 1
The preliminary treatment of titanium-based nano pipe: the titanium-based nano pipe is the hydrogen titanate radical nanopipe that the highly basic hydro-thermal method makes, and internal diameter is 3～5nm, and external diameter is 7～15nm, and length is 50～300nm; The titanium-based nano pipe is inserted soak at room temperature 12h in the excessive propanone solution, for subsequent use behind the suction filtration.
The preparation of the hud typed denitrating catalyst of wide temperature: get the pretreated hydrogen titanate radical nanopipe of 2g, be 50% manganese nitrate solution, 0.7583g cerous nitrate (with the water-soluble solution of 50mL) toward wherein adding the 2.5mL mass fraction, stir dipping 12h under the normal temperature, then 60 ℃ of lower oven dry are warming up to 400 ℃ of roasting 2h with the speed of 5 ℃ of per minutes and obtain the hud typed denitrating catalyst of wide temperature.
The activity of catalyst and selectivity test: the catalyst of 0.5g preparation is put into fixed bed reactors carry out the activity and selectivity test, the test reaction temperature is that 80～450 ℃, air speed are about 100000h
-1, simulated flue gas is by N
2, O
2, NO and NH
3Form NO 700ppm wherein, NH
3700ppm, O
23～5%(percent by volume), N
2Be carrier gas.When reaction temperature was 140～370 ℃, the NO conversion ratio was stabilized in more than 85%, when reaction temperature is lower than 300 ℃, and N
2The growing amount of O is less than 10ppm.
The anticalcium poisoning performance of catalyst test: by dry pigmentation load 0.31g calcium nitrate in the catalyst of 3g preparation, test is active again behind 400 ℃ of calcination 3h, and when reaction temperature was 140～370 ℃, the NO conversion ratio was stabilized in more than 80%, when reaction temperature is lower than 300 ℃, N
2The growing amount of O is less than 10ppm.
Embodiment 2
The preliminary treatment of titanium-based nano pipe: the titanium-based nano pipe is the sodium titanate nanotubes that the highly basic hydro-thermal method makes, and internal diameter is 3～5nm, and external diameter is 7～15nm, and length is 50～300nm; The titanium-based nano pipe is inserted soak at room temperature 12h in the excess ethyl alcohol solution, for subsequent use behind the suction filtration.
The preparation of the hud typed denitrating catalyst of low temperature: get the pretreated sodium titanate nanotubes of 2g, be 50% manganese nitrate solution, 0.06g ammonium ceric nitrate (with the water-soluble solution of 50mL) toward wherein adding the 2.5mL mass fraction, stir dipping 4h under the normal temperature, then 60 ℃ of lower oven dry are warming up to 400 ℃ of roasting 4h with the speed of 10 ℃ of per minutes and obtain the hud typed denitrating catalyst of low temperature.
The activity of catalyst and selectivity test: the catalyst of 0.5g preparation is put into fixed bed reactors carry out the activity and selectivity test, the test reaction temperature is that 80～450 ℃, air speed are about 100000h
-1, simulated flue gas is by N
2, O
2, NO and NH
3Form NO 700ppm wherein, NH
3700ppm, O
23～5%(percent by volume), N
2Be carrier gas.When reaction temperature was 100～200 ℃, the NO conversion ratio was stabilized in more than 85%, N
2The growing amount of O is less than 10ppm.
Anti-potassium intoxication performance test: by infusion process load 0.14g potassium nitrate in the catalyst of 3g preparation, test is active again behind 400 ℃ of calcination 4h, and when reaction temperature was 100～250 ℃, the NO conversion ratio was stabilized in more than 80%, N
2The growing amount of O is less than 10ppm.
Embodiment 3
The preliminary treatment of titanium-based nano pipe: the titanium-based nano pipe is the sodium titanate nanotubes that the highly basic hydro-thermal method makes, and internal diameter is 3～5nm, and external diameter is 7～15nm, and length is 50～300nm; The titanium-based nano pipe is inserted soak at room temperature 6h in the excessive xylene solution, for subsequent use behind the 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 (with the water-soluble solution of 25mL), 0.51g cerous sulfate (with the water-soluble solution of 25mL), stir dipping 16h under the normal temperature, then 80 ℃ of lower oven dry are warming up to 450 ℃ of roasting 5h with the speed of 15 ℃ of per minutes and obtain the hud typed denitrating catalyst of middle temperature.
The activity of catalyst and selectivity test: the catalyst of 0.5g preparation is put into fixed bed reactors carry out the activity and selectivity test, the test reaction temperature is that 80～450 ℃, air speed are about 100000h
-1, simulated flue gas is by N
2, O
2, NO and NH
3Form NO 700ppm wherein, NH
3700ppm, O
23～5%(percent by volume), N
2Be carrier gas.When reaction temperature was 220～450 ℃, the NO conversion ratio was stabilized in more than 85%, when reaction temperature is lower than 430 ℃, and N
2The growing amount of O is less than 10ppm.
The test of anti-sodium poisoning performance: by infusion process load 0.11g sodium nitrate in the catalyst of 3g preparation, test is active again behind 450 ℃ of calcination 4h, and when reaction temperature was 220～450 ℃, the NO conversion ratio was stabilized in more than 80%, when reaction temperature is lower than 430 ℃, and N
2The growing amount of O is less than 10ppm.
Embodiment 4
The preliminary treatment of titanium-based nano pipe: the titanium-based nano pipe is the titania nanotube that anodizing makes, and internal diameter is about 20nm, and length is 1～7 micron; The titanium-based nano pipe is inserted soak at room temperature 24h in the excess ethyl alcohol solution, for subsequent use behind the suction filtration.
The preparation of the hud typed denitrating catalyst of wide temperature: get the pretreated titania nanotube of 2g, stir dipping 16h toward wherein adding under 0.5g manganese carbonate (with the water-soluble solution of 25mL), 1.197g Cericammoniumsulfate (with the water-soluble solution of the 25mL) normal temperature, add again 2.37g wolframic acid ammonia and 1.23g ferrous sulfate, stir dipping 4h under the normal temperature, then 90 ℃ of lower oven dry are warming up to 450 ℃ of roasting 6h with the speed of 25 ℃ of per minutes and obtain the hud typed denitrating catalyst of wide temperature.
The activity of catalyst and selectivity test: the catalyst of 0.5g preparation is put into fixed bed reactors carry out the activity and selectivity test, the test reaction temperature is that 80～450 ℃, air speed are about 100000h
-1, simulated flue gas is by N
2, O
2, NO and NH
3Form NO 700ppm wherein, NH
3700ppm, O
23～5%(percent by volume), N
2Be carrier gas.When reaction temperature was 120～420 ℃, the NO conversion ratio was stabilized in more than 85%, when reaction temperature is lower than 310 ℃, and N
2The growing amount of O is less than 5ppm.
The test of anti-magnesium poisoning performance: by dry pigmentation load 0.2g magnesium nitrate in the catalyst of 3g preparation, test is active again behind 450 ℃ of calcination 4h, and when reaction temperature was 150～350 ℃, the NO conversion ratio was stabilized in more than 80%, when reaction temperature is lower than 310 ℃, and N
2The growing amount of O is less than 5ppm.
Embodiment 5
The preliminary treatment of titanium-based nano pipe: the titanium-based nano pipe is the titania nanotube that anodizing makes, and internal diameter is about 20nm, and length is 1～7 micron; The titanium-based nano pipe inserted in the excessive propanone solution soak 24h under the normal temperature, for subsequent use behind the suction filtration.
The preparation of the hud typed denitrating catalyst of middle temperature: get the pretreated titania nanotube of 3.046g, be 50% manganese nitrate solution, 0.27g cerous nitrate (with the water-soluble solution of 50mL) toward wherein adding the 0.05mL mass fraction, stir dipping 12h under the normal temperature, then 80 ℃ of lower oven dry are warming up to 300 ℃ of roasting 5h with the speed of 10 ℃ of per minutes and obtain the hud typed denitrating catalyst of middle temperature.
The activity of catalyst and selectivity test: the catalyst of 0.5g preparation is put into fixed bed reactors carry out the activity and selectivity test, the test reaction temperature is that 80～450 ℃, air speed are about 100000h
-1, simulated flue gas is by N
2, O
2, NO and NH
3Form NO 700ppm wherein, NH
3700ppm, O
23～5%(percent by volume), N
2Be carrier gas.When reaction temperature was 230～430 ℃, the NO conversion ratio was stabilized in more than 85%, when reaction temperature is lower than 400 ℃, and N
2The growing amount of O is less than 10ppm.
Anti-lead poisoning performance test: by dry pigmentation load 0.41g lead acetate in the hud typed denitrating catalyst of middle temperature of 3g preparation, test is active again behind 400 ℃ of calcination 3h, and when reaction temperature was 230～430 ℃, the NO conversion ratio was stabilized in more than 80%, when reaction temperature is lower than 400 ℃, N
2The growing amount of O is less than 10ppm.
Embodiment 6
The preliminary treatment of titanium-based nano pipe: the titanium-based nano pipe is the hydrogen titanate radical nanopipe that the highly basic hydro-thermal method makes, and internal diameter is 3～5nm, and external diameter is 7～15nm, and length is 50～300nm; The titanium-based nano pipe inserted in the excessive xylene solution soak 12h, for subsequent use behind the 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 (with the water-soluble solution of 20mL), 0.3g ammonium ceric nitrate (with the water-soluble solution of 15mL), 0.3g cerous acetate (with the water-soluble solution of 15mL), stir dipping 12h under the normal temperature, add again the 1.5g ammonium molybdate, stir dipping 4h under the normal temperature, then 80 ℃ of lower oven dry are warming up to 350 ℃ of roasting 4h with the speed of 15 ℃ of per minutes and obtain the hud typed denitrating catalyst of wide temperature.
The activity of catalyst and selectivity test: the catalyst of 0.5g preparation is put into fixed bed reactors carry out the activity and selectivity test, the test reaction temperature is that 80～450 ℃, air speed are about 100000h
-1, simulated flue gas is by N
2, O
2, NO and NH
3Form NO 700ppm wherein, NH
3700ppm, O
23～5%(percent by volume), N
2Be carrier gas.When reaction temperature was 120～400 ℃, the NO conversion ratio was stabilized in more than 85%, when reaction temperature is lower than 360 ℃, and N
2The growing amount of O is less than 5ppm.
The test of anti-sodium poisoning performance: by infusion process load 0.11g sodium nitrate in the catalyst of 3g preparation, test is active again behind 350 ℃ of calcination 4h, and when reaction temperature was 120～400 ℃, the NO conversion ratio was stabilized in more than 85%, when reaction temperature is lower than 360 ℃, and N
2The growing amount of O is less than 5ppm.
Embodiment 7
The preliminary treatment of titanium-based nano pipe: the titanium-based nano pipe is the potassium titanate nanotube that the highly basic hydro-thermal method makes, and internal diameter is 3～5nm, and external diameter is 7～15nm, and length is 50～300nm; The titanium-based nano pipe is inserted soak at room temperature 36h in the excess ethyl alcohol solution, for subsequent use behind the suction filtration.
The preparation of the hud typed denitrating catalyst of low temperature: get the pretreated titanium nanotube of 2g, be 50% manganese nitrate solution, 3.12g manganese carbonate (with the water-soluble solution of 17mL), 0.06g cerous nitrate (with the water-soluble solution of 25mL) toward wherein adding the 8mL mass fraction, stir dipping 12h under the normal temperature, then 30 ℃ of lower oven dry are warming up to 400 ℃ of roasting 6h with the speed of 10 ℃ of per minutes and obtain the hud typed denitrating catalyst of low temperature.
The activity of catalyst and selectivity test: the catalyst of 0.5g preparation is put into fixed bed reactors carry out the activity and selectivity test, the test reaction temperature is that 80～450 ℃, air speed are about 100000h
-1, simulated flue gas is by N
2, O
2, NO and NH
3Form NO 700ppm wherein, NH
3700ppm, O
23～5%(percent by volume), N
2Be carrier gas.When reaction temperature was 80～200 ℃, the NO conversion ratio was stabilized in more than 85%, N
2The growing amount of O is less than 10ppm.
Anti-potassium intoxication performance test: by dry pigmentation load 0.14g potassium nitrate in the catalyst of 3g preparation, test is active again behind 400 ℃ of calcination 4h, and when reaction temperature was 80～200 ℃, the NO conversion ratio was stabilized in more than 80%, N
2The growing amount of O is less than 10ppm.
The molal quantity of titanium, cerium, manganese element and corresponding mol ratio are as shown in table 1 in above-described embodiment:
The molal quantity of table 1. titanium, cerium, manganese element and corresponding mol ratio
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the hud typed denitrating catalyst of low temperature in a kind is characterized in that comprising carrier shell and active nano ion kernel; Described carrier shell is the titanium-based nano pipe, and described active nano ion kernel is the oxide of cerium and the oxide of manganese; The oxide of described cerium and the oxide of manganese are to generate after the soluble-salt roasting by the soluble-salt of cerium and manganese.
2. the hud typed denitrating catalyst of middle low temperature according to claim 1 is characterized in that:
The internal diameter of described titanium-based nano pipe is 2～25nm;
Described titanium-based nano pipe is one or more the combination in titanate nanotube, hydrogen titanate radical nanopipe or the titania nanotube.
3. the hud typed denitrating catalyst of middle low temperature according to claim 1 is characterized in that:
The soluble-salt of described cerium is at least a in cerous nitrate, ammonium ceric nitrate, cerous sulfate, Cericammoniumsulfate and the cerous acetate;
The soluble-salt of described manganese is at least a in manganese nitrate, manganese carbonate, manganese acetate and the manganese sulfate.
4. the hud typed denitrating catalyst of middle low temperature according to claim 1, it is characterized in that: the soluble-salt consumption of the soluble-salt of described cerium and manganese calculates according to the mol ratio of titanium elements in Ce elements and manganese element and the 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 hud typed denitrating catalyst of middle low temperature according to claim 1, it is characterized in that: 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 space 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 ℃, and low-temperature space type temperature range is about 80～200 ℃, and wide warm area type temperature range is about 120～420 ℃.
6. the preparation method of the hud typed denitrating catalyst of each described middle low temperature of claim 1～5 is characterized in that comprising the steps:
(1) preliminary treatment of titanium-based nano pipe: soak the titanium-based nano pipe more than 6 hours with organic solvent;
(2) preparation of the hud typed denitrating catalyst of low temperature in: get a certain amount of pretreated titanium-based nano pipe, the soluble-salt solution that adds cerium and the soluble-salt solution 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 according to warm area requirement control cerium manganese element mol ratio, flooded 4～16 hours, then in 30～90 ℃ of oven dry, with temperature-programmed mode roasting 2～6 hours, obtain the hud typed denitrating catalyst of middle low temperature.
7. the preparation method of the hud typed denitrating catalyst of middle low temperature according to claim 6 is characterized in that:
Organic solvent described in the step (1) is acetone, ethanol or dimethylbenzene;
Immersion described in the step (1) is for soaking at normal temperatures 6～36 hours;
Dipping described in the step (2) is the stirring at normal temperature dipping;
Temperature programming described in the step (2) is for to be warming up to 300～460 ℃ with 5～25 ℃/min.
8. each hud typed denitrating catalyst of described middle low temperature application in denitration of claim 1～5.
9. the application of the hud typed denitrating catalyst of middle low temperature according to claim 8 in denitration is characterized in that: the hud typed denitrating catalyst of described middle low temperature and co-catalyst coupling.
10. the application of the hud typed denitrating catalyst of middle low temperature according to claim 9 in denitration is characterized in that: described co-catalyst is at least a in iron oxide, tungsten oxide and the molybdenum oxide.
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| CN104190408A (en) * | 2014-08-19 | 2014-12-10 | 南京师范大学 | Low-temperature SCR denitration catalyst with titanium-based core-shell structure and preparation method of catalyst |
| CN104785245A (en) * | 2015-04-03 | 2015-07-22 | 中国建筑材料科学研究总院 | Denitration catalyst, preparation method thereof as well as flue gas denitration method |
| CN105457646A (en) * | 2015-12-16 | 2016-04-06 | 浙江天蓝环保技术股份有限公司 | Medium and low temperature denitration catalyst with protective layer and preparation method thereof |
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| CN104785245A (en) * | 2015-04-03 | 2015-07-22 | 中国建筑材料科学研究总院 | Denitration catalyst, preparation method thereof as well as flue gas denitration method |
| CN105457646B (en) * | 2015-12-16 | 2018-08-28 | 浙江天蓝环保技术股份有限公司 | A kind of middle low-temperature denitration catalyst and preparation method thereof with protective layer |
| CN105457646A (en) * | 2015-12-16 | 2016-04-06 | 浙江天蓝环保技术股份有限公司 | Medium and low temperature denitration catalyst with protective layer and preparation method thereof |
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| CN110605122A (en) * | 2018-06-14 | 2019-12-24 | 中国石油化工股份有限公司 | Low-temperature flue gas denitration catalyst and preparation method and application thereof |
| CN109529816A (en) * | 2018-12-25 | 2019-03-29 | 大连理工大学 | A kind of hud typed MnO2@TiO2Catalyst, preparation method and application |
| WO2021223559A1 (en) * | 2020-05-06 | 2021-11-11 | 江苏龙净科杰环保技术有限公司 | Sulfur-resistant and water-resistant manganese-based low-temperature denitration catalyst and preparation method therefor |
| CN112275314A (en) * | 2020-09-14 | 2021-01-29 | 无锡威孚环保催化剂有限公司 | Manganese-cerium-based molecular sieve SCR denitration catalyst and preparation method thereof |
| CN113332976A (en) * | 2021-05-18 | 2021-09-03 | 贵州大学 | CeCO3OH nanosphere wrapped MnCO3Preparation method and application of microsphere composite material |
| CN113332976B (en) * | 2021-05-18 | 2022-06-07 | 贵州大学 | CeCO3OH nanosphere wrapped MnCO3Preparation method and application of microsphere composite material |
| CN113368810A (en) * | 2021-07-14 | 2021-09-10 | 南京信息工程大学 | Core-shell VOCs adsorbent and preparation method thereof |
| CN115445594A (en) * | 2022-09-13 | 2022-12-09 | 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) | SCR catalyst for efficient and synergistic denitration and toluene removal of flue gas as well as preparation method and application of SCR catalyst |
| CN115445594B (en) * | 2022-09-13 | 2024-06-28 | 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) | SCR catalyst for efficient synergistic denitration and de-toluene of flue gas and preparation method and application thereof |
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