CN106179326B - A kind of nano tube supported type denitrating catalyst of manganese oxide and preparation method thereof - Google Patents

A kind of nano tube supported type denitrating catalyst of manganese oxide and preparation method thereof Download PDF

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CN106179326B
CN106179326B CN201610510998.9A CN201610510998A CN106179326B CN 106179326 B CN106179326 B CN 106179326B CN 201610510998 A CN201610510998 A CN 201610510998A CN 106179326 B CN106179326 B CN 106179326B
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catalyst
manganese oxide
manganese
denitrating catalyst
nano tube
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CN106179326A (en
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王海强
王芃芦
吴忠标
陈思
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Zhejiang Tianlan Environmental Protection Technology Co Ltd
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Zhejiang University ZJU
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/40—Mixed oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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Abstract

The invention discloses nano tube supported type denitrating catalyst of a kind of manganese oxide and preparation method thereof, catalyst is made of carrier and the active material being supported on carrier and catalyst aid, and the carrier is manganese oxide nanotube；The active material is the oxide of cerium, vanadium, niobium, chromium, iron or copper, and the catalyst aid is the oxide of molybdenum or tungsten.The denitrating catalyst that the present invention develops can not only obtain superior denitration activity, there is the good ability for resisting a variety of poisonous substances (phosphate, heavy metal, alkali/alkaline earth metal) while poisoning simultaneously, sound assurance is provided to permanently effective use of the SCR denitration on glass kiln, cement furnace, waste incinerator and biomass fuel boiler, and the service life of denitrating catalyst used in traditional industry boiler can be greatly prolonged.

Description

A kind of nano tube supported type denitrating catalyst of manganese oxide and preparation method thereof
Technical field
The present invention relates to technical field of atmospheric pollution control, and in particular to a kind of nano tube supported type denitration catalyst of manganese oxide Agent and preparation method thereof.
Background technology
In recent years, there is serious haze weather in the most areas in China, and the duration is long, and pollution concentration is high.Such Under environmental condition, environmental protection as fundamental state policy and is risen to historic mission by the Chinese government.NOxThe crime formed as haze One of stalwart chief culprit, emission reduction is just particularly important, and China has promulgated multinomial laws and regulations to control NO thusxDischarge. NOxControl discharge in terms of, power plant, cement, steel, Industrial Boiler etc. become emphasis emission control object.Meanwhile to cement Kiln, waste incinerator, glass kiln Deng Fei power plant industry, nitrogen oxides emission reduction also progress into public sight.Numerous Emission-reduction technology in, SCR (selective catalytic reduction) gas denitrifying technology is efficiency highest, most widely used denitration technology, but It is some problems occur in Chinese application, wherein being caused by noxious materials such as alkali/alkaline earth metal, heavy metal and phosphate Catalyst poisoning inactivation it is especially prominent.
In general, the commercial catalyst that most of power plant come into operation at present, working life is shorter, and every 2~5 years i.e. Catalyst need to be carried out replacing comprehensively or thoroughly cleaning, it is complex that this is primarily due to most industrial smoke component, In a large amount of existing alkali/alkaline earth metal (K, Na, Ca), phosphorus compound (phosphate, phosphorous oxide), heavy metals (As, Pb) etc. can make Catalyst contamination or poisoning, cause catalyst inactivation.And for applying in cement kiln, waste incinerator, glass kiln and adopting Biomass or biomass is used to be mixed with coal as the denitrating catalyst in the boiler of fuel, containing more in flue gas composition Alkali/alkaline earth metal, meeting accelerator activator inactivation, makes catalyst life further shorten.In addition, due to coal class and coal quality Difference, heavy metal, phosphate, phosphorous oxide etc. can be generally also contained in coal-fired industry flue gas make catalyst blockage even poisoning and deactivation Substance.Therefore, exploitation has the denitrating catalyst for well resisting a variety of poisonous substances while poisoning performance, has attracted domestic and international many The concern and research of person.
Disclosed patent relates generally to various types of SCR denitration and preparation method thereof both at home and abroad at present, But resist the research of a variety of poisonous substances while poisoning less denitrating catalyst.
Invention content
The present invention provides a kind of denitrifying catalyst with selective catalytic reduction and its synthetic method of function admirable, such catalysis Agent has good improvement to the multiple poisoning effect of alkali/alkaline earth metal, phosphate, heavy metal.
A kind of nano tube supported type denitrating catalyst of manganese oxide, by carrier and the active material being supported on carrier and catalysis Auxiliary agent forms, and the carrier is manganese oxide nanotube；The active material is the oxide of cerium, vanadium, niobium, chromium, iron or copper, described Catalyst aid is the oxide of molybdenum or tungsten.
The denitrating catalyst that the present invention develops can not only obtain superior denitration activity, while have good anti-a variety of Poisonous substance (phosphate, heavy metal, alkali/alkaline earth metal) while the ability of poisoning, to SCR denitration in glass kiln, cement Permanently effective use on stove, waste incinerator and biomass fuel boiler provides sound assurance, and can be significantly Extend the service life of denitrating catalyst used in traditional industry boiler.
The nitrogen oxides tail gas removal that the catalyst of the present invention is suitable for a variety of industrial occasions is handled, especially in the nitrogen of discharge When in oxide tail gas containing more phosphate, heavy metal and alkali/alkaline earth metal, the nano tube supported type of such manganese oxide is de- The denitration efficiency of denox catalyst can obtain preferable effect, namely have preferable anti-toxicity energy.Such as waste incinerator, glass The flue gas that glass stove, cement furnace and biomass fuel boiler etc. are discharged is in denitration process, the application of such catalyst More it is suitble to.
Preferably, the mass ratio of the carrier, active material and co-catalyst is 1:(0.1~1.0):(0~1.0)；Into One step is preferably 1:(0.1~1.0):(0.5~1.0).
Manganese oxide nanotube is by using the solubility salt of manganese, dilute acid soln, deionized water as Material synthesis.It is preferred that Ground, the manganese oxide nanotube there are as below methods prepare：
(1) soluble-salt of manganese and dilute acid soln are add to deionized water together, stirring and dissolving is formed for 1~2 hour Precursor solution；
(2) by gained precursor solution at 100~200 DEG C hydro-thermal process 10~100 hours；
(3) after hydro-thermal process, the sediment washed several times with water that ageing is obtained, removal wherein impurity；Using filter and Manganese oxide nanotube is obtained after drying.
It carries out hydro-thermal process in step (2) to carry out in polytetrafluoroethyllining lining water heating kettle, polytetrafluoroethyllining lining hydro-thermal The compactedness of kettle is 50~80%.Hydrothermal reaction condition in step (2) is further preferred, and the temperature of hydro-thermal process is 100~ 200 DEG C, the time is 10~100 hours.
It is further preferred that the soluble-salt of manganese is potassium permanganate, potassium manganate or manganese acetate, dilute acid soln is hydrochloric acid, nitre Acid or acetic acid, the soluble-salt of manganese and the molar ratio of dilute acid soln are 1~50.
Manganese oxide nanotube prepare when material molar ratio be：The soluble-salt of manganese：Dilute acid soln：Deionized water=1：(5 ~25)：(80~200)；Further preferably 1：(10~20)：(100~150).
Further, by being selected in combining as follows：
Material molar ratio is potassium permanganate：Dilute hydrochloric acid：Water=1：5：80；
Material molar ratio is potassium manganate：Dust technology：Water=1：10：120；
Material molar ratio is manganese acetate：Acetic acid：Water=1：8：100；
Material molar ratio is potassium permanganate：Dilute hydrochloric acid：Water=1：10：150.
Material molar ratio is potassium manganate：Dust technology：Water=1：20：200；
Material molar ratio is manganese acetate：Acetic acid：Water=1：25：200.
The concentration range of dilute acid soln is generally in 0.01mol/L~1.0mol/L.
It is further preferred that the washing is to be washed sample to pH value >=5 with deionized water.
It is further preferred that drying temperature should be less than hydrothermal temperature, it is more suitable with 60~80 DEG C.
The metal oxide that can be used as active material includes the oxide of cerium, vanadium, niobium, chromium, iron, copper, can be used as catalysis and helps The metal oxide of agent includes the oxide of molybdenum or tungsten.The presoma of active material includes the various salt with the metal for cation The presoma of class, catalyst aid includes the various soluble salts of the metal.
The load of active material and catalyst aid is carried out by the method for wet impregnation, the leaching of active material and catalyst aid Stain load can be carried out at the same time, and can also be carried out step by step.When specific operation first by the cationic salts of active metal and catalyst aid can The salt of dissolving is dissolved in a certain amount of deionized water, and manganese oxide nanotube is added thereto continuation magnetic after stirring 0.5~2 hour Power stir process 2~6 hours obtains finished catalyst after after dry and calcination.Wherein, drying temperature is 60~120 DEG C, Calcination temperature is 300~600 DEG C.
Therefore, the present invention also provides a kind of preparation method such as the nano tube supported type denitrating catalyst of the manganese oxide, packets Include following steps：
(1) soluble-salt of manganese and dilute acid soln are add to deionized water together, stirring and dissolving is formed for 1~2 hour Precursor solution；
(2) by gained precursor solution at 100~200 DEG C hydro-thermal process 10~100 hours；
(3) after hydro-thermal process, the sediment washed several times with water that ageing is obtained, removal wherein impurity；Using filter and Manganese oxide nanotube is obtained after drying；
(4) presoma of the presoma of active constituent and catalyst aid is dissolved in deionized water, stirring 0.5~2 is small When after be added the manganese oxide nanotube, continue stir process 2~6 hours, detach taking precipitate, will be calcined after drying precipitate To obtain the final product.
Wherein, drying temperature is 60~120 DEG C, and drying time is 6h~18h, and calcination temperature is 300~600 DEG C, calcination Time is 2h~10h.
The mass ratio of the presoma of active constituent, the presoma of catalyst aid and manganese oxide nanotube is 1：(2~3)：4.
The denitrifying catalyst with selective catalytic reduction that the present invention develops has excellent denitration activity, lower sulfur dioxide Oxygenation efficiency, good nitrogen selective and preferable water resistant sulfur resistance and excellent anti-alkali/alkaline earth metal, heavy metal, phosphorus The multiple poisoning performance of compound.
The manganese oxide nanotube base catalyst is abundant due to the unique nano tubular structure of manganese oxide nanotube itself, surface Acidic site and good redox property so that itself just with certain catalyzing and reducing nitrogen oxides ability； When having loaded active metal thereon, the salting liquid of active metal can be preferentially by entering in dip loading under capillary action In the pipe of vanadium oxide nanometer tube, being carried on the active metal particles in pipe so just can be from (the alkali/alkaline earth of toxicant outside pipe Metal, heavy metal, phosphorus compound etc.) erosion；In order to further increase poisoning shadow of the catalyst series for multiple poisonous substance It rings, has loaded coagent on it, co-catalyst can shift murder by poisoning of a part of toxicant for active phase, to subtract Light influence of the poisonous substance to activated centre, improves its anti-poisoning capability；On the other hand, the addition of catalyst aid also can be significantly Reduce oxidation and the by-product N of sulfur dioxide2The generation of O.
The various excellent specific properties of the catalyst make it have longer service life than traditional commercial catalyst, also more Being suitably applied the poisonous substances such as phosphorus compound, heavy metal, alkali and alkaline earth metal ions has in existing flue gas environment, such as glass Stove, cement furnace, waste incinerator and biomass fuel boiler vent gas treatment on, keep its application prospect very wide.
Description of the drawings
Fig. 1 is the microscopic pattern figure of manganese oxide titanium nanotube made from embodiment 1；
Fig. 2 is the microscopic pattern figure of catalyst made from embodiment 1.
Specific implementation mode
Raw materials used in following embodiment is commercial goods.
Embodiment 1：
The preparation of manganese oxide nanotube：Material molar ratio is potassium permanganate：Dilute hydrochloric acid：Water=1：5：80.By potassium permanganate It is add to deionized water together with dilute hydrochloric acid, stirring and dissolving forms precursor solution in 1 hour；It is subsequently poured into polytetrafluoro liner The compactedness of 150 DEG C of hydro-thermals 24 hours in water heating kettle, water heating kettle is 70%；The sediment that hydro-thermal obtains passes through multiple deionized water Then washing is filtered to pH value >=5, and dry at 60 DEG C, and the microscopic pattern figure of manganese oxide titanium nanotube obtained is such as Shown in Fig. 1.
The preparation of catalyst：1 gram of six nitric hydrate cerium, 2 grams of ammonium tungstates is taken to be added in 100ml deionized waters, stirring and dissolving 1 Hour, 4g manganese oxide nanotubes are added thereto after continuing stirring 6 hours, are dried at 60 DEG C, 450 DEG C of calcinations obtain for 3 hours The microscopic pattern figure of finished catalyst, catalyst obtained is as shown in Figure 2.
The denitration performance of catalyst is tested：The finished catalyst of above-mentioned preparation is put into fixed bed quartz reaction system Carry out activity, N2Selectivity test, reaction temperature is 200~500 DEG C, air speed 80000h-1Under conditions of, denitration efficiency is stablized In 95% or more, SO2Oxygenation efficiency is less than 1%, by-product N2The production quantity of O is less than 10ppm.Simulated flue gas mainly has N2、O2、NO、 NH3And SO2, wherein O23.5%, NO 600ppm, NH3600ppm, SO2600ppm, N2For carrier gas.
The poisoning performance test simultaneously of anti-alkali/alkaline earth metal phosphorus compound：It is loaded simultaneously on a catalyst using infusion process 0.1 gram of potassium nitrate and 0.5 gram of ammonium dihydrogen phosphate, the simulation poisoned catalyst re-test that calcination obtains after 3 hours at 450 DEG C its SCR denitration activity, reaction temperature is 200~500 DEG C, air speed 80000h-1Under conditions of, denitration efficiency stablize 85% with On, SO2Oxygenation efficiency is less than 1%, N2The production quantity of O is less.
Embodiment 2：
The preparation of manganese oxide nanotube：Material molar ratio is potassium manganate：Dust technology：Water=1：10：120.By potassium permanganate It is add to deionized water together with dilute hydrochloric acid, stirring and dissolving forms precursor solution in 2 hours；It is subsequently poured into polytetrafluoro liner The compactedness of 180 DEG C of hydro-thermals 24 hours in water heating kettle, water heating kettle is 60%；The sediment that hydro-thermal obtains passes through multiple deionized water Then washing is filtered to pH value >=5, and dry at 80 DEG C.
The preparation of catalyst：1 gram of five hydrated sulfuric acid vanadyl, 2 grams of ammonium molybdates is taken to be added in 100ml deionized waters, stirring is molten 4g manganese oxide nanotubes are added thereto after continuing stirring 6 hours, are dried at 80 DEG C by solution 1 hour, and 500 DEG C of calcinations obtain for 3 hours To finished catalyst.
The denitration performance of catalyst is tested：The finished catalyst of above-mentioned preparation is put into fixed bed quartz reaction system Carry out activity, N2Selectivity test, reaction temperature is 200~500 DEG C, air speed 80000h-1Under conditions of, denitration efficiency is stablized In 98% or more, SO2Oxygenation efficiency is less than 1%, by-product N2The production quantity of O is less than 10ppm.Simulated flue gas mainly has N2、O2、NO、 NH3And SO2, wherein O23.5%, NO 600ppm, NH3600ppm, SO2600ppm, N2For carrier gas.
The poisoning performance test simultaneously of anti-phosphorus compound ＆ heavy metals：0.5 gram of phosphorus is loaded using infusion process simultaneously on a catalyst Acid dihydride ammonium and 0.3 gram of plumbi nitras, simulation poisoned catalyst re-test its SCR denitration that calcination obtains after 3 hours at 500 DEG C Activity, reaction temperature is 200~500 DEG C, air speed 80000h-1Under conditions of, denitration efficiency is stablized in 90% or more, SO2Oxygen Rate is less than 1%, N2The production quantity of O is less.
Embodiment 3：
The preparation of manganese oxide nanotube：Material molar ratio is manganese acetate：Acetic acid：Water=1：8：100.By manganese acetate and acetic acid It is add to deionized water together, stirring and dissolving forms precursor solution in 2 hours；It is subsequently poured into the water heating kettle of polytetrafluoro liner The compactedness of 130 DEG C of hydro-thermals 24 hours, water heating kettle is 70%；The sediment that hydro-thermal obtains is washed by multiple deionized water to pH Value >=5, is then filtered, and dry at 60 DEG C.
The preparation of catalyst：1 gram of niobium oxalate and 2g ammonium molybdates is taken to be added in 100ml deionized waters, stirring and dissolving 1 hour, 4g manganese oxide nanotubes are added thereto after continuing stirring 6 hours, are dried at 60 DEG C, 400 DEG C of calcinations obtain catalyst in 3 hours Finished product.
The denitration performance of catalyst is tested：The finished catalyst of above-mentioned preparation is put into fixed bed quartz reaction system Carry out activity, N2Selectivity test, reaction temperature is 150~450 DEG C, air speed 80000h-1Under conditions of, denitration efficiency is stablized In 95% or more, SO2Oxygenation efficiency is less than 1%, by-product N2The production quantity of O is less than 5ppm.Simulated flue gas mainly has N2、O2、NO、 NH3And SO2, wherein O23.5%, NO 600ppm, NH3600ppm, SO2600ppm, N2For carrier gas.
The poisoning performance test simultaneously of anti-alkali/alkaline earth metal heavy metal：Using infusion process load 0.1 simultaneously on a catalyst Gram calcium nitrate and 0.3 gram of plumbi nitras, simulation poisoned catalyst re-test its SCR denitration that calcination obtains after 3 hours at 400 DEG C Activity, reaction temperature is 150~450 DEG C, air speed 80000h-1Under conditions of, denitration efficiency is stablized in 85% or more, SO2Oxygen Rate is less than 1%, N2The production quantity of O can be ignored.
Embodiment 4：
The preparation of manganese oxide nanotube：Material molar ratio is potassium permanganate：Dilute hydrochloric acid：Water=1：10：150.By manganese acetate It is add to deionized water together with acetic acid, stirring and dissolving forms precursor solution in 2 hours；It is subsequently poured into the water of polytetrafluoro liner The compactedness of 180 DEG C of hydro-thermals 36 hours in hot kettle, water heating kettle is 60%；The sediment that hydro-thermal obtains is washed by multiple deionization It washs to pH value >=5, is then filtered, and is dry at 80 DEG C.
The preparation of catalyst：1 gram of Gerhardite and 3g ammonium tungstates is taken to be added in 100ml deionized waters, stirring and dissolving 1 Hour, 4g manganese oxide nanotubes are added thereto after continuing stirring 6 hours, are dried at 80 DEG C, 450 DEG C of calcinations obtain for 6 hours Finished catalyst.
The denitration performance of catalyst is tested：The finished catalyst of above-mentioned preparation is put into fixed bed quartz reaction system Carry out activity, N2Selectivity test, reaction temperature is 100~400 DEG C, air speed 80000h-1Under conditions of, denitration efficiency is stablized In 90% or more, SO2Oxygenation efficiency is less than 1%, by-product N2The production quantity of O is less than 10ppm.Simulated flue gas mainly has N2、O2、NO、 NH3And SO2, wherein O23.5%, NO 600ppm, NH3600ppm, SO2600ppm, N2For carrier gas.
The poisoning performance test simultaneously of anti-alkali/alkaline earth metal phosphorus compound：It is loaded simultaneously on a catalyst using infusion process 0.1 gram of sodium nitrate and 0.5 gram of ammonium dihydrogen phosphate, the simulation poisoned catalyst re-test that calcination obtains after 6 hours at 450 DEG C its SCR denitration activity, reaction temperature is 100~400 DEG C, air speed 80000h-1Under conditions of, denitration efficiency stablize 80% with On, SO2Oxygenation efficiency is less than 1%, N2The production quantity of O is less.
Embodiment 5：
The preparation of manganese oxide nanotube：Material molar ratio is potassium manganate：Dust technology：Water=1：20：200.By potassium permanganate It is add to deionized water together with dilute hydrochloric acid, stirring and dissolving forms precursor solution in 3 hours；It is subsequently poured into polytetrafluoro liner The compactedness of 160 DEG C of hydro-thermals 36 hours in water heating kettle, water heating kettle is 70%；The sediment that hydro-thermal obtains passes through multiple deionized water Then washing is filtered to pH value >=5, and dry at 80 DEG C.
The preparation of catalyst：1 gram of Fe(NO3)39H2O, 3 grams of ammonium molybdates is taken to be added in 100ml deionized waters, stirring and dissolving 2 Hour, 4g manganese oxide nanotubes are added thereto after continuing stirring 6 hours, are dried at 80 DEG C, 500 DEG C of calcinations obtain for 6 hours Finished catalyst.
The denitration performance of catalyst is tested：The finished catalyst of above-mentioned preparation is put into fixed bed quartz reaction system Carry out activity, N2Selectivity test, reaction temperature is 150~450 DEG C, air speed 80000h-1Under conditions of, denitration efficiency is stablized In 95% or more, SO2Oxygenation efficiency is less than 1%, by-product N2The production quantity of O is less than 5ppm.Simulated flue gas mainly has N2、O2、NO、 NH3And SO2, wherein O23.5%, NO 600ppm, NH3600ppm, SO2600ppm, N2For carrier gas.
The poisoning performance test simultaneously of anti-phosphorus compound ＆ heavy metals：0.5 gram of phosphorus is loaded using infusion process on a catalyst first Acid dihydride ammonium, the sample that calcination is tentatively poisoned after 6 hours at 500 DEG C.Then by being vapor-deposited in normal direction catalyst Add the As of 0.5wt.%2O3, by preliminary fouled catalyst in 350 DEG C, As2O3/O2/N2Middle calcining 12 hours in atmosphere, it Re-test activity afterwards, reaction temperature is 150~450 DEG C, air speed 80000h-1Under conditions of, denitration efficiency stablize 80% with On, SO2Oxygenation efficiency is less than 1%, N2The production quantity of O is less.
Embodiment 6：
The preparation of manganese oxide nanotube：Material molar ratio is manganese acetate：Acetic acid：Water=1：25：200.By manganese acetate and second Acid is add to deionized water together, and stirring and dissolving forms precursor solution in 3 hours；It is subsequently poured into the water heating kettle of polytetrafluoro liner In 150 DEG C of hydro-thermals 48 hours, the compactedness of water heating kettle is 70%；The sediment that hydro-thermal obtains by multiple deionized water wash to Then pH value >=5 are filtered, and dry at 80 DEG C.
The preparation of catalyst：1 gram of Chromium nitrate (Cr(NO3)3),nonahydrate and 3g ammonium tungstates is taken to be added in 100ml deionized waters, stirring and dissolving 1 Hour, 4g manganese oxide nanotubes are added thereto after continuing stirring 6 hours, are dried at 80 DEG C, 550 DEG C of calcinations obtain for 6 hours Finished catalyst.
The denitration performance of catalyst is tested：The finished catalyst of above-mentioned preparation is put into fixed bed quartz reaction system Carry out activity, N2Selectivity test, reaction temperature is 200~500 DEG C, air speed 80000h-1Under conditions of, denitration efficiency is stablized In 95% or more, SO2Oxygenation efficiency is less than 1%, by-product N2The production quantity of O is less than 5ppm.Simulated flue gas mainly has N2、O2、NO、 NH3And SO2, wherein O23.5%, NO 600ppm, NH3600ppm, SO2600ppm, N2For carrier gas.
The poisoning performance test simultaneously of anti-alkali/alkaline earth metal heavy metal：0.1 is loaded on a catalyst using infusion process first Gram potassium nitrate, the sample that calcination is tentatively poisoned after 6 hours at 550 DEG C.Then by being vapor-deposited in normal direction catalyst Add the As of 0.5wt.%2O3, by preliminary fouled catalyst in 350 DEG C, As2O3/O2/N2Middle calcining 12 hours in atmosphere, it Re-test activity afterwards, reaction temperature is 200~500 DEG C, air speed 80000h-1Under conditions of, denitration efficiency stablize 80% with On, SO2Oxygenation efficiency is less than 1%, N2The production quantity of O is less.
Embodiment described above, only several typical embodiments of the invention, those skilled in the art can To make various modifications within the scope of the appended claims.

Claims (6)

1. a kind of nano tube supported type denitrating catalyst of manganese oxide is helped by carrier and the active material being supported on carrier and catalysis Agent forms, which is characterized in that the carrier is manganese oxide nanotube；The active material is the oxygen of cerium, vanadium, niobium, chromium, iron or copper Compound, the catalyst aid are the oxide of molybdenum or tungsten；The mass ratio of the carrier, active material and co-catalyst is 1:(0.1 ~1.0):(0.5~1.0)；
The manganese oxide nanotube is prepared by the following method：
(1) soluble-salt of manganese and dilute acid soln are add to deionized water together, stirring and dissolving forms forerunner in 1~2 hour Liquid solution；
(2) by gained precursor solution at 100~200 DEG C hydro-thermal process 10~100 hours；
(3) after hydro-thermal process, the sediment washed several times with water that ageing is obtained, removal wherein impurity；Using filter and drying After obtain manganese oxide nanotube.
2. the nano tube supported type denitrating catalyst of manganese oxide according to claim 1, which is characterized in that the soluble-salt of manganese is Potassium permanganate, potassium manganate or manganese acetate, dilute acid soln are hydrochloric acid, nitric acid or acetic acid, the soluble-salt of manganese and rubbing for dilute acid soln You are than being 1~50.
3. the nano tube supported type denitrating catalyst of manganese oxide according to claim 1, which is characterized in that the washing is to spend Ionized water washs sample to pH value >=5.
4. the nano tube supported type denitrating catalyst of manganese oxide according to claim 1, which is characterized in that drying temperature be 60~ 80℃。
5. a kind of preparation method of the nano tube supported type denitrating catalyst of manganese oxide as described in claim 1, which is characterized in that packet Include following steps：
(1) soluble-salt of manganese and dilute acid soln are add to deionized water together, stirring and dissolving forms forerunner in 1~2 hour Liquid solution；
(2) by gained precursor solution at 100~200 DEG C hydro-thermal process 10~100 hours；
(3) after hydro-thermal process, the sediment washed several times with water that ageing is obtained, removal wherein impurity；Using filter and drying After obtain manganese oxide nanotube；
(4) presoma of the presoma of active constituent and catalyst aid is dissolved in deionized water, after stirring 0.5~2 hour The manganese oxide nanotube is added, continues stir process 2~6 hours, detaches taking precipitate, is by calcining after drying precipitate .
6. preparation method according to claim 5, which is characterized in that drying temperature is 60~120 DEG C, calcination temperature 300 ~600 DEG C.
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