CN108283883A

CN108283883A - NO in a kind of removing flue gasxMethod

Info

Publication number: CN108283883A
Application number: CN201710011812.XA
Authority: CN
Inventors: 张秀贤; 王红彬; 曲令多
Original assignee: Qingzhou Nisshin Special Material Co Ltd
Current assignee: Qingzhou Nisshin Special Material Co Ltd
Priority date: 2017-01-09
Filing date: 2017-01-09
Publication date: 2018-07-17

Abstract

A kind of method of NOx in removing flue gas, it is N to be included in catalyzed conversion NOx₂Reaction condition under, by flue gas and catalyst haptoreaction containing NOx, it is characterized in that, the catalyst contains molding containing charcoal, the first adjuvant component and the second adjuvant component, on the basis of the catalyst, the content of the molding containing charcoal is 55 100 weight % in the catalyst, and the content of the first adjuvant component in terms of oxide is 0 45 weight %, and the content of the second adjuvant component in terms of oxide is 0 30 weight %.Compared with prior art, method provided by the invention can reach de- NOx effects well at a lower reaction temperature.In addition, the present invention is not particularly limited to preparing charcoal used in catalyst, method for preparing catalyst is simple, high yield rate, to reducing catalyst cost advantages.

Description

NO in a kind of removing flue gasxMethod

Technical field

The present invention relates to the methods of NOx in removing flue gas a kind of.

Background technology

(95% or more is SO to Atmospheric Sulfur oxide S Ox₂), the pollution problem of nitrogen oxide NOx (90% or more be NO) Getting worse.Industrial smoke is the main source of SOx and NOx, these pernicious gases cause ecological environment and health Serious destruction.

Currently, more mature to the emission control technique of SOx in the world.The method common to the emission control of NOx Including：SCR (Selective Catalytic Reduction) methods or selective non-catalytic reduction SNCR (Selective Non-Catalytic Reduction) method.Such as：

US6521559 discloses a kind of pillared clays catalyst, is suitable for utilizing NH₃Restore the selective catalytic reduction of NO Technology (SCR).The characteristics of this catalyst, mainly introduces metal oxide such as V among argillic horizon₂O₅, CuO, Fe₂O₃, Cr₂O₃, Fe₂O₃-Cr₂O₃, Nb₂O₅Deng carrying out catalysis reduction using the catalysed reductive confrontation NO of metal oxide.The NOx of the material is de- Except rate reaches 95% or more.

US5451387 reports a kind of Fe-ZSM-5 catalyst, is applicable in SCR technology, and the NOx removal rate of the material is reachable 98%.

US6165934 report it is a kind of can from flue gas adsorbing and removing NOx material, the material support be TiO₂、SiO₂、 Al₂O₃Deng active component includes alkali metal, copper, noble metal etc., and the NOx removal rate of the material reaches 70%.

For such reaction, due to there is the intervention of ammonia, it inevitably will appear the consumption and leakage of ammonia, by Also contain nitrogen-atoms in ammonia itself, also there is the possibility that secondary pollution occurs.

In addition, it is N to convert NOx by reducing agent of CO₂It is another selection of existing denitration technology.Such as：

CN201210273896.1 discloses a kind of method reducing NOx emission in FCC regenerative processes, and this method is with fine coal Ash is that raw material prepares fly ash base catalyst, using the CO generated in regenerative process as reducing agent.

CN201210463016.7 discloses one kind by carrier active carbon, Nd₂O₃It is formed with the CoO adjuvant components of selectivity While desulphurization denitration catalyst, reduction components therein be flue gas contained in CO.

CN201210462982.7 discloses one kind by carrier active carbon, Pr₆O₁₁With NiO the or CoO auxiliary agent groups of selectivity Desulphurization denitration catalyst while being grouped as, reduction components therein are CO contained in flue gas.

CN201210581091.3 discloses one kind by carrier active carbon, Y₂O₃With NiO the or CoO adjuvant components of selectivity Desulphurization denitration catalyst while composition, reduction components therein are CO contained in flue gas.

It is de- to boiler smoke desulfurization simultaneously that CN200910075611.1 discloses a kind of activated carbon using under microwave radiation The method of nitre, this method is to be added CuCl as catalyst in activated carbon.Its technical solution is：Flue gas after dedusting is introduced into activated carbon Activated carbon is carried out desulphurization denitration by bed under the conditions of 400-600 DEG C of microwave heating.

CN201110451134.1 discloses a kind of microwave catalysis method of denitration, and the method includes being reacted in microwave catalysis Catalyst filling forms microwave catalysis reaction bed in the reaction tube of device device, and processed gas is passing through microwave catalysis reaction bed Shi Fasheng gas-solid reactions carry out denitration process；The catalyst is the composite catalyst of activated carbon and the mixing of Cu-ZSM-5. Temperature when reaction bed works is 150-650 DEG C, preferably 380-600 DEG C.

The prior art indicate that although having carried out a series of research to de- NOx methods both at home and abroad, effect on the whole Still person of modern times does not anticipate.

Invention content

The technical problem to be solved in the present invention is to provide in the good removing flue gas of a kind of new, efficiency and operating characteristics The method of NOx (nitrogen oxides).

The present invention provides a kind of method removing NOx in flue gas, and it is N to be included in catalyzed conversion NOx₂Reaction condition under, By flue gas and catalyst haptoreaction containing NOx, which is characterized in that the catalyst contains molding containing charcoal, the first auxiliary agent group Point and the second adjuvant component, on the basis of the catalyst, in the catalyst content of the molding containing charcoal be 55-100 weigh % is measured, the content of the first adjuvant component in terms of oxide is 0-45 weight %, and the second adjuvant component in terms of oxide contains Amount is 0-30 weight %.

The method provided by the present invention is suitable for flue qi exhaustion NOx processes, contains particularly suitable for reducibility gas in flue gas It measures low or is free of reducibility gas (for example, the flue gas composition containing NOx meets k=＜ 1, the preferably flue gas of k=0.This In, k=C_CO/C_NO, C_COFor the volumetric concentration of carbon monoxide in the flue gas, C_NOIt is dense for nitric oxide production volume in the flue gas Degree) flue gas take off NOx processes.

Wherein, compared with conventional method, the catalyst used in the method provided by the present invention has the following advantages that：

(1) the heat-resistant inorganic oxide category cheap material in catalyst, is introduced into the dosage that can reduce charcoal in catalyst, right It is advantageous to reduce catalyst use cost.

(2) charcoal for preparing catalyst, derives from a wealth of sources, such as can be one kind in carbon black, coke, petroleum coke or activated carbon Or it is several.Carbonizing method especially provided by the invention can will prepare the raw material source of the invention for providing the charcoal needed for catalyst and open up Exhibition is to include：The organic matter rich in carbon selected from solid；It is preferred that coal, timber, shell, coconut husk, walnut shell, apricot shell, jujube shell, bamboo Deng the ready-mixed oil of, and the rich carbonaceous organic material selected from liquid (with mobility), such as residual oil, pitch and coal tar, starch Slurries, the syrup etc. reconciled with water.

(3) method for preparing catalyst is simple, and high yield rate, catalyst particle size is uniformly easy to control, has in actual use Preferably operation and performance.

To keep the method provided by the present invention more competitive.

Figure of description

Attached drawing is used for a further understanding of the present invention, and a part for constitution instruction, with following specific implementation Mode is used to explain the present invention together, but is not construed as limiting the invention.

Attached drawing 1 is the flow diagram of NOx in a kind of removing flue gas provided by the invention.

Specific implementation mode

In the present invention, the molding containing charcoal can be charcoal through particulate matter that is broken and sieving, can be powdered carbon warp Molding, the molding obtained such as tabletting.

In a preferred embodiment, molding containing charcoal of the present invention is the mixing of charcoal and hydraulicity inorganic coagulation material Molding, on the basis of the mixed-forming object, the content of hydraulicity inorganic coagulation material is 3- in the mixed-forming object The content of 70 weight %, charcoal are 30-97 weight %.

Wherein, the hydraulicity inorganic coagulation material is selected from cement；It preferably is selected from portland cement, aluminate cement, sulfuric acid Salt cement, ferrous aluminate cement, fluoroaluminate cement are main with volcanic ash or latent hydraulicity material and other active material objects One or more of cement of ingredient.

When the molding containing charcoal is the mixed-forming object of charcoal and hydraulicity inorganic coagulation material, it is preferable that with catalysis On the basis of agent, the content of charcoal and the mixed-forming object of hydraulicity inorganic coagulation material is 65-99.4 weight % in the catalyst, The content of the first adjuvant component in terms of oxide is 0.1-30 weight %, and the content of the second adjuvant component in terms of oxide is 0.5-25 weight %.

In a preferred embodiment, molding containing charcoal of the present invention is the mixed-forming of charcoal and heat-resistant inorganic oxide Object, on the basis of the mixed-forming object, the content of heat-resistant inorganic oxide is 3-70 weights in the mixed-forming object % is measured, the content of charcoal is 30-97 weight %.

Wherein, the heat-resistant inorganic oxide be selected from aluminium oxide, silica, titanium oxide, magnesia, silica-alumina, Silica-magnesias, silica-zirconia, silica thoria, silica-berylias, silica-titania, silica- Zirconium oxide, titania-zirconia, silica-alumina thoria, silica-alumina-titania, silica-alumina- One or more of magnesia, silica-alumina, zirconia；Preferably in aluminium oxide, silica, silica-alumina One or more.

When the molding containing charcoal is the mixed-forming object of charcoal and heat-resistant inorganic oxide, using the catalyst as base Standard, the content of the mixed-forming object of charcoal and heat-resistant inorganic oxide is 65-99.4 weight % in the catalyst, in terms of oxide The content of the first adjuvant component be 0.1-30 weight %, the content of the second adjuvant component in terms of oxide is that 0.5-25 is weighed Measure %.

In a preferred embodiment, molding containing charcoal of the present invention is the mixed-forming object of charcoal and resin, with described Mixed-forming object on the basis of, the content of resin is 2-30 weight % in the mixed-forming object, and the content of charcoal is that 70-98 is weighed Measure %.

Wherein, the resin is selected from phenolic resin, urea-formaldehyde resin adhesive, polyimides, Noryl, polyphenylene sulfide, PEEK, high-temperature resistant organic silicon resin.

When the molding containing charcoal is the mixed-forming object of charcoal and resin, it is preferable that described to urge on the basis of catalyst The content of the mixed-forming object of charcoal and resin is 65-99.4 weight % in agent, and the first adjuvant component in terms of oxide contains Amount is 0.1-30 weight %, and the content of the second adjuvant component in terms of oxide is 0.5-25 weight %.

In the metering of the first adjuvant component of the present invention and second adjuvant component, the oxide is (except special Illustrate outer) refer to their highest price oxide.For example, the oxide of the molybdenum selected from group VIB refers to MoO₃。

Preferably, the charcoal is selected from carbon black, coke, petroleum coke, one or more of activated carbon.

In the present invention, the carbon black is different according to the various trait of source and preparation method meeting element, usually black It is powdered or blocky, graininess, cellular.For example, being passed through under conditions of lack of air by coal, natural gas, heavy oil, fuel oil etc. Imperfect combustion or the black powder superfine to be light, loose by carbon black is thermally decomposed to yield.The coke refers to that bituminous coal is empty in isolation Under conditions of gas, it is heated to 950-1050 DEG C, coke is finally made by stages such as drying, pyrolysis, melting, bonding, solidification, contractions Charcoal.The petroleum coke refers to crude oil after distilling and detaching weight matter oil, and the mink cell focus process through hot tearing again is transformed Product.From the appearance point of view, coke is in irregular shape, black not of uniform size is blocky (or particle), there is metallic luster, coke Particle has multi-pore structure.The activated carbon refers to the organic material rich in carbon, such as coal, timber, shell, coconut husk, walnut shell, apricot Shell, jujube shell etc. are transformed under high temperature and certain pressure by pyrolysis in activation furnace.They can be commercially available Commodity can also be prepared using arbitrary existing method.

Preferably, the charcoal is the coke selected from carbon black, petroleum coke, the powder granule object of one or more of activated carbon, The particle diameter distribution of the powder granule object is more than 0 micron to less than equal to 0.2mm.

In the present invention, the grain size of the powder granule object refers to that grain size is more than in powder granule object less than or equal to 0.2mm The particle content of 0.2mm is 1 weight % or less.

In a specific embodiment, the charcoal is at least two in carbon black, coke, petroleum coke, activated carbon Mixture.

Inventor has found, prepares activated carbon using method comprising the following steps, not only raw material sources are extensive, using the work Property the catalyst for preparing of charcoal also there is de- NOx performances well.The method includes：

(1) the charcoal precursor of at least one solid is mixed with the charcoal predecessor of at least one liquid, the charcoal of the solid It precursor and the dosage of the charcoal predecessor of liquid and mixes so that the charcoal precursor of the solid and the charcoal predecessor of liquid are one Kind doughy mix；

(2) doughy mix for obtaining step (1) under anaerobic, activates 1-8 hours in 700-950 DEG C；

(3) product after activating step (2) crushes, is sieved, and it is more than 0 micron to less than to be equal to obtain particle diameter distribution The powder of 0.2mm.

Wherein, the precursor of the charcoal of the solid is selected from the organic matter rich in carbon；It is preferred that coal, timber, shell, coconut husk, core One or more of peach shell, apricot shell, jujube shell, bamboo；The predecessor of the charcoal of the liquid is selected from containing rich carbonaceous organic material；It is described One kind in the example such as pitch of the predecessor of the charcoal of liquid and the ready-mixed oil of coal tar, the slurries of starch and water reconciliation, syrup Or it is several.Wherein, it is the ready-mixed oil of pitch and coal tar when the predecessor of the charcoal of the liquid is selected from containing rich carbonaceous organic material, forms sediment When one or more of slurries that powder and water reconcile, syrup, to meet the predecessor of the charcoal of the liquid and the charcoal of solid Predecessor is mixed into premised on a kind of doughy mix, and those skilled in the art according to specific actual needs adjustment and can determine The mixed proportion of pitch and coal tar, starch and water is not restricted this present invention.

In the present invention, the oxygen free condition refers to that starvation or oxygen-containing gas enter and be during the high-temperature activation System, to avoid the loss of the charcoal because of caused by burning etc..Under the premise of being enough to avoid the charcoal loss caused by burning etc., this hair There is no limit for the bright concrete mode to realizing this process.For example, by the heating charing after charing material is packed into retort Method.

Depending on different requirements, molding containing charcoal of the present invention can be various easily operated moldings, such as microballoon, ball Shape, tablet or bar shaped etc..The forming method conventional method, for example, when the molding containing charcoal is free of other addO-on therapies, It can be by directly by being prepared in a manner of broken, such as the charcoal is cocoanut active charcoal, can pass through side that is broken and sieving Method obtains the charcoal particle of required grain size；Or powdered carbon is pressed into the molding of the charcoal by way of tabletting.Contain charcoal when described When molding contains other addO-on therapies, for example, contain hydraulicity inorganic coagulation material, resin or heat-resistant inorganic oxide, it can To be but not limited to following pass through Chang Fangfa：Compression molding, extruded moulding, roller forming, spray shaping (prepare microballoon molding The methods of object).In order to make molding be smoothed out, depending on the needs of different forming methods, allow waiting for into practical forming process Various necessary addO-on therapies are introduced in the mixed material of type.To prepare carbon and hydraulicity inorganic coagulation material using extrusion method For mixed-forming object, in extruded moulding, need to enter with the mixed material of hydraulicity inorganic coagulation material in the charcoal Water.The dosage of water can be determined premised on the needs for meeting extrusion molding in practical operation by specific condition experiment, this In do not repeat.

It has been observed that in addition to it can obtain the charcoal particle of required grain size by method that is broken and sieving, optionally, other at Include the steps that the charcoal is broken into the powder that can meet forming requirements before type, such as extruded moulding.For example, coconut activated Charcoal, coke etc. are needed through Mechanical Crushing before use into powder.The breaking method is all methods that can be used, including but It is not limited to using crush method, splits broken method, the method that fractures, mill one or more of strip and ballistic method etc. method and be crushed.

According to the method provided by the invention, include drying to molding and roasting in the forming process or do not roast Burn step.For example, when preparing charcoal with the mixed-forming object of resin or hydraulicity inorganic gel material, preferably include to mix described The step of synthesis type object is dried, the drying can be that air-dried, i.e., described mixed-forming object is put naturally at room temperature Set dry method；It can be the method drying for directly heating drying；Molding is first either placed into wind under room temperature environment It is dry, drying is reheated later.

When preparing the mixed-forming object of charcoal and heat-resistant inorganic oxide, dry and calcination steps are preferably included.It is described dry Dry method and drying condition is conventional drying methods and condition, such as the drying means is drying drying, is dried dry Condition includes that temperature is 100 DEG C -300 DEG C, and drying time is 1-12 hours.It is described roasting with remove heat-resistant inorganic oxide (or The precursor of heat-resistant inorganic oxide) for the purpose of the crystallization water that may be present, for example, the forming charcoal and heat-resistant inorganic oxide Mixed-forming object be aluminium oxide precursor boehmite and charcoal mixed-forming object, the purpose of roasting is to remove quasi- The crystallization water contained by boehmite, its usual calcination temperature can be 350-800 DEG C, and roasting time is 2-6 hours (in this process Middle boehmite mutually becomes γ-Al₂O₃).Under the premise of being enough to realize this purpose and meet charcoal and do not burn mistake, the present invention couple Specific method of roasting is not intended to limit.For example, being roasted under inert gas protection.The inert gas such as nitrogen etc. is in height The gas significantly chemically reacted does not occur with charcoal under temperature.

In the present invention, first adjuvant component is transition metal；Preferred transition metal be selected from periodic table of elements IB races, One or more of Group IIB, Group IVB, VB races, group vib, VIIB, VIII group, actinides and rare earth element；Further It is preferred that copper, silver in IB races, the zinc in Group IIB, the titanium in Group IVB, zirconium, the vanadium in VB races, the molybdenum in group vib, tungsten, VIIB races In manganese and lanthanum, cerium, neodymium, praseodymium in iron, cobalt, nickel, platinum, palladium, iridium, ruthenium and rare earth in rhenium, VIII group；Thorium, the uranium of actinium series One or more of.

Second adjuvant component selected from I A, Section II A, Section III A, Section IV A, group V metal or nonmetallic ingredient in One or more；It is preferred that the aluminium of the magnesium of the lithium of group ia, sodium, potassium, caesium, group iia, calcium, strontium, barium, group III A, gallium, indium With boron, the silicon of group IVA, germanium, tin, lead, V A races one or more of phosphorus, antimony and bismuth.

It is being enough for first adjuvant component to be carried on the mixed-forming object of the charcoal and hydraulicity inorganic coagulation material Under the premise of, there is no limit preferred method is infusion process to introducing method of the present invention to first adjuvant component.The leaching Stain method be conventional method, including prepare the solution containing the first adjuvant component compound, be used in combination the solution impregnate it is described at Type object, the method for being dried, roasting later.

The soluble compound that foregoing transition metal is selected from containing the first adjuvant component compound, for example, it is above-mentioned The water soluble salt of transition metal.They can be commercially available commodity, and arbitrary known method can also be used to synthesize to obtain.

When containing the second adjuvant component in the catalyst, it is being enough second adjuvant component introducing the catalysis Under the premise of agent, there is no limit for introducing method of the present invention to second adjuvant component.For example, can charcoal and hydraulic prepared Property inorganic coagulation material mixed-forming object during simultaneously will containing the compound of second adjuvant component introduce；It can also It is introduced using the method for dipping, including prepares the solution containing the second adjuvant component compound, impregnate institute with the solution later Molding is stated, the method for being dried and roasting later.

In the present invention, solvent of the drying to be introduced in Removal of catalyst preparation process, such as the purpose of water, be enough Realize the premise of this purpose, there is no limit for concrete operations condition of the present invention to the drying.It may be used in the prior art Arbitrary drying means is dried.For example, the method for the method of heating, drying, vacuum drying method and natural air drying. The condition of the drying is conventional drying condition.By taking heat drying in an oven as an example, the drying condition includes：Dry temperature Degree is 80-300 DEG C, and preferably 100-200 DEG C, drying time is 1-8 hours, preferably 2-6 hours.

In the present invention, the roasting in the step of loading first adjuvant component or the second adjuvant component, so as to contain The compound of first adjuvant component or the second adjuvant component be at least partly decomposed into its oxide and charcoal and the hydraulicity without For the purpose of charcoal does not burn mistake in the mixed-forming object of machine cementitious material, herein under the premise of, arbitrary existing roasting technology may be used Carry out the roasting.For example, the roasting carried out under the protection of nitrogen, argon gas or carbon dioxide etc., the roasting item Part is conventional roasting condition.By taking the roasting carried out in Ma Fulu as an example, the roasting condition includes：Calcination temperature is 300- 500 DEG C, preferably 350-450 DEG C, roasting time are 1-8 hours, preferably 2-6 hours.

The method provided by the present invention can be used for various to remove the purification of the industrial waste gases of NOx as the main purpose in flue gas.This Invention is especially suitable for processing composition and meets k=＜ 1；The preferably flue gas of k=0.The k=C_CO/C_NO, C_COFor the cigarette The volumetric concentration of carbon monoxide, C in gas_NOFor nitric oxide production volumetric concentration in the flue gas.

Not having to addition using the method for NOx in flue gas removing provided by the invention includes but not limited to：Ammonia (contains liquefied ammonia), carbon Sour hydrogen ammonium, urea, ozone, hydrogen peroxide, CO, hydrazine, H₂, ethylene, acetylene, methane, the hydro carbons auxiliary agent such as ethane, you can expeditiously Carry out de- NOx.

According to the method provided by the invention, the flue gas by containing NOx and catalyst haptoreaction, can be in arbitrary cigarette It is carried out in gas de-NOx devices, for example, can be carried out in fixed bed reactors, can carry out in moving-burden bed reactor, also may be used To be carried out in fluidized-bed reactor.

Under the premise of it is N2 to be enough to convert NOx, the present invention is N to the catalyzed conversion NOx₂Reaction condition without spy It does not limit.Usually, the catalyzed conversion NOx is N₂Reaction condition include：Reaction temperature is 90 DEG C~700 DEG C, preferably 130 DEG C~550 DEG C, more preferably 150~450 DEG C, flue gas air speed are 10-20000h^-1, preferably 50-10000h^-1, more preferably For 100-6000h^-1。

According to the method provided by the invention, preferably before the flue gas that will contain NOx with catalyst haptoreaction, including dedusting The step of, the dedusting makes to be less than 200mg/m with the catalytic dust of catalyst³, preferably shorter than 100mg/ m³, more preferably less than 50mg/m³.Arbitrary existing method can be used, dedirt is carried out to the flue gas, for example, by using cloth bag dedirt device The dedirt of progress.

According to the method provided by the invention, include the steps that washing preferably before the gas discharge after reacting.Not Reaction gas through washing discharges after washing, such as is discharged after spray washing.

Fig. 1 is the flow diagram of NOx methods in removing flue gas provided by the invention.According to the flow, flue gas is through pipeline P-1 enters deduster E-1, removes the solid particle in flue gas, and the flue gas for removing solid particulate matter enters thermosistor E-2 through pipeline P-2 Temperature adjustment, temperature adjustment to reaction temperature, the flue gas after temperature adjustment enter Benitration reactor E-3 through pipeline P-3, and the gas after reaction is through pipe After road P-4 enters shower water cleaning of evaporator (or spray column) elution soluble gas, enter wind turbine E-5 through pipeline P-5, through pipeline (or chimney) P-6 is emitted into air.

The flow provided according to Fig. 1, when handled dust is less than 200mg/m³, preferably shorter than 100mg/m³, more preferably less than 50mg/m³When, the deduster can be saved in the flow.In addition, being enough to make the cigarette Under the premise of temperature when gas enters the reactor reaches temperature, the present invention is not specifically limited the thermosistor.For example, When flue-gas temperature to be dealt with is less than the reaction temperature, the thermosistor can be heating furnace；When cigarette to be dealt with When temperature degree is higher than the reaction temperature, the thermosistor can be heat exchanger.Make institute by the heat exchange of heating furnace or heat exchanger State the temperature of flue gas reached needed for reaction.The effect of wind turbine be to reaction system introduce flue gas and by after reaction flue gas and row Except reactor, it can be placed in after water washing tank or water scrubber, can also be preposition, such as preposition before deduster.

The following examples illustrate the present invention further, but not thereby limiting the invention.

Catalyst performance flue gas is evaluated in embodiment：Wherein NOx：3100mg/m3, water vapour content 3.8v%, oxygen Gas content 19.5v%, carbon monoxide and ammonia content are zero, remaining is nitrogen.

Unless otherwise indicated, other reagents used in embodiment are chemically pure reagent.

The content of first adjuvant component or the second adjuvant component (works as hydraulic using X-ray fluorescence spectra assay Property inorganic coagulation material in contain same composition when, result has deducted the content behind the part).

The assay method of NOx in gas measures gas according to HJ 479-2009 using hydrochloride naphthodiamide spectrophotometry Nitrogen oxides (nitric oxide and nitrogen dioxide) in body.

Butt：A certain amount of aluminium oxide precursor or silica-alumina precursor W are weighed, is placed it in Ma Fulu 600 DEG C roast 4 hours, are cooled to room temperature and are weighed as W1, butt=(W-W1)/W × 100%.

The charcoal used in following embodiment is：

Carbon powder：N121, Jiangxi Black Cat Carbon Black Co., Ltd. (0.5 weight % of content of ashes), grain size ＜ 0.18mm, Particle diameter distribution uses laser scattering method (similarly hereinafter).

Cocoanut active charcoal：The wooden gloomy cocoanut active charcoal of woods (4.4 weight % of content of ashes) comes from Mu Linsentan industry group, Ash content is asked to be less than 5%, water content is less than 10%.Crushed through pulverizer is powder, wherein the granule content of grain size ＞ 0.18mm is small In 1 weight %.

Bamboo charcoal：L101 bamboo charcoal particles, Quzhou Zhu Yuntan industry Co., Ltd (4 weight % of content of ashes), it is desirable that physical and chemical index Meet GBT 26913-2011 primes standards, it is powder to be crushed through pulverizer, wherein the granule content of grain size ＞ 0.18mm is small In 1 weight %.

Active carbon from coal：Anthracite column crushing activated carbon (8.5 weight % of content of ashes), iodine number are more than 1000mg/g, Serge blue is more than 200mg/g, and Shanxi Hua Qing groups, it is powder to be crushed through pulverizer, wherein the granule content of grain size ＞ 0.18mm Less than 1 weight %.

From charcoal processing：Charcoal is mixed with by the charcoal precursor of solid and the charcoal predecessor of at least one liquid.

The charcoal predecessor of solid：

Coconut shell flour 90kg, pine powdered carbon 30kg, 20 mesh of ground mistake sieve, obtain a kind of mixing of the charcoal precursor of solid Object.

The charcoal predecessor of liquid：

Starch: water=1: 35, it is first dissolved with cold water, adds 60 DEG C of warm water to mix well afterwards spare；

Tar storage tank is added in pitch (75~90 DEG C of softening point, ash content 1.0~1.5%), with gear pump by tar (proportion 1.18~1.20,50~60% or more bitumen content, moisture is less than 3%, 95~360 DEG C of boiling range) squeeze into storage tank, wherein pitch: Tar=2: 3, it heats lower stirring to pitch and is completely dissolved, keep 50~60 DEG C of temperature spare.

The mixture 120kg for taking the charcoal precursor of aforesaid solid adds the mixed liquor 50kg of aforementioned pitch and tar, aforementioned shallow lake The mixed liquor 10.0kg of powder and water, stirs evenly, and mediates 2~3 one-tenth bulks repeatedly.The dough is heated to 750 in retort DEG C activation 36 hours.It is powder that activation products are crushed through pulverizer, wherein the granule content of grain size ＞ 0.18mm is less than 1 weight Measure %.The powder ash is 11.3 weight %.

The hydraulicity inorganic coagulation material used in embodiment is：

Cement -1：525 white portland cement of Sheng Dehan boards, Jiangxi Yin Shan white cements Co., Ltd, silicate-type cement.

Cement -2：" middle material " board 525R portland cements, Zhong Cai cement Co., Ltd.

Cement -3：" resistance to all " board, CA-50-X6 aluminate cements, the emerging special cement factory production in Zhengzhou City.

Cement -4：Phosphate cement (aluminium dihydrogen phosphate), the production of Rong Xinnai materials Co., Ltd of Xinxiang City.

The heat-resistant inorganic oxide used in embodiment is：

Aluminium oxide -1：Shandong powder (boehmite (aluminium oxide precursor), Shandong Aluminum Plant, butt 67%).

Aluminium oxide -2：High purity aluminium oxide, the production of SASOL companies, butt 79.1%.

Instant flower bulb ground caustic, RF-3 types, modulus 2.80-3.00, the production of Xiang Li Chemical Co., Ltd.s of Qingzhou in Shandong province.Wherein oxygen SiClx content is that 58.5%, Na2O contents are 21.3%.

Silica-alumina (abbreviation aluminum silicon powder, similarly hereinafter)：Siral2O (silica-alumina precursor, manufacturer SASOL, butt 77.6%, wherein silica content 20%).

Kaolin, Law Firm Suzhou Jiangsu China Kaolin Clay Co., Ltd., butt 83%.

The resin used in embodiment is：

Resin -1：Polyimide resin liquid, Qinyang Tianyi Chemical Co., Ltd.'s production (can be diluted to suitably with acetone Concentration).

Resin -2：2152 liquid phenolic resins (water-soluble 200-280%), Jining Hua Kai resin Co., Ltd.

Resin -3：SH-9601 aminomethyl phenyls polysilicone (can use isopropanol or butyl acetate to dissolve), the new four seas in Hubei Chemical Co., Ltd..

Embodiment 1-1

140 grams of cocoanut active charcoal powders, 60 grams of cement -1, using crowded after they are mixed with 195 milliliters of water are weighed respectively Machine extrusion molding, extrusion are cylindrical orifice plate with orifice plate, and the bore dia of cylindrical orifice plate is 1.6mm.Cylindrical bar is in room temperature Under the conditions of place 6 hours after, be placed in that baking oven is 3 hours dry in 120 DEG C, obtain being mixed into for charcoal and hydraulicity inorganic coagulation material Type object Z1-1, carbon content 65.1% therein, hydraulicity inorganic coagulation material content 34.9%.

It is catalyst C1-1 to take 125 grams of Z1-1.

Embodiment 1-2

Cocoanut active charcoal is crushed and is sieved, it is catalyst C1-2 to take the particle of wherein 8-30 mesh.

Embodiment 1-3

Weigh 126 grams of carbon black powders respectively, 66 grams of cement -1 add water 110mL, using with embodiment 1-1 same procedure systems The mixed-forming object Z1-3 of standby charcoal and hydraulicity inorganic coagulation material, carbon content 65.4% therein, hydraulicity inorganic gel material Expect content 34.6%.

It is catalyst C1-3 to take 125 grams of Z1-3.

Embodiment 1-4

Claim 28.0 grams respectively and takes cocoanut active charcoal powder, 100.8 grams of carbon powders, 65 grams of cement -3, by them and 130 milliliters In banded extruder extrusion molding after water mixing, extrusion is trilobal orifice plate with orifice plate, and the aperture of trilobal orifice plate is 1.6mm, in room After being placed 6 hours under the conditions of temperature, trilobal item is placed in baking oven and is dried 3 hours in 120 DEG C, obtains charcoal and hydraulicity inorganic gel material The mixed-forming object Z1-4 of material, carbon content 65.1% therein, hydraulicity inorganic coagulation material content 34.9%.

It is catalyst C1-4 to take 125 grams of Z1-4.

Embodiment 1-5

135 grams are weighed respectively from charcoal processing, and 62 grams of cement -4 are squeezed out after mixing them with 195 milliliters of water using banded extruder Molding, extrusion are cylindrical orifice plate with orifice plate, and the bore dia of cylindrical orifice plate is 1.6mm.Cylindrical bar is put at ambient temperature After setting 6 hours, it is placed in baking oven and is dried 3 hours in 120 DEG C, obtain the mixed-forming object Z1- of charcoal and hydraulicity inorganic coagulation material 5, carbon content 65.4% therein, hydraulicity inorganic coagulation material content 34.6%.

It is catalyst C1-5 to take 125 grams of Z1-5.

Embodiment 1-6

200 grams of carbon powder is taken, tabletting is carried out with small-sized tablet press machine, is smashed after tabletting, and sieve, take wherein 8-30 purposes Grain is catalyst C1-6

Embodiment 1-7

Active carbon from coal is taken, be crushed and is sieved, it is catalyst C1-7 to take the particle of wherein 8-30 mesh.

The present invention provides catalyst and the use limits of reference catalyst.

Evaluation carries out on 100 milliliters of fixed-bed reactors.60 milliliters of catalyst amount.

It is warming up to reaction temperature under logical nitrogen, is stablized under the reaction temperature 2 hours, introduces flue gas, reaction 2 later Sampling analysis after hour.Specific 270 DEG C of reaction temperature, flue gas air speed 1200h^-1, reaction result is listed in table 1-1.

Table 1-1

Embodiment	1-1	1-2	1-3	1-4	1-5	1-6	1-7
								Catalyst	C1-1	C1-2	C1-3	C1-4	C1-5	C1-6	C1-7
Flue gas analysis after reaction
								NOx content, mg/m3	168	174	177	184	162	185	195
NOx removal rate, %	94.6	94.4	94.3	94.1	94.8	94.0	93.7

Embodiment 1-8

Charcoal and hydraulicity inorganic glue are prepared according to embodiment 1-1 methods (feed intake, be molded and drying condition etc. is identical) The mixed-forming object Z1-8 of gel material, the water absorption rate for measuring Z1-8 are 0.84mL/g, weigh nickel nitrate, and 105.3 grams (AR grades) add Under thermal agitation, it is 103 milliliters to be dissolved in water to solution total amount, after the solution and 125 grams of Z1-8 are mixed, are impregnated 3 hours, in It is dried 3 hours at 120 DEG C, then in nitrogen atmosphere, is roasted 3 hours at 390 DEG C, catalyst C1-8 is obtained, wherein in terms of NiO Nickel content be 17.5 weight %.

Embodiment 1-9

Cocoanut active charcoal is crushed and is sieved, the particle of wherein 8-30 mesh is taken, is denoted as Z1-9.

125 grams of Z1-9 are taken, it is 0.90mL/g to measure its water absorption rate, weighs nickel nitrate, 105.3 grams (AR grades), heating stirring Under be dissolved in water to 113 milliliters, the solution and Z1-9 are mixed, dipping is after 3 hours, dry 3 hours at 120 DEG C, then exist It in N2 atmosphere, is roasted 3 hours at 380 DEG C, obtains catalyst C1-9, wherein the nickel content in terms of NiO is 17.5 weight %.

Embodiment 1-10

126 grams of carbon black powders are weighed respectively, and 40 grams of cement -3 add water 105mL, using method extrusion same as Example 1 And it is dry, prepare the mixed-forming object Z1-10 of charcoal and hydraulicity inorganic coagulation material, carbon content 75.2% therein, the hydraulicity Inorganic coagulation material content 24.8%.

125 grams of Z1-10 are taken, it is 0.90 to measure its water absorption rate, weighing potassium acetate, 61.5 grams (AR grades), is added under heating stirring Water dissolution after the solution and Z1-10 are mixed, impregnated 3 hours, is dried 3 hours, then in N2 gas to 113 milliliters at 120 DEG C It in atmosphere, is roasted 3 hours at 320 DEG C, obtains catalyst C1-10, wherein the potassium content in terms of K2O is 20 weight %.

Embodiment 1-11

140 grams of bamboo-carbon powders are weighed respectively, and 180 grams of cement -1 add water 190mL, using method extrusion same as Example 1 And it is dry, prepare the mixed-forming object Z1-11 of charcoal and hydraulicity inorganic coagulation material, carbon content 39.6% therein, the hydraulicity Inorganic coagulation material content 60.4%.

250 grams of Z1-11 are taken, it is 0.55 to measure its water absorption rate, weighs two ammino palladium of dinitroso, 4.5 grams (AR grades) add water 135 milliliters are dissolved to, after the solution and Z1-11 are mixed, impregnated 3 hours, dries 3 hours at 120 DEG C, then exists, 280 DEG C Lower roasting 3 hours, obtains catalyst C1-11, wherein the palladium content in terms of Metal Palladium is 0.8 weight %.

Embodiment 1-12

Claim 70.0 grams respectively and takes cocoanut active charcoal powder, 63.0 grams of carbon powders, 50 grams of cement -4, by them and 160 milliliters In banded extruder extrusion molding after water mixing, extrusion is trilobal orifice plate with orifice plate, and the aperture of trilobal orifice plate is 1.6mm, in room After being placed 6 hours under the conditions of temperature, trilobal item is placed in baking oven and is dried 3 hours in 120 DEG C, obtains charcoal and hydraulicity inorganic gel material The mixed-forming object Z1-12 of material, carbon content 69.7% therein, hydraulicity inorganic coagulation material content 30.3%.

Take 125 grams of Z1-12, measure its water absorption rate be 0.75, weigh nitric acid cuprammonium, 43.0 grams (AR grades), be dissolved in water to It 95 milliliters, after the solution and Z1-12 are mixed, impregnated 3 hours, is dried 3 hours at 120 DEG C, then in N2 atmosphere, 390 It is roasted 3 hours at DEG C, obtains catalyst C1-12, wherein the copper content in terms of CuO is 12.5 weight %.

Embodiment 1-13

Claim 112.0 grams respectively and takes cocoanut active charcoal powder, 25.2 grams of carbon powders, 80 grams of cement -2, by them and 180 milliliters In banded extruder extrusion molding after water mixing, extrusion is trilobal orifice plate with orifice plate, and the aperture of trilobal orifice plate is 1.6mm, in room After being placed 6 hours under the conditions of temperature, trilobal item is placed in baking oven and is dried 3 hours in 120 DEG C, obtains charcoal and hydraulicity inorganic gel material The mixed-forming object Z1-13 of material, carbon content 59.8% therein, hydraulicity inorganic coagulation material content 40.2%.

The 125 grams of Z1-13 of mixed-forming object for taking charcoal and hydraulicity inorganic coagulation material, it is 0.72 to measure its water absorption rate, is claimed Ammonium metatungstate is measured, 45.2 grams (AR grades) are dissolved in water to 90 milliliters, after the solution and Z1- 13 are mixed, are impregnated 3 hours, in It is dried at 120 DEG C 3 hours, is then roasted 3 hours at 300 DEG C, obtain catalyst C1-13, wherein the W content in terms of WO3 is 25.0 weight %.

Embodiment 1-14

28.0 grams are claimed to take cocoanut active charcoal powder, 100.8 grams of carbon powders, 120 grams of cement -3, by them and 155 millis respectively It rising after water mixing in banded extruder extrusion molding, extrusion is trilobal orifice plate with orifice plate, and the aperture of trilobal orifice plate is 1.6mm, After placing 6 hours under room temperature, trilobal item is placed in baking oven and is dried 3 hours in 120 DEG C, obtains charcoal and hydraulicity inorganic gel The mixed-forming object Z1-14 of material, carbon content 50.5% therein, hydraulicity inorganic coagulation material content 49.5%.

125 grams of Z1-14 are taken, it is 0.55 to measure its water absorption rate, weighing manganese nitrate, 46.3 grams (AR grades), is added under heating stirring Water dissolution after the solution and Z1-14 are mixed, impregnated 3 hours, is dried 3 hours, then in N2 gas to 70 milliliters at 120 DEG C Atmosphere roasts 3 hours at 370 DEG C, obtains catalyst C1-14, wherein the manganese content in terms of MnO2 is 15.0 weight %.

Embodiment 1-15

Claim 140 grams respectively and takes cocoanut active charcoal powder, 150 grams of cement -2, in extrusion after they are mixed with 220 milliliters of water Machine extrusion molding, extrusion are trilobal orifice plate with orifice plate, and the aperture of trilobal orifice plate is 1.6mm, and it is small to place 6 at ambient temperature Shi Hou, trilobal item are placed in baking oven and are dried 3 hours in 120 DEG C, obtain the mixed-forming object of charcoal and hydraulicity inorganic coagulation material Z1-15, carbon content 44.8% therein, hydraulicity inorganic coagulation material content 55.2%.

250 grams of Z1-15 are taken, it is 0.64 to measure its water absorption rate, weighs ferric nitrate, 161.4 grams (AR grades), sodium acetate (AR grades) 84.4g is dissolved in water to 270 milliliters under heating stirring, at twice will dissolving dipping, first the solution and Z1-15 are mixed, saturation Dipping dries 3 hours at 120 DEG C after 3 hours, then impregnates surplus solution again, dried under similarity condition, then in argon Gas atmosphere roasts 3 hours at 390 DEG C, obtains catalyst C1-15, wherein the iron content in terms of Fe2O3 is 10.0 weight %, with The sodium content of Na2O meters is 10.0 weight %.

Embodiment 1-16

Claim 140 grams respectively and is derived from preparing active carbon powder, 140 grams of cement -3, in extrusion after they are mixed with 220 milliliters of water Machine extrusion molding, extrusion are trilobal orifice plate with orifice plate, and the aperture of trilobal orifice plate is 1.6mm, and it is small to place 6 at ambient temperature Shi Hou, trilobal item are placed in baking oven and are dried 3 hours in 120 DEG C, obtain the mixed-forming object of charcoal and hydraulicity inorganic coagulation material Z1-16, carbon content 55.3% therein, hydraulicity inorganic coagulation material content 44.7%.

250 grams of Z1-16 are taken, it is 0.68 to measure its water absorption rate, weighs nickel nitrate, 85.1 grams (AR grades), potassium acetate (AR grades) 30.3g is dissolved in water to 170 milliliters under heating stirring, the solution and Z1-16 is mixed, dipping is after 3 hours, is dried at 120 DEG C It is 3 hours dry, it is then roasted 3 hours at CO2 atmosphere, 350 DEG C, obtains catalyst C1-16, wherein the nickel content in terms of NiO is 7.5 weight %, the potassium content in terms of K2O are 5.0 weight %.

Embodiment 1-17

Claim 140 grams respectively and takes cocoanut active charcoal powder, 220 grams of cement -1, in extrusion after they are mixed with 270 milliliters of water Machine extrusion molding, extrusion are trilobal orifice plate with orifice plate, and the aperture of trilobal orifice plate is 1.6mm, and it is small to place 6 at ambient temperature Shi Hou, trilobal item are placed in baking oven and are dried 3 hours in 120 DEG C, obtain the mixed-forming object of charcoal and hydraulicity inorganic coagulation material Z1-17, carbon content 35.1% therein, hydraulicity inorganic coagulation material content 64.9%.

250 grams of Z1-17 are taken, it is 0.60 to measure its water absorption rate, weighs cobalt nitrate, 61.9 grams (AR grades), calcium nitrate (AR grades) 140.0g is dissolved in water to 255 milliliters under heating stirring, at twice will dissolving dipping, first the solution and Z1-17 are mixed, is full After dipping 3 hours, is dried 3 hours at 120 DEG C, then surplus solution is impregnated again, dries under similarity condition, then exists Nitrogen atmosphere roasts 3 hours at 400 DEG C, obtains catalyst C1-17, wherein the cobalt content in terms of CoO is 5.0 weight %, with The calcium content of CaO meters is 15.0 weight %.

The present invention provides catalyst use limits.

It is warming up to reaction temperature under logical nitrogen, is stablized under the reaction temperature 2 hours, introduces flue gas, reaction 2 later Sampling analysis after hour.Specific reaction temperature, flue gas air speed and reaction result are listed in table 1-2.

Table 1-2

Evaluation result shows that the present invention provides catalyst and has de- NOx performances well.

Embodiment 2-1

140 grams of cocoanut active charcoal powders are weighed respectively, and 70 grams of aluminium oxide -1 in terms of butt by them and contain concentrated nitric acid It is cylinder with orifice plate use banded extruder extrusion molding (liquid powder ratio for 1: 1), extrusion after 6 milliliters of 210 milliliters of aqueous solutions mixing The aperture of orifice plate, cylindrical orifice plate is 1.8mm.Cylindrical bar is placed in baking oven and is dried 4 hours in 120 DEG C, later in nitrogen atmosphere Lower 520 DEG C roast 3 hours, and the cocoanut active charcoal obtained in mixed-forming the object Z2-1, Z2-1 of charcoal and heat-resistant inorganic oxide contains Measure 66.7 weight %, 33.3 weight % of alumina content.

It is catalyst C2-1 to take 125 grams of Z2-1.

Embodiment 2-2

Cocoanut active charcoal is crushed and is sieved, it is catalyst C2-2 to take the particle of wherein 8-30 mesh.

Embodiment 2-3

Weigh 126 grams of carbon powders respectively, 65 grams of aluminium oxide -2 in terms of butt, using with embodiment 2-1 same procedure systems 66.0 weight % of carbon black powder content in mixed-forming the object Z2-3, Z2-3 of standby charcoal and heat-resistant inorganic oxide, alumina content 34.0 weight %.

It is catalyst C2-3 to take 125 grams of Z2-3.

Embodiment 2-4

Weigh 90 grams of carbon powders and 40 grams of cocoanut active charcoal powders respectively, 63 grams of flower bulb ground caustic, using with embodiment 2-1 Same procedure prepares the 46.6 weight % of carbon black powder content in mixed-forming the object Z2-4, Z2-4 of charcoal and heat-resistant inorganic oxide, Coconut activated carbon content is 20.7 weight %, 32.6 weight % of sodium silicate powder content.

It is catalyst C2-4 to take 125 grams of Z2-4.

Embodiment 2-5

132 grams are weighed respectively from charcoal processing, 40 grams of aluminium oxide -1 in terms of butt, 29 grams of silica-oxygen in terms of butt Change aluminium, they are mixed and the method that uses embodiment 2-1 prepare charcoal and aluminium oxide mixed-forming object Z2-5, Z2-5 self-control 65.7 weight % of carbon content, 19.9 weight % of alumina content, silica-alumina content are 14.4 weight %.

It is catalyst C2-5 to take 125 grams of Z2-5.

Embodiment 2-6

200 grams of carbon powder is taken, a small amount of water is added, tabletting is carried out with small-sized tablet press machine, smashes, and sieve, taken wherein after tabletting The particle of 8-30 mesh is catalyst C2-6

Embodiment 2-7

Active carbon from coal is taken, be crushed and is sieved, it is catalyst C2-7 to take the particle of wherein 8-30 mesh.

It is warming up to reaction temperature under logical nitrogen, is stablized under the reaction temperature 2 hours, introduces flue gas, reaction 2 later Sampling analysis after hour.Specific 270 DEG C of reaction temperature, flue gas air speed 1200h^-1, reaction result is listed in table 2-1.

Table 2-1

Embodiment 2-8

The mixing of charcoal and aluminium oxide is prepared according to embodiment 2-1 methods (feed intake, be molded and drying condition etc. is identical) Molding Z2-8..

125 grams of Z2-8 are taken, it is 0.77 to measure its water absorption rate, weighs ferric nitrate, 100.7 grams (AR grades) are dissolved in water to 175 Milliliter first takes solution 95ml and Z2-8 mixing, dipping after 1 hour, is dried 3 hours at 110 DEG C, then take surplus solution, Same dipping and drying, then in CO2 atmosphere, roast 2 hours at 380 DEG C, catalyst C2-8 are obtained, wherein in terms of Fe2O3 Iron content be 13.5 weight %.

Embodiment 2-9

Cocoanut active charcoal is crushed and is sieved, the particle of wherein 8-30 mesh is taken, is denoted as Z2-9.

Take 125 grams of Z2-9, measure its water absorption rate be 0.90mL/g, weigh 100.7 grams of ferric nitrate (AR grades) be dissolved in water to It 200 milliliters, takes solution 110ml and Z2-9 mixing, dipping after 1 hour, is dried 3 hours at 110 DEG C, take remaining solution, After same dipping and drying means processing, in nitrogen atmosphere, is roasted 2 hours at 380 DEG C, obtains catalyst C2-9, Iron content wherein in terms of Fe2O3 is 13.5 weight %.

Embodiment 2-10

126 grams of carbon black powders are weighed respectively, 170 grams of aluminium oxide -2 in terms of butt, and containing 8 milliliters of concentrated nitric acids After the mixing of 230ml water, other uses and embodiment 2-1 same procedures extrusion and drying prepare carrier Z6, carbon powder therein contains Measure 42.6 weight %, the 57.4 weight % of content of aluminium oxide.

5 grams of Z2-10 carrier 12s are taken, it is 0.60 to measure its water absorption rate, weighs sodium acetate, 106.6 grams (AR grades), heating stirring Under be dissolved in water to 135 milliliters, first take the 75ml solution and carrier to mix, dipping is after 3 hours, dried 3 hours at 120 DEG C, Then surplus solution is taken, impregnated using same method and is dried, then in argon gas atmosphere, roasts 3 hours, obtains at 350 DEG C Catalyst C2-10, wherein the sodium content in terms of Na2O is 24 weight %.

Embodiment 2-11

Cocoanut active charcoal is crushed and is sieved, it is carrier Z2-11 to take the particle of wherein 8-30 mesh.

5 grams of Z2-11 carrier 12s are taken, it is 1.05 to measure its water absorption rate, weighs nickel nitrate, 132.0 grams (AR grades) are dissolved in water To 240 milliliters, first takes solution 130ml and carrier mixing, dipping after 3 hours, dried 3 hours at 120 DEG C, then take residue Solution is impregnated and is dried using same method, then in CO2 atmosphere, roasted 3 hours at 370 DEG C, obtain catalyst C2- 11, wherein the nickel content in terms of NiO is 21.0 weight %.

Embodiment 2-12

140 grams of bamboo-carbon powders are weighed respectively, 75 grams of silica-aluminas in terms of butt, and containing 6 milliliters of concentrated nitric acids After the mixing of 190ml water, other uses and embodiment 2-1 same procedures extrusion and drying prepare carrier Z2-12, bamboo charcoal therein 65.1 weight % of powder content, 34.9 weight % of silica-alumina content.

Take 5 grams of Z2-12 carrier 12s, measure its water absorption rate be 0.76, weigh acetic acid iridium, 3.8 grams (AR grades), be dissolved in water to It 95 milliliters, after the solution and carrier are mixed, impregnated 3 hours, is dried 3 hours at 120 DEG C, then exists, 3 are roasted at 260 DEG C Hour, catalyst C2-12 is obtained, wherein the iridium content in terms of metal iridium is 1.5 weight %.

Embodiment 2-13

75.0 grams are claimed to take cocoanut active charcoal powder, 58.0 grams of carbon powders, 75 grams of aluminium oxide -1 in terms of butt, with dry respectively The 63g kaolin of base meter, after being mixed with the 240ml water containing 6 milliliters of concentrated nitric acids, other are used and embodiment 2-1 same procedures Extrusion and drying, obtain carrier Z2-13, and alumina content therein is 36.1 weight %, 36.1 weight of coconut activated carbon content Measure %, 27.8 weight % of carbon black powder content.

5 grams of Z2-13 carrier 12s are taken, it is 0.60 to measure its water absorption rate, weighs vanadyl oxalate, 60.6 grams (AR grades) add water-soluble Solution first takes solution 75ml and carrier mixing, dipping after 3 hours, dries 3 hours, then take surplus at 120 DEG C to 135 milliliters Remaining solution is impregnated and is dried using same method, then in N2 atmosphere, roasted 3 hours at 390 DEG C, obtain catalyst C2-13, wherein the content of vanadium in terms of V2O5 is 15.0 weight %.

Embodiment 2-14

Claim 95.0 grams respectively and take cocoanut active charcoal powder, 40 grams of carbon powders, 100 grams of aluminium oxide -2 mixing in terms of butt with After 220ml water mixing containing 6 milliliters of concentrated nitric acids, other uses and embodiment 2-1 same procedures extrusion and drying obtain carrier Z2-14,40.4 weight % of coconut activated carbon content therein, carbon black powder content are 17.0 weight %, alumina content 42.6 Weight %.

5 grams of Z2-14 carrier 12s are taken, it is 0.68 to measure its water absorption rate, weighs chromic nitrate, 66.4 grams (AR grades) are dissolved in water To 155 milliliters, first takes the 85ml solution and carrier mixing, dipping after 3 hours, dried 3 hours at 120 DEG C, then take residue Solution is impregnated and dry using identical method, is then roasted 3 hours at 410 DEG C, obtain catalyst C2-14, wherein with The chromium content of Cr2O3 meters is 9.0 weight %.

Embodiment 2-15

Claim 40.0 grams respectively and take cocoanut active charcoal powder, 90.0 grams of carbon powders, 20 grams of aluminium oxide -2 in terms of butt and with The 20g silica-aluminas of butt meter mix, and after being mixed with the 220ml water containing 6 milliliters of concentrated nitric acids, other are used and implementation Example 2-1 same procedures extrusion is simultaneously dried to obtain carrier Z2-15, and 23.5 weight % of coconut activated carbon content therein, carbon powder contains Measure 52.9 weight %, 11.8 weight % of alumina content, cobalt oxide he-alumina content is 11.7 weight %.

5 grams of Z2-15 carrier 12s are taken, it is 0.76 to measure its water absorption rate, weighs ferric nitrate, 96.5 grams (AR grades), heating stirring Under be dissolved in water to 170 milliliters, first take solution 95ml and carrier to mix, dipping is after 3 hours, dried 3 hours at 120 DEG C, Then surplus solution is taken, is impregnated using same procedure and dry, is then roasted 3 hours, be catalyzed at N2 atmosphere, 370 DEG C Agent C2-15, wherein the iron content in terms of Fe2O3 is 11.0 weight %.

Embodiment 2-16

Claim 140 grams respectively and take cocoanut active charcoal powder, 60 in terms of butt gram aluminium oxide -1 after mixing, and contains 6 After the 205ml water mixing of milliliter concentrated nitric acid, other uses and embodiment 2-1 same procedures extrusion and drying obtain carrier Z2- 16,70.0% weight of coconut activated carbon content therein, 30.0 weight % of alumina content.

250 grams of Z2-16 carriers are taken, it is 0.86 to measure its water absorption rate, weighs cobalt nitrate, 33.0 grams (AR grades), potassium acetate (AR Grade) 11.8g, it is dissolved in water to 110 milliliters under heating stirring, the solution and carrier is mixed, saturation dipping is after 3 hours, in 120 It is dried at DEG C 3 hours, is then roasted 3 hours at argon gas atmosphere, 400 DEG C, obtain catalyst C2-16, wherein the cobalt in terms of CoO Content is 6.0 weight %, and the potassium content in terms of K2O is 4.0 weight %.

Embodiment 2-17

Claim 140 grams respectively and is derived from preparing active carbon powder, 40 in terms of butt gram aluminium oxide -1 and 36.5 grams of aluminium oxide -2, After mixing, after being mixed with the 225ml water containing 6 milliliters of concentrated nitric acids, other are used with embodiment 2-1 same procedures extrusion simultaneously It is dry, obtain carrier Z2-17,64.7 weight % of self-control activated carbon content therein, 35.3 weight % of alumina content.

5 grams of Z2-17 carrier 12s are taken, it is 0.80 to measure its water absorption rate, weighs nitric acid cuprammonium, 29.5 grams (AR grades), sodium acetate (AR grades) 70.6g is dissolved in water to 180 milliliters under heating stirring, first takes solution 100ml and carrier to mix, dipping 3 hours Afterwards, it is dried 3 hours at 120 DEG C, then takes surplus solution, impregnated using same procedure and dry, it is small that 3 are dried at 120 DEG C When, it is then roasted 3 hours at CO2 atmosphere, 350 DEG C, obtains catalyst C2-17, wherein the copper content in terms of CuO is 7.5 weights % is measured, the sodium content in terms of Na2O is 16.0 weight %.

Embodiment 2-18

Claim 140 grams respectively and takes cocoanut active charcoal powder, 20 grams of flower bulb ground caustics, after mixing, after being mixed with 180ml water, Using with embodiment 2-1 same procedures extrusion and drying, obtain carrier Z2-18,87.5 weight of coconut activated carbon content therein Measure %, 12.5 weight % of sodium silicate powder content.

5 grams of Z2-18 carrier 12s are taken, it is 0.95 to measure its water absorption rate, weighs nickel nitrate, 11.0 grams (AR grades), cadmium acetate (AR Grade) 23.6g, it is dissolved in water to 120 milliliters under heating stirring, the solution and carrier is mixed, saturation dipping is after 3 hours, in 120 It is dried at DEG C 3 hours, is then roasted 3 hours at nitrogen atmosphere, 380 DEG C, obtain catalyst C2-18, wherein the nickel in terms of NiO Content is 2.0 weight %, and the cadmium content in terms of CdO is 8.0 weight %.

The present invention provides catalyst use limits.

It is warming up to reaction temperature under logical nitrogen, is stablized under the reaction temperature 2 hours, introduces flue gas, reaction 2 later Sampling analysis after hour.Specific reaction temperature, flue gas air speed and reaction result are listed in table 2-1.

Table 2-2

Embodiment 3-1

140 grams of cocoanut active charcoal powder is weighed respectively, and the acetone soln 170ml containing 50 grams of resins -1 mixes them It is cylindrical orifice plate with orifice plate to use banded extruder extrusion molding, extrusion afterwards, and the aperture of cylindrical orifice plate is 3mm.Cylindrical bar is set It is 4 hours dry in 120 DEG C in baking oven, the mixed-forming object of charcoal and resin is obtained, the resin content of Z3-1 is 26.3 weight %.Coconut palm 73.7 weight % of shell activated carbon content (charcoal and resin content are calculated according to inventory in mixed-forming object, similarly hereinafter).

It is catalyst C3-1 to take 100 grams of Z3-1.

Embodiment 3-2

Cocoanut active charcoal is crushed and is sieved, it is catalyst C3-2 to take the particle of wherein 8-30 mesh.

Embodiment 3-3

126 grams of carbon black powder is weighed respectively, and the aqueous solution 100ml containing 75 grams of resins -2, other are used and 1 phase of embodiment Tongfang method prepares the 62.7 weight % of carbon black powder content of mixed-forming the object Z3-3, Z3-3 of charcoal and resin, 37.3 weight of resin content Measure %.

It is catalyst C3-3 to take 100 grams of Z3-3.

Embodiment 3-4

40 grams of carbon black powder 90g and cocoanut active charcoal powder, the toluene solution 115ml of 45 grams of resins -3 are weighed respectively), it will They use banded extruder extrusion molding after mixing, other prepare being mixed into for charcoal and resin using with embodiment 3-1 same procedures The carbon black of type object Z3-4, Z3-4 divide content 51.4 weight %, 22.9 weight % of coconut activated carbon content, 25.7 weight of resin content Measure %.

It is catalyst C3-4 to take 100 grams of Z3-4.

Embodiment 3-5

132 grams are weighed respectively from charcoal processing, and 180 milliliters of the aqueous solution of 50 grams of resins -2 mixes them, other are using implementation The method of example 3-1 prepares the 72.5 weight % of self-control carbon content of mixed-forming the object Z3-5, Z3-5 of charcoal and resin, resin content 27.5 weight %.

It is catalyst C3-5 to take 100 grams of Z3-5.

Embodiment 3-6

200 grams of carbon powder is taken, tabletting is carried out with small-sized tablet press machine, is smashed after tabletting, and sieve, take wherein 8-30 purposes Grain is catalyst C3-6

Embodiment 3-7

Active carbon from coal is taken, be crushed and is sieved, it is catalyst C3-7 to take the particle of wherein 8-30 mesh.

It is warming up to reaction temperature under logical nitrogen, is stablized under the reaction temperature 2 hours, introduces flue gas, reaction 2 later Sampling analysis after hour.Specific 280 DEG C of reaction temperature, flue gas air speed 1200h^-1, reaction result is listed in table 3-1.

Table 3-1

Embodiment	3-1	3-2	3-3	3-4	3-5	3-6	3-7
								Catalyst	C3-1	C3-2	C3-3	C3-4	C3-5	C3-6	C3-7
Flue gas analysis after reaction
								NOx content, mg/m3	151	174	165	171	130	185	195
NOx removal rate, %	95.1	94.4	94.7	94.5	95.8	94.0	93.7

Embodiment 3-8

Carrier Z3-8 is prepared according to embodiment 3-1 methods (feed intake, be molded and drying condition etc. is identical), measures carrier Water absorption rate is 0.83mL/g, weighing cobalt nitrate, and under 90.9 grams of (AR grades) heating stirrings, it is 105 millis to be dissolved in water to solution total amount It rises, after the solution and 125 grams of carrier Z3-8 are mixed, impregnated 3 hours, is dried 3 hours at 120 DEG C, then in CO2 atmosphere In, it is roasted 3 hours at 370 DEG C, obtains catalyst C3-8, wherein the cobalt content in terms of CoO is 15.5 weight %.

Embodiment 3-9

Active carbon from coal is taken, be crushed and is sieved, it is carrier to take the particle of wherein 8-30 mesh, and measurement water absorption rate is 0.9mL/g, It is denoted as carrier Z3-9.

5 grams of Z3-9 carrier 12s are taken, it is 0.90 to measure its water absorption rate, weighing cobalt nitrate, 90.9 grams (AR grades), under heating stirring It is dissolved in water to 110 milliliters, after the solution and carrier are mixed, impregnated 3 hours, is dried 3 hours at 120 DEG C, then in N2 It in atmosphere, is roasted 3 hours at 380 DEG C, obtains catalyst C3-9, wherein the cobalt content in terms of CoO is 15.5 weight %.

Embodiment 3-10

126 grams of carbon black powders are weighed respectively, and the mixed liquor containing 130 grams of resins -3 and toluene 105mL, other are used and reality 3-1 same procedures extrusion and a drying are applied, carrier Z3-10,49.2 weight % of carbon black powder content therein, resin content are prepared 50.8 weight %.

5 grams of Z3-10 carrier 12s are taken, it is 0.65 to measure its water absorption rate, weighs calcium nitrate, 93.3 grams (AR grades), heating stirring Under be dissolved in water to 145 milliliters, solution 85ml and carrier are mixed, dipping is after 3 hours, drys 3 hours at 120 DEG C, general Surplus solution and carrier are mixed, and dipping is dried 3 hours after 3 hours at 120 DEG C, then in argon gas atmosphere, 340 DEG C Lower roasting 3 hours, obtains catalyst C3-10, wherein the calcium content in terms of CaO is 20 weight %.

Embodiment 3-11

140 grams of bamboo-carbon powders are weighed respectively, contain the acetone solution 120mL of 70 grams of resins -1, other are using same as Example 1 Method extrusion and drying prepare carrier Z3-11,66.7 weight % of bamboo charcoal powder content therein, resin content 33.3%.

5 grams of Z3-11 carrier 12s are taken, it is 0.77 to measure its water absorption rate, weighing dinitroso diammonia platinum, 0.65 gram (AR grades), It is dissolved in water to 95 milliliters, after the solution and carrier are mixed, impregnated 3 hours, dries 3 hours at 120 DEG C, then exist, 280 It is roasted 3 hours at DEG C, obtains catalyst C3-11, wherein the platinum content in terms of metal platinum is 0.3 weight %.

Embodiment 3-12

Claim 75.0 grams cocoanut active charcoal powder, 58.0 grams of carbon powders is taken to contain the aqueous solution 135ml of 90 grams of resins -2 respectively, In banded extruder extrusion molding after they are mixed, extrusion is trilobal orifice plate with orifice plate, and the aperture of trilobal orifice plate is 1.6mm, It is 3 hours dry in 120 DEG C that trilobal item is placed in baking oven, obtains carrier Z3-12,33.6 weight % of cocoanut active charcoal therein, charcoal 26.0 weight % of black powder content, resin content are 40.4 weight %.

5 grams of Z3-12 carrier 12s are taken, it is 0.65 to measure its water absorption rate, weighs cerous nitrate, 39.8 grams (AR grades) are dissolved in water To 85 milliliters, after the solution and carrier are mixed, impregnated 3 hours, dried 3 hours at 120 DEG C, then in N2 atmosphere, 390 It is roasted 3 hours at DEG C, obtains catalyst C3-12, wherein the cerium content in terms of CeO2 is 11.0 weight %.

Embodiment 3-13

Claim 65.0 grams cocoanut active charcoal powder, 40.0 grams of carbon powders is taken to contain the toluene liquid 160ml of 120 grams of resins -3 respectively, In banded extruder extrusion molding after they are mixed, extrusion is trilobal orifice plate with orifice plate, and the aperture of trilobal orifice plate is 1.6mm, Trilobal item is placed in vacuum drying oven and is dried 3 hours in 120 DEG C, obtains carrier Z3-13, cocoanut active charcoal powder content 28.9 therein Weight %, 17.8 weight % of carbon black powder content, resin content are 53.3 weight %.

5 grams of Z3-13 carrier 12s are taken, it is 0.62 to measure its water absorption rate, weighs ammonium molybdate, 46.7 grams (AR grades) are dissolved in water To 80 milliliters, after the solution and carrier are mixed, impregnated 3 hours, dries 3 hours at 120 DEG C, then roasted at 300 DEG C 3 hours, catalyst C3-13 is obtained, wherein the molybdenum content in terms of MoO3 is 23.0 weight %.

Embodiment 3-14

Claim 40.0 grams cocoanut active charcoal powder, 90.0 grams of carbon powders is taken to contain the acetone soln of 40 grams of resins -1 respectively 120ml in banded extruder extrusion molding, extrusion is trilobal orifice plate with orifice plate after mixing them, and the aperture of trilobal orifice plate is 1.6mm, trilobal item are placed in vacuum drying oven and are dried 3 hours in 120 DEG C, obtain carrier Z3-14, coconut activated carbon content therein 23.5 weight %, 53.0 weight % of content of carbon black, resin content are 23.5 weight %.

5 grams of Z3-14 carrier 12s are taken, it is 0.72 to measure its water absorption rate, weighs nickel nitrate, 74.2 grams (AR grades), heating stirring Under be dissolved in water to 160 milliliters, take that 90ml will the solution and carrier mix, dipping is after 3 hours, dried 3 hours at 120 DEG C, Take that remaining 70ml will the solution and carrier mix, dipping is after 3 hours, dry 3 hours at 120 DEG C, then N2 atmosphere, It is roasted 3 hours at 370 DEG C, obtains catalyst C3-14, wherein the nickel content in terms of NiO is 13.0 weight %.

Embodiment 3-15

Claim 140 grams cocoanut active charcoal powder, 60 grams of resins -3 is taken to be squeezed after mixing them with 175 milliliters of toluene respectively Machine extrusion molding, extrusion are trilobal orifice plate with orifice plate, and the aperture of trilobal orifice plate is 1.6mm, and trilobal item is placed in vacuum Baking oven is 3 hours dry in 120 DEG C, obtains carrier Z3-15,70.0 weight % of coconut activated carbon content therein, and resin content is 30.0 weight %.

5 grams of Z3-15 carrier 12s are taken, it is 0.82 to measure its water absorption rate, weighs nitric acid cuprammonium, 18.5 grams (AR grades), calcium nitrate (AR grades) 20.8g is dissolved in water to 105 milliliters under heating stirring, the solution and carrier is mixed, saturation dipping is after 3 hours, in It is dried at 120 DEG C 3 hours, is then roasted 3 hours at argon gas atmosphere, 380 DEG C, catalyst C3-15 is obtained, wherein in terms of CuO Copper content be 5.5 weight %, calcium content in terms of CaO is 5.0 weight %.

Embodiment 3-16

Claim 140 grams respectively and is derived from preparing active carbon powder, 30 grams of resins -2, in extrusion after they are mixed with 175 milliliters of water Machine extrusion molding, extrusion are trilobal orifice plate with orifice plate, and the aperture of trilobal orifice plate is 1.6mm, trilobal item be placed in baking oven in 120 DEG C of dryings 3 hours obtain carrier Z3-16, and 82.4 weight % of self-control activated carbon content therein, resin content is 17.6 weights Measure %.

5 grams of Z3-16 carrier 12s are taken, it is 0.94 to measure its water absorption rate, weighs cobalt nitrate, 51.5 grams (AR grades), sodium acetate (AR Grade) 65.8g, it is dissolved in water to 210 milliliters under heating stirring, is impregnated at twice, take 115ml solution, saturation leaching for the first time It after stain 3 hours, is dried 3 hours at 120 DEG C, takes remaining 95ml solution saturation dipping after 3 hours for the second time, at 120 DEG C Drying 3 hours.Then it is roasted 3 hours at CO2 atmosphere, 350 DEG C, obtains catalyst C3-16, wherein the cobalt content in terms of CoO For 8.0 weight %, the sodium content in terms of Na2O is 15.0 weight %.

Embodiment 3-17

Claim 140 grams respectively and takes cocoanut active charcoal powder, 110 grams of resins -2, in extrusion after they are mixed with 180 milliliters of water Machine extrusion molding, extrusion are trilobal orifice plate with orifice plate, and the aperture of trilobal orifice plate is 1.6mm, trilobal item be placed in baking oven in 120 DEG C of dryings 3 hours obtain carrier Z3-17, and 56.0 weight % of coconut activated carbon content therein, resin content is 44.0 weights Measure %.

5 grams of Z3-17 carrier 12s are taken, it is 0.74 to measure its water absorption rate, weighs ferric nitrate, 22.2 grams (AR grades), zinc nitrate (AR Grade) 53.6g, it is dissolved in water to 93 milliliters under heating stirring, the solution and carrier is mixed, saturation dipping is after 3 hours, in 120 It is dried at DEG C 3 hours, is then roasted 3 hours at nitrogen atmosphere, 400 DEG C, catalyst C3-17 is obtained, wherein in terms of Fe2O3 Iron content is 3.0 weight %, and the Zn content in terms of ZnO is 10.0 weight %.

The present invention provides catalyst use limits.

It is warming up to reaction temperature under logical nitrogen, is stablized under the reaction temperature 2 hours, introduces flue gas, reaction 2 later Sampling analysis after hour.Specific reaction temperature, flue gas air speed and reaction result are listed in table 3-2.

Table 3-2

Embodiment 4-1

This example demonstrates that the de- NOx effects of the method provided by the present invention.

De- NOx is carried out to flue gas according to the flow of Fig. 1,

Flue gas forms：12.7 volume % of NOx 2836mg/m3, CO2 content, water vapour content are 8.9 volume %, and oxygen contains 3.5 volume % are measured, remaining is nitrogen.

Catalyst is C1-12

Reaction condition：Reaction temperature is 320, reaction pressure 0.11MPa, and flue gas air speed is 1300h^-1, discharge in flue gas The content of NOx is 42mg/m³, NOx removal rate is 98.52%.

Embodiment 4-2

De- NOx is carried out to flue gas according to the flow of Fig. 1,

Flue gas forms：NOx 13421mg/m3, water vapour content 5.5v%, oxygen content 20.5v%, remaining is nitrogen Gas.

Catalyst is C2-11

Reaction condition：Reaction temperature is 190, reaction pressure 0.11MPa, and flue gas air speed is 450h^-1, discharge in flue gas The content of NOx is 106mg/m3, and NOx removal rate is 99.2%.

Embodiment 4-3

De- NOx is carried out to flue gas according to the flow of Fig. 1,

Flue gas forms：NOx 415mg/m3, water vapour content 3.5v%, oxygen content 20.7v%, remaining is nitrogen.

Catalyst is C3-16

Reaction condition：Reaction temperature is 210, reaction pressure 0.1MPa, and flue gas air speed is 3200h^-1, discharge in flue gas The content of NOx is 18mg/m3, and NOx removal rate is 95.6%.

Claims

1. a kind of method of NOx in removing flue gas, it is N to be included in catalyzed conversion NOx₂Reaction condition under, by the flue gas containing NOx With catalyst haptoreaction, which is characterized in that the catalyst contains molding containing charcoal, the first adjuvant component and the second auxiliary agent group Point, on the basis of the catalyst, the content of the molding containing charcoal is 55-100 weight % in the catalyst, in terms of oxide The content of first adjuvant component is 0-45 weight %, and the content of the second adjuvant component in terms of oxide is 0-30 weight %.

2. according to the method described in claim 1, it is characterized in that, the molding containing charcoal is charcoal and hydraulicity inorganic gel material The mixed-forming object of material, on the basis of the carrier, the content of hydraulicity inorganic coagulation material is 3-70 weights in the carrier % is measured, the content of charcoal is 30-97 weight %；Or the mixed-forming object for charcoal and heat-resistant inorganic oxide, it is with the carrier Benchmark, the content of heat-resistant inorganic oxide is 3-70 weight % in the carrier, and the content of charcoal is 30-97 weight %；Or it is The mixed-forming object of charcoal and resin material, on the basis of the carrier, the content of resin material is 2-30 weights in the carrier % is measured, the content of charcoal is 70-98 weight %.

3. according to the method described in claim 1, it is characterized in that, the charcoal is selected from carbon black, coke, petroleum coke, in activated carbon One or more.

4. method according to claim 1 or 3, which is characterized in that the charcoal is selected from carbon black, coke, petroleum coke, activity At least two mixture in charcoal.

5. according to the method described in claim 4, it is characterized in that, the charcoal is selected from carbon black, coke, petroleum coke, activated carbon One or more of powder granule object, the particle diameter distribution of the powder granule object is more than 0 micron to less than to be equal to 0.2mm。

6. according to the method described in claim 1, it is characterized in that, first adjuvant component is transition metal；Preferred mistake It crosses metal and is selected from periodic table of elements IB races, Group IIB, Group IVB, VB races, group vib, VIIB, VIII group, actinides and rare earth One or more of element；In copper, silver in further preferred IB races, the zinc in Group IIB, the titanium in Group IVB, zirconium, VB races Vanadium, the molybdenum in group vib, tungsten, the manganese in VIIB races and the iron in rhenium, VIII group, cobalt, nickel, platinum, palladium, iridium, ruthenium and rare earth In lanthanum, cerium, neodymium, praseodymium；One or more of the thorium of actinium series, uranium；Second adjuvant component is selected from I A, Section II A, the One or more of IIIA, Section IV A, the metal of group V or nonmetallic ingredient；It is preferred that the lithium of group ia, sodium, potassium, caesium, Magnesium, calcium, strontium, barium, the aluminium of group III A, gallium, indium and the boron of Group IIA, the silicon of group IVA, germanium, tin, lead, V A races phosphorus, antimony One or more of with bismuth.

7. according to the method described in claim 1, it is characterized in that, the hydraulicity inorganic coagulation material is selected from cement；It is preferred that From portland cement, aluminate cement, sulfate cement, ferrous aluminate cement, fluoroaluminate cement, with volcanic ash or potential water One or more of the cement of hard material and other active material object main components；The resin is selected from phenolic resin, urea Urea formaldehyde glue, polyimides, Noryl, polyphenylene sulfide, PEEK, high-temperature resistant organic silicon resin；The heat resistant inorganic oxidation Object be selected from aluminium oxide, silica, titanium oxide, magnesia, silica-alumina, silica-magnesias, silica-zirconia, Silica thoria, silica-berylias, silica-titania, silica-zirconia, titania-zirconia, silica- Alumina-thorias, silica-alumina-titania, silicaalumina-magnesia, silica-alumina, zirconia One or more of；Preferably one or more of aluminium oxide, silica, silica-alumina.

8. according to the method described in claim 1, it is characterized in that, the reaction condition that the catalyzed conversion NOx is N2 includes：Temperature Degree is at 130~550 DEG C, and air speed is in 50~10000h^-1；Preferably 150~300 DEG C of temperature, 100~6000h of air speed^-1。

9. according to the method described in claim 1, it is characterized in that, the flue gas composition containing NOx meets K=＜ 1；Preferably K=0, the K=C_CO/C_NO, C_COFor the volumetric concentration of carbon monoxide in the flue gas, C_NOIt is nitric oxide production in the flue gas Volumetric concentration.