CN108722477A - A kind of alkali resistant poisoning high-efficiency denitration catalyst and its preparation method and application - Google Patents

A kind of alkali resistant poisoning high-efficiency denitration catalyst and its preparation method and application Download PDF

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CN108722477A
CN108722477A CN201810573766.7A CN201810573766A CN108722477A CN 108722477 A CN108722477 A CN 108722477A CN 201810573766 A CN201810573766 A CN 201810573766A CN 108722477 A CN108722477 A CN 108722477A
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catalyst
solution
stirring
salt
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CN108722477B (en
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朱廷钰
郭旸旸
郑扬
叶猛
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Institute of Process Engineering of CAS
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • 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

Abstract

The present invention provides a kind of preparation method and applications of alkali resistant poisoning high-efficiency denitration catalyst.The catalyst of the present invention is using titanium doped mesopore molecular sieve as carrier, using vanadium, cerium, zirconium, niobium, manganese as active component, using tungsten, molybdenum, iron, copper as auxiliary agent；Wherein, on the basis of Si elements quality in titanium doped mesopore molecular sieve, the content of doped chemical titanium is 15%~35%；On the basis of titanium doped mesopore molecular sieve carrier quality, active component vanadium, cerium, zirconium, niobium and Mn oxide mass percentage are 1%~5%, and auxiliary agent tungsten, molybdenum, iron and Cu oxide mass percentage are 1%~15%.The catalyst of the present invention has the NO higher than 90% in 300 DEG C~400 DEG C rangesxConversion ratio, most highly active reach 99.7%；With stronger alkali resistant metal, alkaline-earth metal poisoning capability, especially suitable for NO in cement kiln dusty, high basic metal and high alkaline-earth metal flue gasxRemoving.

Description

A kind of alkali resistant poisoning high-efficiency denitration catalyst and its preparation method and application
Technical field
The invention belongs to catalyst technical field, be related to a kind of alkali resistant poisoning high-efficiency denitration catalyst and preparation method thereof and Using, and in particular to it is a kind of using titanium doped mesopore molecular sieve as the alkali resistant of carrier poisoning high-efficiency denitration catalyst and its preparation side Method and application.
Background technology
China is that manufacture of cement and usage amount are maximum national (accounting for 50% or more whole world total amount) in the world, water in 2017 23.16 hundred million tons of mud yield, national cement industry year discharge about 2,000,000 tons of nitrogen oxides, account for national nitrogen oxide emission 10% or so, occupy the third position after thermal power generation and motor vehicle exhaust emission.
It is newest《Cement industry atmosphere pollutants emission standards》(GB4915-2013) concentration of emission from original 800mg/Nm3It is reduced to 400mg/Nm3(key area 300mg/Nm3), some areas standard is stringenter, Jiangsu in 2017 It prints and distributes about development the whole province non-electrical industry NO in province's environmental protection RoomxThe notice of depth emission reduction, it is desirable that before 1 day June in 2019 of cement industry NOxDischarge is not higher than 100mg/Nm3, cement industry NOxIt controls extremely urgent.
Selective catalytic reduction (SCR) technology is the fixed source emission nitrogen oxides in effluent (NO of removingx) effective means. Cement kiln end flue gas has the characteristics that dusty content, high basic metal and alkaline earth metal content, one side dusty easily cause SCR The duct blocking of denitrating catalyst, another aspect high basic metal and alkaline earth metal content easily cause in alkali (soil) metal of catalyst Poison eventually leads to catalyst inactivation, reduces catalyst service life, system operation cost is caused to increase, SCR denitration efficiency drop It is low.
For this problem, CN107983354A discloses a kind of alkali resistant and is poisoned copper-based spinelle low-temperature denitration catalyst Preparation method comprises the following steps：Step 1: mantoquita and metal salt are dissolved in distilled water, stir 2 under the conditions of 30~80 DEG C~ 10h, is slowly added to mixed acid solution while agitating, the mantoquita, metal salt, distilled water and mixed acid solution ratio be 0.025~0.4mol：0.1mol：240mL：300~700mL；Step 2: the solution after step 1 is reacted is put into baking oven, 5~10h is dried under the conditions of 50~100 DEG C, obtains dry solid, by the solid abrasive after the drying and crosses 80~400 mesh Sieve；Step 3: under the conditions of oxygen-enriched atmosphere, by step 2, treated that solid calcines 2~12h, and obtained solid abrasive is equal The even and sieve of 150~400 mesh excessively；Step 4: under reducing atmosphere protection, step 3 obtained solid is forged at 400~700 DEG C Burn 0.5~2h, the as described catalyst.Catalyst prepared by the invention has preferable alkali resistant metal poisoning performance, obtained Potassium intoxication catalyst removal efficiency of NO at 180 DEG C reaches 74%, and at 120~200 DEG C, the removal efficiency of NO reaches 65% or more, But complex manufacturing technology raw material is more expensive, is not suitable for large-scale industrial application.
CN103230813A discloses a kind of preparation method for the denitrating catalyst that the alkali resistant suitable for cement kiln is poisoned, Preparation process is as follows：Mixed solution is stirred to get after manganese salt, cerium salt and auxiliary agent is added in titanium source solution, in above-mentioned mixed solution In be sequentially added into urea liquid, ammonium hydroxide, hydrogen peroxide to no longer generate precipitation until, continue stirring 1~5 hour, then successively It is 8~24 hours dry at 70~105 DEG C with distilled water and absolute ethyl alcohol centrifuge washing, after 450~650 DEG C are calcined 2~6 hours, It is prepared into the catalyst of 40~60 mesh；Wherein, 65~95 DEG C of bath temperature, catalyst preparation process are kept when urea liquid is added Middle manganese salt is any one of manganese acetate, manganese nitrate, manganese sulfate, manganese chloride；The cerium salt is cerous chlorate, cerous nitrate, nitre Any one of sour cerium ammonium or cerous sulfate；The titanium source solution is any one of titanyl sulfate, titanium sulfate, butyl titanate；Institute The auxiliary agent of addition is any one of ferric nitrate, copper nitrate, nickel nitrate, chromic nitrate.The invention passes through addition using coprecipitation Different auxiliary agents prepare the SCR catalyst material with alkali resistant poisoning, and the catalyst of the invention is prepared using coprecipitation, but living Property site utilization rate is not high, catalytic efficiency highest only 99%.
CN103263913A discloses a kind of system of the high-ratio surface alkali resistant poisoning denitrating catalyst suitable for cement kiln Preparation Method, it is characterised in that preparation process is as follows：By titanium source solution and SiO2Colloidal sol is added manganese salt, cerium salt and helps after mixing Continue to stir to get mixed solution after agent, urea liquid, ammonium hydroxide, hydrogen peroxide are sequentially added into above-mentioned mixed solution to no longer Until generating precipitation, continue stirring 1~3 hour, then priority distilled water and absolute ethyl alcohol centrifuge washing, at 75~110 DEG C It is 6~24 hours dry, after 450~650 DEG C are calcined 2~6 hours, it is prepared into the catalyst of 40~60 mesh；Wherein, it is molten that urea is added 65~95 DEG C of bath temperature is kept when liquid, manganese salt is in manganese acetate, manganese nitrate, manganese sulfate, manganese chloride in catalyst preparation process It is any；The cerium salt is any one of cerous chlorate, cerous nitrate, ammonium ceric nitrate or cerous sulfate；The titanium source solution It is any one of titanyl sulfate, titanium sulfate, butyl titanate；The auxiliary agent added is ferric nitrate, copper nitrate, nickel nitrate, nitric acid Any one of chromium；The SiO2Colloidal sol is self-control SiO2The Ludox of colloidal sol or 30wt%；Make SiO by oneself2The preparation method of colloidal sol For ethyl orthosilicate:Ethyl alcohol:Water presses 1:2~5:The solution that 4~8 volume ratios are made into；Wherein elements Si:The molar ratio of Ti is 0.08 ~0.5:1, the catalyst of the invention is prepared using coprecipitation, but active site utilization rate is not high, catalytic efficiency highest Only 98%.
In the research for cement industry SCR denitration, the alkali resistant metal poisoning energy of catalyst is not only improved Power, will also be directed to cement kiln end flue gas dusty the characteristics of, avoid the duct of catalyst from blocking, extend catalyst use the longevity Life, therefore, exploitation are a kind of for dusty content in cement kiln flue gas and rich in the working condition of alkali and alkaline earth metal ions Alkali resistant poisoning high-efficiency denitration catalyst it is necessary.
Invention content
It in view of the deficiencies of the prior art, should the purpose of the present invention is to provide a kind of alkali resistant poisoning high-efficiency denitration catalyst The anti-duct of catalyst blocks and alkali resistant poisoning performance is excellent, the water especially to dusty content and rich in alkali and alkaline earth metal ions The denitration efficiency of stall kiln gas is high, of low cost, simple for process, environmentally friendly and will not cause secondary pollution.
For this purpose, the present invention uses following technical scheme：
A kind of alkali resistant is poisoned high-efficiency denitration catalyst, the catalyst using titanium doped mesopore molecular sieve as carrier, with vanadium, Cerium, zirconium, niobium, manganese are active component, using tungsten, molybdenum, iron, copper as auxiliary agent；Wherein, with Si member quality in titanium doped mesopore molecular sieve On the basis of amount, the content of doped chemical titanium is 15%~35%；On the basis of titanium doped mesopore molecular sieve carrier quality, activearm It is 1%~5% to divide vanadium, cerium, zirconium, niobium and Mn oxide mass percentage, auxiliary agent tungsten, molybdenum, iron and Cu oxide quality percentage Content is 1%~15%.
The present invention alkali resistant be poisoned high-efficiency denitration catalyst, using titanium doped mesopore molecular sieve as carrier, with vanadium, cerium, zirconium, Niobium, manganese are that active component is prepared using tungsten, molybdenum, iron, copper as auxiliary agent using dipping method.The present invention is catalyzed with traditional V-W-Ti Agent is compared, and titanium doped mesopore molecular sieve carrier not only remains synergistic effect of the titanium dioxide in SCR denitration system, but also On the one hand the characteristic that molecular sieve adsorption ability can be utilized strong can improve the fastness of active component and auxiliary agent load, another Aspect can strengthen reaction of the reactant in catalyst surface, improve catalytic efficiency；The catalyst has larger mesopore size With higher specific surface area, catalyst duct can preferably be avoided to block.The main component silica of carrier is chemically Matter is stablized, and the acid reaction not with is conducive to the regeneration of the pickling after catalyst alkalosis, extends service life.
Wherein, on the basis of Si elements quality in titanium doped mesopore molecular sieve, the content of doped chemical titanium is 15%~ 35%, for example, doped chemical titanium content be 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%；With titanium doped mesopore molecular sieve carrier On the basis of quality, wherein active component vanadium, cerium, zirconium, niobium and Mn oxide mass percentage be 1%~5%, such as vanadium, cerium, Zirconium, niobium and Mn oxide mass percentage are 1%, 2%, 3%, 4%, 5%；Auxiliary agent tungsten, molybdenum, iron and Cu oxide quality hundred Point content is 1%~15%, for example, tungsten, molybdenum, iron and Cu oxide mass percentage are 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%.
Wherein, the elemental mole ratios of V/Ce/Zr/Nb/Mn are 1 in the active component:(0.1~10):(0.1~10): (0.1~5):(0.1~10).
Wherein, the elemental mole ratios of W/Mo/Fe/Cu are 1 in the auxiliary agent:(0.1~10):(0.1~10):(0.1~ 5)。
The second object of the present invention is to provide a kind of preparation method of alkali resistant poisoning high-efficiency denitration catalyst, the preparation Method includes the following steps：
1) solution containing template is configured
Take P123 dissolvings in deionized water, stirring obtains mixed solution to homogeneous rear addition HCl after stirring evenly；
2) preparation of titanium doped mesopore molecular sieve carrier
Butyl titanate and tetraethyl orthosilicate are pre-mixed, mixed solution is obtained, is vigorously stirred and lower adds mixed solution dropwise Enter in the mixed solution obtained by step 1), continue stirring and form gel liquid, gel liquid immigration is had into polytetrafluoroethylene (PTFE) It in the spontaneous pressure reaction kettle of liner, takes out, filter after standing, washing, is dry, air roasting in Muffle furnace obtains titanium doped Mesopore molecular sieve carrier；
3) load of catalyst aid
One or more of soluble tungsten salt, molybdenum salt, molysite and mantoquita are weighed, is dissolved in clean water or acid solution, It is agitated to obtain stablizing solution；The catalyst carrier for taking gained in step 2), is impregnated into stablizing solution, dry after stirring, then It is roasted through Muffle furnace, obtains catalyst precursor；
4) load of catalyst activity component
One or more of soluble vanadic salts, cerium salt, zirconates, niobium salt and manganese salt are weighed, clean water or acid molten is dissolved in It is agitated to obtain stablizing solution in liquid；It takes the catalyst precursor of gained in step 3) to be impregnated into stablizing solution, is done after stirring It is dry, then roasted through Muffle furnace, obtain the alkali resistant poisoning high-efficiency denitration catalyst.
In step 1), the molar concentration of the HCl of addition is 0.1~0.3mol/L, such as the molar concentration of the HCl of addition is 0.1mol/L、0.15mol/L、0.2mol/L、0.25mol/L、0.3mol/L。
In step 1), P123 is a kind of triblock copolymer as template, and full name is polyethylene oxide-polycyclic oxygen third Alkane-polyethylene oxide triblock copolymer, molecular formula PEO-PPO-PEO；Preferably, the quality of the HCl is described 15~20 times of the quality of P123, for example, the quality of the HCl is 15 times of quality of the P123,16 times, 17 times, 18 times, 19 times, 20 times.
Preferably, in step 1), it is 20~30 DEG C that the P123, which is dissolved in the whipping temp after deionized water, such as is stirred Temperature is 20 DEG C, 21 DEG C, 22 DEG C, 23 DEG C, 24 DEG C, 25 DEG C, 26 DEG C, 27 DEG C, 28 DEG C, 29 DEG C, 30 DEG C；The stirring after hydrochloric acid is added Temperature is 30~50 DEG C, such as whipping temp is 30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C, 50 DEG C.
In step 2), the quality of the tetraethyl orthosilicate is 2~3 times of the quality of the P123, such as the silicic acid four The quality of ethyl ester is 2 times of quality of the P123,2.1 times, 2.2 times, 2.3 times, 2.4 times, 2.5 times, 2.6 times, 2.7 times, 2.8 Again, 2.9 times, 3 times；The addition of the butyl titanate and tetraethyl orthosilicate according to Ti/Si mass percentage concentrations be 15%~ 35%, for example, the addition of the butyl titanate and tetraethyl orthosilicate according to Ti/Si mass percentage concentrations be 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%.
Preferably, in step 2), stirring formed gel liquid temperature be 30~50 DEG C, such as temperature be 30 DEG C, 35 DEG C, 40℃,45℃,50℃；The time of the stirring be 10~20h, such as stirring time be 10h, 11h, 12h, 13h, 14h, 15h、16h、17h、18h、19h、20h。
Preferably, in step 2), the temperature of the standing is 90~110 DEG C, for example, the temperature of standing is 90 DEG C, 95 DEG C, 100℃,105℃,110℃；The time of the standing be 20~40h, such as standing time be 20h, 21h, 22h, 23h, 24h、25h、26h、27h、28h、29h、30h、31h、32h、33h、34h、35h、36h、37h、38h、39h、40h。
Preferably, in step 2), the temperature of the roasting is 500~600 DEG C, for example, the temperature of roasting is 500 DEG C, 510 ℃,520℃,530℃,540℃,550℃,560℃,570℃,580℃,590℃,600℃；The time of the roasting be 2~ 8h, such as the time of roasting is 2h, 3h, 4h, 5h, 6h, 7h, 8h；The speed of the heating is 1~5 DEG C/min, such as heating Speed be 1 DEG C/min, 2 DEG C/min, 3 DEG C/min, 4 DEG C/min, 5 DEG C/min.
In step 3), the solubility tungsten salt is ammonium tungstate, ammonium paratungstate or ammonium metatungstate；The molybdenum salt is ammonium molybdate； The molysite is ferric nitrate, iron chloride or ferric sulfate；The mantoquita is copper chloride, copper nitrate or copper acetate.
Preferably, in step 3), whipping temp after dipping is 20~30 DEG C, for example, whipping temp is 20 DEG C, 21 DEG C, 22 ℃,23℃,24℃,25℃,26℃,27℃,28℃,29℃,30℃；Time of the stirring is 20~40h, such as stirring Time be 20h, 21h, 22h, 23h, for 24 hours, 25h, 26h, 27h, 28h, 29h, 30h, 31h, 32h, 33h, 34h, 35h, 36h, 37h、38h、39h、40h。
Preferably, in step 3), the drying is oven drying after first revolving drying.
Preferably, in step 3), the temperature of the oven drying is 100~120 DEG C, such as the temperature of oven drying is 100℃,105℃,110℃,115℃,120℃；The time of the oven drying is 10~20h, such as the time of oven drying For 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h.
Preferably, in step 3), the temperature of the roasting is 500~600 DEG C, for example, the temperature of roasting is 500 DEG C, 510 ℃,520℃,530℃,540℃,550℃,560℃,570℃,580℃,590℃,600℃；The time of the roasting be 2~ 8h, such as the time of roasting is 2h, 3h, 4h, 5h, 6h, 7h, 8h；The speed of the heating is 1~5 DEG C/min, such as heating Speed be 1 DEG C/min, 2 DEG C/min, 3 DEG C/min, 4 DEG C/min, 5 DEG C/min.
In step 4), the solubility vanadic salts is ammonium metavanadate；The cerium salt is cerous nitrate, cerium oxalate, cerous carbonate or three Cerium chloride；The zirconates is zirconium oxychloride；The niobium salt is columbium pentachloride or niobium oxalate；The manganese salt is manganese nitrate.
Preferably, in step 4), whipping temp after dipping is 20~30 DEG C, for example, whipping temp is 20 DEG C, 21 DEG C, 22 ℃,23℃,24℃,25℃,26℃,27℃,28℃,29℃,30℃；Time of the stirring is 20~40h, such as stirring Time be 20h, 21h, 22h, 23h, for 24 hours, 25h, 26h, 27h, 28h, 29h, 30h, 31h, 32h, 33h, 34h, 35h, 36h, 37h、38h、39h、40h。
Preferably, in step 4), the drying is oven drying after first revolving drying.
Preferably, in step 4), the temperature of the oven drying is 100~120 DEG C, such as the temperature of oven drying is 100℃,105℃,110℃,115℃,120℃；The time of the oven drying is 10~20h, such as the time of oven drying For 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h.
Preferably, in step 4), the temperature of the roasting is 500~600 DEG C, for example, the temperature of roasting is 500 DEG C, 510 ℃,520℃,530℃,540℃,550℃,560℃,570℃,580℃,590℃,600℃；The time of the roasting be 2~ 8h, such as the time of roasting is 2h, 3h, 4h, 5h, 6h, 7h, 8h；The speed of the heating is 1~5 DEG C/min, such as heating Speed be 1 DEG C/min, 2 DEG C/min, 3 DEG C/min, 4 DEG C/min, 5 DEG C/min.
Preferably, step 3), the acid solution described in step 4) are nitric acid, sulfuric acid or hydrochloric acid.
Preferably, the mass concentration of the acid solution be 5%~15%, such as acid solution mass concentration be 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%.
As the preferred embodiment of the present invention, the preparation method of alkali resistant poisoning high-efficiency denitration catalyst includes the following steps：
1) solution containing template is configured
Take P123 dissolvings in deionized water, 25 DEG C are stirred to homogeneous；The HCl that addition mass concentration is 0.2mol/L, 40 It is sufficiently stirred 1~4h at DEG C, obtains mixed solution；
2) preparation of titanium doped mesopore molecular sieve carrier
Butyl titanate and tetraethyl orthosilicate are pre-mixed, mixed solution is obtained, is vigorously stirred and lower adds mixed solution dropwise Enter in mixed solution obtained by step 1), continues 10~20h of stirring at 40 DEG C；Then the immigration of the gel liquid of formation is had poly- four In the spontaneous pressure reaction kettle of vinyl fluoride liner, at 100 DEG C stand 20~40h, take out, filter, and be washed with deionized to Neutrality, drying at room temperature；With Muffle furnace, air roasting 2~8 hours, heating rate are 1-5 DEG C/min at 550 DEG C；It obtains described Titanium doped mesopore molecular sieve carrier；
3) load of catalyst aid
One or more of soluble tungsten salt, molybdenum salt, molysite and mantoquita are weighed, is dissolved in clean water or acid solution, It is agitated to obtain stablizing solution；The catalyst carrier for taking gained in step 2), is impregnated into solution, stirs 20~40h at room temperature After rotate drying, then with 110 DEG C of dry 10~20h of baking oven, then with air roasting at 550 DEG C of Muffle furnace 2~8 hours, heating speed Rate is 1-5 DEG C/min；Obtain catalyst precursor；
4) load of catalyst activity component
One or more of soluble vanadic salts, cerium salt, zirconates, niobium salt and manganese salt are weighed, clean water or acid molten is dissolved in It is agitated to obtain stablizing solution in liquid；The catalyst precursor for taking gained in step 3), is impregnated into solution, stirs at room temperature Rotate drying after 20~40h, then with 110 DEG C of dry 10~20h of baking oven, then with air roasting at 550 DEG C of Muffle furnace 2~8 hours, Heating rate is 1-5 DEG C/min；Obtain the alkali resistant poisoning high-efficiency denitration catalyst.
The third object of the present invention is to provide a kind of application of alkali resistant poisoning high-efficiency denitration catalyst, will be in the alkali resistant Malicious high-efficiency denitration catalyst is used for cement kiln end flue gas SCR denitration.
Compared with prior art, beneficial effects of the present invention are：
(1) alkali resistant of the invention poisoning high-efficiency denitration catalyst, possesses efficient middling temperature DeNOx in 300~400 DEG C Activity, denitration efficiency are higher than 90%；Catalyst system component is environmental-friendly.
(2) alkali resistant of the invention poisoning high-efficiency denitration catalyst has more compared with commercial vanadium titanium system denitrating catalyst Strong anti-alkali and alkaline earth metal ions poisoning capability, in K2When O and CaO load capacity reaches a certain amount of, K/V molar ratios, Ca/V rub When you are than being respectively 1.0, catalyst still keeps greater activity, and in 330 DEG C~400 DEG C temperature ranges, denitration efficiency still exists 85% or more.
(3) alkali resistant of the invention poisoning high-efficiency denitration catalyst is at low cost, and preparation process is simple, especially suitable for cement kiln NO in stove dusty, high basic metal and high alkaline-earth metal flue gasxRemoving.
Description of the drawings
Fig. 1 is 1V8Mo-15Ti/SiO made from the embodiment of the present invention 12The catalytic effect figure of catalyst；
When Fig. 2 is that K/V molar ratios are respectively 0.5,1.0 and 1.5,1V8Mo-15Ti/ made from the embodiment of the present invention 1 SiO2The toxic effects figure of catalyst；
When Fig. 3 is that Ca/V molar ratios are respectively 0.5,1.0 and 1.5,1V8Mo-15Ti/ made from the embodiment of the present invention 1 SiO2The toxic effects figure of catalyst.
Specific implementation mode
1-3 below in conjunction with the accompanying drawings, and the technical solution further illustrated the present invention by specific implementation mode.
Unless specific instructions, various raw materials of the invention are commercially available buys, or is prepared according to the conventional method of this field It obtains.
Embodiment 1
1) solution containing template is configured
Take 4gP123 dissolvings in deionized water, 25 DEG C of stirrings 4 hours are to homogeneous；The HCl of addition 75g0.2mol/L, 40 It is sufficiently stirred 2h at DEG C, obtains mixed solution.
2) prepared by titanium doped mesopore molecular sieve
1g butyl titanates and 9g tetraethyl orthosilicates are pre-mixed, mixed solution is obtained, be vigorously stirred it is lower by mixed solution by It is added dropwise in step 1) acquired solution, continues to stir 20h at 40 DEG C.Then the immigration of the gel liquid of formation there is into polytetrafluoroethyl-ne It in the spontaneous pressure reaction kettle of alkene liner, is stood at 100 DEG C for 24 hours, takes out, filters, and be washed with deionized to neutrality, room temperature It is dry.With Muffle furnace, air roasting 4 hours, heating rate are 1 DEG C/min at 550 DEG C, obtain titanium doped mesopore molecular sieve Carrier.
3) load of catalyst aid
Ammonium molybdate 1.1g is weighed to be dissolved in 50mL deionized waters, it is agitated to obtain stablizing solution.Take institute in 10g steps 2) Catalyst carrier be impregnated into solution, stir rotate drying afterwards for 24 hours at room temperature, then with 110 DEG C of dry 10h of baking oven, then use Air roasting 6 hours at 550 DEG C of Muffle furnace, heating rate are 1 DEG C/min, obtain catalyst precursor.
4) load of catalyst activity component
Ammonium metavanadate 0.13g is weighed to be dissolved in 50mL oxalic acid solutions, it is agitated to obtain stablizing solution.Take 10g steps 2) The catalyst carrier of middle gained is impregnated into solution, stirs rotate drying afterwards for 24 hours at room temperature, then with 110 DEG C of dry 10h of baking oven, It is 1 DEG C/min to use air roasting 6 hours at 550 DEG C of Muffle furnace, heating rate again, obtains catalyst 1V8Mo-15Ti/SiO2。
5) denitrification rate is tested：
The present invention catalytic reaction condition be：NO：400ppm, NH3：400ppm, O2：10%, N2For Balance Air, total tolerance 400mL/min, catalyst amount 200mg.Denitration evaluation is carried out using gas-chromatography, range of value is 100~400 DEG C, every 25 DEG C of evaluations, one temperature spot, each temperature spot stop 1h.
1V8Mo-15Ti/SiO made from the present embodiment2The catalytic effect of catalyst is as shown in Figure 1, at 300 DEG C~400 DEG C In temperature range, denitration efficiency reaches 90% or more.Fig. 2 and Fig. 3 is respectively that catalyst loads different amounts of K2O and CaO poisonings The denitration activity of catalyst varies with temperature curve.With K it can be seen from Fig. 2, Fig. 32The increase of O and CaO load capacity, is urged The denitration activity of agent decreases；In K2When O and CaO load capacity reaches a certain amount of, K/V molar ratios, Ca/V molar ratios difference When being 1.0, catalyst still keeps greater activity, and in 330 DEG C~400 DEG C temperature ranges, denitration efficiency is still 85% or more.
Embodiment 2
1) solution containing template is configured
Take 4gP123 dissolvings in deionized water, 25 DEG C of stirrings 4 hours are to homogeneous；The HCl of addition 65g0.2mol/L, 40 It is sufficiently stirred 2h at DEG C, obtains mixed solution.
2) prepared by titanium doped mesopore molecular sieve
1.35g butyl titanates and 9g tetraethyl orthosilicates are pre-mixed, mixed solution is obtained, is vigorously stirred lower by mixed solution It is added dropwise in step 1) acquired solution, continues to stir 15h at 40 DEG C.Then the immigration of the gel liquid of formation there is into polytetrafluoro In the spontaneous pressure reaction kettle of ethylene liner, 20h is stood at 100 DEG C, is taken out, is filtered, and is washed with deionized to neutrality, room Temperature is dry.With Muffle furnace, air roasting 6 hours, heating rate are 3 DEG C/min at 550 DEG C, obtain titanium doped mesoporous molecular Sieve carrier.
3) load of catalyst aid
Ammonium metatungstate 6.4g is weighed to be dissolved in 120mL deionized waters, it is agitated to obtain stablizing solution.Take 10g steps 2) The catalyst carrier of middle gained is impregnated into solution, and drying is rotated after stirring 20h at room temperature, then with 110 DEG C of dry 12h of baking oven, It is 2 DEG C/min to use air roasting 6 hours at 550 DEG C of Muffle furnace, heating rate again, obtains catalyst precursor.
4) load of catalyst activity component
Cerous chloride 0.43g and 0.2g columbium pentachloride is weighed to be dissolved in 100mL aqueous solutions, it is agitated obtain stablizing it is molten Liquid.It takes the catalyst carrier of gained in 10g steps 2) to be impregnated into solution, rotates drying after stirring 18h at room temperature, then use baking oven 110 DEG C of dry 14h, then with air roasting at 550 DEG C of Muffle furnace 8 hours, heating rate was 3 DEG C/min, obtains catalyst 1Nb3Ce5W-20Ti/SiO2。
Embodiment 3
1) solution containing template is configured
Take 4gP123 dissolvings in deionized water, 25 DEG C of stirrings 4 hours are to homogeneous；The HCl of addition 80g0.2mol/L, 40 It is sufficiently stirred 1h at DEG C, obtains mixed solution.
2) prepared by titanium doped mesopore molecular sieve
0.68g butyl titanates and 9g tetraethyl orthosilicates are pre-mixed, mixed solution is obtained, is vigorously stirred lower by mixed solution It is added dropwise in step 1) acquired solution, continues to stir 20h at 40 DEG C.Then the immigration of the gel liquid of formation there is into polytetrafluoro In the spontaneous pressure reaction kettle of ethylene liner, 36h is stood at 100 DEG C, is taken out, is filtered, and is washed with deionized to neutrality, room Temperature is dry.With Muffle furnace, air roasting 6 hours, heating rate are 1 DEG C/min at 550 DEG C, obtain titanium doped mesoporous molecular Sieve carrier.
3) load of catalyst aid
Ferric nitrate 0.3g is weighed to be dissolved in 80mL deionized waters, it is agitated to obtain stablizing solution.Take institute in 10g steps 2) Catalyst carrier be impregnated into solution, rotate drying after stirring 40h at room temperature, then with 110 DEG C of dry 20h of baking oven, then use Air roasting 3 hours at 550 DEG C of Muffle furnace, heating rate are 1 DEG C/min, obtain catalyst precursor.
4) load of catalyst activity component
The salpeter solution 0.5g of 50% manganese nitrate is weighed, cerous nitrate 0.76g is dissolved in 120mL oxalic acid solutions, agitated Obtain stablizing solution.It takes the catalyst carrier of gained in 10g steps 2) to be impregnated into solution, stirs to rotate afterwards for 24 hours at room temperature and do It is dry, then with 110 DEG C of dry 18h of baking oven, then with air roasting at 550 DEG C of Muffle furnace 4 hours, heating rate was 2 DEG C/min, is obtained Catalyst 1Mn3Ce10Fe-10Ti/SiO2。
Embodiment 4
1) solution containing template is configured
Take 4gP123 dissolvings in deionized water, 25 DEG C of stirrings 2 hours are to homogeneous；The HCl of addition 80g0.2mol/L, 40 It is sufficiently stirred 1h at DEG C, obtains mixed solution.
2) prepared by titanium doped mesopore molecular sieve
1.1g butyl titanates and 9g tetraethyl orthosilicates are pre-mixed, mixed solution is obtained, is vigorously stirred lower by mixed solution It is added dropwise in step 1) acquired solution, continues to stir 10h at 40 DEG C.Then the immigration of the gel liquid of formation there is into polytetrafluoro It in the spontaneous pressure reaction kettle of ethylene liner, is stood at 100 DEG C for 24 hours, takes out, filters, and be washed with deionized to neutrality, room Temperature is dry.With Muffle furnace, air roasting 8 hours, heating rate are 1 DEG C/min at 550 DEG C, obtain titanium doped mesoporous molecular Sieve carrier.
3) load of catalyst aid
Copper nitrate 1.9g is weighed to be dissolved in 120mL deionized waters, it is agitated to obtain stablizing solution.It takes in 10g steps 2) The catalyst carrier of gained is impregnated into solution, and drying is rotated after stirring 20h at room temperature, then with 110 DEG C of dry 16h of baking oven, then With air roasting at 550 DEG C of Muffle furnace 4 hours, heating rate was 1 DEG C/min, obtains catalyst precursor.
4) load of catalyst activity component
Zirconium oxychloride 0.79g is weighed to be dissolved in 100mL aqueous solutions, it is agitated to obtain stablizing solution.It takes in 10g steps 2) The catalyst carrier of gained is impregnated into solution, stirs rotate drying afterwards for 24 hours at room temperature, then with 110 DEG C of dry 20h of baking oven, then With air roasting at 550 DEG C of Muffle furnace 6 hours, heating rate was 2 DEG C/min, obtains catalyst 3Zr8Cu-16Ti/SiO2。
Comparative example
(sylvite is to V according to the literature2O5/TiO2Catalyst n H3The influence of Selective Catalytic Reduction of NO reaction, China's electricity Machine engineering journal, 2008：28,21-26) when, K/V molar ratios are 1.0, catalytic activity at 350 DEG C is about 88%, this patent hair For bright catalyst when K/V molar ratios are 1.0, catalytic activity at 350 DEG C is 93.1%, still has higher catalysis work Property, illustrate that the catalyst of this patent has stronger alkali resistant metal poisoning performance.
The alkali resistant poisoning high-efficiency denitration catalyst of the present invention, active component used is at low cost, non-toxic, can be highly concentrated It spends under the conditions of calcium oxide, high dust-laden, high-humidity flue gas effectively by NOxIt is converted to N2.The catalyst can be in 300 DEG C~400 DEG C ranges With the NO higher than 90%xConversion ratio, most highly active reach 99.7%；With stronger anti-alkali and alkaline earth metal ions poisoning energy Power；It can effectively be run under high oxidation calcium flue gas condition for a long time, especially suitable for cement kiln dusty, high basic metal and height NO in alkaline-earth metal flue gasxRemoving.
Above example only is used for illustrating the method detailed of the present invention, and the invention is not limited in above-mentioned method detaileds, i.e., Do not mean that the present invention has to rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field is it will be clearly understood that right Any improvement of the present invention, the addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, the selection of concrete mode Deng all falling within protection scope of the present invention and the open scope.

Claims (10)

  1. The high-efficiency denitration catalyst 1. a kind of alkali resistant is poisoned, which is characterized in that the catalyst is with titanium doped mesopore molecular sieve Carrier, using vanadium, cerium, zirconium, niobium, manganese as active component, using tungsten, molybdenum, iron, copper as auxiliary agent；Wherein, with titanium doped mesopore molecular sieve On the basis of middle Si elements quality, the content of doped chemical titanium is 15%~35%；It is with titanium doped mesopore molecular sieve carrier quality Benchmark, active component vanadium, cerium, zirconium, niobium and Mn oxide mass percentage are 1%~5%, auxiliary agent tungsten, molybdenum, iron and copper oxidation Amount of substance percentage composition is 1%~15%.
  2. The high-efficiency denitration catalyst 2. alkali resistant according to claim 1 is poisoned, which is characterized in that V/ in the active component The elemental mole ratios of Ce/Zr/Nb/Mn are 1:(0.1~10):(0.1~10):(0.1~5):(0.1~10).
  3. The high-efficiency denitration catalyst 3. alkali resistant according to claim 1 or 2 is poisoned, which is characterized in that W/Mo/ in the auxiliary agent The elemental mole ratios of Fe/Cu are 1:(0.1~10):(0.1~10):(0.1~5).
  4. 4. a kind of preparation method of alkali resistant poisoning high-efficiency denitration catalyst as described in one of claim 1-3, which is characterized in that The preparation method includes the following steps：
    1) solution containing template is configured
    Take P123 dissolvings in deionized water, stirring obtains mixed solution to homogeneous rear addition HCl after stirring evenly；
    2) preparation of titanium doped mesopore molecular sieve carrier
    Butyl titanate and tetraethyl orthosilicate are pre-mixed, mixed solution is obtained, is vigorously stirred and lower step is added dropwise in mixed solution It is rapid 1) obtained by mixed solution in, continue stirring form gel liquid, by gel liquid immigration have polytetrafluoroethyllining lining Spontaneous pressure reaction kettle in, take out, filter after standing, washing, dry, air roasting in Muffle furnace, obtain titanium doped mesoporous Molecular sieve carrier；
    3) load of catalyst aid
    One or more of soluble tungsten salt, molybdenum salt, molysite and mantoquita are weighed, is dissolved in clean water or acid solution, through stirring It mixes to obtain stablizing solution；The catalyst carrier for taking gained in step 2), is impregnated into stablizing solution, dry after stirring, then through horse Not stove roasts, and obtains catalyst precursor；
    4) load of catalyst activity component
    One or more of soluble vanadic salts, cerium salt, zirconates, niobium salt and manganese salt are weighed, is dissolved in clean water or acid solution, It is agitated to obtain stablizing solution；The catalyst precursor of gained in step 3) is taken to be impregnated into stablizing solution, it is dry after stirring, then It is roasted through Muffle furnace, obtains the alkali resistant poisoning high-efficiency denitration catalyst.
  5. 5. preparation method according to claim 4, which is characterized in that in step 1), the molar concentration of the HCl of addition is 0.1~0.3mol/L；
    Preferably, the quality of the HCl is 15~20 times of quality of the P123；
    Preferably, it is 20~30 DEG C that the P123, which is dissolved in the whipping temp after deionized water,；The whipping temp after hydrochloric acid is added It is 30~50 DEG C.
  6. 6. preparation method according to claim 4 or 5, which is characterized in that in step 2), the quality of the tetraethyl orthosilicate It it is 2~3 times of the quality of the P123, the addition of the butyl titanate and tetraethyl orthosilicate is dense according to Ti/Si mass percentages Degree is 15%~35%；
    Preferably, in step 2), the temperature that stirring forms gel liquid is 30~50 DEG C, and the time of the stirring is 10~20h；
    Preferably, in step 2), the temperature of the standing is 90~110 DEG C, and the time of the standing is 20~40h；
    Preferably, in step 2), the temperature of the roasting is 500~600 DEG C, and the time of the roasting is 2~8h, the heating Speed be 1~5 DEG C/min.
  7. 7. according to the preparation method described in one of claim 4-6, which is characterized in that in step 3), the solubility tungsten salt is Ammonium tungstate, ammonium paratungstate or ammonium metatungstate；The molybdenum salt is ammonium molybdate；The molysite is ferric nitrate, iron chloride or ferric sulfate；Institute It is copper chloride, copper nitrate or copper acetate to state mantoquita；
    Preferably, in step 3), the whipping temp after dipping is 20~30 DEG C, and the time of the stirring is 20~40h；
    Preferably, the drying is oven drying after first revolving drying；
    Preferably, the temperature of the oven drying is 100~120 DEG C, and the time of the oven drying is 10~20h；
    Preferably, the temperature of the roasting is 500~600 DEG C, and the time of the roasting is 2~8h, and the speed of the heating is 1 ~5 DEG C/min.
  8. 8. according to the preparation method described in one of claim 4-7, which is characterized in that in step 4), the solubility vanadic salts is Ammonium metavanadate；The cerium salt is cerous nitrate, cerium oxalate, cerous carbonate or cerous chloride；The zirconates is zirconium oxychloride；The niobium salt For columbium pentachloride or niobium oxalate；The manganese salt is manganese nitrate；
    Preferably, in step 4), the whipping temp after dipping is 20~30 DEG C, and the time of the stirring is 20~40h；
    Preferably, the drying is oven drying after first revolving drying；
    Preferably, the temperature of the oven drying is 100~120 DEG C, and the time of the oven drying is 10~20h；
    Preferably, the temperature of the roasting is 500~600 DEG C, and the time of the roasting is 2~8h, and the speed of the heating is 1 ~5 DEG C/min；
    Preferably, step 3), the acid solution described in step 4) are nitric acid, sulfuric acid or hydrochloric acid；
    Preferably, the mass concentration of the acid solution is 5%~15%.
  9. 9. according to the preparation method described in one of claim 4-8, which is characterized in that the preparation method includes the following steps：
    1) solution containing template is configured
    Take P123 dissolvings in deionized water, 25 DEG C are stirred to homogeneous；Mass concentration is added for the HCl of 0.2mol/L, at 40 DEG C It is sufficiently stirred 1~4h, obtains mixed solution；
    2) preparation of titanium doped mesopore molecular sieve carrier
    Butyl titanate and tetraethyl orthosilicate are pre-mixed, mixed solution is obtained, is vigorously stirred and lower step is added dropwise in mixed solution In rapid 1) gained mixed solution, continue 10~20h of stirring at 40 DEG C；Then the immigration of the gel liquid of formation there is into polytetrafluoroethyl-ne In the spontaneous pressure reaction kettle of alkene liner, 20~40h is stood at 100 DEG C, is taken out, is filtered, and is washed with deionized to neutrality, Drying at room temperature；With Muffle furnace, air roasting 2~8 hours, heating rate are 1-5 DEG C/min at 550 DEG C；It obtains described titanium doped Mesopore molecular sieve carrier；
    3) load of catalyst aid
    One or more of soluble tungsten salt, molybdenum salt, molysite and mantoquita are weighed, is dissolved in clean water or acid solution, through stirring It mixes to obtain stablizing solution；The catalyst carrier for taking gained in step 2), is impregnated into solution, is revolved after stirring 20~40h at room temperature It is evaporated dry, then with 110 DEG C of dry 10~20h of baking oven, then with air roasting at 550 DEG C of Muffle furnace 2~8 hours, heating rate is 1-5℃/min；Obtain catalyst precursor；
    4) load of catalyst activity component
    One or more of soluble vanadic salts, cerium salt, zirconates, niobium salt and manganese salt are weighed, is dissolved in clean water or acid solution, It is agitated to obtain stablizing solution；The catalyst precursor for taking gained in step 3), is impregnated into solution, stir 20 at room temperature~ Rotate drying after 40h, then with 110 DEG C of dry 10~20h of baking oven, then with air roasting at 550 DEG C of Muffle furnace 2~8 hours, heating Rate is 1-5 DEG C/min；Obtain the alkali resistant poisoning high-efficiency denitration catalyst.
  10. 10. a kind of application of alkali resistant poisoning high-efficiency denitration catalyst as described in one of claim 1-3, which is characterized in that will The alkali resistant poisoning high-efficiency denitration catalyst is used for cement kiln end flue gas SCR denitration.
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