CN105126826B - A kind of FCC regenerated flue gas denitration manganese oxide/titanium dioxide catalyst and its production and use - Google Patents

A kind of FCC regenerated flue gas denitration manganese oxide/titanium dioxide catalyst and its production and use Download PDF

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CN105126826B
CN105126826B CN201510563196.XA CN201510563196A CN105126826B CN 105126826 B CN105126826 B CN 105126826B CN 201510563196 A CN201510563196 A CN 201510563196A CN 105126826 B CN105126826 B CN 105126826B
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manganese oxide
titanium dioxide
catalyst
preparation
manganese
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CN105126826A (en
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刘坚
周燕
赵震
于富红
崔丽凤
史恒昌
宋卫余
韦岳长
李建梅
张潇
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SHANDONG HUALU-HENGSHENG CHEMICAL Co Ltd
China University of Petroleum Beijing
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SHANDONG HUALU-HENGSHENG CHEMICAL Co Ltd
China University of Petroleum Beijing
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Abstract

The invention provides a kind of FCC (catalytic cracking) regenerated flue gas denitration manganese oxide/titanium dioxide catalyst and its production and use, the manganese oxide/titanium dioxide catalyst is prepared using hydro-thermal method：Solution containing titanium source is mixed with the solution containing manganese source, expanding agent and optionally ammonium sulfate, hydro-thermal reaction is carried out, reaction product is subjected to separation of solid and liquid, gained solid is scrubbed, dries, and roasting, obtains manganese oxide/titanium dioxide catalyst.The manganese oxide/titanium dioxide catalyst is a kind of supported oxide catalyst of Nano grade, active component good dispersion, preparation method is simple, active temperature windows are wider (150 350 DEG C, 90%) denitration efficiency is more than, preferably (under the conditions of 150 DEG C, denitration efficiency has that reference area is big, heat endurance is high and N up to 98%) to low temperature active2The advantages that selectivity is high, has good application prospect.

Description

A kind of denitration of FCC regenerated flue gas manganese oxide/titanium dioxide catalyst and its preparation side Method and purposes
Technical field
The invention belongs to catalyst technical field, is related to a kind of FCC regenerated flue gas denitration and is catalyzed with manganese oxide/titanium dioxide Agent and its production and use.
Background technology
Catalytic cracking (FCC) device is the significant element in crude oil depth process, and act foot is occupied in petroleum refining industry The status of weight.During catalytic cracking reaction, while cracking occurs for feedstock oil, wherein 30%~50% nitrogenous chemical combination Thing enters oil coke, and is deposited on catalyst surface therewith.Catalyst activity reduction because of surface attachment oil coke, it is necessary to regenerated Processing.In regenerator burning process, most of nitrogen-containing compound is converted into N2, but also there is 10%~30% to be converted into NOX, with Regenerated flue gas is discharged, and wherein main component is NO, and percentage by volume is about 90%, and residue 10% or so is NO2.According to raw material and The difference of operating condition, NO in regenerated flue gasXConcentration is generally higher than there is also difference《Discharge standard of air pollutants》 (GB16297-1996) 420mg/m required in3(device built before 1997) and 240mg/m3(1997 and build later If device), and be not equipped with denitrating flue gas facility.
On the other hand, due to the adverse effect developed rapidly with crude oil in poor quality of crude oil processing industry, the NO of oil refining enterpriseX Discharge capacity is increasing.Generally, regenerated flue gas is oil plant NOXThe main source of discharge, account for the 50% of its total release.Cut Only at present, CNPC shares 41 sets of FCC apparatus, and up to 50,800,000 tons/year, regenerated flue gas total emission volumn exceedes total productive capacity 5000000 Nm3/ h, NOXAnnual emissions are about 1.2 ten thousand tons.If it is handled using gas denitrifying technology, with NOXClearance Calculated for 80%, only this item, so that it may realize group company NOXDischarge capacity reduces by 10%.It can be seen that NO in FCC regenerated flue gasXRow Put problem has turned into the common problem of each oil refining enterprise of CNPC, seriously constrains CNPC's energy-saving and emission-reduction and cleaning is given birth to Production work is pushed ahead.
It is contemplated that increasingly strict with environmental protection standard, each oil refining enterprise of CNPC is to FCC regenerated flue gas denitration skills The production requirement of art will expand rapidly.
At present, the FCC regenerated flue gas denitration technologies of commercial Application include both at home and abroad：Low NOXBurn technology, oxidative absorption Method, addition auxiliary agent method, SNCR (SNCR) method and SCR (SCR) method.Five kinds of FCC regenerated flue gas Denitration technology feature is different, is respectively suitable for different treatment conditions and processing requirement, it is necessary to be selected with suiting measures to local conditions.But It is that for the existing 41 sets of FCC apparatus of China, to solve the problems, such as regenerated flue gas denitration on the whole, selective catalysis is also Former method (SCR) is because for the treatment of effect stabilization, wide adaptation range, technical maturity, undoubtedly most competitive technology.
Traditional SCR catalyst has noble metal catalyst, metal oxide catalyst and molecular sieve catalyst.And in recent years Come, for oxide catalyst because of its short preparation period, cost is low, it is easy to operate the advantages that receive significant attention.Vanadia-based SCR catalysts Industrially applied to stationary source denitration for many years, but still there is operation temperature is higher, operation temperature window is narrower, high temperature when N2Largely generation causes N to O2Selectivity declines, and SO2To SO3The problems such as oxidation.Therefore, exploitation can substantially reduce cost Low-temperature SCR catalyst, the oxide catalyst for finding non-vanadium class be solve these problems main path.In recent years, low temperature Active preferably manganese-based catalyst is to NH3- SCR reactions have higher low-temperature catalytic activity and selectivity, thus receive much concern, into To study more a kind of denitrating catalyst.
Li Huijie is to MnOx-TiO2Catalytic oxidation NO performance is studied, and has mainly investigated single-activity component MnOx To NO catalysed oxidn and H2O、SO2Influence to catalyst activity, and analyze catalyst poisoning mechanism.Research knot Fruit shows that infusion process prepares MnOx-TiO2The optimum condition of catalyst is：Mn contents 20% (wt%), 300 DEG C of roasting 6h, herein Under the conditions of the catalyst for preparing there is very high NO catalytic oxidation activities：Air speed is 10000h-1, reaction temperature be 300 DEG C when NO high conversion rate is up to 89% (University Of Xiangtan, 2011, master thesis).
Li Junhua et al. have studied MnOx/TiO prepared by different manganese sources2Influence to NO reduction reactions, find to use Manganese nitrate is mainly MnO as the MnOx that manganese source obtains2；The MnOx obtained using manganese acetate as manganese source is mainly Mn2O3 (Effects of precursors on the surface Mn species and the activities for NO reduction over MnOx/TiO2catalysts,Catalysis Communications,2007,12(8):1896– 1900)。
Xu Haitao et al. have studied MnOx/TiO2The preparation of catalyst and its low temperature NH3Selective Catalytic Reduction of NO performance, The nano-TiO of different crystalline phases is prepared under different calcining heats using microemulsion method2, and as carrier, utilize dipping Method is prepared for a series of MnOx/TiO2Catalyst.Test result indicates that：With the increase of calcining heat, nano-TiO2From anatase titanium dioxide Gradually change to rutile-type, 700 DEG C are calcined obtained nano-TiO2In mixed crystal phase, 800 DEG C are calcined obtained nano-TiO2It is then Pure rutile type；Anatase titanium dioxide and mixed crystal phase TiO2Carrier and activating oxide MnO2Between interaction it is more strong, work as nanometer TiO2Middle rutile-type and anatase titanium dioxide and when depositing, MnO2Preferentially with dichloride in anatase type TiO2Effect；Pure rutile type nano-TiO2With Interaction between MnOx is weaker, simulates NH, and the reactivity test result of Selective Catalytic Reduction of NO shows that 500 DEG C are forged Burn obtained MnOx/TiO2Catalyst shows higher low temperature active (Southeast China University's journal：Natural science edition, 2012,3, 463-467)。
The A of CN 102553573 disclose a kind of antioxidant nitroxide catalyst, and the catalyst activity component is oxidation Manganese, the manganese oxide load is on inorganic carrier, or manganese oxide and a kind in cobalt oxide, cerium oxide, cupric oxide or at least two kinds of Form O composite metallic oxide catalyst.The carrier is inorganic oxide carrier, preferably silica, alundum (Al2O3), two Titanium oxide or its mixture, preferably alundum (Al2O3) or titanium dioxide, more preferably titanium dioxide.The antioxidant nitroxide is urged For agent under oxygen existence condition, lower temperature can realize nitrogen oxides (such as NO, N2O etc.) arrive nitrogen dioxide conversion. For the catalyst to be made through coprecipitation or infusion process, its main active component is manganese oxide.Applied and be in NO concentration In the cleaning test of 200ppm simulated flue gas, NO to NO is can be realized as in lower temperature2Conversion, NO2Enter back into desulfurizing tower Inside further with reactive desulfurizing agent so as to realizing the removing of nitrogen oxides in effluent.
The A of CN 102319560 disclose a kind of preparation method of manganese titanium catalyst, using manganese nitrate and titanium dioxide as original Material, add in deionized water, ultrasonication after mixing, then through drying, be calcined and produce manganese titanium catalyst, wherein, it is described Manganese titanium catalyst using titanyl compound as carrier, using the oxide of manganese as active component.Mn/TiO2(UI) catalyst series exist Denitration efficiency can reach 70% or so, Mn/TiO at 80 DEG C2(SG) preferable reactivity is also shown, however, Mn/TiO2 (TI) to reach temperature needed for identical NO removal efficiencies will be more than 150 DEG C.
It can be seen that the low-temperature denitration performance of manganese-base oxide catalyst is also undesirable, find that denitration temperature is lower and active temperature The problem of broader manganese-base oxide catalyst in area is still urgent need to resolve.
The content of the invention
It is an object of the invention to provide a kind of denitration of FCC regenerated flue gas manganese oxide/titanium dioxide catalyst and its system Preparation Method and purposes, the manganese oxide/titanium dioxide catalyst are prepared using hydro-thermal method, are a kind of loads of Nano grade Type oxide catalyst, active component manganese oxide are directly dispersing in the skeleton of titanium dioxide, good dispersion, and in catalyst Titanium dioxide is the higher anatase crystal of crystallinity, humidity province of the manganese oxide/titanium dioxide catalyst at 150-350 DEG C Interior denitration efficiency is stably held in more than 90%；And at 125 DEG C, its denitration efficiency is more than 90%；At 150 DEG C, denitration effect Rate reaches 98%.
To use following technical scheme up to this purpose, the present invention：
"/" in heretofore described manganese oxide/titanium dioxide catalyst represent " and " the meaning, manganese oxide/dioxy It is the manganese oxide catalyst mutually compound with titanium dioxide to change titanium catalyst.
An object of the present invention is to provide a kind of FCC regenerated flue gas denitration manganese oxide/titanium dioxide catalyst Preparation method, the preparation method are：By the solution containing titanium source with containing the molten of manganese source, expanding agent and optionally ammonium sulfate Liquid mixes, and carries out hydro-thermal reaction, reaction product is carried out into separation of solid and liquid, and gained solid is scrubbed, dries, and roasting, is aoxidized Manganese/titanium deoxide catalyst.
The manganese oxide/titanium dioxide catalyst is a kind of Nano grade using the method doping manganese in situ of Hydrothermal Synthesiss Supported oxide catalyst, using manganese oxide as active component, using titanium dioxide as carrier, titanium dioxide therein for crystallization The higher anatase crystal titanium dioxide of degree, active component manganese oxide are directly dispersing in the skeleton of titania support, therefore The good dispersion of active component.
The solvent of the solution containing titanium source is the mixed liquor of acetylacetone,2,4-pentanedione and absolute ethyl alcohol.Solution containing titanium source Solvent is different, although the composition of final product is more similar, MnO in its active component2Ratio reduces, and MnO2Catalysis It is active best, therefore catalyst activity can be caused to reduce.
Preferably, the volume ratio of the titanium source, acetylacetone,2,4-pentanedione and absolute ethyl alcohol is 5:(1~5):(10~15), such as 5：2： 11、5：3：12、5：4：14 or 5：2：14 etc..
Preferably, the titanium source is butyl titanate and/or isopropyl titanate.
The manganese source containing manganese source, expanding agent and optionally in the solution of ammonium sulfate, ammonium sulfate, expanding agent and solvent Mass ratio is：(0.8~3.5):1:(3~8):(10~30), such as 1：1：3：15、2：1：4：20、2.5：1：6：25 or 3：1：7： 28 etc..
The addition of the ammonium sulfate can improve the stability of intergranular pore.
Preferably, the manganese source is manganese nitrate and/or manganese acetate.
Preferably, the expanding agent be urea, ammonium hydrogen carbonate or ammonium carbonate in one kind or at least two combination, typical case It is but nonrestrictive to be combined as urea and ammonium hydrogen carbonate, urea and ammonium carbonate, ammonium hydrogen carbonate and ammonium carbonate etc..The expanding agent Addition can make final catalyst aperture increases, specific surface area increase, and enable to active component more preferable on carrier Ground disperses, and improves the activity of catalyst；Being added without expanding agent catalytic activity can reduce.
Preferably, it is described containing manganese source, expanding agent and optionally the solvent of the solution of ammonium sulfate is deionized water.
The mixing is specially：By containing manganese source, expanding agent and optionally the solution of ammonium sulfate is added by membrane diffusion device Enter into the solution containing titanium source, obtain mixed solution.The use of membrane diffusion device, make the solution containing titanium source with containing manganese source, The mixed process of the solution of expanding agent and optionally ammonium sulfate is controllable, so that active component is divided on carrier in final products Dissipate more preferably, be more evenly distributed, be advantageous to improve the activity of catalyst.
Preferably, the membrane diffusion device includes ceramic-film tube, and the size in the hole on the ceramic-film tube is 35~45nm, such as 36nm, 37nm, 38nm, 40nm, 42nm or 44nm etc..
Preferably, the membrane diffusion device is connected with peristaltic pump and gas input device respectively.
Preferably, the flow of gas is 10~100mL/min in the gas input device, such as 15mL/min, 20mL/ Min, 50mL/min, 60mL/min, 70mL/min, 80mL/min or 90mL/min etc..
Preferably, the gas in the gas input device is nitrogen.
The temperature of the hydro-thermal reaction is 80~120 DEG C, such as 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C or 115 ℃.The temperature of hydro-thermal reaction is high, then catalyst crystal grain is big；The temperature of hydro-thermal reaction is low, then catalyst crystal grain is small.
Preferably, the time of the hydro-thermal reaction is 20~30h, such as 22h, 23h, 25h, 26h, 27h or 29h.
Catalyst of the manganese oxide/titanium dioxide catalyst that hydro-thermal method is prepared for Nano grade is used, it compares surface Product is big, and titanium dioxide is the titanium dioxide of anatase crystal, is lacked in the titanium dioxide of anatase crystal containing more Sunken and dislocation, can produce more Lacking oxygens, this part room is easily absorbing oxygen, is advantageous to redox reaction, therefore its Good catalyst activity, active component good dispersion.
Separation of solid and liquid after hydro-thermal reaction is operation commonly used in the art, typical but non-limiting solid-liquid separation method To centrifuge.
The solvent used that washs is deionized water.The number of washing is unrestricted, and those skilled in the art can root Selected according to being actually needed.
Preferably, the temperature of the drying be 100~150 DEG C, such as 105 DEG C, 110 DEG C, 115 DEG C, 120 DEG C, 125 DEG C, 130 DEG C or 140 DEG C etc., the time is 5~10h, such as 6h, 7h, 8h, 9h or 10h.
Preferably, the temperature of the roasting be 350~450 DEG C, such as 360 DEG C, 370 DEG C, 380 DEG C, 390 DEG C, 400 DEG C, 410 DEG C, 420 DEG C, 430 DEG C, 440 DEG C or 445 DEG C etc., the time is 3~6h, such as 3.5h, 4h, 4.5h, 5h, 5.5h or 6h.
Preferably, the roasting is carried out in air atmosphere, and heating rate is 1~2 DEG C/min.
As preferable technical scheme, the preparation method comprises the following steps：
(1) titanium source, acetylacetone,2,4-pentanedione are added in absolute ethyl alcohol and mixed, obtain the solution containing titanium source, wherein, titanium source, The volume ratio of acetylacetone,2,4-pentanedione and absolute ethyl alcohol is 5:(1~5):(10~15)；By manganese source, expanding agent and optionally ammonium sulfate adds Dissolve, obtained containing manganese source, expanding agent and optionally ammonium sulfate into deionized water, wherein, manganese source, ammonium sulfate, reaming The mass ratio of agent and deionized water is (0.8~3.5):1:(3~8):(10~30)；
(2) by containing manganese source, expanding agent and optionally the solution of ammonium sulfate is added to containing titanium source by membrane diffusion device Solution in, obtain mixed solution, wherein, the flow of gas is 10~100mL/min in membrane diffusion device；
(3) mixed solution being transferred in autoclave and carries out hydro-thermal reaction, the temperature of hydro-thermal reaction is 80~120 DEG C, when Between be 20~30h, hydro-thermal reaction product is subjected to separation of solid and liquid, in 100~150 DEG C of dry 5~10h after the washing of gained solid, 3~6h is calcined under 350~450 DEG C of air atmospheres again, obtains manganese oxide/titanium dioxide catalyst.
The second object of the present invention is to provide a kind of FCC regenerated flue gas denitration manganese oxide/titanium dioxide catalyst, institute Manganese oxide/titanium dioxide catalyst is stated to be prepared by preparation method as described above.
The active component of the manganese oxide/titanium dioxide catalyst is manganese oxide, and carrier is titanium dioxide.
Manganese oxide accounts for the quality percentage of manganese oxide/titanium dioxide catalyst and contained in the manganese oxide/titanium dioxide catalyst Measure as 20~40%, such as 22%, 24%, 25%, 26%, 28%, 30%, 32%, 35%, 37% or 39%, be preferably 35%.
Preferably, the manganese oxide in the manganese oxide/titanium dioxide catalyst is MnO, Mn2O3Or MnO2In one kind or At least two combination.
Preferably, the particle size of the manganese oxide/titanium dioxide catalyst is 10~30nm, as 12nm, 15nm, 18nm, 20nm, 22nm, 25nm, 26nm, 28nm or 29nm etc..
The third object of the present invention is to provide a kind of purposes of manganese oxide/titanium dioxide catalyst, and it is used for FCC regeneration Denitrating flue gas field.
Compared with prior art, beneficial effects of the present invention are：
The present invention prepares FCC regenerated flue gas denitration manganese oxide/titanium dioxide catalyst, obtained oxidation using hydro-thermal method Manganese/titanium deoxide catalyst is a kind of supported oxide catalyst of Nano grade, using manganese oxide as active component, with dioxy Change titanium is carrier, and titanium dioxide is the higher anatase crystal titanium dioxide of crystallinity, and active component manganese oxide is directly scattered In the skeleton of titania support, therefore the good dispersion of active component.
Manganese oxide/titanium dioxide catalyst provided by the invention is used compared with common manganese oxide/titanium dioxide catalyst In FCC regenerated flue gas denitrations SCR reaction in active temperature windows it is wider (150-350 DEG C, denitration efficiency be more than 90%), it is low Preferably (under the conditions of 150 DEG C, denitration efficiency has the advantages that reference area is big, heat endurance is high up to 98%) to warm activity.
FCC regenerated flue gas denitration provided by the invention is simple with the preparation method of manganese oxide/titanium dioxide catalyst, prepares Condition is not harsh, short preparation period, has preferable application prospect.
Brief description of the drawings
Fig. 1 is carrier meso-TiO prepared by embodiment 1-62, Mn (20wt.%)/TiO2, Mn (25wt.%)/TiO2、Mn (30wt.%)/TiO2, Mn (35wt.%)/TiO2With Mn (40wt.%)/TiO2X-ray diffractogram.
Fig. 2 is carrier meso-TiO prepared by embodiment 1-62, Mn (20wt.%)/TiO2, Mn (25wt.%)/TiO2、Mn (30wt.%)/TiO2, Mn (35wt.%)/TiO2With Mn (40wt.%)/TiO2BET figure, wherein, Fig. 2 a be different Mn load The N of the catalyst of amount2Adsorption-desorption curve；Fig. 2 b are the graph of pore diameter distribution of the catalyst of different Mn load capacity；Fig. 2 a and Fig. 2 b In a, b, c, d, e and f represent respectively the load capacity of manganese oxide for 0,20wt.%, 25wt.%, 30wt.%, 35wt.% and 40wt.% Mn/TiO2Catalyst series.
Fig. 3 is Mn (20wt.%)/TiO prepared by embodiment 2-62, Mn (25wt.%)/TiO2, Mn (30wt.%)/ TiO2, Mn (35wt.%)/TiO2With Mn (40wt.%)/TiO2Selective catalysis reduction NO active testing result figure.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.
A, B and C in following examples are only used for distinguishing different solution, without other implications.
Embodiment 1：Prepare carrier meso-TiO2
(1) 20mL butyl titanates, 4mL acetylacetone,2,4-pentanediones are added in 60mL absolute ethyl alcohols, are sufficiently stirred, obtain solution A；5g ammonium sulfate and 20g urea are added in 50mL deionized waters, are sufficiently stirred, obtains solution B.
(2) solution B is added in solution A, obtains solution C；Process solution B being added in solution A is：Solution B Enter membrane diffusion device in the presence of peristaltic pump, while start gas input device, nitrogen is through 40nm on two ceramic-film tubes Micropore be diffused into outside membrane tube, produce substantial amounts of nitrogen bubble, promote solution completely to mix, nitrogen flow 10-100mL/ min。
(3) solution C is transferred in autoclave, reacts 24h at 100 DEG C, reacted product is centrifuged, washed Filtering is washed, 120 DEG C of oven drying 8h, then 400 DEG C of roasting 4h in Muffle furnace is put into afterwards, obtains carrier meso-TiO2。
Embodiment 2：Mn (20wt.%)/TiO2The preparation of catalyst
(1) 10mL butyl titanates, 2mL acetylacetone,2,4-pentanediones are added in 20mL absolute ethyl alcohols, are sufficiently stirred, obtain solution A；Manganese nitrate solution, 2.5g ammonium sulfate and 7.5g urea that 4.4734g mass percents are 50% are added to 25mL deionizations In water, it is sufficiently stirred, obtains solution B.
(2) solution B is added in solution A, obtains solution C；The process that solution B is added to solution A is：Solution B is existed Enter membrane diffusion device in the presence of peristaltic pump, while start gas input device, nitrogen is through 40nm on two ceramic-film tubes Micropore is diffused into outside membrane tube, produces substantial amounts of nitrogen bubble, promotes solution completely to mix, nitrogen flow 10-100mL/min.
(3) solution C is transferred in autoclave, in 80 DEG C of crystallization 30h, crystallization product be centrifuged, washed, mistake Filter, 100 DEG C of oven drying 10h are put into, 350 DEG C of roasting 6h of Muffle furnace, obtain Mn (20wt.%)/TiO2Catalyst (manganese oxide with 20%) mass ratio of titanium dioxide is.
Embodiment 3：Mn (25wt.%)/TiO2The preparation of catalyst
(1) 10mL butyl titanates, 10mL acetylacetone,2,4-pentanediones are added in 30mL absolute ethyl alcohols, are sufficiently stirred, obtained molten Liquid A；Manganese nitrate solution, 2.5g ammonium sulfate and 20g urea that 6.3236g mass percents are 50% are added to 75mL deionizations In water, it is sufficiently stirred, obtains solution B.
(2) solution B is added in solution A, obtains solution C；The process that solution B is added to solution A is：By what is configured Solution B enters membrane diffusion device in the presence of peristaltic pump, while starts gas input device, and nitrogen is through on two ceramic-film tubes 40nm micropore is diffused into outside membrane tube, produces substantial amounts of nitrogen bubble, promotes solution completely to mix, nitrogen flow 10- 100mL/min。
(3) solution C is transferred in autoclave, in 120 DEG C of crystallization 20h, crystallization product is centrifuged, washed, Filtering, is put into 150 DEG C of oven drying 5h afterwards, and 450 DEG C of roasting 3h, obtain Mn (25wt.%)/TiO in Muffle furnace2Catalyst (mass ratio of manganese oxide and titanium dioxide is 25%).
Embodiment 4：Mn (30wt.%)/TiO2The preparation of catalyst
(1) 10mL butyl titanates, 6mL acetylacetone,2,4-pentanediones are added in 25mL absolute ethyl alcohols, are sufficiently stirred, obtain solution A；By 8.7321g mass percents be 50% manganese nitrate solution, 2.5g ammonium sulfate and 13.75g urea be added to 50mL go from In sub- water, it is sufficiently stirred, obtains solution B.
(2) solution B is added in solution A, obtains solution C；The process that solution B is added to solution A is：By what is configured Solution B enters membrane diffusion device in the presence of peristaltic pump, while starts gas input device, and nitrogen is through on two ceramic-film tubes 40nm micropore is diffused into outside membrane tube, produces substantial amounts of nitrogen bubble, promotes solution completely to mix, nitrogen flow 10- 100mL/min。
(3) solution C is transferred in autoclave, in 100 DEG C of crystallization 25h, crystallization product is centrifuged, washed, Filtering, 125 DEG C of oven drying 7.5h, then 400 DEG C of roasting 4.5h in Muffle furnace are put into afterwards, obtains Mn (30wt.%)/TiO2 Catalyst (mass ratio of manganese oxide and titanium dioxide is 30%).
Embodiment 5：Mn (35wt.%)/TiO2The preparation of catalyst
(1) 10mL butyl titanates, 2mL acetylacetone,2,4-pentanediones are added in 20mL absolute ethyl alcohols, are sufficiently stirred, obtain solution A；Manganese nitrate solution, 2.5g ammonium sulfate and 7.5g urea that 11.9934g mass percents are 50% are added to 25mL deionizations In water, it is sufficiently stirred, obtains solution B.
(2) solution B is added in solution A, obtains solution C；The process that solution B is added to solution A is：By what is configured Solution B enters membrane diffusion device in the presence of peristaltic pump, while starts gas input device, and nitrogen is through on two ceramic-film tubes 40nm micropore is diffused into outside membrane tube, produces substantial amounts of nitrogen bubble, promotes solution completely to mix, nitrogen flow 10- 100mL/min。
(3) solution C is transferred in autoclave, in 100 DEG C of crystallization 25h, crystallization product is centrifuged, washed, Filtering, 125 DEG C of oven drying 7.5h, then 400 DEG C of roasting 4.5h in Muffle furnace are put into afterwards, obtains Mn (35wt.%)/TiO2 Catalyst (mass ratio of manganese oxide and titanium dioxide is 35%).
Embodiment 6：Mn (40wt.%)/TiO2The preparation of catalyst
(1) 10mL butyl titanates, 2mL acetylacetone,2,4-pentanediones are added in 20mL absolute ethyl alcohols, are sufficiently stirred, obtain solution A；Manganese nitrate solution, 2.5g ammonium sulfate and 7.5g urea that 16.6623g mass percents are 50% are added to 25mL deionizations In water, it is sufficiently stirred, obtains solution B.
(2) solution B is added in solution A, obtains solution C；The process that solution B is added to solution A is：By what is configured Solution B enters membrane diffusion device in the presence of peristaltic pump, while starts gas input device, and nitrogen is through on two ceramic-film tubes 40nm micropore is diffused into outside membrane tube, produces substantial amounts of nitrogen bubble, promotes solution completely to mix, nitrogen flow 10- 100mL/min。
(3) solution C is transferred in autoclave, in 120 DEG C of crystallization 20h, crystallization product is centrifuged, washed, Filtering, 100 DEG C of oven drying 10h, then 450 DEG C of roasting 3h in Muffle furnace are put into afterwards, obtains Mn (40wt.%)/TiO2Urge Agent (mass ratio of manganese oxide and titanium dioxide is 40%).
The carrier meso-TiO that embodiment 1-6 is prepared2, Mn (20wt.%)/TiO2, Mn (25wt.%)/TiO2、 Mn (30wt.%)/TiO2, Mn (35wt.%)/TiO2With Mn (40wt.%)/TiO2Urge and carry out XRD (German Bruker respectively D8Advance Series X-rays diffractometer) characterize, (Merck ＆ Co., Inc Micromeritics ASAP 2020 automatically compare surface to BET Analyzer) characterize and tested with catalytic activity, as a result as Figure 1-3.
Wherein, the activity test method of catalyst is：Sieving is ground after catalyst tabletting, takes the part of 40-60 mesh.Experiment Being carried out on the fixed bed reactors continuously flowed, the catalyst after specifically 0.4g is sieved is encased in quartz glass tube, Temperature carries out temperature programming control by tube type resistance furnace and temperature controller in pipe.Mixed gas simulates true flue gas, as corresponding to it Steel cylinder provide.Corresponding mixed gas, which forms, is：CNO=CNH3=1000ppm, CO2=3%, Balance Air N2, volume space velocity For 16000h-1.NO concentration value is imported and exported by ThermoFisher 42iHL NO analyzer on-line checkings.
The specific formula for calculation of NO conversion ratios is as follows：
Wherein, NOinFor import NO concentration (unit：Ppm), NOoutTo export NO concentration (unit：ppm)
Fig. 1 is the carrier meso-TiO that embodiment 1-6 is prepared2, Mn (20wt.%)/TiO2, Mn (25wt.%)/ TiO2, Mn (30wt.%)/TiO2, Mn (35wt.%)/TiO2With Mn (40wt.%)/TiO2X-ray diffractogram.As a result show Show, carrier meso-TiO prepared by embodiment 12For pure anatase crystal, and crystallinity is higher；Embodiment 2-6 is prepared Titanium dioxide is also the higher pure anatase crystal of crystallinity in catalyst, and without the diffraction maximum for finding manganese oxide, explanation Manganese oxide is preferable in carrier surface dispersiveness.
Fig. 2 is the carrier meso-TiO that embodiment 1-6 is prepared2, Mn (20wt.%)/TiO2, Mn (25wt.%)/ TiO2, Mn (30wt.%)/TiO2, Mn (35wt.%)/TiO2With Mn (40wt.%)/TiO2BET figure.As a result show, implement Carrier meso-TiO prepared by example 12Return stagnant ring-shaped be four type curve H2Type returns stagnant ring, is approached with three-dimensional caged pore structure, and Average pore size is 5.6nm；The stagnant ring-shaped of returning of catalyst prepared by embodiment 2-6 is also four type curve H2Type returns stagnant ring, with three Dimension caged pore structure approaches, and its average pore size illustrates the load of manganese oxide without the hole for blocking titanium dioxide in 5-10nm Gap.
Fig. 3 is Mn (20wt.%)/TiO prepared by embodiment 2-62, Mn (25wt.%)/TiO2, Mn (30wt.%)/ TiO2, Mn (35wt.%)/TiO2With Mn (40wt.%)/TiO2Selective catalysis reduction NO active testing result figure.Test knot Fruit shows：Denitration efficiency of all catalyst at 100 DEG C is more than 25%；In the range of 100-150 DEG C, with temperature Rise, the denitration efficiency of catalyst significantly improves：At 125 DEG C, the denitration efficiency of catalyst is more than 90%；At 150 DEG C, The denitration efficiency of catalyst can reach 98%；And in 150-350 DEG C of temperature range, the denitration efficiency of all catalyst It is stably held in more than 90%；It can be seen that manganese oxide/titanium dioxide catalyst provided by the invention is used for selective catalysis reduction NO's Low temperature active is preferable, and its active warm area is wider.
From this figure it can be seen that when the load capacity of manganese oxide in manganese oxide/titanium dioxide catalyst is 35%, catalysis The catalytic activity of agent is best, and highest denitration rate reaches 100%, and more than 90% conversion ratio can be maintained at 100~350 DEG C.
Comparative example 1
In addition to the membrane diffusion device in step (2), which is mixed, to be replaced with and be stirred, remaining the step of it is same as Example 5. Obtained catalyst is labeled as N-Mn (35wt.%)/TiO2Catalyst (mass ratio of manganese oxide and titanium dioxide is 35%).
Using activity test method same as Example 5 to N-Mn (35wt.%)/TiO2Carry out selective catalysis reduction NO Active testing, as a result show, the active warm area of the denitration efficiency of catalyst more than 90% is 150~325 DEG C.
Comparative example 2
Raw material same as Example 5 is used to prepare the mass ratio of manganese oxide and titanium dioxide by coprecipitation as 35% Catalyst, obtained catalyst is labeled as C-Mn (35wt.%)/TiO2。
Using activity test method same as Example 5 to C-Mn (35wt.%)/TiO2Carry out selective catalysis reduction NO Active testing, as a result show, the active warm area of the denitration efficiency of catalyst more than 90% is 200~250 DEG C.
Comparative example 3
Raw material same as Example 5 is used to prepare the mass ratio of manganese oxide and titanium dioxide by infusion process as 35% Catalyst, obtained catalyst is labeled as I-Mn (35wt.%)/TiO2。
Using activity test method same as Example 5 to I-Mn (35wt.%)/TiO2Carry out selective catalysis reduction NO Active testing, as a result show, the active warm area of the denitration efficiency of catalyst more than 90% is 175~300 DEG C.
Applicant states, the foregoing is only the embodiment of the present invention, but protection scope of the present invention not office It is limited to this, person of ordinary skill in the field is it will be clearly understood that any belong to those skilled in the art and taken off in the present invention In the technical scope of dew, the change or replacement that can readily occur in, all fall within protection scope of the present invention and it is open within the scope of.

Claims (23)

  1. A kind of 1. preparation method of FCC regenerated flue gas denitration manganese oxide/titanium dioxide catalyst, it is characterised in that the system Preparation Method comprises the following steps：
    Solution containing titanium source is mixed with the solution containing manganese source, expanding agent and optionally ammonium sulfate, carries out hydro-thermal reaction, Reaction product is subjected to separation of solid and liquid, gained solid is scrubbed, dries, and roasting, obtains manganese oxide/titanium dioxide catalyst；
    The mixing is specially：By containing manganese source, expanding agent and optionally the solution of ammonium sulfate is added to by membrane diffusion device In solution containing titanium source, mixed solution is obtained；
    The expanding agent is one kind or at least two combination in urea, ammonium hydrogen carbonate or ammonium carbonate；The hydro-thermal reaction Temperature is 80~120 DEG C.
  2. 2. preparation method according to claim 1, it is characterised in that the solvent of the solution containing titanium source is levulinic The mixed liquor of ketone and absolute ethyl alcohol.
  3. 3. preparation method according to claim 2, it is characterised in that the body of the titanium source, acetylacetone,2,4-pentanedione and absolute ethyl alcohol Product is than being 5:(1~5):(10~15).
  4. 4. preparation method according to claim 1, it is characterised in that the titanium source is butyl titanate and/or isopropanol Titanium.
  5. 5. preparation method according to claim 1, it is characterised in that described to contain manganese source, expanding agent and optionally sulphur Manganese source in the solution of sour ammonium, ammonium sulfate, the mass ratio of expanding agent and solvent are：(0.8~3.5):1:(3~8):(10~30).
  6. 6. preparation method according to claim 1, it is characterised in that the manganese source is manganese nitrate and/or manganese acetate.
  7. 7. preparation method according to claim 1, it is characterised in that described to contain manganese source, expanding agent and optionally sulphur The solvent of the solution of sour ammonium is deionized water.
  8. 8. preparation method according to claim 1, it is characterised in that the membrane diffusion device includes ceramic-film tube, the pottery The size in the hole in porcelain membrane tube is 35~45nm.
  9. 9. preparation method according to claim 1, it is characterised in that the membrane diffusion device is defeated with peristaltic pump and gas respectively Enter device to be connected.
  10. 10. preparation method according to claim 9, it is characterised in that the flow of gas is in the gas input device 10~100mL/min.
  11. 11. preparation method according to claim 9, it is characterised in that the gas in the gas input device is nitrogen.
  12. 12. preparation method according to claim 1, it is characterised in that the time of the hydro-thermal reaction is 20~30h.
  13. 13. preparation method according to claim 1, it is characterised in that the solvent used that washs is deionized water.
  14. 14. preparation method according to claim 1, it is characterised in that the temperature of the drying is 100~150 DEG C, the time For 5~10h.
  15. 15. preparation method according to claim 1, it is characterised in that the temperature of the roasting is 350~450 DEG C, the time For 3~6h.
  16. 16. preparation method according to claim 1, it is characterised in that the roasting is carried out in air atmosphere, heating speed Rate is 1~2 DEG C/min.
  17. 17. preparation method according to claim 1, it is characterised in that the preparation method comprises the following steps：
    (1) titanium source, acetylacetone,2,4-pentanedione are added in absolute ethyl alcohol and mixed, obtain the solution containing titanium source, wherein titanium source, levulinic The mass ratio of ketone and absolute ethyl alcohol is 5:(1~5):(10~15)；By manganese source, expanding agent and optionally ammonium sulfate be added to from Dissolve, obtained containing manganese source, expanding agent and the optionally solution of ammonium sulfate in sub- water, wherein, manganese source, ammonium sulfate, expanding agent Mass ratio with deionized water is (0.8~3.5):1:(3~8):(10~30)；
    (2) by containing manganese source, expanding agent and optionally the solution of ammonium sulfate is added to containing the molten of titanium source by membrane diffusion device In liquid, mixed solution is obtained, wherein, the flow of gas is 10~100mL/min in membrane diffusion device；
    (3) mixed solution is transferred in autoclave and carries out hydro-thermal reaction, the temperature of hydro-thermal reaction is 80~120 DEG C, and the time is 20~30h, hydro-thermal reaction product is subjected to separation of solid and liquid, in 100~150 DEG C of dry 5~10h after the washing of gained solid, then 3~6h is calcined under 350~450 DEG C of air atmospheres, obtains manganese oxide/titanium dioxide catalyst.
  18. A kind of 18. FCC regenerated flue gas denitration manganese oxide/titanium dioxide catalyst, it is characterised in that the manganese oxide/dioxy Change preparation method of the titanium catalyst according to one of claim 1-17 to be prepared.
  19. 19. manganese oxide/titanium dioxide catalyst according to claim 18, it is characterised in that the manganese oxide/titanium dioxide The weight/mass percentage composition that manganese oxide accounts for manganese oxide/titanium dioxide catalyst in titanium catalyst is 20~40%.
  20. 20. manganese oxide/titanium dioxide catalyst according to claim 18, it is characterised in that the manganese oxide/titanium dioxide The weight/mass percentage composition that manganese oxide accounts for manganese oxide/titanium dioxide catalyst in titanium catalyst is 35%.
  21. 21. manganese oxide/titanium dioxide catalyst according to claim 18, it is characterised in that the manganese oxide/titanium dioxide Manganese oxide in titanium catalyst is MnO, Mn2O3Or MnO2In one kind or at least two combination.
  22. 22. manganese oxide/titanium dioxide catalyst according to claim 18, it is characterised in that the manganese oxide/titanium dioxide The particle size of titanium catalyst is 10~30nm.
  23. 23. the purposes of manganese oxide/titanium dioxide catalyst according to claim 18, it is used for FCC regenerated flue gas denitrations Field.
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