CN105126826A - Manganese oxide/titanium dioxide catalyst for FCC (catalytic cracking) regenerated flue gas denitrification, preparation method therefore and applications - Google Patents
Manganese oxide/titanium dioxide catalyst for FCC (catalytic cracking) regenerated flue gas denitrification, preparation method therefore and applications Download PDFInfo
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Abstract
The invention provides a manganese oxide/titanium dioxide catalyst for FCC (catalytic cracking) regenerated flue gas denitrification, a preparation method therefore and applications. The manganese oxide/titanium dioxide catalyst is prepared through a hydrothermal method: a solution containing a titanium source and a solution containing a manganese source, pore-enlarging agents and ammonium sulfate optionally are mixed, a hydrothermal reaction is carried out, the reaction products are subjected to solid-liquid separation, the obtained solid is washed, dried and baked, and the manganese oxide/titanium dioxide catalyst is obtained. The manganese oxide/titanium dioxide catalyst is a nano-level load-type oxide catalyst, the dispersibility of active components is good, the preparation method is simple, the active temperature window is wide (at a temperature of 150-350 DEG C, the denitration efficiency is more than 90%), and the low temperature activity is good (at a temperature of 150 DEG C, the denitration efficiency reaches 98%). In addition, the provided catalyst has advantages of large comparison area, high thermal stability, high N2 selectivity and the like, and has good application prospects.
Description
Technical field
The invention belongs to catalyst technical field, relate to a kind of FCC regenerated flue gas denitration manganese oxide/titanium dioxide Catalysts and its preparation method and purposes.
Background technology
Catalytic cracking (FCC) device is the significant element in crude oil depth process, occupies very important status in petroleum refining industry.In catalytic cracking reaction process, while feedstock oil generation cracking, wherein the nitrogen-containing compound of 30% ~ 50% enters oil coke, and is deposited on catalyst surface thereupon.Catalyst is active because of surface attachment oil coke to be reduced, and must carry out regeneration process.In regenerator burning process, most of nitrogen-containing compound is converted into N
2, but also have 10% ~ 30% to be converted into NO
x, discharge with regenerated flue gas, wherein main component is NO, and percentage by volume is about 90%, and residue about 10% is NO
2.According to the difference of raw material and operating condition, NO in regenerated flue gas
xconcentration also there are differences, but generally higher than the 420mg/m required in " discharge standard of air pollutants " (GB16297-1996)
3(device built in the past for 1997) and 240mg/m
3(1997 and the later device built), and be not all equipped with denitrating flue gas facility.
On the other hand, due to the NO developing the adverse effect with crude oil in poor quality, oil refining enterprise rapidly of crude oil processing industry
xdischarge capacity is increasing.Usually, regenerated flue gas is oil plant NO
xthe main source of discharge, accounts for 50% of its total release.Up to now, CNPC has 41 cover FCC apparatus, and total productive capacity reaches 5,080 ten thousand tons/year, and regenerated flue gas total emission volumn is more than 5,000,000 Nm
3/ h, NO
xannual emissions is about 1.2 ten thousand tons.If adopt gas denitrifying technology to process it, with NO
xclearance is 80% calculating, and only this item just can realize group company NO
xdischarge capacity reduces by 10%.Visible, NO in FCC regenerated flue gas
xemission problem has become the common problem of each oil refining enterprise of CNPC, seriously constrains pushing ahead of CNPC's energy-saving and emission-reduction and cleaner production work.
Can predict, along with the increasingly stringent of environmental protection standard, the Production requirement of each oil refining enterprise of CNPC to FCC regenerated flue gas denitration technology will expand rapidly.
At present, the FCC regenerated flue gas denitration technology of commercial Application comprises both at home and abroad: low NO
xburn technology, oxidative absorption method, add auxiliary agent method, SNCR (SNCR) method and SCR (SCR) method.Five kinds of FCC regenerated flue gas denitration technology features are different, are applicable to different treatment conditions and processing requirements respectively, need to select with suiting measures to local conditions.But with regard to the existing 41 cover FCC apparatus of China, to solve regenerated flue gas denitration problem on the whole, selective catalytic reduction (SCR) is because treatment effect is stable, wide accommodation, technical maturity, beyond doubt the most competitive technology.
Traditional SCR catalyst has noble metal catalyst, metal oxide catalyst and molecular sieve catalyst.And in recent years, oxide catalyst because of its manufacturing cycle short, the advantages such as cost is low, easy and simple to handle are subject to extensive concern.Vanadia-based SCR catalysts has industrially applied to stationary source denitration for many years, but still also exist that operating temperature is higher, operating temperature window is narrower, high temperature time N
2o generates in a large number and causes N
2selective decline, and SO
2to SO
3the problems such as oxidation.Therefore, exploitation can reduce costs the low-temperature SCR catalyst of expense greatly, and the oxide catalyst finding non-vanadium class is the main path addressed these problems.In recent years, the good manganese-based catalyst of low temperature active is to NH
3-SCR reaction has higher low-temperature catalytic activity and selective, thus receives much concern, and becomes the class denitrating catalyst that research is more.
Li Huijie is to MnOx-TiO
2catalytic oxidation NO performance is studied, and paper examines single-activity component MnOx is to the catalysed oxidn of NO and H
2o, SO
2on the impact of catalyst activity, and analyze catalyst poisoning mechanism.Result of study shows that infusion process prepares MnOx-TiO
2the optimum condition of catalyst is: Mn content 20% (wt%), 300 DEG C of roasting 6h, and the catalyst prepared with this understanding has very high NO catalytic oxidation activity: air speed is 10000h
-1, reaction temperature NO when being 300 DEG C conversion ratio up to 89% (University Of Xiangtan, 2011, master thesis).
The people such as Li Junhua have studied MnOx/TiO prepared by different manganese sources
2on the impact of NO reduction reaction, find that the MnOx using manganese nitrate to obtain as manganese source is mainly MnO
2; The MnOx using manganese acetate to obtain as manganese source is mainly Mn
2o
3(EffectsofprecursorsonthesurfaceMnspeciesandtheactivities forNOreductionoverMnOx/TiO
2catalysts, CatalysisCommunications, 2007,12 (8): 1896 – 1900).
The people such as Xu Haitao have studied MnOx/TiO
2the preparation of catalyst and low temperature NH thereof
3selective Catalytic Reduction of NO performance, adopts microemulsion method under different calcining heats, prepared the nano-TiO of different crystalline phase
2, and as carrier, a series of MnOx/TiO that utilized infusion process to prepare
2catalyst.Experimental result shows: along with the increase of calcining heat, nano-TiO
2change to rutile-type gradually from anatase titanium dioxide, the nano-TiO that 700 DEG C of calcinings obtain
2in mixed crystal phase, the nano-TiO that 800 DEG C of calcinings obtain
2it is then pure rutile type; Anatase titanium dioxide and mixed crystal phase TiO
2carrier and activating oxide MnO
2between interaction comparatively strong, work as nano-TiO
2middle rutile-type and anatase titanium dioxide when depositing, MnO
2preferential and dichloride in anatase type TiO
2effect; Pure rutile type nano-TiO
2and the interaction between MnOx is more weak, simulation NH, the reactivity test result of Selective Catalytic Reduction of NO shows, the MnOx/TiO that 500 DEG C of calcinings obtain
2catalyst shows higher low temperature active (Southeast China University's journal: natural science edition, 2012,3,463-467).
CN102553573A discloses a kind of antioxidant nitroxide catalyst, described catalyst activity component is manganese oxide, described manganese oxide load is on inorganic carrier, or manganese oxide and cobalt oxide, cerium oxide, in cupric oxide a kind or at least 2 kinds form O composite metallic oxide catalyst.Described carrier is inorganic oxide carrier, and preferred silica, alundum (Al2O3), titanium dioxide or its mixture, preferred alundum (Al2O3) or titanium dioxide, be more preferably titanium dioxide.Described antioxidant nitroxide catalyst is under oxygen existence condition, and lower temperature just can realize nitrogen oxide (such as NO, N
2o etc.) to the conversion of nitrogen dioxide.This catalyst is obtain through coprecipitation or infusion process, and its main active component is manganese oxide.Being applied in NO concentration is in the cleaning test of the simulated flue gas of 200ppm, just can realize NO to NO at lower temperature
2conversion, NO
2to enter again in desulfurizing tower and realize removing of nitrogen oxides in effluent with reactive desulfurizing agent further.
CN102319560A discloses a kind of preparation method of manganese titanium catalyst, with manganese nitrate and titanium dioxide for raw material, add in deionized water, ultrasonic wave process after mix and blend, namely drying, roasting obtain manganese titanium catalyst again, wherein, described manganese titanium catalyst take titanyl compound as carrier, with the oxide of manganese for active component.Mn/TiO
2(UI) catalyst series denitration efficiency 80 DEG C time can reach about 70%, Mn/TiO
2(SG) good reactivity is also shown, but, Mn/TiO
2(TI) will reach that identical NO removal efficiency is temperature required will more than 150 DEG C.
Visible, the low-temperature denitration performance of manganese-base oxide catalyst is also undesirable, finds lower and that active warm area the is wider manganese-base oxide catalyst of denitration temperature and is still the problem needing solution badly.
Summary of the invention
The object of the present invention is to provide a kind of FCC regenerated flue gas denitration manganese oxide/titanium dioxide Catalysts and its preparation method and purposes, described manganese oxide/titanium dioxide catalyst adopts hydro-thermal method to prepare, it is a kind of supported oxide catalyst of Nano grade, active component manganese oxide is directly dispersed in the skeleton of titanium dioxide, good dispersion, and the titanium dioxide in catalyst is the anatase crystal that degree of crystallinity is higher, described manganese oxide/titanium dioxide catalyst denitration efficiency in the temperature range of 150-350 DEG C is stable remains on more than 90%; And when 125 DEG C, its denitration efficiency is greater than 90%; When 150 DEG C, denitration efficiency reaches 98%.
For reaching this object, the present invention by the following technical solutions:
"/" in manganese oxide/titanium dioxide catalyst described in the present invention represents " with " the meaning, the catalyst of manganese oxide/titanium dioxide catalyst and manganese oxide and titanium dioxide phase compound.
An object of the present invention is the preparation method providing a kind of FCC regenerated flue gas denitration manganese oxide/titanium dioxide catalyst, described preparation method is: mixed with the solution containing manganese source, expanding agent and optionally ammonium sulfate by the solution containing titanium source, carry out hydro-thermal reaction, product is carried out Separation of Solid and Liquid, gained solid is through washing, drying, roasting, obtains manganese oxide/titanium dioxide catalyst.
Described manganese oxide/titanium dioxide catalyst adopts the in-situ doped manganese of method of Hydrothermal Synthesis, it is a kind of supported oxide catalyst of Nano grade, take manganese oxide as active component, take titanium dioxide as carrier, titanium dioxide is wherein the anatase crystal titanium dioxide that degree of crystallinity is higher, active component manganese oxide is directly dispersed in the skeleton of titania support, therefore the good dispersion of active component.
The solvent of the described solution containing titanium source is the mixed liquor of acetylacetone,2,4-pentanedione and absolute ethyl alcohol.The solvent of the solution containing titanium source is different, although the composition of end product is more similar, and MnO in its active component
2ratio reduces, and MnO
2catalytic activity best, catalyst activity therefore can be caused to reduce.
Preferably, the volume ratio of described titanium source, acetylacetone,2,4-pentanedione and absolute ethyl alcohol is 5:(1 ~ 5): (10 ~ 15), as 5:2:11,5:3:12,5:4:14 or 5:2:14 etc.
Preferably, described titanium source is butyl titanate and/or isopropyl titanate.
The mass ratio of manganese source in the described solution containing manganese source, expanding agent and optionally ammonium sulfate, ammonium sulfate, expanding agent and solvent is: (0.8 ~ 3.5): 1:(3 ~ 8): (10 ~ 30), as 1:1:3:15,2:1:4:20,2.5:1:6:25 or 3:1:7:28 etc.
Described ammonium sulfate add the stability that can improve intergranular pore.
Preferably, described manganese source is manganese nitrate and/or manganese acetate.
Preferably, described expanding agent is the combination of a kind of in urea, carbonic hydroammonium or ammonium carbonate or at least two kinds, is typical but non-limitingly combined as urea and carbonic hydroammonium, urea and ammonium carbonate, carbonic hydroammonium and ammonium carbonate etc.Adding of described expanding agent can make final catalyst aperture increase, and specific area increases, and active component can be made to disperse better on carrier, improves the activity of catalyst; Do not add expanding agent catalytic activity can reduce.
Preferably, the described solvent containing manganese source, expanding agent and the optionally solution of ammonium sulfate is deionized water.
Described mixing is specially: joined in the solution containing titanium source by membrane diffusion device by the solution containing manganese source, expanding agent and optionally ammonium sulfate, obtain mixed solution.The use of membrane diffusion device, make the solution containing titanium source controlled with the mixed process containing manganese source, expanding agent and the optionally solution of ammonium sulfate, thus make active component in final products disperse better on carrier, be more evenly distributed, be conducive to the activity improving catalyst.
Preferably, described membrane diffusion device comprises ceramic-film tube, and the size in the hole on described ceramic-film tube is 35 ~ 45nm, as 36nm, 37nm, 38nm, 40nm, 42nm or 44nm etc.
Preferably, described membrane diffusion device is connected with gas input device with peristaltic pump respectively.
Preferably, in described gas input device, the flow of gas is 10 ~ 100mL/min, as 15mL/min, 20mL/min, 50mL/min, 60mL/min, 70mL/min, 80mL/min or 90mL/min etc.
Preferably, the gas in described gas input device is nitrogen.
The temperature of described hydro-thermal reaction is 80 ~ 120 DEG C, as 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C or 115 DEG C.The temperature of hydro-thermal reaction is high, then catalyst crystal grain is large; The temperature of hydro-thermal reaction is low, then catalyst crystal grain is little.
Preferably, the time of described hydro-thermal reaction is 20 ~ 30h, as 22h, 23h, 25h, 26h, 27h or 29h etc.
The manganese oxide/titanium dioxide catalyst adopting hydro-thermal method to prepare is the catalyst of Nano grade, its specific area is large, and titanium dioxide is the titanium dioxide of anatase crystal, containing more defect and dislocation in the titanium dioxide of anatase crystal, can produce more Lacking oxygen, this part room is easy to adsorb oxygen, is conducive to redox reaction, therefore its good catalyst activity, active component good dispersion.
Separation of Solid and Liquid after hydro-thermal reaction is the operation that this area is commonly used, and typical but non-limiting solid-liquid separation method is centrifugation.
The solvent that described washing uses is deionized water.The number of times of washing is unrestricted, and those skilled in the art can select according to actual needs.
Preferably, the temperature of described drying is 100 ~ 150 DEG C, and 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, as 6h, 7h, 8h, 9h or 10h etc.
Preferably, the temperature of described roasting is 350 ~ 450 DEG C, and 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, as 3.5h, 4h, 4.5h, 5h, 5.5h or 6h etc.
Preferably, described roasting is carried out in air atmosphere, and heating rate is 1 ~ 2 DEG C/min.
As preferred technical scheme, described preparation method comprises the steps:
(1) titanium source, acetylacetone,2,4-pentanedione are joined in absolute ethyl alcohol and mixed, obtain the solution containing titanium source, wherein, the volume ratio of titanium source, acetylacetone,2,4-pentanedione and absolute ethyl alcohol is 5:(1 ~ 5): (10 ~ 15); By manganese source, expanding agent and optionally ammonium sulfate join in deionized water and dissolve, obtain containing manganese source, expanding agent and optionally ammonium sulfate, wherein, the mass ratio of manganese source, ammonium sulfate, expanding agent and deionized water is (0.8 ~ 3.5): 1:(3 ~ 8): (10 ~ 30);
(2) joined in the solution containing titanium source by membrane diffusion device by the solution containing manganese source, expanding agent and optionally ammonium sulfate, obtain mixed solution, wherein, in membrane diffusion device, the flow of gas is 10 ~ 100mL/min;
(3) mixed solution is transferred in autoclave carries out hydro-thermal reaction, the temperature of hydro-thermal reaction is 80 ~ 120 DEG C, time is 20 ~ 30h, hydro-thermal reaction product is carried out Separation of Solid and Liquid, at 100 ~ 150 DEG C of drying 5 ~ 10h after gained solids wash, roasting 3 ~ 6h under 350 ~ 450 DEG C of air atmospheres, obtains manganese oxide/titanium dioxide catalyst again.
Two of object of the present invention is to provide a kind of FCC regenerated flue gas denitration manganese oxide/titanium dioxide catalyst, and described manganese oxide/titanium dioxide catalyst is prepared by preparation method as above.
The active component of described manganese oxide/titanium dioxide catalyst is manganese oxide, and carrier is titanium dioxide.
In described manganese oxide/titanium dioxide catalyst, manganese oxide accounts for the mass percentage of manganese oxide/titanium dioxide catalyst is 20 ~ 40%, as 22%, 24%, 25%, 26%, 28%, 30%, 32%, 35%, 37% or 39% etc., is preferably 35%.
Preferably, the manganese oxide in described manganese oxide/titanium dioxide catalyst is MnO, Mn
2o
3or MnO
2in a kind of or combination of at least two kinds.
Preferably, the particle size of described manganese oxide/titanium dioxide catalyst is 10 ~ 30nm, as 12nm, 15nm, 18nm, 20nm, 22nm, 25nm, 26nm, 28nm or 29nm etc.
Three of object of the present invention is the purposes providing a kind of manganese oxide/titanium dioxide catalyst, and it is for FCC regenerated flue gas denitration field.
Compared with prior art, beneficial effect of the present invention is:
The present invention adopts hydro-thermal method to prepare FCC regenerated flue gas denitration manganese oxide/titanium dioxide catalyst, obtained manganese oxide/titanium dioxide catalyst is a kind of supported oxide catalyst of Nano grade, take manganese oxide as active component, take titanium dioxide as carrier, and the titanium dioxide anatase crystal titanium dioxide that to be degree of crystallinity higher, active component manganese oxide is directly dispersed in the skeleton of titania support, therefore the good dispersion of active component.
Manganese oxide/titanium dioxide catalyst provided by the invention is compared with common manganese oxide/titanium dioxide catalyst, for the wider (150-350 DEG C of active temperature windows in the SCR reaction of FCC regenerated flue gas denitration, denitration efficiency is greater than 90%), low temperature active is better (under 150 DEG C of conditions, denitration efficiency reaches 98%), have that reference area is large, heat endurance advantages of higher simultaneously.
The preparation method of FCC regenerated flue gas denitration manganese oxide/titanium dioxide catalyst provided by the invention is simple, and preparation condition is not harsh, and manufacturing cycle is short, has good application prospect.
Accompanying drawing explanation
Fig. 1 is carrier meso-TiO prepared by embodiment 1-6
2, Mn (20wt.%)/TiO
2, Mn (25wt.%)/TiO
2, Mn (30wt.%)/TiO
2, Mn (35wt.%)/TiO
2with Mn (40wt.%)/TiO
2x-ray diffractogram.
Fig. 2 is carrier meso-TiO prepared by embodiment 1-6
2, Mn (20wt.%)/TiO
2, Mn (25wt.%)/TiO
2, Mn (30wt.%)/TiO
2, Mn (35wt.%)/TiO
2with Mn (40wt.%)/TiO
2bET figure, wherein, Fig. 2 a is the N of the catalyst of different Mn load capacity
2adsorption-desorption curve; Fig. 2 b is the graph of pore diameter distribution of the catalyst of different Mn load capacity; A, b, c, d, e and f in Fig. 2 a and Fig. 2 b represent that the load capacity of manganese oxide is 0, the Mn/TiO of 20wt.%, 25wt.%, 30wt.%, 35wt.% and 40wt.% respectively
2catalyst series.
Fig. 3 is Mn (20wt.%)/TiO prepared by embodiment 2-6
2, Mn (25wt.%)/TiO
2, Mn (30wt.%)/TiO
2, Mn (35wt.%)/TiO
2with Mn (40wt.%)/TiO
2the active testing result figure of Selective catalytic reduction NO.
Detailed description of the invention
Technical scheme of the present invention is further illustrated by detailed description of the invention below in conjunction with accompanying drawing.
A, B and C in following examples only for distinguishing different solution, without other implications.
Embodiment 1: prepare carrier meso-TiO
2
(1) 20mL butyl titanate, 4mL acetylacetone,2,4-pentanedione are joined in 60mL absolute ethyl alcohol, fully stir, obtain solution A; 5g ammonium sulfate and 20g urea are joined in 50mL deionized water, fully stirs, obtain solution B.
(2) solution B is joined in solution A, obtain solution C; Process solution B joined in solution A is: solution B enters membrane diffusion device under the effect of peristaltic pump, start gas input device simultaneously, nitrogen is diffused into outside film pipe through the micropore of 40nm on two ceramic-film tubes, produce a large amount of nitrogen bubble, promote that solution mixes completely, nitrogen flow is 10-100mL/min.
(3) solution C is transferred in autoclave, 100 DEG C reaction 24h, reacted product is carried out centrifugation, washing and filtering, puts into 120 DEG C of oven drying 8h afterwards, then in Muffle furnace 400 DEG C of roasting 4h, obtain carrier meso-TiO
2.
Embodiment 2:Mn (20wt.%)/TiO
2the preparation of catalyst
(1) 10mL butyl titanate, 2mL acetylacetone,2,4-pentanedione are joined in 20mL absolute ethyl alcohol, fully stir, obtain solution A; Be that the manganese nitrate solution of 50%, 2.5g ammonium sulfate and 7.5g urea join in 25mL deionized water by 4.4734g mass percent, fully stir, obtain solution B.
(2) solution B is joined in solution A, obtain solution C; The process that solution B joins solution A is: solution B is entered membrane diffusion device under the effect of peristaltic pump, start gas input device simultaneously, nitrogen is diffused into outside film pipe through the micropore of 40nm on two ceramic-film tubes, produce a large amount of nitrogen bubble, promote that solution mixes completely, nitrogen flow is 10-100mL/min.
(3) be transferred in autoclave by solution C, at 80 DEG C of crystallization 30h, crystallization product carried out centrifugation, washing, filter, put into 100 DEG C of oven drying 10h, Muffle furnace 350 DEG C of roasting 6h, obtain Mn (20wt.%)/TiO
2catalyst (mass ratio of manganese oxide and titanium dioxide is 20%).
Embodiment 3:Mn (25wt.%)/TiO
2the preparation of catalyst
(1) 10mL butyl titanate, 10mL acetylacetone,2,4-pentanedione are joined in 30mL absolute ethyl alcohol, fully stir, obtain solution A; Be that the manganese nitrate solution of 50%, 2.5g ammonium sulfate and 20g urea join in 75mL deionized water by 6.3236g mass percent, fully stir, obtain solution B.
(2) solution B is joined in solution A, obtain solution C; The process that solution B joins solution A is: the solution B configured is entered membrane diffusion device under the effect of peristaltic pump, start gas input device simultaneously, nitrogen is diffused into outside film pipe through the micropore of 40nm on two ceramic-film tubes, produce a large amount of nitrogen bubble, promote that solution mixes completely, nitrogen flow is 10-100mL/min.
(3) be transferred in autoclave by solution C, at 120 DEG C of crystallization 20h, crystallization product carried out centrifugation, washing, filter, put into 150 DEG C of oven drying 5h afterwards, 450 DEG C of roasting 3h in Muffle furnace, obtain Mn (25wt.%)/TiO
2catalyst (mass ratio of manganese oxide and titanium dioxide is 25%).
Embodiment 4:Mn (30wt.%)/TiO
2the preparation of catalyst
(1) 10mL butyl titanate, 6mL acetylacetone,2,4-pentanedione are joined in 25mL absolute ethyl alcohol, fully stir, obtain solution A; Be that the manganese nitrate solution of 50%, 2.5g ammonium sulfate and 13.75g urea join in 50mL deionized water by 8.7321g mass percent, fully stir, obtain solution B.
(2) solution B is joined in solution A, obtain solution C; The process that solution B joins solution A is: the solution B configured is entered membrane diffusion device under the effect of peristaltic pump, start gas input device simultaneously, nitrogen is diffused into outside film pipe through the micropore of 40nm on two ceramic-film tubes, produce a large amount of nitrogen bubble, promote that solution mixes completely, nitrogen flow is 10-100mL/min.
(3) solution C is transferred in autoclave, at 100 DEG C of crystallization 25h, crystallization product is carried out centrifugation, washing, filter, put into 125 DEG C of oven drying 7.5h afterwards, then in Muffle furnace 400 DEG C of roasting 4.5h, obtain Mn (30wt.%)/TiO
2catalyst (mass ratio of manganese oxide and titanium dioxide is 30%).
Embodiment 5:Mn (35wt.%)/TiO
2the preparation of catalyst
(1) 10mL butyl titanate, 2mL acetylacetone,2,4-pentanedione are joined in 20mL absolute ethyl alcohol, fully stir, obtain solution A; Be that the manganese nitrate solution of 50%, 2.5g ammonium sulfate and 7.5g urea join in 25mL deionized water by 11.9934g mass percent, fully stir, obtain solution B.
(2) solution B is joined in solution A, obtain solution C; The process that solution B joins solution A is: the solution B configured is entered membrane diffusion device under the effect of peristaltic pump, start gas input device simultaneously, nitrogen is diffused into outside film pipe through the micropore of 40nm on two ceramic-film tubes, produce a large amount of nitrogen bubble, promote that solution mixes completely, nitrogen flow is 10-100mL/min.
(3) solution C is transferred in autoclave, at 100 DEG C of crystallization 25h, crystallization product is carried out centrifugation, washing, filter, put into 125 DEG C of oven drying 7.5h afterwards, then in Muffle furnace 400 DEG C of roasting 4.5h, obtain Mn (35wt.%)/TiO
2catalyst (mass ratio of manganese oxide and titanium dioxide is 35%).
Embodiment 6:Mn (40wt.%)/TiO
2the preparation of catalyst
(1) 10mL butyl titanate, 2mL acetylacetone,2,4-pentanedione are joined in 20mL absolute ethyl alcohol, fully stir, obtain solution A; Be that the manganese nitrate solution of 50%, 2.5g ammonium sulfate and 7.5g urea join in 25mL deionized water by 16.6623g mass percent, fully stir, obtain solution B.
(2) solution B is joined in solution A, obtain solution C; The process that solution B joins solution A is: the solution B configured is entered membrane diffusion device under the effect of peristaltic pump, start gas input device simultaneously, nitrogen is diffused into outside film pipe through the micropore of 40nm on two ceramic-film tubes, produce a large amount of nitrogen bubble, promote that solution mixes completely, nitrogen flow is 10-100mL/min.
(3) solution C is transferred in autoclave, at 120 DEG C of crystallization 20h, crystallization product is carried out centrifugation, washing, filter, put into 100 DEG C of oven drying 10h afterwards, then in Muffle furnace 450 DEG C of roasting 3h, obtain Mn (40wt.%)/TiO
2catalyst (mass ratio of manganese oxide and titanium dioxide is 40%).
To the carrier meso-TiO that embodiment 1-6 prepares
2, Mn (20wt.%)/TiO
2, Mn (25wt.%)/TiO
2, Mn (30wt.%)/TiO
2, Mn (35wt.%)/TiO
2with Mn (40wt.%)/TiO
2urge and carry out XRD (German BrukerD8Advance Series X-ray diffractometer) sign, BET (the full-automatic surface analysis instrument of Merck & Co., Inc MicromeriticsASAP2020) sign and catalytic activity test respectively, result as Figure 1-3.
Wherein, the activity test method of catalyst is: after catalyst compressing tablet, grinding is sieved, and gets 40-60 object part.Experiment is carried out on the fixed bed reactors of continuous-flow, and the catalyst after specifically being sieved by 0.4g is encased in quartz glass tube, and the interior temperature of pipe is carried out temperature programming by tube type resistance furnace and temperature controller and controlled.Mist Reality simulation flue gas, the steel cylinder corresponding to it provides.Corresponding mist consists of: C
nO=C
nH3=1000ppm, CO
2=3%, Balance Air is N
2, volume space velocity is 16000h
-1.Import and export the concentration value of NO by ThermoFisher42iHLNO analyzer on-line checkingi.
The specific formula for calculation of NO conversion ratio is as follows:
Wherein, NO
infor the concentration (unit: ppm) of import NO, NO
outfor exporting the concentration (unit: ppm) of NO
Fig. 1 is the carrier meso-TiO that embodiment 1-6 prepares
2, Mn (20wt.%)/TiO
2, Mn (25wt.%)/TiO
2, Mn (30wt.%)/TiO
2, Mn (35wt.%)/TiO
2with Mn (40wt.%)/TiO
2x-ray diffractogram.Result shows, carrier meso-TiO prepared by embodiment 1
2for pure anatase crystal, and degree of crystallinity is higher; In the catalyst that embodiment 2-6 prepares, titanium dioxide is also the pure anatase crystal that degree of crystallinity is higher, and does not find the diffraction maximum of manganese oxide, illustrates that manganese oxide is better dispersed at carrier surface.
Fig. 2 is the carrier meso-TiO that embodiment 1-6 prepares
2, Mn (20wt.%)/TiO
2, Mn (25wt.%)/TiO
2, Mn (30wt.%)/TiO
2, Mn (35wt.%)/TiO
2with Mn (40wt.%)/TiO
2bET figure.Result shows, carrier meso-TiO prepared by embodiment 1
2return stagnant ring-shaped be four type curve H
2type returns stagnant ring, close with three-dimensional caged pore structure, and average pore size is 5.6nm; Time stagnant ring-shaped of catalyst prepared by embodiment 2-6 is also four type curve H
2type returns stagnant ring, close with three-dimensional caged pore structure, and its average pore size is all at 5-10nm, illustrates that the load of manganese oxide does not block the hole of titanium dioxide.
Fig. 3 is Mn (20wt.%)/TiO prepared by embodiment 2-6
2, Mn (25wt.%)/TiO
2, Mn (30wt.%)/TiO
2, Mn (35wt.%)/TiO
2with Mn (40wt.%)/TiO
2the active testing result figure of Selective catalytic reduction NO.Test result shows: the denitration efficiency of all catalyst 100 DEG C time is all more than 25%; In the scope of 100-150 DEG C, along with the rising of temperature, the denitration efficiency of catalyst significantly improves: when 125 DEG C, and the denitration efficiency of catalyst is all more than 90%; When 150 DEG C, the denitration efficiency of catalyst all can reach 98%; And in the temperature range of 150-350 DEG C, the denitration efficiency of all catalyst is stable remains on more than 90%; Visible, the low temperature active that manganese oxide/titanium dioxide catalyst provided by the invention is used for Selective catalytic reduction NO is better, and its active warm area is wider.
It can also be seen that from figure, when in manganese oxide/titanium dioxide catalyst, the load capacity of manganese oxide is 35%, the catalytic activity of catalyst is best, and the highest denitration rate reaches 100%, can remain on the conversion ratio of more than 90% at 100 ~ 350 DEG C.
Comparative example 1
Except the membrane diffusion device mixing in step (2) being replaced with and being uniformly mixed, remaining step is identical with embodiment 5.Obtained catalyst is labeled as N-Mn (35wt.%)/TiO
2catalyst (mass ratio of manganese oxide and titanium dioxide is 35%).
Adopt the activity test method identical with embodiment 5 to N-Mn (35wt.%)/TiO
2carry out the active testing of Selective catalytic reduction NO, result shows, and the active warm area of denitration efficiency more than 90% of catalyst is 150 ~ 325 DEG C.
Comparative example 2
The mass ratio adopting the raw material identical with embodiment 5 to prepare manganese oxide and titanium dioxide by coprecipitation is the catalyst of 35%, obtained catalyst is labeled as C-Mn (35wt.%)/TiO
2.
Adopt the activity test method identical with embodiment 5 to C-Mn (35wt.%)/TiO
2carry out the active testing of Selective catalytic reduction NO, result shows, and the active warm area of denitration efficiency more than 90% of catalyst is 200 ~ 250 DEG C.
Comparative example 3
The mass ratio adopting the raw material identical with embodiment 5 to prepare manganese oxide and titanium dioxide by infusion process is the catalyst of 35%, obtained catalyst is labeled as I-Mn (35wt.%)/TiO
2.
Adopt the activity test method identical with embodiment 5 to I-Mn (35wt.%)/TiO
2carry out the active testing of Selective catalytic reduction NO, result shows, and the active warm area of denitration efficiency more than 90% of catalyst is 175 ~ 300 DEG C.
Applicant states; the foregoing is only the specific embodiment of the present invention; but protection scope of the present invention is not limited thereto; person of ordinary skill in the field should understand; anyly belong to those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all drop within protection scope of the present invention and open scope.
Claims (10)
1. a FCC regenerated flue gas denitration preparation method for manganese oxide/titanium dioxide catalyst, is characterized in that, described preparation method comprises the following steps:
Mixed with the solution containing manganese source, expanding agent and optionally ammonium sulfate by solution containing titanium source, carry out hydro-thermal reaction, product is carried out Separation of Solid and Liquid, gained solid is through washing, and dry, roasting, obtains manganese oxide/titanium dioxide catalyst.
2. preparation method according to claim 1, is characterized in that, the solvent of the described solution containing titanium source is the mixed liquor of acetylacetone,2,4-pentanedione and absolute ethyl alcohol;
Preferably, the volume ratio of described titanium source, acetylacetone,2,4-pentanedione and absolute ethyl alcohol is 5:(1 ~ 5): (10 ~ 15);
Preferably, described titanium source is butyl titanate and/or isopropyl titanate.
3. preparation method according to claim 1 and 2, it is characterized in that, the mass ratio of manganese source in the described solution containing manganese source, expanding agent and optionally ammonium sulfate, ammonium sulfate, expanding agent and solvent is: (0.8 ~ 3.5): 1:(3 ~ 8): (10 ~ 30);
Preferably, described manganese source is manganese nitrate and/or manganese acetate;
Preferably, described expanding agent is the combination of a kind of in urea, carbonic hydroammonium or ammonium carbonate or at least two kinds;
Preferably, the described solvent containing manganese source, expanding agent and the optionally solution of ammonium sulfate is deionized water.
4. according to the preparation method one of claim 1-3 Suo Shu, it is characterized in that, described mixing is specially: joined in the solution containing titanium source by membrane diffusion device by the solution containing manganese source, expanding agent and optionally ammonium sulfate, obtain mixed solution;
Preferably, described membrane diffusion device comprises ceramic-film tube, and the size in the hole on described ceramic-film tube is 35 ~ 45nm;
Preferably, described membrane diffusion device is connected with gas input device with peristaltic pump respectively;
Preferably, in described gas input device, the flow of gas is 10 ~ 100mL/min;
Preferably, the gas in described gas input device is nitrogen.
5. according to the preparation method one of claim 1-4 Suo Shu, it is characterized in that, the temperature of described hydro-thermal reaction is 80 ~ 120 DEG C;
Preferably, the time of described hydro-thermal reaction is 20 ~ 30h.
6. according to the preparation method one of claim 1-5 Suo Shu, it is characterized in that, the solvent that described washing uses is deionized water;
Preferably, the temperature of described drying is 100 ~ 150 DEG C, and the time is 5 ~ 10h;
Preferably, the temperature of described roasting is 350 ~ 450 DEG C, and the time is 3 ~ 6h;
Preferably, described roasting is carried out in air atmosphere, and heating rate is 1 ~ 2 DEG C/min.
7. according to the preparation method one of claim 1-6 Suo Shu, it is characterized in that, described preparation method comprises the steps:
(1) titanium source, acetylacetone,2,4-pentanedione are joined in absolute ethyl alcohol and mixed, obtain the solution containing titanium source, wherein the mass ratio of titanium source, acetylacetone,2,4-pentanedione and absolute ethyl alcohol is 5:(1 ~ 5): (10 ~ 15); By manganese source, expanding agent and optionally ammonium sulfate join in deionized water and dissolve, obtain the solution containing manganese source, expanding agent and optionally ammonium sulfate, wherein, the mass ratio of manganese source, ammonium sulfate, expanding agent and deionized water is (0.8 ~ 3.5): 1:(3 ~ 8): (10 ~ 30);
(2) joined in the solution containing titanium source by membrane diffusion device by the solution containing manganese source, expanding agent and optionally ammonium sulfate, obtain mixed solution, wherein, in membrane diffusion device, the flow of gas is 10 ~ 100mL/min;
(3) mixed solution is transferred in autoclave carries out hydro-thermal reaction, the temperature of hydro-thermal reaction is 80 ~ 120 DEG C, time is 20 ~ 30h, hydro-thermal reaction product is carried out Separation of Solid and Liquid, at 100 ~ 150 DEG C of drying 5 ~ 10h after gained solids wash, roasting 3 ~ 6h under 350 ~ 450 DEG C of air atmospheres, obtains manganese oxide/titanium dioxide catalyst again.
8. a FCC regenerated flue gas denitration manganese oxide/titanium dioxide catalyst, is characterized in that, described manganese oxide/titanium dioxide catalyst prepares according to the preparation method one of claim 1-7 Suo Shu.
9. manganese oxide/titanium dioxide catalyst according to claim 8, is characterized in that, in described manganese oxide/titanium dioxide catalyst, manganese oxide accounts for the mass percentage of manganese oxide/titanium dioxide catalyst is 20 ~ 40%, is preferably 35%;
Preferably, the manganese oxide in described manganese oxide/titanium dioxide catalyst is MnO, Mn
2o
3or MnO
2in a kind of or combination of at least two kinds;
Preferably, the particle size of described manganese oxide/titanium dioxide catalyst is 10 ~ 30nm.
10. the purposes of manganese oxide/titanium dioxide catalyst according to claim 8 or claim 9, it is for FCC regenerated flue gas denitration field.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110270325A (en) * | 2019-06-25 | 2019-09-24 | 新疆金禾山能源科技有限公司 | A kind of production method that denitrfying agent is used in the processing of efficient energy-saving coal-firing boiler smoke |
| CN110508275A (en) * | 2019-08-21 | 2019-11-29 | 上海应用技术大学 | A kind of mesoporous material load manganese dioxide-catalyst and preparation method thereof |
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| CN110270325A (en) * | 2019-06-25 | 2019-09-24 | 新疆金禾山能源科技有限公司 | A kind of production method that denitrfying agent is used in the processing of efficient energy-saving coal-firing boiler smoke |
| CN110508275A (en) * | 2019-08-21 | 2019-11-29 | 上海应用技术大学 | A kind of mesoporous material load manganese dioxide-catalyst and preparation method thereof |
| CN110508275B (en) * | 2019-08-21 | 2022-08-26 | 上海应用技术大学 | Mesoporous material loaded manganese dioxide catalyst and preparation method thereof |
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