CN105056923A - Anti-water and anti-sulfur denitration catalyst, preparation method and application thereof - Google Patents
Anti-water and anti-sulfur denitration catalyst, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an anti-water and anti-sulfur denitration catalyst, a preparation method and application thereof. The catalyst includes titanium dioxide and an additive, both of which are used as the main components, wherein the additive is a combination of any four or more of zirconium oxide, copper oxide, molybdenum oxide, cerium oxide, iron oxide, nickel oxide, cobalt oxide, and tungsten oxide; the surface of the catalyst is coated with a silica coating; the catalyst can be used in the selective catalytic reduction (NH3-SCR) and purification processes of the nitrogen oxides in the flue gas of a stationary source and mobile source. The catalyst adopts non-toxic and harmless raw materials, and has the advantages of being simple and convenient in preparation method, high in catalytic activity, wide in active window, resistant to SO2 poisoning and vapor poisoning for a long time, and environment-friendly.
Description
Technical field
The invention belongs to catalyst preparation technical field, be specifically related to a kind of water resistant sulfur resistive type denitrating catalyst, preparation method and application thereof.
Background technology
Along with China's expanding economy, the consumption of energy-output ratio, particularly fossil energy increases considerably.Corresponding therewith, the pollution level of air is also increasingly sharpened, and the energy resource structure based on coal is the principal element affecting China's atmosphere quality.At present, the thermal power plant of China more than 95% is based on fire coal, is difficult in a short time change.The sulfur dioxide discharged in coal-fired process, carbon dioxide, nitrogen oxide and dust account for 87%, 71%, 67% and 60% of China's discharge capacity respectively.AND ENERGY RESOURCES CONSUMPTION IN CHINA accounts for 8% ~ 9% of the world, but NO
xdischarge capacity but reaches about 10%; The NO wherein discharged by fire coal
xaccount for 67% of national NO total emission volumn.Fluid catalytic cracking in petroleum refining industry (FCC) device is the significant element in crude oil depth process, 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 nitrogen, but also has 10% ~ 30% to be converted into NO
x, discharge with regenerated flue gas.Regenerated flue gas is oil plant NO
xthe main source of discharge, accounts for 50% of its total release.Up to now, China has 158 cover FCC apparatus, and total productive capacity reaches 14,560 ten thousand tons/year, NO
xannual emissions 3.6 ten thousand tons.Large petrochemical plant NO on the other hand
xannual emissions usually also between a few kiloton and even ton up to ten thousand.The primary discharge source of Ethylene Complex unit comprises boiler, ethane cracking furnace and heating furnace etc.The pernicious gas that these stationary source flue gases produce (comprises SO
2and NO
x) very serious harm is caused to the ecological environment of China.
NH
3-SCR technology is with NH
3for reducing agent under the effect of catalyst by NO
xbe reduced to N
2and H
2the gas denitrifying technology of O.Stationary source NO is applied to from 20 century 70s
xsince removing, NH
3-SCR technology reaches its maturity, NO in control air
xpollution aspect has played very important effect.Catalyst is NH
3core component in-SCR technology, according to the difference in SCR catalyst optimum activity interval, high temperature section catalyst (450 ~ 600 DEG C), middle-temperature section catalyst (300 ~ 450 DEG C) and low-temperature zone catalyst (120 ~ 300 DEG C) can be divided into.Current industrial conventional commercial catalyst system is V
2o
5-WO
3(MoO
3)/TiO
2, optimum activity temperature is about 350 DEG C, but the active component V of this catalyst
2o
5bio-toxicity is had to human body; Simultaneously at V
2o
5the lower SO of effect
2also SO can be oxidized to
3, and generate NH further
4hSO
4(NH
4)
2sO
4cause the problems such as equipment rotten candle, the blocking of catalyst activity position; When temperature is higher can there is side reaction in (350 DEG C), the N of generation
2o is strong greenhouse gases.On August 7th, 2014, Chinese Chinese Ministry of Environmental Protection issued " notice about strengthening waste flue gas denitration catalyst supervision ", and waste flue gas denitration catalyst management, regeneration and utilization are included in the useless management of danger, requirement improves its regeneration and utilizes disposing capacity.Be somebody's turn to do " notice " requirement, waste flue gas denitration catalyst (vanadium titanium system) is included hazardous waste in and is managed, and classified as " other refuses of HW49 " in " National Hazard refuse register ", industrial source is " nonspecific industry ", and refuse title is decided to be " waste flue gas denitration catalyst (vanadium titanium system) that industrial smoke the selective catalytic denitrification process process produces ".The dong, Shandong Province province environmental protection Room issues for 2014 " notice about carrying out < Shandong Province SCR (SCR) denitrating catalyst technical requirement > provincial standard in real earnest ", require to need to utilize SCR technology to carry out enterprise and the unit of nitrogen oxide improvement from 1 day November in 2014, the denitrating catalyst used containing poisonous and harmful substance (as vanadic anhydride) must not be bought again.All relate to poisonous and harmful denitrating catalyst production, regeneration, process treatment, the environmental protection Room, Shandong Province and inside the province environmental administration at different levels all will not examine.Therefore the non-vanadium catalyst of development of new environment-friendly high-efficiency replaces vanadium series catalyst imperative, and improves the anti-SO of non-vanadium catalyst
2and H
2the stability of O is that it can be able to the key of practical application.
CN103071506A discloses a kind of iron cerium and titanium compound oxide catalyst, and employing excess urea is precipitating reagent, without SO
2under existing with water, air speed 50000h
-1time, 300 ~ 400 DEG C time, denitration efficiency can reach more than 85%, and selective is 100%, but this prior art does not investigate its water resistant sulfur resistance, does not investigate the water resistant sulfur resistive stability of catalyst under water and the simultaneous situation of sulphur.CN102310001A discloses the denitrating catalyst that a kind of active component is ferrous sulfate, and this catalyst is at NH
3/ NO=1 and air speed are 40000h
-1true flue gas condition under, at the denitration efficiencies of 350 DEG C more than 80%, after continuously running 60h, there is not obvious decline in activity.But the air speed that this catalyst is investigated is lower, the testing time is shorter, cannot truly reflect catalyst sulphur and water simultaneously in the presence of stability.CN101785994A discloses a kind of nanocrystalline Ce titanium compound oxide catalyst for ammonia selective reducing nitrogen oxide, and this catalyst is passing into 100ppmSO
2, air speed is 150000h
-1time, it can reach 98% the activity of 350 DEG C, but the smoke test condition of this catalyst does not have water flowing, does not test the sulfur resistance of this long-lasting catalytic yet.(WenqingXu, YunboYu, ChangbinZhang, HongHe, the SelectivecatalyticreductionofNObyNH such as Xu
3overaCe/TiO
2catalyst.CatalysisCommunications9 (2008) 1453 – 1457) adopt the Ce/TiO for preparing of infusion process
2catalyst realizes more than 95% NO conversion ratio (GHSV=25000h within the scope of 250 ~ 375 DEG C
-1), at 300 DEG C containing 3%H
2o+100ppmSO
2flue gas atmosphere under test 12h, NO conversion ratio stability is at 90% (GHSV=50000h
-1).(WenpoShan, FudongLiu, HongHe, XiaoyanShi, ChangbinZhang, the Anenvironmentally-benignCeO such as Shan
2-TiO
2catalystfortheselectivecatalyticreductionofNOxwithNH
3insimulateddieselexhaust.CatalysisToday184 (2012) 160-165) CeO that adopts coprecipitation to prepare
2-TiO
2compared to Ce/TiO
2(mentioned above) low temperature active obviously increases, and especially when reaction temperature is 200 DEG C, conversion rate of NOx improves more than 40%, CeO
2-TiO
2resistance to high-speed ability and high high-temp stability also significantly improve.(WenpoShan, FudongLiu, HongHe, XiaoyanShi, ChangbinZhang, the AsuperiorCe-W-Timixedoxidecatalystfortheselectivecatalyt icreductionofNOxwithNH such as Shan
3.AppliedCatalysisB:Environmental115 – 116 (2012) 100 – 106) prepare CeWTiO by containing transition metal W
xcatalyst, can realize the NO of 100% in very wide operating temperature window (250 ~ 400 DEG C)
xconversion ratio and N
2generate selective (GHSV=250000h
-1), there is excellent resistance to high-speed performance, high high-temp stability simultaneously, at 300 DEG C containing 5%H
2o+100ppmSO
2flue gas atmosphere under test 12h, NO
xconversion ratio is down to 60% (GHSV=250000h by initial 100%
-1).(LiangChen, JunhuaLi, MaofaGe, RonghaiZhu, the EnhancedactivityoftungstenmodifiedCeO such as Chen
2/ TiO
2forselectivecatalyticreductionofNOxwithammonia.Catalysis Today153 (2010) 77 – 83) adopt the CeW for preparing of coprecipitation
6ti at 250 ~ 500 DEG C, NO
xconversion ratio more than 95%, within the scope of 150 ~ 500 DEG C, N
2selective close to 100% (GHSV=28000h
-1), containing 10%H
2o+100ppmSO
2flue gas atmosphere under test, within the scope of 200 ~ 500 DEG C, NO
xconversion ratio is (GHSV=28000h more than 80%
-1).Catalyst disclosed in CN101069855A adopts mesoporous molecular sieve etc. as carrier, and heteropoly compound is active component.Catalyst denitration efficiency 150 DEG C time prepared by the method can reach 92%.Catalyst disclosed in CN101028594A comprises carrier and catalytic active component, and described active component is manganese cobalt and cerium compound oxide, adopts dipping method to be impregnated on carrier by activating oxide.CN102764643A discloses the poisoning vanadium titanium oxide catalyst of a kind of anti-alkali and alkaline earth metal ions, described catalyst in vanadium titanium oxide catalyst doped with Elements C e.Described catalyst has the performance of excellent alkali resistant metal poisoning, and the cerium component of especially adulterating is improve V
2o
5/ (MoO
3)
x(WO
3) 1-x-TiO
2while catalyst alkali resistant metal poisoning performance, active in impact on its SCR catalyst.CN103252232A discloses vanadium oxide catalyst that a kind of zirconium for ammine selectivity catalytic reduction nitrous oxides adulterates and preparation method thereof.Described catalyst is the oxide carried metal oxide catalyst formed to titanium tungsten powder surface of zirconium and vanadium.This invention significantly can improve high-temperature stability and the N of traditional catalytic component based on vanadium by the method that zirconium adulterates
2generate selective catalytic performance of Denging.CN103240079A discloses a kind of cerium zirconium tungsten composite oxide catalysts, preparation method and its usage for ammine selectivity catalytic reduction nitrous oxides.Described catalyst is the composite oxide of metal that cerium, zirconium and tungsten three kinds of metals form.This invention adopts nontoxic raw material, is prepared and can adapt to high-speed reaction condition, and have catalytic activity excellence, N by simple method
2generate the cerium zirconium tungsten composite oxide catalysts of the features such as selective height, operating temperature window be wide.CN103816891A discloses a kind of cerium molybdenum zirconium mixed oxide catalyst, and in described catalyst, the mol ratio of Ce and Zr is 1:2; The mol ratio of Mo and Ce is 0.1 ~ 1.5.This invention is by cerium molybdenum zirconium mixed oxide catalyst, and the adjustment of cerium, molybdenum, zirconium three kinds of element ratios, obtain temperature window wide, conversion ratio is high, the catalyst for conversion of nitrogen oxides of heat endurance and anti-caking power excellence.CN104368329A discloses a kind of cerium niobium zirconium mixed oxide catalyst, preparation method and its usage.Described catalyst has following chemical composition: CeNb
azr
2o
x, wherein a is 0 ~ 1.0 and does not comprise 0.The low temperature active of described catalyst is excellent, operating temperature window is wide, N
2selective height and NO
xconversion ratio is high, can be used for NH
3-SCR reacts.But disclosed in above-mentioned prior art there is anti-SO in non-vanadium denitration catalyst equally
2and H
2the problem of O less stable.
Summary of the invention
According to the anti-SO that current non-vanadium denitration catalyst exists
2and H
2the problem of O less stable, the object of the present invention is to provide a kind of water resistant sulfur resistive type catalyst for denitrating flue gas, preparation method and its usage, and described catalyst, under guarantee has the prerequisite of high denitration activity, has good water resistant sulfur resistive stability.
To achieve these goals, present invention employs following technical scheme:
A kind of water resistant sulfur resistive type catalyst for denitrating flue gas, comprise the titanium dioxide as key component and auxiliary agent, auxiliary agent is the combination of any more than four kinds or four kinds in Cu oxide, Zirconium oxide, molybdenum oxide, cerium oxide, ferriferous oxide, nickel oxide, cobalt/cobalt oxide or tungsten oxide, and the surface coverage of described catalyst has silica dioxide coating.
The present invention is by adopting titanium dioxide as the key component of catalyst, specific transition metal oxide is as coagent, utilize the cooperative effect between composite metal oxide, the catalyst obtained is made to have excellent denitration activity and water resistant sulfur resistance, and, surface modification is carried out to it, catalyst surface is made to cover silica inert coatings, it has good hydrophobicity, ammonium hydrogen sulfate can be prevented in the generation of catalyst surface, thus further increase the water resistant sulfur resistive stability of catalyst, obtain the catalyst of water resistant sulfur resistive excellent in stability.
Described combination refers to, described auxiliary agent is the composite oxides of at least four kinds of metals by Co deposited synthesis.
Preferably, in auxiliary agent, the mol ratio of each metal and titanium element is 0.01 ~ 1.0 all independently, and preferably, each metal and titanium mol ratio are 0.01 ~ 0.5, such as 0.01,0.02,0.05,0.1,0.2,0.3,0.4 or 0.5 all independently.Adopt the mol ratio of the promoter metal of above-mentioned scope and Ti that the catalyst prepared can be made to have good denitration performance, and the denitration performance exceeding the catalyst prepared by above-mentioned scope reduce relatively.
Exemplary water resistant sulfur resistive type denitration powder catalyst is:
The mol ratio of Ti, Cu, Zr, Ni, Ce five kinds of elements is the titanium copper zirconium nickel cerium catalyst of 1:0.01:0.01:0.02:0.1; The mol ratio of Ti, Fe, Cu, Zr, Ni and Ce six kinds of elements is the ferrotianium copper zirconium nickel cerium catalyst of 1:1.0:0.01:0.1:0.01:1.0; The mol ratio of Ti, Cu, Zr, Co, Ce five kinds of elements is the titanium copper zirconium cobalt cerium catalyst of 1:1.0:0.01:0.01:0.2; The mol ratio of Ti, Fe, Cu, Zr, Co five kinds of elements is the ferrotianium copper zirconium Co catalysts of 1:0.01:0.01:1.0:0.1; The mol ratio of Ti, Fe, Cu, W, Co, Ni, Ce seven kinds of elements is the ferrotianium copper tungsten cobalt nickel cerium catalyst of 1:0.15:0.2:0.01:1.0:0.05:1.0; The mol ratio of Ti, Fe, W, Zr and Ni five kinds of elements is the ferrotianium tungsten zirconium Raney nickel of 1:0.2:0.1:0.01:1.0; The mol ratio of Ti, Fe, Zr, Co and Ce five kinds of elements is the ferrotianium cobalt zirconium cerium catalyst of 1:0.01:0.01:1.0:0.01; The mol ratio of Ti, Cu, Zr, Co, Ce, Mo six kinds of elements is the titanium copper cobalt cerium zirconium molybdenum catalyst of 1:0.01:1:0.02:0.01:0.02; The mol ratio of Ti, Cu, Fe, Zr, Co, Ni, Mo seven kinds of elements is the titanium copper iron cobalt zirconium nickel molybdenum catalyst of 1:1.0:0.1:0.01:0.01:1:0.02; The mol ratio of Ti, Zr, Co, Ni, Ce five kinds of elements is the titanium cobalt cerium zirconium Raney nickel of 1:0.01:1:0.01:0.2; The mol ratio of Ti, Fe, Co, Ni, Ce five kinds of elements is the ferrotianium cerium cobalt Raney nickel of 1:1:0.01:0.05:1.0.All there is silica dioxide coating on the surface of above-mentioned catalyst, and all can realize following technique effect:
Above-mentioned catalyst has excellent water resistant sulfur resistance and denitration activity, is 1000ppm, O at NO
2be 3%, air speed 200000h
-1, 2000ppmSO
2, 10% steam condition under, 300 DEG C time, denitration efficiency is 72%, and 350 DEG C time, denitration efficiency can reach more than 85%, and 350 DEG C of tests through 350h, its activity can remain on more than 80%, has good stability.
Two of object of the present invention is the preparation method providing a kind of water resistant sulfur resistive type denitrating catalyst as above, and described method comprises employing coprecipitation and prepares catalyst and carry out to it step that surface modification obtains silica dioxide coating.
Preferably, the method adopting coprecipitation to prepare catalyst comprises the following steps:
(1) combination of any more than four kinds or four kinds taken in soluble copper source, zirconium source, molybdenum source, cerium source, source of iron, nickel source, cobalt source or tungsten source solution joins in the solution of soluble titanium source, mixes, obtains metal mixed solution;
(2) metal mixed solution is mixed with precipitant solution, control the temperature of mixed solution, pH value, mixing speed and time, make precipitation by metallic ion complete, then static aging, the precipitation suspension obtained is separated and obtains filter cake, washing, drying, roasting, obtains catalyst.
Preferably, described titanium source is selected from the mixture of any one or at least two kinds in titanium tetrachloride, metatitanic acid, titanyl sulfate or butyl titanate.
Preferably, described copper source is selected from the mixture of any one or at least two kinds in copper nitrate, copper chloride or copper sulphate.
Preferably, described zirconium source is selected from the mixture of any one or at least two kinds in zirconium nitrate, zirconium oxychloride, acetic acid zirconium or zirconium sulfate.
Preferably, described molybdenum source is selected from ammonium molybdate or/and sodium molybdate.
Preferably, described source of iron is selected from the mixture of any one or at least two kinds in ferric nitrate, iron chloride, ferric sulfate or ferric phosphate.
Preferably, described nickel source is selected from the mixture of any one or at least two kinds in nickel nitrate, nickel acetate or nickel chloride.
Preferably, described cobalt source is selected from the mixture of any one or at least two kinds in cobalt nitrate, cobalt chloride, cobalt acetate or cobalt oxalate.
Preferably, described tungsten source is selected from the mixture of any one or at least two kinds in ammonium tungstate, potassium tungstate or sodium tungstate.
Preferably, described cerium source is selected from the mixture of any one or at least two kinds of cerous nitrate, cerous sulfate or cerous chlorate.
Preferably, described precipitating reagent is the mixture of any one or at least two kinds in sodium carbonate, ammoniacal liquor or urea.
Preferably, metal mixed solution is added drop-wise in precipitant solution by step (2), or precipitant solution is added drop-wise in metal mixed solution.
Preferably, when adopting sodium carbonate or ammoniacal liquor to be precipitating reagent, the temperature controlling mixed solution is 0 ~ 40 DEG C, such as 5 DEG C, 10 DEG C, 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C or 35 DEG C, (i.e. precipitation temperature), adopt urea when being precipitating reagent, the temperature controlling mixed solution is 80 ~ 100 DEG C, such as 82 DEG C, 84 DEG C, 86 DEG C, 88 DEG C, 90 DEG C, 92 DEG C, 94 DEG C, 96 DEG C or 98 DEG C (precipitation temperature).
Preferably, control the pH value of mixed solution 6 ~ 12, such as 6.5,7,7.5,8,8.5,9,9.5,10,10.5,11 or 11.5, preferably 8 ~ 11.PH value is very large to sediment performance impact, not only there is impact to the accumulation, crystalline phase etc. of slaine hydrolysis, the gel polymerization speed of solution, granular size, primary particle and secondary particle, and have impact to catalyst pore structure, intensity and catalytic performance, when use various metals salting liquid generates precipitation, for making precipitation even, reply pH value is controlled.When multicomponent co-precipitation, should consider that the solubility product of different component is different.In acid solution, degree of supersaturation is low, and deposit seed is large, component skewness; In alkaline solution, degree of supersaturation is high, and deposit seed is little, uniform component distribution.
Preferably, control mixing time is 1 ~ 10h, preferably 2 ~ 4h.That is, in the present invention, described precipitation is carried out under agitation.
Preferably, controlling mixing speed is 100 ~ 4000 revs/min, preferably 600 ~ 1000 revs/min.
Preferably, described standing ageing time is 1 ~ 24h, such as 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h or 22h, preferably 6 ~ 12h.Precipitation completely after, allow newborn precipitation place a period of time together with mother liquor, this process is called " aging ", and object removes the impurity that comprises in precipitation and allow precipitating crystalline grow to increase crystal particle diameter, make its distribution of particles more even.
Preferably, the precipitation suspension suction filtration obtained is obtained filter cake.
Preferably, deionized water or distilled water is adopted to wash, washing times 2 ~ 4 times, preferably 3 times.Concrete mode of washing is such as: in filter cake, add appropriate amount of deionized water or distilled water carries out pulling an oar, stirring and suction filtration, repeated washing like this, obtains the hydrogel removing heteroion substantially completely.
Preferably, the temperature of described drying is 80 ~ 120 DEG C, preferably 100 ~ 120 DEG C.
Preferably, described drying time is 3 ~ 24h, preferably 8 ~ 12h.
Preferably, described sintering temperature is 400 ~ 600 DEG C, such as 420 DEG C, 440 DEG C, 460 DEG C, 480 DEG C, 500 DEG C, 520 DEG C, 540 DEG C, 560 DEG C or 580 DEG C, preferably 500 DEG C; If sintering temperature is lower than 400 DEG C, the hydroxide of metal can be caused to decompose not exclusively; If sintering temperature is higher than 600 DEG C, easily cause the sintering of catalyst, and the TiO generated
2there is crystal transfer (Anatase is to Rutile Type), be unfavorable for denitration reaction.Described roasting time is 4 ~ 8h, such as 4.3h, 4.6h, 4.9h, 5.2h, 5.5h, 5.8h, 6.1h, 6.4h, 6.7h, 7h, 7.3h or 7.6h, preferred 5h.
Preferably, carry out the method that surface modification obtains silica dioxide coating to comprise the following steps:
(1) catalyst adopting coprecipitation to prepare is placed in organic solvent, add organosilicon modifier, stir 2 ~ 12h (such as 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or 11h) at 20 ~ 90 DEG C (such as 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C or 85 DEG C);
(2) evaporate, dry, roasting, is converted into inorganic silicon to make organosilicon;
Optionally, step (1) and (2) is repeated.
The present invention is under organic solvent environment, using organo-silicon compound as modifier, adopt chemical liquid deposition modification, catalyst to be carried out once or repeatedly organic-silicon-modified, the final silica inert coatings forming one deck or multiple dense at catalyst surface, solves water and SO
2to the poisoning problem of catalyst.
Preferably, described organosilicon modifier quality is 0.1 ~ 10% of the catalyst quality adopting coprecipitation to prepare, if organosilicon modifier quality is too high, then can make catalyst activity reduction, if organosilicon modifier quality is too low, then can reduce the water resistant resistance to SO_2 of catalyst.Such as 0.1%, 0.3%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%, preferably 0.1 ~ 5%.
Preferably, the organic solvent of every 100ml, the catalyst that the employing coprecipitation adding 10 ~ 20g (such as 11g, 12g, 13g, 14g, 15g, 16g, 17g, 18g or 19g) prepares.
Preferably, described organic solvent is the mixture of any one or at least two kinds in cyclohexane, ethanol, DMF (DMF), normal heptane or trimethylbenzene.
Preferably, described organosilicon modifier is the mixture of any one or at least two kinds in ethyl orthosilicate, dimethicone, dimethyl silicone polymer or poly-hydroxymethyl siloxanes.
Preferably, 3 ~ 6h is stirred at 50 ~ 80 DEG C.
Preferably, described in be evaporated to rotary evaporation, object for removing organic solvent.
Preferably, described baking temperature is 80 ~ 110 DEG C, and drying time is 12 ~ 24h.
Preferably, described sintering temperature is 450 ~ 550 DEG C, such as 460 DEG C, 470 DEG C, 480 DEG C, 490 DEG C, 500 DEG C, 510 DEG C, 520 DEG C, 530 DEG C or 540 DEG C, roasting time is 4 ~ 6h, such as 4.2h, 4.4h, 4.6h, 4.8h, 5h, 5.2h, 5.4h, 5.6h or 5.8h.
Preferably, the preparation method of described water resistant sulfur resistive type catalyst for denitrating flue gas comprises the following steps:
(1) combination of any more than four kinds or four kinds taken in soluble copper source, zirconium source, molybdenum source, cerium source, source of iron, nickel source, cobalt source or tungsten source solution joins in the solution of soluble titanium source, mixes, obtains metal mixed solution;
(2) metal mixed solution is mixed with precipitant solution, control the temperature of mixed solution, pH value, mixing speed and time, make precipitation by metallic ion complete, then static aging, the precipitation suspension obtained is separated and obtains filter cake, washing, drying, roasting, obtains catalyst;
(3) catalyst modification
The catalyst claiming step (2) to obtain is placed in organic solvent, adds organosilicon modifier, stirs 2 ~ 12h at 20 ~ 90 DEG C;
(4) evaporate, dry, roasting, to make organosilicon be converted into inorganic silicon, obtains water resistant sulfur resistive type catalyst for denitrating flue gas, for Powdered.
Three of object of the present invention is the purposes providing a kind of water resistant sulfur resistive type catalyst for denitrating flue gas as above, and described catalyst is used for the purification of nitrogen oxides of stationary source (as thermal power plant and the denitration of oil plant FCC regeneration fume from catalytic cracking) and moving source (as exhaust gas from diesel vehicle).
Compared with the prior art, the present invention has following beneficial effect:
Catalyst of the present invention has excellent water resistant sulfur resistance and denitration activity, is 1000ppm, O at NO
2be 3%, air speed 200000h
-1, 2000ppmSO
2, 10% steam condition under, 300 DEG C time, denitration efficiency is 72%, and 350 DEG C time, denitration efficiency can reach more than 85%, and 350 DEG C of tests through 350h, its activity can remain on more than 80%, has good stability.
In the present invention, the doping of auxiliary agent transition metal also increases the acidic site of catalyst component, improves catalytic activity, has widened temperature window.
In addition, the preparation technology of catalyst provided by the present invention is simpler, the catalyst environmental protection of gained, cheapness, efficient, and (BET specific surface area is 100 ~ 200m to have very large specific area
2/ g).
Accompanying drawing explanation
Fig. 1 is embodiment 6 prepared catalyst denitration stability curve at 350 DEG C.
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.
Embodiment 1
Configuration titanyl sulfate, copper nitrate, zirconium oxychloride, nickel nitrate, cerous nitrate solution and 10wt% sodium carbonate liquor, titanyl sulfate, copper nitrate, zirconium oxychloride, nickel nitrate, cerous nitrate solution are mixed, obtain mixed solution, the mol ratio controlling Ti, Cu, Zr, Ni, Ce five kinds of elements in mixed solution is 1:0.01:0.01:0.02:0.1.In 25 DEG C of waters bath with thermostatic control, drip above-mentioned titanium copper zirconium nickel cerium salt mixed liquor with sodium carbonate liquor, make titanium, copper, zirconium, nickel, cerium ion precipitate completely, drip and terminate rear control pH=6, stir 1h, filtration washing, 80 DEG C of dry 24h, 400 DEG C of roasting 4h.
Take the titanium copper zirconium nickel cerium catalyst of Co deposited synthesis, be placed in round-bottomed flask, then take a certain amount of tetraethyl orthosilicate, tetraethyl orthosilicate quality is 0.1% of catalyst quality.Be dissolved in organic solvent cyclohexane, 20 DEG C of stirring in water bath 12h, then rotary evaporations, removing organic solvent, spends the night and dries, then dry 12h under 80 DEG C of conditions, 450 DEG C of roasting 6h.After cooling, grinding is sieved, and get 60 ~ 80 order powder as the water resistant sulfur resistive type catalyst for denitrating flue gas after Si modification, it is Powdered.
Obtained fine catalyst activity test method is: fine catalyst is put into the reactor being connected with simulation coal-fired plant flue gas, measure NO with flue gas analyzer
xinitial concentration, then measure each temperature section flue gas by NO remaining after catalyst
xconcentration, then calculate NO
xconversion ratio and SO
2oxygenation efficiency, finally obtain the Evaluation results of catalyst.
The denitration evaluation result of catalyst is: catalyst is at NO concentration 1000ppm, O
2concentration 3%, NH
3concentration 1000ppm, SO
2concentration 2000ppm, water vapor concentration 10%, air speed 200000h
-1, when 350 DEG C, NO
xconversion ratio be 85%, after 350h, NO
xconversion ratio still maintain more than 81%.
Embodiment 2
Configuration titanyl sulfate, ferric nitrate, copper nitrate, zirconium oxychloride, nickel nitrate, cerous nitrate solution and 10wt% sodium carbonate liquor; Titanyl sulfate, ferric nitrate, copper nitrate, zirconium oxychloride, nickel nitrate, cerous nitrate solution are mixed, obtain mixed solution, the mol ratio controlling Ti, Fe, Cu, Zr, Ni and Ce six kinds of elements in mixed solution is 1:1.0:0.01:0.1:0.01:1.0; In 25 DEG C of waters bath with thermostatic control, drip above-mentioned ferrotianium copper zirconium nickel cerium salt mixed liquor with sodium carbonate liquor, make titanium, iron, copper, zirconium, nickel, cerium ion precipitate completely, dropping terminates rear control pH=12, stirs 10h, filtration washing, 120 DEG C of dry 3h, 600 DEG C of roasting 8h.
Take the ferrotianium copper zirconium nickel cerium catalyst of Co deposited synthesis, be placed in round-bottomed flask, then take a certain amount of tetraethyl orthosilicate, tetraethyl orthosilicate quality accounts for 2.5% of catalyst.Be dissolved in organic solvent cyclohexane, 90 DEG C of stirring in water bath 2h, then rotary evaporations, removing organic solvent, spends the night and dries, then dry 12h under 110 DEG C of conditions, 550 DEG C of roasting 4h.After cooling, grinding is sieved, and get 60 ~ 80 order powder as the water resistant sulfur resistive type catalyst for denitrating flue gas after Si modification, it is Powdered.
Obtained fine catalyst activity test method is: fine catalyst is put into the reactor being connected with simulation coal-fired plant flue gas, measure NO with flue gas analyzer
xinitial concentration, then measure each temperature section flue gas by NO remaining after catalyst
xconcentration, then calculate NO
xconversion ratio and SO
2oxygenation efficiency, finally obtain the Evaluation results of catalyst.
The denitration evaluation result of catalyst is: catalyst is at NO concentration 1000ppm, O
2concentration 3%, NH
3concentration 1000ppm, SO
2concentration 2000ppm, water vapor concentration 10%, air speed 200000h
-1, when 350 DEG C, NO
xconversion ratio be 86%, after 350h, NO
xconversion ratio still maintain more than 80%.
Embodiment 3
Configuration titanyl sulfate, copper nitrate, zirconium oxychloride, cobalt nitrate, cerous nitrate solution and 10wt% sodium carbonate liquor; Titanyl sulfate, copper nitrate, zirconium oxychloride, cobalt nitrate, cerous nitrate are mixed, obtain mixed solution, the mol ratio controlling Ti, Cu, Zr, Co, Ce five kinds of elements in mixed solution is 1:1.0:0.01:0.01:0.2; In 25 DEG C of waters bath with thermostatic control, drip above-mentioned titanium copper zirconium cobalt cerium salt mixed liquor with sodium carbonate liquor, make titanium, copper, zirconium, cobalt, cerium ion precipitate completely, drip and terminate rear control pH=11, stir 3h, filtration washing, 110 DEG C of dry 8h, 500 DEG C of roasting 5h.。
Take the titanium copper zirconium cobalt cerium catalyst of Co deposited synthesis, be placed in round-bottomed flask, then take a certain amount of dimethicone, dimethyl-silicon oil quality accounts for 6.5% of catalyst.Be dissolved in organic solvent cyclohexane, 80 DEG C of stirring in water bath 4h, then rotary evaporations, removing organic solvent, spends the night and dries, then dry 12h under 110 DEG C of conditions, 500 DEG C of roasting 5h.After cooling, grinding is sieved, and get 60 ~ 80 order powder as the water resistant sulfur resistive type catalyst for denitrating flue gas after Si modification, it is Powdered.
Obtained fine catalyst activity test method is: fine catalyst is put into the reactor being connected with simulation coal-fired plant flue gas, measure NO with flue gas analyzer
xinitial concentration, then measure each temperature section flue gas by NO remaining after catalyst
xconcentration, then calculate NO
xconversion ratio and SO
2oxygenation efficiency, finally obtain the Evaluation results of catalyst.
The denitration evaluation result of catalyst is: catalyst is at NO concentration 1000ppm, O
2concentration 3%, NH
3concentration 1000ppm, SO
2concentration 2000ppm, water vapor concentration 10%, air speed 200000h
-1, when 350 DEG C, NO
xconversion ratio be 87%, after 350h, NO
xconversion ratio still maintain more than 82%.
Embodiment 4
Configuration titanyl sulfate, ferric nitrate, copper nitrate, zirconium oxychloride, cobalt nitrate solution and 10wt% sodium carbonate liquor; Titanyl sulfate, ferric nitrate, copper nitrate, zirconium oxychloride, cobalt nitrate solution are mixed, obtain mixed solution, the mol ratio controlling Ti, Fe, Cu, Zr, Co five kinds of elements in mixed solution is 1:0.01:0.01:1.0:0.1; In 25 DEG C of waters bath with thermostatic control, drip above-mentioned ferrotianium copper zirconium cobalt salt mixed liquor with ammonia spirit, make titanium, iron, copper, zirconium, cobalt ions precipitate completely, drip and terminate rear control pH=9 ~ 11, stir 3h, filtration washing, 110 DEG C of dry 5h, 500 DEG C of roasting 5h.
Take the ferrotianium copper zirconium Co catalysts of Co deposited synthesis, be placed in round-bottomed flask, then take a certain amount of dimethicone, dimethyl-silicon oil quality accounts for 0.5% of catalyst.Be dissolved in organic solvent normal heptane, 70 DEG C of stirring in water bath 4h, then rotary evaporations, removing organic solvent, spends the night and dries, then dry 12h under 110 DEG C of conditions, 500 DEG C of roasting 5h.After cooling, grinding is sieved, and get 60 ~ 80 order powder as the water resistant sulfur resistive type catalyst for denitrating flue gas after Si modification, it is Powdered.
Obtained fine catalyst activity test method is: fine catalyst is put into the reactor being connected with simulation coal-fired plant flue gas, measure NO with flue gas analyzer
xinitial concentration, then measure each temperature section flue gas by NO remaining after catalyst
xconcentration, then calculate NO
xconversion ratio and SO
2oxygenation efficiency, finally obtain the Evaluation results of catalyst.
The denitration evaluation result of catalyst is: catalyst is at NO concentration 1000ppm, O
2concentration 3%, NH
3concentration 1000ppm, SO
2concentration 2000ppm, water vapor concentration 10%, air speed 200000h
-1, when 350 DEG C, NO
xconversion ratio be 88%, after 350h, NO
xconversion ratio still maintain more than 82%.
Embodiment 5
Configuration titanium tetrachloride, ferric nitrate, copper sulphate, nickel nitrate, cobalt nitrate, cerous sulfate solution and 5wt% ammonia spirit; Titanium tetrachloride, ferric nitrate, copper sulphate, nickel nitrate, cobalt nitrate, cerous sulfate solution are mixed, obtain mixed solution, the mol ratio controlling Ti, Fe, Cu, Co, Ni, Ce six kinds of elements in mixed solution is 1:0.01:0.1:0.01:0.1:0.05; In 25 DEG C of waters bath with thermostatic control, drip above-mentioned ferrotianium copper cobalt nickel cerium salt mixed liquor with ammonia spirit, make titanium, iron, copper, cobalt, nickel, cerium ion precipitate completely, dropping terminates rear control pH=9 ~ 11, stirs 3h, filtration washing, 110 DEG C of dry 12h, 500 DEG C of roasting 5h.
Take the ferrotianium copper cobalt nickel cerium catalyst of Co deposited synthesis, be placed in round-bottomed flask, then take a certain amount of tetraethyl orthosilicate, tetraethyl orthosilicate quality accounts for 5.5% of catalyst.Be dissolved in organic solvent cyclohexane, 80 DEG C of stirring in water bath 3h, then rotary evaporations, removing organic solvent, spends the night and dries, then dry 12h under 110 DEG C of conditions, 500 DEG C of roasting 5h.After cooling, grinding is sieved, and get 60 ~ 80 order powder as the water resistant sulfur resistive type catalyst for denitrating flue gas after Si modification, it is Powdered.
Obtained fine catalyst activity test method is: fine catalyst is put into the reactor being connected with simulation coal-fired plant flue gas, measure NO with flue gas analyzer
xinitial concentration, then measure each temperature section flue gas by NO remaining after catalyst
xconcentration, then calculate NO
xconversion ratio and SO
2oxygenation efficiency, finally obtain the Evaluation results of catalyst.
The denitration evaluation result of catalyst is: catalyst is at NO concentration 1000ppm, O
2concentration 3%, NH
3concentration 1000ppm, SO
2concentration 2000ppm, water vapor concentration 10%, air speed 200000h
-1, when 350 DEG C, NO
xconversion ratio be 85%, after 350h, NO
xconversion ratio still maintain more than 81%.
Embodiment 6
Configuration titanyl sulfate, ferric nitrate, copper nitrate, the ammonium metatungstate solution being dissolved in oxalic acid, cobalt nitrate, nickel nitrate, cerous nitrate solution and 10wt% sodium carbonate liquor; Ferric nitrate, copper nitrate, the ammonium metatungstate solution being dissolved in oxalic acid, cobalt nitrate, nickel nitrate, cerous nitrate solution are mixed, obtain mixed solution, the mol ratio controlling Ti, Fe, Cu, W, Co, Ni, Ce seven kinds of elements in mixed solution is 1:0.15:0.2:0.01:1.0:0.05:1.0; In 25 DEG C of waters bath with thermostatic control, drip above-mentioned ferrotianium copper tungsten cobalt nickel cerium salt mixed liquor with ammonia spirit, make titanium, iron, copper, tungsten, cobalt, nickel, cerium ion precipitate completely, dropping terminates rear control pH=9 ~ 11, stirs 6h, filtration washing, 110 DEG C of dry 5h, 500 DEG C of roasting 5h.
Take the ferrotianium copper tungsten cobalt nickel cerium catalyst of Co deposited synthesis, be placed in round-bottomed flask, then take a certain amount of tetraethyl orthosilicate, tetraethyl orthosilicate quality accounts for 0.5% of catalyst.Be dissolved in organic solvent cyclohexane, 80 DEG C of stirring in water bath 3h, then rotary evaporations, removing organic solvent, spends the night and dries, then dry 12h under 110 DEG C of conditions, 500 DEG C of roasting 5h.After cooling, grinding is sieved, and get 60 ~ 80 order powder as the water resistant sulfur resistive type catalyst for denitrating flue gas after Si modification, it is Powdered.
Obtained fine catalyst activity test method is: fine catalyst is put into the reactor being connected with simulation coal-fired plant flue gas, measure NO with flue gas analyzer
xinitial concentration, then measure each temperature section flue gas by NO remaining after catalyst
xconcentration, then calculate NO
xconversion ratio and SO
2oxygenation efficiency, finally obtain the Evaluation results of catalyst.
The denitration evaluation result of catalyst is: catalyst is at NO concentration 1000ppm, O
2concentration 3%, NH
3concentration 1000ppm, SO
2concentration 2000ppm, water vapor concentration 10%, air speed 200000h
-1, when 350 DEG C, NO
xconversion ratio be 89%, after 350h, NO
xconversion ratio still maintain more than 84%.
Embodiment 7
Configuration titanium tetrachloride, ferric nitrate, the ammonium metatungstate solution being dissolved in oxalic acid, zirconium nitrate, nickel nitrate solution; Titanium tetrachloride, ferric nitrate, the ammonium metatungstate solution being dissolved in oxalic acid, zirconium nitrate, nickel nitrate solution are mixed, obtain mixed solution, the mol ratio controlling Ti, Fe, W, Zr and Ni five kinds of elements in mixed solution is 1:0.2:0.1:0.01:1.0; In 90 DEG C of waters bath with thermostatic control, urea is joined above-mentioned ferrotianium tungsten zirconium nickel salt mixed liquor, make titanium, iron, tungsten, zirconium, nickel ion precipitate completely, drip and terminate rear control pH=8, stir 3h, filtration washing, 110 DEG C of dry 12h, 500 DEG C of roasting 5h.
Take the ferrotianium tungsten zirconium Raney nickel of Co deposited synthesis, be placed in round-bottomed flask, then take a certain amount of tetraethyl orthosilicate, tetraethyl orthosilicate quality accounts for 10% of catalyst.Be dissolved in organic solvent cyclohexane, 80 DEG C of stirring in water bath 3h, then rotary evaporations, removing organic solvent, spends the night and dries, then dry 12h under 110 DEG C of conditions, 500 DEG C of roasting 5h.After cooling, grinding is sieved, and get 60 ~ 80 order powder as the water resistant sulfur resistive type catalyst for denitrating flue gas after Si modification, it is Powdered.
Obtained fine catalyst activity test method is: fine catalyst is put into the reactor being connected with simulation coal-fired plant flue gas, measure NO with flue gas analyzer
xinitial concentration, then measure each temperature section flue gas by NO remaining after catalyst
xconcentration, then calculate NO
xconversion ratio and SO
2oxygenation efficiency, finally obtain the Evaluation results of catalyst.
The denitration evaluation result of catalyst is: catalyst is at NO concentration 1000ppm, O
2concentration 3%, NH
3concentration 1000ppm, SO
2concentration 2000ppm, water vapor concentration 10%, air speed 200000h
-1, when 350 DEG C, NO
xconversion ratio be 85%, after 350h, NO
xconversion ratio still maintain more than 82%.
Embodiment 8
Configuration titanium tetrachloride, ferric nitrate, zirconium nitrate, cobalt nitrate, cerous nitrate, 10wt% sodium carbonate liquor; Titanium tetrachloride, ferric nitrate, zirconium nitrate, cobalt nitrate, cerous nitrate solution are mixed, obtain mixed solution, the mol ratio controlling Ti, Fe, Zr, Co and Ce five kinds of elements in mixed solution is 1:0.01:0.01:1.0:0.01; In 10 DEG C of waters bath with thermostatic control, drip above-mentioned ferrotianium zirconium cobalt cerium salt mixed liquor with sodium carbonate liquor, make titanium, iron, zirconium, cobalt, cerium ion precipitate completely, drip and terminate rear control pH=9 ~ 10, stir 3h, filtration washing, 110 DEG C of dry 5h, 500 DEG C of roasting 5h.
Take the ferrotianium cobalt zirconium cerium catalyst of Co deposited synthesis, be placed in round-bottomed flask, then take a certain amount of tetraethyl orthosilicate, tetraethyl orthosilicate quality accounts for 5% of catalyst.Be dissolved in organic solvent cyclohexane, 80 DEG C of stirring in water bath 3h, then rotary evaporations, removing organic solvent, spends the night and dries, then dry 12h under 110 DEG C of conditions, 500 DEG C of roasting 5h.After cooling, grinding is sieved, and get 60 ~ 80 order powder as the water resistant sulfur resistive type catalyst for denitrating flue gas after Si modification, it is Powdered.
Obtained fine catalyst activity test method is: fine catalyst is put into the reactor being connected with simulation coal-fired plant flue gas, measure NO with flue gas analyzer
xinitial concentration, then measure each temperature section flue gas by NO remaining after catalyst
xconcentration, then calculate NO
xconversion ratio and SO
2oxygenation efficiency, finally obtain the Evaluation results of catalyst.
The denitration evaluation result of catalyst is: catalyst is at NO concentration 1000ppm, O
2concentration 3%, NH
3concentration 1000ppm, SO
2concentration 2000ppm, water vapor concentration 10%, air speed 200000h
-1, when 350 DEG C, NO
xconversion ratio be 88%, after 350h, NO
xconversion ratio still maintain more than 80%.
Embodiment 9
Configuration titanium tetrachloride, copper nitrate, zirconium nitrate, cobalt nitrate, cerous nitrate solution and be dissolved in ammonium molybdate solution, the 5wt% ammoniacal liquor of oxalic acid; Titanium tetrachloride, copper nitrate, zirconium nitrate, cobalt nitrate, cerous nitrate solution and ammonium molybdate solution are mixed, obtain mixed solution, the mol ratio controlling Ti, Cu, Zr, Co, Ce, Mo six kinds of elements in mixed solution is 1:0.01:1:0.02:0.01:0.02; In 10 DEG C of waters bath with thermostatic control, drip above-mentioned titanium copper zirconium cobalt cerium molybdenum salt mixed liquor with ammoniacal liquor, make titanium, copper, zirconium, cobalt, cerium, molybdenum ion precipitate completely, drip and terminate rear control pH=8 ~ 12, stir 2h, filtration washing, 110 DEG C of dry 5h, 500 DEG C of roasting 5h.
Take the titanium copper cobalt cerium zirconium molybdenum catalyst of Co deposited synthesis, be placed in round-bottomed flask, then take a certain amount of tetraethyl orthosilicate, tetraethyl orthosilicate quality accounts for 2% of catalyst.Be dissolved in organic solvent cyclohexane, 80 DEG C of stirring in water bath 3h, then rotary evaporations, removing organic solvent, spends the night and dries, then dry 12h under 110 DEG C of conditions, 500 DEG C of roasting 5h.After cooling, grinding is sieved, and get 60 ~ 80 order powder as the water resistant sulfur resistive type catalyst for denitrating flue gas after Si modification, it is Powdered.
Obtained fine catalyst activity test method is: fine catalyst is put into the reactor being connected with simulation coal-fired plant flue gas, measure NO with flue gas analyzer
xinitial concentration, then measure each temperature section flue gas by NO remaining after catalyst
xconcentration, then calculate NO
xconversion ratio and SO
2oxygenation efficiency, finally obtain the Evaluation results of catalyst.
The denitration evaluation result of catalyst is: catalyst is at NO concentration 1000ppm, O
2concentration 3%, NH
3concentration 1000ppm, SO
2concentration 2000ppm, water vapor concentration 10%, air speed 200000h
-1, when 350 DEG C, NO
xconversion ratio be 87%, after 350h, NO
xconversion ratio still maintain more than 82%.
Embodiment 10
Configuration titanium tetrachloride, copper nitrate, ferric nitrate, zirconium nitrate, cobalt nitrate solution, nickel nitrate and be dissolved in ammonium molybdate solution, the 10wt% sodium carbonate liquor of oxalic acid; Titanium tetrachloride, copper nitrate, ferric nitrate, zirconium nitrate, cobalt nitrate solution, nickel nitrate and ammonium molybdate solution are mixed, obtain mixed solution, the mol ratio controlling Ti, Cu, Fe, Zr, Co, Ni, Mo seven kinds of elements in mixed solution is 1:1.0:0.1:0.01:0.01:1:0.02; In 25 DEG C of waters bath with thermostatic control, drip above-mentioned titanium copper ferrozirconium cobalt molybdenum salt mixed liquor with sodium carbonate liquor, make titanium, copper, iron, zirconium, cobalt, molybdenum ion precipitate completely, dropping terminates rear control pH=6 ~ 9, mix and blend 2h, filtration washing, 110 DEG C of dry 5h, 500 DEG C of roasting 5h.
Take the titanium copper iron cobalt zirconium nickel molybdenum catalyst of Co deposited synthesis, be placed in round-bottomed flask, then take a certain amount of tetraethyl orthosilicate, tetraethyl orthosilicate quality accounts for 0.1% of catalyst.Be dissolved in organic solvent cyclohexane, 80 DEG C of stirring in water bath 3h, then rotary evaporations, removing organic solvent, spends the night and dries, then dry 12h under 110 DEG C of conditions, 500 DEG C of roasting 5h.After cooling, grinding is sieved, and get 60 ~ 80 order powder as the water resistant sulfur resistive type catalyst for denitrating flue gas after Si modification, it is Powdered.
Obtained fine catalyst activity test method is: fine catalyst is put into the reactor being connected with simulation coal-fired plant flue gas, measure NO with flue gas analyzer
xinitial concentration, then measure each temperature section flue gas by NO remaining after catalyst
xconcentration, then calculate NO
xconversion ratio and SO
2oxygenation efficiency, finally obtain the Evaluation results of catalyst.
The denitration evaluation result of catalyst is: catalyst is at NO concentration 1000ppm, O
2concentration 3%, NH
3concentration 1000ppm, SO
2concentration 2000ppm, water vapor concentration 10%, air speed 200000h
-1, when 350 DEG C, NO
xconversion ratio be 85%, after 350h, NO
xconversion ratio still maintain more than 80%.
Embodiment 11
Configuration titanium tetrachloride, zirconium oxychloride, cobalt nitrate, nickel nitrate, cerous nitrate solution, 10wt% sodium carbonate liquor; Titanium tetrachloride, zirconium oxychloride, cobalt nitrate, nickel nitrate, cerous nitrate solution are mixed, obtain mixed solution, the mol ratio controlling Ti, Zr, Co, Ni, Ce five kinds of elements in mixed solution is 1:0.01:1:0.01:0.2; In 25 DEG C of waters bath with thermostatic control, drip above-mentioned titanium zirconium cobalt nickel cerium salt mixed liquor with sodium carbonate liquor, make titanium, zirconium, cobalt, nickel, cerium ion precipitate completely, drip and terminate rear control pH=8 ~ 11, stir 2h, filtration washing, 110 DEG C of dry 5h, 500 DEG C of roasting 5h.
Take the titanium cobalt cerium zirconium Raney nickel of Co deposited synthesis, be placed in round-bottomed flask, then take a certain amount of tetraethyl orthosilicate, tetraethyl orthosilicate quality accounts for 4% of catalyst.Be dissolved in organic solvent cyclohexane, 80 DEG C of stirring in water bath 3h, then rotary evaporations, removing organic solvent, spends the night and dries, then dry 12h under 110 DEG C of conditions, 500 DEG C of roasting 5h.After cooling, grinding is sieved, and get 60 ~ 80 order powder as the water resistant sulfur resistive type catalyst for denitrating flue gas after Si modification, it is Powdered.
Obtained fine catalyst activity test method is: fine catalyst is put into the reactor being connected with simulation coal-fired plant flue gas, measure NO with flue gas analyzer
xinitial concentration, then measure each temperature section flue gas by NO remaining after catalyst
xconcentration, then calculate NO
xconversion ratio and SO
2oxygenation efficiency, finally obtain the Evaluation results of catalyst.
The denitration evaluation result of catalyst is: catalyst is at NO concentration 1000ppm, O
2concentration 3%, NH
3concentration 1000ppm, SO
2concentration 2000ppm, water vapor concentration 10%, air speed 200000h
-1, when 350 DEG C, NO
xconversion ratio be 85%, after 350h, NO
xconversion ratio still maintain more than 81%.
Embodiment 12
Configuration titanium tetrachloride, ferric nitrate, cobalt nitrate, nickel nitrate, cerous nitrate solution and 5wt% ammonia spirit; Titanium tetrachloride, ferric nitrate, cobalt nitrate, nickel nitrate, cerous nitrate solution are mixed, obtain mixed solution, the mol ratio controlling Ti, Fe, Co, Ni, Ce five kinds of elements in mixed solution is 1:1:0.01:0.05:1.0; In 10 DEG C of waters bath with thermostatic control, drip above-mentioned titanium iron-cobalt-nickel cerium salt mixed liquor with ammonia spirit, make titanium, iron, cobalt, nickel, cerium ion precipitate completely, drip and terminate rear control pH=8 ~ 11, stir 2h, filtration washing, 110 DEG C of dry 5h, 500 DEG C of roasting 5h.
Take the ferrotianium cerium cobalt Raney nickel of Co deposited synthesis, be placed in round-bottomed flask, then take a certain amount of tetraethyl orthosilicate, tetraethyl orthosilicate quality accounts for 7% of catalyst.Be dissolved in organic solvent cyclohexane, 80 DEG C of stirring in water bath 3h, then rotary evaporations, removing organic solvent, spends the night and dries, then dry 12h under 110 DEG C of conditions, 500 DEG C of roasting 5h.After cooling, grinding is sieved, and get 60 ~ 80 order powder as the water resistant sulfur resistive type catalyst for denitrating flue gas after Si modification, it is Powdered.
Obtained fine catalyst activity test method is: fine catalyst is put into the reactor being connected with simulation coal-fired plant flue gas, measure NO with flue gas analyzer
xinitial concentration, then measure each temperature section flue gas by NO remaining after catalyst
xconcentration, then calculate NO
xconversion ratio and SO
2oxygenation efficiency, finally obtain the Evaluation results of catalyst.
The denitration evaluation result of catalyst is: catalyst is at NO concentration 1000ppm, O
2concentration 3%, NH
3concentration 1000ppm, SO
2concentration 2000ppm, water vapor concentration 10%, air speed 200000h
-1, when 350 DEG C, NO
xconversion ratio be 86%, after 350h, NO
xconversion ratio still maintain more than 82%.
Embodiment 13
All the other are identical with embodiment 6, and except the addition by controlling each raw material, regulate the content of ferrotianium copper tungsten cobalt nickel cerium catalyst and tetraethyl orthosilicate, tetraethyl orthosilicate quality accounts for 1% of catalyst.
Embodiment 14
All the other are identical with embodiment 6, and except the addition by controlling each raw material, regulate the content of ferrotianium copper tungsten cobalt nickel cerium catalyst and tetraethyl orthosilicate, tetraethyl orthosilicate quality accounts for 3% of catalyst.
Embodiment 15
All the other are identical with embodiment 6, and except the addition by controlling each raw material, regulate the content of ferrotianium copper tungsten cobalt nickel cerium catalyst and tetraethyl orthosilicate, tetraethyl orthosilicate quality accounts for 4% of catalyst.
Embodiment 16
All the other are identical with embodiment 6, and except the addition by controlling each raw material, regulate the content of ferrotianium copper tungsten cobalt nickel cerium catalyst and tetraethyl orthosilicate, tetraethyl orthosilicate quality accounts for 5% of catalyst.
Embodiment 17
All the other are identical with embodiment 6, and except the addition by controlling each raw material, regulate the content of ferrotianium copper tungsten cobalt nickel cerium catalyst and tetraethyl orthosilicate, tetraethyl orthosilicate quality accounts for 8% of catalyst.
Embodiment 18
All the other are identical with embodiment 6, and except the addition by controlling each raw material, regulate the content of ferrotianium copper tungsten cobalt nickel cerium catalyst and tetraethyl orthosilicate, tetraethyl orthosilicate quality accounts for 10% of catalyst.
Be positioned in tubular fixed-bed reactor by the catalyst of 0.036mL embodiment 13 ~ 18, experiment condition is as follows: reaction condition is: NO concentration 1000ppm, O
2concentration 3%, NH
3concentration 1000ppm, SO
2concentration 2000ppm, water vapor concentration 10%, air speed 200000h
-1.The conversion ratio of detecting catalyst at 350 DEG C of temperature and after reaction 350h, reaction result is as shown in the table:
| Embodiment | Initial NO xConversion ratio (%) | NO after 350h xConversion ratio (%) |
| 13 | 88％ | 82％ |
| 14 | 87％ | 81％ |
| 15 | 86％ | 80％ |
| 16 | 85％ | 80％ |
| 17 | 83％ | 79％ |
| 18 | 81％ | 77％ |
Comparative example 1
Iron cerium and titanium compound oxide catalyst disclosed in patent CN103071506A, and adopt the method identical with embodiment 2 to carry out organic-silicon-modified to it.
Comparative example 2
Nanocrystalline Ce titanium compound oxide catalyst disclosed in patent CN101785994A, and adopt the method identical with embodiment 2 to carry out organic-silicon-modified to it.
Comparative example 3
Titanium cerium zirconium W Fe catalyst disclosed in patent CN103846094A, and adopt the method identical with embodiment 2 to carry out organic-silicon-modified to it.
Be positioned in tubular fixed-bed reactor by the catalyst of 0.036mL comparative example 1 ~ 3, experiment condition is as follows:
NO concentration 1000ppm, O
2concentration 3%, NH
3concentration 1000ppm, SO
2concentration 2000ppm, water vapor concentration 10%, air speed 200000h
-1.The conversion ratio of detecting catalyst at 350 DEG C of temperature and after reaction 350h, reaction result is as shown in the table:
| Comparative example | Initial NO xConversion ratio (%) | NO after 350h xConversion ratio (%) |
| 1 | 72％ | 65％ |
| 2 | 75％ | 68％ |
| 3 | 71％ | 64％ |
Comparative example 4
All the other are identical with embodiment 1, and except the addition by controlling each raw material, the mol ratio regulating Cu and Ti element is 1.2.
Comparative example 5
All the other are identical with embodiment 1, and except the addition by controlling each raw material, the mol ratio regulating Zr and Ti element is 1.2.
Comparative example 6
All the other are identical with embodiment 1, and except the addition by controlling each raw material, the mol ratio regulating Ni and Ti element is 1.2.
Comparative example 7
All the other are identical with embodiment 1, and except the addition by controlling each raw material, the mol ratio regulating Ce and Ti element is 1.2.
Comparative example 8
All the other are identical with embodiment 1, and except the addition by controlling each raw material, the mol ratio regulating Cu and Ti element is 0.005.
Comparative example 9
All the other are identical with embodiment 1, and except the addition by controlling each raw material, the mol ratio regulating Zr and Ti element is 0.005.
Comparative example 10
All the other are identical with embodiment 1, and except the addition by controlling each raw material, the mol ratio regulating Ni and Ti element is 0.005.
Comparative example 11
All the other are identical with embodiment 1, and except the addition by controlling each raw material, the mol ratio regulating Ce and Ti element is 0.005.
Comparative example 12
All the other are identical with embodiment 1, except not adding titanium source, obtain the catalyst that catalytic component is copper zirconium nickel cerium composite oxides.
Comparative example 13
All the other are identical with embodiment 1, except not adding zirconium source, obtain the catalyst that catalytic component is titanium copper nickel cerium composite oxides.
Comparative example 14
All the other are identical with embodiment 1, except not adding copper source, obtain the catalyst that catalytic component is titanium zirconium nickel cerium composite oxides.
Comparative example 15
All the other are identical with embodiment 1, except not adding nickel source, obtain the catalyst that catalytic component is titanium copper zirconia-ceria mixed oxide.
Comparative example 16
All the other are identical with embodiment 1, except not adding cerium source, obtain the catalyst that catalytic component is titanium copper zirconium ni compound oxide.
Be positioned in tubular fixed-bed reactor by the catalyst of 0.036mL comparative example 4 ~ 16, experiment condition is as follows: reaction condition is: NO concentration 1000ppm, O
2concentration 3%, NH
3concentration 1000ppm, SO
2concentration 2000ppm, water vapor concentration 10%, air speed 200000h
-1.The conversion ratio of detecting catalyst at 350 DEG C of temperature and after reaction 350h, reaction result is as shown in the table:
| Comparative example | Initial NO xConversion ratio (%) | NO after 350h xConversion ratio (%) |
| 4 | 75％ | 62％ |
| 5 | 76％ | 64％ |
| 6 | 73％ | 60％ |
| 7 | 79％ | 67％ |
| 8 | 80％ | 70％ |
| 9 | 80％ | 73％ |
| 10 | 76％ | 65％ |
| 11 | 74％ | 62％ |
| 12 | 78％ | 71％ |
| 13 | 68％ | 58％ |
| 14 | 82％ | 75％ |
| 15 | 77％ | 70％ |
| 16 | 81％ | 73％ |
Comparative example 17
Catalyst Ce disclosed in CN102764643 embodiment 1
4vWTi, and adopt the method identical with embodiment 2 to carry out organic-silicon-modified to it.
Comparative example 18
Catalyst 3%V disclosed in CN103252232A embodiment 2
2o
5-2%ZrO
2/ 10%WO
3-TiO
2, and adopt the method identical with embodiment 2 to carry out organic-silicon-modified to it.
Comparative example 19
Cerium zirconium tungsten composite oxide catalysts disclosed in CN103240079A embodiment 1, and adopt the method identical with embodiment 2 to carry out organic-silicon-modified to it.
Comparative example 20
Molybdenum cerium zirconium compound oxide catalyst disclosed in CN103816891 embodiment 1, and adopt the method identical with embodiment 2 to carry out organic-silicon-modified to it.
Comparative example 21
Niobium cerium zirconium compound oxide catalyst disclosed in CN104368329A embodiment 1, and adopt the method identical with embodiment 2 to carry out organic-silicon-modified to it.
Be positioned in tubular fixed-bed reactor by the catalyst of 0.036mL comparative example 17 ~ 21, experiment condition is as follows: reaction condition is: NO concentration 1000ppm, O
2concentration 3%, NH
3concentration 1000ppm, SO
2concentration 2000ppm, water vapor concentration 10%, air speed 200000h
-1.The conversion ratio of detecting catalyst at 350 DEG C of temperature and after reaction 350h, reaction result is as shown in the table:
| Comparative example | Initial NO xConversion ratio (%) | NO after 350h xConversion ratio (%) |
| 17 | 79％ | 67％ |
| 18 | 80％ | 70％ |
| 19 | 80％ | 73％ |
| 20 | 75％ | 68％ |
| 21 | 71％ | 64％ |
In sum, catalyst of the present invention, 250 ~ 350 DEG C of temperature ranges, after carrying out Si modification, its specific activity non-vanadium catalyst of the same type is high, at 350 DEG C after the water resistant sulfur resistive of 350h, the catalyst that its specific activity does not carry out Si modification is high, shows excellent water resistant sulfur resistive stability under high-sulfur high water vapor, high-speed condition.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned one exemplary embodiment, and when not deviating from spirit of the present invention or essential characteristic, the present invention can be realized in other specific forms.Therefore, no matter from which point, all should embodiment be regarded as exemplary, and be nonrestrictive, scope of the present invention is limited by claims instead of above-mentioned explanation, and all changes be therefore intended in the implication of the equivalency by dropping on claim and scope are included in the present invention.
In addition, be to be understood that, although this description is described according to embodiment, but not each embodiment only comprises an independently technical scheme, this narrating mode of description is only for clarity sake, those skilled in the art should by description integrally, and the technical scheme in each embodiment also through appropriately combined, can form other embodiments that it will be appreciated by those skilled in the art that.
Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a water resistant sulfur resistive type denitration powder catalyst, comprise the titanium dioxide as key component and auxiliary agent, auxiliary agent is the combination of any more than four kinds or four kinds in Cu oxide, Zirconium oxide, molybdenum oxide, cerium oxide, ferriferous oxide, nickel oxide, cobalt/cobalt oxide or tungsten oxide, and the surface coverage of described catalyst has silica dioxide coating.
2. catalyst as claimed in claim 1, it is characterized in that, in auxiliary agent, the mol ratio of each metal and titanium element is (0.01 ~ 1.0) all independently, preferably 0.01 ~ 0.5.
3. a preparation method for the water resistant sulfur resistive type denitrating catalyst as described in one of claim 1-2, described method comprises employing coprecipitation and prepares catalyst and carry out to it step that surface modification obtains silica dioxide coating.
4. method as claimed in claim 3, is characterized in that, the method adopting coprecipitation to prepare catalyst comprises the following steps:
(1) combination of any more than four kinds or four kinds taken in soluble copper source, zirconium source, molybdenum source, cerium source, source of iron, nickel source, cobalt source or tungsten source solution joins in the solution of soluble titanium source, mixes, obtains metal mixed solution;
(2) metal mixed solution is mixed with precipitant solution, control the temperature of mixed solution, pH value, mixing speed and time, make precipitation by metallic ion complete, then static aging, the precipitation suspension obtained is separated and obtains filter cake, washing, drying, roasting, obtains catalyst.
5. method as claimed in claim 4, is characterized in that, described titanium source is selected from the mixture of any one or at least two kinds in titanium tetrachloride, metatitanic acid, titanyl sulfate or butyl titanate;
Preferably, described copper source is selected from the mixture of any one or at least two kinds in copper nitrate, copper chloride or copper sulphate;
Preferably, described zirconium source is selected from the mixture of any one or at least two kinds in zirconium nitrate, zirconium oxychloride, acetic acid zirconium or zirconium sulfate;
Preferably, described molybdenum source is selected from ammonium molybdate or/and sodium molybdate;
Preferably, described source of iron is selected from the mixture of any one or at least two kinds in ferric nitrate, iron chloride, ferric sulfate or ferric phosphate;
Preferably, described nickel source is selected from the mixture of any one or at least two kinds in nickel nitrate, nickel acetate or nickel chloride;
Preferably, described cobalt source is selected from the mixture of any one or at least two kinds in cobalt nitrate, cobalt chloride, cobalt acetate or cobalt oxalate;
Preferably, described tungsten source is selected from the mixture of any one or at least two kinds in ammonium tungstate, potassium tungstate or sodium tungstate.
Preferably, described cerium source is selected from the mixture of any one or at least two kinds of cerous nitrate, cerous sulfate or cerous chlorate.
6. the method as described in claim 4 or 5, is characterized in that, described precipitating reagent is the mixture of any one or at least two kinds in sodium carbonate, ammoniacal liquor or urea;
Preferably, metal mixed solution is added drop-wise in precipitant solution by step (3), or precipitant solution is added drop-wise in metal mixed solution;
Preferably, when adopting sodium carbonate or ammoniacal liquor to be precipitating reagent, the temperature controlling mixed solution is 0 ~ 40 DEG C, and when adopting urea to be precipitating reagent, the temperature controlling mixed solution is 80 ~ 100 DEG C;
Preferably, control the pH value of mixed solution 6 ~ 12, preferably 8 ~ 11;
Preferably, control mixing time is 1 ~ 10h, preferably 2 ~ 4h;
Preferably, controlling mixing speed is 100 ~ 4000 revs/min, preferably 600 ~ 1000 revs/min.
7. the method as described in one of claim 4-6, is characterized in that, described standing ageing time is 1 ~ 24h, preferably 6 ~ 12h;
Preferably, the precipitation suspension suction filtration obtained is obtained filter cake;
Preferably, deionized water or distilled water is adopted to wash, washing times 2 ~ 4 times, preferably 3 times;
Preferably, the temperature of described drying is 80 ~ 120 DEG C, preferably 100 ~ 120 DEG C;
Preferably, described drying time is 3 ~ 24h, preferably 8 ~ 12h;
Preferably, described sintering temperature is 400 ~ 600 DEG C, preferably 500 DEG C;
Preferably, described roasting time is 4 ~ 8h, preferred 5h.
8. the method as described in one of claim 3-7, is characterized in that, carries out the method that surface modification obtains silica dioxide coating and comprises the following steps:
(1) catalyst adopting coprecipitation to prepare is placed in organic solvent, adds organosilicon modifier, stir 2 ~ 12h at 20 ~ 90 DEG C;
(2) evaporate, dry, roasting, is converted into inorganic silicon to make organosilicon;
Optionally, step (1) and (2) is repeated.
9. method as claimed in claim 8, is characterized in that, described organosilicon modifier quality is 0.1 ~ 10% of the catalyst quality adopting coprecipitation to prepare, preferably 0.1 ~ 5%;
Preferably, the organic solvent of every 100mL, the catalyst that the employing coprecipitation adding 10 ~ 20g prepares;
Preferably, described organic solvent is the mixture of any one or at least two kinds in cyclohexane, ethanol, DMF, normal heptane or trimethylbenzene;
Preferably, described organosilicon modifier is the mixture of any one or at least two kinds in ethyl orthosilicate, dimethicone, dimethyl silicone polymer or poly-hydroxymethyl siloxanes;
Preferably, 3 ~ 6h is stirred at 50 ~ 80 DEG C;
Preferably, rotary evaporation is evaporated to described in;
Preferably, described baking temperature is 80 ~ 110 DEG C, and drying time is 12 ~ 24h.
Preferably, described sintering temperature is 450 ~ 550 DEG C in air atmosphere, and roasting time is 4 ~ 6h.
10. a purposes for the water resistant sulfur resistive type denitrating catalyst as described in one of claim 1-2, described catalyst is used for the purification of nitrogen oxides of stationary source and moving source.
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