CN109603814A - A kind of SCR denitration and preparation method thereof of anti-arsenic alkali resistant metal poisoning - Google Patents
A kind of SCR denitration and preparation method thereof of anti-arsenic alkali resistant metal poisoning Download PDFInfo
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Abstract
The invention discloses a kind of SCR denitrations and preparation method thereof of anti-arsenic alkali resistant metal poisoning.The SCR denitration includes the active component of carrier and load thereon, the carrier is the complex carrier for including titanium dioxide and silica, carrier aperture is optimized by the cooperation of titanium dioxide and silica initiatively, makes carrier that there are more mesoporous, reduces As2O3" capillary condensation " phenomenon in pore.Meanwhile unique pore structure can make carrier in the case where partial pore and mesoporous block, reactant still can spread to active sites, and catalyst is made to keep preferable catalytic activity.Furthermore the active component on carrier is carried on by reasonable disposition, SCR denitration can be effectively improved to the tolerance level of arsenic and alkali metal, the deposition and accumulation of the toxic species such as arsenic and alkali metal is effectively overcome, improves the catalytic performance of SCR denitration.
Description
Technical field
The invention belongs to air contaminant treatment fields, and in particular to a kind of SCR denitration catalysis of anti-arsenic alkali resistant metal poisoning
Agent and preparation method thereof.
Background technique
In China's thermoelectricity internal structure based on coal fired power generation, coal fired power generation can discharge oxynitrides (NOx), and arrange
The NOx being put into atmosphere is to cause one of main sources of pollutions such as atmosphere acid rain, photochemical fog, Environmental Protection in China goal
Strict control thermal power plant NOxDischarge amount.Domestic and international at present is more than that 90% coal-burning power plant uses selective catalytic reduction (SCR)
Technology removes the NO in power plant's tail flue gasx。
In industrial application, SCR denitration system generallys use high ash method for arranging, catalyst be in for a long time containing flying dust,
SOx, in the flue gases such as alkali metal (K, Na etc.) and Hg, As, easily catalyst poisoning is caused to inactivate.Wherein, arsenic poisoning is to cause
One of common cause of catalyst inactivation will lead to denitration efficiency reduction, and ammonia slip concentration increases, and downstream air preheater low-temperature zone is rotten
Phenomena such as erosion.Arsenic content changes greatly in coal quality, and content is in 0.5~80 μ g/g.If the mass fraction of arsenic is more than 3 × 10 in coal-6,
The SCR denitration service life will reduce by 30% or so.
Currently, applying most commercial catalysts in engineering is vanadium Titanium series catalyst.The catalyst powder is with anatase two
Titanium oxide is carrier, V2O5For active component, WO3For coagent, shaping assistant then uses binder, pore creating material and lubricant
Deng mixture.But in actual use, performance of the vanadium Titanium series catalyst in terms of anti-arsenic alkali resistant metal poisoning still has
Wait improve.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is that existing SCR denitration is in anti-arsenic alkali resistant metal poisoning side
The performance in face defect still to be improved, to provide the SCR denitration and its preparation of a kind of anti-arsenic alkali resistant metal poisoning
Method.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows:
The SCR denitration of anti-arsenic alkali resistant metal poisoning provided by the present invention, which is characterized in that including carrier and bear
Active component thereon is carried, the carrier includes the complex carrier of titanium dioxide and silica, dioxy in the complex carrier
The mass ratio for changing titanium and silica is (320-550): (30-110)；
The active component is oxide, the oxide of molybdenum and the oxide of tungsten of vanadium, in terms of the metal salt of respective metal,
The mass ratio (5~20) of the oxide of the oxide of the vanadium, the oxide of molybdenum and tungsten: (10~140): (20~80).
Further, the oxide of vanadium can be V2O5；The oxide of molybdenum can be MoO3；The oxide of tungsten can be WO3。
It further, further include coagent in the complex carrier, the mass ratio of the coagent and titanium dioxide
For (3-10): (320-550).
It further, further include lubricant, structural promoter and reinforcing agent, the lubricant, structure in the complex carrier
Auxiliary agent, reinforcing agent, silica mass ratio be (2-8): (1-5): (5-20): (30-110).
Further, the coagent includes nickel oxide powder and/or zirconium dioxide powder；
The lubricant includes at least one of polyethylene glycol oxide, sesbania powder, paraffin, graphite or talcum powder；
The structural promoter includes sodium isethionate oleate, cocounut oil acid esters, aliphatic alkane alcohol amide, poly- second two
At least one of alcohol, ethylene oxide, alkylcellulose, methyl cellulose, POLYPROPYLENE GLYCOL and methylcellulose sodium salt；
The reinforcing agent includes glass fibre and/or alumino-silicate；
The silica is the mesoporous silicon oxide that average particle size is 0.1~2mm.
Further, the coagent is made of nickel oxide powder and zirconium dioxide powder, the nickel oxide powder and
The mass ratio of zirconium dioxide powder is (1~2): (2~5).
Further, in terms of the metal salt of respective metal, the quality of silica in the active component and the carrier
Than for (80-240): (30-110).
Further, the metal salt of vanadium is ammonium metavanadate；The metal salt of molybdenum is ammonium paramolybdate；The metal salt of tungsten is metatungstic acid
Ammonium.
In addition, the present invention also provides the preparation methods of above-mentioned SCR denitration, which is characterized in that including walking as follows
It is rapid:
By complex carrier incipient impregnation in the maceration extract containing vanadium source, molybdenum source and tungsten source；
After dipping, the carrier is successively dried and is roasted, SCR denitration is made.
Further, the maceration extract containing vanadium source, molybdenum source and tungsten source is by ammonium metavanadate, ammonium paramolybdate, metatungstic acid
Ammonium and oxalic acid are add to deionized water, and are warming up to 50~80 DEG C, and 1~3h, the metavanadic acid are stirred at 50~80 DEG C
Ammonium, ammonium paramolybdate, ammonium metatungstate, oxalic acid and deionized water mass ratio be (5~20): (10~140): (20~80): (10~
20): (100~500)；
The temperature of the incipient impregnation is 50~80 DEG C, time 0.5-1.5h；
The temperature of the drying is 110-130 DEG C, time 6-24h；
The temperature of the roasting is 500~550 DEG C, and the time is 4~12h.
Further, the preparation method of the complex carrier, includes the following steps:
Titanium dioxide, mesoporous silicon oxide, lubricant, structural promoter and coagent are added in batch mixer, and in
2~10min, the titanium dioxide, mesoporous silicon oxide, lubricant, structural promoter are mixed under the revolving speed of 1000~1500r/min
Mass ratio with coagent is 300~450:25~100:2~8:1~5:3~10；
Deionized water, ammonium hydroxide and lactic acid are successively added in the batch mixer, and in the revolving speed of 1000~1500r/min
5~10min of lower stirring, deionized water, ammonium hydroxide, lactic acid mass ratio are 100~150:10~30:10~50.
Then, reinforcing agent, remaining titanium dioxide, remaining mesoporous silicon oxide, ammonium hydroxide are added in batch mixer to stating, and in
10~15min, reinforcing agent, remaining titanium dioxide, remaining mesoporous silicon oxide, ammonia are stirred under the revolving speed of 1000~1500r/min
5~20:20 of mass ratio~100:5~10:2~5 of water；
Furthermore by mixture under the revolving speed of 300~500r/min 2~3h of kneading, after kneading, in the pressure of 4~6MPa
Lower extrusion, obtains the predecessor of honeycomb support；
Finally, the predecessor of honeycomb support to be successively dried and roast, dry temperature is 80~120 DEG C, when
Between for 12~for 24 hours, the temperature of roasting is 500~550 DEG C, the time be 12~for 24 hours.
Further, the preparation method of mesoporous silicon oxide, includes the following steps:
Under agitation, the dropwise addition concentrated sulfuric acid, polyethylene glycol and nine water sodium metasilicate into deionized water, stirring 20~
30min is uniformly mixed it, obtains precursor solution, the molar ratio of the concentrated sulfuric acid, polyethylene glycol, nine water sodium metasilicate and deionized water
For 2~10:0.05~0.2:10~50:200~500；
By precursor solution at 120~180 DEG C 12~48h of crystallization, product centrifuge separation is taken out after natural cooling, then use
Deionized water and ethyl alcohol rinse product 2~3 times；
Product is successively dried and is roasted, dry temperature is 80~120 DEG C, the time be 8~for 24 hours, the temperature of roasting
Degree is 500~580 DEG C, the time be 8~for 24 hours, obtain mesoporous silicon oxide.
Compared with prior art, technical solution of the present invention has the advantages that
1, the present invention provides a kind of SCR denitrations of anti-arsenic alkali resistant metal poisoning comprising carrier and loads it
On active component, which is the complex carrier for including titanium dioxide and silica, initiatively by titanium dioxide and
The cooperation of silica optimizes carrier aperture, and carrier is made to have more mesoporous, reduces As2O3In pore " capillary is cold
It is solidifying " phenomenon.Meanwhile unique pore structure can make carrier in the case where partial pore and mesoporous block, reactant still may be used
Active sites are diffused to, catalyst is made to keep preferable catalytic activity.Furthermore the active group being carried on by reasonable disposition on carrier
Point, SCR denitration can be effectively improved to the tolerance level of arsenic and alkali metal, effectively overcome the toxic species such as arsenic and alkali metal
Deposition and accumulation, improve the catalytic performance of SCR denitration.
2, the present invention provides a kind of SCR denitrations of anti-arsenic alkali resistant metal poisoning, by the way that work is added in the carrier
Property auxiliary agent, which can be nickel oxide and zirconium dioxide, can enhance the acidic site of SCR denitration, improve SCR denitration
The catalytic performance of catalyst.
3, the present invention provides a kind of preparation methods of the SCR denitration of anti-arsenic alkali resistant metal poisoning, by compound load
Body incipient impregnation is in the maceration extract containing vanadium source, molybdenum source and tungsten source；After dipping, the carrier is successively dried
And roasting, SCR denitration is made, the catalysis using vanadium, molybdenum and tungsten mixture as active component is obtained by high-temperature roasting
Agent increases the absorptive capacity of arsenide, and the performance of the anti-arsenic poisoning of catalyst is remarkably reinforced.
4, the present invention provides a kind of preparation methods of the SCR denitration of anti-arsenic alkali resistant metal poisoning, by specific
Preparation method complex carrier is made, can advanced optimize the aperture of carrier, improve the SCR denitration as made from the complex carrier and urge
The catalytic performance of agent.During the preparation process, each raw material can effectively be dispersed by ammonium hydroxide being added, and avoid reuniting；By the way that lactic acid tune is added
PH is saved, complex carrier is presented acid.
5, the present invention provides a kind of preparation methods of the SCR denitration of anti-arsenic alkali resistant metal poisoning, by specific
Preparation method mesoporous silicon oxide is made, the aperture of mesoporous silicon oxide can be optimized, to help to optimize complex carrier
Structure.
Specific embodiment
Technical solution of the present invention will be clearly and completely described below, it is clear that described embodiment is this hair
Bright a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having
Every other embodiment obtained under the premise of creative work is made, shall fall within the protection scope of the present invention.
Reagents or instruments used without specified manufacturer in following each embodiments, being can be by the normal of commercially available acquisition
Advise reagent manufacture or instrument.
Embodiment 1
Present embodiments provide a kind of SCR denitration and preparation method thereof of anti-arsenic alkali resistant metal poisoning.The SCR is de-
Denox catalyst includes carrier and load active component thereon, in terms of the metal salt of respective metal, the active component with it is described
The mass ratio of silica is 120:43 in carrier；
Wherein, the carrier includes titanium dioxide, silica, coagent, lubricant, structural promoter and reinforcing agent
Complex carrier, the matter of titanium dioxide, silica, coagent, lubricant, structural promoter and reinforcing agent in the complex carrier
Amount is than being 425:43:4.5:6:4:8；The nickel oxide powder and zirconium dioxide powder that the coagent is 1.5:3 by mass ratio
Composition；The lubricant is polyethylene glycol oxide；The structural promoter is methylcellulose sodium salt；The reinforcing agent is glass fibers
Dimension；The silica is the mesoporous silicon oxide that average particle size is 1mm；
The active component is oxide, the oxide of molybdenum and the oxide of tungsten of vanadium, in terms of the metal salt of respective metal,
The mass ratio 10:50:60 of the oxide of the oxide of the vanadium, the oxide of molybdenum and tungsten；
The preparation method of above-mentioned SCR denitration, includes the following steps:
One, hydro-thermal method synthesizing mesoporous silicon dioxide:
(1) under conditions of magnetic agitation, the concentrated sulfuric acid (concentration 98.3%), poly- second are successively slowly added dropwise into deionized water
Two pure and mild nine water sodium metasilicate, stirring 25min are uniformly mixed it, obtain precursor solution, wherein the concentrated sulfuric acid (concentration
98.3%), the molar ratio of polyethylene glycol, nine water sodium metasilicate and deionized water is 5:0.1:25:300；
(2) precursor solution is transferred in crystallizing kettle, crystallization takes out product centrifugation for 24 hours, after natural cooling at 150 DEG C
Separation, then rinsed reactant 3 times with deionized water and ethyl alcohol, it is put into 80 DEG C of baking ovens dry 12h, is finally putting into Muffle furnace,
12h is roasted at 550 DEG C, obtains mesoporous silicon dioxide powder, being crushed to average particle size is that 1mm is spare；
Two, the complex carrier of SCR catalyst is prepared:
(1) by the titanium dioxide of 400g, the mesoporous silicon oxide of 38g, the coagent of 4.5g, the lubricant of 6g and 4g
Structural promoter is added in batch mixer, and mixes 5min under the revolving speed of 1200r/min；
(2) lactic acid of the deionized water of 100g, the ammonium hydroxide of 15g and 20g is successively added in the batch mixer, and in
8min is stirred under the revolving speed of 1200r/min；
(3) then, to stating the remaining titanium dioxide of the reinforcing agent, 25g that add 8g in batch mixer, the residue mesoporous two of 5g
The ammonium hydroxide of silica, 3g, and 12min is stirred under the revolving speed of 1200r/min；
(4) furthermore, by mixture under the revolving speed of 400r/min kneading 2.5h, after kneading, squeezed out under the pressure of 5MPa,
Obtain the predecessor of honeycomb support；
(5) finally, the predecessor of honeycomb support to be successively dried and roast, dry temperature is 100 DEG C, time
For 18h, the temperature of roasting is 520 DEG C, time 18h；
Three, SCR catalyst is prepared:
(1) configure the maceration extract containing vanadium source, molybdenum source and tungsten source: weigh the ammonium metavanadate of 10g, the ammonium paramolybdate of 50g,
The ammonium metatungstate of 60g and the oxalic acid of 15g are added in the deionized water of 120g, and mixture aqueous solution slowly rises under magnetic stirring
Temperature stirs 2h to 70 DEG C, and at 70 DEG C；
(2) by complex carrier incipient impregnation in the maceration extract containing vanadium source, molybdenum source and tungsten source, the temperature of incipient impregnation
Degree is 70 DEG C, stands 1h；
(3) after impregnating, complex carrier is put into 120 DEG C of baking ovens dry 8h, is finally putting into Muffle furnace, in air
Under atmosphere, 8h is roasted at 550 DEG C, obtains SCR denitration.
Embodiment 2
Present embodiments provide a kind of SCR denitration and preparation method thereof of anti-arsenic alkali resistant metal poisoning.The SCR is de-
Denox catalyst includes carrier and load active component thereon, in terms of the metal salt of respective metal, the active component with it is described
The mass ratio of silica is 95:110 in carrier；
Wherein, the carrier includes titanium dioxide, silica, coagent, lubricant, structural promoter and reinforcing agent
Complex carrier, the matter of titanium dioxide, silica, coagent, lubricant, structural promoter and reinforcing agent in the complex carrier
Amount is than being 320:110:3:8:1:20；The nickel oxide powder and zirconium dioxide powder group that the coagent is 1:5 by mass ratio
At；The lubricant is paraffin；The structural promoter is polyethylene glycol；The reinforcing agent is sodium silicoaluminate；The silica
It is the mesoporous silicon oxide that average particle size is 2mm；
The active component is oxide, the oxide of molybdenum and the oxide of tungsten of vanadium, in terms of the metal salt of respective metal,
The mass ratio 5:10:80 of the oxide of the oxide of the vanadium, the oxide of molybdenum and tungsten；
The preparation method of above-mentioned SCR denitration, includes the following steps:
One, hydro-thermal method synthesizing mesoporous silicon dioxide:
(1) under conditions of magnetic agitation, the concentrated sulfuric acid (concentration 98.3%), poly- second are successively slowly added dropwise into deionized water
Two pure and mild nine water sodium metasilicate, stirring 20min are uniformly mixed it, obtain precursor solution, wherein the concentrated sulfuric acid (concentration
98.3%), the molar ratio of polyethylene glycol, nine water sodium metasilicate and deionized water is 10:0.05:50:200；
(2) precursor solution is transferred in crystallizing kettle, the crystallization 12h at 180 DEG C, product centrifugation is taken out after natural cooling
Separation, then rinsed reactant 2 times with deionized water and ethyl alcohol, it is put into 100 DEG C of baking ovens dry 20h, is finally putting into Muffle furnace,
It is roasted at 500 DEG C for 24 hours, obtains mesoporous silicon dioxide powder, being crushed to average particle size is that 2mm is spare；
Two, the complex carrier of SCR catalyst is prepared:
(1) by the titanium dioxide of 300g, the mesoporous silicon oxide of 100g, the coagent of 3g, the lubricant of 8g and 1g
Structural promoter is added in batch mixer, and mixes 10min under the revolving speed of 1000r/min；
(2) lactic acid of the deionized water of 130g, the ammonium hydroxide of 10g and 50g is successively added in the batch mixer, and in
5min is stirred under the revolving speed of 1500r/min；
(3) then, mesoporous to the residue for stating the remaining titanium dioxide of the reinforcing agent, 20g that add 20g in batch mixer, 10g
The ammonium hydroxide of silica, 5g, and 10min is stirred under the revolving speed of 1500r/min；
(4) furthermore, by mixture under the revolving speed of 300r/min kneading 3h, after kneading, squeeze out, obtain under the pressure of 6MPa
To the predecessor of honeycomb support；
(5) finally, the predecessor of honeycomb support to be successively dried and roast, dry temperature is 80 DEG C, time
For for 24 hours, the temperature of roasting is 550 DEG C, time 12h；
Three, SCR catalyst is prepared:
(1) it configures the maceration extract containing vanadium source, molybdenum source and tungsten source: weighing the ammonium metavanadate of 5g, the ammonium paramolybdate of 10g, 80g
Ammonium metatungstate and the oxalic acid of 10g be added in the deionized water of 500g, mixture aqueous solution slowly heats up under magnetic stirring
3h is stirred to 50 DEG C, and at 50 DEG C；
(2) by complex carrier incipient impregnation in the maceration extract containing vanadium source, molybdenum source and tungsten source, the temperature of incipient impregnation
Degree is 50 DEG C, stands 1.5h；
(3) after impregnating, complex carrier is put into 130 DEG C of baking ovens dry 6h, is finally putting into Muffle furnace, in air
Under atmosphere, 12h is roasted at 500 DEG C, obtains SCR denitration.
Embodiment 3
Present embodiments provide a kind of SCR denitration and preparation method thereof of anti-arsenic alkali resistant metal poisoning.The SCR is de-
Denox catalyst includes carrier and load active component thereon, in terms of the metal salt of respective metal, the active component with it is described
The mass ratio of silica is 110:30 in carrier；
Wherein, the carrier includes titanium dioxide, silica, coagent, lubricant, structural promoter and reinforcing agent
Complex carrier, the matter of titanium dioxide, silica, coagent, lubricant, structural promoter and reinforcing agent in the complex carrier
Amount is than being 550:30:10:2:5:5；The nickel oxide powder and zirconium dioxide powder group that the coagent is 2:2 by mass ratio
At；The lubricant is graphite；The structural promoter is POLYPROPYLENE GLYCOL；The reinforcing agent is glass fibre；The silica
It is the mesoporous silicon oxide that average particle size is 0.1mm；
The active component is oxide, the oxide of molybdenum and the oxide of tungsten of vanadium, in terms of the metal salt of respective metal,
The mass ratio 20:10:80 of the oxide of the oxide of the vanadium, the oxide of molybdenum and tungsten；
The preparation method of above-mentioned SCR denitration, includes the following steps:
One, hydro-thermal method synthesizing mesoporous silicon dioxide:
(1) under conditions of magnetic agitation, the concentrated sulfuric acid (concentration 98.3%), poly- second are successively slowly added dropwise into deionized water
Two pure and mild nine water sodium metasilicate, stirring 30min are uniformly mixed it, obtain precursor solution, wherein the concentrated sulfuric acid (concentration
98.3%), the molar ratio of polyethylene glycol, nine water sodium metasilicate and deionized water is 2:0.2:10:500；
(2) precursor solution is transferred in crystallizing kettle, the crystallization 48h at 120 DEG C, product centrifugation is taken out after natural cooling
Separation, then rinsed reactant 3 times with deionized water and ethyl alcohol, it is put into 120 DEG C of baking ovens dry 8h, is finally putting into Muffle furnace,
8h is roasted at 580 DEG C, obtains mesoporous silicon dioxide powder, being crushed to average particle size is that 0.1mm is spare；
Two, the complex carrier of SCR catalyst is prepared:
(1) by the titanium dioxide of 450g, the mesoporous silicon oxide of 25g, the coagent of 10g, the lubricant of 2g and 5g
Structural promoter is added in batch mixer, and mixes 2min under the revolving speed of 1500r/min；
(2) lactic acid of the deionized water of 150g, the ammonium hydroxide of 30g and 10g is successively added in the batch mixer, and in
10min is stirred under the revolving speed of 1000r/min；
(3) then, mesoporous to the residue for stating the remaining titanium dioxide of the reinforcing agent, 100g that add 5g in batch mixer, 5g
The ammonium hydroxide of silica, 2g, and 15min is stirred under the revolving speed of 1000r/min；
(4) furthermore, by mixture under the revolving speed of 500r/min kneading 2h, after kneading, squeeze out, obtain under the pressure of 4MPa
To the predecessor of honeycomb support；
(5) finally, the predecessor of honeycomb support to be successively dried and roast, dry temperature is 120 DEG C, time
For 12h, the temperature of roasting is 500 DEG C, the time is for 24 hours；
Three, SCR catalyst is prepared:
(1) configure the maceration extract containing vanadium source, molybdenum source and tungsten source: weigh the ammonium metavanadate of 20g, the ammonium paramolybdate of 10g,
The ammonium metatungstate of 80g and the oxalic acid of 20g are added in the deionized water of 100g, and mixture aqueous solution slowly rises under magnetic stirring
Temperature stirs 1h to 80 DEG C, and at 80 DEG C；
(2) by complex carrier incipient impregnation in the maceration extract containing vanadium source, molybdenum source and tungsten source, the temperature of incipient impregnation
Degree is 80 DEG C, stands 0.5h；
(3) after impregnating, complex carrier is put into drying in 110 DEG C of baking ovens and for 24 hours, is finally putting into Muffle furnace, in sky
Under atmosphere is enclosed, 4h is roasted at 550 DEG C, obtains SCR denitration.
Embodiment 4
Present embodiments provide a kind of SCR denitration and preparation method thereof of anti-arsenic alkali resistant metal poisoning.The SCR is de-
Denox catalyst includes carrier and load active component thereon, in terms of the metal salt of respective metal, the active component with it is described
The mass ratio of silica is 145:80 in carrier；
Wherein, the carrier includes titanium dioxide, silica, coagent, lubricant, structural promoter and reinforcing agent
Complex carrier, the matter of titanium dioxide, silica, coagent, lubricant, structural promoter and reinforcing agent in the complex carrier
Amount is than being 500:80:6:3:2:17；The nickel oxide powder and zirconium dioxide powder group that the coagent is 1.8:4 by mass ratio
At；The lubricant is talcum powder；The structural promoter is methyl cellulose；The reinforcing agent is glass fibre；The dioxy
SiClx is the mesoporous silicon oxide that average particle size is 1mm；
The active component is oxide, the oxide of molybdenum and the oxide of tungsten of vanadium, in terms of the metal salt of respective metal,
The mass ratio 15:90:40 of the oxide of the oxide of the vanadium, the oxide of molybdenum and tungsten；
The preparation method of above-mentioned SCR denitration, includes the following steps:
One, hydro-thermal method synthesizing mesoporous silicon dioxide:
(1) under conditions of magnetic agitation, the concentrated sulfuric acid (concentration 98.3%), poly- second are successively slowly added dropwise into deionized water
Two pure and mild nine water sodium metasilicate, stirring 18min are uniformly mixed it, obtain precursor solution, wherein the concentrated sulfuric acid (concentration
98.3%), the molar ratio of polyethylene glycol, nine water sodium metasilicate and deionized water is 7:0.08:42:400；
(2) precursor solution is transferred in crystallizing kettle, the crystallization 18h at 130 DEG C, product centrifugation is taken out after natural cooling
Separation, then rinsed reactant 3 times with deionized water and ethyl alcohol, it is put into 110 DEG C of baking ovens dry 15h, is finally putting into Muffle furnace,
15h is roasted at 520 DEG C, obtains mesoporous silicon dioxide powder, being crushed to average particle size is that 1mm is spare；
Two, the complex carrier of SCR catalyst is prepared:
(1) by the titanium dioxide of 440g, the mesoporous silicon oxide of 70g, the coagent of 6g, the lubricant of 3g and 2g knot
Structure auxiliary agent is added in batch mixer, and mixes 5min under the revolving speed of 1200r/min；
(2) lactic acid of the deionized water of 100g, the ammonium hydroxide of 15g and 20g is successively added in the batch mixer, and in
8min is stirred under the revolving speed of 1200r/min；
(3) then, mesoporous to the residue for stating the remaining titanium dioxide of the reinforcing agent, 60g that add 17g in batch mixer, 10g
The ammonium hydroxide of silica, 4g, and 12min is stirred under the revolving speed of 1200r/min；
(4) furthermore, by mixture under the revolving speed of 400r/min kneading 2.5h, after kneading, squeezed out under the pressure of 5MPa,
Obtain the predecessor of honeycomb support；
(5) finally, the predecessor of honeycomb support to be successively dried and roast, dry temperature is 100 DEG C, time
For 18h, the temperature of roasting is 520 DEG C, time 18h；
Three, SCR catalyst is prepared:
(1) configure the maceration extract containing vanadium source, molybdenum source and tungsten source: weigh the ammonium metavanadate of 15g, the ammonium paramolybdate of 90g,
The ammonium metatungstate of 40g and the oxalic acid of 18g are added in the deionized water of 250g, and mixture aqueous solution slowly rises under magnetic stirring
Temperature stirs 2h to 70 DEG C, and at 70 DEG C；
(2) by complex carrier incipient impregnation in the maceration extract containing vanadium source, molybdenum source and tungsten source, the temperature of incipient impregnation
Degree is 70 DEG C, stands 1h；
(3) after impregnating, complex carrier is put into 120 DEG C of baking ovens dry 8h, is finally putting into Muffle furnace, in air
Under atmosphere, 8h is roasted at 550 DEG C, obtains SCR denitration.
Comparative example 1
This comparative example provides a kind of SCR denitration and preparation method thereof of anti-arsenic alkali resistant metal poisoning.With implementation
Example 1, only difference is that: silica is not added in this comparative example in SCR denitration.
Comparative example 2
This comparative example provides a kind of SCR denitration and preparation method thereof of anti-arsenic alkali resistant metal poisoning.With implementation
Example 1, only difference is that: the mass ratio of titanium dioxide and silica is 290 in complex carrier described in this comparative example:
120。
Experimental example 1
It measures in embodiment 1-4 intermediary hole silica, titanium dioxide, SCR denitration and comparative example 1-2 respectively
Specific surface area, average pore size and the total pore volume of SCR denitration, corresponding test result is as follows shown in table 1:
Specific surface area, average pore size and the total pore volume of 1 raw material of table and catalyst
Experimental example 2
The SCR denitration of embodiment 1-4 and comparative example 1-2 are subjected to denitration performance survey on fixed bed reactors
Examination, corresponding test condition are as follows: SCR denitration being loaded in fixed bed reactors, the flue gas for being 420 DEG C by temperature
It is de- to calculate by the component difference for calculating import flue gas and exiting flue gas with the air speed of 10000/h by fixed bed reactors
Nitre efficiency, wherein contain 0.02vol%SO in flue gas2, 5vol%O2, 16vol%H2O, 1000ppm NH3, 10ppm's
As2O3, NH3Molar ratio=1 of/NOx.Denitration efficiency is shown in Table 2.
The denitration efficiency of SCR denitration under the conditions of arsenical fume of table 2
Experimental example 3
The SCR denitration of embodiment 1-4 and comparative example 1-2 are subjected to denitration performance survey on fixed bed reactors
Examination, corresponding test condition are as follows: SCR denitration being loaded in fixed bed reactors, the flue gas for being 420 DEG C by temperature
It is de- to calculate by the component difference for calculating import flue gas and exiting flue gas with the air speed of 10000/h by fixed bed reactors
Nitre efficiency, wherein contain 0.02vol%SO in flue gas2, 5vol%O2, 16vol%H2O, 1000ppm NH3, the oxidation of 10ppm
Potassium, NH3Molar ratio=1 of/NOx.Denitration efficiency is shown in Table 3.
Table 3 is in the denitration efficiency of the SCR denitration of under the conditions of containing potassium oxide
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (11)
1. a kind of SCR denitration of anti-arsenic alkali resistant metal poisoning, which is characterized in that including the activity of carrier and load thereon
Component, the carrier include the complex carrier of titanium dioxide and silica, titanium dioxide and titanium dioxide in the complex carrier
The mass ratio of silicon is (320-550): (30-110)；
The active component is oxide, the oxide of molybdenum and the oxide of tungsten of vanadium, described in terms of the metal salt of respective metal
The mass ratio (5~20) of the oxide of the oxide of vanadium, the oxide of molybdenum and tungsten: (10~140): (20~80).
2. SCR denitration according to claim 1, which is characterized in that further include that activity helps in the complex carrier
The mass ratio of agent, the coagent and titanium dioxide is (3-10): (320-550).
3. SCR denitration according to claim 3, which is characterized in that further include in the complex carrier lubricant,
Structural promoter and reinforcing agent, the lubricant, structural promoter, reinforcing agent, silica mass ratio be (2-8): (1-5): (5-
20): (30-110).
4. SCR denitration according to claim 3, which is characterized in that the coagent includes nickel oxide powder
And/or zirconium dioxide powder；
The lubricant includes at least one of polyethylene glycol oxide, sesbania powder, paraffin, graphite or talcum powder；
The structural promoter includes sodium isethionate oleate, cocounut oil acid esters, aliphatic alkane alcohol amide, polyethylene glycol, ring
At least one of oxidative ethane, alkylcellulose, methyl cellulose, POLYPROPYLENE GLYCOL and methylcellulose sodium salt；
The reinforcing agent includes glass fibre and/or alumino-silicate；
The silica is the mesoporous silicon oxide that average particle size is 0.1~2mm.
5. SCR denitration according to claim 4, which is characterized in that the coagent by nickel oxide powder and
The mass ratio of zirconium dioxide powder composition, the nickel oxide powder and zirconium dioxide powder is (1~2): (2~5).
6. SCR denitration according to any one of claims 1-5, which is characterized in that with the metal of respective metal
The mass ratio of silica is (80-240): (30-110) in salt meter, the active component and the carrier.
7. SCR denitration according to claim 6, which is characterized in that the metal salt of vanadium is ammonium metavanadate；The gold of molybdenum
Category salt is ammonium paramolybdate；The metal salt of tungsten is ammonium metatungstate.
8. a kind of preparation method of SCR denitration of any of claims 1-7, which is characterized in that including such as
Lower step:
By complex carrier incipient impregnation in the maceration extract containing vanadium source, molybdenum source and tungsten source；
After dipping, the carrier is successively dried and is roasted, SCR denitration is made.
9. preparation method according to claim 9, which is characterized in that the maceration extract containing vanadium source, molybdenum source and tungsten source
For ammonium metavanadate, ammonium paramolybdate, ammonium metatungstate and oxalic acid to be add to deionized water, and 50~80 DEG C are warming up to, and 50
Stir 1~3h at~80 DEG C, the ammonium metavanadate, ammonium paramolybdate, ammonium metatungstate, oxalic acid and deionized water mass ratio be (5~
20): (10~140): (20~80): (10~20): (100~500)；
The temperature of the incipient impregnation is 50~80 DEG C, time 0.5-1.5h；
The temperature of the drying is 110-130 DEG C, time 6-24h；
The temperature of the roasting is 500~550 DEG C, and the time is 4~12h.
10. preparation method according to claim 8 or claim 9, which is characterized in that the preparation method of the complex carrier, including
Following steps:
Titanium dioxide, mesoporous silicon oxide, lubricant, structural promoter and coagent are added in batch mixer, and in 1000
2~10min, the titanium dioxide, mesoporous silicon oxide, lubricant, structural promoter and work are mixed under the revolving speed of~1500r/min
Property auxiliary agent mass ratio be 300~450:25~100:2~8:1~5:3~10；
Deionized water, ammonium hydroxide and lactic acid are successively added in the batch mixer, and stirred under the revolving speed of 1000~1500r/min
5~10min is mixed, deionized water, ammonium hydroxide, lactic acid mass ratio are 100~150:10~30:10~50.
Then, reinforcing agent, remaining titanium dioxide, remaining mesoporous silicon oxide, ammonium hydroxide are added in batch mixer to stating, and in 1000
Stir 10~15min under the revolving speed of~1500r/min, reinforcing agent, remaining titanium dioxide, remaining mesoporous silicon oxide, ammonium hydroxide
5~20:20 of mass ratio~100:5~10:2~5；
Furthermore by mixture under the revolving speed of 300~500r/min 2~3h of kneading, after kneading, squeezed under the pressure of 4~6MPa
Out, the predecessor of honeycomb support is obtained；
Finally, the predecessor of honeycomb support to be successively dried and roast, dry temperature is 80~120 DEG C, the time is
12~for 24 hours, the temperature of roasting is 500~550 DEG C, the time be 12~for 24 hours.
11. preparation method according to claim 10, which is characterized in that the preparation method of mesoporous silicon oxide, including such as
Lower step:
Under agitation, the concentrated sulfuric acid, polyethylene glycol and nine water sodium metasilicate are added dropwise into deionized water, 20~30min of stirring makes
It is uniformly mixed, and obtains precursor solution, the concentrated sulfuric acid, polyethylene glycol, nine water sodium metasilicate and deionized water molar ratio be 2~
10:0.05~0.2:10~50:200~500；
By precursor solution at 120~180 DEG C 12~48h of crystallization, product centrifuge separation is taken out after natural cooling, then spend from
Sub- water and ethyl alcohol rinse product 2~3 times；
Product is successively dried and is roasted, dry temperature is 80~120 DEG C, the time be 8~for 24 hours, the temperature of roasting is
500~580 DEG C, the time be 8~for 24 hours, obtain mesoporous silicon oxide.
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