CN101791551B - Honeycomb catalyst for denitration of glass furnace fume and preparation method thereof - Google Patents
Honeycomb catalyst for denitration of glass furnace fume and preparation method thereof Download PDFInfo
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- CN101791551B CN101791551B CN2010101534718A CN201010153471A CN101791551B CN 101791551 B CN101791551 B CN 101791551B CN 2010101534718 A CN2010101534718 A CN 2010101534718A CN 201010153471 A CN201010153471 A CN 201010153471A CN 101791551 B CN101791551 B CN 101791551B
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Abstract
The invention discloses a honeycomb catalyst for fume SCR (Selective Catalytic Reduction) denitration of a glass furnace, which comprises a carrier and active components. The honeycomb catalyst is characterized in that the carrier is a honeycomb titanium-silicon carrier which contains 30-50 wt.% of TiO2-SiO2 powder, 10-20 wt.% of TiO2 and 20-50 wt.% of high-viscosity attapulgite; the active components comprise amorphous MnOx, V2O5 and WO3, wherein the amorphous MnOx accounts for 5-25.0% of the total weight of the catalyst, the V2O5 accounts for 0.5-5.0% of the total weight of the catalyst, and the WO3 accounts for 0.1-8.0% of the total weight of the catalyst. By adopting the high-viscosity attapulgite, the catalyst has high plasticity, strong binding power and strong water absorption; by selecting the TiO2-SiO2 powder, not only the apparent structures, such as the specific surface, the pore volume and the like, of the carrier can be improved, but also the conversion rate of SO2 to SO3 is inhibited. The selective reducing catalyst can be widely applied to selective reduction of nitrogen oxide in glass furnace fume.
Description
Technical field
The present invention relates to a kind of catalyst, a kind of specifically honeycombed catalyst that is used for glass furnace fume SCR (SCR) denitration and preparation method thereof.
Background technology
According to statistics: national SO in 2000
2About 1,990 ten thousand tons of discharge capacity, NO
xAbout 1,170 ten thousand tons of discharge capacity, acid rain region area have influence on the whole nation 40% nearly 4,000,000 square kilometres.This brings enormous economic loss to national economy, also heavy damage human rely according to survival environment [because: 1. nitrogen oxide heavy damage atmospheric ozone layer, 2. nitrogen nitride and erythrocytic affinity above 1000 times of carbon monoxide, 3. acid rain directly endangers the growth of plant and crops, 4. nitrogen oxide also can influence phreatic quality ...And the expansion that utilizes along with solar energy composite, the enforcement of " goldentop plan " bring unprecedented opportunities will inevitably for the great development of glass industry.The develop rapidly of glass industry is so created condition for the development of glass furnace., the denitration of glass furnace fume has also been mentioned on the agenda.
The glass furnace fume composition mainly is: (1) NO concentration 3200ppm, NO
2Concentration 1200ppm; (2) NO
xTotal concentration 3000-7000ppm; (3) EGT is low: 50-70 ℃; (4) air speed 3000-5000h-1; (5) oxygen content: 20%.This shows, compare with coal steam-electric plant smoke at a distance of very big.Therefore, purify this process conditions that partly high concentration nitrogen oxide, reaction temperature again need be lower, catalyst is had higher requirement.The applicant selects a kind of novel catalyst for use through a large amount of tests, and the available air dilution method is diluted to high concentrate NOx below the 2500ppm, the oxidizability of NOx is improved, thereby it is easier that NOx is removed.
The method of handling glass furnace fume has three kinds: 1. liquid absorption method: liquid absorption method comprises six kinds of water absorption methods, rare nitric acid absorption process, alkaline solution absorption process, oxidation-absorption process, absorption-reducing process, complexed absorption method.Water absorption method: use water as absorbent to NO
x, absorb, absorption efficiency is low, only can be used for narrow-minded, purify less demanding occasion, can not purify that to contain NO be main NO
xRare nitric acid absorption process: make absorbent to NO with rare nitric acid
xCarry out Physical Absorption and chemical absorbing, can reclaim NO
x, consumption of power is bigger.Alkaline solution absorption process: with NaOH, Na
2CO
3, Ca (OH)
2, NH
4Aqueous slkalis such as OH are made absorbent to NO
xCarry out chemical absorbing, for containing the more NO of NO
xWaste gas, purification efficiency is low.Oxidation-absorption process: for containing the more NO of NO
xWaste gas is with red fuming nitric acid (RFNA), O
3, KMnO
4, etc. make oxidant, earlier with NO
xIn the NO partial oxygen change into NO
2, and then, purification efficiency is improved with the aqueous slkali absorption.Absorption-reducing process: with NO
xAbsorb in the solution, with (NH
4)
2SO
3, (NH
4) HSO
3, Na
2SO
3Deng reducing agent reaction, NO
xBe reduced to N
2, purification efficiency is better.Complexed absorption method: utilize complexed absorption agent FeSO
4Fe (II)-EDTA and Fe (II)-EDTA-Na
2SO
3With the NO reaction, the complex compound that NO generates discharges NO when heating again Deng directly, thereby makes NO ability enriching and recovering.In six kinds of liquid absorption methods, commonly used is alkali absorption method and oxidation-absorption process.2. solid absorption method: the solid absorption method is with the NO in the absorption waste gas such as mordenite molecular sieve, mud coal, weathered coal
x, with waste gas purification.3. catalytic reduction method: catalytic reduction method comprises two kinds of non-selective catalytic reduction and selective catalytic reductions: non-selective catalytic reduction: use CH
4, H
2, CO and other fuel gas makes reducing agent and NO
xCarry out catalytic reduction reaction, the oxygen in the waste gas is participated in reaction, and thermal discharge is big.Selective catalytic reduction: use NH
3Make reducing agent, with NO
xCatalytic reduction is N
2, the oxygen in the waste gas seldom with NH
3Reaction, thermal discharge is little.This method has more superiority with respect to liquid absorption method and solid absorption method.
Ammine selectivity catalytic reduction method (SCR) be at present universally acknowledged application at most, the most ripe, the most fruitful a kind of gas denitrifying technology.The core technology of this method is a catalyst.And at present coal steam-electric plant smoke SCR catalyst is also existed: 1. the key technology of the prescription of catalyst and production technology is had by overseas enterprise.2. domestic enterprise has introduced foreign technology in recent years, but small scale, raw materials for production still need import.3. catalyst costs an arm and a leg, and every cubic metre about about 50,000 yuan, accounts for about 40% of whole that denitration construction costs.4. catalyst is short service life, needs about 3 years to change, and annual replacing catalyst costs is also higher.The production capacity of 5. several foreign SCR catalyst manufacturers had only for 10 ten thousand stere/years, and it has satisfied not the demand of China far away.In sum, be not difficult to find out that the problem that current Catalyst Production, use exist is one of bottleneck of restriction denitrating flue gas engineering.The SCR denitration efficiency is high; Be most widely used, if but not well production domesticization of catalyst, main production technology and raw material are grasped in foreigner's hand; Whole nation enforcement nitrogen oxide control discharging is very passive so, and it will seriously hinder the sound development of China's denitrating flue gas industry! As far as glass furnace fume, its quantity is many, distributing is only second to thermal power plant, smeltery than dispersion, total emission volumn.This industry that even more serious is also is in the improvement of flue gas nitrogen oxide " zero " state.And in the reproducibility catalyst in the past, also use amorphous MnO
x, but this amorphous MnO
x, it is water funk is afraid of sulphur again, it is raw material that poor activity, and these reproducibility catalyst is at low temperatures selected metatitanic acid, supports V
2O
5After, make the SO in the flue gas easily
2Change into SO
3, this is that any catalyst is not hoped the result that obtains.
Summary of the invention
In view of the problem that background technology exists, the technical problem that the present invention will solve provides a kind of high shape Catalysts and its preparation method of honeybee that is used for glass furnace fume SCR glass furnace fume nitrogen oxide.
For this reason; The present invention adopts following technical scheme to realize: a kind of honeycombed catalyst that is used for glass furnace fume SCR denitration; Be made up of carrier and active component, it is characterized in that said carrier is cellularly to admire-silicon carrier, it contains the TiO that weight ratio is 30-50%
2-SiO
2The TiO of powder, 10-20%
2With the sticking attapulgite of the height of 20-50%; Said active component comprises amorphous MnO
x, V
2O
5And WO
3, wherein amorphous MnOx accounts for the 5-25.0% of total catalyst weight, V
2O
5Account for the 0.5-5.0% of total catalyst weight, WO
3Account for the 0.1-8.0% of total catalyst weight;
Said active component also comprises CeO
2, said CeO
2Account for 0.01～1.5% of catalyst total amount.
Among the present invention; Adopt high sticking attapulgite; It has stronger adsorption capacity, unique dispersiveness, high temperature resistant, anti-saline and alkaline, higher plasticity and cohesive force, the light weight of mineral own are arranged, property is crisp, water imbibition is strong, dry after-contraction is little, do not show crackle, the water logging bubble collapses diffusing; Suspension is met dielectric and is not flocculated, do not precipitate, and test shows: select for use high sticking attapulgite can increase premium properties such as the specific surface of catalyst carrier, pore volume, intensity.And selection TiO
2-SiO
2Powder, apparent structures such as the specific surface of the carrier that not only improves, pore volume, but also suppressed SO
2Change into SO
3Conversion ratio, this selective reduction catalyst can be widely used in the selective reduction of nitrogen oxide in the glass furnace fume, in the presence of catalyst of the present invention, reaction as follows takes place:
4NO+4NH
3+ O
2_ _ _ _ _ catalyst _ _ _ _ _ 4N
2+ 6H
2O
6NO
2+ 8NH
3_ _ _ _ _ catalyst _ _ _ _ _ 7N
2+ 12H
2O
The present invention also provides above-mentioned Preparation of catalysts method, and concrete preparation method is following: a kind of preparation method who is used for the honeycombed catalyst of glass furnace fume SCR denitration is characterized in that comprising the steps:
1) amorphous MnO
xPreparation:
A, select commercially available KMnO for use
4, KOH, MnSO
4, with KMnO
4With KOH be dissolved into earlier in the deionized water subsequent use,
B, with MnSO
4Be dissolved in the deionized water subsequent use;
C, the solution among the step a is added one be with in the intensively stirred flask, under the stirring of 80～180 rev/mins of rotating speeds, drip the solution among the step b, in accomplishing at normal temperatures and co-precipitation.Solution among the step b added in about 40 minutes, and wearing out was filtered into filter cake after 30 minutes again;
D, the filter cake of gained is removed K with starching WATER-WASHING METHOD again
2SO
4, washings are used deionized water, wash oven dry under 100～110 ℃ temperature, broken, levigate again, promptly synthetic amorphous MnO 2-3 time
x
2) preparation of cellular titanium-silicon carrier:
A, get the sticking attapulgite of commercially available height, subsequent use through ultra-fine grinding;
B, use commercially available metatitanic acid to be raw material,, wash, filter, remove the SO that does not clean with the deionized water making beating
4 2-, make SO
4 2-Be controlled at TiO
2The 3-4% of weight meter, subsequent use;
C, employing TiO
2-SiO
2Powder, subsequent use;
D, get the metatitanic acid of step b gained, add the amorphous MnO for preparing in the step 1)
x, and after fully mediating, add the TiO among high sticking attapulgite and the step c
2-SiO
2Powder adds entry again, adds reaming, lubricant simultaneously, after fully mediating, in vacuum deairing machine, removes bubble, pushes through mould again, just becomes cellular titanium-silicon carrier;
3) supporting of active component:
A, with step 2) in the cellular titanium-silicon honeybee carrier that makes immerse in the metavanadic acid solution, dipping temperature is a room temperature to 60 ℃; Dip time is 2～5 hours, so just supports active component V
2O
5
B, with supporting V among the step a
2O
5Cellular titanium-silicon carrier immerse in the ammonium metatungstate solution, dipping temperature is a room temperature to 60 ℃; Dip time is 2～5 hours, so just supports active component WO
3
4) drying and activation
Cellular titanium-the silicon carrier that supports behind the active constituent is carried out drying, and its baking temperature is 60-100 ℃, and be 16～144 hours drying time, and activation temperature is 350～500 ℃, and soak time is 8～24 hours.
So just make a kind of honeycombed catalyst that is used for glass furnace fume SCR denitration.
The present invention also provides another kind of above-mentioned Preparation of catalysts method, and is specific as follows: a kind of preparation method who is used for the honeycombed catalyst of glass furnace fume SCR denitration is characterized in that comprising the steps:
1) amorphous MnO
xPreparation:
A, select commercially available KMnO for use
4, KOH, MnSO
4, with KMnO
4With KOH be dissolved into earlier in the deionized water subsequent use,
B, with MnSO
4Be dissolved in the deionized water subsequent use;
C, the solution among the step a is added one be with in the intensively stirred flask, under the stirring of 80～180 rev/mins of rotating speeds, drip the solution among the step b, in accomplishing at normal temperatures and co-precipitation.Solution among the step b added in about 40 minutes, and wearing out was filtered into filter cake after 30 minutes again;
D, the filter cake of gained is removed K with starching WATER-WASHING METHOD again
2SO
4, washings are used deionized water, wash oven dry under 100～110 ℃ temperature, broken, levigate again, promptly synthetic amorphous MnO 2-3 time
x
2) preparation of cellular titanium-silicon carrier:
A, get the sticking attapulgite of commercially available height, subsequent use through ultra-fine grinding;
B, use commercially available metatitanic acid to be raw material,, wash, filter, remove the SO that does not clean with the deionized water making beating
4 2-, make SO
4 2-Be controlled at TiO
2The 3-4% of weight meter, subsequent use;
C, employing TiO
2-SiO
2Powder, subsequent use;
D, get the metatitanic acid of step b gained, add a certain amount of deionized water making beating, and in making beating, add the metavanadic acid oxalic acid solution; Behind metavanadic acid oxalic acid solution and the abundant mixing of metatitanic acid; Dropping ammonia is adjusted to 8-10 with solution PH again, filter then, wash, dry, pulverize subsequent use;
E, the material that adds vanadium in the steps d added the amorphous MnO for preparing in the step 1)
x, and after fully mediating, add the TiO among high sticking attapulgite and the step c
2-SiO
2Powder adds entry again, adds reaming, lubricant simultaneously, after fully mediating, in vacuum deairing machine, removes bubble, pushes through mould again, just becomes cellular titanium-silicon carrier;
3) supporting of active component:
With step 2) in the cellular titanium-silicon carrier that makes immerse in the ammonium metatungstate solution, dipping temperature is a room temperature to 60 ℃; Dip time is 2～5 hours, so just supports active component WO
3
4) the dry and activation cellular titanium-silicon carrier that will support behind the active constituent carries out drying, and its baking temperature is 60-100 ℃, and be 16～144 hours drying time, and activation temperature is 350～500 ℃, and soak time is 8～24 hours.
So just make a kind of honeycombed catalyst that is used for glass furnace fume SCR denitration.
Among first kind of above-mentioned preparation method, also can be with supporting V
2O
3And WO
3After material soak altogether at cerous nitrate solution or in ammonium metatungstate solution again, support active component CeO again
2
Among second kind of above-mentioned preparation method, also can just support active component WO
3Material soak altogether at cerous nitrate solution or in ammonium metatungstate solution again, support active component CeO like this
2
Among two kinds of above-mentioned preparation methods, said reaming, lubricant are a kind of in field work cyanines powder, carboxymethyl cellulose, the hydroxypropyl methylcellulose or two kinds.
Among two kinds of above-mentioned preparation methods, also can after adding reaming, lubricant, also add moulding reinforcing agent glass fibre.
Among the preparation method of the present invention, with amorphous MnO
xWith the TiO in the metatitanic acid
2Fully mix and pinch evenly, changed amorphous MnO
xPerformance; Make it under the situation of water content, also not influence its activity 10%; Possess outstanding low temperature active,, have bigger specific surface, very high denitration activity and good low temperature (120-200 ℃) denitration activity according to the catalyst of the inventive method preparation; Water-fast sulfur tolerance is good in the reaction, possesses outstanding substantive distinguishing features and obvious improvement.
The specific embodiment
The present invention obviously is different from the existing SCR catalyst on catalyst formulation and preparing carriers.It is made up of carrier and active component, and said carrier is cellular titanium-silicon carrier, and it contains the TiO that weight ratio is 30-50%
2-SiO
2The TiO of powder, 10-20%
2With the sticking attapulgite of the height of 20-50%; Said active component comprises amorphous MnO
x, V
2O
5And WO
3, wherein amorphous MnO
xAccount for the 5-25.0% of total catalyst weight, V
2O
5Account for the 0.5-5.0% of total catalyst weight, WO
3Account for the 0.1-8.0% of total catalyst weight; Said active component also comprises CeO
2, said CeO
2Account for 0.01～1.5% of catalyst total amount.
Amorphous MnO of the present invention
xMake through following method:
A, select commercially available KMnO for use
4, KOH, MnSO
4, with KMnO
4With KOH be dissolved into earlier in the deionized water subsequent use,
B, with MnSO
4Be dissolved in the deionized water subsequent use;
C, the solution among the step a is added one be with in the intensively stirred flask, under the stirring of 80～180 rev/mins of rotating speeds, drip the solution among the step b, in accomplishing at normal temperatures and co-precipitation.Solution among the step b added in about 40 minutes, and wearing out was filtered into filter cake after 30 minutes again;
D, the filter cake of gained is removed K with starching WATER-WASHING METHOD again
2SO
4, washings are used deionized water, wash oven dry under 100～110 ℃ temperature, broken, levigate again, promptly synthetic amorphous MnO 2-3 time
x
Embodiment 1:
Choosing commercially available metatitanic acid is raw material, with the deionized water making beating, washes, filters, and removes the SO that does not clean
4 2-, make SO
4 2-Be controlled at 3-4% (with TiO
2Meter), following degree is the percentage of catalyst total amount.
Get the metatitanic acid 667g after cleaning, wherein TiO
2Weight ratio 45% accounts for catalyst weight 30%, add the deionized water making beating of 2000ml, and adding contains 3% V in making beating
2O
5Metavanadic acid, this metavanadic acid dissolves down metavanadic acid with 5% oxalic acid solution in heating.Behind metavanadic acid oxalic acid solution and the abundant mixing of metatitanic acid, drip 8mol ammoniacal liquor again, solution PH is adjusted to 9.0-9.2.Filter then, wash, dry, pulverize subsequent use;
Get the above-mentioned metatitanic acid mixture 330g that supports vanadium, account for 33% of catalyst weight, add unformed MnOx50g (accounting for catalyst weight 5%), fully mediate; Add TiO again
2-SiO
2Powder 450g (accounting for catalyst weight 39%), increase sticking attapulgite 200g (accounting for catalyst weight 15%), add reaming, lubricant and moulding reinforcing agent: sesbania powder 30g, plasticizer hydroxypropyl methylcellulose 15g, glass fibre 30g (accounting for catalyst weight 3%) and appropriate amount of deionized water; Mediate then; In vacuum deairing machine, remove bubble; On mould, be extruded into the honeycomb substrate of 50 * 50 * 200mm again, the honeycomb aperture is 3 * 3mm.Carrier adopt the dry railway carriage or compartment of constant-humidity constant-temperature through 96 hours dryings of 40-105 ℃ of temperature programming, subsequent use after adopting Muffle furnace through 100-450 ℃ of temperature programming roasting in 16 hours again; After high-temperature roasting, the whole charings of additive, all burn at last, have only glass fibre to exist. so when calculating, only the oxide on the catalyst has been done metering, following examples are all calculated with this.
With above-mentioned 5% the amorphous MnO that contains
x, 3% V
2O
5Honeycomb titanium-silicon carrier immerse according to the carrier water absorption rate and require to flood dipping temperature in the ammonium metatungstate solution (138.9g/l) of preparation: room temperature; Dip time: 4 hours.The WO that supports like this
35.0%.
Drying and the activation that has supported the cellular titanium-silicon carrier behind the active constituent will be controlled its process conditions well: according to the indication and the actual measurement situation of differential thermal analyzer, baking temperature: 80-120 ℃, the best is 105 ℃; Drying time: 16-38 hour, the best was 24 hours; Activation temperature: 300-400 ℃, preferably 350 ℃; Soak time: 2-8 hour, preferably 6 hours.So just make the high shape catalyst of SCR of the present invention (SCR) denitration honeybee.
The above-mentioned catalyst sample that makes is estimated on the denitration activity evaluating apparatus: air speed 5000h-1, NO1500ppm, 200 ℃ of temperature, denitration rate 93%.
Embodiment 2:
Metatitanic acid after getting that embodiment 1 is said and cleaning accounts for 30% of total catalyst weight, adds the amorphous MnO of catalyst gross weight 5%
xFully mediate, add the TiO of catalyst gross weight 30% again
2-SiO
2Powder, add the sticking attapulgite of height of catalyst gross weight 24% and contain 3%V
2O
5Metavanadic acid, and add proper amount of deionized water and mix and pinch.Make the abundant mixing of active constituent.Add reaming, lubricant and moulding reinforcing agent then: hydroxypropyl methylcellulose 3.5%, glass fibre 3%, proceed to mediate again; In vacuum deairing machine, remove bubble; On mould, be extruded into 50 * 50 * 200mm honeycomb substrate again, the honeycomb aperture is 3 * 3mm.Carrier through dry, roasting is subsequent use, and is wherein dry, roasting is identical with embodiment 1.
To contain 5% amorphous MnO
x, 3% V
2O
5Cellular titanium-silicon carrier immerse according to the carrier water absorption rate and require dipping in the ammonium metatungstate solution (138.9g/l) of preparation, temperature room temperature, 4 hours time. 5.0% the WO that just supports
3
Drying and the activation that has supported the honeycombed catalyst behind the active constituent will be controlled its process conditions well, and its process conditions are identical with embodiment 1.
The catalyst that present embodiment makes is estimated on the denitration activity evaluating apparatus: air speed 5000h-1, NO1500ppm, 200 ℃ of temperature, denitration rate 89%.
Embodiment 3:
Get the metatitanic acid 30% after cleaning, add the deionized water making beating of 2 times of weight, and adding contains V in making beating
2O
53% metavanadic acid, this metavanadic acid dissolve under heating with 5% oxalic acid solution and form.Behind metavanadic acid oxalic acid solution and the abundant mixing of metatitanic acid, drip 8mol ammoniacal liquor again, solution PH is adjusted to 9.0-9.2.Filter then, wash, dry, pulverize subsequent use.
Get the metatitanic acid 33% that supports vanadium, add 5% amorphous MnO
xFully mediate, add TiO again
2-SiO
2Powder 20%, increase sticking attapulgite 34%, add reaming, lubricant and moulding reinforcing agent: sesbania powder 3%, hydroxypropyl methylcellulose 1.5%, glass fibre 3.0%; Mediate then; In vacuum deairing machine, remove bubble, on mould, be extruded into 50 * 50 * 200mm honeycomb substrate again, the honeycomb aperture is 3 * 3mm; Carrier through dry, roasting is subsequent use, its drying, roasting are identical with embodiment 1.
To contain 5% amorphous MnO
x, 3% V
2O
5Titanium-silicon honeycomb substrate immerse according to the carrier water absorption rate and require to flood dipping temperature in the ammonium metatungstate solution (138.9g/l) of preparation: room temperature; Dip time: 2 hours.5.0% the WO that so just supports
3
Drying and the activation that has supported the cellular titanium carrier behind the active constituent will be controlled its process conditions well: according to the indication and the actual measurement situation of differential thermal analyzer, press embodiment 1 operation.
The catalyst that present embodiment obtains is estimated on the denitration activity evaluating apparatus: air speed 5000h-1, NO1500ppm, 200 ℃ of temperature, denitration rate 87%.
Embodiment 4:
Choosing commercially available metatitanic acid is raw material, with the deionized water making beating, washes, filters, and removes the SO that does not clean
4 2-, make SO
4 2-Be controlled at 4-5% (with TiO
2Meter).
Get the metatitanic acid 20% after cleaning, add 10% amorphous MnO
xFully mediate, add TiO again
2-SiO
2Powder 30%, increase sticking attapulgite 29% and contain 3%V
2O
5Metavanadic acid, and add proper amount of deionized water and mix and pinch, make the abundant mixing of active constituent.Add reaming, lubricant and moulding reinforcing agent then: hydroxypropyl methylcellulose 3.5%, glass fibre 3% are proceeded to mediate again; In vacuum deairing machine, remove bubble; On mould, be extruded into 50 * 50 * 200mm honeycomb substrate again, the honeycomb aperture is 3 * 3mm.Carrier through dry, roasting is subsequent use, and is dry, roasting is identical with embodiment 1.
To contain 10% amorphous MnO
x, 3% V
2O
5Cellular titanium-silicon carrier immerse require preparation according to the carrier water absorption rate metatungstic acid by flooding dipping temperature in the solution (138.9g/l): room temperature; Dip time: 4 hours.5.0% the WO that supports like this
3
Drying and the activation that has supported the cellular titanium catalyst behind the active constituent will be controlled its process conditions well: undertaken by embodiment 1..
Present embodiment makes catalyst and on the denitration activity evaluating apparatus, estimates: air speed 5000h-1, NO1500ppm, 200 ℃ of temperature, denitration rate 95%.
Embodiment 5:
Choosing commercially available metatitanic acid is raw material, with the deionized water making beating, washes, filters, and removes the SO that does not clean
4 2-, make SO
4 2-Be controlled at 4-5% (with TiO
2Meter).
Get the metatitanic acid 10% after cleaning, add 15% amorphous MnO
xFully mediate, add TiO2-SiO
2Powder 30%, increase sticking attapulgite 34% and contain 3%V
2O
5Metavanadic acid and contain 5.0% WO
3Metatungstic acid by and add proper amount of deionized water and mix and pinch, make the abundant mixing of active constituent.Add hydroxypropyl methylcellulose 3.5%, glass fibre 3% then and proceed to mediate again, in vacuum deairing machine, remove bubble, on mould, be extruded into 50 * 50 * 200mm honeycomb catalyst presoma again, the honeycomb aperture is 3 * 3mm.The honeycomb catalyst presoma is through dry, the disposable honeycombed catalyst that becomes of roasting, and its drying, roasting are identical with embodiment 1.
The catalyst that present embodiment makes is estimated on the denitration activity evaluating apparatus: air speed 5000h-1, NO1500ppm, 200 ℃ of temperature, denitration rate 98%.
Embodiment 6:
Get the metatitanic acid 20% after cleaning, add 5% amorphous MnO
xFully mediate, add TiO again
2-SiO
2Powder 30%, increase sticking attapulgite 34% and contain 3% V
2O
5Metavanadic acid, and add proper amount of deionized water and mix and pinch, make the abundant mixing of active constituent.Add reaming, lubricant and reinforcing agent then: hydroxypropyl methylcellulose 1.5%, sesbania powder 3%, glass fibre 3%; Proceed again to mediate; In vacuum deairing machine, remove bubble, on mould, be extruded into the cellular titanium-silicon carrier of 50 * 50 * 200mm again, the honeycomb aperture is 3 * 3mm.Carrier through dry, roasting is subsequent use, its drying, roasting are identical with embodiment 1.
To contain 5% amorphous MnO
x, 3% V
2O
5Cellular titanium-silicon carrier immerse according to the carrier water absorption rate and require to flood dipping temperature in the ammonium metatungstate solution (138.9g/l) of preparation: room temperature; Dip time: 2 hours.5.0% the WO that supports like this
3
Drying and the activation that has supported the cellular titanium-silicon carrier behind the active constituent will be controlled its process conditions well: undertaken by embodiment 1.
The catalyst that present embodiment makes is estimated on the denitration activity evaluating apparatus: air speed 5000h-1, NO1500ppm, 200 ℃ of temperature, denitration rate 90%.
Embodiment 7:
Choosing commercially available metatitanic acid is raw material, with the deionized water making beating, washes, filters, and removes the SO that does not clean
4 2-, make SO
4 2-Be controlled at 4-5% (with TiO
2Meter).
Get the metatitanic acid 20% after cleaning, add 5% amorphous MnO
xFully mediate. add TiO
2-SiO
2Powder 38%, increase sticking attapulgite 30% and contain 1%V
2O
5Metavanadic acid, and add proper amount of deionized water and mix and pinch.Make the abundant mixing of active constituent.Add reaming, lubricant and moulding reinforcing agent then: hydroxypropyl methylcellulose 1.5%, sesbania powder 3%, glass fibre 3%; Proceed again to mediate; In vacuum deairing machine, remove bubble, on mould, be extruded into 50 * 50 * 200mm honeycomb support again, the honeycomb aperture is 3 * 3mm.Carrier through dry, roasting is subsequent use, its drying, roasting are identical with embodiment 1.
To contain 5% amorphous MnO
x, 1% V
2O
5Cellular titanium-silicon carrier immerse ammonium metatungstate solution (83.3g/l) dipping that requires preparation according to the carrier water absorption rate, dipping temperature: room temperature; Dip time: 4 hours.Support 3.0% WO like this
3
Drying and the activation that has supported the cellular titanium-silicon carrier behind the active constituent will be controlled its process conditions well: undertaken by embodiment 1.
The catalyst that present embodiment makes is estimated on the denitration activity evaluating apparatus: air speed 5000h-1, NO1500ppm, 200 ℃ of temperature, denitration rate 85%.
Embodiment 8:
Choosing commercially available metatitanic acid is raw material, with the deionized water making beating, washes, filters, and removes the SO that does not clean
4 2-, make SO
4 2-Be controlled at 4-5% (with TiO
2Meter).
Get the metatitanic acid 20% after cleaning, add 5% amorphous MnO again
x, fully mix and pinch, add TiO again
2-SiO
2Powder 37%, increase sticking attapulgite 30% and contain 1%V
2O
5Metavanadic acid, and add proper amount of deionized water and mix and pinch.Make the abundant mixing of active constituent.Add reaming, lubricant and moulding reinforcing agent then: hydroxypropyl methylcellulose 1.5%, sesbania powder 3%, glass fibre 3%; Proceed again to mediate; In vacuum deairing machine, remove bubble, on mould, be extruded into 50 * 50 * 200mm honeycomb support again, the honeycomb aperture is 3 * 3mm.Carrier through dry, roasting is subsequent use, and is dry, roasting is identical with embodiment 1.
To contain 5% amorphous MnO
x, 1% V
2O
5Cellular titanium-silicon carrier immerse require preparation according to the carrier water absorption rate metatungstic acid by soaking dipping temperature altogether in solution (83.3g/l) cerous nitrate solution (64.0g/l): room temperature; Dip time: 2 hours.Support 3.0% WO like this
3, 1.0% CeO
2
Drying and the activation that has supported the cellular titanium catalyst behind the active constituent will be controlled its process conditions well: undertaken by embodiment 1..
This sample is estimated on the denitration activity evaluating apparatus: air speed 5000h-1, NO1500ppm, 200 ℃ of temperature, denitration rate 87%.
Embodiment 9:
Choosing commercially available metatitanic acid is raw material, with the deionized water making beating, washes, filters, and removes the SO that does not clean
4 2-, make SO
4 2-Be controlled at 4-5% (with TiO
2Meter).
Get the metatitanic acid 20% after cleaning, add 5% amorphous MnO again
xFully mix and pinch, add TiO
2-SiO
2Powder 36.5%, increase sticking attapulgite 30% and contain 1%V
2O
5Metavanadic acid, and add proper amount of deionized water and mix and pinch.Make the abundant mixing of active constituent.Add reaming, lubricant and moulding reinforcing agent then: hydroxypropyl methylcellulose 1.5%, carboxymethyl cellulose 3%, glass fibre 3%; Proceed again to mediate; In vacuum deairing machine, remove bubble, on mould, be extruded into 50 * 50 * 200mm honeycomb substrate again, the honeycomb aperture is 3 * 3mm.Carrier through dry, roasting is subsequent use, and is dry, roasting is identical with embodiment 1.
To contain 5% amorphous MnO
x, 1% V
2O
5Titanium-silicon honeycomb substrate immerse according to the carrier water absorption rate and require to soak dipping temperature altogether in the ammonium metatungstate solution (83.0g/l), cerous nitrate solution (96.0g/l) of preparation: room temperature; Dip time: 2 hours.Support 3.0% WO like this
3(W), 1.5% CeO
2
Drying and the activation that has supported the cellular titanium catalyst behind the active constituent will be controlled its process conditions well: undertaken by embodiment 1..
The catalyst that present embodiment makes is estimated on the denitration activity evaluating apparatus: air speed 5000h-1, No1500ppm, 200 ℃ of temperature, denitration rate 89%.
Embodiment 10:
Choosing commercially available metatitanic acid is raw material, with the deionized water making beating, washes, filters, and removes the SO that does not clean
4 2-, make SO
4 2-Be controlled at 4-5% (with TiO
2Meter).
Get the metatitanic acid 20% after cleaning, add 20% the invisible MnO of deciding again
xCarry out fully mixing pinching, add TiO again
2-SiO
2Powder 21%, increase sticking attapulgite 30% and contain 1%V
2O
5Metavanadic acid, and add proper amount of deionized water and mix and pinch.Make the abundant mixing of active constituent.Add reaming, lubricant and moulding reinforcing agent then: hydroxypropyl methylcellulose 3.5% (W), glass fibre 3%; Proceed again to mediate; In vacuum deairing machine, remove bubble, on mould, be extruded into 50 * 50 * 200mm honeycomb substrate again, the honeycomb aperture is 3 * 3mm.Carrier through dry, roasting is subsequent use, dry, roasting is identical with embodiment 1).
To contain 20% amorphous MnO
x, 1% V
2O
5Cellular titanium-silicon carrier immerse according to the carrier water absorption rate and require to flood dipping temperature in the ammonium metatungstate solution (138.9g/l) of preparation: room temperature; Dip time: 4 hours.Support 5.0% WO like this
3
Drying and the activation that has supported the cellular titanium catalyst behind the active constituent will be controlled its process conditions well: undertaken by embodiment 1.
The present embodiment sample is estimated on the denitration activity evaluating apparatus: air speed 5000h-1, NO1500ppm, 200 ℃ of temperature, denitration rate 96%.
SCR evaluating catalyst condition is following: the activity of such catalysts evaluation is carried out on the continuous activity rating device of 4 gas circuit stainless steel fixed bed reactors of computer recording.Reaction distribution simulate glass kiln gas gets into the reactor of external electric.Reaction temperature is with the thermocouple indication and the control of inserting the catalyst cover.
With the distribution of steel cylinder gas simulated flue gas composition, NO steel cylinder gas and SO
2Steel cylinder gas all dilutes with high pure nitrogen.NO is made into 500-2500PPPM, SO
2Be made into 500-1000PPM, balance gas is compressed air, O
2Be 21% (volume ratio), gas flow 180L/h, this gas feed earlier and fill in the there-necked flask of water; There-necked flask heats on the crucible furnace of controllable temperature, and water temperature can be regulated arbitrarily, when water temperature is 46 ℃; Water content in the saturated steam is 10%, and catalyst system therefor rounds piece catalyst 50--70ml.Air speed 3000--8000.h-1, NH
3Gas concentration is analyzed with the AVLDigas4000light five gas analyzer continuously before and after/NO=1-1.2 (mol ratio) NO.SO
2The front and back gas concentration is measured with the HC-2 trace sulfur analyzer.
With above-mentioned catalyst test apparatus, embodiment SCR sample is carried out estimating under the equal conditions, be of the influence of checking water vapour to denitration performance, the applicant has been switched distribution, makes the balance flow of QI being obstructed cross the there-necked flask that is filled with water, and is just not moisture in the reaction gas like this.The sample denitration rate that record this moment does not almost change, so this catalyst does not receive water vapour to do sorrow.
SO
2The concentration determination of entering the reactor front and back is evaluation SO
2Change into SO
3Foundation.Mensuration result shows: owing to adopt TiO
2-SiO
2Be carrier, SO
2Advance the concentration of reactor front and back and also do not have significant change.So this catalyst V
2O
5Content is SO when 1-5%
2Change into SO
3Conversion ratio＜1%.
Claims (2)
1. the preparation method of the honeycombed catalyst in the glass furnace fume SCR denitration is characterized in that comprising the steps:
1) amorphous MnO
xPreparation:
A, select commercially available KMnO for use
4, KOH, MnSO
4, with KMnO
4With KOH be dissolved into earlier in the deionized water subsequent use,
B, with MnSO
4Be dissolved in the deionized water subsequent use;
C, the solution among the step a is added one be with in the intensively stirred flask, under the stirring of 80-180 rev/mins of rotating speeds, drip the solution among the step b, in accomplishing at normal temperatures and co-precipitation; Solution among the step b added in 40 minutes, and wearing out was filtered into filter cake after 30 minutes again;
D, the filter cake of gained is removed K with starching WATER-WASHING METHOD again
2SO
4, washings are used deionized water, wash oven dry under 100-110 ℃ temperature, broken, levigate again, promptly synthetic amorphous MnO 2-3 times
x
2) preparation of cellular titanium-silicon carrier:
A, get the sticking attapulgite of commercially available height, subsequent use through ultra-fine grinding;
B, use commercially available metatitanic acid to be raw material,, wash, filter, remove the SO that does not clean with the deionized water making beating
4 2-, make SO
4 2-Be controlled at TiO
23-4% of weight meter, subsequent use;
C, employing TiO
2-SiO
2Powder, subsequent use;
d?, taking steps? b? metatitanic obtained by adding steps? 1?) prepared amorphous? MnO
x ?, and by adding viscosity sufficiently kneaded attapulgite and steps? c? in? TiO
2 -SiO
2 ? powder, then add water, while adding reaming, lubricants, after fully kneaded in a vacuum pug mill in the removal of air bubbles, and then through the extrusion die, they become honeycomb Ti - silicon carrier;
3) supporting of active component:
A, with step 2) in the cellular titanium-silicon carrier that makes immerse in the metavanadic acid solution, dipping temperature be room temperature extremely
60 ℃; Dip time is 2-5 hours, so just supports active component V
2O
5
B, with supporting V among the step a
2O
5Cellular titanium-silicon carrier immerse in the ammonium metatungstate solution, dipping temperature is a room temperature to 60 ℃; Dip time is 2-5 hours, so just supports active component WO
3;
4) drying and activation
Cellular titanium-the silicon carrier that supports behind the active constituent is carried out drying, and its baking temperature is 60-100 ℃, and be 16-144 hours drying time, and activation temperature is 350-500 ℃, and soak time is 8-24 hours;
So just make a kind of honeycombed catalyst that is used for glass furnace fume SCR denitration.
2. according to the preparation method of the honeycombed catalyst in the described glass furnace fume SCR of claim 1 denitration, it is characterized in that said reaming, lubricant are a kind of in sesbania powder, carboxymethyl cellulose, the hydroxypropyl methylcellulose or two kinds.
3. according to the preparation method of the honeycombed catalyst in the described glass furnace fume SCR of claim 1 denitration, it is characterized in that after adding reaming, lubricant, also adding moulding reinforcing agent glass fibre.
4. the preparation method of the honeycombed catalyst in a kind of glass furnace fume SCR denitration is characterized in that comprising the steps:
1) amorphous MnO
xPreparation:
A, select commercially available KMnO for use
4, KOH, MnSO
4, with KMnO
4With KOH be dissolved into earlier in the deionized water subsequent use,
B, with MnSO
4Be dissolved in the deionized water subsequent use;
C, the solution among the step a is added one be with in the intensively stirred flask, under the stirring of 80-180 rev/mins of rotating speeds, drip the solution among the step b, in accomplishing at normal temperatures and co-precipitation; Solution among the step b added in 40 minutes, and wearing out was filtered into filter cake after 30 minutes again;
D, the filter cake of gained is removed K with starching WATER-WASHING METHOD again
2SO
4, washings are used deionized water, wash oven dry under 100-110 ℃ temperature, broken, levigate again, promptly synthetic amorphous MnO 2-3 times
x
2) preparation of cellular titanium-silicon carrier:
A, get the sticking attapulgite of commercially available height, subsequent use through ultra-fine grinding;
B, use commercially available metatitanic acid to be raw material,, wash, filter, remove the SO that does not clean with the deionized water making beating
4 2-, make SO
4 2-Be controlled at TiO
23-4% of weight meter, subsequent use;
C, employing TiO
2-SiO
2Powder, subsequent use;
D, get the metatitanic acid of step b gained, add a certain amount of deionized water making beating, and in making beating, add the metavanadic acid oxalic acid solution; Behind metavanadic acid oxalic acid solution and the abundant mixing of metatitanic acid; Dropping ammonia is adjusted to 8-10 with solution PH again, filter then, wash, dry, pulverize subsequent use;
e?, step d plus vanadium material added in step 1) prepared in the amorphous MnO
x ?, and sufficiently kneaded by adding viscosity and step c attapulgite The? TiO
2 -SiO
2 ? powder, then add water, while adding reaming, lubricants, after full After kneading in a vacuum pug mill in the removal of air bubbles, and then through the extrusion die, they become honeycombed titanium - silicon carrier;
3) supporting of active component:
With step 2) in the cellular titanium-silicon carrier that makes immerse in the ammonium metatungstate solution, dipping temperature is a room temperature to 60 ℃; Dip time is 2-5 hours, so just supports active component WO
3;
4) drying and activation
Cellular titanium-the silicon carrier that supports behind the active constituent is carried out drying, and its baking temperature is 60-100 ℃, and be 16-144 hours drying time, and activation temperature is 350-500 ℃, and soak time is 8-24 hours; So just make a kind of honeycombed catalyst that is used for glass furnace fume SCR denitration.
5. according to the preparation method of the honeycombed catalyst in the described glass furnace fume SCR of claim 4 denitration, it is characterized in that said reaming, lubricant are a kind of in sesbania powder, carboxymethyl cellulose, the hydroxypropyl methylcellulose or two kinds.
6. according to the preparation method of the honeycombed catalyst in the described glass furnace fume SCR of claim 4 denitration, it is characterized in that after adding reaming, lubricant, also adding moulding reinforcing agent glass fibre.
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| CN101862648A (en) * | 2010-06-03 | 2010-10-20 | 石磊 | SCR deNOx catalyst added with attapulgite and preparation method thereof |
| CN102101048B (en) * | 2011-01-25 | 2013-04-03 | 清华大学 | Cerium-based denitration catalyst with titanium-silicon compound oxide as carrier and preparation and application thereof |
| CN102179241B (en) * | 2011-03-17 | 2015-06-17 | 浙江三龙催化剂有限公司 | Catalyst for removing organic sulfur in clean coal gas through hydrolysis and preparation method thereof |
| CN102500359B (en) * | 2011-11-14 | 2014-07-30 | 天津大学 | Vanadium based SCR catalyst as well as preparation and application thereof in tail gas NOx desorption after acrylonitrile oxidation |
| CN102921405B (en) * | 2012-09-29 | 2014-10-08 | 重庆大学 | SiO2-containing denitration catalyst and preparation method thereof |
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| CN103623808A (en) * | 2013-12-10 | 2014-03-12 | 柳景惠 | Selective catalytic reduction (SCR) catalyst and preparation method thereof |
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| CN106345269A (en) * | 2016-10-24 | 2017-01-25 | 马鞍山科宇环境工程有限公司 | Coal denitration agent |
| CN106807360B (en) * | 2017-03-13 | 2019-07-09 | 内蒙古科技大学 | A kind of preparation method of sulfur resistive denitrating catalyst |
| CN108940299A (en) * | 2018-01-08 | 2018-12-07 | 南京东南工业装备股份有限公司 | A kind of diesel engine vent gas NOxPurify vanadium Ti-base catalyst and preparation method |
| CN109224874A (en) * | 2018-11-05 | 2019-01-18 | 南京工业大学 | A kind of catalytic membrane and preparation method thereof for air cleaning |
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| CN112226264B (en) * | 2020-10-19 | 2021-07-23 | 中国科学院兰州化学物理研究所 | Attapulgite-titanium dioxide modified ultra-high molecular weight polyethylene composite material and preparation method and application thereof |
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