CN106732759A - A kind of SCR catalyst for denitrating flue gas and preparation method thereof - Google Patents
A kind of SCR catalyst for denitrating flue gas and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of SCR catalyst for denitrating flue gas, including（1）The mixed solution of titanium sulfate and aminocarboxylate being prepared first, powdered molecular sieve being added in the mixed solution and is impregnated, TiO is obtained through drying and being calcined2- molecular sieve complex carrier；（2）By step（1）The TiO of preparation2- molecular sieve complex carrier is impregnated into the maceration extract containing active component and auxiliary agent precursor, and denitrating catalyst powder is obtained after drying and roasting；（3）By step（2）After denitrating catalyst powder mixes with glass fibre, wood pulp, polyacrylamide, carboxymethylcellulose calcium, ammoniacal liquor, deionized water, Faveolate denitration catalyst is obtained through mediating, being aged, extrude, dry and be calcined.Preparation process is simple of the present invention, with low cost, the active temperature range that prepared denitrating catalyst is adapted to is wide, and denitration activity is high, anti-SO2And H2O poisoning capabilities are strong.
Description
Technical field
The present invention relates to environment-friendlydenitration denitration catalyst, and in particular to a kind of SCR catalyst for denitrating flue gas and preparation method thereof, denitrating flue gas treatment is particularly well-suited to.
Background technology
Nitrogen oxides（NOx）It is one of the arch-criminal for causing haze, acid rain, photochemical fog and greenhouse effects.China is the big NOx discharges state of the first in the world, and NOx discharge reaches 22,400,000 tons within 2013, and NOx is administered turns into the emphasis that national " 12 " atmosphere pollution is controlled by force.Selective catalytic reduction（Selective Catalytic Reduction, abbreviation SCR）Maturation, efficiency high, good stability, as the current mainstream technology and developing direction for administering NOx both at home and abroad, wherein, SCR technology core is denitrating catalyst.
At present, the SCR catalyst of large-scale application is with V2O5As active component, TiO2As carrier, WO is added3Or MoO3As the high temperature catalyst of co-catalyst, although this kind of catalyst can efficiently purify NOx, some problems are still suffered from actual use.First, the larger requirement of temperature change under the active temperature range of the catalyst to be that scope is narrower between 300-400 DEG C can not usually meet use condition；Secondly, as the V of main active component2O5It is a kind of extremely toxic substance, secondary pollution easily is produced to human body and environment；Furthermore, V2O5Easily by the SO in flue gas2It is oxidized to SO3, SO3Meeting and NH3Reaction generation ammonium sulfate and ammonium hydrogen sulfate block Benitration reactor so as to cause catalyst activity reduction.Because this kind of catalyst only just has activity higher when temperature is higher than 300 DEG C, so typically SCR reactors can only be arranged between economizer and deduster.But existing boiler does not reserve denitration space mostly in the position, therefore application to SCR techniques brings very big difficulty.Additionally, containing high concentration dust in the flue gas of the process section, there are alkali metal, arsenic and mercury etc. that the material of toxic action can be produced to catalyst in dust, influence its denitration efficiency and service life.Therefore research and development active temperature range catalyst for denitrating flue gas wide, nontoxic, efficient, economic is always the focus in denitrating flue gas field.
It is domestic at present it has been reported that the SCR denitration of some research and development, and major part all shows excellent NOx detergent powers.CN101204650A discloses a kind of cerium and titanium compound oxide catalyst preparation method and applications, main composition is cerium oxide and titanium dioxide, prepared by infusion process or coprecipitation, reducing agent ammonia is sprayed into the upstream of catalyst or urea mixes with tail gas, make gaseous mixture in the range of 250-450 DEG C and catalyst is contacted, so that nitrogen oxides is reduced to nitrogen and water.CN101185886A discloses a kind of preparation method of SCR denitration, and cordierite honeycomb ceramic is immersed in into Al2O3-SiO2-TiO2In complex sol, the raffinate in after-blow clear opening road is taken out, dry and be calcined；Activity component impregnation liquid is to be dissolved in deionized water after mixing lanthanum nitrate, ammonium metavanadate, ammonium paratungstate, adds oxalic acid, ageing；By above-mentioned carrier impregnation in activity component impregnation liquid load active component.But in fact, this kind of catalyst mostly only just shows denitration ability higher under the conditions of not sulfur-bearing, anhydrous high temperature, the performance of long-time water resistant sulfur resistive is not had, low temperature active is not good, also has certain limitation in practical application.
CN102500358A discloses a kind of denitrifying catalyst with selective catalytic reduction, including carrier, active material and co-catalyst, described carrier is the titanium nanotube of protonation, described active material is the transition metal oxide obtained by active material presoma calcination, and described co-catalyst is the transition metal oxide obtained by co-catalyst presoma calcination；The load capacity of described active material and co-catalyst on carrier represents that load capacity is 0.005-1 with the metal in transition metal oxide with the mol ratio of titanium elements.The preparation method of above-mentioned denitrifying catalyst with selective catalytic reduction is by TiO2Particle and the advanced water-filling heat treatment of strong base solution, then the titanium nanotube protonated through pickling, washing, organic solvent immersion and after drying, then with infusion process carrying active substance and co-catalyst.It with the titanium nanotube for protonating is carrier that the invention is, so as to improve anti-alkali and alkaline earth metal ions poisoning capability, the titanium nanotube of protonation is expensive, prepares excessively complicated, and has extremely toxic substance vanadium in active component, easily causes secondary pollution.
CN103240081A is prepared for TiO2-SiO2It is the manganese-based low-temperature denitration catalyst of carrier, MnOx/TiO is prepared using sol-gel process2-SiO2Catalyst, wherein SiO2The mass ratio of complex carrier is accounted for for 40%-60%, Mn with（Ti+Si）Material amount ratio be 0.5-1.0:1, it is characterized in SiO2Addition greatly increased the specific surface area of carrier, be conducive to dispersion and stability of the active material on its surface, and with TiO2-SiO2The alkali resistant metal poisoning performance of catalyst can be improved for complex carrier；Active component low cost, it is non-toxic, and can just have good denitration catalyst activity at a lower temperature, therefore suitable for the denitration catalyst of NOx under low temperature environment after cement kiln dedusting.But manganese based denitration catalyst runs into SO2Inactivation is easy to, sulfur resistance is not good.
CN103230813A discloses a kind of preparation method of the denitrating catalyst of the alkali resistant poisoning suitable for cement kiln, the catalyst uses coprecipitation, stirring obtains mixed solution after adding manganese salt, cerium salt and auxiliary agent in titanium source solution, be sequentially added into above-mentioned mixed solution urea liquid, ammoniacal liquor, hydrogen peroxide to no longer produce precipitation, continue to stir 1-5 hours, then priority distilled water and absolute ethyl alcohol centrifuge washing, dry 8-24 hours at 70-105 DEG C, the catalyst powder of prepared high-specific surface area after 450-650 DEG C of calcining 2-6 hour.Such catalyst has denitration rate high and alkali-resisting advantage compared with the catalyst prepared with the sol-gal process of component, infusion process.The catalyst is suitable to relatively low denitration temperature, but when optimal denitration temperature is less than 250 DEG C, equally runs into SO2It is easy to inactivation.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide a kind of SCR catalyst for denitrating flue gas and preparation method thereof.Preparation process is simple of the present invention, with low cost, the active temperature range that prepared denitrating catalyst is adapted to is wide, and denitration activity is high, anti-SO2And H2O poisoning capabilities are strong.
The preparation method of SCR catalyst for denitrating flue gas of the present invention, comprises the following steps：
（1）TiO2The preparation of-molecular sieve complex carrier：The mixed solution of titanium sulfate and aminocarboxylate being prepared first, powdered molecular sieve being added in the mixed solution and is impregnated, TiO is obtained through drying and being calcined2- molecular sieve complex carrier；
（2）The load of active component and auxiliary agent：By step（1）The TiO of preparation2- molecular sieve complex carrier is impregnated into the maceration extract containing active component and auxiliary agent precursor, and denitrating catalyst powder is obtained after drying and roasting；
（3）Faveolate denitration catalyst is molded：By step（2）After obtained denitrating catalyst powder and glass fibre, wood pulp, polyacrylamide, carboxymethylcellulose calcium, ammoniacal liquor, deionized water etc. mix, through mediating, ageing, extrusion, dry and roasting is obtained Faveolate denitration catalyst.
Step of the present invention（1）In obtained mixed solution, the concentration of titanium sulfate is generally 500-3000g/L, preferably 1500-2500g/L.Described aminocarboxylate is sodium ammonium triacetate（NTA）, edetate (such as can be EDETATE SODIUM or four sodium), diethylenetriamine pentacarboxylic acid salt（DTPA）One or more in；The concentration of described aminocarboxylate is generally 20-200g/L, preferably 50-150g/L.It is possible to further add a certain amount of monoethanolamine in mixed solution, concentration is 10-100g/L, is favorably improved TiO2With molecular sieve binding ability.
Molecular sieve of the present invention is H type molecular sieves, such as can be HZSM-5 molecular sieves, HA type molecular sieves, and one or more in HY type molecular sieves etc., 0.1-50 μm of particle diameter, specific surface area is more than 200mg/m3, purity is more than 99.9%；Addition is that molecular sieve concentration is 200-1000g/L, preferably 200-400g/L in making mixed solution.
Dipping method of the present invention is known for those skilled in the art, it is preferred to use equi-volume impregnating.
In the present invention, step（2）Described in active component be selected from Mn, Ce, W and Mo etc. one or more, Ce and W is preferably contained simultaneously, the elemental mole ratios of wherein Ce and W are 0.3-5.Described auxiliary agent is selected from one or more in Fe, Cu, La, Sn etc., preferably Sn.The content of every kind of active component presoma is 0.1-1mol/L wherein in maceration extract, and the content of every kind of adjuvant component presoma is 0.1-0.5mol/L.The presoma of active component or adjuvant component refers generally to their soluble-salt, such as nitrate.
In the present invention, step（1）And step（2）Described drying temperature is 80-120 DEG C, and drying time is 1-12 hours；Described sintering temperature is 300-600 DEG C, and roasting time is 1-6 hours.
In the present invention, step（3）In described honeycomb ceramics denitrating catalyst forming process, it is respectively in parts by weight：75-90 parts, glass fibre 2-6 parts, wood pulp 0.1-2 parts, polyacrylamide 0.1-2 parts, carboxymethylcellulose calcium 0.1-2 parts, ammoniacal liquor 5-10 parts, deionized water 10-40 parts of denitrating catalyst powder.A diameter of 10 ± 1.5 μm of wherein described glass fibre, 5 ± 1.5 μm of length, loss on drying（105 DEG C of dryings are to constant weight）≤10%.The wood pulp is softwood pulp and hardwood pulp.The polyacrylamide is anion-polyacrylamide, and molecular weight is 700-900 ten thousand.1% solution viscosity of the carboxymethylcellulose calcium is 100-300mPas, loss on drying（105 DEG C of dryings are to constant weight）≤20%.
In the present invention, step（3）The operations such as described kneading, ageing, extrusion, dry and roasting are the routine operation of this area.Described digestion time is generally 12-48 hours.Described drying temperature is generally 20-70 DEG C, and humidity is 20%-90%, 1-5 days drying time.Described sintering temperature is 300-600 DEG C, roasting time 3-10h.Described roasting process can be carried out as follows：With 5-80 DEG C/h 300-400 DEG C, constant temperature 3-10 hours is risen to from room temperature；500-600 DEG C is at the uniform velocity warming up to 5-80 DEG C/h again, constant temperature 3-10 hours, roasting terminated.Using baking inphases mode, organic matter can be made fully to decompose, burn off, inorganic salts fully decompose generation metal oxide and make Active components distribution uniform.
Denitrating catalyst of the present invention is prepared using the invention described above method.In prepared Faveolate denitration catalyst：On the basis of catalyst gross mass, molecular sieve content is 5%-30%, TiO in catalyst2Content is 50%-85%, and content of glass fiber is 1%-8%, and active component content is calculated as 0.5%-10% with oxide, and adjuvant component content is calculated as 1%-10% with oxide, and sulfate radical content is 1%-10%.Wherein active component preferably contains Ce and W simultaneously selected from one or more in Mn, Ce, W and Mo etc., and the mol ratio of wherein Ce and W is 0.3-5.The adjuvant component is selected from one or more in Fe, Cu, La, Sn etc., preferably Sn.
Compared with prior art, the invention has the advantages that：
（1）TiO is used for using aminocarboxylate and titanium sulfate2The preparation of-molecular sieve complex carrier, aminocarboxylate forms complex compound with titanium ion, and powdered molecular sieve is impregnated with this complex solution, so as to TiO is obtained2- molecular sieve complex carrier.The strong complexing of aminocarboxylate causes TiO2It is tightly combined between molecular sieve surface, interaction is strengthened, so as to the denitrating catalyst prepared with the complex carrier has good catalysis activity, mechanical strength and anti-wear performance.
（2）Preparing TiO2Monoethanolamine is added in the mixed solution of-molecular sieve complex carrier, titanium ion hydrolysis rate can be prevented too fast, make that complex solution is more homogeneous, stabilization, therefore the titanium dioxide uniform particle diameter that is formed and be evenly distributed in around molecular sieve, and be tightly combined.
（3）Mixed as carrier with titanium dioxide using H type molecular sieves, while make use of the hydrophobic performance of molecular sieve and the acidic site of hydrogen type molecular sieve and pore passage structure, may advantageously facilitate NH3In the absorption and activation of catalyst surface, and then increase the active and anti-SO of catalyst2And H2O poisoning capabilities.
（4）Catalyst adaptive temperature wide ranges prepared by the present invention, are owned by efficient SCR denitration activities in 160-450 DEG C, and thermal stability is good, and denitration activity is high.
Specific embodiment
Technical scheme is described in detail with reference to embodiment.
A diameter of 10 ± 1.5 μm of the glass fibre that the embodiment of the present invention is used, 5 ± 1.5 μm of length, loss on drying（105 DEG C of dryings are to constant weight）≤10%.The wood pulp is softwood pulp or hardwood pulp.The polyacrylamide is anion-polyacrylamide, and molecular weight is 8,000,000.1% solution viscosity of the carboxymethylcellulose calcium is 200mPas, loss on drying（Dried at 105 DEG C）≤20%.
Embodiment 1
（1）TiO2The preparation of-molecular sieve complex carrier：4Kg titanium sulfates and 0.2Kg sodium ammonium triacetates are dissolved into the deionized water of 2L are first made mixed solution；The powdered HZSM-5 molecular sieves of 0.4Kg are added in above-mentioned mixed solution carries out incipient impregnation；In 80 DEG C of dryings 12 hours；400 DEG C of roastings can be prepared by TiO in 5 hours2- molecular sieve complex carrier.
（2）The load of active component and auxiliary agent：By step（1）The TiO of preparation2- molecular sieve complex carrier impregnated in 0.2mol/L cerous nitrates, 0.15mol/L ammonium metatungstates and 0.1mol/L
In the mixed solution of ferric nitrate, take out, dried 6 hours at 120 DEG C of temperature, 10 hours prepared denitrating catalyst powders are calcined at 450 DEG C.
（3）Faveolate denitration catalyst is molded：By step（2）Through the operation extrusion honeycomb ceramics such as kneading, ageing, extrusion after 80 parts of obtained denitrating catalyst powder, 6 parts of glass fibre, 0.1 part of softwood pulp, 0.5 part of polyacrylamide, 2 parts of carboxymethylcellulose calcium, 8 parts of ammoniacal liquor, 20 parts of mixing of deionized water；Honeycomb ceramics temperature be 70 DEG C, humidity be 20% under conditions of dry 3 days；After drying, in 550 DEG C of constant temperature calcining 6h, it is down to room temperature and can be prepared by Faveolate denitration catalyst.
Denitrating catalyst prepared by the inventive method, in terms of catalyst gross mass, TiO in catalyst2Content 75%, molecular sieve content 10%, content of glass fiber 8%, CeO2Content 2%, WO3Content 1%, Fe2O3Content 1%, sulfate radical content 3%.
Embodiment 2
（1）TiO2The preparation of-molecular sieve complex carrier：4Kg titanium sulfates and 0.15Kg disodium ethylene diamine tetraacetates are dissolved into the deionized water of 2L are first made mixed solution；The powdered HZSM-5 molecular sieves of 0.4Kg are added in above-mentioned mixed solution carries out incipient impregnation；In 120 DEG C of dryings 6 hours；500 DEG C of roastings can be prepared by TiO in 1 hour2- molecular sieve complex carrier.
（2）The load of active component and auxiliary agent：By step（1）The TiO of preparation2In impregnated in the mixed solution of 0.3mol/L cerous nitrates, 0.1mol/L ammonium metatungstates and 0.4 mol/L butters of tin on-molecular sieve complex carrier, take out, dried 12 hours at 110 DEG C of temperature, 5 hours prepared denitrating catalyst powders are calcined at 550 DEG C.
（3）Faveolate denitration catalyst is molded：By step（2）Through the operation extrusion honeycomb ceramics such as kneading, ageing, extrusion after 90 parts of obtained denitrating catalyst powder, 4 parts of glass fibre, 0.2 part of wood pulp, 1 part of polyacrylamide, 0.5 part of carboxymethylcellulose calcium, 10 parts of ammoniacal liquor, 15 parts of mixing of deionized water；Honeycomb ceramics temperature be 40 DEG C, humidity be 40% under conditions of dry 2 days；In 500 DEG C of constant temperature calcinings 8 hours after drying, it is down to room temperature and can be prepared by Faveolate denitration catalyst.
Denitrating catalyst prepared by the inventive method, in terms of catalyst gross mass, TiO in catalyst2Content 78.5%, molecular sieve content 8%, content of glass fiber 5%, CeO2Content 2.5%, WO3Content 1%, SnO2Content 3%, sulfate radical content 2%.
Embodiment 3
（1）TiO2The preparation of-molecular sieve complex carrier：4Kg titanium sulfates and 0.1Kg tetrasodium ethylenediamine tetraacetates are dissolved in the deionized water of 2L are first made mixed solution；The powdered HY molecular sieves of 0.8Kg are added in above-mentioned mixed solution carries out incipient impregnation；In 110 DEG C of dryings 6 hours；600 DEG C of roastings can be prepared by TiO in 2 hours2- molecular sieve complex carrier.
（2）The load of active component and auxiliary agent：By step（1）The TiO of preparation2In impregnated in the mixed solution of 0.2mol/L cerous nitrates, 0.1mol/L ammonium metatungstates and 0.3mol/L copper nitrates on-molecular sieve complex carrier, take out, dried 6 hours at 120 DEG C of temperature, 6 hours prepared denitrating catalyst powders are calcined at 450 DEG C.
（3）Faveolate denitration catalyst is molded：By step（2）Through the operation extrusion honeycomb ceramics such as kneading, ageing, extrusion after 75 parts of obtained denitrating catalyst powder, 6 parts of glass fibre, 2 parts of wood pulp, 2 parts of polyacrylamide, 0.1 part of carboxymethylcellulose calcium, 5 parts of ammoniacal liquor, 40 parts of mixing of deionized water；Honeycomb ceramics temperature be 30 DEG C, humidity be 50% under conditions of dry 4 days；After drying, in 600 DEG C of constant temperature calcining 5h, it is down to room temperature and can be prepared by Faveolate denitration catalyst.
Denitrating catalyst prepared by the inventive method, in terms of catalyst gross mass, molecular sieve content 20% in catalyst, TiO2Content 65%, content of glass fiber 4%, CeO2Content 3%, WO3Content 2%, CuO contents 5%, sulfate radical content 1%.
Embodiment 4
（1）TiO2The preparation of-molecular sieve complex carrier：3Kg titanium sulfates and 0.3Kg diethylenetriamine pentacarboxylic acid sodium are dissolved into the deionized water of 2L and are made mixed solution first；The powdered HA molecular sieves of 0.6Kg are added in above-mentioned mixed solution carries out incipient impregnation；In 100 DEG C of dryings 6 hours；550 DEG C of roastings can be prepared by TiO in 4 hours2- molecular sieve complex carrier.
（2）The load of active component and auxiliary agent：By step（1）The TiO of preparation2In impregnated in 0.4mol/L ammonium metatungstates, 0.2mol/L cerous nitrates, the mixed solution of 0.1mol/L lanthanum nitrates on-molecular sieve complex carrier, take out, dried 24 hours at 80 DEG C of temperature, 10 hours prepared denitrating catalyst powders are calcined at 450 DEG C.
（3）Faveolate denitration catalyst is molded：By step（2）Through the operation extrusion honeycomb ceramics such as kneading, ageing, extrusion after 80 parts of obtained denitrating catalyst powder, 2 parts of glass fibre, 1 part of wood pulp, 1 part of polyacrylamide, 0.5 part of carboxymethylcellulose calcium, 5 parts of ammoniacal liquor, 30 parts of mixing of deionized water；Honeycomb ceramics temperature be 40 DEG C, humidity be 30% under conditions of dry 1 day；After drying, in 450 DEG C of constant temperature calcining 10h, it is down to room temperature and can be prepared by Faveolate denitration catalyst.
Denitrating catalyst prepared by the inventive method, in terms of catalyst gross mass, TiO in catalyst2Content 75%, molecular sieve content 12.8%, content of glass fiber 3.2%, WO3Content 3%, Ce2O contents 2%, La2O3Content 1%, sulfate radical content 2%.
Embodiment 5
（1）TiO2The preparation of-molecular sieve complex carrier：5Kg titanium sulfates and 0.3Kg sodium ethylene diamine tetracetates are dissolved into the deionized water of 2L are first made mixed solution；The powdered HZSM-5 molecular sieves molecular sieves of 0.8Kg are added in above-mentioned mixed solution carries out incipient impregnation；In 100 DEG C of dryings 6 hours；600 DEG C of roastings can be prepared by TiO in 5 hours2- molecular sieve complex carrier.
（2）The load of active component and auxiliary agent：By step（1）The TiO of preparation2In impregnated in the mixed solution of 0.3mol/L ammonium metatungstates, 0.2mol/L cerous nitrates, 0.2mol/L copper nitrates and 0.1mol/L ferric nitrates on-molecular sieve complex carrier, take out, dried 24 hours at 80 DEG C of temperature, 10 hours prepared denitrating catalyst powders are calcined at 450 DEG C.
（3）Faveolate denitration catalyst is molded：By step（2）Through the operation extrusion honeycomb ceramics such as kneading, ageing, extrusion after 80 parts of obtained denitrating catalyst powder, 2 parts of glass fibre, 1 part of wood pulp, 1 part of polyacrylamide, 0.5 part of carboxymethylcellulose calcium, 5 parts of ammoniacal liquor, 30 parts of mixing of deionized water；Honeycomb ceramics temperature be 40 DEG C, humidity be 30% under conditions of dry 1 day；After drying, in 450 DEG C of constant temperature calcining 10h, it is down to room temperature and can be prepared by Faveolate denitration catalyst.
Denitrating catalyst prepared by the inventive method, in terms of catalyst gross mass, TiO in catalyst2Content 75%, molecular sieve content 14%, content of glass fiber 2%, WO3Content 3%, Ce2O contents 2%, Fe2O3Content 1%, CuO contents 1%, sulfate radical content 2%.
Embodiment 6
, with embodiment 1, difference is in step for preparation technology and operating condition（1）TiO2In the preparation process of-molecular sieve complex carrier, 0.2Kg is being added
0.1 Kg monoethanolamines are added while sodium ammonium triacetate.In preparing catalyst, in terms of catalyst gross mass, TiO in catalyst2Content 75%, molecular sieve content 10%, content of glass fiber 8%, CeO2Content 2%, WO3Content 1%, Fe2O3Content 1%, sulfate radical content 3%.
Embodiment 7
, with embodiment 1, difference is that auxiliary agent uses butter of tin for preparation technology and operating condition.In the catalyst for preparing, in terms of catalyst gross mass, TiO in catalyst2Content 75.5%, molecular sieve content 10%, content of glass fiber 5%, CeO2Content 2.5%, WO3Content 2%, SnO2Content 2%, sulfate radical content 3%.
Embodiment 8
, with embodiment 1, difference is step for preparation technology and operating condition（3）In, dried roasting technique at the uniform velocity rose to 300 DEG C, constant temperature 5 hours from room temperature with 5 hours；At the uniform velocity rise within 9 hours 600 DEG C, constant temperature 6 hours；Room temperature was down to through 8 hours can be prepared by Faveolate denitration catalyst.
Comparative example 1
Replace HZSM-5 molecular sieves using ZSM-5 molecular sieve, other are with embodiment 2.
Comparative example 2
Replace titanium sulfate using tetra-n-butyl titanate, other are with embodiment 2.
Comparative example 3
Without sodium ammonium triacetate, other are with embodiment 2.
Comparative example 4
Molecular sieve-TiO2Complex carrier is by molecular sieve and TiO2In mass ratio 1:10 mechanical mixtures are obtained.Remaining is with embodiment 2.
Catalyst denitration activity method of testing is as follows：Experimental provision is controlled by air distribution system, flow（Mass flowmenter）, gas mixer, gas preheater, catalytic reactor and flue gas analysis system constitute.By self-contained honeycomb catalyst（150×150×1000 mm）It is cut into small-sized detection block（45×45×50mm）, small-sized detection block is then put into fixing tubular reactor.Simulated flue gas are constituted：NO、NH3、O2And carrier gas N2Composition, mixed gas total flow 608L/h, air speed is 5000 h-1, NH3Concentration, NO concentration：1000ppm, NH3/ NO=1, SO2Concentration：1000ppm, H2O steam：10%, reaction temperature is controlled at 160-450 DEG C.Each gas flow is controlled by mass flowmenter and spinner flowmeter.Gas is preheated by preheater again into gas mixer mixing is first passed through before reactor.Air inlet is determined with the NO concentration of gas outlet by flue gas analyzer.In order to eliminate the influence of adsorption, system starts collecting test in stable 20 ~ 30 minutes in ventilation.
The catalysis activity of catalyst is reflected that the denitration activity of NO is calculated by following formula by the denitration activity of NO：
Denitration activity=[(C0-C)/C0]×100%。
In formula, C0It is NO initial concentrations, C is NO concentration in gas after treatment.
Strength test is according to standard GB/T/T1964-1996《Porous ceramics compressive strength test method》Carry out.Wear test is that catalyst is placed in the air testing device containing dust to wash away 5 hours, and dust content is 150g/m3, air velocity 20m/s.It is specific as shown in table 1.
The different catalysts of table 1 denitration effect at different temperatures
In sum, the catalyst for preparing of the present invention is at 160-450 DEG C of temperature window, particularly in high concentration H2O and SO2Still there is denitration efficiency higher under conditions of coexisting, particularly with preferably low-temperature denitration activity, therefore be more conducive to make SCR denitration device be arranged in temperature range flue gas section wider, expanded the range of application of SCR.Catalyst has good intensity and abrasion resistance.
Claims (15)
1. a kind of preparation method of SCR catalyst for denitrating flue gas, it is characterised in that comprise the following steps：
（1）TiO2The preparation of-molecular sieve complex carrier：The mixed solution of titanium sulfate and aminocarboxylate being prepared first, powdered molecular sieve being added in the mixed solution and is impregnated, TiO is obtained through drying and being calcined2- molecular sieve complex carrier；
（2）Active component and auxiliary agent are loaded：By step（1）The TiO of preparation2- molecular sieve complex carrier is impregnated into the maceration extract containing active component and auxiliary agent precursor, and denitrating catalyst powder is obtained after drying and roasting；
（3）Faveolate denitration catalyst is molded：By step（2）After obtained denitrating catalyst powder mixes with glass fibre, wood pulp, polyacrylamide, carboxymethylcellulose calcium, ammoniacal liquor, deionized water, Faveolate denitration catalyst is obtained through mediating, being aged, extrude, dry and be calcined.
2. method according to claim 1, it is characterised in that：Step（1）In obtained mixed solution, the concentration of titanium sulfate is 500-3000g/L.
3. method according to claim 1, it is characterised in that：Step（1）Described aminocarboxylate is one or more in sodium ammonium triacetate, edetate, diethylenetriamine pentacarboxylic acid salt, and the concentration of aminocarboxylate is 20-200g/L in mixed solution.
4. method according to claim 1, it is characterised in that：Step（1）A certain amount of monoethanolamine is added simultaneously in described mixed solution, concentration is 10-100g/L.
5. method according to claim 1, it is characterised in that：Step（1）Described molecular sieve is H type molecular sieves, and 0.1-50 μm of the particle diameter of molecular sieve, specific surface area is more than 200mg/m3；Molecular sieve concentration is 200-1000g/L in making mixed solution after addition.
6. method according to claim 1 or 5, it is characterised in that：Step（1）The molecular sieve is one or more in HZSM-5 molecular sieves, HA types molecular sieve, HY type molecular sieves, and molecular sieve concentration is 200-400g/L during mixed solution is made after addition.
7. method according to claim 1, it is characterised in that：Step（2）Described in active component be Mn, Ce, W and Mo in one or more, the auxiliary agent be Fe, Cu, La, Sn in one or more.
8. the method according to claim 1 or 7, it is characterised in that：Step（2）The active component is Ce and W, and the elemental mole ratios of wherein Ce and W are 0.3-5；The auxiliary agent is Sn.
9. method according to claim 1, it is characterised in that：Step（2）The content of every kind of active component presoma is 0.1-1mol/L in maceration extract, and the content of every kind of adjuvant component presoma is 0.1-0.5mol/L.
10. method according to claim 1, it is characterised in that：Step（1）And step（2）Described drying temperature is 80-120 DEG C, and drying time is 1-12 hours；Described sintering temperature is 300-600 DEG C, and roasting time is 1-6 hours.
11. methods according to claim 1, it is characterised in that：Step（3）In described honeycomb ceramics denitrating catalyst forming process, it is respectively in parts by weight：75-90 parts, glass fibre 2-6 parts, wood pulp 0.1-2 parts, polyacrylamide 0.1-2 parts, carboxymethylcellulose calcium 0.1-2 parts, ammoniacal liquor 5-10 parts, deionized water 10-40 parts of denitrating catalyst powder.
12. methods according to claim 11, it is characterised in that：A diameter of 10 ± 1.5 μm of described glass fibre, 5 ± 1.5 μm of length, loss on drying≤10%；The wood pulp is softwood pulp and hardwood pulp；The polyacrylamide is anion-polyacrylamide, and molecular weight is 700-900 ten thousand；1% solution viscosity of the carboxymethylcellulose calcium is 100-300mPas, loss on drying≤20%.
13. methods according to claim 1, it is characterised in that：Step（3）The digestion time is 12-48 hours；The drying temperature is 20-70 DEG C, and humidity is 20%-90%, 1-5 days drying time；The sintering temperature is 300-600 DEG C, roasting time 3-10h.
14. methods according to claim 1, it is characterised in that：Step（3）The roasting process is carried out as follows：With 5-80 DEG C/h 200-300 DEG C, constant temperature 3-10 hours is risen to from room temperature；500-600 DEG C is at the uniform velocity warming up to 5-80 DEG C/h again, constant temperature 3-10 hours, roasting terminated.
Faveolate denitration catalyst prepared by any methods describeds of 15. claim 1-14, it is characterised in that：On the basis of catalyst gross mass, molecular sieve content is 5%-30%, Ti in catalystO2Content is 50%-85%, and content of glass fiber is 1%-8%, and active component content is calculated as 0.5%-10% with oxide, and adjuvant component counts content as 1%-10% with oxide, and sulfate radical content is 1%-10%；, selected from one or more in Mn, Ce, W and Mo, auxiliary agent is selected from one or more in Fe, Cu, La, Sn for active component.
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