CN103464142A - Catalyst for removing nitrogen oxide through ammonia selective catalytic reduction and preparation method of catalyst - Google Patents
Catalyst for removing nitrogen oxide through ammonia selective catalytic reduction and preparation method of catalyst Download PDFInfo
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Abstract
The invention discloses a catalyst for removing nitrogen oxide through ammonia selective catalytic reduction. The catalyst comprises a carrier and active components, wherein the active components comprise cerium dioxide, tungsten trioxide and zirconium dioxide, the carrier is anatase type TiO2, the molar ratio of the cerium dioxide, the tungsten trioxide and the zirconium dioxide is (1-2):(1-2):(1-2), and the mass ratio of the active components and the carrier is 1:(10-20). In addition, the invention further discloses a preparation method of the catalyst. The catalyst has good vapour resistance and sulfur dioxide poisoning resistance, has the high activity to selectively reduce the nitrogen oxide in a wide temperature range, is high in selectivity and strong in stability, catalytically reduces the nitrogen oxide to harmless nitrogen and water, and reacts continuously for 50h at the temperature of 350 DEG C without inactivation, and the conversion rate is more than 90%.
Description
Technical field
The invention belongs to the low-temperature denitration catalyst preparing technical field, be specifically related to a kind of Catalysts and its preparation method that removes nitrogen oxide for the reduction of ammonia selective catalysis.
Background technology
Nitrogen oxide is that fossil fuel and air produce when high-temp combustion, and the NO more than 90% derives from the combustion process of fossil fuel (as coal, oil, natural gas etc.).Due to the excessive discharge of coal-fired flue-gas, vehicle exhaust, NO in atmosphere
x(NO>90%, NO
2<10%) concentration is in rising trend.NO, under effect of sunlight, easily forms chemical fumes, the respiratory system of harmful to human, and NO still destroys atmospheric ozone layer and forms one of precursor gas of acid rain.For protection of the environment, countries in the world particularly developed country to NO
xdischarge has strict restriction, and discharge standard is more and more stricter.The NO that " fossil-fuel power plant atmospheric pollutant emission standard " that China came into effect from 1 day January in 2012 (GB13223-2011) stipulated
xemission limit is (with NO
2meter), require most of coal-burning boiler to carry out 100mg/m
3standard, the partial fuel coal boiler is carried out 200mg/m
3standard; Newly-built oil burning boiler is all carried out 100mg/m
3standard, existing oil burning boiler is all carried out 200mg/m
3standard.
How effectively to eliminate NO
xtechnology has become the important topic in current environmental protection.At numerous NO
xin purification techniques, with NH
3compounds is reducing agent selective reduction NO under the effect of catalyst
xbecome N
2technology (referred to as NH
3-SCR) be to reduce stationary source and moving source NO
xone of effective technology of discharge.The maximum commercial catalyst of application is V at present
2o
5-WO
3/ TiO
2or V
2o
5-MoO
3/ TiO
2.The advantage of this catalyst is to have higher NO
xelimination activity, and with TiO
2for the anti-SO of carrier
2poisoning performance is better.But there are some problems in actual applications in this catalyst: the one, and serviceability temperature mostly is 350-450 ℃, has the narrow shortcoming of temperature window, and, in temperature generation due to the non-selection oxidation reaction of NH3 during higher than 400 ℃, can generate relatively large greenhouse gases N
2o; The 2nd, the active component V in catalyst system itself is exactly a kind of noxious material.In view of the above problems, need the novel non-vanadium System Catalyst of research and development.New catalyst has higher NO in wider temperature range
xelimination activity and selective, and ecological environment is not had to toxic action, can be used for the NO in flue gas or diesel engine and exhaust of lean-burn automotive
xelimination.
Chinese patent CN2024119884A discloses the catalyst that a kind of ferrotitanium composite oxides thing adds other transition metal oxides.This catalyst has higher activity and stability at middle low temperature (150-300 ℃).But this catalyst is 350 ℃ of high-temperature areas (>) active poor.Catalyst at manganese base system row has shown low temperature bar denitration activity preferably, but due to manganese series catalyzer at Shortcomings aspect water resistant steam poisoning capability, so limit the application (Chemical engineering journal, 195 – 196:323 – 331,2012) of this kind of catalyst.Chinese patent CN1166438C discloses a kind of with NH
3for reducing agent can generate N by selective reduction NO
2catalyst.This catalyst be take ZSM-5 molecular sieve as carrier, and iron that mass fraction is 0.5-10% and the molybdenum of 0.1-15% are take in load.This catalyst is 60000-80000h at 400 ℃, air speed
-1conversion ratio etc. NO under condition all reaches more than 96%.Its catalytic activity of life test of process 50h is without any impact.But this catalyst is active poor at low-temperature region (<400 ℃).
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned the deficiencies in the prior art, and a kind of catalyst that removes nitrogen oxide for the reduction of ammonia selective catalysis is provided.This catalyst has water resistant steam, anti-sulfur dioxide poisoning performance preferably, has overcome current NH commonly used simultaneously
3n when-SCR vanadium-based catalyst systems exists operating temperature window narrows, high temperature
2generate selective low and ecological environment and health are existed to the potential defects such as harm.This catalyst can have higher selective reduction nitrogen oxide activity at wider temperature range (200 ℃～500 ℃), and selective high, stability is strong, and at 350 ℃ of successive reaction 50h non-inactivations, conversion ratio is more than 90%.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of catalyst that removes nitrogen oxide for the reduction of ammonia selective catalysis, comprise carrier and active component, it is characterized in that, described active component is ceria, tungstic acid and zirconium dioxide, and described carrier is Detitanium-ore-type TiO
2, the mol ratio of described ceria, tungstic acid and zirconium dioxide is (1～2): (1～2): (1～2), the mass ratio of described active component and carrier is 1: (10～20).
The above-mentioned catalyst that removes nitrogen oxide for the reduction of ammonia selective catalysis, the mol ratio of described ceria, tungstic acid and zirconium dioxide is (1.2～1.5): 2: (1.2～1.5), the mass ratio of described active component and carrier is (1.2～1.5): 20.
The above-mentioned catalyst that removes nitrogen oxide for the reduction of ammonia selective catalysis, the mol ratio of described ceria, tungstic acid and zirconium dioxide is 1.4: 2: 1.2, the mass ratio of described active component and carrier is 1.3: 20.
In addition, the present invention also provides the preparation method of above-mentioned catalyst, it is characterized in that, the method comprises the following steps:
Step 1, cerous nitrate, ammonium metatungstate and zirconium nitrate are dissolved in the water, stir and obtain mixed solution;
Step 2, by technical grade Detitanium-ore-type TiO
2impregnated in described in step 1 in mixed solution, then under stirring condition, in mixed solution, add urea, mixed solution is heated to 95 ℃～100 ℃ after urea dissolves fully, insulated and stirred is until obtain thick liquid-solid mixture; The addition of described urea is TiO
25%～8% of quality;
Step 3, by the dry 6h～10h under 100 ℃～120 ℃ of thick liquid-solid mixture described in step 2, then, at 400 ℃～550 ℃ lower roasting 3h～5h, obtain the catalyst for the selective catalysis nitrogen oxides reduction.
Above-mentioned method, the addition of urea described in step 2 is TiO
26% of quality.
Above-mentioned method, temperature dry described in step 3 is 110 ℃, be 8h drying time.
Above-mentioned method, the temperature of roasting described in step 3 is 500 ℃, roasting time is 4h.
The present invention compared with prior art has the following advantages:
1, cheap being easy to get of catalyst raw materials of the present invention, preparation process is simple, service condition is wide in range.
2, catalyst of the present invention can have higher selective reduction nitrogen oxide activity at wider temperature range (200 ℃～500 ℃), and selective high, stability is strong.
3, catalyst of the present invention is easy to be coated on ceramic honey comb, is expected to replace the catalyst based flue gas that can be used for coal-burning power plant, tail gas and the diesel engine vent gas purification techniques of nitric acid production factory of becoming of V.
4, catalyst nitrogen oxides reduction of the present invention is harmless nitrogen G&W, and at 350 ℃ of successive reaction 50h non-inactivations, conversion ratio is more than 90%.
5, catalyst of the present invention has water resistant steam, anti-sulfur dioxide poisoning performance preferably, has overcome current NH commonly used simultaneously
3n when-SCR vanadium-based catalyst systems exists operating temperature window narrows, high temperature
2generate selective low and ecological environment and health are existed to the potential defects such as harm.
6, catalyst of the present invention can be used for the purification that moving source or fixed combustion device comprise various motor car engines and coal-burning power plant's tail gas nitrogen oxide.Be placed in exhaust pipe during use, spray into reducing agent ammonia and tail gas in the upstream of catalyst and mix, wherein with NH
3the mol ratio of meter consumption and NO is 1.
Below by embodiment, technical scheme of the present invention is described in further detail.
The specific embodiment
Embodiment 1
The present embodiment remove the catalyst of nitrogen oxide for ammonia selective catalysis reduction, comprise carrier and active component, described active component is ceria, tungstic acid and zirconium dioxide, described carrier is Detitanium-ore-type TiO
2, the mol ratio of described ceria, tungstic acid and zirconium dioxide is 1: 1: 1, the mass ratio of described active component and carrier is 1: 19.
The preparation method of the catalyst of the present embodiment is:
Step 1, by 4.34g cerous nitrate (Ce (NO
3)
36H
2o), 2.64g ammonium metatungstate (tungstic acid content is not less than 88wt%, in 88wt%) and 4.29g five water zirconium nitrates are dissolved in the water, stir and obtain mixed solution;
Step 2, by 100g technical grade Detitanium-ore-type TiO
2powder impregnated in described in step 1 in mixed solution, then under stirring condition, in mixed solution, adds 6g urea, after urea dissolves fully, mixed solution is heated to 98 ℃, and insulated and stirred is until obtain thick liquid-solid mixture;
Step 3, by the dry 8h under 110 ℃ of thick liquid-solid mixture described in step 2, then, at 500 ℃ of lower roasting 4h, obtain the catalyst for the selective catalysis nitrogen oxides reduction.
Embodiment 2
The present embodiment remove the catalyst of nitrogen oxide for ammonia selective catalysis reduction, comprise carrier and active component, described active component is ceria, tungstic acid and zirconium dioxide, described carrier is Detitanium-ore-type TiO
2, the mol ratio of described ceria, tungstic acid and zirconium dioxide is 2: 1: 1, the mass ratio of described active component and carrier is 1: 14.3.
The preparation method of the catalyst of the present embodiment is:
Step 1, by 8.68g cerous nitrate (Ce (NO
3)
36H
2o), 2.64g ammonium metatungstate (tungstic acid content is not less than 88wt%, in 88wt%) and 4.29g five water zirconium nitrates are dissolved in the water, stir and obtain mixed solution;
Step 2, by 100g technical grade Detitanium-ore-type TiO
2powder impregnated in described in step 1 in mixed solution, then under stirring condition, in mixed solution, adds 5g urea, after urea dissolves fully, mixed solution is heated to 100 ℃, and insulated and stirred is until obtain thick liquid-solid mixture;
Step 3, by the dry 6h under 120 ℃ of thick liquid-solid mixture described in step 2, then, at 550 ℃ of lower roasting 3h, obtain the catalyst for the selective catalysis nitrogen oxides reduction.
Embodiment 3
The present embodiment remove the catalyst of nitrogen oxide for ammonia selective catalysis reduction, comprise carrier and active component, described active component is ceria, tungstic acid and zirconium dioxide, described carrier is Detitanium-ore-type TiO
2, the mol ratio of described ceria, tungstic acid and zirconium dioxide is 2: 1: 2, the mass ratio of described active component and carrier is 1: 12.2.
The preparation method of the catalyst of the present embodiment is:
Step 1, by 8.68g cerous nitrate (Ce (NO
3)
36H
2o), 2.64g ammonium metatungstate (tungstic acid content is not less than 88wt%, in 88wt%) and 8.58g five water zirconium nitrates are dissolved in the water, stir and obtain mixed solution;
Step 2, by 100g technical grade Detitanium-ore-type TiO
2powder impregnated in described in step 1 in mixed solution, then under stirring condition, in mixed solution, adds 8g urea, after urea dissolves fully, mixed solution is heated to 95 ℃, and insulated and stirred is until obtain thick liquid-solid mixture;
Step 3, by the dry 10h under 100 ℃ of thick liquid-solid mixture described in step 2, then, at 400 ℃ of lower roasting 5h, obtain the catalyst for the selective catalysis nitrogen oxides reduction.
Embodiment 4
The present embodiment remove the catalyst of nitrogen oxide for ammonia selective catalysis reduction, comprise carrier and active component, described active component is ceria, tungstic acid and zirconium dioxide, described carrier is Detitanium-ore-type TiO
2, the mol ratio of described ceria, tungstic acid and zirconium dioxide is 2: 2: 2, the mass ratio of described active component and carrier is 1: 10.
The preparation method of the catalyst of the present embodiment is:
Step 1, by 8.68g cerous nitrate (Ce (NO
3)
36H
2o), 5.28g ammonium metatungstate (tungstic acid content is not less than 88wt%, in 88wt%) and 8.58g five water zirconium nitrates are dissolved in the water, stir and obtain mixed solution;
Step 2, by 105.4g technical grade Detitanium-ore-type TiO
2powder impregnated in described in step 1 in mixed solution, then under stirring condition, in mixed solution, adds 6g urea, after urea dissolves fully, mixed solution is heated to 98 ℃, and insulated and stirred is until obtain thick liquid-solid mixture;
Step 3, by the dry 8h under 110 ℃ of thick liquid-solid mixture described in step 2, then, at 500 ℃ of lower roasting 4h, obtain the catalyst for the selective catalysis nitrogen oxides reduction.
Embodiment 5
The present embodiment remove the catalyst of nitrogen oxide for ammonia selective catalysis reduction, comprise carrier and active component, described active component is ceria, tungstic acid and zirconium dioxide, described carrier is Detitanium-ore-type TiO
2, the mol ratio of described ceria, tungstic acid and zirconium dioxide is 1: 2: 2, the mass ratio of described active component and carrier is 1: 11.
The preparation method of the catalyst of the present embodiment is:
Step 1, by 4.34g cerous nitrate (Ce (NO
3)
36H
2o), 5.28g ammonium metatungstate (tungstic acid content is not less than 88wt%, in 88wt%) and 8.58g five water zirconium nitrates are dissolved in the water, stir and obtain mixed solution;
Step 2, by 100g technical grade Detitanium-ore-type TiO
2powder impregnated in described in step 1 in mixed solution, then under stirring condition, in mixed solution, adds 6g urea, after urea dissolves fully, mixed solution is heated to 98 ℃, and insulated and stirred is until obtain thick liquid-solid mixture;
Step 3, by the dry 6h under 120 ℃ of thick liquid-solid mixture described in step 2, then, at 550 ℃ of lower roasting 4h, obtain the catalyst for the selective catalysis nitrogen oxides reduction.
Embodiment 6
The present embodiment remove the catalyst of nitrogen oxide for ammonia selective catalysis reduction, comprise carrier and active component, described active component is ceria, tungstic acid and zirconium dioxide, described carrier is Detitanium-ore-type TiO
2, the mol ratio of described ceria, tungstic acid and zirconium dioxide is 1: 1: 2, the mass ratio of described active component and carrier is 1: 15.4.
The preparation method of the catalyst of the present embodiment is:
Step 1, by 4.34g cerous nitrate (Ce (NO
3)
36H
2o), 2.64g ammonium metatungstate (tungstic acid content is not less than 88wt%, in 88wt%) and 8.58g five water zirconium nitrates are dissolved in the water, stir and obtain mixed solution;
Step 2, by 100g technical grade Detitanium-ore-type TiO
2powder impregnated in described in step 1 in mixed solution, then under stirring condition, in mixed solution, adds 7g urea, after urea dissolves fully, mixed solution is heated to 95 ℃, and insulated and stirred is until obtain thick liquid-solid mixture;
Step 3, by the dry 10h under 100 ℃ of thick liquid-solid mixture described in step 2, then, at 450 ℃ of lower roasting 3h, obtain the catalyst for the selective catalysis nitrogen oxides reduction.
Embodiment 7
The present embodiment remove the catalyst of nitrogen oxide for ammonia selective catalysis reduction, comprise carrier and active component, described active component is ceria, tungstic acid and zirconium dioxide, described carrier is Detitanium-ore-type TiO
2, the mol ratio of described ceria, tungstic acid and zirconium dioxide is 1: 2: 1, the mass ratio of described active component and carrier is 1: 20.
The preparation method of the catalyst of the present embodiment is:
Step 1, by 4.34g cerous nitrate (Ce (NO
3)
36H
2o), 5.28g ammonium metatungstate (tungstic acid content is not less than 88wt%, in 88wt%) and 4.29g five water zirconium nitrates are dissolved in the water, stir and obtain mixed solution;
Step 2, by 151.8g technical grade Detitanium-ore-type TiO
2powder impregnated in described in step 1 in mixed solution, then under stirring condition, in mixed solution, adds 12g urea, after urea dissolves fully, mixed solution is heated to 99 ℃, and insulated and stirred is until obtain thick liquid-solid mixture;
Step 3, by the dry 9h under 100 ℃ of thick liquid-solid mixture described in step 2, then, at 400 ℃ of lower roasting 5h, obtain the catalyst for the selective catalysis nitrogen oxides reduction.
Embodiment 8
The present embodiment remove the catalyst of nitrogen oxide for ammonia selective catalysis reduction, comprise carrier and active component, described active component is ceria, tungstic acid and zirconium dioxide, described carrier is Detitanium-ore-type TiO
2, the mol ratio of described ceria, tungstic acid and zirconium dioxide is 2: 2: 1, the mass ratio of described active component and carrier is 1: 10.7.
The preparation method of the catalyst of the present embodiment is:
Step 1, by 8.68g cerous nitrate (Ce (NO
3)
36H
2o), 5.28g ammonium metatungstate (tungstic acid content is not less than 88wt%, in 88wt%) and 4.29g five water zirconium nitrates are dissolved in the water, stir and obtain mixed solution;
Step 2, by 100g technical grade Detitanium-ore-type TiO
2powder impregnated in described in step 1 in mixed solution, then under stirring condition, in mixed solution, adds 6g urea, after urea dissolves fully, mixed solution is heated to 98 ℃, and insulated and stirred is until obtain thick liquid-solid mixture;
Step 3, by the dry 8h under 110 ℃ of thick liquid-solid mixture described in step 2, then, at 500 ℃ of lower roasting 4h, obtain the catalyst for the selective catalysis nitrogen oxides reduction.
Embodiment 9
The present embodiment remove the catalyst of nitrogen oxide for ammonia selective catalysis reduction, comprise carrier and active component, described active component is ceria, tungstic acid and zirconium dioxide, described carrier is Detitanium-ore-type TiO
2, the mol ratio of described ceria, tungstic acid and zirconium dioxide is 1.4: 2: 1.2, the mass ratio of described active component and carrier is 1.3: 20.
The preparation method of the catalyst of the present embodiment is:
Step 1, by 6.08g cerous nitrate (Ce (NO
3)
36H
2o), 5.28g ammonium metatungstate (tungstic acid content is not less than 88wt%, in 88wt%) and 5.15g five water zirconium nitrates are dissolved in the water, stir and obtain mixed solution;
Step 2, by 131g technical grade Detitanium-ore-type TiO
2powder impregnated in described in step 1 in mixed solution, then under stirring condition, in mixed solution, adds 7.86g urea, after urea dissolves fully, mixed solution is heated to 98 ℃, and insulated and stirred is until obtain thick liquid-solid mixture;
Step 3, by the dry 8h under 110 ℃ of thick liquid-solid mixture described in step 2, then, at 500 ℃ of lower roasting 4h, obtain the catalyst for the selective catalysis nitrogen oxides reduction.
Embodiment 10
The present embodiment remove the catalyst of nitrogen oxide for ammonia selective catalysis reduction, comprise carrier and active component, described active component is ceria, tungstic acid and zirconium dioxide, described carrier is Detitanium-ore-type TiO
2, the mol ratio of described ceria, tungstic acid and zirconium dioxide is 1.2: 2: 1.5, the mass ratio of described active component and carrier is 1.4: 20.
The preparation method of the catalyst of the present embodiment is:
Step 1, by 5.21g cerous nitrate (Ce (NO
3)
36H
2o), 5.28g ammonium metatungstate (tungstic acid content is not less than 88wt%, in 88wt%) and 6.44g five water zirconium nitrates are dissolved in the water, stir and obtain mixed solution;
Step 2, by 122g technical grade Detitanium-ore-type TiO
2powder impregnated in described in step 1 in mixed solution, then under stirring condition, in mixed solution, adds 8.5g urea, after urea dissolves fully, mixed solution is heated to 95 ℃, and insulated and stirred is until obtain thick liquid-solid mixture;
Step 3, by the dry 10h under 100 ℃ of thick liquid-solid mixture described in step 2, then, at 450 ℃ of lower roasting 3h, obtain the catalyst for the selective catalysis nitrogen oxides reduction.
Embodiment 11
The present embodiment remove the catalyst of nitrogen oxide for ammonia selective catalysis reduction, comprise carrier and active component, described active component is ceria, tungstic acid and zirconium dioxide, described carrier is Detitanium-ore-type TiO
2, the mol ratio of described ceria, tungstic acid and zirconium dioxide is 1.2: 2: 1.2, the mass ratio of described active component and carrier is 1.2: 20.
The preparation method of the catalyst of the present embodiment is:
Step 1, by 5.21g cerous nitrate (Ce (NO
3)
36H
2o), 5.28g ammonium metatungstate (tungstic acid content is not less than 88wt%, in 88wt%) and 5.15g five water zirconium nitrates are dissolved in the water, stir and obtain mixed solution;
Step 2, by 136g technical grade Detitanium-ore-type TiO
2powder impregnated in described in step 1 in mixed solution, then under stirring condition, in mixed solution, adds 10.9g urea, after urea dissolves fully, mixed solution is heated to 99 ℃, and insulated and stirred is until obtain thick liquid-solid mixture;
Step 3, by the dry 9h under 100 ℃ of thick liquid-solid mixture described in step 2, then, at 400 ℃ of lower roasting 5h, obtain the catalyst for the selective catalysis nitrogen oxides reduction.
Embodiment 12
The present embodiment remove the catalyst of nitrogen oxide for ammonia selective catalysis reduction, comprise carrier and active component, described active component is ceria, tungstic acid and zirconium dioxide, described carrier is Detitanium-ore-type TiO
2, the mol ratio of described ceria, tungstic acid and zirconium dioxide is 1.5: 2: 1.2, the mass ratio of described active component and carrier is 1.3: 20.
The preparation method of the catalyst of the present embodiment is:
Step 1, by 6.51g cerous nitrate (Ce (NO
3)
36H
2o), 5.28g ammonium metatungstate (tungstic acid content is not less than 88wt%, in 88wt%) and 5.15g five water zirconium nitrates are dissolved in the water, stir and obtain mixed solution;
Step 2, by 134g technical grade Detitanium-ore-type TiO
2powder impregnated in described in step 1 in mixed solution, then under stirring condition, in mixed solution, adds 8g urea, after urea dissolves fully, mixed solution is heated to 98 ℃, and insulated and stirred is until obtain thick liquid-solid mixture;
Step 3, by the dry 8h under 110 ℃ of thick liquid-solid mixture described in step 2, then, at 500 ℃ of lower roasting 4h, obtain the catalyst for the selective catalysis nitrogen oxides reduction.
Embodiment 13
The present embodiment remove the catalyst of nitrogen oxide for ammonia selective catalysis reduction, comprise carrier and active component, described active component is ceria, tungstic acid and zirconium dioxide, described carrier is Detitanium-ore-type TiO
2, the mol ratio of described ceria, tungstic acid and zirconium dioxide is 1.5: 2: 1.5, the mass ratio of described active component and carrier is 1.5: 20.
The preparation method of the catalyst of the present embodiment is:
Step 1, by 6.51g cerous nitrate (Ce (NO
3)
36H
2o), 5.28g ammonium metatungstate (tungstic acid content is not less than 88wt%, in 88wt%) and 6.44g five water zirconium nitrates are dissolved in the water, stir and obtain mixed solution;
Step 2, by 121g technical grade Detitanium-ore-type TiO
2powder impregnated in described in step 1 in mixed solution, then under stirring condition, in mixed solution, adds 7.3g urea, after urea dissolves fully, mixed solution is heated to 98 ℃, and insulated and stirred is until obtain thick liquid-solid mixture;
Step 3, by the dry 8h under 110 ℃ of thick liquid-solid mixture described in step 2, then, at 500 ℃ of lower roasting 4h, obtain the catalyst for the selective catalysis nitrogen oxides reduction.
The catalytic activity experiment:
By the catalyst of 0.40g embodiment 1-13 respectively compressing tablet grind, screening is got 40-80 order size particles and is positioned in tubular fixed-bed reactor and reacts, reaction condition is NO:1000ppm, NH
3: 1000ppm, O
2: 10%, Ar is Balance Air, and total gas flow rate is 100mL/min, and reaction velocity (GHSV) is 20000h
-1.The reaction temperature interval is from 200 ℃ to 550 ℃.
The activity of catalyst nitrogen oxides reduction at table 1 differential responses temperature
Stability experiment:
By the catalyst of 0.40g embodiment 1-13 respectively compressing tablet grind, screening is got 40-80 order size particles and is positioned in tubular fixed-bed reactor and reacts, reaction condition is NO:1000ppm; NH
3: 1000ppm; SO
2, 50ppm; O
2: 10%; Ar is Balance Air, and total gas flow rate is 100mL/min, and reaction velocity (GHSV) is 20000h
-1.Reaction temperature is set in 350 ℃, successive reaction 50h, and carry out active testing one time every 3h～5h.Experimental result shows, the conversion ratio of catalyst nitrogen oxide remains on more than 90% always, the phenomenon of inactivation or activity decreased do not occur.
The above; it is only preferred embodiment of the present invention; not the present invention is imposed any restrictions, every any simple modification, change and equivalent structure transformation of above embodiment being done according to the technology of the present invention essence, all still belong in the protection domain of technical solution of the present invention.
Claims (7)
1. a catalyst that removes nitrogen oxide for the reduction of ammonia selective catalysis, comprise carrier and active component, it is characterized in that, described active component is ceria, tungstic acid and zirconium dioxide, and described carrier is Detitanium-ore-type TiO
2, the mol ratio of described ceria, tungstic acid and zirconium dioxide is (1～2): (1～2): (1～2), the mass ratio of described active component and carrier is 1: (10～20).
2. the catalyst that removes nitrogen oxide for ammonia selective catalysis reduction according to claim 1, it is characterized in that, the mol ratio of described ceria, tungstic acid and zirconium dioxide is (1.2～1.5): 2: (1.2～1.5), the mass ratio of described active component and carrier is (1.2～1.5): 20.
3. the catalyst that removes nitrogen oxide for ammonia selective catalysis reduction according to claim 2, it is characterized in that, the mol ratio of described ceria, tungstic acid and zirconium dioxide is 1.4: 2: 1.2, and the mass ratio of described active component and carrier is 1.3: 20.
4. the method prepared as catalyst as described in claim 1,2 or 3, is characterized in that, the method comprises the following steps:
Step 1, cerous nitrate, ammonium metatungstate and zirconium nitrate are dissolved in the water, stir and obtain mixed solution;
Step 2, by technical grade Detitanium-ore-type TiO
2impregnated in described in step 1 in mixed solution, then under stirring condition, in mixed solution, add urea, mixed solution is heated to 95 ℃～100 ℃ after urea dissolves fully, insulated and stirred is until obtain thick liquid-solid mixture; The addition of described urea is TiO
25%～8% of quality;
Step 3, by the dry 6h～10h under 100 ℃～120 ℃ of thick liquid-solid mixture described in step 2, then, at 400 ℃～550 ℃ lower roasting 3h～5h, obtain the catalyst for the selective catalysis nitrogen oxides reduction.
5. method according to claim 4, is characterized in that, the addition of urea described in step 2 is TiO
26% of quality.
6. method according to claim 4, is characterized in that, temperature dry described in step 3 is 110 ℃, and be 8h drying time.
7. method according to claim 4, is characterized in that, the temperature of roasting described in step 3 is 500 ℃, and roasting time is 4h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN109513438A (en) * | 2018-11-21 | 2019-03-26 | 南京工业大学 | A kind of environmentally friendly high temperature denitrating catalyst and preparation method thereof |
| WO2020103848A1 (en) * | 2018-11-21 | 2020-05-28 | 南京工业大学 | Environmentally-friendly high-temperature denitration catalyst and preparation method therefor |
| CN109513438B (en) * | 2018-11-21 | 2022-07-08 | 南京工业大学 | Environment-friendly high-temperature denitration catalyst and preparation method thereof |
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