CN103464142B - 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 low-temperature denitration catalyst preparing technical field, be specifically related to a kind of Catalysts and its preparation method removing nitrogen oxide for ammonia Selective catalytic reduction.
Background technology
Nitrogen oxide is that fossil fuel and air produce when high-temp combustion, and the NO of more than 90% derives from the combustion process of fossil fuel (as coal, oil, natural gas etc.).Due to the excess emissions of coal-fired flue-gas, vehicle exhaust, NO in air
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 one of atmospheric ozone layer and the precursor gas forming acid rain.In order to 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 " (GB13223-2011) that Qi China came into effect from January 1 in 2012 specifies
xemission limit is (with NO
2meter), require that most of coal-burning boiler performs 100mg/m
3standard, partial fuel coal boiler perform 200mg/m
3standard; Newly-built oil burning boiler all performs 100mg/m
3standard, existing oil burning boiler all performs 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 reduce stationary source and moving source NO
xone of effective technology for discharge.The maximum commercial catalyst of current application is V
2o
5-WO
3/ TiO
2or V
2o
5-MoO
3/ TiO
2.The advantage of this catalyst has 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: one is that serviceability temperature mostly is 350-450 DEG C, has the shortcoming that temperature window is narrow, and temperature higher than when 400 DEG C due to the generation of the non-selection oxidation reaction of NH3, relatively large greenhouse gases N can be generated
2o; Two is the active component V inherently a kind of noxious materials in catalyst system.In view of the above problems, need to research and develop novel non-vanadium System Catalyst.New catalyst has higher NO in wider temperature range
xelimination activity and selective, and do not have toxic action to ecological environment, 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 DEG C).But this catalyst is active poor at high-temperature area (>350 DEG C).Good low temperature bar denitration activity is shown at the catalyst of manganese base system row, but due to manganese series catalyzer Shortcomings in vapour resistant poisoning capability, so limit the application (Chemical engineeringjournal, 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 take ZSM-5 molecular sieve as carrier, and load take mass fraction as the iron of 0.5-10% and the molybdenum of 0.1-15%.This catalyst 400 DEG C, air speed is 60000-80000h
-1all more than 96% is reached etc. the conversion ratio of NO under condition.Through its catalytic activity of life test of 50h without any impact.But this catalyst is active poor at low-temperature region (<400 DEG C).
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned the deficiencies in the prior art, provides a kind of catalyst removing nitrogen oxide for ammonia Selective catalytic reduction.This catalyst has good vapour resistant, anti-sulfur dioxide poisoning performance, overcomes NH conventional at present simultaneously
3n when-SCR vanadium-based catalyst systems exists operating temperature window narrows, high temperature
2generate selective low and the defects such as potential harm are existed to ecological environment and health.This catalyst can have higher selective reduction nitrogen oxide in wider temperature range (200 DEG C ~ 500 DEG C) active, selective height, and stability is strong, and at 350 DEG C 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 removing nitrogen oxide for ammonia Selective catalytic reduction, 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), and the mass ratio of described active component and carrier is 1: (10 ~ 20).
The above-mentioned catalyst removing nitrogen oxide for ammonia Selective catalytic reduction, the mol ratio of described ceria, tungstic acid and zirconium dioxide is (1.2 ~ 1.5): 2: (1.2 ~ 1.5), and the mass ratio of described active component and carrier is (1.2 ~ 1.5): 20.
The above-mentioned catalyst removing nitrogen oxide for ammonia Selective catalytic reduction, 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.
In addition, present invention also offers the preparation method of above-mentioned catalyst, it is characterized in that, the method comprises the following steps:
Step one, cerous nitrate, ammonium metatungstate and zirconium nitrate to be dissolved in the water, to stir and obtain mixed solution;
Step 2, by technical grade Detitanium-ore-type TiO
2impregnated in mixed solution described in step one, then in mixed solution, add urea under agitation, after urea dissolves completely, mixed solution is heated to 95 DEG C ~ 100 DEG C, insulated and stirred is until obtain thick liquid-solid mixture; The addition of described urea is TiO
25% ~ 8% of quality;
Step 3, by liquid-solid mixture thick described in step 2 dry 6h ~ 10h at 100 DEG C ~ 120 DEG C, then roasting 3h ~ 5h at 400 DEG C ~ 550 DEG C, obtains the catalyst for Selective catalytic reduction nitrogen oxide.
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 DEG C, and drying time is 8h.
Above-mentioned method, the temperature of roasting described in step 3 is 500 DEG C, and roasting time is 4h.
The present invention compared with prior art has the following advantages:
1, catalyst preparation materials of the present invention is cheap is easy to get, and preparation process is simple, service condition is wide in range.
2, catalyst of the present invention can have higher selective reduction nitrogen oxide activity in wider temperature range (200 DEG C ~ 500 DEG C), and selective height, stability is strong.
3, catalyst of the present invention is easy to be coated on ceramic honey comb, is expected to replace catalyst based the becoming of V and can be used for the flue gas of coal-burning power plant, the tail gas of nitric acid plant and diesel engine vent gas purification techniques.
4, catalyst nitrogen oxides reduction of the present invention is harmless nitrogen and water, and at 350 DEG C of successive reaction 50h non-inactivations, conversion ratio is more than 90%.
5, catalyst of the present invention has good vapour resistant, anti-sulfur dioxide poisoning performance, overcomes NH conventional at present simultaneously
3n when-SCR vanadium-based catalyst systems exists operating temperature window narrows, high temperature
2generate selective low and the defects such as potential harm are existed to ecological environment and health.
6, catalyst of the present invention can be used for the purification that moving source or fixed combustion device comprise various motor car engine 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 mixing in the upstream of catalyst, 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.
Detailed description of the invention
Embodiment 1
The catalyst removing nitrogen oxide for ammonia Selective catalytic reduction of the present embodiment, comprises carrier and active component, and 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: 1: 1, and the mass ratio of described active component and carrier is 1: 19.
The preparation method of the catalyst of the present embodiment is:
Step one, 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 nitrate be dissolved in the water, and stirs and obtain mixed solution;
Step 2, by 100g technical grade Detitanium-ore-type TiO
2powder infusion, in mixed solution described in step one, then adds 6g urea under agitation in mixed solution, after urea dissolves completely, mixed solution is heated to 98 DEG C, and insulated and stirred is until obtain thick liquid-solid mixture;
Step 3, by liquid-solid mixture thick described in step 2 dry 8h at 110 DEG C, then roasting 4h at 500 DEG C, obtains the catalyst for Selective catalytic reduction nitrogen oxide.
Embodiment 2
The catalyst removing nitrogen oxide for ammonia Selective catalytic reduction of the present embodiment, comprises carrier and active component, and 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 2: 1: 1, and 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 one, 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 nitrate be dissolved in the water, and stirs and obtain mixed solution;
Step 2, by 100g technical grade Detitanium-ore-type TiO
2powder infusion, in mixed solution described in step one, then adds 5g urea under agitation in mixed solution, after urea dissolves completely, mixed solution is heated to 100 DEG C, and insulated and stirred is until obtain thick liquid-solid mixture;
Step 3, by liquid-solid mixture thick described in step 2 dry 6h at 120 DEG C, then roasting 3h at 550 DEG C, obtains the catalyst for Selective catalytic reduction nitrogen oxide.
Embodiment 3
The catalyst removing nitrogen oxide for ammonia Selective catalytic reduction of the present embodiment, comprises carrier and active component, and 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 2: 1: 2, and 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 one, 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 nitrate be dissolved in the water, and stirs and obtain mixed solution;
Step 2, by 100g technical grade Detitanium-ore-type TiO
2powder infusion, in mixed solution described in step one, then adds 8g urea under agitation in mixed solution, after urea dissolves completely, mixed solution is heated to 95 DEG C, and insulated and stirred is until obtain thick liquid-solid mixture;
Step 3, by liquid-solid mixture thick described in step 2 dry 10h at 100 DEG C, then roasting 5h at 400 DEG C, obtains the catalyst for Selective catalytic reduction nitrogen oxide.
Embodiment 4
The catalyst removing nitrogen oxide for ammonia Selective catalytic reduction of the present embodiment, comprises carrier and active component, and 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 2: 2: 2, and the mass ratio of described active component and carrier is 1: 10.
The preparation method of the catalyst of the present embodiment is:
Step one, 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 nitrate be dissolved in the water, and stirs and obtain mixed solution;
Step 2, by 105.4g technical grade Detitanium-ore-type TiO
2powder infusion, in mixed solution described in step one, then adds 6g urea under agitation in mixed solution, after urea dissolves completely, mixed solution is heated to 98 DEG C, and insulated and stirred is until obtain thick liquid-solid mixture;
Step 3, by liquid-solid mixture thick described in step 2 dry 8h at 110 DEG C, then roasting 4h at 500 DEG C, obtains the catalyst for Selective catalytic reduction nitrogen oxide.
Embodiment 5
The catalyst removing nitrogen oxide for ammonia Selective catalytic reduction of the present embodiment, comprises carrier and active component, and 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: 2, and the mass ratio of described active component and carrier is 1: 11.
The preparation method of the catalyst of the present embodiment is:
Step one, 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 nitrate be dissolved in the water, and stirs and obtain mixed solution;
Step 2, by 100g technical grade Detitanium-ore-type TiO
2powder infusion, in mixed solution described in step one, then adds 6g urea under agitation in mixed solution, after urea dissolves completely, mixed solution is heated to 98 DEG C, and insulated and stirred is until obtain thick liquid-solid mixture;
Step 3, by liquid-solid mixture thick described in step 2 dry 6h at 120 DEG C, then roasting 4h at 550 DEG C, obtains the catalyst for Selective catalytic reduction nitrogen oxide.
Embodiment 6
The catalyst removing nitrogen oxide for ammonia Selective catalytic reduction of the present embodiment, comprises carrier and active component, and 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: 1: 2, and 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 one, 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 nitrate be dissolved in the water, and stirs and obtain mixed solution;
Step 2, by 100g technical grade Detitanium-ore-type TiO
2powder infusion, in mixed solution described in step one, then adds 7g urea under agitation in mixed solution, after urea dissolves completely, mixed solution is heated to 95 DEG C, and insulated and stirred is until obtain thick liquid-solid mixture;
Step 3, by liquid-solid mixture thick described in step 2 dry 10h at 100 DEG C, then roasting 3h at 450 DEG C, obtains the catalyst for Selective catalytic reduction nitrogen oxide.
Embodiment 7
The catalyst removing nitrogen oxide for ammonia Selective catalytic reduction of the present embodiment, comprises carrier and active component, and 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, and the mass ratio of described active component and carrier is 1: 20.
The preparation method of the catalyst of the present embodiment is:
Step one, 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 nitrate be dissolved in the water, and stirs and obtain mixed solution;
Step 2, by 151.8g technical grade Detitanium-ore-type TiO
2powder infusion, in mixed solution described in step one, then adds 12g urea under agitation in mixed solution, after urea dissolves completely, mixed solution is heated to 99 DEG C, and insulated and stirred is until obtain thick liquid-solid mixture;
Step 3, by liquid-solid mixture thick described in step 2 dry 9h at 100 DEG C, then roasting 5h at 400 DEG C, obtains the catalyst for Selective catalytic reduction nitrogen oxide.
Embodiment 8
The catalyst removing nitrogen oxide for ammonia Selective catalytic reduction of the present embodiment, comprises carrier and active component, and 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 2: 2: 1, and 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 one, 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 nitrate be dissolved in the water, and stirs and obtain mixed solution;
Step 2, by 100g technical grade Detitanium-ore-type TiO
2powder infusion, in mixed solution described in step one, then adds 6g urea under agitation in mixed solution, after urea dissolves completely, mixed solution is heated to 98 DEG C, and insulated and stirred is until obtain thick liquid-solid mixture;
Step 3, by liquid-solid mixture thick described in step 2 dry 8h at 110 DEG C, then roasting 4h at 500 DEG C, obtains the catalyst for Selective catalytic reduction nitrogen oxide.
Embodiment 9
The catalyst removing nitrogen oxide for ammonia Selective catalytic reduction of the present embodiment, comprises carrier and active component, and 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 1.4: 2: 1.2, and 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 one, 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 nitrate be dissolved in the water, and stirs and obtain mixed solution;
Step 2, by 131g technical grade Detitanium-ore-type TiO
2powder infusion, in mixed solution described in step one, then adds 7.86g urea under agitation in mixed solution, after urea dissolves completely, mixed solution is heated to 98 DEG C, and insulated and stirred is until obtain thick liquid-solid mixture;
Step 3, by liquid-solid mixture thick described in step 2 dry 8h at 110 DEG C, then roasting 4h at 500 DEG C, obtains the catalyst for Selective catalytic reduction nitrogen oxide.
Embodiment 10
The catalyst removing nitrogen oxide for ammonia Selective catalytic reduction of the present embodiment, comprises carrier and active component, and 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: 2: 1.5, and 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 one, 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 nitrate be dissolved in the water, and stirs and obtain mixed solution;
Step 2, by 122g technical grade Detitanium-ore-type TiO
2powder infusion, in mixed solution described in step one, then adds 8.5g urea under agitation in mixed solution, after urea dissolves completely, mixed solution is heated to 95 DEG C, and insulated and stirred is until obtain thick liquid-solid mixture;
Step 3, by liquid-solid mixture thick described in step 2 dry 10h at 100 DEG C, then roasting 3h at 450 DEG C, obtains the catalyst for Selective catalytic reduction nitrogen oxide.
Embodiment 11
The catalyst removing nitrogen oxide for ammonia Selective catalytic reduction of the present embodiment, comprises carrier and active component, and 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: 2: 1.2, and 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 one, 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 nitrate be dissolved in the water, and stirs and obtain mixed solution;
Step 2, by 136g technical grade Detitanium-ore-type TiO
2powder infusion, in mixed solution described in step one, then adds 10.9g urea under agitation in mixed solution, after urea dissolves completely, mixed solution is heated to 99 DEG C, and insulated and stirred is until obtain thick liquid-solid mixture;
Step 3, by liquid-solid mixture thick described in step 2 dry 9h at 100 DEG C, then roasting 5h at 400 DEG C, obtains the catalyst for Selective catalytic reduction nitrogen oxide.
Embodiment 12
The catalyst removing nitrogen oxide for ammonia Selective catalytic reduction of the present embodiment, comprises carrier and active component, and 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 1.5: 2: 1.2, and 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 one, 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 nitrate be dissolved in the water, and stirs and obtain mixed solution;
Step 2, by 134g technical grade Detitanium-ore-type TiO
2powder infusion, in mixed solution described in step one, then adds 8g urea under agitation in mixed solution, after urea dissolves completely, mixed solution is heated to 98 DEG C, and insulated and stirred is until obtain thick liquid-solid mixture;
Step 3, by liquid-solid mixture thick described in step 2 dry 8h at 110 DEG C, then roasting 4h at 500 DEG C, obtains the catalyst for Selective catalytic reduction nitrogen oxide.
Embodiment 13
The catalyst removing nitrogen oxide for ammonia Selective catalytic reduction of the present embodiment, comprises carrier and active component, and 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 1.5: 2: 1.5, and 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 one, 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 nitrate be dissolved in the water, and stirs and obtain mixed solution;
Step 2, by 121g technical grade Detitanium-ore-type TiO
2powder infusion, in mixed solution described in step one, then adds 7.3g urea under agitation in mixed solution, after urea dissolves completely, mixed solution is heated to 98 DEG C, and insulated and stirred is until obtain thick liquid-solid mixture;
Step 3, by liquid-solid mixture thick described in step 2 dry 8h at 110 DEG C, then roasting 4h at 500 DEG C, obtains the catalyst for Selective catalytic reduction nitrogen oxide.
Catalytic activity is tested:
By the respectively compressing tablet grinding of the catalyst of 0.40g embodiment 1-13, screening is got 40-80 order size particles and is positioned in tubular fixed-bed reactor and reacts, and 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.Reaction temperature is interval from 200 DEG C to 550 DEG C.
The activity of catalyst nitrogen oxides reduction at table 1 differential responses temperature
Stability experiment:
By the respectively compressing tablet grinding of the catalyst of 0.40g embodiment 1-13, screening is got 40-80 order size particles and is positioned in tubular fixed-bed reactor and reacts, and 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 DEG C, successive reaction 50h, and carries out an active testing every 3h ~ 5h.Experimental result shows, the conversion ratio of catalyst nitrogen oxide remains on more than 90% always, does not occur inactivation or the active phenomenon reduced.
The above; it is only preferred embodiment of the present invention; not the present invention is imposed any restrictions, every above embodiment is done according to the technology of the present invention essence any simple modification, change and equivalent structure transformation, all still belong in the protection domain of technical solution of the present invention.
Claims (5)
1. remove a catalyst for nitrogen oxide for ammonia Selective catalytic reduction, 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 1.4: 2: 1.2, and the mass ratio of described active component and carrier is 1.3: 20.
2. prepare a method for catalyst as claimed in claim 1, it is characterized in that, the method comprises the following steps:
Step one, cerous nitrate, ammonium metatungstate and zirconium nitrate to be dissolved in the water, to stir and obtain mixed solution;
Step 2, by technical grade Detitanium-ore-type TiO
2impregnated in mixed solution described in step one, then in mixed solution, add urea under agitation, after urea dissolves completely, mixed solution is heated to 95 DEG C ~ 100 DEG C, insulated and stirred is until obtain thick liquid-solid mixture; The addition of described urea is TiO
25% ~ 8% of quality;
Step 3, by liquid-solid mixture thick described in step 2 dry 6h ~ 10h at 100 DEG C ~ 120 DEG C, then roasting 3h ~ 5h at 400 DEG C ~ 550 DEG C, obtains the catalyst for Selective catalytic reduction nitrogen oxide.
3. method according to claim 2, is characterized in that, the addition of urea described in step 2 is TiO
26% of quality.
4. method according to claim 2, is characterized in that, temperature dry described in step 3 is 110 DEG C, and drying time is 8h.
5. method according to claim 2, is characterized in that, the temperature of roasting described in step 3 is 500 DEG C, and roasting time is 4h.
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| CN105435776A (en) * | 2014-08-20 | 2016-03-30 | 上海郎特汽车净化器有限公司 | Honeycomb-like cerium-zirconium-tungsten-titanium-based denitration catalyst and preparation method thereof |
| CN105214480A (en) * | 2015-11-13 | 2016-01-06 | 朱忠良 | A kind of flue gas purifying technique |
| CN105231528A (en) * | 2015-11-13 | 2016-01-13 | 朱忠良 | Mask |
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| CN101522298A (en) * | 2006-08-25 | 2009-09-02 | 东京滤器株式会社 | Catalyst, method and apparatus for purifying nitrogen oxide |
| CN102658118A (en) * | 2012-01-19 | 2012-09-12 | 中国汽车技术研究中心 | A kind of environmentally friendly NOx selective catalytic reduction catalyst and preparation method |
| CN103240079A (en) * | 2013-05-30 | 2013-08-14 | 中国科学院生态环境研究中心 | Cerium-zirconium-tungsten composite oxide catalyst as well as preparation method and usage thereof |
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| WO2012090557A1 (en) * | 2010-12-27 | 2012-07-05 | エヌ・イー ケムキャット株式会社 | Selective reduction catalyst, and exhaust gas purification device and exhaust gas purification method using same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101522298A (en) * | 2006-08-25 | 2009-09-02 | 东京滤器株式会社 | Catalyst, method and apparatus for purifying nitrogen oxide |
| CN102658118A (en) * | 2012-01-19 | 2012-09-12 | 中国汽车技术研究中心 | A kind of environmentally friendly NOx selective catalytic reduction catalyst and preparation method |
| CN103240079A (en) * | 2013-05-30 | 2013-08-14 | 中国科学院生态环境研究中心 | Cerium-zirconium-tungsten composite oxide catalyst as well as preparation method and usage thereof |
Non-Patent Citations (1)
| Title |
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| Enhanced activity of tungsten modified CeO2/TiO2 for selective catalytic reduction of NOx with ammonia;Liang Chen et al.,;《Catalysis Today》;20100315;第153卷;第78页第2.1节，第79页Fig. 7a * |
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