CN105478158A - Preparation method of composite molecular sieve catalyst for diesel-car tail gas - Google Patents
Preparation method of composite molecular sieve catalyst for diesel-car tail gas Download PDFInfo
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- CN105478158A CN105478158A CN201510749160.0A CN201510749160A CN105478158A CN 105478158 A CN105478158 A CN 105478158A CN 201510749160 A CN201510749160 A CN 201510749160A CN 105478158 A CN105478158 A CN 105478158A
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Abstract
A related preparation method of a composite molecular sieve catalyst for diesel-car tail gas is characterized by comprising the following preparation steps: (1) preparing a dipping liquid, concretely comprising a) fully mixing a copper salt, an auxiliary-agent metal salt and deionized water with stirring, so as to prepare a multi-metal-ion turbid solution, b) adding a molecular sieve carrier and a surface dispersant, mixing with stirring for 4-24 h, then adding an active-composition introduction agent ammonia water with the mass fraction of 25%-28%, and continuing to stir for 2-24 h, and c) adding a solid metal oxide, uniformly mixing with stirring, and standing and dipping for 2-6 h; and (2) performing drying, grinding and calcining on the dipping liquid, and grinding, so as to obtain the composite molecular sieve catalyst for diesel-car tail gas. The catalyst prepared according to the method possesses relatively good low-temperature De-NOx effect, and a once ion exchange-dipping combined process is employed, so that the preparation process is simplified and industrialized batch production is easy to realize.
Description
Technical field
The present invention relates to a kind of preparation method of exhaust gas from diesel vehicle composite molecular sieve catalyst, belong to motor vehicle emission technical field, especially belong to the field of catalyst preparation of SCR denitration.
Background technology
While automobile brings convenience to people's lives, vehicle exhaust also becomes one of air primary pollution source, particularly NOx and brings great harm to human environment and health.Along with the continuous upgrading of environmental regulation, SCR technology has become medium and heavy-duty engines enterprise first-selection and has reduced NOx technology path, and more and more by people are accepted and become diesel engine vent gas NOx post processing mainstream research direction.This technology utilizes reducing agent NH
3on a catalyst by NO
xbe reduced to harmless N
2and H
2o.The core of SCR technology is the catalyst of high activity and stability.Most SCR catalyst is catalytic component based on vanadium in the market, and its temperature window is narrow, only has good NOx at 280 ~ 420 DEG C active, and lower than 280 DEG C and be greater than 420 DEG C, NOx activity is extremely low.In addition, catalytic component based on vanadium is can decompose higher than when 450 DEG C, and the V2O5 of generation has severe toxicity, to environment and harm very big.Thus, catalytic component based on vanadium can only be a kind of temporal transition technology, can not meet more strict emission regulation demands.
Thus, exploitation efficient, good stability, eco-friendly Novel SCR catalyst is the focus direction that current catalyst industry makes great efforts to explore always.Much research shows, molecular sieve catalyst has high catalytic activity to selective reduction NOx, and active temperature windows is wider, receives much concern in Selective catalytic reduction NOx technology.It is based on its special microcellular structure that molecular sieve is used as catalyst, and mainly comprises Fe for the metallic element of modification, Cu, Mn, Ce, Co and Ni etc.For NOx purification in motor-vehicle tail-gas, what current industrial quarters was relatively more good is for metal active constituent with Cu, Fe, MFI, CHA, MEL, MOR, Bea are the catalyst of carrier, have higher catalytic activity, have broad application prospects to the nitrogen oxide in vehicle exhaust.
At present, in domestic molecular sieve catalyst purifying motor tail gas, NOx technology is in the starting stage, the heat endurance of catalyst and low temperature conversion rate is low etc. that problem is the key issue that such catalyst needs to solve in actual applications.The mentality of designing of this patent is the Cu that the metal promoter ion added can promote in active component on the one hand
2+dispersion, and then be conducive to promote Cu
2+with H on molecular sieve
+exchange reaction, the void structure had in metal promoter molecule is on the other hand conducive to improving its storage oxygen and oxygen release ability, thus overcomes the problem of poor performance at low temperatures; Add active component imported agent first with Cu
2+there is chemical reaction and form a kind of transitory intermediates, transitory intermediates again with active position H on molecular sieve
+react, and then Cu
2+be loaded on molecular sieve surface, no matter in molecular sieve pore passage or surface is all by the activity component metal that load is more like this, the De-NOx drastically increasing catalyst is active, overcomes a difficult problem for catalyst De-NOx poor activity; The transition metal oxide added, the quantity that can improve molecular sieve surface metal active material can reduce catalyst cost again; The present invention adopts primary ions to exchange-flood combined techniques, simplifies preparation process, and synthesis condition is easy to control, and is easy to realize industrial volume production.
Summary of the invention
The object of the invention is the preparation method being to provide a kind of exhaust gas from diesel vehicle composite molecular sieve catalyst, compared with existing SCR catalyst preparation method, this method load active component efficiency is high, solves the problem of loss of active component.Simultaneously, the void structure had in promoter metal molecule is conducive to improving its storage oxygen and oxygen release ability, and then the standby catalyst of this legal system has good low temperature De-NOx effect, its adopt primary ions exchange-dipping combines method, simplification preparation process can be made and be easy to realize industrial volume production.
Technical scheme of the present invention is achieved in that a kind of preparation method of exhaust gas from diesel vehicle composite molecular sieve catalyst, it is characterized in that concrete preparation process is as follows: the preparation of (1) maceration extract: a) by mantoquita, promoter metal salt, the abundant mix and blend of deionized water, be made into many kinds of metal ions turbid solution; B) add molecular sieve carrier, surface dispersant, mix and blend 4 ~ 24h, then add the active component imported agent ammoniacal liquor that mass fraction is 25% ~ 28%, continue stirring 2 ~ 4h; C) solid metal oxide is added, mixing and stirring, static dipping 2 ~ 6h; (2) by maceration extract drying, grinding, calcining, its bake out temperature is 105 ~ 150 DEG C, the temperature of high-temperature calcination is 450 ~ 520 DEG C, calcination time is 4h ~ 6h, and the size and distribution D50 of grinding is between 500nm ~ 3000nm; Namely a kind of exhaust gas from diesel vehicle composite molecular sieve catalyst is obtained,
The quality proportioning of the mantoquita contained in described maceration extract, metal promoter, deionized water, molecular sieve, active component imported agent, surface dispersant, metal oxide is mantoquita 4 ~ 12 parts, metal promoter 1.8 ~ 4 parts, 41 ~ 57 parts, water, 22 ~ 34 parts, molecular sieve, active component imported agent 5 ~ 10 parts, surface dispersant 1.3 ~ 2.3 parts and metal oxide 1 ~ 4 part.
Described mantoquita is one or both in the copper nitrate of solubility or copper acetate, particularly, and copper nitrate/copper acetate mass ratio=0 ~ 1/0 ~ 1.
Described metal promoter is one or more in rare earth element ce, La and transition metal Co, Zr, Cr, Mn metal nitrate, Ce/La/Co/Zr/Cr/Mn mass ratio=0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1, particularly Ce/Mn mass ratio=0 ~ 1/1 ~ 0.
Described molecular sieve is the one of MFI, MEL, CHA, BEA, FAU, LTA, MOR.
Described surface dispersant is low-molecular-weight alcohols, and particularly, its surface tension is not more than 45dyn/cm.
Described metal oxide is one or several in transition metal Co, Zr, Cr, Mn, Fe and Cu metal oxide, Co/Zr/Cr/Mn/Fe/Cu oxide mass is than=0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1, further preferably, Cu/Mn/Fe metal oxide mass ratio=0 ~ 1/0 ~ 1/0 ~ 1, metal oxide size and distribution D50 is between 500nm ~ 3000nm.
Good effect of the present invention is that the void structure had in promoter metal molecule is conducive to improving its storage oxygen and oxygen release ability, and then the standby catalyst of this legal system has good low temperature De-NOx effect, it adopts primary ions to exchange-flood the method that combines, and can make simplification preparation process and be easy to realize industrial volume production.
Accompanying drawing explanation
Fig. 1 is that the embodiment of the present invention 1 describes the isothermal adsorption/desorption curve preparing material.
Fig. 2 is for temperature is on the impact of catalyst efficiency synthesized by embodiment 1.
Fig. 3 is for air speed is on the impact of catalyst efficiency synthesized by embodiment 1.
Fig. 4 is the H2-TPR curve of embodiment product.
Fig. 5 is the H2-TPR curve of certain commercialization copper based molecular sieve catalyst.
Fig. 6 is comparative example 1 product NOx conversion efficiency curve.
Fig. 7 is that comparative example 2 containing transition metal oxide mode is on the impact of conversion ratio.
Detailed description of the invention
In following concrete example describes, give a large amount of concrete details so that more deep understanding the present invention.But, it will be apparent to one skilled in the art that the present invention can be implemented without the need to these details one or more.
Embodiment 1
Take the Cu (NO of 900g
3)
2﹒ 3H
2o and 126gCe (NO
3)
3﹒ 6H
2o dissolves in 3700g deionized water for stirring; The mass fraction adding 805g after adding the absolute ethyl alcohol mix and blend 4h of 3000gZSM-5 molecular sieve and 100g is 25% ammoniacal liquor, continues mix and blend 2h; The D90 adding 300g is the cupric oxide powder of 500nm, after mixing and stirring, after static dipping 2h, put into disk in the oven dry of 105 DEG C, baking oven, smash in the blocks of solid of having dried and pulverizer, calcine 6h at being placed in Muffle furnace 450 DEG C, powder grinder after calcining is further processed as the powder that particle diameter D50 is 500nm, namely obtains exhaust gas from diesel vehicle composite molecular sieve catalyst.
By isothermal nitrogen adsorption-desorption curve test, see Fig. 1, meet the H4 type slit pore hysteresis loop of Kelvin equation in the four class hysteresis loops according to IUPAC classification, testimonial material has the narrow slit structure of the mesoporous yardstick of class quasi-lamellar structure.
Adopt 5 BET method mappings to obtain to adsorption isotherm, in all embodiments of the present invention, BET specific surface area sees the following form, and sample specific area prepared by visible all embodiments is all at 226m
2/ more than g, has very large response area, promotes the transformation efficiency of NOx.
Use fixed-bed micro-reactor, five gas analyzers carry out NH to catalyst fines
3-SCR conversion efficiency is tested, and experiment condition is: air speed 100000h
-1, NO500ppm, O
25%, NH
3500ppm.Conversion results is shown in Fig. 2, and at 220 ~ 450 DEG C, have better NOx active, more than Transformation efficiency is up to 90 %, in this temperature range, stability is better; In addition, even if when low temperature 150 DEG C, conversion ratio is still up to more than 55%.
Improve air speed to 200000h
-1, conversion results is shown in Fig. 3, and as seen under higher air speed, transformation efficiency declines slightly, but still keeps higher conversion ratio, has good stability.
3h is activated in 300 DEG C of He gas, cool to room temperature 25 DEG C, pass into 10%H2-90%Ar, 10 DEG C/min heating rate is to 700 DEG C, thermostatic 1h carries out H2-TPR analysis, the initial reduction temperature 133 DEG C of embodiment 1 product as can be seen from Figure 4, and the initial reduction temperature 258 DEG C of the commercial molecular sieve catalyst of Fig. 5, therefore the low temperature active of embodiment 1 Kaolinite Preparation of Catalyst is better.
Comparative example 1:
Take the Cu (NO of 900g
3)
2﹒ 3H
2o and 126gCe (NO
3)
3﹒ 6H
2o dissolves in 3700g deionized water for stirring; Add the absolute ethyl alcohol mix and blend 2h of 3000gZSM-5 molecular sieve and 100g; The D90 adding 300g is the cupric oxide powder of 500nm, after mixing and stirring, and static dipping 2h; Put into disk in the oven dry of 105 DEG C, baking oven, smash in the blocks of solid of having dried and pulverizer, 6h is calcined at being placed in Muffle furnace 450 DEG C, powder grinder after calcining is further processed as the powder that particle diameter D50 is 500nm, namely obtains that comparative example 1 uses fixed-bed micro-reactor, five gas analyzers carry out NH to catalyst fines
3-SCR conversion efficiency is tested, and experiment condition is: air speed 100000h
-1, NO500ppm, O
25%, NH
3500ppm.Conversion results is shown in Fig. 6, and at 150 ~ 550 DEG C, conversion rate of NOx is up to 58%, does not add the pay(useful) load that active component imported agent can affect active component as seen, very large on final conversion rate of NOx impact.
Comparative example 2:
Take the Cu (NO of 900g
3)
2﹒ 3H
2o and 126gCe (NO
3)
3﹒ 6H
2o dissolves in 3700g deionized water for stirring; The mass fraction adding 805g after adding the absolute ethyl alcohol mix and blend 4h of 3000gZSM-5 molecular sieve and 100g is 25% ammoniacal liquor, continues mix and blend 2h; The D90 adding 300g is the cupric oxide powder of 500nm, after mixing and stirring, and static dipping 2h; Put into disk in the oven dry of 105 DEG C, baking oven, mechanical lapping is carried out together with the cupric oxide powder that the blocks of solid of having dried and the D90 of 300g are 500nm, powder after grinding calcines 6h at being placed in Muffle furnace 450 DEG C, powder grinder after calcining is further processed as the powder that particle diameter D50 is 500nm, namely obtains comparative example 2 catalyst.
Use fixed-bed micro-reactor, five gas analyzers carry out NH to catalyst fines
3-SCR conversion efficiency is tested, and experiment condition is: air speed 100000h
-1, NO500ppm, O
25%, NH
3500ppm.Conversion results is shown in Fig. 7, as seen its transformation efficiency comparatively embodiment 1 compare and significantly decrease.In addition, the specific area of catalyst prepared by this mechanical doping is also relatively low, this also illustrates this doping way and is unfavorable for improving NOx conversion efficiency.
Embodiment 2
Take the Cu (NO of 1500g
3)
2﹒ 3H
2o and 577gMn (NO
3)
2﹒ 4H
2o in 6200g deionized water, stirring and dissolving; The mass fraction adding 1215g after adding the absolute ethyl alcohol mix and blend 5h of 3000gZSM-5 molecular sieve and 300g is 28% ammoniacal liquor, mix and blend 4h; The D90 adding 100g is the manganese oxide powder of 3000nm, after mixing and stirring, and static dipping 6h; Put into disk in the oven dry of 150 DEG C, baking oven, the blocks of solid of having dried is smashed in pulverizer, calcine 4h at being placed in Muffle furnace 520 DEG C, powder grinder after calcining is further processed as the powder that particle diameter D50 is 2000nm, namely obtains exhaust gas from diesel vehicle composite molecular sieve catalyst.
Embodiment 3
Take the Cu (CH of 900g
3cOO)
2﹒ H
2o, 200gCe (NO
3)
3﹒ 6H
2o and 300gMn (NO
3)
2﹒ 4H
2o in 6000g deionized water, stirring and dissolving; Add the methyl alcohol of 3000gSAPO-34 molecular sieve and 200g, the mass fraction adding 505g after mix and blend 4h is 28% ammoniacal liquor, mix and blend 4h; The D90 adding 300g is the croci of 1000nm, after stirring, leaves standstill dipping 2h; Put into disk in the oven dry of 120 DEG C, baking oven, the blocks of solid of having dried is smashed in pulverizer, calcine 4h at being placed in Muffle furnace 520 DEG C, powder grinder after calcining is further processed as the powder that particle diameter D50 is 2000nm, namely obtains exhaust gas from diesel vehicle composite molecular sieve catalyst.
Embodiment 4
Take the Cu (NO of 500g
3)
2﹒ 3H
2cu (the CH of O, 900g
3cOO)
2﹒ H
2o, 173g zirconium nitrate in 7715g deionized water, stirring and dissolving; The mass fraction adding 953g after adding the propyl alcohol stirring 4h of 3000gSSZ-13 molecular sieve and 180g is 28% ammoniacal liquor, mix and blend 5h; Add 100g cupric oxide powder, 100g zirconia and 50g chromium oxide that D90 is 1000nm, after stirring, leave standstill dipping 4h; Put into disk in the oven dry of 135 DEG C, baking oven, the blocks of solid of having dried is smashed in pulverizer, calcine 6h at being placed in Muffle furnace 450 DEG C, powder grinder after calcining is further processed as the powder that particle diameter D50 is 2000nm, namely obtains exhaust gas from diesel vehicle composite molecular sieve catalyst.
Embodiment 5
Take the Cu (NO3) of 900g
2﹒ 3H
2the cobalt nitrate of O, 388g and 132g chromic nitrate in 7000g deionized water, stirring and dissolving; Add the n-butanol of 3000gZSM-5 molecular sieve and 200g, the mass fraction adding 1310g after stirring 4h is 28% ammoniacal liquor, mix and blend 4h; The D90 adding 150g is the cupric oxide powder of 1000nm and 150gD90 is the croci of 1000nm, after stirring, leaves standstill dipping 4h; Put into disk in the oven dry of 125 DEG C, baking oven, the blocks of solid of having dried is smashed in pulverizer, calcine 6h at being placed in Muffle furnace 450 DEG C, powder grinder after calcining is further processed as the powder that particle diameter D50 is 2000nm, namely obtains exhaust gas from diesel vehicle composite molecular sieve catalyst.
Embodiment 6
Take the Cu (NO3) of 1200g
2﹒ 3H2O and 400g lanthanum nitrate in 5000g deionized water, stirring and dissolving; The mass fraction adding 1150g after adding the isobutanol stirring 4h of 3000gZSM-5 molecular sieve and 150g is 28% ammoniacal liquor, mix and blend 4h; The oxidation two manganese powder end that the D90 adding 100g is the cupric oxide powder of 1000nm, the D90 of 150g is 1000nm and the D90 of 150g are the croci of 1000nm, after stirring, leave standstill dipping 2h; Put into disk in the oven dry of 140 DEG C, baking oven, the blocks of solid of having dried is smashed in pulverizer, calcine 5h at being placed in Muffle furnace 450 DEG C, powder grinder after calcining is further processed as the powder that particle diameter D50 is 2000nm, namely obtains exhaust gas from diesel vehicle composite molecular sieve catalyst.
Embodiment 7
Take the Cu (NO3) of 900g
2﹒ 3H
2o, 350g cobalt nitrate in 7000g deionized water, stirring and dissolving; Add the isopropyl alcohol of 3000gZSM-5 molecular sieve and 210g, the mass fraction adding 1300g after stirring 4h is 28% ammoniacal liquor, mix and blend 4h; The manganese oxide that the D90 adding 50g is the cupric oxide powder of 1000nm, the D90 of 50g is the cobalt oxide of 1000nm, the D90 of 50g is the zirconia of 1000nm, the D90 of 50g is the chromium oxide of 1000nm, the D90 of 50g is 1000nm and 50gD90 are the croci of 1000nm, after stirring, leave standstill dipping 4h; Put into disk in the oven dry of 125 DEG C, baking oven, the blocks of solid of having dried is smashed in pulverizer, calcine 5h at being placed in Muffle furnace 520 DEG C, powder grinder after calcining is further processed as the powder that particle diameter D50 is 2000nm, namely obtains exhaust gas from diesel vehicle composite molecular sieve catalyst.
Embodiment 8
Take the Cu (NO of 520g
3)
2﹒ 3H
2cu (the CH of O, 900g
3cOO)
2﹒ H
2o, 75g chromic nitrate, 50g cobalt nitrate, 60g zirconium nitrate, 50g manganese nitrate, 65g ferric nitrate and 50g copper nitrate in 7680g deionized water, stirring and dissolving; The mass fraction adding 1020g after adding the absolute ethyl alcohol and stirring 4h of 3000gSSZ-13 molecular sieve and 200g is 28% ammoniacal liquor, mix and blend 5h; Add the 200g cobalt oxide powder that D90 is 1000nm, after stirring, leave standstill dipping 5h; Put into disk in the oven dry of 125 DEG C, baking oven, the blocks of solid of having dried is smashed in pulverizer, calcine 6h at being placed in Muffle furnace 520 DEG C, powder grinder after calcining is further processed as the powder that particle diameter D50 is 2000nm, namely obtains exhaust gas from diesel vehicle composite molecular sieve catalyst.
Embodiment 9
Take the Cu (CH of 900g
3cOO)
2﹒ H
2o, 350g zirconium nitrate and 300gMn (NO
3)
2﹒ 4H
2o in 6000g deionized water, stirring and dissolving; Add the methyl alcohol of 3000gSAPO-34 molecular sieve and 200g, the mass fraction adding 505g after mix and blend 4h is 28% ammoniacal liquor, mix and blend 4h; The D90 adding 300g is the Zirconium oxide powder of 1000nm, after stirring, leaves standstill dipping 3h; Put into disk in the oven dry of 125 DEG C, baking oven, the blocks of solid of having dried is smashed in pulverizer, calcine 5h at being placed in Muffle furnace 500 DEG C, powder grinder after calcining is further processed as the powder that particle diameter D50 is 2000nm, namely obtains exhaust gas from diesel vehicle composite molecular sieve catalyst.
Embodiment 10
Take Cu (NO3) the 2 ﹒ 3H2O of 1200g and 400g lanthanum nitrate in 5000g deionized water, stirring and dissolving; The mass fraction adding 1150g after adding the isobutanol stirring 4h of 3000gZSM-5 molecular sieve and 150g is 28% ammoniacal liquor, mix and blend 4h; The D90 adding 400g is the chromium oxide powder of 1000nm, after stirring, leaves standstill dipping 4h; Put into disk in the oven dry of 125 DEG C, baking oven, the blocks of solid of having dried is smashed in pulverizer, calcine 5h at being placed in Muffle furnace 500 DEG C, powder grinder after calcining is further processed as the powder that particle diameter D50 is 2000nm, namely obtains exhaust gas from diesel vehicle composite molecular sieve catalyst.
Claims (7)
1. the preparation method of an exhaust gas from diesel vehicle composite molecular sieve catalyst, it is characterized in that concrete preparation process is as follows: the preparation of (1) maceration extract: a) by mantoquita, promoter metal salt, the abundant mix and blend of deionized water, be made into many kinds of metal ions turbid solution; B) add molecular sieve carrier, surface dispersant, mix and blend 4 ~ 24h, then add the active component imported agent ammoniacal liquor that mass fraction is 25% ~ 28%, continue stirring 2 ~ 4h; C) solid metal oxide is added, mixing and stirring, static dipping 2 ~ 6h; (2) by maceration extract drying, grinding, calcining, its bake out temperature is 105 ~ 150 DEG C, the temperature of high-temperature calcination is 450 ~ 520 DEG C, calcination time is 4h ~ 6h, and the size and distribution D50 of grinding is between 500nm ~ 3000nm; Namely a kind of exhaust gas from diesel vehicle composite molecular sieve catalyst is obtained.
2., according to the preparation method of a kind of exhaust gas from diesel vehicle composite molecular sieve catalyst described in claim 1, the quality proportioning of the mantoquita that it is characterized in that containing in described maceration extract, metal promoter, deionized water, molecular sieve, active component imported agent, surface dispersant, metal oxide is mantoquita 4 ~ 12 parts, metal promoter 1.8 ~ 4 parts, 41 ~ 57 parts, water, 22 ~ 34 parts, molecular sieve, active component imported agent 5 ~ 10 parts, surface dispersant 1.3 ~ 2.3 parts and metal oxide 1 ~ 4 part.
3. according to the preparation method of a kind of exhaust gas from diesel vehicle composite molecular sieve catalyst described in claim 1, it is characterized in that described mantoquita is one or both in the copper nitrate of solubility or copper acetate, particularly, copper nitrate/copper acetate mass ratio=0 ~ 1/0 ~ 1.
4. according to the preparation method of a kind of exhaust gas from diesel vehicle composite molecular sieve catalyst described in claim 1, it is characterized in that described metal promoter is one or more in rare earth element ce, La and transition metal Co, Zr, Cr, Mn metal nitrate, Ce/La/Co/Zr/Cr/Mn mass ratio=0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1, particularly Ce/Mn mass ratio=0 ~ 1/1 ~ 0.
5., according to the preparation method of a kind of exhaust gas from diesel vehicle composite molecular sieve catalyst described in claim 1, it is characterized in that described molecular sieve is the one of MFI, MEL, CHA, BEA, FAU, LTA, MOR.
6., according to the preparation method of a kind of exhaust gas from diesel vehicle composite molecular sieve catalyst described in claim 1, it is characterized in that described surface dispersant is low-molecular-weight alcohols, particularly, its surface tension is not more than 45dyn/cm.
7. according to the preparation method of a kind of exhaust gas from diesel vehicle composite molecular sieve catalyst described in claim 1, it is characterized in that described metal oxide is one or several in transition metal Co, Zr, Cr, Mn, Fe and Cu metal oxide, Co/Zr/Cr/Mn/Fe/Cu oxide mass is than=0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1, further preferably, Cu/Mn/Fe metal oxide mass ratio=0 ~ 1/0 ~ 1/0 ~ 1, metal oxide size and distribution D50 is between 500nm ~ 3000nm.
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| CN106669843A (en) * | 2016-11-14 | 2017-05-17 | 天津大学 | Cuprous modified zeolite diesel engine emission pollutant oxidation and purification catalyst |
| CN106669843B (en) * | 2016-11-14 | 2019-12-03 | 天津大学 | Monovalence copper modified molecular screen diesel engine discharges pollutants oxidation, purification catalyst |
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| CN106984357A (en) * | 2017-04-17 | 2017-07-28 | 中自环保科技股份有限公司 | It is a kind of for SCR catalyst of diesel car tail gas refining and preparation method thereof |
| CN106984357B (en) * | 2017-04-17 | 2019-10-15 | 中自环保科技股份有限公司 | A kind of SCR catalyst and preparation method thereof for diesel car tail gas refining |
| CN111068764A (en) * | 2019-11-29 | 2020-04-28 | 天津大学 | NH for diesel vehicle exhaust3-SCO catalyst and preparation method thereof |
| CN111068764B (en) * | 2019-11-29 | 2023-04-28 | 天津大学 | NH for tail gas of diesel vehicle 3 SCO catalyst and preparation method thereof |
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