CN105032410B - A kind of Ag/Al2O3Catalyst, preparation method and its usage - Google Patents
A kind of Ag/Al2O3Catalyst, preparation method and its usage Download PDFInfo
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- CN105032410B CN105032410B CN201510300400.9A CN201510300400A CN105032410B CN 105032410 B CN105032410 B CN 105032410B CN 201510300400 A CN201510300400 A CN 201510300400A CN 105032410 B CN105032410 B CN 105032410B
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Abstract
The invention provides a kind of Ag/Al2O3Catalyst, preparation method and its usage.The catalyst is made up of carrier and active component, and the carrier is Al2O3, the active component include the first active component and the second active component, the first active component be Ag2O, the presoma of the second active component is NbCl5、TiO2、SiO2、AlCl3、AgAlO2, in GaN, AlN or InN any one or at least two mixture.The present invention is by using the second active component to Ag/Al2O3Catalyst is doped modification, significantly improves the low temperature HC SCR catalytic activity of catalyst, can evade because of conventional Ag/Al2O3Catalyst low-temperature activity is good and the online hydrogen supply equipment of additional.
Description
Technical field
The invention belongs to catalyst technical field, it is related to a kind of Ag/Al2O3Catalyst, preparation method and its usage.
Background technology
With the continuous growth and the swift and violent increase of vehicle guaranteeding organic quantity of energy-consuming, because a large amount of Fossil fuel consumptions (Gu
Determine source and moving source) it is discharged into the nitrogen oxides (NO in airx) pollution level constantly aggravate, the acid deposition that thus triggers,
Photochemical fog and gray haze have turned into the current environmental problem protruded the most.North China of China since especially in January, 2013
The serious gray haze contamination accident occurred makes it is appreciated that controlling the motor-vehicle tail-gas NO using diesel vehicle as representativexDischarge is still
Shoulder heavy responsibilities.So far, NOxElimination, especially NO under excess oxygenxPurification remain a major challenge that people face.
By taking diesel vehicle typical condition as an example, the mode of oxygen-enriched combusting causes in exhaust gas from diesel vehicle oxygen excessive and reduced
Agent absolute magnitude is not enough.For purifying tail gas of diesel vehicles NOx, need to separately add reducing agent.According to the difference of additional reducing agent, SCR skills
Art is divided into NH3- SCR and HC-SCR.At present, the NH of ammonia is replaced with aqueous solution of urea3The scale of-SCR technology is applied to diesel vehicle
There is more deficiency during popularization and application in the purification of tail gas, the technology：The cloth at reducing agent aqueous solution of urea addition station
Build costly, especially in the vast country in territory；Because the change of engine operating condition can cause the instantaneous leak of ammonia.HC-SCR skills
Art is applied to diesel motor exhaust NOxThe sharpest edges of purification are final source that can be by reducing agent of vehicle-mounted oil product, i.e.,
By the dual-use function of vehicle-mounted oil product to evade NH3- SCR deficiency, therefore HC-SCR technologies receive much attention always.
Above-mentioned reason is based on, 2 months 2009, GE and Tenneco companies endorsed strategic cooperation agreement, it is intended to develop
Efficient and complete HC-SCR post-processing technologies, and carry out the technology in the exhaust NOx purifications of diesel vehicle, ship and stationary source
Using.
CN1439455A (Rarefied combustion tail gas nitrogen oxide purification catalyst and purification method) discloses a kind of utilize and added
Plus hydrocarbon is at 150-600 DEG C of temperature, in Ag/Al2O3Realized on catalyst to NOxReduction catalystses purification side
Method.
CN103159242A (a kind of preparation method and its usage of promise gibbsite) prepares Ag/ by promise gibbsite
Al2O3The carrier of catalyst realizes the expansion of operation temperature window, and reducing agent is optimal using ethanol.
In numerous HC-SCR catalyst system and catalyzings, silver/aluminum oxide (Ag/Al2O3) because with excellent catalysis HC and especially
Oxygen-containing HC (such as ethanol) selective reduction NOxActive, stronger water resistant sulfur tolerance and by the extensive concern of researcher.But
It is, in order to meet increasingly strict Abgasgesetz, the low temperature work that temperature or stationary source tail-gas temperature characterisitic match to be arranged with diesel vehicle
Property improve be also faced with great challenge.It is worth mentioning that：Also there is typical H in HC-SCR2Effect, i.e. be mixed into tail gas
A small amount of H2Ag/Al can be obviously improved2O3The low temperature active of catalyst.But in view of the skill of moving source or the online hydrogen supply of stationary source
Art barrier, the catalyst that exploitation possesses superior low-temperature activity is only real technological break-through mouthful.
Therefore, in order to realize to moving source and stationary source NOxEffective control of discharge, the air for protecting us to depend on for existence
Environment, research and development possess low-temperature catalyzed HC selective reductions NOxAnd environment-friendly catalyst has important practical significance.
The content of the invention
The problem of for prior art, an object of the present invention is to provide a kind of Ag/Al2O3Catalyst, the catalyst
Effective lifting of low temperature HC-SCR catalytic activity can be realized, it is to avoid need online to provide the cumbersome of hydrogen in gas cleaning
Step.
In order to achieve the above object, present invention employs following technical scheme：
A kind of Ag/Al2O3Catalyst, it is made up of carrier and active component, and the carrier is Al2O3, the activearm
Dividing includes the first active component and the second active component, and the first active component is Ag2O, the presoma of the second active component is
NbCl5、TiO2、SiO2、AlCl3、AgAlO2, in GaN, AlN or InN any one or at least two mixture.
Preferably, the presoma of second active component is any one in GaN, AlN or InN or at least two
Mixture, preferably GaN or/and InN, further preferred GaN.GaN especially AlN meeting denitrogenations in preparation process aoxidize to be formed
The grappling of more defective bits and favorable activity argent, therefore, when the second active component presoma is GaN or/and InN, catalysis
The low temperature active improvement of agent compared with other more preferably, wherein, when the presoma of the second active component is GaN, the low temperature of catalyst
Active improvement is optimal, and 90% is can reach in 250 DEG C of conversion rate of NOx.
Preferably, in terms of metal Ag mass, the first active component A g2O is carrier Al2O3Quality 0~10% and do not include
0, such as 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%,
7.5%th, 8%, 8.5%, 9% or 9.5%, preferably 2~4wt%, now the catalytic activity of catalyst is best.
Preferably, the quality of the second active component presoma and metal Ag mass ratio are 30:1~1:1, such as 28:1、
25:1、22:1、20:1、15:1、12:1、9:1、6:1 or 3:1, preferably 5:1~1:1, further preferred 2:1, it is now low-temperature catalyzed
Activity is the most excellent, and cost is minimum.
The second object of the present invention is to provide a kind of Ag/Al as described above2O3The preparation method of catalyst, the side
Method is infusion process, is comprised the following steps：
By the first active component A g2The aqueous solution of O presomas, carrier Al2O3The aqueous slurry of presoma and the second activearm
Divide the aqueous solution mixing of presoma, obtained slurries are rotated, drying is calcined and optionally crushed, obtains Ag/Al2O3Catalysis
Agent.
Preferably, it the described method comprises the following steps：
(1) by the first active component A g2The aqueous solution of O presomas and carrier Al2O3The aqueous slurry of presoma is well mixed；
(2) aqueous solution of the second active component presoma is added in the slurries obtained in step (1), by obtained slurries
Revolving, drying is calcined and optionally crushed, obtains Ag/Al2O3Catalyst.
Preferably, the carrier Al2O3Presoma be boehmite (AlOOH) or/and activated alumina (γ-
Al2O3)。
Exemplary configuration carrier Al2O3The method of the aqueous slurry of presoma is：Weigh carrier Al2O3Presoma is such as intended thin
Diaspore (AlOOH) or/and activated alumina (γ-Al2O3), then add deionized water mixing and be beaten and continue stirring.
Preferably, the first active component presoma is AgNO3、Ag2SO4、C2H3AgO2Or Ag2In O any one or
At least two mixture.
The operating method of exemplary step (2) is：By the first active component A g2After O presomas are dissolved in the water, directly
It is placed in carrier Al2O3The aqueous slurry uniform stirring of presoma.
Preferably, after after uniform stirring at least 1h, then obtained slurries are rotated.
Preferably, gained slurries are transferred in revolving bottle, vacuum decompression heating revolving water-bath is 30~90 DEG C, preferably 60
℃。
Preferably, the drying temperature is 100~180 DEG C, and the drying time is 6-36h；
Preferably, drying temperature is 120 DEG C, and the drying time is 12h.
Preferably, in roasting process heating rate be 1 DEG C~20 DEG C/min, such as 2 DEG C/min, 4 DEG C/min, 6 DEG C/min,
8 DEG C/min, 10 DEG C/min, 12 DEG C/min, 14 DEG C/min, 16 DEG C/min or 18 DEG C/min, sintering temperature is 600~800 DEG C, example
Such as 620 DEG C, 640 DEG C, 660 DEG C, 680 DEG C, 700 DEG C, 720 DEG C, 740 DEG C, 760 DEG C or 780 DEG C.
Preferably, the atmosphere of roasting is O2、H2O or NH3In any one or at least two combination and N2Mixing
Gas.
Preferably, the atmosphere of roasting is N2And O2Mixed gas, N2And H2O mixed gas, N2、H2O and O2Mixing
Gas or N2、NH3And H2Any one in O mixed gas.
Preferably, N2And O2Mixed gas in, O2Volume content is 0~20vol%, and does not include 0.
Preferably, N2And H2In O mixed gas, H2O volume content is 1~20vol%.
Preferably, N2、H2O and O2Mixed gas in, H2O volume content is 0~10vol% and not including 0, O2Body
Product content is 0~20vol% and not including 0.
Preferably, N2、NH3And H2In O mixed gas, NH3Volume content for 0~0.12vol% and not include 0, H2O's
Volume content is 0~10vol% and not including 0.
In above-mentioned mixed gas, N2It is used as balanced gas.
Preferably, calcination atmosphere range of flow is 500~1000mL/min.
Preferably, it is ground into the particle of 20~40 mesh.
The third object of the present invention is a kind of Ag/Al as described above2O3The preparation method of catalyst, methods described is
Dry ball milling, comprises the following steps：
(1) by carrier Al2O3Presoma, the first active component A g2O presomas and the mixing of the second active component presoma, so
After add water and soak biased sample；
(2) biased sample for obtaining step (1) carries out ball milling, is calcined and optionally crushes, obtains Ag/Al2O3Catalysis
Agent.
Preferably, it the described method comprises the following steps：
(1) by carrier Al2O3Presoma, the first active component A g2O presomas and the second active component presoma add successively
Enter in ball grinder, then adding water soaks biased sample；
(2) biased sample for obtaining step (1) carries out ball milling, is calcined and optionally crushes, obtains Ag/Al2O3Catalysis
Agent.
Preferably, the carrier Al2O3Presoma be boehmite (AlOOH) or/and activated alumina (γ-
Al2O3)。
Preferably, the first active component presoma is AgNO3、Ag2SO4、C2H3AgO2Or Ag2In O any one or
At least two mixture.
Preferably, the ball milling is carried out in ball grinder.
Preferably, there is Ф 10mm bead 5~30 in the ball grinder, Ф 20mm bead 0~20, such as 2,
5,8,12,15 or 18.
Preferably, the ball milling is carried out in planetary ball mill.
Preferably, the rotational speed of ball-mill be 100~400r/min, such as 130r/min, 160r/min, 190r/min,
220r/min, 250r/min, 280r/min, 310r/min, 340r/min or 370r/min, Ball-milling Time are 1~9h, for example
1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h or 8.5h.
Preferably, in roasting process heating rate be 1 DEG C~20 DEG C/min, such as 2 DEG C/min, 4 DEG C/min, 6 DEG C/min,
8 DEG C/min, 10 DEG C/min, 12 DEG C/min, 14 DEG C/min, 16 DEG C/min or 18 DEG C/min, sintering temperature is 600~800 DEG C, example
Such as 620 DEG C, 640 DEG C, 660 DEG C, 680 DEG C, 700 DEG C, 720 DEG C, 740 DEG C, 760 DEG C or 780 DEG C.
Preferably, the atmosphere of roasting is O2、H2O or NH3In any one or at least two combination and N2Mixing
Gas.
Preferably, the atmosphere of roasting is N2And O2Mixed gas, N2And H2O mixed gas, N2、H2O and O2Mixing
Gas or N2、NH3And H2Any one in O mixed gas.
Preferably, N2And O2Mixed gas in, O2Volume content is 0~20vol%, and does not include 0.
Preferably, N2And H2In O mixed gas, H2O volume content is 1~20vol%.
Preferably, N2、H2O and O2Mixed gas in, H2O volume content is 0~10vol% and not including 0, O2Body
Product content is 0~20vol% and not including 0.
Preferably, N2、NH3And H2In O mixed gas, NH3Volume content for 0~0.12vol% and not include 0, H2O's
Volume content is 0~10vol% and not including 0.
In above-mentioned mixed gas, N2It is used as balanced gas.
Preferably, calcination atmosphere range of flow is 500~1000mL/min.
Preferably, it is ground into the particle of 20~40 mesh.
The fourth object of the present invention is to provide a kind of Ag/Al as described above2O3The purposes of catalyst, it is used for HC-
SCR reacts.
Consider the environment friendly and reactivity of reducing agent, reducing agent is preferably ethanol.
Compared with the prior art, the present invention has the advantages that：
The present invention is by using the second active component to Ag/Al2O3Catalyst is doped modification, significantly improves catalysis
The low temperature HC-SCR catalytic activity of agent, can evade because of conventional Ag/Al2O3Catalyst low-temperature activity is good and additional it is online
Hydrogen supply equipment.
The Ag/Al of the present invention2O3Catalyst can be prepared using wet impregnation or dry ball milling, simple and easy to control, preparation parameter
It is easy to adjust to be easy to amplify preparative-scale.
Brief description of the drawings
Fig. 1 is the NO of embodiment 1 and the catalyst of embodiment 2xConversion ratio evaluation figure；
Fig. 2 is the NO of embodiment 1 and the catalyst of embodiment 3xConversion ratio evaluation figure；
Fig. 3 is the NO of embodiment 1 and the catalyst of embodiment 4xConversion ratio evaluation figure；
Fig. 4 is the NO of embodiment 1 and the catalyst of embodiment 5xConversion ratio evaluation figure；
Fig. 5 is the NO of embodiment 1 and the catalyst of embodiment 6xConversion ratio evaluation figure；
Fig. 6 is embodiment 1,2 and embodiment 5,6 catalyst activity comparison diagrams；
Fig. 7 is the Ag/Al of different silver contents2O3The activity contrast of catalyst, it can be seen that in terms of metal Ag mass, first
Active component A g2O is carrier Al2O3Quality for 2~4wt% when, catalytic activity is excellent.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.
Embodiment 1：
Catalyst preparation：Weigh 25 grams of Al2O3Add deionized water mixing to be beaten and stir, weigh 0.7875 gram
AgNO3Solid adds deionized water dissolving, and the solution of configuration is added to Al2O3Among slurries and continue stir 1h.By resulting solution
Insert in revolving bottle, heating under reduced pressure rotary evaporation is to 60 DEG C.Drying sample is removed in 120 degree of oven dried overnights, afterwards by sample
Product take into atmosphere furnace roasting.Roasting condition is：N2+O2(20vol%), total flow 600mL/min.Heating rate is 10 DEG C/min,
It is warming up to 600 DEG C of holding 3h.Then naturally near room temperature.Taking out sample, to be crushed to 20-40 mesh through tabletting standby, that is, obtains conventional
2wt%Ag/Al prepared by infusion process2O3Catalyst.
Purify reaction condition：The sample of embodiment 1, weight is：0.3 gram is put into catalyst activity evaluating apparatus, activity rating
Carried out in fixed bed reactors.Simulated flue gas composition is (1565ppm C2H5OH, 800ppm NO, 10%O2, 10%H2O), N2
For Balance Air, total flow is 1000mL/min, and reaction velocity is 100000h-1。
Clean-up effect：In 300~500 DEG C of range of reaction temperature, the catalyst has 100% conversion NOx ability.It is low
Temp effect is not good, and at 250 DEG C, conversion rate of NOx is only 50%.Concrete outcome is as shown in Figure 1.
Embodiment 2：
Catalyst preparation：Method for preparing catalyst is as described in Example 1.
Purify reaction condition：The sample of embodiment 1, weight is：0.3 gram is put into catalyst activity evaluating apparatus, activity rating
Carried out in fixed bed reactors.Simulated flue gas composition is (1565ppm C2H5OH, 800ppm NO, 10%O2, 10%H2O,
1%H2), N2For Balance Air, total flow is 1000mL/min, and reaction velocity is 100000h-1。
Clean-up effect：
Concrete outcome is as shown in Figure 1.
Embodiment 3：
Catalyst preparation：Weigh 25 grams of Al2O3It is positioned in 125mL corundum ball grinders, weighs 0.7875 gram of AgNO3Solid
It is directly placed into above-mentioned grinding pot and uniformly mixes, then weighs 1.08 grams of NbCl5Insert in above-mentioned aggregate sample.Injected using 10mL
Device, is slowly dropped into 10mL deionized waters while stirring powder biased sample.Grinding pot is inserted in planetary ball mill instrument afterwards and carried out
Milled processed.Treatment conditions are：Rotating speed 300r/min, milling time is 1h.The sample ground by ball milling instrument is sieved through sieve
Afterwards, it is placed in atmosphere furnace roasting.Roasting condition is：N2+O2(20vol%)+H2O (10vol%), total flow 600mL/min.Heating
Speed is 5 DEG C/min, is warming up to 600 DEG C of holding 3h, then naturally near room temperature.Take out sample and be crushed to 20-40 mesh through tabletting
It is standby, that is, obtain the 2wt%Ag/Al that dry ball milling prepares addition Nb elements2O3Catalyst.
Purify reaction condition：With embodiment 1.
Clean-up effect：
Concrete outcome is as shown in Figure 2.
Embodiment 4：
Catalyst preparation：Weigh 25 grams of Al2O3It is positioned in 125mL corundum ball grinders, weighs 0.7875 gram of AgNO3Solid
It is directly placed into above-mentioned grinding pot and uniformly mixes, then weigh 0.82 gram of AlN and inserts in above-mentioned aggregate sample.Using 10mL syringes,
10mL deionized waters are slowly dropped into while stirring powder biased sample.Grinding pot is inserted afterwards and is ground in planetary ball mill instrument
Processing.Treatment conditions are：Rotating speed 300r/min. milling times are 1h.After the sample that ball milling instrument is ground is sieved through sieve,
It is placed in atmosphere furnace roasting.Roasting condition is：N2+O2(20vol%, total flow 600mL/min.Heating rate is 5 DEG C/min, heating
3h are kept to 600 DEG C, then naturally near room temperature.Taking out sample, to be crushed to 20-40 mesh through tabletting standby, that is, obtains dry ball milling
Prepare the 2wt%Ag/Al of addition AlN structures2O3Catalyst.
Purify reaction condition：With embodiment 1.
Clean-up effect：
Concrete outcome is as shown in Figure 3.
Embodiment 5：
Catalyst preparation：Weigh 25 grams of Al2O3It is positioned in 125mL corundum ball grinders, weighs 0.7875 gram of AgNO3Solid
It is directly placed into above-mentioned grinding pot and uniformly mixes, then weigh 0.84 gram of GaN and inserts in above-mentioned aggregate sample.Using 10mL syringes,
10mL deionized waters are slowly dropped into while stirring powder biased sample.Grinding pot is inserted afterwards and is ground in planetary ball mill instrument
Processing.Treatment conditions are：Rotating speed 300r/min. milling times are 1h.After the sample that ball milling instrument is ground is sieved through sieve, put
In atmosphere furnace roasting.Roasting condition is：N2+O2(20vol%)+H2O (10vol%), total flow 600mL/min.Heating rate is
5 DEG C/min, 600 DEG C of holding 3h are warming up to, then naturally near room temperature.Taking out sample, to be crushed to 20-40 mesh through tabletting standby, i.e.,
Obtain the 2wt%Ag/Al that dry ball milling prepares addition GaN structures2O3Catalyst.
Purify reaction condition：Be the same as Example 1.
Clean-up effect：
Concrete outcome is as shown in Figure 4.
Embodiment 6：
Catalyst preparation：Weigh 32 grams of AlOOH to add deionized water mixing mashing and stir, weigh 0.7875 gram
AgNO3Solid adds deionized water dissolving, and the solution of configuration is added among AlOOH slurries.Then AlN solids are weighed：0.84
Gram and delivered as among above-mentioned slurries and continued to stir 1h.Resulting solution is inserted in revolving bottle, heating under reduced pressure rotary evaporation
To 60 DEG C.Drying sample is removed in 120 degree of oven dried overnights, sample is taken into atmosphere furnace roasting afterwards.Roasting condition is：N2
+O2(20vol%)+NH3 (0.12vol%), total flow 600mL/min.Heating rate is 1 DEG C/min, is warming up to 600 DEG C of holdings
3h, then naturally near room temperature.Taking out sample, to be crushed to 20-40 mesh through tabletting standby, that is, obtains conventional impregnation method addition AlN knots
The 2wt%Ag/Al of structure2O3Catalyst.
Purify reaction condition：Be the same as Example 1.
Clean-up effect：
Concrete outcome is as shown in Figure 5.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and being open.
Claims (42)
1. a kind of Ag/Al2O3Catalyst, it is made up of carrier and active component, and the carrier is Al2O3, the activearm subpackage
The first active component and the second active component are included, the first active component is Ag2O, the presoma of the second active component is GaN, AlN
Or in InN any one or at least two mixture；In terms of metal Ag mass, the first active component A g2O is carrier
Al2O3Quality 0 ~ 10% and not include 0；The quality of second active component presoma is 30 with metal Ag mass ratio:1~1:1.
2. catalyst as claimed in claim 1, it is characterised in that the presoma of second active component be GaN or/and
InN。
3. catalyst as claimed in claim 2, it is characterised in that the presoma of second active component is GaN.
4. catalyst as claimed in claim 1, it is characterised in that in terms of metal Ag mass, the first active component A g2O is carrier
Al2O32 ~ 4wt% of quality.
5. catalyst as claimed in claim 1, it is characterised in that the quality of the second active component presoma and metal Ag matter
Amount is than being 5:1~1:1.
6. catalyst as claimed in claim 5, it is characterised in that the quality of the second active component presoma and metal Ag matter
Amount is than being 2:1.
7. a kind of Ag/Al as claimed in claim 1 or 22O3The preparation method of catalyst, methods described is infusion process, including with
Lower step：
By the first active component A g2The aqueous solution of O presomas, carrier Al2O3Before the aqueous slurry of presoma and the second active component
Body mixing is driven, obtained slurries are rotated, drying is calcined and crushed, obtains Ag/Al2O3Catalyst.
8. method as claimed in claim 7, it is characterised in that the described method comprises the following steps：
（1）By the first active component A g2The aqueous solution of O presomas and carrier Al2O3The aqueous slurry of presoma is well mixed；
（2）Second active component presoma is added into step（1）In in obtained slurries, obtained slurries are rotated, dried, roasting
Burn and crush, obtain Ag/Al2O3Catalyst.
9. method as claimed in claim 7, it is characterised in that the carrier Al2O3Presoma is boehmite or/and work
Property aluminum oxide.
10. method as claimed in claim 7, it is characterised in that the first active component presoma is AgNO3、Ag2SO4、
C2H3AgO2Or Ag2In O any one or at least two mixture.
11. method as claimed in claim 7, it is characterised in that after after uniform stirring at least 1h, then obtained slurries are revolved
Steam.
12. method as claimed in claim 7, it is characterised in that gained slurries are transferred in revolving bottle, vacuum decompression heating
It is 30 ~ 90 DEG C to rotate water-bath.
13. method as claimed in claim 12, it is characterised in that vacuum decompression heating revolving water-bath is 60 DEG C.
14. method as claimed in claim 7, it is characterised in that the drying temperature is 100 ~ 180 DEG C, the drying time
For 6-36h.
15. method as claimed in claim 14, it is characterised in that drying temperature is 120 DEG C, the drying time is 12h.
16. method as claimed in claim 7, it is characterised in that heating rate is 1 DEG C ~ 20 DEG C/min, roasting in roasting process
Temperature is 600 ~ 800 DEG C.
17. method as claimed in claim 7, it is characterised in that the atmosphere of roasting is O2、H2O or NH3At least one of and N2
Mixed gas.
18. method as claimed in claim 7, it is characterised in that the atmosphere of roasting is N2And O2Mixed gas, N2And H2O's
Mixed gas, N2、H2O and O2Mixed gas, or N2、NH3And H2Any one in O mixed gas.
19. method as claimed in claim 18, it is characterised in that N2And O2Mixed gas in, O2Volume content be 0 ~
20vol%, and do not include 0.
20. method as claimed in claim 18, it is characterised in that N2And H2In O mixed gas, H2O volume content be 1 ~
20vol%。
21. method as claimed in claim 18, it is characterised in that N2、H2O and O2Mixed gas in, H2O volume content is
0 ~ 10vol% and not include 0, O2Volume content for 0 ~ 20vol% and not include 0.
22. method as claimed in claim 18, it is characterised in that N2、NH3And H2In O mixed gas, NH3Volume content be 0
~ 0.12vol% and not include 0, H2O volume content is 0 ~ 10vol% and not including 0.
23. method as claimed in claim 7, it is characterised in that calcination atmosphere range of flow is 500 ~ 1000mL/min.
24. method as claimed in claim 7, it is characterised in that be ground into the particle of 20 ~ 40 mesh.
25. a kind of Ag/Al as claimed in claim 1 or 22O3The preparation method of catalyst, methods described is dry ball milling, bag
Include following steps：
（1）By carrier Al2O3Presoma, the first active component A g2O presomas and the mixing of the second active component presoma, Ran Houjia
Water soaks biased sample；
（2）By step（1）Obtained biased sample carries out ball milling, roasting and crushing, obtains Ag/Al2O3Catalyst.
26. method as claimed in claim 25, it is characterised in that the described method comprises the following steps：
（1）By carrier Al2O3Presoma, the first active component A g2O presomas and the second active component presoma sequentially add ball
In grinding jar, then adding water soaks biased sample；
（2）By step（1）Obtained biased sample carries out ball milling, roasting and crushing, obtains Ag/Al2O3Catalyst.
27. method as claimed in claim 25, it is characterised in that the carrier Al2O3Presoma be boehmite or/and
Activated alumina.
28. method as claimed in claim 25, it is characterised in that the first active component presoma is AgNO3、Ag2SO4、
C2H3AgO2Or Ag2In O any one or at least two mixture.
29. method as claimed in claim 25, it is characterised in that the ball milling is carried out in ball grinder.
30. method as claimed in claim 29, it is characterised in that have Ф 10mm bead 5 ~ 30, Ф in the ball grinder
20mm bead 0 ~ 20.
31. method as claimed in claim 25, it is characterised in that the ball milling is carried out in planetary ball mill.
32. method as claimed in claim 25, it is characterised in that the rotational speed of ball-mill is 100 ~ 400r/min, Ball-milling Time
For 1 ~ 9h.
33. method as claimed in claim 25, it is characterised in that heating rate is 1 DEG C ~ 20 DEG C/min, roasting in roasting process
It is 600 ~ 800 DEG C to burn temperature.
34. method as claimed in claim 25, it is characterised in that the atmosphere of roasting is O2、H2O or NH3At least one of with
N2Mixed gas.
35. method as claimed in claim 25, it is characterised in that the atmosphere of roasting is N2And O2Mixed gas, N2And H2O's
Mixed gas, N2、H2O and O2Mixed gas, or N2、NH3And H2Any one in O mixed gas.
36. method as claimed in claim 35, it is characterised in that N2And O2Mixed gas in, O2Volume content be 0 ~
20vol%, and do not include 0.
37. method as claimed in claim 35, it is characterised in that N2And H2In O mixed gas, H2O volume content be 1 ~
20vol%。
38. method as claimed in claim 35, it is characterised in that N2、H2O and O2Mixed gas in, H2O volume content is
0 ~ 10vol% and not include 0, O2Volume content for 0 ~ 20vol% and not include 0.
39. method as claimed in claim 35, it is characterised in that N2、NH3And H2In O mixed gas, NH3Volume content be 0
~ 0.12vol% and not include 0, H2O volume content is 0 ~ 10vol% and not including 0.
40. method as claimed in claim 25, it is characterised in that calcination atmosphere range of flow is 500 ~ 1000mL/min.
41. method as claimed in claim 25, it is characterised in that be ground into the particle of 20 ~ 40 mesh.
42. a kind of Ag/Al as claimed in claim 1 or 22O3The purposes of catalyst, it is used for HC-SCR reactions.
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