CN109499608A - A kind of Cu-SSZ-13/ porous ceramic catalyst and the preparation method and application thereof - Google Patents
A kind of Cu-SSZ-13/ porous ceramic catalyst and the preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to catalyst preparation technical fields, and in particular to a kind of Cu-SSZ-13/ porous ceramic catalyst, and preparation method is further disclosed, and the application in motor-vehicle tail-gas denitration field.Cu-SSZ-13/ porous ceramic catalyst of the present invention, it is that molecular sieve coating is prepared on a catalyst support directly with in-situ synthesis, direct in-situ synthesizes SSZ-13 molecular sieve i.e. on porous ceramics, so that SSZ-13 molecular sieve obtained is directly chemically combined with selected cellular ceramic substrate in the form of chemical bond, to be grown on carrier securely.Cu-SSZ-13/ porous ceramic catalyst of the present invention has the advantage that catalyst coat is secured, active material load capacity is high, with the advantage that catalytic eliminating NOx activity is high and water resistant heat ageing activity is good, can be widely applied to motor-vehicle tail-gas denitrating technique.
Description
Technical field
The invention belongs to catalyst preparation technical fields, and in particular to a kind of Cu-SSZ-13/ porous ceramic catalyst, and
Preparation method, and the application in motor-vehicle tail-gas denitration field are further disclosed.
Background technique
Currently, global Ecological Environment Crisis is got worse, and exhaust gas from diesel vehicle always is urban air pollution source
One of, the nitrogen oxides contained in tail gas is even more one of the major source for polluting urban atmosphere.And showing with human lives
Generationization and urbanization, automobile using more and more common, the discharge amount of tail gas is increasing, causes to atmospheric environment serious
Pollution.
Currently, most widely used purification of nitrogen oxides technology is exactly to use HN in world wide3Carry out selective catalysis also
Original, i.e. HN3- SCR (Selective Catalytic Reduction, SCR) technology, i.e., using ammonia as reducing agent harmful
Nitrous oxides selectivity catalysis be reduced to harmless N2And H2O。NH3SCR technology is initially applied in stationary source denitration field, mesh
It is preceding to be successfully introduced motor-vehicle tail-gas process field, and be used widely.NH3SCR technology is considered as most having at present
One of motor-vehicle tail-gas denitration technology of prospect, the core of technology are the research and development of efficient stable catalyst.Currently, industrialization
The SCR catalyst of application is mainly WO3Or MoO3The V of doping2O5/TiO2Catalyst.But there is such as have for the catalyst
There is the V of bio-toxicity2O5It falls off in use, V under high temperature2O5Volatilization and TiO2Crystal transfer cause thermal stability poor
The defects of.Therefore, the direction that the environmental-friendly catalyst of new efficient stable is SCR catalyst development is developed.
In recent years, Cu-SSZ-13 catalyst due to catalytic activity height, good hydrothermal stability, anti-HCs poisoning capability it is strong, with
And excellent denitration activity and receive significant attention and be used for denitration reaction.But in industrial application, Cu-SSZ-13 catalyst
It has to be prepared into integral catalyzer and be applied, be further processed into honeycombed catalyst such as to improve catalysis and heat transfer effect
Rate.If Chinese patent CN102099293B is to report Cu-SSZ-13 catalyst coated using the method for coating in porous pottery
Scheme of the configuration catalyst for denitration reaction is prepared on porcelain, and achieves efficient catalytic activity.But the program
In the catalyst that is prepared with coating process, not only the coated weight of catalyst is few, and the intensity of coating is also slightly poor, and exists easy
The case where falling off, this is also the technical problem for restricting cladding process and preparing configuration catalyst.As it can be seen that developing a kind of catalyst knot
The Cu-SSZ-13 configuration catalyst that resultant is high and carrier bond strength is high has product for motor-vehicle tail-gas denitrating technique
The meaning of pole.
Summary of the invention
For this purpose, porous technical problem to be solved by the present invention lies in a kind of in-situ synthesis preparation Cu-SSZ-13/ is provided
The method of ceramic catalyst, to solve, Cu-SSZ-13 supported catalyst load capacity and bond strength are poor in the prior art
Problem；
Second Problem to be solved by this invention is that the Cu-SSZ-13/ for providing above-mentioned in-situ synthesis preparation is porous
Ceramic catalyst, and Cu-SSZ-13/ porous ceramic catalyst the answering in motor-vehicle tail-gas denitration field is further disclosed
With.
In order to solve the above technical problems, a kind of side for preparing Cu-SSZ-13/ porous ceramic catalyst of the present invention
Method includes the following steps:
(1) silicon source material, silicon source material and organic formwork agent are taken, preparation obtains molecular sieve mother liquor, and adjusts pH value to alkali
Property, it is spare；
(2) it takes cellular ceramic substrate to mix with the molecular sieve mother liquor, carries out crystallization；
(3) by cellular ceramic substrate described after Crystallizing treatment and copper source material carry out ion exchange to get.
Preferably, in the step (1), in the molecular sieve mother liquor:
The molar ratio of Al is 10-50:1 in Si and silicon source material in the silicon source material, and preferred 15-35:1；
The molar ratio of Si and the organic formwork agent is 0.5-1.5:1 in the silicon source material, and preferred 0.7-1.0:1；
The molar ratio of the silicon source material Si and deionized water is 1:2-6, and preferably 1:3-4.
Specifically, in the step (1), in the molecular sieve mother liquor:
The silicon source material includes SiO2, one or more of ethyl orthosilicate or silicic acid mixture；
Source of aluminium material includes aluminium isopropoxide, aluminum sulfate, sodium metaaluminate, aluminium hydroxide, aluminum aluminum sulfate, aluminium chloride or oxygen
Change the mixture of one or more of aluminium；
The organic formwork agent includes N, N, N- trimethyl -1- adamantyl ammonium chloride, N, N, N- trimethyl -1- adamantane
Base ammonium bromide, N, N, N- trimethyl -1- adamantyl ammonium iodide, N, N, N- trimethyl -1- adamantyl ammonium hydroxide, tetramethyl
The mixture of one or more of ammonium hydroxide, choline chloride or triethylamine.
Preferably, in the step (1), the pH value of the molecular sieve mother liquor is controlled as 10-14, and preferable ph 13-14.
Specifically, in the step (2), the cellular ceramic substrate be hole density 200-600cpsi (per square inch
Hole count) and wall thickness be 2-6.5mil porous ceramics.
Preferably, in the step (2), the cellular ceramic substrate include one of cordierite, SiC, aluminium oxide or
A variety of mixtures.
It more preferably, further include the dust technology with mass content for 15-20wt%, in 70-90 DEG C in the step (2)
At a temperature of to the cellular ceramic substrate carry out pretreatment the step of.
More preferably, preferred 80-85 DEG C of the reaction temperature of the immersion pre-treatment step, the immersion pre-treatment step it is anti-
It is 1-3h between seasonable, and preferred 2h.
More preferably, in the step (2), the temperature for controlling the crystallization steps is 140-180 DEG C, and preferred 165-175
℃；The time for controlling the crystallization steps is 1-7 days, and preferably 3-5 days.
Specifically, in the step (3):
Copper source material includes one or more of copper sulphate, copper acetate, copper nitrate, copper chloride or cuprammonium complex
Mixture；
The concentration of Cu ion in copper source material is controlled as 0.025-1.5mol/l, and preferred 0.5-1mol/l.
Preferably, in the step (3), the temperature for controlling the ion-exchange step is 25-95 DEG C, and preferred 50-75
℃；The time of the ion-exchange step is controlled as 0.5-3h, and preferred 1-1.5h.
It more preferably, further include washing the cellular ceramic substrate after Crystallizing treatment to neutrality in the step (3),
And the step of through high-temperature roasting.
Specifically, the temperature for controlling the high temperature firing steps is 200-600 DEG C, and preferably 500-600 DEG C；Described in control
The time of high temperature firing steps is 1-4h, and preferably 2.5-3.5h.
The invention also discloses the Cu-SSZ-13/ porous ceramic catalysts being prepared by the method.
The invention also discloses the Cu-SSZ-13/ porous ceramic catalysts in motor-vehicle tail-gas denitration field
Using.
Cu-SSZ-13/ porous ceramic catalyst of the present invention is directly made on a catalyst support with in-situ synthesis
Standby molecular sieve coating, i.e., direct in-situ synthesizes SSZ-13 molecular sieve on porous ceramics so that SSZ-13 molecular sieve obtained with
The form of chemical bond is directly chemically combined with selected cellular ceramic substrate, to be grown on carrier securely.This hair
The bright Cu-SSZ-13/ porous ceramic catalyst has the advantage that catalyst coat is secured, active material load capacity is high, has
The advantage that catalytic eliminating NOx activity is high and water resistant heat ageing activity is good, can be widely applied to motor-vehicle tail-gas denitrating technique.
The preparation method of Cu-SSZ-13/ porous ceramic catalyst of the present invention is sieved with in-situ synthesis binding molecule and is applied
Layer, entire technical process is simple and easy, and preparation time is short, can carry out industrialization large-scale production.
Specific embodiment
Embodiment 1
The present embodiment provides a kind of preparation methods of Cu-SSZ-13/ porous ceramic catalyst, specifically comprise the following steps:
(1) taking ethyl orthosilicate is silicon source material, aluminium isopropoxide is silicon source material, N, N, N- trimethyl -1- adamantyl
Ammonium hydroxide is organic formwork agent；Above-mentioned silicon source material, organic formwork agent and water are mixed, and described being stirring evenly and then adding into
Silicon source material, the mol ratio for controlling above-mentioned each component is SiO2: Al2O3: C13H25NO:H2O=30:1:24:120 adds hydrogen
Sodium oxide molybdena adjusts mixed liquor pH value 13-14, molecular sieve mother liquor needed for being made, and is beaten mixed liquor repeatedly using mechanical stirring device
Slurry carries out emulsification 2h, spare；
(2) take cellular cellular ceramic substrate cordierite (specification: 400cpsi, 6.5mil) be cut into 10mm × 10mm ×
The square of 10mm size is blocky, is then soaked in the dilute nitric acid solution of 15v/v%, is pre-processed at 80 DEG C
Then neutrality is washed with deionized in 2h, stand-by after drying；
Molecular sieve mother liquor after above-mentioned emulsification is placed in hydrothermal reaction kettle together with the pretreated cordierite and is mixed
It closes, is carried out Crystallizing treatment 3 days at 170 DEG C；
(3) cordierite after taking out crystallization is washed to neutrality, and carries out high-temperature roasting 3 hours at 600 DEG C to remove mould
Plate agent；And by after roasting the cordierite leaching set in the copper acetate solution of 1mol/l, using ion-exchange in 60 DEG C into
Row ion-exchange reactions 1h, is cooled to room temperature taking-up cordierite, is put into oven drying after being cleaned multiple times with deionized water, then weight
Multiple above-mentioned ion-exchange step 3 times, obtain Cu-SSZ-13/ cordierite catalyst.Measuring copper content in gained catalyst is
2.75wt% or so.
Embodiment 2
The present embodiment provides a kind of preparation methods of Cu-SSZ-13/ porous ceramic catalyst, specifically comprise the following steps:
(1) taking ethyl orthosilicate is silicon source material, aluminium isopropoxide is silicon source material, N, N, N- trimethyl -1- adamantyl
Ammonium hydroxide is organic formwork agent；Above-mentioned silicon source material, organic formwork agent and water are mixed, and described being stirring evenly and then adding into
Silicon source material, the mol ratio for controlling above-mentioned each component is SiO2: Al2O3: C13H25NO:H2O=30:1:24:120 adds hydrogen
Sodium oxide molybdena adjusts mixed liquor pH value 13-14, molecular sieve mother liquor needed for being made, and is beaten mixed liquor repeatedly using mechanical stirring device
Slurry carries out emulsification 2h, spare；
(2) take cellular cellular ceramic substrate cordierite (specification: 400cpsi, 6.5mil) be cut into 10mm × 10mm ×
The square of 10mm size is blocky, is then soaked in the dilute nitric acid solution of 20v/v%, is pre-processed at 85 DEG C
Then neutrality is washed with deionized in 3h, stand-by after drying；
Molecular sieve mother liquor after above-mentioned emulsification is placed in hydrothermal reaction kettle together with the pretreated cordierite and is mixed
It closes, is carried out Crystallizing treatment 3 days at 170 DEG C；
(3) cordierite after taking out crystallization is washed to neutrality, and carries out high-temperature roasting 3 hours at 600 DEG C to remove mould
Plate agent；And by after roasting the cordierite leaching set in the copper acetate solution of 1mol/l, using ion-exchange in 75 DEG C into
Row ion-exchange reactions 1.5h, is cooled to room temperature taking-up cordierite, is cleaned multiple times with deionized water and is put into oven drying, in repetition
It states ion-exchange step 3 times, obtains Cu-SSZ-13/ cordierite catalyst.Measuring copper content in gained catalyst is 2.5wt%
Left and right.
Embodiment 3
The present embodiment provides a kind of preparation methods of Cu-SSZ-13/ porous ceramic catalyst, specifically comprise the following steps:
(1) taking ethyl orthosilicate is silicon source material, aluminum sulfate is silicon source material, N, N, N- trimethyl -1- adamantyl hydrogen
Amine-oxides are organic formwork agent；Above-mentioned silicon source material, organic formwork agent and water are mixed, and are being stirring evenly and then adding into the aluminium
Source material, the mol ratio for controlling above-mentioned each component is SiO2: Al2O3: C13H25NO:H2O=30:1:24:120 (is converted to SiO2
And Al2O3Meter), it adds sodium hydroxide and adjusts pH value 13-14, molecular sieve mother liquor needed for being made, and will using mechanical stirring device
Mixed liquor is beaten repeatedly carries out emulsification 2h, spare；
(2) take cellular cellular ceramic substrate cordierite (specification: 600cpsi, 4mil) be cut into 10mm × 10mm ×
The square of 10mm size is blocky, is then soaked in the dilute nitric acid solution of 20v/v%, carries out lower pretreatment at 85 DEG C
Then neutrality is washed with deionized in 3h, stand-by after drying；
Molecular sieve mother liquor after above-mentioned emulsification is placed in hydrothermal reaction kettle together with the pretreated cordierite and is mixed
It closes, is carried out Crystallizing treatment 3 days at 170 DEG C；
(3) cordierite after taking out crystallization is washed to neutrality, and carries out high-temperature roasting 3 hours at 600 DEG C to remove mould
Plate agent；And by after roasting the cordierite leaching set in the copper acetate solution of 1mol/l, using ion-exchange in 50 DEG C into
Row ion-exchange reactions 2h, is cooled to room temperature taking-up cordierite, is cleaned multiple times with deionized water and is put into oven drying, repeats above-mentioned
Ion-exchange step 3 times, obtain Cu-SSZ-13/ cordierite catalyst.Measuring copper content in gained catalyst is 2.5wt% left
It is right.
Embodiment 4
The present embodiment provides a kind of preparation methods of Cu-SSZ-13/ porous ceramic catalyst, specifically comprise the following steps:
(1) using silica as silicon source material, sodium metaaluminate is silicon source material, N, N, N- trimethyl -1- adamantyl hydrogen
Amine-oxides are template；Above-mentioned silicon source material, organic formwork agent and water are mixed, and are being stirring evenly and then adding into source of aluminium material
Material, the mol ratio for controlling above-mentioned each component is SiO2: Al2O3: C13H25NO:H2O=30:2:24:120 adds sodium hydroxide
Mixed liquor pH value 13-14 is adjusted, molecular sieve mother liquor needed for being made, and mixed liquor is beaten using mechanical stirring device by progress repeatedly
2h is emulsified, it is spare；
(2) take cellular cellular ceramic substrate cordierite (specification: 600cpsi, 4mil) be cut into 10mm × 10mm ×
The square of 10mm size is blocky, is then soaked in the dilute nitric acid solution of 20v/v%, is pre-processed at 85 DEG C
Then neutrality is washed with deionized in 3h, stand-by after drying；
Molecular sieve mother liquor after above-mentioned emulsification is placed in hydrothermal reaction kettle together with the pretreated cordierite and is mixed
It closes, is carried out Crystallizing treatment 3 days at 170 DEG C；
(3) cordierite after taking out crystallization is washed to neutrality, and carries out high-temperature roasting 3 hours at 600 DEG C to remove mould
Plate agent；And by after roasting the cordierite leaching set in the copper acetate solution of 1mol/l, using ion-exchange in 95 DEG C into
Row ion-exchange reactions 0.5h, is cooled to room temperature taking-up cordierite, is cleaned multiple times with deionized water and is put into oven drying, in repetition
It states ion-exchange step 3 times, obtains Cu-SSZ-13/ cordierite catalyst.Measuring copper content in gained catalyst is 3.0wt%
Left and right.
Embodiment 5
The present embodiment provides a kind of preparation methods of Cu-SSZ-13/ porous ceramic catalyst, specifically comprise the following steps:
(1) taking silicic acid is silicon source material, aluminium hydroxide is silicon source material, N, N, N- trimethyl -1- adamantyl ammonium chloride
For organic formwork agent；Above-mentioned silicon source material, organic formwork agent and water are mixed, and are being stirring evenly and then adding into source of aluminium material
Material controls each component molar ratio are as follows: the SiO2: Al2O3=50:1, the SiO2: organic formwork agent=1.5:1, the SiO2:
Water=1:5 adds sodium hydroxide and adjusts mixed liquor pH value 10-11, molecular sieve mother liquor needed for being made, and is filled using mechanical stirring
It sets for mixed liquor to be beaten repeatedly and carries out emulsification 2h, it is spare；
(2) cellular cellular ceramic substrate SiC (specification: 400cpsi, 2mil) is taken to be cut into 10mm × 10mm × 10mm big
Small square is blocky, is then soaked in the dilute nitric acid solution of 15v/v%, pretreatment 3h is carried out at 70 DEG C, then
Neutrality is washed with deionized, it is stand-by after drying；
Molecular sieve mother liquor after above-mentioned emulsification is placed in hydrothermal reaction kettle together with the pretreated SiC and is mixed,
It is carried out Crystallizing treatment 4 days at 175 DEG C；
(3) SiC after taking out crystallization is washed to neutrality, and carries out high-temperature roasting 4 hours at 200 DEG C to remove removing template
Agent；And the SiC leaching after roasting is set in the copper-bath of 1.5mol/l, carried out using ion-exchange in 25 DEG C from
Sub- exchange reaction 3h is cooled to room temperature and takes out SiC, is cleaned multiple times with deionized water and is put into oven drying, repeats above-mentioned ion and hands over
Step 3 time is changed, Cu-SSZ-13/SiC catalyst is obtained.
Embodiment 6
The present embodiment provides a kind of preparation methods of Cu-SSZ-13/ porous ceramic catalyst, specifically comprise the following steps:
(1) taking ethyl orthosilicate is silicon source material, aluminum aluminum sulfate is silicon source material, triethylamine is organic formwork agent；It will be upper
Silicon source material, organic formwork agent and water mixing are stated, and is being stirring evenly and then adding into source of aluminium material, controls each component molar ratio
Are as follows: the SiO2: Al2O3=10:1, the SiO2: organic formwork agent=0.5:1, the SiO2: water=1:3 adds hydrogen-oxygen
Change sodium and adjusts mixed liquor pH value 11-12, molecular sieve mother liquor needed for being made, and be beaten mixed liquor repeatedly using mechanical stirring device
Emulsification 2h is carried out, it is spare；
(2) take cellular cellular ceramic substrate aluminium oxide (specification: 300cpsi, 4mil) be cut into 10mm × 10mm ×
The square of 10mm size is blocky, is then soaked in the dilute nitric acid solution of 18v/v%, is pre-processed at 90 DEG C
Then neutrality is washed with deionized in 1h, stand-by after drying；
Molecular sieve mother liquor after above-mentioned emulsification is placed in hydrothermal reaction kettle together with the pretreated aluminium oxide and is mixed
It closes, is carried out Crystallizing treatment 5 days at 165 DEG C；
(3) aluminium oxide after taking out crystallization is washed to neutrality, and carries out high-temperature roasting 2.5 hours at 500 DEG C with removal
Template；And set the aluminium oxide leaching after roasting in the copper nitrate solution of 0.5mol/l, using ion-exchange in 60
DEG C carry out ion-exchange reactions 2h, be cooled to room temperature taking-up aluminium oxide, be cleaned multiple times with deionized water and be put into oven drying, repeat
Above-mentioned ion-exchange step 3 times, obtains Cu-SSZ-13/ aluminium oxide catalyst.
Embodiment 7
The present embodiment provides a kind of preparation methods of Cu-SSZ-13/ porous ceramic catalyst, specifically comprise the following steps:
(1) taking silica is silicon source material, aluminium oxide is silicon source material, choline chloride is organic formwork agent；It will be above-mentioned
Silicon source material, organic formwork agent and water mixing, and it is being stirring evenly and then adding into source of aluminium material, control each component molar ratio
Are as follows: the SiO2: Al2O3=15:1, the SiO2: organic formwork agent=0.7:1, it is described to have SiO2: water=1:3 adds hydrogen
Sodium oxide molybdena adjusts mixed liquor pH value 13-14, molecular sieve mother liquor needed for being made, and is beaten mixed liquor repeatedly using mechanical stirring device
Slurry carries out emulsification 2h, spare；
(2) take cellular cellular ceramic substrate cordierite (specification: 300cpsi, 4mil) be cut into 10mm × 10mm ×
The square of 10mm size is blocky, is then soaked in the dilute nitric acid solution of 18v/v%, is pre-processed at 85 DEG C
Then neutrality is washed with deionized in 2h, stand-by after drying；
Molecular sieve mother liquor after above-mentioned emulsification is placed in hydrothermal reaction kettle together with the pretreated cordierite and is mixed
It closes, is carried out Crystallizing treatment 1 day at 180 DEG C；
(3) cordierite after taking out crystallization is washed to neutrality, and carries out high-temperature roasting 3.5 hours at 600 DEG C with removal
Template；And by after roasting the cordierite leaching set in the copper chloride solution of 0.025mol/l, using ion-exchange in
60 DEG C of progress ion-exchange reactions 2h, are cooled to room temperature taking-up cordierite, are cleaned multiple times with deionized water and are put into oven drying, weight
Multiple above-mentioned ion-exchange step 3 times, obtain Cu-SSZ-13/ cordierite catalyst.
Embodiment 8
The present embodiment provides a kind of preparation methods of Cu-SSZ-13/ porous ceramic catalyst, specifically comprise the following steps:
(1) taking silica is silicon source material, aluminium chloride is silicon source material, tetramethylammonium hydroxide is organic formwork agent；
Above-mentioned silicon source material, organic formwork agent and water are mixed, and are being stirring evenly and then adding into source of aluminium material, controls each group centimorgan
That ratio are as follows: the SiO2: Al2O3=35:1, the SiO2: organic formwork agent=1.0:1, the SiO2: water=1:4 adds
Sodium hydroxide adjusts mixed liquor pH value 13-14, molecular sieve mother liquor needed for being made, and using mechanical stirring device by mixed liquor repeatedly
Mashing carries out emulsification 2h, spare；
(2) cellular cellular ceramic substrate cordierite (600cpsi, 2mil) is taken to be cut into 10mm × 10mm × 10mm size
Square it is blocky, be then soaked in the dilute nitric acid solution of 18v/v%, pretreatment 2h carried out at 80 DEG C, is then used
Deionized water is washed to neutrality, stand-by after drying；
Molecular sieve mother liquor after above-mentioned emulsification is placed in hydrothermal reaction kettle together with the pretreated cordierite and is mixed
It closes, is carried out Crystallizing treatment 7 days at 140 DEG C；
(3) cordierite after taking out crystallization is washed to neutrality, and carries out high-temperature roasting 3 hours at 600 DEG C to remove mould
Plate agent；And by after roasting the cordierite leaching set in the cuprammonium complex solution of 1.0mol/l, using ion-exchange in
60 DEG C of progress ion-exchange reactions 2h, are cooled to room temperature taking-up cordierite, are cleaned multiple times with deionized water and are put into oven drying, weight
Multiple above-mentioned ion-exchange step 3 times, obtain Cu-SSZ-13/ cordierite catalyst.
Experimental example
1, the catalytic denitration performance of catalyst
Catalyst prepared by above-described embodiment 1-8 is investigated into its denitration performance, experiment condition is as follows: 500ppm NO,
500ppm NH3, 10%O2, 10%H2O controls volume space velocity 80000h-1, it is as shown in table 1 below to test its catalytic performance result.
The catalytic denitration performance of 1 catalyst of table
| Embodiment | Temperature (DEG C) | NO conversion ratio (%) | Temperature (DEG C) | NO conversion ratio (%) |
| 1 | 200 | 78 | 400 | 88 |
| 2 | 200 | 74 | 400 | 85 |
| 3 | 200 | 65 | 400 | 82 |
| 4 | 200 | 70 | 400 | 80 |
| 5 | 200 | 60 | 400 | 70 |
| 6 | 200 | 63 | 400 | 75 |
| 7 | 200 | 55 | 400 | 60 |
| 8 | 200 | 61 | 400 | 69 |
From upper table data as it can be seen that the catalytic denitration performance for the Cu-SSZ-13/ porous ceramic catalyst that the present invention is prepared
Preferably.
2, the catalytic denitration performance of aging rear catalyst
In practical applications, catalyst anti-aging property index is also extremely important, therefore will test it after catalyst aging
Performance.
Hydrothermal aging conditions: with 10%H at 800 DEG C2O pre-processes 50h.
The catalytic performance of catalyst after test aging see the table below shown in 2.
The catalytic performance of 2 aging rear catalyst of table
From upper table data as it can be seen that the Cu-SSZ-13/ porous ceramic catalyst that the present invention is prepared, even if after weathering
Still there is preferable catalytic denitration performance.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (14)
1. a kind of method for preparing Cu-SSZ-13/ porous ceramic catalyst, which comprises the steps of:
(1) silicon source material, silicon source material, organic formwork agent and deionized water are taken, preparation obtains molecular sieve mother liquor, and adjusts pH value
It is spare to alkalinity；
(2) it takes cellular ceramic substrate to mix with the molecular sieve mother liquor, carries out crystallization；
(3) by cellular ceramic substrate described after Crystallizing treatment and copper source material carry out ion exchange to get.
2. the method according to claim 1 for preparing Cu-SSZ-13/ porous ceramic catalyst, which is characterized in that the step
Suddenly in (1), in the molecular sieve mother liquor:
The molar ratio of Si and Al in silicon source material is 10-50:1 in the silicon source material；
The molar ratio of Si and the organic formwork agent is 0.5-1.5:1 in the silicon source material；
The molar ratio of Si and deionized water is 1:2-6 in the silicon source material.
3. the method according to claim 1 or 2 for preparing Cu-SSZ-13/ porous ceramic catalyst, which is characterized in that institute
It states in step (1), in the molecular sieve mother liquor:
The silicon source material includes SiO2, one or more of ethyl orthosilicate or silicic acid mixture；
Source of aluminium material includes aluminium isopropoxide, aluminum sulfate, sodium metaaluminate, aluminium hydroxide, aluminum aluminum sulfate, aluminium chloride or aluminium oxide
One or more of mixture；
The organic formwork agent includes N, N, N- trimethyl -1- adamantyl ammonium chloride, N, N, N- trimethyl -1- adamantane bromide
Change ammonium, N, N, N- trimethyl -1- adamantyl ammonium iodide, N, N, N- trimethyl -1- adamantyl ammonium hydroxide, tetramethyl hydrogen-oxygen
Change the mixture of one or more of ammonium, choline chloride or triethylamine.
4. the method according to claim 1-3 for preparing Cu-SSZ-13/ porous ceramic catalyst, feature exist
In in the step (1), the pH value for controlling the molecular sieve mother liquor is 10-14.
5. the method according to claim 1-4 for preparing Cu-SSZ-13/ porous ceramic catalyst, feature exist
In in the step (2), the cellular ceramic substrate is hole density in 200-600cpsi and wall thickness is the porous of 2-6.5mil
Ceramics.
6. the method according to claim 5 for preparing Cu-SSZ-13/ porous ceramic catalyst, which is characterized in that the step
Suddenly in (2), the cellular ceramic substrate includes one of cordierite, SiC, aluminium oxide or a variety of mixtures.
7. the method according to claim 5 or 6 for preparing Cu-SSZ-13/ porous ceramic catalyst, which is characterized in that institute
It states in step (2), further includes the dust technology with mass content for 15-20wt%, to the porous pottery at a temperature of 70-90 DEG C
Ceramic carrier carries out the step of pretreatment.
8. the method according to claim 1-7 for preparing Cu-SSZ-13/ porous ceramic catalyst, feature exist
In in the step (2), the temperature for controlling the crystallization steps is 140-180 DEG C, and the time for controlling the crystallization steps is 1-
7 days.
9. the method according to claim 1-8 for preparing Cu-SSZ-13/ porous ceramic catalyst, feature exist
In in the step (3):
Copper source material includes the mixed of one or more of copper sulphate, copper acetate, copper nitrate, copper chloride or cuprammonium complex
Close object；
The concentration for controlling Cu ion in copper source material is 0.025-1.5mol/l.
10. the method according to claim 9 for preparing Cu-SSZ-13/ porous ceramic catalyst, which is characterized in that described
In step (3), the temperature for controlling the ion-exchange step is 25-95 DEG C, and the time for controlling the ion-exchange step is
0.5-3h。
11. -10 described in any item methods for preparing Cu-SSZ-13/ porous ceramic catalyst according to claim 1, feature
It is, further includes washing the cellular ceramic substrate after Crystallizing treatment to neutrality, and roasted through high temperature in the step (3)
The step of burning.
12. the method according to claim 11 for preparing Cu-SSZ-13/ porous ceramic catalyst, which is characterized in that control
The temperature of the high temperature firing steps is 200-600 DEG C, and the time for controlling the high temperature firing steps is 1-4h.
13. the Cu-SSZ-13/ porous ceramic catalyst being prepared by any one of claim 1-12 the method.
14. application of the Cu-SSZ-13/ porous ceramic catalyst described in claim 13 in motor-vehicle tail-gas denitration field.
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