CN110078090A - A kind of modified Cu-SSZ-13 molecular sieve and its preparation method and application - Google Patents
A kind of modified Cu-SSZ-13 molecular sieve and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of modified Cu-SSZ-13 molecular sieves and its preparation method and application.Silicon source, alkali metal hydroxide, template, silicon source and water are mixed, starting sol is obtained；It will be roasted after starting sol hydrothermal crystallizing, obtain M-SSZ-13 molecular sieve；It is roasted after M-SSZ-13 molecular sieve is carried out ion-exchange reactions with ammonium salt, obtains H-SSZ-13 molecular sieve；Then it is roasted after carrying out ion-exchange reactions with cupric salt, obtains modified Cu-SSZ-13 molecular sieve.The Cu-SSZ-13 molecular sieve that the present invention passes through the different alkali metal hydroxide fabricated in situ different-shapes of addition.The present invention is directly added into the hydroxide of different alkali metal in the synthesis process, changes the pattern and grain size of molecular sieve while introducing alkali metal ion.The modified Cu-SSZ-13 molecular sieve crystallinity of gained of the invention is high, and pure phase is high, shows higher low temperature active and nitrogen selective in low-temperature denitration reaction.
Description
Technical field
The present invention relates to technical field of molecular sieve, and in particular to a kind of modified Cu-SSZ-13 molecular sieve and preparation method thereof
And application.
Background technique
Automobile is broadly divided into gasoline car, diesel vehicle and substitute fuel car, wherein it is the most universal with the usage amount of gasoline car, with
The resources such as global fossil fuel it is increasingly in short supply, increasing environmental pollution, diesel vehicle is because its fuel economy is good, power is strong, room temperature
Gas discharges less, highly-safe, service life is long and gradually by weighing High-Powered Vehicle (such as motorbus, large-sized truck) in terms of
Depending on.Diesel vehicle uses Lean Burning Technique, although HC, CO, CO2Discharge amount is low, but will lead to the nitrogen oxides NO in tail gasxRow
High-volume relatively high, this will become serious and restrict an important factor for diesel vehicle is promoted.
Exhaust gas from diesel vehicle post-processing technology mainly includes NO at presentxDirect catalytic decomposition technology, NOxStorage-reduction catalysis
Purification techniques (NSR), SCR technology (SCR) and plasma technique etc..Wherein SCR technology
Because it can more preferably remove NOxAnd the deep favor by numerous researchers.It is discharged in face of increasingly strict exhaust gas from diesel vehicle
Regulation, ammine selectivity catalytic reduction technology have excellent removing NO because of it within the scope of very wide temperaturexPerformance has obtained wide
General application.For NOxEmission control, gasoline car mainly passes through three-way catalyst simultaneously by CO, HC, NOxPurification.And diesel oil
The combustion mode of vehicle is different from gasoline car, and the oxygen content in tail gas is high, under these conditions, NOxReduction it is extremely difficult, pass
The three-way catalyst of system is no longer satisfied requirement.
SSZ-13 is a kind of Si-Al molecular sieve of chabazite structure, three-dimensional octatomic ring pore canal system, has superior hydro-thermal
Stability.Cu-SSZ-13 is that metallic copper is loaded to SSZ-13 molecular sieve, is had in catalytic oxidation-reduction reaction extraordinary
Catalytic performance.This kind of molecular sieve has the three-dimensional open-framework of octatomic ring, has very high specific surface area, has at low temperature very
High catalytic activity and hydrothermal stability, to NOxSelective catalytic reduction (SCR) have good activity, special N2Selection
Property, show wide use prospect and good potentiality to be exploited.But at 150 DEG C and hereinafter, the SCR activity of Cu-SSZ-13 still
So lower, the conversion ratio of NO can only achieve 20 ~ 40%, N2Selectivity generally below 80%.For current status, it would be desirable to do
It improves out.
Summary of the invention
The present invention is intended to provide a kind of modified Cu-SSZ-13 molecular sieve and its preparation method and application.It is provided by the invention
Preparation method is simple, and gained molecular sieve crystallinity is high, and pure phase is high, shown in low-temperature denitration reaction higher low temperature active and
Nitrogen selective, the NO conversion ratio at 150 DEG C is up to 60% ~ 70%, and nitrogen selective is up to 80 ~ 95%.
The present invention provides a kind of preparation methods of modified Cu-SSZ-13 molecular sieve, comprising the following steps:
1) silicon source, alkali metal hydroxide, template, silicon source and water are mixed, obtains starting sol；
2) it will be roasted after starting sol hydrothermal crystallizing, obtain M-SSZ-13 molecular sieve, the M is alkali metal；
3) it is roasted after M-SSZ-13 molecular sieve being carried out ion-exchange reactions with ammonium salt, obtains H-SSZ-13 molecular sieve；
4) it is roasted after H-SSZ-13 molecular sieve being carried out ion-exchange reactions with cupric salt, obtains modified Cu-SSZ-13 molecular sieve.
Preferably, source of aluminium is one or more of aluminum sulfate, aluminum nitrate, aluminium hydroxide, sodium metaaluminate；The alkali
Metal hydroxides is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide or cesium hydroxide.The template is excellent
It is selected as N, N, N- trimethyl -1- adamantane ammonium hydroxide (TMAdaOH), cuprammonium complex (Cu-TEPA)；The silicon source is preferably
One or more of silica solution, fumed silica, tetraethyl orthosilicate.
Preferably, the aluminium element in the step 1) in silicon source, alkali metal hydroxide, template, the silicon in silica solution
The molar ratio of element and water is 0.005 ~ 0.8: 0.05 ~ 0.6: 0.05 ~ 0.6: 1: 22 ~ 88.Further, in silicon source
Aluminium element, alkali metal hydroxide, template, the element silicon in silica solution and water molar ratio be 0.02 ~ 0.5: 0.15 ~
0.25 : 0.2~0.3 : 1 : 50~80。
Preferably, the temperature of hydrothermal crystallizing is 120 ~ 200 DEG C in the step 2, and the time of the hydrothermal crystallizing is 2 ~ 14
It；The temperature of the roasting is 300 ~ 700 DEG C, and the time of roasting is 2h ~ 15h.
Further, the temperature of the hydrothermal crystallizing is preferably 140 ~ 160 DEG C, and the time of the hydrothermal crystallizing is preferably 5 ~
8 days；The maturing temperature is preferably 500 ~ 600 DEG C.
The present invention carries out hydrothermal crystallizing preferably in high-pressure hydrothermal reaction kettle；After the reaction was completed, the present invention is excellent for hydrothermal crystallizing
Hydrothermal crystallizing reaction solution is successively filtered, washs, drying by choosing, obtains hydrothermal crystallizing product.
Preferably, the temperature of the step 3) intermediate ion exchange reaction be 40 ~ 120 DEG C, the ion-exchange reactions when
Between be 2h ~ 20h.The temperature roasted in the step 3) is 300 ~ 700 DEG C, and the time of roasting is 2h ~ 15h.
The ammonium salt is preferably one of ammonium chloride, ammonium sulfate, ammonium nitrate, more preferably ammonium nitrate；The ion is handed over
The temperature for changing reaction is preferably 60 ~ 80 DEG C；The time of the ion-exchange reactions is preferably 6 ~ 10h, and the present invention preferably will be described
M-SSZ-13 molecular sieve, ammonium salt and water mixing after carry out ion-exchange reactions.The maturing temperature is preferably 500 ~ 600 DEG C,
The calcining time is preferably 6 ~ 8h.After the completion of carrying out ion-exchange reactions with ammonium ion, the present invention is preferably by ion exchange
Reaction solution is successively filtered, washs, dries, and obtains ion-exchange reactions product.
Preferably, cupric salt is one or more of copper sulphate, copper nitrate or copper chloride in the step 4)；It is more excellent
It is selected as copper sulphate or copper nitrate.The temperature of ion-exchange reactions is 40 ~ 120 DEG C, and the time of ion-exchange reactions is 2h ~ 20h；Roasting
The temperature of burning is 300 ~ 700 DEG C, and the time of roasting is 2h ~ 15h.Further, the temperature of the ion-exchange reactions is preferably
60 ~ 80 DEG C, the time of the ion-exchange reactions is preferably 6 ~ 10h.The present invention is preferably by the H-SSZ-13 molecular sieve, divalent
Mantoquita carries out ion-exchange reactions after mixing with water.The maturing temperature is preferably 500 ~ 600 DEG C；The calcining time is preferably
6~8h.After the completion of ion-exchange reactions, gained ion-exchange reactions liquid is preferably successively filtered, washs, dries by the present invention
Obtain Copper Ion Exchange reaction product.
The present invention also provides the modification Cu-SSZ-13 molecular sieve being prepared using the above method, the molecular sieve
Copper load capacity is 1 ~ 5wt%；The different-shapes such as the crystal of the molecular sieve is spherical in shape, the square bodily form, truncated cubic, elliposoidal,
Crystal particle diameter is 0.38 ~ 6.19 μm.
Modified Cu-SSZ-13 molecular sieve made from the above method is used for low-temperature denitration reaction.0.2g catalyst is taken to be placed in
In the quartz tube reactor of internal diameter 12mm, it is passed through 500ppm NO, 500ppm NH3, 5% O2, N2The reaction gas of Balance Air carries out
Activity rating, volume space velocity 50000h-1.Heating rate when evaluation is 5 DEG C/min, keeps the temperature 0.5 hour every 50 DEG C and surveys
Measure the concentration of each component in a tail gas.
Modified Cu-SSZ-13 molecular sieve provided by the invention shows higher low temperature active in low-temperature denitration reaction
And nitrogen selective, at 100 DEG C, NO starts to convert, and conversion ratio is close to 20%, and at 125 DEG C, the conversion ratio of NO is had reached
30% ~ 40%, for the NO conversion ratio at 150 DEG C up to 60% ~ 70%, nitrogen selective reduces the life of by-product up to 80%-95%
At avoiding secondary pollution.
Beneficial effects of the present invention:
(1) present invention is introduced directly into alkali metal ion in crystallization process, and the four sides for generating distortion is induced using alkali metal ion
Body framework aluminum, and then during loading copper ion, the distributing position of copper ion is influenced, the double hexatomic ring tables of SSZ-13 molecular sieve are made
The bivalent cupric ion active site in face changes, to improve the low-temperature catalytic activity of catalyst；
(2) preparation method provided by the invention is simple, and gained molecular sieve crystallinity is high, and pure phase is high, and in low-temperature denitration reaction
Show higher low temperature active and nitrogen selective.
Detailed description of the invention
Fig. 1 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 1；
Fig. 2 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 2；
Fig. 3 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 3；
Fig. 4 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 4；
Fig. 5 is the XRD diagram of the modified Cu-SSZ-13 molecular sieve of gained in embodiment 1 ~ 4；
Fig. 6 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 5；
Fig. 7 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 6；
Fig. 8 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 7；
Fig. 9 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 8；
Figure 10 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 9；
Figure 11 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 10；
Figure 12 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 11；
Figure 13 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 12；
Figure 14 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 13；
Figure 15 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 14.
Specific embodiment
The present invention is further illustrated below by embodiment, but is not limited to following embodiment.
The present invention provides a kind of preparation methods of modified Cu-SSZ-13 molecular sieve, comprising the following steps:
1) silicon source, alkali metal hydroxide, template, silicon source and water are mixed, obtains starting sol；
2) it will be roasted after the starting sol hydrothermal crystallizing, obtain M-SSZ-13 molecular sieve, the M is alkali metal；
3) it is roasted after the M-SSZ-13 molecular sieve being carried out ion-exchange reactions with ammonium salt, obtains H-SSZ-13 molecular sieve；
4) it is roasted after the H-SSZ-13 molecular sieve being carried out ion-exchange reactions with cupric salt, obtains modified Cu-SSZ-13 points
Son sieve.
The present invention mixes silicon source, alkali metal hydroxide, template, silicon source and water, obtains starting sol.In the present invention
In, source of aluminium is preferably one or more of aluminum sulfate, aluminum nitrate, aluminium hydroxide, sodium metaaluminate, most preferably 18 water
Aluminum sulfate.In the present invention, the alkali metal hydroxide is preferably sodium hydroxide, potassium hydroxide, lithium hydroxide or hydroxide
One or more of caesium, more preferably sodium hydroxide or lithium hydroxide.In the present invention, the template is preferably N, N, N-
Trimethyl -1- adamantane ammonium hydroxide (TMAdaOH), cuprammonium complex (Cu-TEPA), more preferably N, N, N- trimethyl -1-
Adamantane ammonium hydroxide (TMAdaOH).In the present invention, the silicon source is preferably silica solution, fumed silica, positive silicic acid four
One or more of ethyl ester, more preferably silica solution or tetraethyl orthosilicate.
In the present invention, the aluminium element in source of aluminium, alkali metal hydroxide, template, the element silicon in silicon source and
The molar ratio of water is preferably 0.005 ~ 0.8: 0.05 ~ 0.6: 0.05 ~ 0.6: 1: 22 ~ 88, and more preferably 0.02 ~ 0.5:
0.15~0.25 : 0.2~0.3 : 1 : 50~80。
The sequence that the present invention mixes silicon source, alkali metal hydroxide, template, silicon source and water does not have particular/special requirement,
In the present invention, preferably alkali metal hydroxide, silicon source, template, silicon source are sequentially added and obtained just after being stirred in deionized water
Beginning colloidal sol.The present invention is not particularly limited the specific method of the stirring, using stirring side well known to those skilled in the art
Method.
After obtaining starting sol, the present invention will roast after the starting sol hydrothermal crystallizing, obtain M-SSZ-13 molecular sieve, institute
Stating M is alkali metal.In the present invention, the temperature of the hydrothermal crystallizing is preferably 120 ~ 200 DEG C, and more preferably 140 ~ 160 DEG C, institute
The time for stating hydrothermal crystallizing is preferably 2 ~ 14 days, and more preferably 5 ~ 8 days.The present invention does not have the device of the hydrothermal crystallizing reaction
Have specifically limited, select hydro-thermal reaction device conventional in the art, the present invention preferably in high-pressure hydrothermal reaction kettle into
Row hydrothermal crystallizing.
After the reaction was completed, hydrothermal crystallizing reaction solution is preferably successively filtered, washs, dries hydrothermal crystallizing by the present invention,
Obtain hydrothermal crystallizing product.The present invention is not particularly limited the method for filtering, selects filtering well known to those skilled in the art
Method；The present invention preferably washs the solid product obtained after filtering to neutrality, and the washing is preferably adopted in the present invention
It is washed with deionized water, the present invention is not particularly limited washing methods, selects washing well known to those skilled in the art
Method；The present invention is not particularly limited drying means, selects drying means commonly used in the art.
After obtaining hydrothermal crystallizing product, the present invention roasts hydrothermal crystallizing product, obtains M-SSZ-13 molecular sieve, the M
For alkali metal.In the present invention, the maturing temperature is preferably 300 ~ 700 DEG C, and more preferably 500 ~ 600 DEG C.
In hydrothermal crystallization process of the invention, the mixture of silicon source, silicon source and template forms gel and crystallization nucleation,
Obtained sial skeleton, ultimately forms molecular sieve structure.The present invention is introduced directly into variety classes and non-same amount in crystallization process
Alkali metal ion, control forms the molecular sieve of different-shape, and alkali metal amount is more, and particle radius is bigger, and with alkali gold
The pattern that increases for belonging to dosage spherical becomes cube from irregular.The tetrahedron bone for generating distortion is induced using alkali metal ion
Frame aluminium, and then during loading copper ion, the distributing position of copper ion is influenced, the double hexa-atomic ring surfaces of SSZ-13 molecular sieve are made
Bivalent cupric ion active site changes, to change the low-temperature catalytic activity of catalyst, finally makes modified Cu-SSZ-13 points
Son sieve shows higher low temperature active and nitrogen selective in low-temperature denitration reaction.
In the present invention, after the reaction was completed, alkali metal ion passes through electrostatic adsorption and SSZ-13 molecule to hydrothermal crystallizing
Sieve skeleton frame combines, and forms M-SSZ-13 molecular sieve；The present invention generates the tetrahedral framework of distortion using alkali metal ion induction
Aluminium, then in subsequent steps removed alkali metal ion by a series of ion exchanges, copper ion is supported on the four of distortion
On the body framework aluminum of face, modified Cu-SSZ-13 molecular sieve is obtained.
After obtaining M-SSZ-13 molecular sieve, the M-SSZ-13 molecular sieve and ammonium salt are carried out ion-exchange reactions by the present invention
After roast, obtain H-SSZ-13 molecular sieve.In the present invention, the ammonium salt is preferably ammonium chloride, ammonium sulfate, ammonium nitrate, more preferably
For ammonium nitrate；The temperature of the ion-exchange reactions is preferably 40 ~ 120 DEG C, and more preferably 60 ~ 80 DEG C；The ion exchange is anti-
The time answered is preferably 2 ~ 20h, more preferably 6 ~ 10h, and the present invention preferably mixes M-SSZ-13 molecular sieve, ammonium salt and the water
Ion-exchange reactions is carried out after conjunction.
After the completion of carrying out ion-exchange reactions with ammonium ion, the present invention preferably successively carried out ion-exchange reactions liquid
Filter, washing, drying, obtain ion-exchange reactions product.The present invention is not particularly limited the method for filtering, selects art technology
Filter method known to personnel；The present invention preferably washs the solid product being obtained by filtration to neutrality, in the present invention, institute
It states washing preferably to be washed using deionized water, the present invention is not particularly limited washing methods, selects those skilled in the art
Washing methods known to member；The present invention is not particularly limited drying means, selects drying means commonly used in the art
?.
After obtaining ion-exchange reactions product, the present invention roasts ion-exchange reactions product, obtains H-SSZ-13 molecule
Sieve.In the present invention, the maturing temperature is preferably 300 ~ 700 DEG C, and more preferably 500 ~ 600 DEG C, the calcining time is preferred
For 2 ~ 15h, more preferably 6 ~ 8h.
In the present invention, during M-SSZ-13 molecular sieve and ammonium salt carry out ion-exchange reactions, alkali metal ion is complete
Replaced by ammonium ion, ammonium ion becomes hydrogen ion after roasting, to obtain H-SSZ-13 molecular sieve.
After obtaining H-SSZ-13 molecular sieve, the H-SSZ-13 molecular sieve and cupric salt are carried out ion exchange by the present invention
It is roasted after reaction, obtains modified Cu-SSZ-13 molecular sieve.In the present invention, the temperature of the ion-exchange reactions be preferably 40 ~
120 DEG C, more preferably 60 ~ 80 DEG C, the time of the ion-exchange reactions is preferably 2 ~ 20h, more preferably 6 ~ 10h.In this hair
In bright, the cupric salt is preferably one or more of copper sulphate, copper nitrate and copper chloride, more preferably copper sulphate or nitre
Sour copper, the present invention carry out ion-exchange reactions after preferably mixing the H-SSZ-13 molecular sieve, cupric salt with water.
After the completion of ion-exchange reactions, gained ion-exchange reactions liquid is preferably successively filtered, washs, does by the present invention
It is dry to obtain Copper Ion Exchange reaction product.The present invention is not particularly limited the method for filtering, selects those skilled in the art ripe
The filter method known；The present invention preferably washs the solid product being obtained by filtration to neutrality, the in the present invention washing
It is preferred that being washed using deionized water, the present invention is not particularly limited washing methods, selects those skilled in the art known
Washing methods；The present invention is not particularly limited drying means, selects drying means commonly used in the art.
After obtaining Copper Ion Exchange reaction product, the present invention roasts the ion-exchange reactions product, obtains modification
Cu-SSZ-13 molecular sieve.In the present invention, the maturing temperature is preferably 300 ~ 700 DEG C, and more preferably 500 ~ 600 DEG C；It is described
Calcining time is preferably 2 ~ 15h, more preferably 6 ~ 8h.
In the present invention, during H-SSZ-13 molecular sieve and cupric carry out ion-exchange reactions, hydrogen ion by copper from
Subdivision replaces, and unsubstituted hydrogen ion forms B acid site, and roasting removes remaining nitrate ion after the completion of exchange.
The present invention also provides modified Cu-SSZ-13 molecular sieves prepared by the preparation method.In the present invention,
The copper load capacity of the molecular sieve be preferably 1 ~ 5wt%, more preferably 2 ~ 3%；The crystal particle diameter of the molecular sieve is preferably
0.38 ~ 6.19 μm, more preferably 0.45 ~ 6.0 μm.
Modified Cu-SSZ-13 molecular sieve provided by the invention and preparation method thereof is carried out below with reference to embodiment detailed
Illustrate, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
1) 0.432g lithium hydroxide is dissolved in 44ml deionized water, then above-mentioned solution is added in 1.998g aluminum sulfate octadecahydrate
And stir 3-5 minutes, continue that 20.256g template TMAdaOH(25% is added into solution), after stirring to solution clear,
14.580g silica solution JN25 is added as silicon source, continues to obtain starting sol after stirring 2h.Aluminium element, alkali metal hydrogen-oxygen at this time
Compound, template, the element silicon in silicon source and water molar ratio be 0.1: 0.3: 0.4: 1: 66.
2) starting sol will be obtained to be transferred in the stainless steel cauldron of polytetrafluoroethyllining lining, the crystallization 6 at 150 DEG C
It.It is cooled to room temperature after the reaction was completed, is sufficiently washed and dried with deionized water after filtering, then roasted 6 hours at 550 DEG C
It removes template and obtains Li-SSZ-13 molecular sieve.
3) it takes above-mentioned Li-SSZ-13 molecular sieve 2g to be added in 100ml deionized water, 8g ammonium nitrate is then added, at 80 DEG C
Water bath condition under stirring 8h swap, sufficiently wash after the completion of exchange, after filtering with deionized water and is dried, then existed
6h is roasted at 550 DEG C, obtained H-SSZ-13 molecular sieve.
4) 2.416 grams of nitrate trihydrate copper are made into the copper nitrate solution of 100ml, above-mentioned H-SSZ-13 molecular sieve 1g is taken to be added
In solution, 3h is stirred under 80 DEG C of water bath condition and is swapped, after the completion of exchange, is sufficiently washed simultaneously after filtering with deionized water
It is dry, 5h is then roasted at 550 DEG C, gained molecular sieve is modified Cu-SSZ-13 molecular sieve.
Fig. 1 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 1, it can be seen from the figure that modified in embodiment 1
Cu-SSZ-13 molecular sieve crystal particle size is 3.42 μm；
Curve a is the XRD diagram of modified Cu-SSZ-13 molecular sieve in embodiment 1 in Fig. 5, it can be seen from the figure that in embodiment 1
Modified Cu-SSZ-13 molecular sieve has the pure phase structure of SSZ-13.
Embodiment 2
1) 0.722g sodium hydroxide is dissolved in 44ml deionized water, then 0.246g sodium metaaluminate is added in above-mentioned solution and is stirred
It mixes 3-5 minutes.Continue that 20.281g template TMAdaOH(25% is added into solution), after stirring to solution clear, it is added
14.838g silica solution obtains starting sol after continuing to stir after 2h as silicon source.Aluminium element, alkali metal hydroxide, mould at this time
The molar ratio of element silicon and water in plate agent, silicon source is 0.1: 0.3: 0.4: 1: 66.
2) obtained starting sol is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining, the crystallization 6 at 150 DEG C
It.It is cooled to room temperature after the reaction was completed, is sufficiently washed and dried with deionized water after filtering, then roasted 6 hours at 550 DEG C
It removes template and obtains Na-SSZ-13 molecular sieve.
3) it takes above-mentioned Na-SSZ-13 molecular sieve 2g to be added in 100ml deionized water, 8g ammonium nitrate is then added, at 80 DEG C
Water bath condition under stirring 8h swap, sufficiently wash after the completion of exchange, after filtering with deionized water and is dried, then existed
6h is roasted at 550 DEG C, obtained H-SSZ-13 molecular sieve.
4) 1.704 grams of Copper dichloride dihydrates are made into the copper chloride solution of 100ml, above-mentioned H-SSZ-13 molecular sieve 1g is taken to add
Enter in solution, 3h is stirred under 80 DEG C of water bath condition and is swapped, after the completion of exchange, is sufficiently washed after filtering with deionized water
And it is dry, 5h is then roasted at 550 DEG C, gained molecular sieve is modified Cu-SSZ-13 molecular sieve.
Fig. 2 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 2, it can be seen from the figure that modified in embodiment 2
Cu-SSZ-13 molecular sieve crystal particle size is 0.48 μm；
Curve b is the XRD diagram of modified Cu-SSZ-13 molecular sieve in embodiment 2 in Fig. 5, it can be seen from the figure that in embodiment 2
Modified Cu-SSZ-13 molecular sieve has the pure phase structure of SSZ-13.
Embodiment 3
1) 1.011g potassium hydroxide is dissolved in 44ml deionized water, then 0.234g aluminium hydroxide is added in above-mentioned solution and is stirred
Mix 3-5 minutes, continue that 20.256g template TMAdaOH(25% is added into solution), after stirring to solution clear, it is added
14.580g silica solution continues to obtain starting sol after stirring 2h as silicon source.Aluminium element, alkali metal hydroxide, template at this time
The molar ratio of element silicon and water in agent, silicon source is 0.1: 0.3: 0.4: 1: 66.
2) obtained starting sol is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining, the crystallization 6 at 150 DEG C
It.It is cooled to room temperature after the reaction was completed, is sufficiently washed and dried with deionized water after filtering, then roasting 20 is small at 300 DEG C
When remove template obtain K-SSZ-13 molecular sieve.
3) it takes above-mentioned K-SSZ-13 molecular sieve 2g to be added in 100ml deionized water, 8g ammonium nitrate is then added, at 120 DEG C
Water bath condition under stirring 2h swap, sufficiently wash after the completion of exchange, after filtering with deionized water and is dried, then existed
15h is roasted at 300 DEG C, obtained H-SSZ-13 molecular sieve.
4) 1.704 grams of Copper dichloride dihydrates are made into the copper chloride solution of 100ml, above-mentioned H-SSZ-13 molecular sieve 1g is taken to add
Enter in solution, 2h is stirred under 120 DEG C of water bath condition and is swapped, after the completion of exchange, is sufficiently washed after filtering with deionized water
It washs and dries, 15h is then roasted at 300 DEG C, gained molecular sieve is modified Cu-SSZ-13 molecular sieve.
Fig. 3 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 3, it can be seen from the figure that modified in embodiment 3
Cu-SSZ-13 molecular sieve crystal particle size is 4.45 μm；
Curve c is the XRD diagram of modified Cu-SSZ-13 molecular sieve in embodiment 3 in Fig. 5, it can be seen from the figure that in embodiment 3
Modified Cu-SSZ-13 molecular sieve has the pure phase structure of SSZ-13.
Embodiment 4
1) the cesium hydroxide aqueous solution of 5.394g 50% is added in 41ml deionized water, then by 1.998g aluminum sulfate octadecahydrate
It is added in above-mentioned solution and stirs 3-5 minutes.Continue that 20.256g template TMAdaOH(25% is added into solution), it stirs to molten
After liquid clear, 14.580g silica solution is added as silicon source, continues to obtain starting sol after stirring 2h, at this time aluminium element, alkali
Metal hydroxides, template, the element silicon in silicon source and water molar ratio be 0.1: 0.3: 0.4: 1: 66.
2) obtained starting sol is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining, the crystallization 8 at 150 DEG C
It.It is cooled to room temperature after the reaction was completed, is sufficiently washed and dried with deionized water after filtering, then roasted 2 hours at 700 DEG C
It removes template and obtains Cs-SSZ-13 molecular sieve.
3) it takes above-mentioned Cs-SSZ-13 molecular sieve 2g to be added in 100ml deionized water, 8g ammonium nitrate is then added, at 40 DEG C
Water bath condition under stirring 20h swap, sufficiently wash after the completion of exchange, after filtering with deionized water and is dried, then existed
2h is roasted at 700 DEG C, obtained H-SSZ-13 molecular sieve.
4) 1.704 grams of Copper dichloride dihydrates are made into the copper chloride solution of 100ml, above-mentioned H-SSZ-13 molecular sieve 1g is taken to add
Enter in solution, 20h is stirred under 40 DEG C of water bath condition and is swapped, after the completion of exchange, is sufficiently washed after filtering with deionized water
It washs and dries, 2h is then roasted at 700 DEG C, gained molecular sieve is modified Cu-SSZ-13 molecular sieve.
Fig. 4 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 4, it can be seen from the figure that modified in embodiment 4
Cu-SSZ-13 molecular sieve crystal particle size is 2.68 μm；
Curve d is the XRD diagram of modified Cu-SSZ-13 molecular sieve in embodiment 4 in Fig. 5, it can be seen from the figure that in embodiment 4
Modified Cu-SSZ-13 molecular sieve has the pure phase structure of SSZ-13.
Embodiment 5
The additional amount for changing lithium hydroxide is 0.864g, and the amount for changing simultaneously water is 59ml, remaining step and the complete phase of embodiment 1
Together, the molar ratio of aluminium element, alkali metal hydroxide, template, the element silicon in silicon source and water is 0.1: 0.6 at this time:
0.4 : 1 : 88.Obtain modified Cu-SSZ-13 molecular sieve.
Fig. 6 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 5, it can be seen from the figure that modified in embodiment 5
Cu-SSZ-13 molecular sieve grain crystal diameter size is 0.92 μm.
Embodiment 6
The additional amount of lithium hydroxide is changed to 0.072g, the amount for changing simultaneously water is 15ml, remaining step and the complete phase of embodiment 1
Together, the molar ratio of aluminium element, alkali metal hydroxide, template, the element silicon in silicon source and water is 0.1: 0.05 at this time:
0.4 : 1 : 22。
Fig. 7 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 6, it can be seen from the figure that modified in embodiment 6
Cu-SSZ-13 molecular sieve crystal particle size is 3.73 μm.
Embodiment 7
The additional amount of aluminum sulfate octadecahydrate is changed to 0.1g, the amount of TMAdaOH is changed to 30.384g, and the amount of water is changed to 36ml therewith,
Remaining step is identical with embodiment 1, at this time aluminium element, alkali metal hydroxide, template, element silicon and water in silicon source
Molar ratio be 0.005: 0.3: 0.6: 1: 66.Obtain modified Cu-SSZ-13 molecular sieve.
Fig. 8 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 7, it can be seen from the figure that modified in embodiment 7
Cu-SSZ-13 molecular sieve crystal particle size is 2.82 μm.
Embodiment 8
The additional amount of aluminum sulfate octadecahydrate is changed to 15.2g, remaining step is identical with embodiment 1, at this time aluminium element, alkali gold
The molar ratio for belonging to hydroxide, template, the element silicon in silicon source and water is 0.8: 0.3: 0.4: 1: 66.Changed
The Cu-SSZ-13 molecular sieve of property.
Fig. 9 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 8, it can be seen from the figure that modified in embodiment 8
Cu-SSZ-13 molecular sieve crystal particle size is 6.19 μm.
Embodiment 9
The additional amount of TMAdaOH is changed to 2.5g, the additional amount of water is changed to 57ml therewith, remaining step and the complete phase of embodiment 3
Together, the molar ratio of aluminium element, alkali metal hydroxide, template, the element silicon in silicon source and water is 0.1: 0.3 at this time:
0.05 : 1 : 66.Obtain modified Cu-SSZ-13 molecular sieve.
Figure 10 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 9, it can be seen from the figure that changing in embodiment 9
Property Cu-SSZ-13 molecular sieve crystal particle size be 4.76 μm.
Embodiment 10
The additional amount of aluminum sulfate octadecahydrate is changed to as 0.500g, and crystallization temperature and time are become into 120 DEG C and 14 respectively
It, remaining step is identical with embodiment 3, at this time aluminium element, alkali metal hydroxide, template, the element silicon in silicon source
Molar ratio with water is 0.025: 0.3: 0.4: 1: 66.Obtain modified Cu-SSZ-13 molecular sieve.
Figure 11 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 10, it can be seen from the figure that in embodiment 10
Modified Cu-SSZ-13 molecular sieve crystal particle size is 1.38 μm.
Embodiment 11
The additional amount of aluminum sulfate octadecahydrate is changed to 0.999g, and crystallization temperature and crystallization time are changed to 200 DEG C and 2 respectively
It.Remaining step is identical with embodiment 4, at this time aluminium element, alkali metal hydroxide, template, the element silicon in silicon source
Molar ratio with water is 0.05: 0.3: 0.4: 1: 66.Obtain modified Cu-SSZ-13 molecular sieve.
Figure 12 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 11, it can be seen from the figure that in embodiment 11
Modified Cu-SSZ-13 molecular sieve crystal particle size is 3.44 μm.
Embodiment 12
1) 0.432g lithium hydroxide is dissolved in 52ml deionized water, then above-mentioned solution is added in 1.126g ANN aluminium nitrate nonahydrate
And stir 3-5 minutes, continue that 20.256g template TMAdaOH is added into solution, after stirring to solution clear, is added
12.640g tetraethyl orthosilicate is as silicon source.Continue to obtain starting sol after stirring 2h.Aluminium element, alkali metal hydroxide at this time
Object, template, the element silicon in silicon source and water molar ratio be 0.1: 0.3: 0.4: 1: 66.
2) starting sol will be obtained to be transferred in the stainless steel cauldron of polytetrafluoroethyllining lining, the crystallization 7 at 140 DEG C
It.It is cooled to room temperature after the reaction was completed, is sufficiently washed and dried with deionized water after filtering, then roasting 10 is small at 500 DEG C
When remove template obtain Li-SSZ-13 molecular sieve.
3) it takes above-mentioned Li-SSZ-13 molecular sieve 2g to be added in 100ml deionized water, 5.4g ammonium chloride is then added, 40
DEG C water bath condition under stirring 20h swap, sufficiently wash after the completion of exchange, after filtering with deionized water and is dried, then
2h is roasted at 700 DEG C, obtained H-SSZ-13 molecular sieve.
4) 2.50g anhydrous cupric sulfate is made into the copper-bath of 100ml, takes above-mentioned H-SSZ-13 molecular sieve 1g to be added molten
In liquid, 20h is stirred under 40 DEG C of water bath condition and is swapped, after the completion of exchange, is sufficiently washed simultaneously after filtering with deionized water
It is dry, 2h is then roasted at 700 DEG C, gained molecular sieve is modified Cu-SSZ-13 molecular sieve.
Figure 13 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 12, it can be seen from the figure that in embodiment 12
Modified Cu-SSZ-13 molecular sieve crystal particle size is 1.67 μm.
Embodiment 13
1) 0.722g sodium hydroxide is dissolved in 59ml deionized water, then above-mentioned solution is added in 1.126g ANN aluminium nitrate nonahydrate
Middle stirring 3 ~ 5 minutes, continuing the addition template Cu-TEPA into solution, (2.523g TEPA mixes system with 2.997g copper sulphate
At), after stirring to solution clear, 3.57g white carbon black is added as silicon source, continues to obtain starting sol after stirring 2h.
2) obtained starting sol is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining, the crystallization 7 at 150 DEG C
It.It is cooled to room temperature after the reaction was completed, is sufficiently washed and dried with deionized water after filtering, then roasted 5 hours at 650 DEG C
It removes template and obtains Cu-Na-SSZ-13 molecular sieve.
3) it takes above-mentioned Na-SSZ-13 molecular sieve 2g to be added in 100ml deionized water, 5.4g ammonium chloride is then added, 80
DEG C water bath condition under stirring 8h swap, copper ion and alkali metal that will be extra in the obtained Cu-Na-SSZ-13 of synthesis from
Son replaces, and after the completion of exchange, is sufficiently washed and is dried with deionized water after filtering, then roasted 8h at 600 DEG C, obtain
Cu-SSZ-13 molecular sieve.
Figure 14 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 13, it can be seen from the figure that in embodiment 13
Modified Cu-SSZ-13 molecular sieve crystal particle size is 4.32 μm.
Embodiment 14
1) 1.011g potassium hydroxide is dissolved in 44ml deionized water, then 0.25g sodium metaaluminate is added in above-mentioned solution and is stirred
It mixes 3-5 minutes, continues that Cu-TEPA (2.523g TEPA and 2.997g copper sulphate are mixed) is added into solution, stirring is extremely
After solution clear, 3.57g white carbon black is added as silicon source, continues to obtain starting sol after stirring 2h.
2) obtained starting sol is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining, the crystallization 6 at 150 DEG C
It.It is cooled to room temperature after the reaction was completed, is sufficiently washed and dried with deionized water after filtering, then roasted 6 hours at 550 DEG C
It removes template and obtains Cu-K-SSZ-13 molecular sieve.
3) it takes above-mentioned K-SSZ-13 molecular sieve 2g to be added in 100ml deionized water, 5.4g ammonium chloride is then added, at 80 DEG C
Water bath condition under stirring 8h swap, copper ion and alkali metal ion that will be extra in the obtained Cu-K-SSZ-13 of synthesis
After the completion of replacing exchange, is sufficiently washed and dried with deionized water after filtering, then roasted 8h at 600 DEG C, obtain
Cu-SSZ-13 molecular sieve.
Figure 15 is the SEM figure of modified Cu-SSZ-13 molecular sieve in embodiment 14, it can be seen from the figure that in embodiment 14
Modified Cu-SSZ-13 molecular sieve crystal particle size is 2.40 μm.
Obtained above-mentioned catalyst is reacted for ammine selectivity catalytic reduction.0.2g catalyst is taken to be placed in internal diameter 12mm's
In quartz tube reactor, it is passed through 500ppm NO, 500ppm NH3,5% O2, N2The reaction gas of Balance Air carries out activity rating,
Volume space velocity is 50000h-1.Heating rate when evaluation is 5 DEG C/min, keeps the temperature 0.5 hour every 50 DEG C and measures a tail gas
The concentration of middle each component.
Table 1 is the NO conversion ratio and N of gained sample at different temperatures in the embodiment of the present invention 1 ~ 142Selectivity, by table 1
It is found that the modification Cu-SSZ-13 molecular sieve catalyst being prepared using preparation method of the invention, in low-temperature denitration reaction
Higher low temperature active and nitrogen selective are shown, at 100 DEG C, NO starts to convert, and conversion ratio is close to 20%, at 125 DEG C
The conversion ratio of NO has reached 47%, and the NO conversion ratio at 150 DEG C is up to 68%, under 100 ~ 150 DEG C of low temperature environment, nitrogen
Selectivity is up to 80% ~ 99%.
The NO conversion ratio and N of 1 embodiment of table, 1 ~ 14 gained sample at different temperatures2Selectivity
The present invention is the above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill of the art
For personnel, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (12)
1. a kind of preparation method of modified Cu-SSZ-13 molecular sieve, it is characterised in that the following steps are included:
1) silicon source, alkali metal hydroxide, template, silicon source and water are mixed, obtains starting sol；
2) it will be roasted after starting sol hydrothermal crystallizing, obtain M-SSZ-13 molecular sieve, the M is alkali metal；
3) it is roasted after M-SSZ-13 molecular sieve being carried out ion-exchange reactions with ammonium salt, obtains H-SSZ-13 molecular sieve；
4) it is roasted after H-SSZ-13 molecular sieve being carried out ion-exchange reactions with cupric salt, obtains modified Cu-SSZ-13 molecular sieve.
2. the preparation method of modified Cu-SSZ-13 molecular sieve according to claim 1, it is characterised in that: the alkali metal
Hydroxide is the mixing of one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide or cesium hydroxide；Source of aluminium is
One or more of aluminum sulfate, aluminum nitrate, aluminium hydroxide, sodium metaaluminate；The template is N, N, N- trimethyl -1- Buddha's warrior attendant
Alkane ammonium hydroxide or cuprammonium complex；The silicon source is one of silica solution, fumed silica, tetraethyl orthosilicate or several
Kind；
The molar ratio of aluminium element, alkali metal hydroxide, template in silicon source, the element silicon in silica solution and water be 0.005 ~
0.8 : 0.05~0.6 : 0.05~0.6 : 1 : 22~88。
3. the preparation method of modified Cu-SSZ-13 molecular sieve according to claim 2, it is characterised in that: in source of aluminium
Aluminium element, alkali metal hydroxide, template, the element silicon in silica solution and water molar ratio be 0.02 ~ 0.5: 0.15 ~
0.25 : 0.2~0.3 : 1 : 50~80。
4. the preparation method of modified Cu-SSZ-13 molecular sieve according to claim 1, it is characterised in that: the step 2
In hydrothermal crystallizing is carried out in high-pressure hydrothermal reaction kettle；The temperature of hydrothermal crystallizing is 120 ~ 200 DEG C, the time of the hydrothermal crystallizing
It is 2 ~ 14 days；The temperature of the roasting is 300 ~ 700 DEG C, and the time of roasting is 2h ~ 15h；
After the reaction was completed, hydrothermal crystallizing reaction solution is preferably successively filtered, washs, dries hydrothermal crystallizing by the present invention, obtains
Hydrothermal crystallizing product.
5. the preparation method of modified Cu-SSZ-13 molecular sieve according to claim 4, it is characterised in that: the hydro-thermal is brilliant
The temperature of change is 140 ~ 160 DEG C, and the time of the hydrothermal crystallizing is 5 ~ 8 days；The maturing temperature is 500 ~ 600 DEG C.
6. the preparation method of modified Cu-SSZ-13 molecular sieve according to claim 1, it is characterised in that: the step 3)
In, the ammonium salt is one of ammonium chloride, ammonium sulfate, ammonium nitrate, and the M-SSZ-13 molecular sieve, ammonium salt and water are mixed
After carry out ion-exchange reactions；The temperature of ion-exchange reactions is 40 ~ 120 DEG C, time of the ion-exchange reactions be 2h ~
20h；After the completion of carrying out ion-exchange reactions with ammonium ion, ion-exchange reactions liquid is successively filtered, wash, is dried,
Obtain ion-exchange reactions product；
The temperature of the roasting is 300 ~ 700 DEG C, and the time of roasting is 2h ~ 15h.
7. the preparation method of modified Cu-SSZ-13 molecular sieve according to claim 6, it is characterised in that: the ion is handed over
The temperature for changing reaction is 60 ~ 80 DEG C；The time of ion-exchange reactions is 6 ~ 10h, and the maturing temperature is 500 ~ 600 DEG C, described
Calcining time is 6 ~ 8h.
8. the preparation method of modified Cu-SSZ-13 molecular sieve according to claim 1, it is characterised in that: the step 4)
Middle cupric salt is one or more of copper sulphate, copper nitrate or copper chloride；By the H-SSZ-13 molecular sieve, cupric salt
Ion-exchange reactions is carried out after mixing with water；The temperature of ion-exchange reactions is 40 ~ 120 DEG C, and the time of ion-exchange reactions is
2h~20h；After the completion of ion-exchange reactions, gained ion-exchange reactions liquid is successively filtered, is washed, be dried to obtain copper from
Sub- exchange reaction product；
The temperature of the roasting is 300 ~ 700 DEG C, and the time of roasting is 2h ~ 15h.
9. the preparation method of modified Cu-SSZ-13 molecular sieve according to claim 8, it is characterised in that: the ion is handed over
The temperature for changing reaction is 60 ~ 80 DEG C, and the time of ion-exchange reactions is 6 ~ 10h；The maturing temperature is 500 ~ 600 DEG C；Roasting
Time is 6 ~ 8h.
10. it is a kind of using modified Cu-SSZ-13 molecular sieve made from the described in any item preparation methods of claim 1 ~ 9, it is special
Sign is: the copper load capacity of the molecular sieve is 1 ~ 5wt%；The crystal particle diameter of the molecular sieve is 0.38 ~ 6.19 μm.
11. a kind of application of modified Cu-SSZ-13 molecular sieve described in any one of claim 10 in low-temperature denitration reaction, feature exist
In: it takes 0.2g catalyst to be placed in the quartz tube reactor of internal diameter 12mm, is passed through 500ppm NO, 500ppm NH3, 5% O2, N2
The reaction gas of Balance Air carries out activity rating, volume space velocity 50000h-1；Heating rate when evaluation is 5 DEG C/min, every
50 DEG C of concentration for keeping the temperature 0.5 hour and measuring each component in a tail gas.
12. application according to claim 11, it is characterised in that: the modified Cu-SSZ-13 molecular sieve of gained, in low-temperature denitration
Higher low temperature active and nitrogen selective are shown in reaction, up to 60% ~ 70%, nitrogen selects the NO conversion ratio at 150 DEG C
Property is up to 80 ~ 95%.
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| CN113213505A (en) * | 2021-06-23 | 2021-08-06 | 吉林大学 | SSZ-13 molecular sieve, preparation method thereof and Cu-SSZ-13 molecular sieve |
| CN113480196A (en) * | 2021-07-30 | 2021-10-08 | Oppo广东移动通信有限公司 | Composition for glass strengthening, preparation method thereof and glass strengthening method |
| CN113716585A (en) * | 2021-09-08 | 2021-11-30 | 天津派森新材料技术有限责任公司 | Method for preparing Cu-SSZ-13 molecular sieve by one-step method |
| CN113842943A (en) * | 2021-09-26 | 2021-12-28 | 中国科学院山西煤炭化学研究所 | B-doped Cu-SSZ-13 molecular sieve and preparation method and application thereof |
| CN113842943B (en) * | 2021-09-26 | 2023-03-14 | 中国科学院山西煤炭化学研究所 | B-doped Cu-SSZ-13 molecular sieve and preparation method and application thereof |
| CN114162832A (en) * | 2021-12-13 | 2022-03-11 | 大连理工大学 | Synthesis method and application of SSZ-13 molecular sieve in ultra-low template system |
| CN114538467A (en) * | 2022-04-14 | 2022-05-27 | 安徽纳蓝环保科技有限公司 | SSZ-13 molecular sieve, method for regulating and controlling crystal morphology thereof and application thereof |
| CN114538467B (en) * | 2022-04-14 | 2023-08-25 | 安徽纳蓝环保科技有限公司 | SSZ-13 molecular sieve, method for regulating and controlling crystal morphology of SSZ-13 molecular sieve and application of SSZ-13 molecular sieve |
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