CN104209141A - Cu-SAPO-34 molecular sieve catalyst and preparation method and application thereof - Google Patents
Cu-SAPO-34 molecular sieve catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a Cu-SAPO-34 molecular sieve catalyst and a preparation method and application thereof. The method includes the steps of adding pseudo-boehmite to deionized water, stirring, adding fumed silica or silica sol and orthophosphoric acid, uniformly mixing, adding copper sulfate and tetraethylenepentamine, fully stirring, and adding diethylamine, triethylamine or n-propylamine; placing fully stirred gel in a hydrothermal reaction kettle for crystallization, cooling at room temperature, separating a solid crystalline product from the mother liquor, washing to be in neutral, drying, and calcinating in air at the temperature of 600 DEG C to 850 DEG C to obtain the Cu-SAPO-34 molecular sieve catalyst. The Cu-SAPO-34 molecular sieve catalyst prepared through a one-step hydrothermal synthesis method. And the molecular sieve catalyst of good NH3-SCR catalytic activity and hydrothermal stability is obtained by controlling the using amount of copper sulfate, tetraethylenepentamine and fumed silica or silica sol and the calcination temperature.
Description
Technical field
The invention belongs to catalyst technical field, relate to a kind of Cu-SAPO-34 molecular sieve catalyst, preparation method and its usage.
Background technology
With NH
3for reducing agent Selective Catalytic Reduction of NO x and NH
3-SCR technology, has very important effect in the process of catalytic elimination NOx, and its key core is the exploitation of SCR catalyst system.Because diesel vehicle operating condition is changeable, the feature such as exhaust gas temperature change amplitude is large, tail gas composition is complicated, changes in flow rate is fast, excellent automotive catalyst need possess following performance: have at wide temperature window that higher catalytic activity, hydrothermal stability are high, mechanical strength is high, anti-SO
2strong etc. with strong, the anti-high-speed ability of HC poisoning capability.And V conventional at present
2o
5-WO
3(MoO
3)/TiO
2although catalyst commercial Application for many years, but still also exists some shortcomings that self cannot overcome, such as operating temperature window is narrower, high temperature time N
2o generates in a large number and causes N
2generate selective decline, SO
2to SO
3be oxidized serious and active component V
2o
5there is bio-toxicity, be detrimental to health.Therefore, the non-vanadium NH of development of new
3-SCR catalyst system becomes the focus of scientific research personnel and NOx emission control worker research.
Small pore molecular sieve Cu-SAPO-34 possesses high activity, high N due to it simultaneously
2selective and excellent hydrothermal stability and anti-HC poisoning capability and be subject to extensive concern.The Cu-SAPO-34 molecular sieve of current major part report all adopts mantoquita presoma and SAPO-34 molecular sieve to carry out ion-exchange and prepares.Ion-exchange relates to the processes such as exchange, filtration, washing, and due to the restriction of SAPO-34 molecular sieve pore passage size and exchange capacity, improve Cu load capacity need repeated exchanged step or extend swap time, limit the investigation and application of Cu-SAPO-34 molecular sieve to a great extent.
CN 102259895A discloses for a kind of method of synthesizing phosphor-silicon-aluminum molecular sieve using metal-amine-complex as template.The method is that boehmite or aluminium hydroxide are added deionized water, dropwise adds phosphoric acid, adds amorphous silica after stirring; Divalent metal salt and organic amine is added successively after being mixed, the pH value of gel is made to reach between 7 ~ 9, stirred at ambient temperature is after 12 hours, load crystallization in reactor, by solid crystallized product washing to neutral, obtain molecular sieve powder after drying, then 550 DEG C of roastings, obtain the zeolite product removing template.But if copper content is too high, easily forming more CuO, there is non-selective oxidation reduction NH in high temperature section (350-550 DEG C)
3, cause catalytic activity and N
2selective reduction.If sintering temperature is on the low side, the organic amine as template can not be removed completely, causes the degree of crystallinity of molecular sieve lower, specific area and pore volume less than normal, catalytic activity also can reduce.
Summary of the invention
For the problem of prior art, an object of the present invention is the preparation method providing a kind of Cu-SAPO-34 molecular sieve catalyst, and the catalyst adopting the method to obtain has excellent NH
3-SCR catalytic activity and hydrothermal stability.
In order to achieve the above object, present invention employs following technical scheme:
A preparation method for Cu-SAPO-34 molecular sieve catalyst, said method comprising the steps of:
(1) boehmite is added in deionized water stir, then any one and the orthophosphoric acid in aerosil or Ludox is added, after mixing, add copper sulphate and TEPA, after fully stirring, add diethylamine, triethylamine or n-propylamine;
(2) will stir gel completely and load crystallization in hydrothermal reaction kettle, after crystallization completes, room temperature cooling, is separated solid crystallized product with mother liquor, spend deionized water to neutral, drying, then in atmosphere 600 ~ 850 DEG C of roastings, namely obtains Cu-SAPO-34 molecular sieve catalyst;
In the method, the consumption controlling each reactant makes to possess following quality proportion relation in reaction system, namely
Al
2o
3, P
2o
5, SiO
2, H
2the mol ratio of O, copper sulphate-TEPA and organic amine is 1:1.14:0.25 ~ 0.8:75:0.04 ~ 0.5:3.4.Wherein, organic amine is diethylamine, triethylamine or n-propylamine.
In the preparation process of Cu-SAPO-34 molecular sieve catalyst, sintering temperature directly affects degree of crystallinity and the catalytic activity of molecular sieve; Transition metal copper is because of its load capacity difference, and state and the distribution thereof of copper are different, cause NH
3-SCR catalytic activity and hydrothermal stability have larger difference; Silicone content and replacement mode affect structural stability and the hydrothermal stability of catalyst to a certain extent.The present invention adopts a step hydrothermal synthesis method to prepare Cu-SAPO-34 molecular sieve catalyst, and further by controlling the input amount of copper sulphate-TEPA, to control copper load capacity be that the input amount of 0 ~ 10wt% (not comprising 0), aerosil or Ludox is to control silicone content at 7 ~ 11wt% and to control sintering temperature be 600 ~ 850 DEG C, to obtain NH
3the molecular sieve catalyst of-SCR catalytic activity and hydrothermal stability excellence.
In the present invention, control Al
2o
3, P
2o
5, SiO
2, H
2the mol ratio of O, copper sulphate-TEPA and organic amine is 1:1.14:0.65:75:0.04:3.4,1:1.14:0.65:75:0.08:3.4,1:1.14:0.65:75:0.12:3.4,1:1.14:0.65:75:0.2:3.4,1:1.14:0.65:75:0.3:3.4,1:1.14:0.65:75:0.5:3.4,1:1.14:0.25:75:0.12:3.4,1:1.14:0.45:75:0.12:3.4,1:1.14:0.65:75:0.12:3.4,1:1.14:0.8:75:0.12:3.4, wherein, organic amine is diethylamine, triethylamine or n-propylamine.
Preferably, control Al
2o
3, P
2o
5, SiO
2, H
2the mol ratio of O, copper sulphate-TEPA and organic amine is 1:1.14:0.65:75:0.08 ~ 0.3:3.4, the load capacity of the copper of the molecular sieve catalyst now obtained is 3.14 ~ 5.57%, preferred 1:1.14:0.65:75:0.12:3.4, the load capacity of the copper of the molecular sieve catalyst now obtained is 3.44wt%.
Preferably, control Al
2o
3, P
2o
5, SiO
2, H
2the mol ratio of O, copper sulphate-TEPA and organic amine is 1:1.14:0.25 ~ 0.65:75:0.12:3.4, the silicone content of the molecular sieve catalyst now obtained is 7.36 ~ 10.13%, preferred 1:1.14:0.45:75:0.12:3.4, the silicone content of the molecular sieve catalyst now obtained is 8.48wt%.
Preferably, the temperature of crystallization is 150 ~ 200 DEG C, such as 155 DEG C, 160 DEG C, 165 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 190 DEG C or 195 DEG C, preferably 180 DEG C.
Preferably, the temperature of crystallization is 24 ~ 72 hours, such as 28 hours, 35 hours, 40 hours, 45 hours, 50 hours, 55 hours, 60 hours, 65 hours or 70 hours, preferably 72 hours.
In the present invention, the temperature of described drying is 80-120 DEG C, and the dry time is 6-18 hour, and the temperature of preferred described drying is 100 DEG C, and the dry time is 12 hours.
In the present invention, sintering temperature is 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, 780 DEG C, 800 DEG C, 820 DEG C or 840 DEG C, and preferred described sintering temperature is 700 ~ 800 DEG C, preferably 700 DEG C further.
In the present invention, roasting time is 3 ~ 8 hours, preferably 5 hours.
In the present invention, the heating rate in roasting process is 0.5-2 DEG C/min, preferably 1 DEG C/min.
As the preferred technical solution of the present invention, a kind of preparation method of Cu-SAPO-34 molecular sieve catalyst, said method comprising the steps of:
Boehmite is added in deionized water and stirs, then add any one and the orthophosphoric acid in aerosil or Ludox, after mixing, add copper sulphate and TEPA, after fully stirring, add diethylamine, triethylamine or n-propylamine;
To stir gel completely and load crystallization in hydrothermal reaction kettle, after crystallization completes, room temperature cooling, is separated solid crystallized product with mother liquor, spend deionized water to neutral, drying, then in atmosphere 700 DEG C of roastings, namely obtains Cu-SAPO-34 molecular sieve catalyst;
In the method, control Al
2o
3, P
2o
5, SiO
2, H
2the mol ratio of O, copper sulphate-TEPA and organic amine is 1:1.14:0.45:75:0.12:3.4, wherein, organic amine is diethylamine, triethylamine or n-propylamine, and the load capacity of the copper of the molecular sieve catalyst now obtained is 3.44wt%, and silicone content is 8.48wt%.
The catalyst adopting this optimal technical scheme to obtain has excellent catalytic activity and hydrothermal stability, and it has the NO higher than 80% in 200 ~ 500 DEG C
xconversion ratio, at 750 DEG C, 10%H
2o hydrothermal aging 16 hours or 800 DEG C, 10%H
2o hydrothermal aging is after 16 hours, and the catalyst obtained still has the NO higher than 80% in 200 ~ 500 DEG C
xconversion ratio.Therefore, in technique scheme, by controlling addition and the sintering temperature 700 DEG C of raw material, and then control copper load capacity is 3.44wt%, and silicone content 8.48wt%, this molecular sieve shows excellent NH
3-SCR catalytic activity and hydrothermal stability.
Two of object of the present invention is to provide a kind of Cu-SAPO-34 molecular sieve catalyst prepared by method described above.
Three of object of the present invention is the purposes providing a kind of Cu-SAPO-34 molecular sieve catalyst as above, and it is for NH
3-SCR reacts.
Compared with the prior art, the present invention has following beneficial effect:
Cu-SAPO-34 molecular sieve catalyst of the present invention adopts a step hydrothermal synthesis method preparation, simple and easy to control, and activity component load quantity can adjustment in (0-10%) in a big way.
In addition, after preferably, the Cu-SAPO-34 molecular sieve catalyst of preparation has excellent NH
3-SCR activity and hydrothermal stability, still can the complete and good catalytic activity of holding structure after 800 DEG C of hydrothermal agings.
Accompanying drawing explanation
Fig. 1 is the NO of embodiment 1 catalyst
xconversion ratio evaluation map;
Fig. 2 is the N of embodiment 1 catalyst
2selective evaluation figure;
Fig. 3 is the XRD figure of embodiment 1 catalyst;
Fig. 4 is the NO before and after the hydrothermal aging of embodiment 1 catalyst
xconversion ratio evaluation map;
Fig. 5 is the NO of embodiment 2 catalyst
xconversion ratio evaluation map;
Fig. 6 is the XRD figure of embodiment 2 catalyst;
Fig. 7 is the NO of embodiment 3 catalyst
xconversion ratio evaluation map;
Fig. 8 is the NO of embodiment 4 catalyst
xconversion ratio evaluation map.
Detailed description of the invention
Technical scheme of the present invention is further illustrated by detailed description of the invention below in conjunction with accompanying drawing.
In the present invention, the evaluation of catalyst is adopted with the following method:
Get Cu-SAPO-34 molecular sieve catalyst, 40-60 order, put into catalyst activity evaluating apparatus respectively, activity rating carries out in fixed bed reactors.Simulated flue gas consists of (500ppm NH
3, 500ppm NO, 5%O
2), N
2for Balance Air, total flow is 500mL/min, and reaction velocity is 400000h
-1.
Embodiment 1
Boehmite is added in deionized water and stirs, then add any one and the orthophosphoric acid in aerosil or Ludox, after mixing, add copper sulphate and TEPA, after fully stirring, add diethylamine, triethylamine or n-propylamine;
Gel completely will be stirred and to load in hydrothermal reaction kettle 180 DEG C of crystallization 72 hours, room temperature cooling after crystallization completes, solid crystallized product is separated with mother liquor, spend deionized water to neutral, 100 DEG C of dryings 12 hours, then roasting in atmosphere, sintering temperature is 700 DEG C, in roasting process, heating rate is 1 DEG C/min, and roasting time is 5 hours, obtains Cu-SAPO-34 molecular sieve catalyst.
The consumption controlling each reactant makes to possess following quality proportion relation in reaction system:
Al
2o
3, P
2o
5, SiO
2, H
2the mol ratio of O, copper sulphate-TEPA and organic amine is 1:1.14:0.65:75:0.08 ~ 0.5:3.4, the load capacity of copper is made to be respectively 2.19%, 3.14%, 3.44%, 5.02%, 5.57% and 9.50%, wherein, organic amine is diethylamine, triethylamine or n-propylamine.
Be the catalytic performance test figure of the molecular sieve catalyst of the load capacity of different Cu shown in Fig. 1 ~ 4, this figure shows, the molecular sieve of different Cu load capacity shows different catalytic activitys, N
2selective and hydrothermal stability, wherein, best copper load capacity is 3.44%.
Embodiment 2
Boehmite is added in deionized water and stirs, then add any one and the orthophosphoric acid in aerosil or Ludox, after mixing, add copper sulphate and TEPA, after fully stirring, add diethylamine, triethylamine or n-propylamine;
Gel completely will be stirred and to load in hydrothermal reaction kettle 180 DEG C of crystallization 72 hours, room temperature cooling after crystallization completes, solid crystallized product is separated with mother liquor, spend deionized water to neutral, 100 DEG C of dryings 12 hours, then carry out roasting at different temperatures in atmosphere, in roasting process, heating rate is 1 DEG C/min, roasting time is 5 hours, obtains Cu-SAPO-34 molecular sieve catalyst.
In the method, the consumption controlling each reactant makes to possess following quality proportion relation in reaction system:
Al
2o
3, P
2o
5, SiO
2, H
2the mol ratio of O, copper sulphate-TEPA and organic amine is 1:1.14:0.65:75:0.12:3.4, makes the load capacity of copper be respectively 3.44%, and wherein, organic amine is diethylamine, triethylamine or n-propylamine.
The catalytic performance test figure of the catalyst that Fig. 5 and 6 to be sintering temperature be respectively 600 DEG C, 700 DEG C, 800 DEG C and 850 DEG C of roastings obtains, this figure shows, select copper load capacity be 3.44wt% basis on carry out roasting at different temperatures, there is some difference for the degree of crystallinity of molecular sieve and catalytic activity, consider economic factor, 700 DEG C is optimum calcination temperature.
Embodiment 3
Boehmite is added in deionized water and stirs, then add any one and the orthophosphoric acid in aerosil or Ludox, after mixing, add copper sulphate and TEPA, after fully stirring, add diethylamine, triethylamine or n-propylamine;
Gel completely will be stirred and to load in hydrothermal reaction kettle 180 DEG C of crystallization 72 hours, room temperature cooling after crystallization completes, solid crystallized product is separated with mother liquor, spend deionized water to neutral, 100 DEG C of dryings 12 hours, then carry out roasting at 700 DEG C in atmosphere, in roasting process, heating rate is 1 DEG C/min, roasting time is 5 hours, namely obtains Cu-SAPO-34 molecular sieve catalyst.
In the method, the consumption controlling each reactant makes to possess following quality proportion relation in reaction system: Al
2o
3, P
2o
5, SiO
2, H
2the mol ratio of O, copper sulphate-TEPA and organic amine is 1:1.14:0.25 ~ 0.8:75:0.12:3.4, makes silicone content be respectively 7.36%, 8.48%, 10.13% and 10.75%, and wherein, organic amine is diethylamine, triethylamine or n-propylamine.
Fig. 7 is the catalytic performance test figure of the catalyst of Different Silicon content, and this figure shows, best copper load capacity 3.44% and optimum calcination temperature 700 DEG C of bases regulate Different Silicon content, and silicone content is optimum in the catalytic activity of the molecular sieve catalyst of about 8.48wt%.
Embodiment 4
Boehmite is added in deionized water and stirs, then add any one and the orthophosphoric acid in aerosil or Ludox, after mixing, add copper sulphate and TEPA, after fully stirring, add diethylamine, triethylamine or n-propylamine;
Gel completely will be stirred and to load in hydrothermal reaction kettle 180 DEG C of crystallization 72 hours, room temperature cooling after crystallization completes, solid crystallized product is separated with mother liquor, spend deionized water to neutral, 100 DEG C of dryings 12 hours, then carry out roasting at 700 DEG C in atmosphere, in roasting process, heating rate is 1 DEG C/min, roasting time is 5 hours, namely obtains Cu-SAPO-34 molecular sieve catalyst.
In the method, the consumption controlling each reactant makes to possess following quality proportion relation in reaction system: Al
2o
3, P
2o
5, SiO
2, H
2the mol ratio of O, copper sulphate-TEPA and organic amine is 1:1.14:0.45:75:0.12:3.4, and make copper load capacity be 3.44%, silicone content is 8.48%, and wherein, organic amine is diethylamine, triethylamine or n-propylamine.
Fig. 8 is the catalytic performance test figure of catalyst, and this figure shows, select copper load capacity 3.44%, sintering temperature 700 DEG C, silicone content 8.48% prepares Cu-SAPO-34 molecular sieve, and this molecular sieve shows excellent NH
3-SCR catalytic activity and hydrothermal stability.
Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a preparation method for Cu-SAPO-34 molecular sieve catalyst, is characterized in that, said method comprising the steps of:
(1) boehmite is added in deionized water stir, then any one and the orthophosphoric acid in aerosil or Ludox is added, after mixing, add copper sulphate and TEPA, after fully stirring, add diethylamine, triethylamine or n-propylamine;
(2) will stir gel completely and load crystallization in hydrothermal reaction kettle, after crystallization completes, room temperature cooling, is separated solid crystallized product with mother liquor, spend deionized water to neutral, drying, then in atmosphere 600 ~ 850 DEG C of roastings, obtains Cu-SAPO-34 molecular sieve catalyst;
In the method, the consumption controlling each reactant makes to possess following quality proportion relation in reaction system, namely
Al
2o
3, P
2o
5, SiO
2, H
2the mol ratio of O, copper sulphate-TEPA and organic amine is 1:1.14:0.25 ~ 0.8:75:0.04 ~ 0.5:3.4, and wherein, organic amine is diethylamine, triethylamine or n-propylamine.
2. the method for claim 1, is characterized in that, control Al
2o
3, P
2o
5, SiO
2, H
2the mol ratio of O, copper sulphate-TEPA and organic amine is 1:1.14:0.65:75:0.04 ~ 0.5:3.4, preferred 1:1.14:0.65:75:0.12:3.4, and wherein, organic amine is diethylamine, triethylamine or n-propylamine.
3. method as claimed in claim 1 or 2, is characterized in that, control Al
2o
3, P
2o
5, SiO
2, H
2the mol ratio of O, copper sulphate-TEPA and organic amine is 1:1.14:0.25 ~ 0.8:75:0.12:3.4, preferred 1:1.14:0.45:75:0.12:3.4, and wherein, organic amine is diethylamine, triethylamine or n-propylamine.
4. the method as described in one of claim 1-3, is characterized in that, the temperature of crystallization is 150 ~ 200 DEG C, preferably 180 DEG C.
5. the method as described in one of claim 1-4, is characterized in that, the temperature of crystallization is 24 ~ 72 hours, preferably 72 hours.
6. the method as described in one of claim 1-5, is characterized in that, the temperature of described drying is 80-120 DEG C, and the dry time is 6-18 hour, and preferred baking temperature is 100 DEG C, and drying time is 12 hours.
7. the method as described in one of claim 1-6, is characterized in that, sintering temperature is 700 ~ 800 DEG C, preferably 700 DEG C further;
Preferably, roasting time is 3-8 hour, preferably 5 hours.
Preferably, the heating rate in roasting process is 0.5-2 DEG C/min, preferably 1 DEG C/min.
8. the method as described in one of claim 1-7, is characterized in that, said method comprising the steps of:
Boehmite is added in deionized water and stirs, then add any one and the orthophosphoric acid in aerosil or Ludox, after mixing, add copper sulphate and TEPA, after fully stirring, add diethylamine, triethylamine or n-propylamine;
To stir gel completely and load crystallization in hydrothermal reaction kettle, after crystallization completes, room temperature cooling, is separated solid crystallized product with mother liquor, spend deionized water to neutral, drying, then in atmosphere 700 DEG C of roastings, obtains Cu-SAPO-34 molecular sieve catalyst;
In the method, control Al
2o
3, P
2o
5, SiO
2, H
2the mol ratio of O, copper sulphate-TEPA and organic amine is 1:1.14:0.45:75:0.12:3.4, and wherein, organic amine is diethylamine, triethylamine or n-propylamine.
9. the Cu-SAPO-34 molecular sieve catalyst prepared by method as described in one of claim 1-8.
10. a purposes for Cu-SAPO-34 molecular sieve catalyst as claimed in claim 9, it is for NH
3-SCR reacts.
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