CN106608632B - The preparation and application thereof of hierarchical porous structure SAPO-34 molecular sieves - Google Patents
The preparation and application thereof of hierarchical porous structure SAPO-34 molecular sieves Download PDFInfo
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Abstract
The present invention relates to a kind of application of hierarchical porous structure SAPO-34 molecular sieves in C4 olefins by catalytic cracking, mainly solves the problems, such as existing catalyst there are propene yields and is low.The present invention hydrolyzes under the conditions of -20 DEG C~100 DEG C by using the mixture of the silicon source of water, organic formwork agent R1, nano carbon black R2, phosphorus source, silicon source and alkali process and obtains colloidal sol, then places it in and carries out crystallization in reaction kettle；Sample is washed after crystallization, dried and is roasted to obtain the technical solution of hierarchical porous structure SAPO molecular sieve, preferably solves the problems, such as this, can be used in the industrial production of hierarchical porous structure molecular sieve.
Description
Technical field
The present invention relates to a kind of application of hierarchical porous structure SAPO-34 molecular sieves in C4 olefins by catalytic cracking.
Background technology
SAPO-34 molecular sieves are the molecular sieve of the silicoaluminophosphate series of U.S. combinating carbide company (UCC) exploitation, tool
There are suitable acidity and pore passage structure, larger specific surface area, preferable absorption property and thermal stability and hydrothermal stability,
It can be described as promoting the optimal catalyst of methanol-to-olefins reaction process at present.However, typical gas-solid heterogeneous as one
It reacts, easily carbon distribution is generated because of inside and outside diffusional resistance in SAPO-34 molecular sieve pore passages, in addition the strongly exothermic spy of reaction itself
Property, so as to cause rapid catalyst deactivation.
In order to solve the above problem, Recent study person takes a series of means from the different angles such as pore structure and crystalline size
Improve the performance of catalyst, result of study shows：The SAPO-34 molecular sieves of hierarchical porous structure are conducive to carrying for catalytic performance
Height, especially mesoporous presence, it is conducive to shorten the diffusion path of reactant and product molecule, weakens the limitation of diffusion
(Selvin R., Hsu H.L, Her T.M.Catalysis Communications[J],2008,10,169；Bi Y.Sh., L
üG.X..Chem.J.Chinese Universities[J], 2009,30 (1), 129), it is anti-in MTO reactions to improve it
Coking deactivation ability is to extend catalyst life.Currently, the report in relation to hierarchical porous structure SAPO-34 molecular sieves is less, it is main
There are following methods：Chen Lu etc. use multi-functional long chain organic silanes for mesoporous template one-step synthesis have multistage pore canal and
Compared with SAPO-34 molecular sieves (Chen Lu, Wang Runwei, the equal Chemical Journal of Chinese Universities of fourth pair, 2010,31 (9) of low in acidity：1693-
1696.).Yang etc. is that mesoporous template converts with multistage pore canal xerogel to tetraethyl ammonium hydroxide (TEAOH)
SAPO-34 molecular sieves show higher urge compared to traditional SAPO-34 in methanol-to-olefins reaction (MTO) reaction
Change activity (Yang Heqin, Liu Zhicheng, Gao Huanxin, et al.J.Mater.Chem., 2010,20：3227-
3231.).In addition to this, Zhu and Liu et al. have studied has micropore-using kaolin and SBA-15 as raw material hydro-thermal one-step synthesis method
Mesoporous multilevel hierarchy SAPO-34 molecular sieves (Zhu Jie, Gui Yu, Wang Yao, et al.Chem.Commun., 2009,
3282-3284；Liu Yuanlin,Wang Lingzhi,Zhang Jinlong,et al.Microporous and
Mesoporous Materials 145(2011)150-156)。
Although various countries researcher develops the synthetic method of numerous hierarchical porous structure molecular sieves, current multi-stage porous knot
The preparation of structure SAPO molecular sieve is still one of the difficult point in synthesis field.It can be seen that it is simple to develop a kind of preparation process, to ring
Border is friendly and there is the preparation method of the hierarchical porous structure aluminium silicophosphate molecular sieve of preferable mass-transfer performance to be realization and expand in fact
The key point of border application.
Invention content
The first technical problem to be solved by the present invention is existing SAPO molecular sieve performance in C4 olefins by catalytic cracking
Poor problem.The present invention provides a kind of new hierarchical porous structure SAPO molecular sieve, which has preferable diffusion,
It is functional in C4 olefins by catalytic cracking.
The two of technology to be solved by this invention are to provide a kind of hierarchical porous structure of one of solution technical problem newly
The preparation method of SAPO molecular sieve.
The three of technology to be solved by this invention are to provide a kind of hierarchical porous structure of one of solution technical problem newly
The purposes of SAPO molecular sieve.
One of to solve above-mentioned technical problem, the technical solution adopted by the present invention is as follows：It is hierarchical porous structure SAPO points a kind of
Son sieve, it is characterised in that micropore size is distributed as 0.1~0.7 nanometer；Mesoporous pore size is distributed as 2~200 nanometers；Specific surface area is
100~1300m2·g-1；0.05~1.5cm of Kong Rongwei3·g–1；Mesoporous hole holds 1~90%, and Micropore volume accounts for 1%~90%.
In above-mentioned technical proposal, preferred technical solution is that micropore size is distributed in 0.2~0.6 nanometer；Mesoporous pore size point
Cloth is 2.5~100 nanometers；Specific surface area is 200~1100m2·g-1；0.1~1.4cm of Kong Rongwei3·g–1；Mesoporous hole holds 10%
~80%, Micropore volume accounts for 10%~80%.
In above technical scheme, the pattern of SAPO molecular sieve is spherical.
To solve above-mentioned technical problem two, the technical solution adopted by the present invention is as follows：It is hierarchical porous structure SAPO points a kind of
The preparation method of son sieve, includes the following steps：
A) silicon source is heated to reflux a few hours in aqueous slkali first；
B) by the mixture of the silicon source of water, organic formwork agent R1, phosphorus source, silicon source and alkali process in -20 DEG C~100 DEG C conditions
Under, hydrolysis obtains silicon phosphorus aluminum oxide colloidal sol, wherein phosphorus source generates P by theoretical2O5Gauge, silicon source generate Al by theoretical2O3Amount
Meter, silicon source generate SiO by theoretical2Gauge, mixture weight become than group：R1/Al2O3=0.1~30；H2O/Al2O3=2.56
~15.37；SiO2/Al2O3=0.03~0.90；P2O5/Al2O3=0.05~2.80；
C) nano carbon black R2 is added in b) obtained silicon phosphorus aluminum oxide colloidal sol, and strong stirring or ultrasonic wave
Concussion makes it be uniformly dispersed, and mixture weight becomes than group：R2/Al2O3=0.01~1.0；
D) above-mentioned silicon phosphorus aluminum oxide is placed in reaction kettle, crystallization 0.1~4 day at 150~220 DEG C；Reaction terminates
Sample is washed afterwards, is dried and roasting obtains hierarchical porous structure SAPO molecular sieve；
In above-mentioned technical proposal, silicon source be selected from Ludox, positive quanmethyl silicate, tetraethyl orthosilicate, positive silicic acid orthocarbonate,
Positive at least one of tetrabutyl silicate or Ludox；Silicon source is selected from aluminium isopropoxide, boehmite, aluminium oxide, aluminum nitrate, chlorine
Change at least one of aluminium or aluminum sulfate；Phosphorus source is selected from phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, ammonium hydrogen phosphate, potassium phosphate, phosphoric acid
At least one of hydrogen dipotassium, potassium hydrogen phosphate, sodium phosphate, disodium hydrogen phosphate or dibastic sodium phosphate.The temperature of processing silicon source in step a)
It is 40~110 DEG C to spend preferred scope, and processing time is 1.5~22 hours.Mixture weight is than composition preferred scope in step b)
For：R1/Al2O3=0.5~20；R2/Al2O3=0.02~0.9；H2O/Al2O3=3.00~13.00；SiO2/Al2O3=0.07
~0.80；P2O5/Al2O3Between=0.06~2.30.Organic amine template preferred embodiment is tetraethyl hydroxide in step b)
At least one of amine, tetraethylammonium bromide, triethylamine or ethylenediamine.Crystallization temperature preferred scope is 160~200 in step c)
DEG C, crystallization time is 0.2~3 day.
To solve above-mentioned technical problem two, the technical solution adopted by the present invention is as follows：A kind of C4 olefin crackings ethylene
Method, using C4 alkene as raw material, reaction temperature be 300~850 DEG C, reaction meter pressure be 0.01MPa~1MPa, reaction weigh
Amount air speed is 0.1~6h-1Under conditions of, raw material is contacted by catalyst bed with catalyst, and reaction generates low-carbon alkene, used
Catalyst be hierarchical porous structure SAPO molecular sieve, micropore size is distributed as 0.1~0.7 nanometer；Mesoporous pore size is distributed as 2~
200 nanometers；Specific surface area is 100~1300m2·g-1；0.05~1.5cm of Kong Rongwei3·g–1；Mesoporous hole holds 1~90%, micropore
Kong Rong accounts for 1%~90%.
In above-mentioned technical proposal, preferred technical solution is that reaction temperature is 350~750 DEG C；Reacting meter pressure is
0.1MPa~0.8MPa；It is 0.2~5 hour to react weight space velocity-1。
Currently, the molecular sieve of hierarchical porous structure is concentrated mainly on Si-Al molecular sieve, for the silicon phosphorus aluminium of hierarchical porous structure
The preparation method report of Zn-Al-P-Si-oxide molecular sieve is less.The present invention first by silicon source carry out alkali process, then by with silicon source,
Phosphorus source and template are mixed to get hierarchical porous structure aluminium silicophosphate molecular sieve, and can be obtained by adjusting crystallization time and temperature
The molecular screen material of different crystallization degrees.This method preparation process is simple, is easy to control, and crystallinity is high, achieves preferable
Technique effect.
Currently, the fireballing problem of generally existing catalyst inactivation in the reaction of C4 olefins by catalytic cracking.This is mainly due to
Catalyst diffusion is poor, caused by leading to easy carbon distribution.Carbon distribution mainly influences the activity of catalyst in terms of two:On the one hand it is long-pending
The active sites of carbon covering catalyst cause to inactivate；On the other hand it is the duct of clogged with soot catalyst so that reactant can not expand
Catalyst duct can not be diffused out by being scattered to up to active sites or product.The present invention uses the SAPO molecular sieve conduct of hierarchical porous structure
The catalyst of C4 preparing propylene by catalytic cracking olefin, since its meso-hole structure is conducive to the activated centre of reactant molecule and catalyst
Contact, while it being also beneficial to the duct that reaction product quickly diffuses out catalyst, to reduce the generation of carbon deposit, make its catalytic
Can have than previous catalyst and be obviously improved, while by adjusting reaction condition, the selectivity of propylene and yield be made to significantly improve,
Achieve preferable technique effect.
Description of the drawings
Fig. 1 is【Embodiment 1】The SEM of obtained hierarchical porous structure SAPO molecular sieve schemes.
Fig. 2 is【Embodiment 1】The XRD diagram of obtained hierarchical porous structure SAPO molecular sieve.
The present invention will be further described below by way of examples.
Specific implementation mode
【Embodiment 1】
Into 45 grams of deionized waters, it sequentially adds 12.3 grams of aluminium isopropoxides, 11.97 grams of orthophosphoric acid (85% weight), fully
Solution a is formed after stirring；60 grams of tetraethyl ammonium hydroxides (25% weight), 6 grams of Ludox (40% weight) and 0.6 gram of nanometer
Carbon black is uniformly mixed and forms solution b；The crystalline substance for obtaining synthesis SAPO-34 molecular sieves for 6 hours is stirred at room temperature in a and b after mixing
Change liquid；Ageing is stirred at room temperature for 24 hours in prepared crystallization liquid, the crystallization liquid being aged, which is packed into, carries polytetrafluoroethyllining lining
Crystallizing kettle in, crystallization 24 hours at 200 DEG C；
The weight ratio of each component is：R1/Al2O3=10；R2/Al2O3=0.1；H2O/Al2O3=7；SiO2/Al2O3=
0.4；P2O5/Al2O3=1.1, wherein R1, R2 respectively represent TEAOH (tetraethyl ammonium hydroxide) and nano carbon black.
Products therefrom is washed, centrifugation, 110 DEG C dry to obtain solid sample, XRD the result shows that, products obtained therefrom SAPO-34
Molecular screen primary powder.SEM is shown in that Fig. 1, XRD are shown in Fig. 2.
【Embodiment 2~14】
According to【Embodiment 1】Each Step By Condition, hierarchical porous structure molecular sieve is made, only feed change (table 1)
The parameters such as proportioning, the type of alkali, alkali purification temp, are specifically listed in table 1.The product of synthesis through characterization illustrate its result have with
【Embodiment 1】, the similar crystal structure of product, specific physico-chemical parameter is shown in Table 2.
Table 1
Table 2
【Embodiment 15】
Using fixed-bed catalytic reactor, reactor is stainless steel tube, and C4 alkene is carried out to catalyst prepared by embodiment 1
Hydrocarbon catalytic cracking reaction activity rating, investigating process conditions used is：Loaded catalyst 0.5g, reaction temperature are 650 DEG C,
Reaction pressure is 0.1MPa, weight space velocity 1h-1.Full product on-line analysis.Appraisal result is as shown in table 3.
Table 3
【Embodiment 16~18】
According to【Embodiment 15】It is anti-that process conditions used carry out C4 olefins by catalytic cracking to catalyst prepared by embodiment 1
Activity rating is answered, reaction temperature is only changed, appraisal result is as shown in table 4.
Table 4
【Embodiment 19~21】
According to【Embodiment 15】It is anti-that process conditions used carry out C4 olefins by catalytic cracking to catalyst prepared by embodiment 3
Activity rating is answered, reaction pressure is only changed, appraisal result is as shown in table 6.
Table 6
【Embodiment 22~24】
According to【Embodiment 15】It is anti-that process conditions used carry out C4 olefins by catalytic cracking to catalyst prepared by embodiment 3
Activity rating is answered, weight space velocity is only changed, appraisal result is as shown in table 7.
Table 7
【Comparative example 1】It is catalyst with traditional SAPO-34 molecular sieves
According to【Embodiment 15】Prepared by the catalyst (A) and conventional method that process conditions used prepare embodiment 1
Catalyst (B) carries out the evaluation of C4 olefins by catalytic cracking reactivities.Appraisal result is as shown in table 8.
As shown in table 8
【Comparative example 2】It is catalyst that few step (a), which prepares obtained material,
According to【Embodiment 15】The catalyst (A) and few step (a) that process conditions used prepare embodiment 1 prepare institute
Obtained material is that catalyst (B) carries out the evaluation of C4 olefins by catalytic cracking reactivities.Appraisal result is as shown in table 9.
Table 9
【Comparative example 3】It is catalyst without the material prepared by nano carbon black
According to【Embodiment 15】The catalyst (A) and do not have to nano carbon black institute that process conditions used prepare embodiment 1
The material of preparation is that catalyst (B) carries out the evaluation of C4 olefins by catalytic cracking reactivities.Appraisal result is as shown in table 10.
Table 10
Claims (10)
1. a kind of preparation method of hierarchical porous structure SAPO molecular sieve, includes the following steps：
A) silicon source in alkaline solution is heated to reflux to a few hours, carry out alkali process；
B) by the mixture of the silicon source of water, organic formwork agent R1, phosphorus source, silicon source and alkali process under the conditions of -20 DEG C~100 DEG C,
Hydrolysis obtains silicon phosphorus aluminum oxide colloidal sol, wherein phosphorus source generates P by theoretical2O5Gauge, silicon source generate Al by theoretical2O3Gauge,
Silicon source generates SiO by theoretical2Gauge, mixture weight become than group：R1/Al2O3=0.1~30；H2O/Al2O3=2.56~
15.37；SiO2/Al2O3=0.03~0.90；P2O5/Al2O3=0.05~2.80；
C) nano carbon black R2 is added in b) obtained silicon phosphorus aluminum oxide colloidal sol, and strong stirring or ultrasonic oscillation
It is set to be uniformly dispersed, mixture weight becomes than group：R2/Al2O3=0.01~1.0；
D) said mixture is placed in reaction kettle, crystallization 0.1~4 day at 150~220 DEG C；After reaction to sample into
Row washing, dry and roasting obtain hierarchical porous structure SAPO molecular sieve；
The silicon source of alkali process is selected from Ludox, positive quanmethyl silicate, tetraethyl orthosilicate, positive silicic acid orthocarbonate, four fourth of positive silicic acid
At least one of ester or Ludox；Silicon source is selected from aluminium isopropoxide, boehmite, aluminium oxide, aluminum nitrate, aluminium chloride or sulfuric acid
At least one of aluminium；Phosphorus source is selected from phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, ammonium hydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, phosphoric acid
At least one of hydrogen potassium, sodium phosphate, disodium hydrogen phosphate or dibastic sodium phosphate；The alkaline solution of processing silicon source is selected from hydrogen in step a)
At least one of sodium oxide molybdena, potassium hydroxide, ammonium hydroxide, tetraethyl ammonium hydroxide, tetraethylammonium bromide, triethylamine or ethylenediamine
Solution.
2. the preparation method of hierarchical porous structure SAPO molecular sieve according to claim 1, it is characterised in that processing in step a)
The temperature of silicon source is 30~120 DEG C, and processing time is 1~24 hour.
3. the preparation method of hierarchical porous structure SAPO molecular sieve according to claim 1, it is characterised in that mixing in step b)
Object weight ratio composition is selected from：R1/Al2O3=0.5~20；R2/Al2O3=0.02~0.9；H2O/Al2O3=3.00~13.00；
SiO2/Al2O3=0.07~0.80；P2O5/Al2O3Between=0.06~2.30.
4. the preparation method of hierarchical porous structure SAPO molecular sieve according to claim 3, it is characterised in that organic formwork agent R1
Selected from least one of tetraethyl ammonium hydroxide, tetraethylammonium bromide, triethylamine or ethylenediamine.
5. the preparation method of hierarchical porous structure SAPO molecular sieve according to claim 1, it is characterised in that crystallization in step d)
Temperature is 160~200 DEG C, and crystallization time is 0.2~3 day.
6. the hierarchical porous structure SAPO molecular sieve obtained by the preparation method described in any one of claim 1-5.
7. hierarchical porous structure SAPO molecular sieve according to claim 6, it is characterised in that micropore size is distributed as 0.1~0.7
Nanometer；Mesoporous pore size is distributed as 2~200 nanometers；Specific surface area is 100~1300m2·g-1；0.05~1.5cm of Kong Rongwei3·g–1；Mesoporous hole holds 1~90%, and Micropore volume accounts for 1%~90%.
8. hierarchical porous structure SAPO molecular sieve according to claim 6, it is characterised in that micropore size is distributed as 0.2~0.6
Nanometer；Mesoporous pore size is distributed as 2.5~100 nanometers；Specific surface area is 200~1100m2·g-1；0.1~1.4cm of Kong Rongwei3·
g–1；Mesoporous hole holds 10%~80%, and Micropore volume accounts for 10%~80%.
9. a kind of method of C4 olefin crackings ethylene is 300~850 DEG C in reaction temperature, reacts gauge pressure using butylene as raw material
Power is 0.01MPa~1MPa, and reaction weight space velocity is 0.1~6h-1, raw material in catalyst bed and claim 6-8 by appointing
One catalyst contact, reaction generate low-carbon alkene.
10. the method for C4 olefin crackings ethylene according to claim 9, it is characterised in that reaction temperature is 350~750
℃；Reaction meter pressure is 0.1MPa~0.8MPa；It is 0.2~6 hour to react weight space velocity-1。
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