CN104556140B - A kind of synthetic method of fine grain SAPO-34 molecular sieve - Google Patents
A kind of synthetic method of fine grain SAPO-34 molecular sieve Download PDFInfo
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- CN104556140B CN104556140B CN201310511412.7A CN201310511412A CN104556140B CN 104556140 B CN104556140 B CN 104556140B CN 201310511412 A CN201310511412 A CN 201310511412A CN 104556140 B CN104556140 B CN 104556140B
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Abstract
The invention discloses the synthetic method of a kind of little crystal grain SAPO 34 molecular sieve, it is characterised in that include template M1 being joined in aluminum source after mix homogeneously, the solution being mixed to get with deionized water with phosphorus source carries out contacting, mix homogeneously obtains mixture；Silicon source, template M2 and deionized water are joined in said mixture, is uniformly mixing to obtain crystallization liquid, mole consisting of of described crystallization liquid: SiO2:Al2O3:P2O5:SDA:H2: (0.1 3): (20 80), wherein SDA represent the kind of template M1 and M2, template M1 and M2 identical or different O=(0.1 1.5): 1:(0.6 1.2)；Crystallization liquid being placed in closed reactor under self-generated pressure crystallization and reclaims product, wherein, described crystallization is that segmentation is carried out.This method can synthesize and obtains crystal grain at 400 800nm, size is uniform, degree of crystallinity is high SAPO 34 molecular sieve, and its MTO diene selective is high.
Description
Technical field
The present invention relates to the synthetic method of a kind of SAPO-34 molecular sieve, more specifically to a kind of little crystal grain
The synthetic method of SAPO-34 molecular sieve.
Background technology
SAPO-34 molecular sieve is a kind of phosphor-silicon-aluminum molecular sieve that connection C.-Chem AG of the U.S. developed in 1984,
Belong to the chabasie CHA structure of octatomic ring, belong to cubic system, aperture at about 0.43nm, with ethylene and
The molecular diameter of propylene is close, and SAPO-34 molecular sieve has suitable acid strength, pore passage structure and good
Hydrothermal stability, shows the catalytic performance of excellence in preparing light olefins from methanol (MTO).
The synthesis of SAPO-34 molecular sieve has a lot of method, such as Hydrothermal Synthesis, microwave synthesis, liquid phase synthesis,
Gas phase transfer synthetic method etc..Conventional is hydrothermal synthesis method, such as, CN101121529A,
CN101633508A etc. are to use hydrothermal synthesis method, its step approximately as: (1) prepares crystallization liquid:
Calculate the addition of raw material according to certain proportion relation, the orthophosphoric acid of 85% is mixed with water, this phosphoric acid water
Solution is labeled as A, is mixed homogeneously with a certain amount of deionized water in aluminum source and obtains mixture B, A is joined B
In quickly stir, be eventually adding organic formwork agent, silicon source and deionized water, quickly stir a period of time,
Crystallization liquid is ready；(2) ageing: crystallization liquid is encased in rustless steel crystallizing kettle, the oldest
Change certain time；(3) crystallization: by rustless steel crystallizing kettle temperature programming to 180-250 DEG C, dynamically or statically
Crystallization certain time, it is down to room temperature and takes out sample filtering or centrifugation, be washed with deionized water to neutrality, put
Enter and 80-120 DEG C of thermostatic drier is dried to obtain SAPO-34 molecular screen primary powder.
At present, the SAPO-34 zeolite crystal that hydrothermal crystallizing synthesis obtains is generally more than 1 micron, and crystal grain is big
SAPO molecular sieve when catalytic process, product diffusion is slow, easy coking and deactivation.
It is big that fine grain SAPO-34 molecular sieve has surface area, and product diffusion is fast, it is not easy to the advantages such as coking.
CN101462742A, US5096684 use fluoride or Fluohydric acid. as structure directing agent synthesizing small-grain
SAPO-34 molecular sieve, although fluorion can promote silicon source and the depolymerization in aluminum source, obtains substantial amounts of nucleus,
The SAPO-34 zeolite crystal of synthesis is little, but owing to fluorion has severe corrosive and toxicity, limits fluorine
The commercial Application of ion.EP541915 is open uses dynamic agitation crystallization liquid to synthesize 600nm to 1400nm
SAPO-34 molecular sieve.Method disclosed in CN102275948A utilizes high-temp in-situ to synthesize 800nm's
SAPO-34 molecular sieve, although crystal grain has obtained further improvement, but high-temp in-situ synthesis of molecular sieve is to crystalline substance
Change still and require higher, limit commercial Application.
Summary of the invention
It is an object of the invention to problem bigger than normal for SAPO-34 zeolite crystal, that reaction condition is harsher,
The synthetic method of a kind of fine grain SAPO-34 molecular sieve is provided.
The synthetic method of a kind of fine grain SAPO-34 molecular sieve that the present invention provides, it is characterised in that include by
Template M1 joins in aluminum source after mix homogeneously, and the solution being mixed to get with phosphorus source and deionized water connects
Touch, mix homogeneously obtains mixture；Silicon source, template M2 and deionized water are joined in said mixture,
It is uniformly mixing to obtain crystallization liquid, mole consisting of of described crystallization liquid:
SiO2:Al2O3:P2O5:SDA:H2: (0.1-3): (20-80), wherein O=(0.1-1.5): 1:(0.6-1.2)
SDA represents that the kind of template M1 and M2, template M1 and M2 is identical or different；Crystallization liquid is placed in close
Closing in reactor under self-generated pressure crystallization and reclaim product, wherein, described crystallization is in temperature from low to high
In degree interval, order point three sections is carried out, and the crystallization temperature of adjacent two sections differs and rear one section of crystallization temperature is higher than
The last period, temperature crystallization was no less than 40 DEG C, and three sections of described crystallization temperatures are respectively 20～90 DEG C, 90～150
DEG C and 150～250 DEG C.
In the synthetic method that the present invention provides, aluminum source and segment template agent mix homogeneously pre-activate, beneficially aluminum
Source is dissolved and the formation of primary structure units, in conjunction with the generation using segmentation crystallization to be conducive to nucleus.And,
The zeolite crystal size obtained synthesized by the inventive method is uniformly, crystal grain is between 400-800nm, crystallization
Degree is high, MTO diene selective is high.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of embodiment 1 synthetic sample.
Fig. 2 is the SEM photograph of embodiment 1 synthetic sample.
Fig. 3 is the XRD spectra of embodiment 2-in-1 one-tenth sample.
The SEM photograph of Fig. 4 embodiment 2-in-1 one-tenth sample.
Fig. 5 is the XRD spectra of embodiment 3 synthetic sample.
Fig. 6 is the SEM photograph of embodiment 3 synthetic sample.
Fig. 7 is the XRD spectra of comparative example 1 synthetic sample.
Fig. 8 is the SEM photograph of comparative example 2-in-1 one-tenth sample.
Detailed description of the invention
The synthetic method of a kind of fine grain SAPO-34 molecular sieve that the present invention provides, it is characterised in that include by
Template M1 joins in aluminum source after mix homogeneously, and the solution being mixed to get with phosphorus source and deionized water connects
Touch, mix homogeneously obtains mixture；Silicon source, template M2 and deionized water are joined in said mixture,
It is uniformly mixing to obtain crystallization liquid, mole consisting of of described crystallization liquid:
SiO2:Al2O3:P2O5:SDA:H2: (0.1-3): (20-80), wherein O=(0.1-1.5): 1:(0.6-1.2)
SDA represents that the kind of template M1 and M2, M1 and M2 is identical or different；Crystallization liquid is placed in confined reaction
Crystallization reclaim product under self-generated pressure in still, wherein, described crystallization is in temperature range from low to high
Middle order divides three sections to carry out, and the crystallization temperature of adjacent two sections differs and rear one section of crystallization temperature is higher than the last period
Temperature crystallization be no less than 40 DEG C, three sections of described crystallization temperatures be respectively 20～90 DEG C, 90～150 DEG C and
150～250 DEG C.
In the method for the present invention, described template can be selected from tetraethyl ammonium hydroxide, triethylamine, diethylamine,
Any one or several mixture in morpholine, wherein preferably tetraethyl ammonium hydroxide, triethylamine and morpholine.
The molal quantity of described template M2 accounts for the 20～90% of the molal quantity sum of template M1 and template M2,
Preferably 25～75%.Further preferably, template M1 is different with the kind of M2, and M1 is preferably tetraethyl hydrogen
Amine-oxides, M2 is preferably the molar ratio of triethylamine, described tetraethyl ammonium hydroxide and triethylamine more preferably
For 1:(0.6～1).
Source of aluminium can be selected from dry glue powder, boehmite, SB powder, aluminum alkoxide any one or
Several mixture, wherein preferred dry glue powder and SB powder, more preferably Al2O3Content is the dry glue powder of 75%.
Phosphorus source can be industrial raw material, selected from monoammonium phosphate, phosphoric acid and ammonium dihydrogen phosphate.Preferably
Mass fraction is the phosphoric acid of 20%-85%, the orthophosphoric acid of more preferably 85%.
Described silicon source can be selected from acidic silicasol, white carbon, particulate silica gel, positive esters of silicon acis any one
Or several mixture, wherein preferred acidic Ludox, white carbon, the acidic silicasol of more preferably 30%.
A mole composition for described crystallization liquid is preferably: SiO2:Al2O3:P2O5:SDA:H2O=(0.1-0.8):1:
(0.9-1): (0.5-2.5): (40-60).
In the method for the present invention, described crystallization liquid is placed in closed reactor crystallization under self-generated pressure, adopts
Carry out by the mode of segmentation crystallization, including 20-90 DEG C of aging, 90-150 DEG C of nucleus generation and 150-250 DEG C of crystalline substance
Core production process.The crystallization temperature of adjacent two sections differs and rear one section of crystallization temperature is brilliant higher than temperature the last period
Change no less than 40 DEG C, preferably 60～70 DEG C.Three sections of described crystallization temperatures be respectively 20～90 DEG C, 90～
150 DEG C and 150～250 DEG C, preferably 20～60 DEG C, 110～130 DEG C and 180～210 DEG C.The most excellent
The crystallization time that choosing is total controlled at 30-90 hour.Such as, in a specific embodiment of the present invention,
Crystallization process be 25-35 DEG C of crystallization 5-10 hour, 100-150 DEG C of crystallization 10-20 hour, 150-200 DEG C
Crystallization 10-45 hour.
The described process reclaiming product is known to those skilled in the art, such as include filtering, washing,
It is dried and roasting etc..Described being dried can be to carry out at 100-110 DEG C, described roasting can be
Carry out under 400-600 DEG C of constant temperature.
Below by embodiment, the present invention is further detailed, but not thereby limiting the invention
Content.
In embodiment, XRD spectra is measured by Rigaku D/MAX-III A type diffractometer；SEM photograph is by FEI
The Quanta200F type scanning electron microscope that company produces measures.
Embodiment 1
Weigh 7gSB powder and join in 30g tetraethyl ammonium hydroxide, after stirring, analyze pure phosphorus with 85%
Acid 11g joins the solution mixing formed that stirs in 10g deionized water, stirs and is mixed for 15 minutes
Thing, is added separately to 5g triethylamine, 3g acidic silicasol and 19g water in said mixture, quickly stirs
Mix 2 hours and obtain colloidal sol.
Colloidal sol is placed in 100 milliliters of rustless steel autoclaves, order carry out 25 DEG C of aging 10h, 120
DEG C crystallization 20h and 180 DEG C of crystallization 45h, take out crystallization product, sample when autoclave temperature is down to room temperature
Product, through filtering or centrifugation, are washed with deionized water to neutrality, are placed in the thermostatic drying chamber of 80-120 DEG C dry
Dry, it is finally putting in Muffle furnace and is warming up to 550 DEG C of constant temperature calcinings 4 hours.
The XRD spectra of sample is shown in that Fig. 1, SEM photograph are shown in Fig. 2, it can be seen that do not have stray crystal to occur in sample,
Grain morphology is regular, and crystallite dimension is less than 500nm.
Embodiment 2
Weigh 7g dry glue powder and add in tetraethyl ammonium hydroxide, with 85% analytical pure orthophosphoric acid 11g after stirring
Join the solution stirring being uniformly mixing to obtain in 10g deionized water and obtain mixture in 15 minutes；5g tri-
Ethamine, 8.2g acidic silicasol and 9g water are added separately in said mixture, and quickly stirring obtains for 2 hours
To colloidal sol.
Being placed in by colloidal sol in 100 milliliters of rustless steel autoclaves, order carries out segmentation crystallization: aged at room temperature
10h, 150 DEG C of crystallization 10h and 180 DEG C of crystallization 45h, wait high pressure temperature of reaction kettle to be down to during room temperature and take out crystallization
Product, sample, through filtering or centrifugation, is washed with deionized water to neutrality, and the constant temperature being placed in 80-120 DEG C is done
Dry case is dried, is finally putting in Muffle furnace and is warming up to 550 DEG C of constant temperature calcinings 4 hours.
The XRD spectra of sample is shown in Fig. 3, and it is SAPO-34 molecular sieve.SEM photograph is shown in that Fig. 4, crystal grain exist
200-500nm。
Embodiment 3
Weigh 7gSB powder join 30g tetraethyl ammonium hydroxide stirs after with by 85% analyze pure phosphorus
Acid 11g joins the solution mixing formed that stirs in 10g deionized water, stirs and is mixed for 15 minutes
Thing；3.1g triethylamine, 3g acidic silicasol and 19g water are added separately in said mixture, quickly
Stir and obtain colloidal sol in 2 hours.
Being placed in by colloidal sol in 100 milliliters of rustless steel autoclaves, order carries out segmentation crystallization: aged at room temperature
5h, 150 DEG C of crystallization 20h and 180 DEG C of crystallization 40h, take out crystallization when autoclave temperature is down to room temperature
Product, sample, through filtering or centrifugation, is washed with deionized water to neutrality, and the constant temperature being placed in 80-120 DEG C is done
Dry case is dried, is finally putting in Muffle furnace and is warming up to 550 DEG C of constant temperature calcinings 4 hours.
The XRD spectra of sample is shown in Fig. 5, and it is SAPO-34 molecular sieve.SEM photograph is shown in Fig. 6, and crystal grain is minimum
For 100nm, crystal grain is the cube of tabular superposition.
Comparative example 1
The explanation of this comparative example does not use process and the result of aluminum source pre-activate process.
Synthesizing SAPO-34 molecular sieve with embodiment 1 proportion scale and crystallization condition, difference is this comparative example
Aluminum source pre-activate is not used to process.
The XRD spectra of sample is shown in Fig. 7, shows in sample containing AFI stray crystal.
Comparative example 2
The explanation of this comparative example does not use process and the result of segmentation crystallization.
According to proportion scale and the pretreatment mode synthesis SAPO-34 molecular sieve of embodiment 2, difference is this
Comparative example does not use segmentation crystallization, but crystallization 65h at 180 DEG C.
Fig. 8 is shown in by the scanning electron microscope sem photo of sample, and the crystal grain of display sample is cube, and crystal grain is more than 4
Micron.
Comparative example 3-4
Comparative example 3-4 explanation comparative example 1 and comparative example 2 gained sieve sample are in methanol to olefins reaction
Catalytic performance result.Sample tabletting after comparative example 1 and 2 roasting is sieved, chooses the sample of 20-40 mesh
Product, are respectively labeled as C-1 and C-2.Evaluating apparatus is fixed bed reactors, and appreciation condition is: catalyst
Loadings is 3g, and reactant is methanol, mass space velocity 1h-1, carrier gas is nitrogen, and nitrogen flow is 350ml/min,
Reaction temperature 450 DEG C, reaction pressure is 0.1Mpa.Product is with ethylene and propylene as target product, instead
Answering product by gas chromatogram on-line analysis, MTO catalytic performance result is as shown in table 1.
Embodiment 4-6
This example demonstrates that embodiment 1-3 gained sieve sample catalytic performance in methanol to olefins reaction
Effect.Embodiment 1-3 gained roasting sample sieves through tabletting, takes 20-40 mesh molecular sieve, is respectively labeled as
C-3、C-4、C-5.Evaluation methodology and condition are identical with comparative example 3-4, MTO catalytic performance result such as table 1
Shown in.
As can be seen from Table 1, the product of the present invention has higher diene selective, the wherein diene of C-5
Selectivity is up to 84.661%.The inventive method obtains small crystal grain molecular sieve, has reached to improve olefin yields
Purpose.
Table 1
Claims (14)
1. the synthetic method of a fine grain SAPO-34 molecular sieve, it is characterised in that include adding template M1
In aluminum source after mix homogeneously, the solution being mixed to get with deionized water with phosphorus source carries out contacting, mixing all
Even obtain mixture；Silicon source, template M2 and deionized water are joined in said mixture, stirring
Uniformly obtain crystallization liquid, mole consisting of of described crystallization liquid:
SiO2:Al2O3:P205:SDA:H2: (0.1-3): (20-80), O=(0.1-1.5): 1:(0.6-1.2) its
Middle SDA represents that the kind of template M1 and M2, M1 and M2 is identical or different；Crystallization liquid is placed in close
Closing in reactor under self-generated pressure crystallization and reclaim product, wherein, described crystallization is from low to high
In temperature range, order point three sections is carried out, and the crystallization temperature of adjacent two sections differs and rear one section of crystallization temperature
Higher than temperature crystallization the last period no less than 40 DEG C, three sections of described crystallization temperatures be respectively 20～90 DEG C,
90～150 DEG C and 150～250 DEG C.
2. according to the synthetic method of claim 1, wherein, mole the consisting of of described crystallization liquid:
SiO2:Al2O3:P205:SDA:H2: (0.5-2.5): (40-60) O=(0.1-0.8): 1:(0.9-1).
3. according to the synthetic method of claim 1, wherein, described template is tetraethyl ammonium hydroxide, three second
The mixture of one or more in amine, diethylamine and morpholine.
4. according to the synthetic method of claim 1, wherein, described aluminum source is dry glue powder, boehmite, SB
The mixture of one or more in powder and aluminum alkoxide.
5., according to the process of claim 1 wherein, described phosphorus source is monoammonium phosphate, phosphoric acid and biphosphate
One or more in ammonium.
6. according to the synthetic method of claim 1, wherein, described phosphorus source is 85% orthophosphoric acid.
7. according to the synthetic method of claim 1, wherein, described silicon source is acidic silicasol, white carbon, thin
The mixture of one or more in grain silica gel, positive esters of silicon acis.
8. the molal quantity of according to the synthetic method of claim 1, wherein, described template M2 accounts for template M1
With the molal quantity sum of template M2 20～90%.
9. the molal quantity of according to the synthetic method of claim 8, wherein, described template M2 accounts for template M1
With the molal quantity sum of template M2 25～75%.
10. according to the synthetic method of claim 1,8 or 9, wherein, M1 is tetraethyl ammonium hydroxide, and M2 is three
Ethamine.
11. according to the synthetic method of claim 10, and wherein, the molar ratio of M1 Yu M2 is 1:(0.6-1).
12. according to the synthetic method of claim 1, wherein, three sections of described crystallization temperatures be respectively 20～60 DEG C,
110～130 DEG C and 180～210 DEG C.
13. according to the synthetic method of claim 1, and wherein, described crystallization is little 25-35 DEG C of crystallization 5-10
Time, 100-150 DEG C of crystallization 10-20 hour, 150-200 DEG C of crystallization 10-45 hour.
14., according to the method for claim 1 or 12, wherein, described crystallization, control at 30-90 its total time
Hour.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1087292A (en) * | 1992-11-24 | 1994-06-01 | 中国科学院大连化学物理研究所 | A kind of is the synthesized silicon phosphor aluminum molecular sieve and the preparation thereof of template with the triethylamine |
| CN101284674A (en) * | 2008-04-24 | 2008-10-15 | 中国石油化工股份有限公司 | Process for synthesizing SAPO molecular sieve |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1087292A (en) * | 1992-11-24 | 1994-06-01 | 中国科学院大连化学物理研究所 | A kind of is the synthesized silicon phosphor aluminum molecular sieve and the preparation thereof of template with the triethylamine |
| CN101284674A (en) * | 2008-04-24 | 2008-10-15 | 中国石油化工股份有限公司 | Process for synthesizing SAPO molecular sieve |
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