CN104556141B - Synthetic method of SAPO-34 molecular sieve - Google Patents
Synthetic method of SAPO-34 molecular sieve Download PDFInfo
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Abstract
The invention discloses a synthetic method of an SAPO-34 molecular sieve. The synthetic method is characterized by comprising the following steps: uniformly mixing a silicon source, a phosphorus source and an aluminum source according to a feeding proportion that a weight ratio of P2O5 to SiO2 to Al2O3 to H2O is equal to (0.6-1.2):(0.01-0.8):(0.6-1.2):(20-100), drying to obtain a silicon-phosphorus-aluminum dry glue of which the solid content is not less than 60%, and mixing the silicon-phosphorus-aluminum dry glue with a template agent, wherein according to the content of 1mol of Al2O3 in the silicon-phosphorus-aluminum dry glue, the adding amount of the template agent is 1-2.5mol; adding the template agent and part of water to obtain a mixture under the condition that a molar ratio of water in the mixture to the aluminum source calculated based on Al2O3 is not more than 20; and putting the mixture into a sealed reaction kettle, performing segmented crystallization under self-generated pressure, and recycling products. The synthetic method disclosed by the invention is low in water-aluminum ratio, and ensures that the single kettle yield can be improved; meanwhile, the sewage discharge quantity can be greatly reduced, and the cost reduction and environment protection can be facilitated; and an induction period can be greatly shortened when the synthesized molecular sieve is applied to MTO reaction, and the diene selectivity can reach 85.9%.
Description
Technical field
The invention provides a kind of method that low water aluminum ratio synthesizes SAPO-34 molecular sieve.
Background technology
SAPO-34 molecular sieve is that the U.S. joins C.-Chem AG in a kind of phosphor-silicon-aluminum molecular sieve of exploitation in 1984, belongs to eight
Yuan of rings chabasie CHA structure, cubic system, octatomic ring aperture is 0.43nm × 0.43nm, octatomic ring aperture and ethene and propylene
Molecular dynamics diameter close.SAPO-34 molecular sieve has suitable acid strength, total acid content and good hydrothermal stability,
Show excellent catalytic performance in preparing light olefins from methanol (MTO).
In the last thirty years, in terms of the synthesis of SAPO-34 molecular sieve, domestic and international researcher has done substantial amounts of work.
The synthesis of SAPO-34 molecular sieve has a lot of methods, such as hydrothermal synthesis method, microwave process for synthesizing, the gentle phase transfer of liquid phase synthesizing method
Synthetic method etc., the most frequently used is hydrothermal synthesis method.Chinese patent CN101121529A, CN101633508A etc. are to adopt hydro-thermal
Synthetic method.Synthesis step approximately as：(1) prepare crystallization liquid：Calculate the addition of raw material according to certain charge ratio relation
Amount, 85% orthophosphoric acid is mixed with deionized water, this phosphate aqueous solution is labeled as A, then silicon source is mixed all with deionized water
Even obtain mixture B, A is added in B and quickly stirs, be eventually adding organic formwork agent, silicon source and remaining deionized water,
Quickly stir, crystallization liquid is ready；(2) it is aged：Crystallization liquid is transferred in crystallizing kettle, room temperature is aged；(3) crystallization：
By crystallizing kettle temperature programming to 180-250 DEG C of crystallization；Finally by sample filtering or be centrifugally separating to obtain SAPO-34 molecular screen primary
Powder.Document (Chemical Reaction Engineering and technique, 2009,25,523-525) points out that liquid phase crystallization method and gas phase crystallization method are silicon phosphorus
Aluminium is prepared into dry glue, is subsequently adding organic formwork agent and crystal, is finally centrifuged, filters and is dried to obtain SAPO-34 molecular sieve.
Patent (CN101743061A, CN101121529A, CN101830482A) has synthesized pure phase using hydrothermal synthesis method
SAPO-34 molecular sieve, its n (H2O)/n(Al2O3) ratio more than 30, document (Materials Chemistry and Physics,
123 (2010) 507 509) synthesize SAPO-34 molecular sieve n (H2O)/n(Al2O3) than be 77.n(H2O)/n(Al2O3) easier than bigger than normal
Lead to environmental pollution, cost increase and one-pot yield low.
Content of the invention
The purpose of the present invention is the H existing for prior art2O/Al2O3Higher, environmental pollution is serious and one-pot yield is inclined
Low problem, proposes one kind in low H2O/Al2O3Than under the conditions of, go out high-crystallinity pure phase using silicon phosphorus aluminium precursor Hydrothermal Synthesiss
SAPO34 molecular sieve method.
The synthetic method of the SAPO-34 molecular sieve that the present invention provides is it is characterised in that according to charge ratio：(0.6～1.2)
P2O5:(0.01～0.8) SiO2:(0.6～1.2) Al2O3:(20～100) H2O, silicon source, phosphorus source and silicon source are mixed, and do
Dry obtain the silicon phosphorus aluminium dry glue that solid content is not less than 60%, silicon phosphorus aluminium dry glue is mixed with template, rubs with silicon phosphorus aluminium dry glue 1
You are Al2O3Meter, the addition of described template is 1-2.5 mole, adds template and part water to obtain mixture, gained mixes
Compound Zhong Shui with Al2O3The mol ratio of the silicon source of meter is not more than 20, mixture is placed under self-generated pressure in closed reactor brilliant
Change and recovery product, wherein, described crystallization is sequentially to divide three sections to carry out in temperature range from low to high, adjacent two sections
Crystallization temperature differs and rear one section of crystallization temperature is higher than that the last period temperature crystallization is no less than 40 DEG C, described three sections of crystallization temperatures
It is respectively 20～90 DEG C, 90～150 DEG C and 150～250 DEG C.
The method that the present invention provides, is mixed using phosphorus source, silicon source, silicon source and portions of de-ionized water and generates Gui Lin aluminium glue predecessor
Thing, water aluminum ratio is not more than 20, and crystallization process adopts segmentation crystallization, obtains low silicon SAPO-34 molecular sieve, amplify reproducible,
Relative crystallinity reaches more than 100%, improves one-pot yield, and MTO decomposition induction time is greatly shortened and diene selective reaches
85.9%, simultaneously quantity of wastewater effluent be greatly reduced, advantageously reduce cost and environmental protection.
Brief description
Fig. 1 is the ESEM shape appearance figure of comparative example 1 synthetic sample.
Fig. 2 is the ESEM shape appearance figure of comparative example 2-in-1 one-tenth sample.
Fig. 3 is the XRD spectra of embodiment 1 synthetic sample.
Fig. 4 is the ESEM shape appearance figure of embodiment 1 synthetic sample.
Fig. 5 is the XRD spectra of embodiment 2-in-1 one-tenth sample.
Fig. 6 is the ESEM shape appearance figure of embodiment 2-in-1 one-tenth sample.
Fig. 7 is the XRD spectra of embodiment 3 synthetic sample.
Fig. 8 is the ESEM shape appearance figure of embodiment 4 synthetic sample.
Specific embodiment
The synthetic method of the SAPO-34 molecular sieve that the present invention provides is it is characterised in that according to charge ratio：(0.6～1.2)
P2O5:(0.01～0.8) SiO2:(0.6～1.2) Al2O3:(20～100) H2O, silicon source, phosphorus source and silicon source are mixed, and do
Dry obtain the silicon phosphorus aluminium dry glue that solid content is not less than 60%, silicon phosphorus aluminium dry glue is mixed with template, rubs with silicon phosphorus aluminium dry glue 1
You are Al2O3Meter, the addition of described template is 1～2.5 mole, adds template and part water to obtain mixture, gained mixes
Compound Zhong Shui with Al2O3The mol ratio of the silicon source of meter is not more than 20, mixture is placed under self-generated pressure in closed reactor brilliant
Change and recovery product, wherein, described crystallization is sequentially to divide three sections to carry out in temperature range from low to high, adjacent two sections
Crystallization temperature differs and rear one section of crystallization temperature is higher than that the last period temperature crystallization is no less than 40 DEG C, described three sections of crystallization temperatures
It is respectively 20～90 DEG C, 90～150 DEG C and 150～250 DEG C.
In the method for the present invention, described silicon source is acidic silicasol, white carbon, particulate silica gel, any one in positive esters of silicon acis
Plant or several mixtures, preferred acidic Ludox and white carbon；Silicon source is dry glue powder, boehmite, SB powder, alkoxyl
Any one or several mixtures in aluminium, preferably dry glue powder and SB powder；Phosphorus source is preferably 85% orthophosphoric acid；Template is four
Any one or several mixtures in ethyl ammonium hydroxide, triethylamine, diethylamine, morpholine, the four of wherein preferably 25%
Ethyl ammonium hydroxide and 100% triethylamine.The preferred tetraethyl ammonium hydroxide of described template and the mixture of triethylamine, enter
One step preferably, in the mixture of described tetraethyl ammonium hydroxide and triethylamine, tetraethyl ammonium hydroxide and triethylamine mole
Ratio is (0.1～2)：1.
Preferably, described mixture Zhong Shui with Al2O3The mol ratio of the silicon source of meter is less than 16, more preferably in mixture
Water with Al2O3The mol ratio of the silicon source of meter is 10-16.
In the method for the present invention, described is placed in crystallization under self-generated pressure in closed reactor by mixture, using segmentation
The mode of crystallization is carried out, including 20-90 DEG C of aging, 90-150 DEG C of nucleus generation and 150-250 DEG C of nucleus production process.Adjacent two
The crystallization temperature of section differs and rear one section of crystallization temperature is higher than that the last period temperature crystallization is no less than 40 DEG C, preferably 60～70 DEG C.
Three sections of described crystallization temperatures are 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.It is further preferred that total crystallization time controls in 30-90 hour.For example, a tool of the present invention
In the embodiment of body, crystallization process is in 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 process of described recovery product is known to those skilled in the art, for example, include filtering, wash, be dried and roasting
Burn etc..Described drying can be carried out at 100-110 DEG C, and described roasting can be carried out under 400-600 DEG C of constant temperature.
The invention will be further described by the following examples, but content not thereby limiting the invention.
In embodiment, XRD spectra is measured by Rigaku D/MAX- III A type diffractometer；ESEM shape appearance figure is public by FEI
The Quanta 200F type ESEM that department produces measures.
Comparative example 1
Process and the product of SAPO-34 molecular sieve is prepared in the explanation of this comparative example according to CN101633508A.
85% orthophosphoric acid (analysis is pure) 11g is added in 10g deionized water, is quickly uniformly mixing to obtain solution A；Another title
Take 7g dry glue powder to be dissolved in 10g deionized water, stir and add template 6g tetraethyl ammonium hydroxide, stir, then
Above-mentioned solution A is added, stirring obtains uniform colloidal sol in 2 hours.The 3g acidic silicasol that mass fraction is 30% adds respectively
Enter in above-mentioned colloidal sol, being uniformly mixing to obtain molar ratio is 0.1SiO2:1Al2O3:1P205:0.2TEAOH:1.4TEA:60H2O
Initial crystallization colloidal sol, then initial crystallization colloidal sol is placed in 100 milliliters of stainless steel closed reactors, 120 DEG C of crystallization 5h；Kettle
Temperature drop adds 7g triethylamine to room temperature, then is warming up to 190 DEG C of continuation crystallization 8 hours, takes out crystallization when kettle temperature is down to room temperature
Product, filters or centrifugation deionized water is washed till neutrality, is placed in 100-110 DEG C of thermostatic drying chamber and is dried, is finally putting into horse
Not it is warming up to 550 DEG C of constant temperature calcinings in stove and obtain within 4 hours the former powder of product.
This comparative sample ESEM shape appearance figure (SEM) is shown in Fig. 1, shows that grain morphology is cube, and it is micro- that crystal grain is more than 2
Rice.
Comparative example 2
The process of SAPO-34 molecular sieve is prepared in the explanation of this comparative example according to CN101633508A.
With comparative example 1, difference is that water aluminum ratio therein is changed into 50
The SEM photograph of this comparative sample is shown in Fig. 2, shows that grain morphology is cube, and crystallite dimension is 800nm.
Embodiment 1
According to 0.3SiO2:1Al2O3:1P205:30H2O adds ratio, will be thin to 30% acidic silicasol, 85% phosphoric acid, plan
Diaspore and water are sufficiently mixed uniformly, are placed in and 24h is dried in 80 DEG C of driers obtains the silicon phosphorus aluminium dry glue that solid content is 80%.Claim
Take silicon phosphorus aluminium glue 180g, be added to 1L crystallizing kettle.Add 171gTEAOH and 122gTEA, mix, add 40g water, stir
Mix uniformly.The additional proportion of each component：0.3SiO2:1Al2O3:1P205:0.5TEAOH:2TEA:13H2O.
Mixture is placed in 1L stainless steel autoclave, segmentation crystallization：Aged at room temperature 10h, 100 DEG C of crystallization 10h and
180 DEG C of crystallization 40h, take out crystallization product, sample is through filtration or centrifugation deionization when autoclave temperature is down to room temperature
It is washed to neutrality, be placed in 120 DEG C of thermostatic drying chamber and be dried, be finally putting in roaster and be warming up to 550 DEG C of constant temperature calcining 5h
Obtain molecular screen primary powder.
The XRD diffraction spectrogram of gained sample and SEM photograph are shown in Fig. 3 and Fig. 4 respectively, and XRD diffraction spectrogram shows that sample is
SAPO-34 molecular sieve, no stray crystal phase, SEM photograph shows that crystal grain is tabular cube, and crystallite dimension is 500nm, and thickness is
200nm.
Embodiment 2
Identical with the method that embodiment 1 prepares silicon phosphorus aluminium dry glue, weigh the silicon phosphorus aluminium glue 76g preparing, be added to 300mL
Crystallizing kettle, is subsequently adding 164gTEAOH and 6gTEA, mixes, and adds 26g water, stirs, the addition ratio of each component
Example：0.15SiO2:1Al2O3:1P205:0.8TEAOH:0.5TEA:20H2O.
Mixture is placed in 300mL stainless steel autoclave, segmentation crystallization：Aged at room temperature 10h, 100 DEG C of crystallization 10h
And 180 DEG C of crystallization 40h, when autoclave temperature is down to room temperature take out crystallization product, sample through filter or centrifugation spend from
Son is washed to neutrality, is placed in 80-120 DEG C of thermostatic drying chamber and is dried, and is finally putting in roaster and is warming up to 550 DEG C of constant temperature roastings
Burn 5h and obtain SAPO-34 molecular screen primary powder.
The XRD diffraction spectrogram of gained sample and SEM photograph are shown in Fig. 5 and Fig. 6 respectively, and XRD diffraction spectrogram explanation sample is
SAPO-34, no stray crystal phase, SEM photograph shows that crystal grain is cube, and crystallite dimension is 600nm.
Embodiment 3
Identical with the method that embodiment 1 prepares silicon phosphorus aluminium dry glue, weigh the silicon phosphorus aluminium glue 80g preparing, be added to 600mL
Crystallizing kettle, is subsequently adding 320gTEAOH and 12gTEA, mixes.The additional proportion of each component：0.6SiO2:1Al2O3:
1P205:1.6TEAOH:1TEA:13H2O.
Mixture is placed in 600mL closed reactor, segmentation crystallization：Aged at room temperature 10h, 100 DEG C of crystallization 10h and 180
DEG C crystallization 40h, takes out crystallization product when autoclave temperature is down to room temperature, and sample is through filtering or centrifugation is washed with deionized water
To neutral, it be placed in 80-120 DEG C of thermostatic drying chamber and be dried, be finally putting in roaster and be warming up to 550 DEG C of constant temperature calcining 5h and obtain
To molecular screen primary powder.
The XRD diffraction spectrogram of sample is shown in Fig. 7, shows that sample is SAPO-34.
Embodiment 4
Identical with the method that embodiment 1 prepares silicon phosphorus aluminium dry glue, weigh the silicon phosphorus aluminium glue 180g preparing, be added to 1L brilliant
Change kettle.Be subsequently adding 171gTEAOH and 140gTEA, mix, add 40g water, stirring all with.The addition ratio of each component
Example：0.3SiO2:1Al2O3:1P205:0.6TEAOH:3TEA:13H2O.
Mixture is placed in 1L stainless steel autoclave, segmentation crystallization：Aged at room temperature 10h, 100 DEG C of crystallization 10h and
180 DEG C of crystallization 40h, take out crystallization product, sample is through filtration or centrifugation deionization when autoclave temperature is down to room temperature
It is washed to neutrality, be placed in 120 DEG C of thermostatic drying chamber and be dried, be finally putting in roaster and be warming up to 550 DEG C of constant temperature calcining 5h
Obtain molecular screen primary powder.
The ESEM shape appearance figure of gained sample is shown in Fig. 8, shows that crystal grain is cube, and crystallite dimension is 800nm.
Comparative example 3-4
This comparative example illustrates catalytic performance result in methanol to olefins reaction for the comparative example 1 and 2.
The sample compressing tablet of the comparative example 1 and 2 after roasting is sieved, chooses the sample of 20-40 mesh, be labeled as C-1 and C-2.
Evaluating apparatus are fixed bed reactors, and appreciation condition is：Loaded catalyst is 3g, and reactant is methyl alcohol, mass space velocity 1h-1,
Carrier gas is nitrogen, and nitrogen flow is 350mL/min, 450 DEG C of reaction temperature, and reaction pressure is 0.25Mpa, and product is with ethene
It is target product with propylene, by gas-chromatography on-line analysis, reaction result is as shown in table 1 for product.
Embodiment 5-8
This example demonstrates that catalytic performance effect in methanol to olefins reaction for the embodiment 1-3 gained sample.
Embodiment 1-4 gained roasting sample sieves through compressing tablet, takes 20-40 mesh sample, is labeled as C-3, C-4, C-5 and C-6.
Evaluation method and condition are identical with comparative example 3-4, and MTO catalytic performance result is as shown in table 1.
Table 1
As can be seen from Table 1, the SAPO-34 sieve sample of the low water aluminum ratio method synthesis that the present invention provides is anti-in MTO
Comparative sample, diene (C are all better than on Ying Zhong, single pass life and diene selective2 =+C3 =) selectively reach as high as 85.94%,
MTO single pass life, up to 10h, shows that the SAPO-34 molecular sieve of low water aluminum ratio synthesis has excellent MTO catalytic performance.
Claims (12)
1. a kind of synthetic method of SAPO-34 molecular sieve is it is characterised in that according to charge ratio：(0.6～1.2) P2O5:(0.01
～0.8) SiO2:(0.6～1.2) Al2O3:(20～100) H2O, silicon source, phosphorus source and silicon source is mixed, is dried to obtain and admittedly contains
Amount is not less than 60% silicon phosphorus aluminium dry glue, silicon phosphorus aluminium dry glue is mixed with template, with 1 mole of Al in silicon phosphorus aluminium dry glue2O3Meter,
The addition of described template is 1～2.5 mole, adds template and part water to obtain mixture, water in gained mixture
With with Al2O3The mol ratio of silicon source of meter is not more than 20, mixture is placed under self-generated pressure in closed reactor crystallization and reclaims
Product, wherein, described template is the mixture of tetraethyl ammonium hydroxide and triethylamine, and described crystallization is from low to high
Temperature range in sequentially divide three sections to carry out, adjacent two sections of crystallization temperature differ and rear one section of crystallization temperature be higher than the last period
Temperature crystallization is 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.
2., according to the method for claim 1 wherein, described silicon source is acidic silicasol, white carbon, particulate silica gel, positive esters of silicon acis
One or more of mixture.
3., according to the method for claim 1 wherein, described phosphorus source is in monoammonium phosphate, phosphoric acid and ammonium dihydrogen phosphate
Plant or multiple.
4., according to the method for claim 1 wherein, described phosphorus source is 85% orthophosphoric acid.
5. according to the method for claim 1 wherein, described silicon source be one of dry glue powder, SB powder and aluminum alkoxide or
Several mixtures.
6. according to the method for claim 1 wherein, described silicon source for alumina content be 75% dry glue powder and SB powder.
7. according to the method for claim 1 wherein, in the mixture of described tetraethyl ammonium hydroxide and triethylamine, tetraethyl
The molar ratio of ammonium hydroxide and triethylamine is (0.1～0.2)：1.
8. according to the method for claim 1 wherein, mixture Zhong Shui with Al2O3The mol ratio of the silicon source of meter is less than 16.
9. according to the method for claim 1 wherein, mixture Zhong Shui with Al2O3The mol ratio of the silicon source of meter is 10-16.
10., according to the method for claim 1 wherein, described crystallization temperature is respectively 20～60 DEG C, 110～130 DEG C and 180
～210 DEG C.
11. according to claim 1 method, described crystallization process is in 25-35 DEG C of crystallization 5-10 hour, 100-150 DEG C of crystalline substance
Change 10-20 hour, 150-200 DEG C of crystallization 10-45 hour.
12. according to claim 1,10 or 11 method, wherein, described crystallization, control in 30-90 hour its total time.
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| CN109467100B (en) * | 2017-09-07 | 2020-11-13 | 中国石油化工股份有限公司 | Synthesis method and application of SAPO-34 molecular sieve |
| CN112624150B (en) * | 2019-09-24 | 2022-09-06 | 中国石油化工股份有限公司 | Synthetic method of SAPO-34 molecular sieve, synthetic molecular sieve and application thereof |
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| CN101125665A (en) * | 2007-08-08 | 2008-02-20 | 华陆工程科技有限责任公司 | Method for preparing SAPO-34 molecular sieve by liquid phase crystallization method |
| CN101481121A (en) * | 2008-01-09 | 2009-07-15 | 中国石油化工股份有限公司 | Silicoaluminophosphate molecular sieve composition and synthesizing method thereof |
| CN102336413A (en) * | 2010-11-29 | 2012-02-01 | 中国科学院大连化学物理研究所 | Synthesis method of low-silicon SAPO-34 molecular sieves |
| KR101142350B1 (en) * | 2006-08-08 | 2012-05-18 | 달리안 인스티튜트 오브 케미컬 피직스 | SAPO-34 Molecular Sieve having both Micropores and Mesopores and Synthesis Method thereof |
| CN102530989A (en) * | 2011-12-15 | 2012-07-04 | 神华集团有限责任公司 | Method for preparing large-crystal SAPO-34 molecular sieve, product obtained by the method and application of the product |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101142350B1 (en) * | 2006-08-08 | 2012-05-18 | 달리안 인스티튜트 오브 케미컬 피직스 | SAPO-34 Molecular Sieve having both Micropores and Mesopores and Synthesis Method thereof |
| CN101125665A (en) * | 2007-08-08 | 2008-02-20 | 华陆工程科技有限责任公司 | Method for preparing SAPO-34 molecular sieve by liquid phase crystallization method |
| CN101481121A (en) * | 2008-01-09 | 2009-07-15 | 中国石油化工股份有限公司 | Silicoaluminophosphate molecular sieve composition and synthesizing method thereof |
| CN102336413A (en) * | 2010-11-29 | 2012-02-01 | 中国科学院大连化学物理研究所 | Synthesis method of low-silicon SAPO-34 molecular sieves |
| CN102530989A (en) * | 2011-12-15 | 2012-07-04 | 神华集团有限责任公司 | Method for preparing large-crystal SAPO-34 molecular sieve, product obtained by the method and application of the product |
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