CN1048429C - Method of synthesizing aluminosilico-phosphate molecular sieve using double template agent - Google Patents
Method of synthesizing aluminosilico-phosphate molecular sieve using double template agent Download PDFInfo
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- CN1048429C CN1048429C CN94110059A CN94110059A CN1048429C CN 1048429 C CN1048429 C CN 1048429C CN 94110059 A CN94110059 A CN 94110059A CN 94110059 A CN94110059 A CN 94110059A CN 1048429 C CN1048429 C CN 1048429C
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- molecular sieve
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to a double mould plate agent synthetic method for silicon aluminum phosphate molecular sieves SAPO-34. The present invention is characterized in that a double mould plate agent is the mixture of triethylamine and tetraethyl ammonium hydroxide. The crystal size of the SAPO-34 molecular sieves synthesized by the method of the present invention can be changed by changing the mole ratio of the triethylamine and the tetraethyl ammonium hydroxide of the double mould plate agent. The catalyst made by the molecular sieves is used for converting methyl alcohol or / and methyl oxide into low-carbon alkene, and can further enhance the selectivity of the low-carbon alkene in products.
Description
The present invention relates to a kind of synthetic method of molecular sieve, specifically just provided a kind of tetraethyl ammonium hydroxide (TEAOH) and triethylamine (TEA) used and be the method for template synthesized silicon-aluminum phosphate SAPO-34 molecular sieve.This molecular sieve can by methyl alcohol or/and dimethyl ether conversion is to use in the catalyzed reaction of low-carbon alkene.
Synthesized silicon-aluminum phosphate SAPO-34 molecular sieve is a kind ofly to be made up of phosphorus, silicon, aluminium and oxygen, has the molecular sieve of class chabazite structure.Its structural unit is by PO
+ 2, AlO
- 2And SiO
2Tetrahedron constitutes.Anhydrous chemical constitution can be expressed as: mR (Si
xAl
yP
z) O
2, wherein R is the template that is present in the molecular sieve crystal micropore, and m is the mole number of R, and x, y, z are respectively the mole fraction of Si, Al, P, and satisfy x+y+z=1.European patent EP 0103117 discloses a kind of hydrothermal synthesis method of SAPO-34 molecular sieve, and one of its technical characterstic is to have used tetraethyl ammonium hydroxide in the building-up process, Isopropylamine or be template with the mixture of tetraethyl ammonium hydroxide and di-n-propylamine.After this, U.S. Pat 4440871 has reported that again relevant SAPO-34 molecular sieve synthetic improves one's methods, but adopts identical template.Because these template cost an arm and a leg, the source difficulty is difficult in the industrial production and adopts.Present inventors had once proposed two kinds of technology (CN92112230.6 and CN93112015.2) that are suitable for the synthetic SAPO-34 molecular sieve of suitability for industrialized production employing in advance, and promptly adopting triethylamine or diethylamine is the template synthesized silicon-aluminum phosphate molecular sieve.Adopt this technology synthetic SAPO-34 of institute molecular sieve after roasting, activation treatment, to can be used as by methyl alcohol or/and dimethyl ether conversion is the low-carbon alkene catalyst for reaction.But it is adopt above-mentioned its crystal grain of the technology synthetic SAPO-34 of institute molecular sieve bigger, and also restive to the size of crystal grain.
But the method that the purpose of this invention is to provide a kind of synthetic this molecular sieve of modulation SAPO-34 zeolite crystal size, adopt this method can synthesize the SAPO-34 molecular sieve of different grain sizes, can be prepared into catalyzer after treatment, be used for methyl alcohol or/and dimethyl ether conversion is the low-carbon alkene reaction, make the transformation efficiency of methyl alcohol or/or dme can reach 100%, the selectivity of low-carbon alkene also adopts the selectivity of prior art institute synthetic molecular sieve to want high.
The invention provides the synthetic SAPO-34 of method institute molecular sieve, the still available mR (Si of its structural formula
xAl
yP
z) O
2Expression, wherein x, y, z are respectively the mole fraction of Si, Al, P, and satisfy x+y+z=1; R is a template, and m is the mole number of template, and m=0.03～0.6, simultaneously, and x=0.01～0.98, y=0.01～0.60, z=0.01～0.60; It is characterized in that R is the double template that tetraethyl ammonium hydroxide and triethylamine are formed, and the mole fraction of every kind of template in double template is all non-vanishing.
During above-mentioned molecular sieve synthetic, its silicon source can be silicon sol, active silica or positive silicon ester, and the aluminium source can be aluminum alkoxide, pseudobochmite or activated alumina, and the phosphorus source can be ortho-phosphoric acid, aluminum phosphate, and its synthetic primary process is as follows:
(1) according to above-mentioned catalyst structure formula mR (Si
xAl
yP
z) O
2: 2～500H
2The amount of O takes by weighing a certain amount of template, silicon source, aluminium source, phosphorus source and water;
(2), fully stir again and make gel with above-mentioned each mixing of materials;
(3) with gel in 100～250 ℃ of crystallization, the crystallization time is not shorter than 0.5 hour;
(4) complete after-filtration of crystallization or centrifugation, washing, drying again, drying can be carried out under the condition of air and 0～120 ℃, can synthesize the SAPO-34 molecular sieve.Above-mentioned building-up process is characterised in that the double template that added template R is made up of tetraethyl ammonium hydroxide and triethylamine, the composition proportioning that adds template by changing, but the grain size of modulation synthesis of molecular sieve, the available R=kTEAOH+lTEA of the composition of its template represents, wherein: k+l=1, and k, l ≠ 0.
The SAPO-34 molecular sieve of synthetic double template of the present invention can carry out following processing, makes catalyzer:
1. the roasting in air and 300～700 ℃ of temperature ranges of exsiccant SAPO-34 molecular sieve is become active catalyst to remove template;
2. the SAPO-34 molecular sieve of calcination process being crossed adds binding agent, for example Al
2O
3, SiO
2, MgO or TiO etc. mix, moulding, drying are carried out roasting through 300～700 ℃ of temperature ranges again and are made catalyzer.
SAPO-34 molecular sieve catalyst after will handling through above-mentioned 1 or 1 and 2 be used for catalysis methanol or/and dimethyl ether conversion when being the reaction of low-carbon alkene, and temperature of reaction is 300～550 ℃, and preferable temperature of reaction is 400～500 ℃.Methyl alcohol is or/and the weight space velocity WHSV=1～5h of dme
-1The time, conversion of raw material can reach 100%, C
2～C
4Selectivity of light olefin is higher than employing triethylamine or the single template of the tetraethyl ammonium hydroxide synthetic SAPO-34 of institute molecular sieve catalyst.
Following illustrative example is described further technology of the present invention.
Synthesizing of embodiment 1～6 SAPO-34 molecular sieve
According to formula (kTEAOH+lTEA): 0.3SiO
2: Al
2O
3: 1.05P
2O
5: 100H
2O takes by weighing raw material.Value such as the table 1 of k, l are listed.Table 1 molecular sieve compound experiment acetonideexample production code member TEAOH: TEA XRD is size of microcrystal as a result
(mole) (μm) 1 SAP01 1.0∶0.0 SAPO-34 0.5 2 SAP02 0.8∶0.2 SAPO-34 1.8 3 SAP03 0.6∶0.4 SAPO-34 2.6 4 SAP04 0.4∶0.6 SAPO-34 4.4 5 SAP05 0.2∶0.8 SAPO-34 6.6 6 SAP06 0.0∶1.0 SAPO-34 7.8
Earlier with Al
2O
3Content is 75.0% pseudobochmite sheet and H
3PO
4After aqueous solution is even, adds and contain SiO
2The silicon sol of 39.3wt% and water stir.Add template triethylamine and tetraethyl ammonium hydroxide then, stir, make gel.Gel is encapsulated in the autoclave of inner liner polytetrafluoroethylene, crystallization is 100 hours under 200 ℃ and autogenous pressure.Solid phase prod after filtration, do that scanning electron microscope is measured and X-ray powder diffraction is identified after the washing, drying, the results are shown in table 1.
Table 1 confirms that the composition difference of template, the grain size of SAPO-34 molecular sieve are also different.Therefore, the ratio of control double template just can be controlled the grain size of molecular sieve.
Embodiment 7 SAPO-34 molecular sieve catalysts preparation 1
With embodiment 1～6 synthetic SAPO-34 molecular screen primary powder through 350 ℃ 1 hour, 450 ℃ 1 hour, 500 ℃ 0.5 hour, 550 ℃ 0.5 hour, after 600 ℃ of roastings in 6 hours, be cooled to room temperature, with a part of compressing tablet, smash, the sieve particle that sieves out 20-40 order granularity is catalyzer a, its numbering with table 1 in identical.
Embodiment 8 catalyzed reactions test 1
Adopt atmospheric fixed bed reaction unit, reactor is a quartz glass tube, utilizes the catalyzer a of embodiment 7 preparations.The 1.28 gram catalyzer a that pack in reactor are warmed up to 500 ℃ and constant temperature earlier and activated in 1 hour in flow velocity is the nitrogen gas stream of 60 ml/min, be cooled to 450 ℃ then, bring reaction raw materials methyl alcohol into reactor with nitrogen.The mole fraction of methyl alcohol is 35% in the unstripped gas, and the weight space velocity of methyl alcohol is WHSV=2h
-1, reaction pressure is 0.1～0.15MPa, and reaction proceeds to the composition of using the gas chromatographic analysis product after 3 minutes, and its hydrocarbon distribution the results are shown in table 2, and the transformation efficiency of reactant methanol is 100%.Table 2 fixed bed methanol conversion reaction result catalyzer a hydrocarbon product distribution (wt%)
CH
4 C
2H
4 C
2H
6 C
3H
6 C
3H
8 C
4H
8C
4H
10 C
5+?C
2 --C
4 -SAP01 2.49 29.73 3.00 29.24 19.09 6.25 9.20 0 66.22SAP02 6.95 33.11 2.11 40.53 6.00 1.65 8.65 0 75.29SAP03 5.19 41.17 3.14 37.62 12.04 2.57 0 0 81.36SAP04 6.19 53.62 1.18 35.50 3.48 0 0 0 89.12SAP05 6.21 39.74 1.80 35.29 12.60 4.33 0 0 79.36SAP06 5.23 32.22 1.79 33.31 9.87 8.26 8.77 0 74.34
Table 2 illustrates, C in the product of methyl alcohol conversion reaction under existing with tetraethyl ammonium hydroxide-triethylamine double template synthetic SAPO-34 molecular sieve catalyst
2 -And C
2 -～C
4 -Selectivity under the selectivity of low-carbon alkene is significantly higher than and exists with tetraethyl ammonium hydroxide or the single template synthetic of triethylamine SAPO-34 molecular sieve.
Embodiment 9 SAPO-34 molecular sieve catalysts preparation 2
Baked SAPO-34 sieve sample and silicon sol among the embodiment 7 (are contained SiO
240%wt) mix, after moulding, the drying, 600 ℃ of roastings in 4 hours.After being cooled to room temperature, with the sample compressing tablet, fragmentation, the particle that sieves out 100-210 order granularity is catalyzer b, the content of its SAPO-34 molecular sieve is 50%wt.Identical in the numbering of catalyzer b and the table 1.
Embodiment 10 catalyzed reactions test 2
Adopt miniature fluidized bed device to carry out the dimethyl ether conversion test.Reactor is a quartz glass tube, 20 millimeters of internal diameters.Adopt the catalyzer b of embodiment 9 preparations, earlier 500 ℃ with nitrogen with catalyst activation 1 hour, feed dme again and nitrogen mixture reacts.Reaction conditions is: catalyst weight 5.6356 grams, dme weight space velocity 2.52h
-1, the mole of dme in air-flow is separated into 0.109, and the bed linear velocity is 0.11 meter per second, 500 ℃ of temperature of reaction, synthesis under normal pressure.After the dme charging 5 minutes, divide the plate reaction product to form with online gas-chromatography.The result is: the dimethyl ether conversion rate is 100%, and hydrocarbon product distributes as shown in table 4.As seen C
2 -And C
2 -～C
4 -The selectivity of low-carbon alkene all is higher than corresponding fixed bed test-results.And adopt the inventive method institute synthetic catalyzer, its catalytic performance is better with tetraethyl ammonium hydroxide or triethylamine template synthetic SAPO-34 molecular sieve catalyst than single
Table 4 fluidized-bed methanol conversion reaction result catalyzer b hydrocarbon product distribution (wt%)
CH
4 C
2H
4 C
2H
6 C
3H
6 C
3H
8?C
4H
8?C
4H
10 C
6+ C
2 --C
4 -SAP01 0.65 33.26 1.14 22.05 20.12 10.25 12.53 0 65.57SAPO4 1.59 59.97 0.45 26.77 5.49 4.46 1.27 0 91.20SAP06 1.34 36.04 2.01 30.73 10.65 9.12 10.11 0 75.89
In sum, compare with single organic formwork agent, with double template method synthetic SAPO-34 molecular sieve provided by the invention to methyl alcohol or/and the dimethyl ether conversion producing light olefins has more excellent katalysis.In addition, the controllable SAPO-34 molecular sieve of this grain size also can be used for other catalyzed reaction.
Claims (1)
1. method that adopts template synthesized silicon-aluminum phosphate SAPO-34 molecular sieve, the structural formula of SAPO-34 molecular sieve is mR (Si
xAl
yP
z) O
2, wherein x, y, z are respectively the mole fraction of Si, Al, P, and satisfy x+y+z=1, and R is a template, and m is the mole number of template, m=0.03～0.6, while x=0.01～0.98, y=0.01～0.6, z=0.01～0.6; Its synthetic primary process is as follows:
(1) according to above-mentioned catalyst structure formula mR (Si
xAl
yP
z) O
2: 2～500H
2The amount of O takes by weighing a certain amount of template, silicon source, aluminium source, phosphorus source and water;
(2), fully stir again and make gel with above-mentioned each mixing of materials;
(3) with gel in 100～250 ℃ of crystallization, the crystallization time is not shorter than 0.5 hour;
(4) complete after-filtration of crystallization or centrifugation, washing, drying drier are carried out under the condition of air and 0～120 ℃, can synthesize the SAPO-34 molecular sieve;
Described silicon source is selected from silicon sol, active silica or positive silicon ester, and the aluminium source is selected from aluminum alkoxide, pseudobochmite or activated alumina, and the phosphorus source is selected from ortho-phosphoric acid, aluminum phosphate;
It is characterized in that: the double template that added template R is made up of tetraethyl ammonium hydroxide and triethylamine, the composition of its template represent with R=kTEAOH+lTEA, wherein: k+l=1, and k, l ≠ 0.
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|---|---|---|---|
| CN94110059A CN1048429C (en) | 1994-02-05 | 1994-02-05 | Method of synthesizing aluminosilico-phosphate molecular sieve using double template agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94110059A CN1048429C (en) | 1994-02-05 | 1994-02-05 | Method of synthesizing aluminosilico-phosphate molecular sieve using double template agent |
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|---|---|
| CN1106715A CN1106715A (en) | 1995-08-16 |
| CN1048429C true CN1048429C (en) | 2000-01-19 |
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| CN94110059A Expired - Fee Related CN1048429C (en) | 1994-02-05 | 1994-02-05 | Method of synthesizing aluminosilico-phosphate molecular sieve using double template agent |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10259757B2 (en) | 2006-08-23 | 2019-04-16 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for starting up a fluidized catalytic reaction apparatus used for producing lower olefins |
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|---|---|---|---|---|
| CN1067603C (en) * | 1996-06-07 | 2001-06-27 | 中国科学院大连化学物理研究所 | Metal modified small-porosity P-Si-Al molecular sieve catalyst, its preparing process and use thereof |
| CN1076219C (en) * | 1996-08-02 | 2001-12-19 | 中国科学院大连化学物理研究所 | Silicon phosphorus aluminium molecular sieve containing alkaline earth metal and its synthesis |
| WO2001025150A1 (en) * | 1999-10-01 | 2001-04-12 | Pop, Grigore | Process for the synthesis of silicoaluminophosphate molecular sieves |
| CN101443298A (en) | 2006-05-15 | 2009-05-27 | 科罗拉多州立大学董事会 | High flux and selectivity SAPO-34 membranes for CO/CH4 separations |
| CN101121533B (en) * | 2006-08-08 | 2010-05-19 | 中国科学院大连化学物理研究所 | SAPO-34 molecular sieve with micropore and mesopore structure and synthetic method thereof |
| CN100584758C (en) * | 2006-08-08 | 2010-01-27 | 中国科学院大连化学物理研究所 | Fast synthetic method for phosphorus-silicon-aluminum molecular sieve |
| WO2008112520A1 (en) | 2007-03-09 | 2008-09-18 | The Regents Of The University Of Colorado, A Body Corporate | Synthesis of zeolites and zeolite membranes using multiple structure directing agents |
| CN101306821B (en) * | 2007-05-16 | 2011-12-21 | 中国石油化工股份有限公司 | Process for preparing UFI zeolite |
| CN101935049B (en) * | 2009-06-30 | 2012-10-10 | 中国石油化工股份有限公司 | Silicoaluminophosphate molecular sieve |
| US8679227B2 (en) | 2010-04-29 | 2014-03-25 | The Regents Of The University Of Colorado | High flux SAPO-34 membranes for CO2/CH4 separation and template removal method |
| CN103030155B (en) * | 2011-09-30 | 2015-05-13 | 中国石油化工股份有限公司 | Synthesis method of silicoaluminophosphate (SAPO)-44 molecular sieve |
| CN103274426A (en) * | 2013-05-08 | 2013-09-04 | 天津众智科技有限公司 | High-temperature hydro-thermal synthesis method for preparing SAPO-34 molecular sieve by using double templates |
| CN106082269A (en) * | 2016-06-22 | 2016-11-09 | 华微科技（苏州）有限公司 | The method being template synthesis SAPO 34 molecular sieve with triethylamine and diethylamine |
| CN106904629B (en) * | 2017-02-28 | 2018-12-04 | 西北大学 | SAPO-34 multistage porous molecular sieve of nanometer sheet vortex shape self assembly and preparation method thereof |
| CN110092390B (en) * | 2019-04-17 | 2022-03-22 | 汕头大学 | Loose porous spherical SAPO-34 molecular sieve and preparation and application thereof |
| CN113278097B (en) * | 2021-06-03 | 2023-03-17 | 上海廷锦技术有限公司 | Silica gel supported metallocene catalyst, and preparation method and application thereof |
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Patent Citations (6)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US10259757B2 (en) | 2006-08-23 | 2019-04-16 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for starting up a fluidized catalytic reaction apparatus used for producing lower olefins |
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| CN1106715A (en) | 1995-08-16 |
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