CN1351960A - Aluminium silkicon phosphate molecular sieve and its preparing method - Google Patents
Aluminium silkicon phosphate molecular sieve and its preparing method Download PDFInfo
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Abstract
An aluminium silicon phosphate molecular sieve SAPO-11 is synthesized in a two-phase medium by using nitrogen-contained organic compounds with diisopropylamine as main component as template agent. The molecular sieve has strong acidity and special activity and selectivity, and may be used as active component of organic chemical reaction catalyst for hydrogenation and isomerization of straight chain alkane, etc..
Description
The present invention relates to a kind of molecular sieve and synthetic method thereof, relate to a kind of pure aluminium silicophosphate SAPO-11 molecular sieve and preparation method thereof specifically.
Along with developing rapidly of mechanical industry, requirement to quality of lubrication oil is more and more higher, and the appearance of worldwide crude oil poor qualityization and heaviness trend, make that the disparities between supply and demand of high quality lubricating oil are more outstanding, industrial extensive employing at present be that lubricant base is produced in catalytic dewaxing and solvent dewaxing, isomery takes off cured as a kind of new Technology, compare advantage with preceding two kinds of technologies and gain great popularity, discover that aluminium silicophosphate SAPO-11 molecular sieve is the ideal composition that a kind of isomery takes off cured catalyzer with yield of lubricating oil height, good product quality.
A kind of novel aluminum phosphate AlPO4-11 molecular sieve is that the eighties is synthetic first by U.S. UCC company, and it is by PO
4 +, AlO
4 -Tetrahedron produces the acid site by the three-dimensional neutral backbone structure that alternately forms of strictness for making it, and with forming aluminium silicophosphate SAPO-11 molecular sieve behind the quaternary silicon replacement pentavalent phosphorus wherein, it is a kind zeolite-type molecular sieves, and its structural unit is by PO
4 +, AlO
4 -And SiO
4The three-dimensional framework structure that tetrahedron constitutes has ellipse one dimension straight hole road, and its anhydrous experience chemical constitution can be expressed as: mR: Al
2O
3: nP
2O
5: qSiO
2, " R " for being present in the template in the microporous molecular sieve, " m " is the mole number of template " R ".United States Patent (USP) U.S.P.4,440,871 disclose a kind of hydrothermal synthesis method of SAPO-11 molecular sieve.One of its technical characterstic is not add organic solvent or tensio-active agent in the building-up process, uses single template synthetic under aqueous systems.On this basis, United States Patent (USP) U.S.P.5,208,005 propose with the certain crystallization condition of control, prepare little crystal grain, SAPO-11 molecular sieve that surface silicon content is higher than body phase silicone content.Find after deliberation, as use single template, the product crystalline phase that obtains is become the glue influence of temperature change, what often obtain is the mixture of several crystalline phases, for example: when being template with the Diisopropylamine, the product crystalline phase is the mixture of SAPO-11 (AEL) and SAPO-5 (AFI), and when being template with the di-n-propylamine, the product crystalline phase is the mixture of SAPO-11 (AEL) and SAPO-31 (ATO).Because the acidity and the pore structure that obtain different crystalline phases all have difference, will cause the selectivity of catalyzed reaction to reduce when doing the acidity of catalyst component with mixed crystal.When literature method prepares molecular sieve in addition, owing to be, make two kinds of silicon substitution mechanisms take place simultaneously that (first kind of silicon substitution mechanism is that a Si replaces a P and produces a B acid site simultaneously easily at aqueous phase; Second kind of silicon substitution mechanism is that two Si replace an Al and a P simultaneously and do not produce acid sites.)。Cause a little less than the acidity of molecular sieve, its infrared acidity generally is not more than 0.2mmol/g, NH
3-TPD acidity generally is not more than 0.50mmol/g.It is lower that the isomery of preparation takes off cured activity of such catalysts, as promoting temperature of reaction, the selectivity of target product reduced, and equipment and life of catalyst are shortened.
The purpose of this invention is to provide a kind of preparation method of new molecular sieve, can prepare crystalline phase single S APO-11 molecular sieve, improve the acidity of molecular sieve simultaneously with this method.The present invention provides the more highly acid molecular sieve that has with this method preparation simultaneously in addition.
The building-up process of SAPO-11 molecular sieve of the present invention can be expressed as: (a) template, silicon source, aluminium source, phosphoric acid, organic solvent and water mixing, stirring are obtained gel; (b) gel that (a) made carries out crystallization, and solid in the filtration product obtains molecular sieve through washing, drying
Former powder; (c) molecular screen primary powder that roasting (b) makes removes template and obtains molecular sieve.
Said template is the organic compounds containing nitrogen group based on Diisopropylamine, and wherein Diisopropylamine weight in template should be not less than 50%.Other organic compounds containing nitrogen is one or more of Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, triethylamine, tripropylamine, di-n-propylamine, isopropylamine or pyridine.Preparation is pure AEL type SAPO-11 molecular sieve in this way, and is not become glue temperature effect.For avoiding two kinds of silicon substitution mechanisms to take place simultaneously, the present invention adopts in the gel of step (a) gained and adds certain amount of organic solvent in addition, and organic solvent is one or more in n-hexyl alcohol, Virahol, ethylene glycol, glycerol or the hexanediamine here.Make and produce two-phase interface in the system, silicon slowly by the interface, effectively replaces the phosphorus in the molecular sieve, and first kind of silicon substitution mechanism only takes place, thereby the acidity of molecular sieve is improved.
The mole proportioning of each material is in the step (a):
0.2～6.0R: Al
2O
3: 0.7～1.5P
2O
5: 0.01～4.0SiO
2: 1～100G: 10～500H
2O is preferably: 0.5～3.0R: Al
2O
3: 0.8～1.2P
2O
5: 0.1～2SiO
2: 2.～50G: 2.～200H
2O is preferably: 0.7～2.5R: Al
2O
3: 0.9～1.1P
2O
5: 0.3～1.5SiO
2: 4～20G: 30～100H
2O.Here " R " is template, and " G " is organic solvent.
Said crystallization is carried out in the interior autoclave that is lined with tetrafluoroethylene in the step (b), and crystallization temperature is 150～2400 ℃, is preferably 180～220 ℃, is preferably 190～210 ℃; Crystallization time is 1～150 hour, is preferably 10～72 hours, is preferably 20～50 hours.
Said maturing temperature is 400～700 ℃ in the step (c), is preferably 450～650 ℃, is preferably 500～600 ℃.Roasting time is 4～24 hours, is preferably 8～16 hours.
Basic experience chemical constitution with the aluminium silicophosphate molecular sieve anhydride of the inventive method preparation is: mR: Al
2O
3: nP
2O
5: qSiO
2, " R " for being present in the template in the microporous molecular sieve, " m " is the mole number of template " R ", and the value of " m " is 0.2～6, and the value of " n " is 0.8～1.5, and the value of " q " is 0.01～4.The molecular sieve that obtains has following characteristics: 1. the result that records of synthesis of molecular sieve X powder ray diffraction method has table 1 feature.2. the specific surface area of synthesis of molecular sieve is generally 140～240m
2/ g is preferably 160～220m
2/ g is preferably 170～210m
2/ g.3. the pore volume of synthesis of molecular sieve is generally 0.1～0.3ml/g, is preferably 0.15～0.25ml/g, is preferably 0.17～0.22ml/g.4. the infrared acidity of synthesis of molecular sieve is preferably in 0.25～0.50mmol/g generally at 0.20～0.50mmol/g; NH
3-TPD acidity is preferably in 0.60～1.00mmol/g generally at 0.50～1.00mmol/g.
Give further instruction below by embodiment to technology of the present invention.The preparation 1 of embodiment 1 SAPO-11 molecular sieve
The ortho-phosphoric acid of getting 23 grams 85% mixes with 30 gram deionized waters, add 41 gram aluminum isopropylates then, after being stirred to evenly, add 20.8 gram tetraethoxys successively, 9.1 gram Diisopropylamine, 7.8 the gram pyridine, 40 gram n-hexyl alcohols and 42 gram deionized waters and abundant the stirring obtain gel, and it consists of: 1.0R: 1.0Al
2O
3: 1.0P
2O
5: 1.0SiO
2: 4G: 40H
2O.
Above-mentioned gel is enclosed in the autoclave of inner liner polytetrafluoroethylene, in 190 ℃ of thermostatic crystallizations 24 hours, filtration product gained solid was through washing, and 110 ℃ of dryings are carried out the X-ray powder diffraction and measured after 4 hours, must table 1 column data.This result shows that the gained synthetic product is pure SAPO-11 molecular sieve, and it basic composition is: 1.0Al
2O
3: 0.86P
2O
5: 0.91SiO
2
The XRD result of table 1 embodiment 1 sample
X-ray diffraction measure to adopt D/MAX-RA type x-ray diffractometer of science, and source of radiation is the copper target, the filtering of graphite monocrystalline, operation tube voltage 35KV, tube current 30～50mA, sweep velocity (2 θ) be 4 degree/minute, sweep limit is 4～35 degree.The preparation 2 of embodiment 2 SAPO-11 molecular sieves
| ?Peak?No. | ?2Theta(°) | ????d-value | ?100×I/I 0 |
| ????1 | ????8.10 | ????10.9063 | ????20 |
| ????2 | ????9.50 | ????9.3020 | ????26 |
| ????3 | ????15.70 | ????5.6398 | ????28 |
| ????4 | ????20.40 | ????4.3498 | ????42 |
| ????5 | ????21.10 | ????4.2070 | ????100 |
| ????6 | ????22.10 | ????4.0189 | ????52 |
| ????7 | ????22.50 | ????3.9483 | ????42 |
| ????8 | ????22.70 | ????3.9140 | ????48 |
| ????9 | ????23.20 | ????3.8308 | ????66 |
| ????10 | ????26.40 | ????3.3732 | ????26 |
| ????11 | ????28.70 | ????3.1079 | ????20 |
Get 26 grams, 85% ortho-phosphoric acid and mix, add 41 then and restrain aluminum isopropylates with 108 gram deionized waters, be stirred to even after, add 41 gram tetraethoxys successively, 10 gram Diisopropylamines, 6 gram di-n-propylamines, 100 gram n-hexyl alcohols and abundant the stirring obtain gel, and it consists of: 1.8R: 1.0Al
2O
3: 1.1P
2O
5: 2.2SiO
2: 10G: 60H
2O.
Above-mentioned gel is enclosed in the autoclave of inner liner polytetrafluoroethylene, in 210 ℃ of thermostatic crystallizations 24 hours, filtration product gained solid was through washing, 110 ℃ of dryings 15 hours, the X-ray powder diffraction confirms that the gained synthetic product is pure SAPO-11 molecular sieve, and it basic composition is: 1.0Al
2O
3: 0.93P
2O
5: 1.54SiO
2The preparation 3 of embodiment 3 SAPO-11 molecular sieves
Get 21 grams, 85% ortho-phosphoric acid and mix, add 41 gram aluminum isopropylates then with 120 gram deionized waters, be stirred to even after, add 12 successively and restrain and contain SiO
2Be 30% silicon sol, 17 gram Diisopropylamines, 6 gram triethylamines, 160 gram n-hexyl alcohols also fully stir and obtain gel, and it consists of: 2.3R: 1.0Al
2O
3: 0.9P
2O
5: 0.6SiO
2: 16G: 70H
2O.Above-mentioned gel is enclosed in the autoclave of inner liner polytetrafluoroethylene, in 200 thermostatic crystallizations 48 hours, filtration product gained solid was through washing, 110 ℃ of dryings 6 hours, the X-ray powder diffraction confirms that the gained synthetic product is pure SAPO-11 molecular sieve, and it basic composition is: 1.0Al
2O
3: 0.77P
2O
5: 0.54SiO
2The preparation 4 of embodiment 4 SAPO-11 molecular sieves
The ortho-phosphoric acid of getting 32 grams 85% mixes with 74 gram deionized waters, the pseudo-boehmite that adds 14.1 grams moisture 28% then, after being stirred to evenly, add the white carbon black of 2 grams successively, 18.4 gram Diisopropylamine, the tetraethyl ammonium hydroxide of 14 grams 10%, 300 gram n-hexyl alcohols and abundant the stirring obtain gel, and it consists of: 3.0R: 1.0Al
2O
3: 1.4P
2O
5: 0.3SiO
2: 30G: 41H
2O.
Above-mentioned gel is enclosed in the autoclave of inner liner polytetrafluoroethylene, in 195 ℃ of thermostatic crystallizations 36 hours, filtration product gained solid was through washing, 110 ℃ of dryings 8 hours, the X-ray powder diffraction is surveyed and is confirmed that the gained synthetic product is pure SAPO-11 molecular sieve, and it basic composition is: 1.0Al
2O
3: 0.93P
2O
5: 0.29SiO
2The preparation 5 of embodiment 5 SAPO-11 molecular sieves
Get 26 grams, 85% ortho-phosphoric acid and mix, add the pseudo-boehmite of 15 grams moisture 28% then with 60 gram deionized waters, be stirred to even after, add 14 successively and restrain and contain SiO
2Be 30% silicon sol, 8 gram Diisopropylamines, 4.5 gram di-n-propylamines, 120 gram n-hexyl alcohols, 10 gram Virahols also fully stir and obtain gel, and it consists of: 1.3R: Al
2O
3: 1.1P
2O
5: 0.7SiO
2: 24G: 30H
2O.
Above-mentioned gel is enclosed in the autoclave of inner liner polytetrafluoroethylene, in 240 ℃ of thermostatic crystallizations 20 hours, filtration product gained solid was through washing, 110 ℃ of dryings 5 hours, the X-ray powder diffraction is surveyed and is confirmed that the gained synthetic product is pure SAPO-11 molecular sieve, and it basic composition is: 1.0Al
2O
3: 0.88P
2O
5: 0.72SiO
2The preparation 6 of embodiment 6 SAPO-11 molecular sieves
Get 26 grams, 85% ortho-phosphoric acid and mix, add 41 then and restrain aluminum isopropylates with 40 gram deionized waters, be stirred to even after, add 26 gram tetraethoxys successively, 9.5 gram Diisopropylamines, 4.5 gram di-n-propylamines, 32 gram ethylene glycol and abundant the stirring obtain gel, and it consists of: 1.5R: 1.0Al
2O
3: 1.1P
2O
5: 1.3SiO
2: 5G: 25H
2O.
Above-mentioned gel is enclosed in the autoclave of inner liner polytetrafluoroethylene, in 185 ℃ of thermostatic crystallizations 72 hours, filtration product gained solid was through washing, 110 ℃ of dryings 6 hours, the X-ray powder diffraction confirms that the gained synthetic product is pure SAPO-11 molecular sieve, and it basic composition is: 1.0Al
2O
3: 0.92P
2O
5: 1.33SiO
2The preparation 7 of embodiment 7 SAPO-11 molecular sieves
Get 23 grams, 85% ortho-phosphoric acid and mix, add the pseudo-boehmite of 14 grams moisture 28% then with 160 gram deionized waters, be stirred to even after, add 16 successively and restrain and contain SiO
2Be 30% silicon sol, 14 gram Diisopropylamines, 54 restrain oneself diamines and fully stir and obtain gel.It consists of: 1.4R: 1.0Al
2O
3: 1.0P
2O
5: 0.8SiO
2: 3.7G: 90H
2O.
Above-mentioned gel is enclosed in the autoclave of inner liner polytetrafluoroethylene, in 195 ℃ of thermostatic crystallizations 36 hours, filtration product gained solid was through washing, 110 ℃ of dryings 4 hours, the X-ray powder diffraction is surveyed and is confirmed that the gained synthetic product is pure SAPO-11 molecular sieve, and it basic composition is: 1.0Al
2O
3: 0.82P
2O
5: 0.75SiO
2Comparative example
With U.S. Patent No. 4,440,871 methods of announcing are listed in table 2 with the character of the molecular sieve for preparing with the inventive method
The SAPO-11 molecular sieve property list of table 2 different methods preparation
Annotate: be numbered in this table: 0-contrasts patented method; 1～4-the inventive method.
| Numbering | Form | Acidity (mmol/g) | ||
| Gel | Molecular sieve | Infrared | NH 3-TPD | |
| ?0 | ?1.0Al 2O 3∶1.0P 2O 5∶0.30SiO 2 | ?1.0Al 2O 3∶0.92P 2O 5∶0.21SiO 2 | ?0.17 | ??0.42 |
| ?1 | ?1.0Al 2O 3∶1.0P 2O 5∶0.30SiO 2 | ?1.0Al 2O 3∶0.89P 2O 5∶0.28SiO 2 | ?0.33 | ??0.67 |
| ?2 | ?1.0Al 2O 3∶1.1P 2O 5∶0.75SiO 2 | ?1.0Al 2O 3∶0.91P 2O 5∶0.60SiO 2 | ?0.25 | ??0.55 |
| ?3 | ?1.0Al 2O 3∶1.2P 2O 5∶0.50SiO 2 | ?1.0Al 2O 3∶0.98P 2O 5∶0.41SiO 2 | ?0.44 | ??0.88 |
| ?4 | ?1.0Al 2O 3∶0.9P 2O 5∶0.28SiO 2 | ?1.0Al 2O 3∶0.73P 2O 5∶0.31SiO 2 | ?0.36 | ??0.85 |
Claims (13)
1. the synthetic method of a SAPO-11 molecular sieve may further comprise the steps: (a) template, silicon source, aluminium source, phosphoric acid, organic solvent and water mixing, stirring are obtained gel; (b) gel that (a) made carries out crystallization, and solid in the filtration product obtains molecular sieve through washing, drying
Former powder; (c) molecular screen primary powder that roasting (b) makes removes template and obtains molecular sieve;
It is characterized in that said template is the organic compounds containing nitrogen group based on Diisopropylamine.
2. weight should be more than or equal to 50% in template to it is characterized in that said Diisopropylamine according to the described synthetic method of claim 1.
3. according to the described synthetic method of claim 1, it is characterized in that also containing in the said organic compounds containing nitrogen group one or more of Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, triethylamine, tripropylamine, di-n-propylamine, isopropylamine or pyridine.
4. according to the described synthetic method of claim 1, it is characterized in that in the gel of step (a) gained, adding organic solvent.
5. according to the described synthetic method of claim 4, it is characterized in that said organic solvent is one or more in n-hexyl alcohol, Virahol, ethylene glycol, glycerol or the hexanediamine.
6. according to the described synthetic method of claim 1, it is characterized in that the mole proportioning of each material in the step (a) is: 0.2～6.0R: Al
2O
3: 0.7～1.5P
2O
5: 0.01～4.0SiO
2: 1～100G: 10～500H
2O, " R " is template here, " G " is organic solvent.
7. according to the described synthetic method of claim 6, it is characterized in that the mole proportioning of each material in the step (a) is: 0.5～3.0R: Al
2O
3: 0.8～1.2P
2O
5: 0.1～2SiO
2: 2.～50G: 2.～200H
2O.
8. according to the described synthetic method of claim 6, it is characterized in that the mole proportioning of each material in the step (a) is: 0.7～2.5R: Al
2O
3: 0.9～1.1P
2O
5: 0.3～1.5SiO
2: 4～20G: 30～100H
2O.
9. aluminium silicophosphate molecular sieve, the basic experience chemical constitution of its anhydride is: mR: Al
2O
3: nP
2O
5: qSiO
2, " R " for being present in the template in the microporous molecular sieve, " m " is the mole number of template " R ", the value of " m " is 0.2～6, the value of " n " is 0.8～1.5, and the value of " q " is 0.01～4, and this molecular sieve is characterised in that: infrared acidity is generally at 0.20～0.50mmol/g; NH
3-TPD acidity is generally at 0.50～1.00mmol/g.
10. according to the described molecular sieve of claim 9, it is characterized in that the infrared acidity of this sub-sieve is at 0.25～0.50mmol/g; NH
3-TPD acidity is at 0.60～1.00mmol/g.
11. according to the described molecular sieve of claim 9, the specific surface area that it is characterized in that said molecular sieve is 140～240m
2/ g, pore volume are 0.1～0.3ml/g.Be preferably 160～220m
2/ g is preferably 170～210m
2/ g.
12. according to the described molecular sieve of claim 9, the specific surface area that it is characterized in that said molecular sieve is 160～220m
2/ g, pore volume are 0.15～0.25ml/g.
13. according to the described molecular sieve of claim 9, the specific surface area that it is characterized in that said molecular sieve is 170～210m
2/ g, pore volume are 0.17～0.22ml/g.
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| CN1314587C (en) * | 2005-04-14 | 2007-05-09 | 南京工业大学 | Preparation method of SAPO-34 molecular sieve |
| CN102530987A (en) * | 2010-12-29 | 2012-07-04 | 中国科学院大连化学物理研究所 | Solvent thermal synthesis method of SAPO (silicoaluminophosphate) molecular sieve and catalyst prepared by SAPO molecular sieve |
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| CN1314587C (en) * | 2005-04-14 | 2007-05-09 | 南京工业大学 | Preparation method of SAPO-34 molecular sieve |
| US9795949B2 (en) | 2006-05-08 | 2017-10-24 | Exxonmobil Chemical Patents Inc. | Catalyst composition |
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| CN102530987A (en) * | 2010-12-29 | 2012-07-04 | 中国科学院大连化学物理研究所 | Solvent thermal synthesis method of SAPO (silicoaluminophosphate) molecular sieve and catalyst prepared by SAPO molecular sieve |
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| CN105110348A (en) * | 2010-12-29 | 2015-12-02 | 中国科学院大连化学物理研究所 | Solvothermal synthesis method of SAPO molecular sieve and catalyst using same |
| AU2011349908B2 (en) * | 2010-12-29 | 2014-11-27 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for synthesizing SAPO molecular sieve by solvothermal method and catalyst prepared thereby |
| CN104108728B (en) * | 2013-04-18 | 2016-04-27 | 中国石油化工股份有限公司 | A kind of SAPO-11 molecular sieve |
| CN104108728A (en) * | 2013-04-18 | 2014-10-22 | 中国石油化工股份有限公司 | SAPO-11 molecular sieve |
| CN103232045B (en) * | 2013-05-13 | 2015-09-16 | 神华集团有限责任公司 | A kind of synthetic method of molecular sieve |
| CN103232045A (en) * | 2013-05-13 | 2013-08-07 | 神华集团有限责任公司 | Synthesis method of molecular sieve |
| CN103864088B (en) * | 2014-03-07 | 2015-12-09 | 浙江大学 | By the method for solid-phase grinding synthesis of molecular sieve |
| CN103864088A (en) * | 2014-03-07 | 2014-06-18 | 浙江大学 | Method for synthesizing molecular sieve by solid phase grinding |
| CN106800300A (en) * | 2015-11-26 | 2017-06-06 | 中国科学院大连化学物理研究所 | A kind of SAPO composite molecular screen and preparation method thereof |
| CN106800300B (en) * | 2015-11-26 | 2018-09-28 | 中国科学院大连化学物理研究所 | A kind of silicoaluminophosphate composite molecular screen and preparation method thereof |
| CN108246247A (en) * | 2018-01-03 | 2018-07-06 | 昆明理工大学 | A kind of modified phosphate aluminum molecular screen flue gas sorbing material and preparation method and application |
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