CN102992350B - SAPO-31 molecular sieve and preparation method thereof - Google Patents
SAPO-31 molecular sieve and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of an SAPO-31 molecular sieve. The invention aims to solve problems in an existing preparation method of the SAPO-31 molecular sieve, such as long crystallization time, low yield, complex operation, unsuitability for mass production, high cost of the prepared SAPO-31, and easy generation of SAPO-5 mixed crystal, SAPO-11 mixed crystal and SiO2 mixed crystal. The SAPO-31molecular sieve is prepared from phosphoric acid, pseudoboehmite, silica sol and di-n-butylamine. The preparation method comprises steps of: 1. initial gel preparation; 2. crystallization; and 3. roasting to obtain the SAP-O31 molecular sieve. The invention is applicable to the fields of catalyst and petrochemical processing.
Description
Technical field
The present invention relates to SAPO-31 molecular sieve and preparation method thereof.
Background technology
There is aluminosilicophosphate SAPO-31 molecular sieve (the ATO type topological framework of twelve-ring one-dimensional tunnel structure, pore size is 0.54 × 0.54nm), due to the effect of contraction in its duct, be conducive to the generation of the less single branched chain isomer of molecular dynamics size, the two side chain making molecular dynamics size relatively large or the generation of highly-branched chain isomerous body limited.Due to SAPO-31 molecular sieve there is suitable pore passage structure size, gentleness can the acidity of modulation, so SAPO-31 molecular sieve supports dual-function catalyst prepared by precious metal/base metal as acid carrier show good catalytic activity and isomerisation selectivity in Long carbon chain normal paraffin hygrogenating isomerization reaction.
Expensive and that safety in utilization is poor aluminum isopropylate is adopted to be aluminium source in the preparation method of current SAPO-31 molecular sieve, adopting the higher silicon aerosol of price to be silicon source and the di-n-propylamine easily guiding multiple crystalline formation is template, crystallization time needed for preparation SAPO-31 molecular sieve is long, yield is lower, complicated operation, can not carry out scale operation, there is cost height and easily occur SAPO-5 stray crystal, SAPO-11 stray crystal and SiO in the SAPO-31 molecular sieve prepared
2the problem of stray crystal.
Summary of the invention
The present invention exists in the preparation method that will solve existing SAPO-31 molecular sieve that crystallization time is long, yield is lower, complicated operation, can not carry out scale operation, and it is high and easily occur SAPO-5 stray crystal, SAPO-11 stray crystal and SiO that the SAPO-31 prepared exists cost
2the problem of stray crystal, and provide the new preparation method of a kind of SAPO-31 molecular sieve.
A kind of SAPO-31 molecular sieve is prepared from by phosphoric acid, pseudo-boehmite, silicon sol and Di-n-Butyl Amine; Wherein, the mass ratio of pseudo-boehmite and phosphoric acid is (0.40 ~ 0.70): 1, and the mass ratio of silicon sol and phosphoric acid is (0.30 ~ 0.90): 1, and the mass ratio of Di-n-Butyl Amine and phosphoric acid is (0.50 ~ 0.90): 1.
A preparation method for SAPO-31 molecular sieve, specifically completes according to the following steps:
One, in phosphoric acid, add pseudo-boehmite, silicon sol, Di-n-Butyl Amine and water, stir 5h ~ 7h in the stir speed (S.S.) of 800r/min ~ 1000r/min, obtain Primogel; Wherein, the mass ratio of pseudo-boehmite and phosphoric acid is (0.40 ~ 0.70): 1, the mass ratio of silicon sol and phosphoric acid is (0.30 ~ 0.90): 1, the mass ratio of Di-n-Butyl Amine and phosphoric acid is (0.50 ~ 0.90): 1, and the mass ratio of water and phosphoric acid is (2.0 ~ 4.0): 1;
Two, the Primogel that step one obtains is joined in crystallizing kettle, crystallization 2h ~ 48h at the temperature of 170 DEG C ~ 190 DEG C, be cooled to 20 DEG C ~ 25 DEG C, obtain solidliquid mixture, by the solidliquid mixture that obtains dry 10h ~ 24h after centrifugal, washing, at the temperature of 100 DEG C ~ 120 DEG C, obtain solid;
Three, solid step 2 obtained, at the temperature of 500 DEG C ~ 700 DEG C, constant temperature calcining 6h ~ 8h, naturally cools to 20 DEG C ~ 30 DEG C, namely obtains SAPO-31 molecular sieve.
Advantage of the present invention: one, a kind of SAPO-31 molecular sieve provided by the invention and preparation method thereof, cheap pseudo-boehmite and silicon sol is adopted to be respectively aluminium source and silicon source, cheap Di-n-Butyl Amine is adopted to be template, not only cost is low for the SAPO-31 molecular sieve prepared, and owing to adopting Di-n-Butyl Amine to be template, not easily there is SAPO-5, SAPO-11 and SiO in synthesized SAPO-31 molecular sieve
2stray crystal; Two, a kind of SAPO-31 molecular sieve provided by the invention and preparation method thereof, preparation process is simple, easy handling, and yield is Gao Keda more than 85% comparatively, is applicable to industrialization scale operation; Three, a kind of SAPO-31 molecular sieve provided by the invention and preparation method thereof, can prepare the SAPO-31 molecular sieve of wider silica alumina ratio scope, makes SAPO-31 molecular sieve have wider acid density and strength of acid variable range.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the SAPO-31 molecular sieve that test one prepares.
Fig. 2 is the scanning electron microscope diagram of the SAPO-31 molecular sieve that test one prepares.
Fig. 3 is the X-ray diffractogram of the SAPO-31 molecular sieve that test two prepares.
Fig. 4 is the scanning electron microscope diagram of the SAPO-31 molecular sieve that test two prepares.
Fig. 5 is the X-ray diffractogram of the SAPO-31 molecular sieve that test three prepares.
Fig. 6 is the scanning electron microscope diagram of the SAPO-31 molecular sieve that test three prepares.
Fig. 7 is the X-ray diffractogram of the SAPO-31 molecular sieve that test four prepares.
Fig. 8 is the scanning electron microscope diagram of the SAPO-31 molecular sieve that test four prepares.
Embodiment
Embodiment one: present embodiment provides a kind of SAPO-31 molecular sieve, is prepared from by phosphoric acid, pseudo-boehmite, silicon sol and Di-n-Butyl Amine; Wherein, the mass ratio of pseudo-boehmite and phosphoric acid is (0.40 ~ 0.70): 1, and the mass ratio of silicon sol and phosphoric acid is (0.30 ~ 0.90): 1, and the mass ratio of Di-n-Butyl Amine and phosphoric acid is (0.50 ~ 0.90): 1.
Present embodiment has the following advantages: one, the SAPO-31 molecular sieve that provides of present embodiment, cheap pseudo-boehmite and silicon sol is adopted to be respectively aluminium source and silicon source, cheap Di-n-Butyl Amine is adopted to be template, not only cost is low for the SAPO-31 molecular sieve prepared, and owing to adopting Di-n-Butyl Amine to be template, not easily there is SAPO-5, SAPO-11 and SiO in synthesized SAPO-31 molecular sieve
2stray crystal; Two, the SAPO-31 molecular sieve that provides of present embodiment, has wider silica alumina ratio scope, makes SAPO-31 molecular sieve have wider acid density and strength of acid variable range.
Embodiment two: the difference of present embodiment and embodiment one is, the mass percent concentration of described phosphoric acid is 85%.Other is identical with embodiment one.
Embodiment three: present embodiment is the method for a kind of SAPO-31 molecular sieve of preparation described in embodiment one, specifically completes according to the following steps:
One, in phosphoric acid, add pseudo-boehmite, silicon sol, Di-n-Butyl Amine and water, stir 5h ~ 7h in the stir speed (S.S.) of 800r/min ~ 1000r/min, obtain Primogel; Wherein, the mass ratio of pseudo-boehmite and phosphoric acid is (0.40 ~ 0.70): 1, the mass ratio of silicon sol and phosphoric acid is (0.30 ~ 0.90): 1, the mass ratio of Di-n-Butyl Amine and phosphoric acid is (0.50 ~ 0.90): 1, and the mass ratio of water and phosphoric acid is (2.0 ~ 4.0): 1;
Two, the Primogel that step one obtains is joined in crystallizing kettle, crystallization 2h ~ 48h at the temperature of 170 DEG C ~ 190 DEG C, be cooled to 20 DEG C ~ 25 DEG C, obtain solidliquid mixture, by the solidliquid mixture that obtains dry 10h ~ 24h after centrifugal, washing, at the temperature of 100 DEG C ~ 120 DEG C, obtain solid;
Three, solid step 2 obtained, at the temperature of 500 DEG C ~ 700 DEG C, constant temperature calcining 6h ~ 8h, naturally cools to 20 DEG C ~ 30 DEG C, namely obtains SAPO-31 molecular sieve.
Present embodiment has the following advantages: one, a kind of SAPO-31 molecular sieve of providing of present embodiment and preparation method thereof, cheap pseudo-boehmite and silicon sol is adopted to be respectively aluminium source and silicon source, cheap Di-n-Butyl Amine is adopted to be template, not only cost is low for the SAPO-31 molecular sieve prepared, and owing to adopting Di-n-Butyl Amine to be template, not easily there is SAPO-5, SAPO-11 and SiO in synthesized SAPO-31 molecular sieve
2stray crystal; Two, a kind of SAPO-31 molecular sieve of providing of present embodiment and preparation method thereof, preparation process is simple, easy handling, and yield is Gao Keda more than 90% comparatively, is applicable to industrialization scale operation; Three, a kind of SAPO-31 molecular sieve of providing of present embodiment and preparation method thereof, can prepare the SAPO-31 molecular sieve of wider silica alumina ratio scope, make SAPO-31 molecular sieve have wider acid density and strength of acid variable range.
Embodiment four: the difference of present embodiment and embodiment three is, the mass percent concentration of the phosphoric acid of described step one is 85%.Other is identical with embodiment three.
Embodiment five: the difference of present embodiment and embodiment three or four is, the water of described step one is deionized water.Other is identical with embodiment three or four.
Embodiment six: the difference of one of present embodiment and embodiment three to five is, the stir speed (S.S.) of described step one is 1000r/min, and churning time is 6h.Other is identical with one of embodiment three to five.
Embodiment seven: the difference of one of present embodiment and embodiment three to six is, the condition of the crystallization of described step 2 is crystallization 2h at the temperature of 180 DEG C.Other is identical with embodiment three to six.
Embodiment eight: the difference of one of present embodiment and embodiment three to seven is, the condition of the crystallization of described step 2 is crystallization 20h at the temperature of 180 DEG C.Other is identical with embodiment three to seven.
Embodiment nine: the difference of one of present embodiment and embodiment three to eight is, the drying mode of described step 2 is dry 12h at the temperature of 110 DEG C.Other is identical with embodiment three to eight.
Embodiment ten: the difference of one of present embodiment and embodiment three to nine is, the condition of the constant temperature calcining of described step 3 is constant temperature calcining 6h at the temperature of 600 DEG C.Other is identical with embodiment three to nine.
Adopt following verification experimental verification effect of the present invention:
Test one: a kind of preparation method of SAPO-31 molecular sieve, specifically completes according to the following steps:
One, in phosphoric acid, add pseudo-boehmite, silicon sol, Di-n-Butyl Amine and water, stir 6h in the stir speed (S.S.) of 1000r/min, obtain Primogel; Wherein, the mass ratio of pseudo-boehmite and phosphoric acid is 0.6:1, and the mass ratio of silicon sol and phosphoric acid is 0.6:1, and the mass ratio of Di-n-Butyl Amine and phosphoric acid is 0.8:1, and the mass ratio of water and phosphoric acid is 3:1;
Two, join in crystallizing kettle by the Primogel that step one obtains, crystallization 2h at the temperature of 180 DEG C, is cooled to 25 DEG C, obtains solidliquid mixture, and by the solidliquid mixture that obtains after centrifugal, washing, at the temperature of 110 DEG C, dry 12h, obtains solid;
Three, solid step 2 obtained, at the temperature of 600 DEG C, constant temperature calcining 6h, naturally cools to 25 DEG C, namely obtains SAPO-31 molecular sieve.Its yield can reach 79.3%.
X-ray diffraction test is carried out to the SAPO-31 molecular sieve that test one prepares, obtains Fig. 1.From Fig. 1, can observe at 2 θ is 8.5 °, 20.2 °, 22.0 ° and the 22.5 ° characteristic diffraction peaks locating all to have SAPO-31 molecular sieve, and without other stray crystal.
Scanning electron microscope test is carried out to the SAPO-31 molecular sieve that test one prepares, obtains Fig. 2.From Fig. 2, can observe SAPO-31 molecular sieve is bar-like grains.
Test two: a kind of preparation method of SAPO-31 molecular sieve, specifically completes according to the following steps:
One, in phosphoric acid, add pseudo-boehmite, silicon sol, Di-n-Butyl Amine and water, stir 6h in the stir speed (S.S.) of 1000r/min, obtain Primogel; Wherein, the mass ratio of pseudo-boehmite and phosphoric acid is 0.6:1, and the mass ratio of silicon sol and phosphoric acid is 0.6:1, and the mass ratio of Di-n-Butyl Amine and phosphoric acid is 0.8:1, and the mass ratio of water and phosphoric acid is 3:1;
Two, join in crystallizing kettle by the Primogel that step one obtains, crystallization 20h at the temperature of 180 DEG C, is cooled to 25 DEG C, obtains solidliquid mixture, and by the solidliquid mixture that obtains after centrifugal, washing, at the temperature of 110 DEG C, dry 12h, obtains solid;
Three, solid step 2 obtained, at the temperature of 600 DEG C, constant temperature calcining 6h, naturally cools to 25 DEG C, namely obtains SAPO-31 molecular sieve.Its yield can reach 85.1%.
X-ray diffraction test is carried out to the SAPO-31 molecular sieve that test two prepares, obtains Fig. 3.From Fig. 3, can observe at 2 θ is 8.5 °, 20.2 °, 22.0 ° and the 22.5 ° characteristic diffraction peaks locating all to have SAPO-31 molecular sieve, and without other stray crystal.
Scanning electron microscope test is carried out to the SAPO-31 molecular sieve that test two prepares, obtains Fig. 4.From Fig. 4, can observe SAPO-31 molecular sieve is bar-like grains.
Test three: a kind of preparation method of SAPO-31 molecular sieve, specifically completes according to the following steps:
One, in phosphoric acid, add pseudo-boehmite, silicon sol, Di-n-Butyl Amine and water, stir 6h in the stir speed (S.S.) of 1000r/min, obtain Primogel; Wherein, the mass ratio of pseudo-boehmite and phosphoric acid is 0.6:1, and the mass ratio of silicon sol and phosphoric acid is 0.5:1, and the mass ratio of Di-n-Butyl Amine and phosphoric acid is 0.8:1, and the mass ratio of water and phosphoric acid is 3:1;
Two, join in crystallizing kettle by the Primogel that step one obtains, crystallization 24h at the temperature of 180 DEG C, is cooled to 25 DEG C, obtains solidliquid mixture, by the solidliquid mixture that obtains dry 12h after centrifugal, washing, at the temperature of 110 DEG C, obtains solid;
Three, solid step 2 obtained, at the temperature of 600 DEG C, constant temperature calcining 6h, naturally cools to 25 DEG C, namely obtains SAPO-31 molecular sieve.Its yield can reach 88.7%.
X-ray diffraction test is carried out to the SAPO-31 molecular sieve that test three prepares, obtains Fig. 5.From Fig. 5, can observe at 2 θ is 8.5 °, 20.2 °, 22.0 ° and the 22.5 ° characteristic diffraction peaks locating all to have SAPO-31 molecular sieve, and without other stray crystal.
Scanning electron microscope test is carried out to the SAPO-31 molecular sieve that test three prepares, obtains Fig. 6.From Fig. 6, can observe SAPO-31 molecular sieve is bar-like grains.
Test four: a kind of preparation method of SAPO-31 molecular sieve, specifically completes according to the following steps:
One, in phosphoric acid, add pseudo-boehmite, silicon sol, Di-n-Butyl Amine and water, stir 6h in the stir speed (S.S.) of 1000r/min, obtain Primogel; Wherein, the mass ratio of pseudo-boehmite and phosphoric acid is 0.6:1, and the mass ratio of silicon sol and phosphoric acid is 0.8:1, and the mass ratio of Di-n-Butyl Amine and phosphoric acid is 0.8:1, and the mass ratio of water and phosphoric acid is 3:1;
Two, join in crystallizing kettle by the Primogel that step one obtains, crystallization 24h at the temperature of 180 DEG C, is cooled to 25 DEG C, obtains solidliquid mixture, by the solidliquid mixture that obtains dry 12h after centrifugal, washing, at the temperature of 110 DEG C, obtains solid;
Three, solid step 2 obtained, at the temperature of 600 DEG C, constant temperature calcining 6h, naturally cools to 25 DEG C, namely obtains SAPO-31 molecular sieve.Its yield can reach 89.1%.
X-ray diffraction test is carried out to the SAPO-31 molecular sieve that test four prepares, obtains Fig. 7.From Fig. 7, can observe at 2 θ is 8.5 °, 20.2 °, 22.0 ° and the 22.5 ° characteristic diffraction peaks locating all to have SAPO-31 molecular sieve, and without other stray crystal.
Scanning electron microscope test is carried out to the SAPO-31 molecular sieve that test one prepares, obtains Fig. 8.From Fig. 8, can observe SAPO-31 molecular sieve is bar-like grains.
Claims (8)
1. a preparation method for SAPO-31 molecular sieve, is characterized in that: preparation method specifically completes according to the following steps:
One, in phosphoric acid, add pseudo-boehmite, silicon sol, Di-n-Butyl Amine and water, stir 5h ~ 7h in the stir speed (S.S.) of 800r/min ~ 1000r/min, obtain Primogel; Wherein, the mass ratio of pseudo-boehmite and phosphoric acid is (0.40 ~ 0.70): 1, the mass ratio of silicon sol and phosphoric acid is (0.30 ~ 0.90): 1, the mass ratio of Di-n-Butyl Amine and phosphoric acid is (0.50 ~ 0.90): 1, and the mass ratio of water and phosphoric acid is (2.0 ~ 4.0): 1;
Two, the Primogel that step one obtains is joined in crystallizing kettle, crystallization 2h ~ 48h at the temperature of 170 DEG C ~ 190 DEG C, be cooled to 20 DEG C ~ 25 DEG C, obtain solidliquid mixture, by the solidliquid mixture that obtains after centrifugal, washing, dry 10h ~ 24h at the temperature of 100 DEG C ~ 120 DEG C, obtains solid;
Three, solid step 2 obtained, at the temperature of 500 DEG C ~ 700 DEG C, after constant temperature calcining 6h ~ 8h, naturally cools to 20 DEG C ~ 30 DEG C, namely obtains SAPO-31 molecular sieve.
2. the preparation method of a kind of SAPO-31 molecular sieve according to claim 1, is characterized in that: the mass percent concentration of the phosphoric acid of described step one is 85%.
3. the preparation method of a kind of SAPO-31 molecular sieve according to claim 1 and 2, is characterized in that: the water of described step one is deionized water.
4. the preparation method of a kind of SAPO-31 molecular sieve according to claim 1 and 2, it is characterized in that: the stir speed (S.S.) of described step one is 1000r/min, churning time is 6h.
5. the preparation method of a kind of SAPO-31 molecular sieve according to claim 1, is characterized in that: the condition of the crystallization of described step 2 is crystallization 2h at the temperature of 180 DEG C.
6. the preparation method of a kind of SAPO-31 molecular sieve according to claim 1,2 or 5, is characterized in that: the condition of the crystallization of described step 2 is crystallization 20h at the temperature of 180 DEG C.
7. the preparation method of a kind of SAPO-31 molecular sieve according to claim 1,2 or 5, is characterized in that: the drying mode of described step 2 is dry 12h at the temperature of 110 DEG C.
8. the preparation method of a kind of SAPO-31 molecular sieve according to claim 1,2 or 5, is characterized in that: the roasting condition of described step 3 is the roasting temperature 6h at 600 DEG C.
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