CN102815720A - Synthetic method for SAPO-11 molecular sieve - Google Patents
Synthetic method for SAPO-11 molecular sieve Download PDFInfo
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- CN102815720A CN102815720A CN2012102567027A CN201210256702A CN102815720A CN 102815720 A CN102815720 A CN 102815720A CN 2012102567027 A CN2012102567027 A CN 2012102567027A CN 201210256702 A CN201210256702 A CN 201210256702A CN 102815720 A CN102815720 A CN 102815720A
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Abstract
The invention provides a synthetic method for an SAPO-11 molecular sieve, which relates to synthetic methods for molecular sieves. The invention aims to overcome the technical problems of long crystallization time, appearance of stray crystals in a product and high cost of a template in conventional preparation methods for the SAPO-11 molecular sieve. The method provided by the invention comprises the following steps: uniformly mixing phosphoric acid, pseudo-boehmite, silica sol, di-n-butylamine, HF and water to prepare initial gel; placing the initial gel in a stainless steel crystallization kettle lined with polytetrafluoroethylene; carrying out crystallization at a temperature of 170 to 190 DEG C for 12 to 36 h; then carrying out centrifugation, washing and drying; and finally carrying out roasting in a muffle furnace so as to prepare the SAPO-11 molecular sieve. The SAPO-11 molecular sieve synthesized by using the method provided by the invention is in a form of cubic crystal grains; crystallization time for the SAPO-11 molecular sieve in the method is 1/2 to 1/3 of the crystallization time in the prior art; and the SAPO-11 molecular sieve is in a pure phase, does not contain stray crystals and can be used as a catalyst in petrochemical production.
Description
Technical field
The present invention relates to the method for synthesis of molecular sieve.
Background technology
The SAPO-11 molecular sieve is a kind of Silicophosphoaluminaand molecular sieve of the AEL of having type topological framework, has the oval ten-ring straight hole of one dimension road, and the duct is of a size of 0.39 * 0.64nm.Because SAPO-11 has gentle acidity and unique pore passage structure and size, the SAPO-11 molecular sieve supports the precious metal preparation as acid carrier dual-function catalyst shows excellent catalytic activity and isomerizing selectivity in long carbochain normal paraffin hygrogenating isomerization reaction.
U.S. Pat P4440871, USP4701485, USP4943424 etc. have reported that respectively with di-n-propylamine be the method for the synthetic SAPO-11 molecular sieve of template with the mixture of di-n-propylamine and Diisopropylamine perhaps.Because di-n-propylamine can cause comprising SAPO-5; SAPO-11; The formation of crystalline phase more than eight kinds such as SAPO-31 and SAPO-41, thus the stray crystal of these molecular sieves often appears in the crystallization product, in addition; Costing an arm and a leg of these two kinds of template is unfavorable for realizing the large batch of suitability for industrialized production of carrying out.It is thus clear that there is following problem in existing SAPO-11 molecular sieve preparation method: crystallization time is long, is prone to stray crystal in the product, the template cost is high.
Summary of the invention
The present invention be to solve that the crystallization time that existing SAPO-11 molecular sieve preparation method exists is long, be prone to stray crystal in the product, technical problem that the template cost is high, a kind of novel method of synthetic SAPO-11 molecular sieve is provided.
The novel method of a kind of synthetic SAPO-11 molecular sieve of the present invention is carried out according to the following steps:
One, taking by weighing massfraction is that 85% phosphoric acid, pseudo-boehmite, silicon sol, Di-n-Butyl Amine, massfraction are 40% HF and deionized water; Wherein massfraction is that 85% phosphoric acid, pseudo-boehmite, silicon sol, Di-n-Butyl Amine, massfraction are that 40% the HF and the ratio of weight and number of water are 1: (0.40～0.60): (0.30～0.80): (0.30～0.90): (0.01～0.03): (2.0～4.0); With massfraction is that 85% phosphoric acid, pseudo-boehmite, silicon sol, Di-n-Butyl Amine and massfraction are that 40% HF joins in the deionized water successively, under the rotating speed of 600～1000r/min, fully stirs 5～7h and makes initial gel;
Two, the initial gel that obtains in the step 1 is placed teflon-lined stainless steel crystallizing kettle; Crystallization 12～36h under 170～190 ℃ of conditions is cooled to 20～25 ℃, and crystallization product is through centrifugal, washing, drying; Roasting in retort furnace again makes the SAPO-11 molecular sieve.
The present invention adopts and introduces HF, and the pure phase SAPO-11 molecular sieve of the method for crystallization 12h～36h preparation is a cubic grain under hydrothermal condition; Crystallization time has only 1/2～1/3 when not introducing HF, and crystallization time shortens significantly; Product is the SAPO-11 molecular sieve of pure phase, does not have SAPO-5, stray crystals such as SAPO-31 and SAPO-41; The employing Di-n-Butyl Amine is a template, and low price has reduced cost greatly.Adopt the inventive method can synthesizing Si-Al than the SAPO-11 molecular sieve that in relative broad range, changes, make the acid Modulatory character of molecular sieve stronger, acidic site density is higher, can be used as catalyzer and is widely used in the industry-by-industry in the petrochemical complex production.
Description of drawings
Fig. 1 is the XRD spectra of the SAPO-11 molecular sieve of test one preparation;
Fig. 2 is the SEM photo of the SAPO-11 molecular sieve of test one preparation;
Fig. 3 is the XRD spectra of the SAPO-11 molecular sieve of test two preparations;
Fig. 4 is the SEM photo of the SAPO-11 molecular sieve of test two preparations;
Fig. 5 is the XRD spectra of the SAPO-11 molecular sieve of test three preparations;
Fig. 6 is the SEM photo of the SAPO-11 molecular sieve of test three preparations.
Embodiment
Embodiment one: a kind of method of synthetic SAPO-11 molecular sieve is carried out according to the following steps in this embodiment:
One, taking by weighing massfraction is that 85% phosphoric acid, pseudo-boehmite, silicon sol, Di-n-Butyl Amine, massfraction are 40% HF and deionized water; Wherein massfraction is that 85% phosphoric acid, pseudo-boehmite, silicon sol, Di-n-Butyl Amine, massfraction are that 40% the HF and the ratio of weight and number of water are 1: (0.40～0.60): (0.30～0.80): (0.30～0.90): (0.01～0.03): (2.0～4.0); With massfraction is that 85% phosphoric acid, pseudo-boehmite, silicon sol, Di-n-Butyl Amine and massfraction are that 40% HF joins in the deionized water successively, under the rotating speed of 600～1000r/min, fully stirs 5～7h and makes initial gel;
Two, the initial gel that obtains in the step 1 is placed teflon-lined stainless steel crystallizing kettle; Crystallization 12～36h under 170～190 ℃ of conditions is cooled to 20～25 ℃, and crystallization product is through centrifugal, washing, drying; Roasting in retort furnace again makes the SAPO-11 molecular sieve.
This embodiment adopts introduces HF, and the pure phase SAPO-11 molecular sieve of the method for crystallization 12h～36h preparation is a cubic grain under hydrothermal condition; Crystallization time has only 1/2～1/3 when not introducing HF, and crystallization time shortens significantly; Product is the SAPO-11 molecular sieve of pure phase, does not have SAPO-5, stray crystals such as SAPO-31 and SAPO-41; The employing Di-n-Butyl Amine is a template, and low price has reduced cost greatly.Adopt this embodiment method can synthesizing Si-Al than the SAPO-11 molecular sieve that in relative broad range, changes, make the acid Modulatory character of molecular sieve stronger, acidic site density is higher, can be used as catalyzer and is widely used in the industry-by-industry of petrochemical complex in producing.
Embodiment two: what this embodiment and embodiment one were different is: crystallization time is 12h～24h in the step 2.Other is identical with embodiment one.
Embodiment three: what this embodiment was different with one of embodiment one to two is: centrifugal rotational speed is 3000r/min～4000r/min in the step 2, and centrifugation time is 10min～20min.Other is identical with one of embodiment one to two.
Embodiment four: what this embodiment was different with one of embodiment one to three is: centrifugal rotational speed is 4000r/min in the step 2, and centrifugation time is 15min.Other is identical with one of embodiment one to three.
Embodiment five: what this embodiment was different with one of embodiment one to four is: drying temperature is 100 ℃～120 ℃ in the step 2, and be 12h～24h time of drying.Other is identical with one of embodiment one to four.
Embodiment six: what this embodiment was different with one of embodiment one to five is: maturing temperature is 500 ℃～700 ℃ in the step 2, and roasting time is 6h～8h.Other is identical with one of embodiment one to five.
Embodiment seven: what this embodiment was different with one of embodiment one to six is: maturing temperature is 600 ℃ in the step 2, and roasting time is 7h.Other is identical with one of embodiment one to six.
Through following verification experimental verification beneficial effect of the present invention:
Test one: the method for a kind of synthetic SAPO-11 molecular sieve of this test is to realize by following method:
One, is that 85% phosphoric acid, 10.24g pseudo-boehmite, 7.05g silicon sol, 15g Di-n-Butyl Amine and 0.4g massfraction are that 40% HF joins in the 54ml deionized water successively with the 18.16g massfraction, under the rotating speed of 800r/min, fully stirs 6h and make initial gel;
Two, the initial gel that obtains in the step 1 is placed teflon-lined stainless steel crystallizing kettle; Crystallization 24h under 170 ℃ of conditions is cooled to 20～25 ℃, and crystallization product is through the centrifugal 15min of 4000r/min; Washing; 110 ℃ of dry 12h with 600 ℃ of roasting 7h, make the SAPO-11 molecular sieve in retort furnace.
The SAPO-11 molecular sieve of this test one preparation adopts introduces HF, and crystallization is 24 hours under hydrothermal condition, is 1/2～1/3 of prior art crystallization time, explains that crystallization time shortens significantly;
It is template that the SAPO-11 molecular sieve of this test one preparation adopts Di-n-Butyl Amine, and low price has reduced cost;
The XRD spectra of the SAPO-11 molecular sieve of this test one preparation is as shown in Figure 1, as can beappreciated from fig. 1, is 8.1 ° at 2 θ only; 9.4 °, 13.1 °, 15.6 °; 20.3 °, 21.0 ° and 22.1 ° of-23.2 ° of characteristic diffraction peaks of locating all to have the SAPO-11 molecular sieve are explained and are not had other stray crystal;
The SEM photo of the SAPO-11 molecular sieve of this test one preparation is as shown in Figure 2, and as can beappreciated from fig. 2, the SAPO-11 molecular sieve that makes exists for the cubic grain form.
Test two: the method for a kind of synthetic SAPO-11 molecular sieve of this test is to realize by following method:
One, is that 85% phosphoric acid, 10.24g pseudo-boehmite, 10.58g silicon sol, 15g Di-n-Butyl Amine and 0.4g massfraction are that 40% HF joins in the 54ml deionized water successively with the 18.16g massfraction, under the rotating speed of 900r/min, fully stirs 6h and make initial gel;
Two, the initial gel that obtains in the step 1 is placed teflon-lined stainless steel crystallizing kettle; Crystallization 24h under 180 ℃ of conditions is cooled to 20～25 ℃, and crystallization product is through the centrifugal 15min of 4000r/min; Washing; 110 ℃ of dry 12h with 600 ℃ of roasting 7h, make the SAPO-11 molecular sieve in retort furnace.
The SAPO-11 molecular sieve of this test two preparations adopts introduces HF, and crystallization is 24 hours under hydrothermal condition, is 1/2～1/3 of prior art crystallization time, explains that crystallization time shortens significantly;
It is template that the SAPO-11 molecular sieve of this test two preparations adopts Di-n-Butyl Amine, and low price has reduced cost;
The XRD spectra of the SAPO-11 molecular sieve of this test two preparations is as shown in Figure 3, as can beappreciated from fig. 3, is 8.1 ° at 2 θ; 9.4 °, 13.1 °, 15.6 °; 20.3 °, 21.0 ° and 22.1 ° of-23.2 ° of characteristic diffraction peaks of locating all to have the SAPO-11 molecular sieve are explained and are not had other stray crystal;
The SEM photo of the SAPO-11 molecular sieve of this test two preparations is as shown in Figure 4, and as can beappreciated from fig. 4, the SAPO-11 molecular sieve that makes exists for the cubic grain form.
Test three: the method for a kind of synthetic SAPO-11 molecular sieve of this test is to realize by following method:
One, is that 85% phosphoric acid, 10.24g pseudo-boehmite, 14.10g silicon sol, 15g Di-n-Butyl Amine and 0.4g massfraction are that 40% HF joins in the 54ml deionized water successively with the 18.16g massfraction, under the rotating speed of 1000r/min, fully stirs 6h and make initial gel;
Two, the initial gel that obtains in the step 1 is placed teflon-lined stainless steel crystallizing kettle; Crystallization 24h under 190 ℃ of conditions is cooled to 20～25 ℃, and crystallization product is through the centrifugal 15min of 4000r/min; Washing; 110 ℃ of dry 12h with 600 ℃ of roasting 7h, make the SAPO-11 molecular sieve in retort furnace.
The SAPO-11 molecular sieve of this test three preparations adopts introduces HF, and crystallization is 24 hours under hydrothermal condition, is 1/2～1/3 of prior art crystallization time, explains that crystallization time shortens significantly;
It is template that the SAPO-11 molecular sieve of this test three preparations adopts Di-n-Butyl Amine, and low price has reduced cost;
The XRD spectra of the SAPO-11 molecular sieve of this test three preparations is as shown in Figure 5, as can beappreciated from fig. 5, is 8.1 ° at 2 θ only; 9.4 °, 13.1 °, 15.6 °; 20.3 °, 21.0 ° and 22.1 ° of-23.2 ° of characteristic diffraction peaks of locating all to have the SAPO-11 molecular sieve are explained and are not had other stray crystal;
The SEM photo of the SAPO-11 molecular sieve of this test three preparations is as shown in Figure 6, and as can beappreciated from fig. 6, the SAPO-11 molecular sieve that makes exists for the cubic grain form.
Claims (5)
1. the method for a synthetic SAPO-11 molecular sieve is characterized in that the method for synthetic SAPO-11 molecular sieve is to carry out according to the following steps:
One, taking by weighing massfraction is that 85% phosphoric acid, pseudo-boehmite, silicon sol, Di-n-Butyl Amine, massfraction are 40% HF and deionized water; Wherein massfraction is that 85% phosphoric acid, pseudo-boehmite, silicon sol, Di-n-Butyl Amine, massfraction are that 40% the HF and the ratio of weight and number of deionized water are 1: (0.40～0.60): (0.30～0.80): (0.30～0.90): (0.01～0.03): (2.0～4.0); With massfraction is that 85% phosphoric acid, pseudo-boehmite, silicon sol, Di-n-Butyl Amine and massfraction are that 40% HF joins in the deionized water successively, under the rotating speed of 600～1000r/min, fully stirs 5～7h and makes initial gel;
Two, the initial gel that obtains in the step 1 is placed teflon-lined stainless steel crystallizing kettle; Crystallization 12～36h under 170～190 ℃ of conditions is cooled to 20～25 ℃, and crystallization product is through centrifugal, washing, drying; Roasting in retort furnace again makes the SAPO-11 molecular sieve.
2. the method for a kind of synthetic SAPO-11 molecular sieve according to claim 1 is characterized in that crystallization time is 12～24h in the step 2.
3. the method for a kind of synthetic SAPO-11 molecular sieve according to claim 1 is characterized in that centrifugal rotational speed is 4000r/min in the step 2, and centrifugation time is 10min～20min.
4. the method for a kind of synthetic SAPO-11 molecular sieve according to claim 1 is characterized in that drying temperature is 100 ℃～120 ℃ in the step 2, and be 12h～24h time of drying.
5. the method for a kind of synthetic SAPO-11 molecular sieve according to claim 1 is characterized in that maturing temperature is 500～700 ℃ in the step 2, and roasting time is 6h～8h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103523795A (en) * | 2013-11-07 | 2014-01-22 | 黑龙江大学 | Method for preparing SAPO-11 molecular sieve |
| CN105439172A (en) * | 2015-12-30 | 2016-03-30 | 山西大同大学 | Preparation method of phosphorous-aluminum microporous molecular sieve |
| CN106629759A (en) * | 2017-01-03 | 2017-05-10 | 兰州理工大学 | Synthetic method of AEL type silicoaluminophosphate molecular sieve |
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| US4310440A (en) * | 1980-07-07 | 1982-01-12 | Union Carbide Corporation | Crystalline metallophosphate compositions |
| CN101786640A (en) * | 2010-02-12 | 2010-07-28 | 黑龙江大学 | Method for synthesizing SAPO-31 molecular sieves through microwave heating |
| CN102275949A (en) * | 2011-07-14 | 2011-12-14 | 黑龙江大学 | Preparation method of nano SAPO-31 molecular sieve |
| CN102372289A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Synthetic method of SAPO (Silicoaluminophosphate)-11 molecular sieve |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4310440A (en) * | 1980-07-07 | 1982-01-12 | Union Carbide Corporation | Crystalline metallophosphate compositions |
| CN101786640A (en) * | 2010-02-12 | 2010-07-28 | 黑龙江大学 | Method for synthesizing SAPO-31 molecular sieves through microwave heating |
| CN102372289A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Synthetic method of SAPO (Silicoaluminophosphate)-11 molecular sieve |
| CN102275949A (en) * | 2011-07-14 | 2011-12-14 | 黑龙江大学 | Preparation method of nano SAPO-31 molecular sieve |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103523795A (en) * | 2013-11-07 | 2014-01-22 | 黑龙江大学 | Method for preparing SAPO-11 molecular sieve |
| CN105439172A (en) * | 2015-12-30 | 2016-03-30 | 山西大同大学 | Preparation method of phosphorous-aluminum microporous molecular sieve |
| CN106629759A (en) * | 2017-01-03 | 2017-05-10 | 兰州理工大学 | Synthetic method of AEL type silicoaluminophosphate molecular sieve |
| CN106629759B (en) * | 2017-01-03 | 2018-10-02 | 兰州理工大学 | A kind of synthetic method of AEL types silicoaluminophosphamolecular molecular sieves |
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