CN104743574A - Preparation method of high-purity SAPO-44 microporous molecular sieve - Google Patents
Preparation method of high-purity SAPO-44 microporous molecular sieve Download PDFInfo
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Abstract
The invention discloses a preparation method of a high-purity SAPO-44 microporous molecular sieve. The method comprises the following steps: preparing mixture gel by taking a phosphorus source, an aluminum source, a silicon source, a composite template agent and water as raw materials, performing closed crystallization on the mixture gel, washing, drying and roasting the obtained crystalized product to remove the composite template agent, to obtain an SAPO-44 microporous sieve, wherein the composite template agent is R1 and R2, the R1 is ethanediamine (EDA), diethylenetriamine (DETA), triethylene tetramine (TETA), tetraethylenepentamine (TEPA) or pentaethylenehexamine (PEHA), and R2 is N,N,N',N'-tetramethyl-1,6-hexamethylenediamine (TMHD). The formation of the SAPO-44 is promoted by using an organic composite template agent, the high-purity SAPO-44 molecular sieve can be obtained only by once crystallization through adjustment of the usage amount, the preparation process is easy to operate, the period is short, and the industrial application is facilitated.
Description
Technical field
The present invention relates to a kind of preparation method of SAPO-44 micro porous molecular sieve, be specifically related to a kind of preparation method of high purity SAPO-44 micro porous molecular sieve, belong to technical field of molecular sieve preparation.
Background technology
Silicoaluminophosphamolecular molecular sieves (SAPO-n) is that U.S. combinating carbide company develops, by SiO
2, PO
2 +and AlO
2 -the microporous crystals that three kinds of tetrahedrons are formed, wherein n represents different crystalline structure.The structure species of SAPO series is numerous, according to the size in its aperture can be divided into be greater than 50 nm wide aperture molecular sieve (as SAPO-5), between 2-50 nm mesoporous molecular sieve (as SAPO-11) and be less than the small-bore molecular sieve (as SAPO-34, SAPO-44) etc. of 2 nm.Good pore passage structure makes SAPO-n molecular sieve have excellent selective activization, can be used in many hydrocarbon conversion reactions as catalyzer, or as sorbent material separating mixture.
The basic structural unit of SAPO-44 molecular sieve is two six-rings, and these pair of six-ring is connected by part tetra-atomic ring, defines the three-dimensional open-framework with octatomic ring, belongs to pinhole type molecular sieve.SAPO-44 molecular sieve, except possessing good thermostability, also has acidity and ion exchangeable, and this makes it be used widely in various fields.Due to pore passage structure and the acidity of its uniqueness, be widely used in all kinds of catalyzed reaction, comprise oxidation, acid catalysis and isomerization reaction etc.
US Patent No. 4440871A discloses the hydrothermal synthesis method of a kind of SAPO-44, the method with moisture silicon solution, phosphoric acid, aluminum isopropylate and organic formwork agent hexahydroaniline for raw material, react 52 hours at 200 DEG C, obtained SAPO-44, in products therefrom, SAPO-44 occurs as principal phase, cannot obtain highly purified SAPO-44 molecular sieve.Patent WO99/19254(CN1278780A) also disclose the synthetic method of a kind of SAPO-44, the method take also hexahydroaniline as template, and the product obtained is essentially SAPO-44, but also has dephasign.In order to improve the purity of SAPO-44, patent CN201210363833.5 and CN201310499121.0 adopts composite mould plate agent, synthesizes SAPO-44 through the crystallization process of twice differing temps, but the preparation process of these approaches increases, what make preparation process become is loaded down with trivial details.
Summary of the invention
The object of this invention is to provide a kind of preparation method of high purity SAPO-44 micro porous molecular sieve, the method preparation process easy handling, the SAPO-44 micro porous molecular sieve purity of gained is high, without dephasign.
The present invention selects special composite mould plate agent, only can obtain the higher SAPO-44 molecular sieve of purity through a crystallization, and under the cooperation of preparation process and processing parameter, effect is better, and concrete technical scheme is as follows:
A kind of preparation method of high purity SAPO-44 micro porous molecular sieve, with phosphorus source, aluminium source, silicon source, composite mould plate agent and water are that raw material obtains mixture gel, by airtight for mixture gel crystallization, gained crystallization product washs, dry, roasting removing composite mould plate agent, obtain SAPO-44 micro porous molecular sieve, composite mould plate agent used is R1 and R2, described R1 is quadrol (EDA), diethylenetriamine (DETA), triethylene tetramine (TETA), tetraethylene pentamine (TEPA) or five ethene hexamines (PEHA), described R2 is N, N, N ', N '-tetramethyl--1, 6-hexanediamine (TMHD).
Contriver, through large quantity research, finds to adopt the generation of compound organic amine template to molecular sieve to play the effect of synergy, can contribute to the nucleation of gel, be more conducive to the generation of SAPO-44 micro porous molecular sieve.
In above-mentioned preparation method, the Al that composite mould plate agent and aluminium source are brought into
2o
3mol ratio be: Al
2o
3: R1:R2=1:0.27-0.9:2.0-3.0, is preferably 1:0.5-0.6:2.4-2.6.
In above-mentioned preparation method, described phosphorus source comes from phosphoric acid, phosphorous acid or phosphoric acid salt.
In above-mentioned preparation method, described aluminium source comes from boehmite, pseudo-boehmite or aluminum oxyhydroxide.
In above-mentioned preparation method, described silicon source comes from tetraethoxy, silicon sol or water glass.
In above-mentioned preparation method, the consumption of silicon source, aluminium source, phosphorus source and water meets following mol ratio: SiO
2: Al
2o
3: P
2o
5: H
2o=0.5-1.0:1:1.0-1.5:30-70, preferred 0.7-0.8:1:1.2-1.3:35-50.
In above-mentioned preparation method, crystallization temperature is 150-250 DEG C, is preferably 190-210 DEG C.
In above-mentioned preparation method, crystallization time is 48-108 hour, is preferably 96 hours.
In above-mentioned preparation method, crystallization product 450-650 DEG C of roasting, preferably 550 DEG C of roastings.
In above-mentioned preparation method, roasting time is 4-8 hour, is preferably 6 hours.
In above-mentioned preparation method, crystallization product is dry 6-24 hour at 80-120 DEG C.
In above-mentioned preparation method, crystallization product preferably at 100 DEG C dry 12 hours.
In above-mentioned preparation method, when preparing mixture gel, the addition sequence of composite mould plate agent does not affect obtaining highly purified SAPO-44 molecular sieve.
All can obtain highly purified molecular sieve under above-mentioned processing condition, when selecting optimizing technology parameters, gained molecular sieve crystallinity is better.
The present invention uses organic amine composite mould plate agent, promotes the formation of SAPO-44, by the adjustment to its usage quantity, only needs a crystallization can obtain highly purified SAPO-44 molecular sieve, and preparation process easy handling, cycle are short, are convenient to industrial applications.In addition, preferred by processing condition, can improve the degree of crystallinity of molecular sieve, make its effect better.
Accompanying drawing explanation
The XRD spectra of Fig. 1 embodiment 1 products therefrom.
The XRD spectra of Fig. 2 comparative example 1 products therefrom.
The XRD spectra of Fig. 3 comparative example 2 products therefrom.
The N of Fig. 4 embodiment 1 products therefrom
2adsorption isothermal curve.
The XRD spectra of Fig. 5 comparative example 3 products therefrom.
Embodiment
Molecular sieve preparation method of the present invention, specifically comprises the following steps:
(1) composite mould plate agent, phosphorus source, aluminium source, silicon source, water are mixed, obtain mixture gel.
(2) mixture gel is transferred in reactor, is airtightly heated to 150-250 DEG C, thermostatic crystallization for some time at autogenous pressures, crystallization completely after, naturally cool to room temperature.
(3) the product centrifugation after crystallization, washing are to neutral, dry, and dried solid product in atmosphere 450-650 DEG C of roasting, to remove composite mould plate agent completely, namely obtains SAPO-44 micro porous molecular sieve.
, exemplify several object lesson of the present invention below, following embodiment, only for explaining the present invention, does not limit its content.
embodiment 1
Prepare SAPO-44 with tetraethylene pentamine (TEPA) and TMHD double template, step is as follows:
1, according to mol ratio SiO
2: Al
2o
3: P
2o
5: TEPA:TMHD:H
2o=0.75:1:1.25:0.54:2.5:50 takes silicon sol, pseudo-boehmite, phosphoric acid, TEPA, TMHD and water.
2,0.8280g TEPA is dissolved in 7.2g deionized water, adds 2.3058g phosphoric acid, 1.0461g pseudo-boehmite, 1.2267g silicon sol and 3.4746g TMHD successively, continue stirring 12 hours.By reactant transfer in stainless steel cauldron, be airtightly heated to 200 DEG C, thermostatic crystallization is after 96 hours at autogenous pressures, naturally cools to room temperature.Product also by deionized water repeatedly washing precipitation extremely neutrality, is put into loft drier 100 DEG C of dryings 12 hours, tube furnace 550 DEG C of roastings and is obtained pressed powder after 6 hours by centrifugation crystallization product.Products obtained therefrom is pure SAPO-44 micro porous molecular sieve through XRD diffraction analysis (Fig. 1), without dephasign.The N of product
2as shown in Figure 4, as can be seen from Figure 4, this molecular sieve is micro porous molecular sieve to adsorption isothermal curve, and its BET specific surface area is 343 m after tested
2/ g.
embodiment 2
1, according to mol ratio SiO
2: Al
2o
3: P
2o
5: DETA:TMHD:H
2o=0.8:1:1.2:0.6:2.5:50 takes tetraethoxy, aluminum oxyhydroxide, phosphorous acid, DETA, TMHD and water.
2,0.4952g DETA is dissolved in 7.2g deionized water.Add 1.8522g phosphorous acid, 1.2307g aluminum oxyhydroxide, 4.5357g tetraethoxy and 3.4746gTMHD successively, continue stirring 12 hours.By reactant transfer in stainless steel autoclave, be airtightly heated to 210 DEG C, under pressure itself, thermostatic crystallization is after 96 hours, naturally cools to room temperature.With deionized water, repeatedly washing precipitation is aobvious neutral to filtrate, product is put into loft drier 100 DEG C of dryings 12 hours, tube furnace 550 DEG C of roastings and obtains pressed powder after 6 hours.Products obtained therefrom is pure SAPO-44 micro porous molecular sieve through XRD diffraction analysis, without dephasign.
embodiment 3
SAPO-44 is prepared according to the method for embodiment 1, unlike: template used dose of R1 is five ethene hexamines (PEHA).Products obtained therefrom is pure SAPO-44 micro porous molecular sieve through XRD diffraction analysis, without dephasign.
embodiment 4
SAPO-44 is prepared according to the method for embodiment 1, unlike: template used dose of R1 is triethylene tetramine (TETA).Products obtained therefrom is pure SAPO-44 micro porous molecular sieve through XRD diffraction analysis, without dephasign.
embodiment 5
SAPO-44 is prepared according to the method for embodiment 1, unlike: template used dose of R1 is quadrol (EDA).Products obtained therefrom is pure SAPO-44 micro porous molecular sieve through XRD diffraction analysis, without dephasign.
embodiment 6
Preparing SAPO-44 according to the method for embodiment 1, is 150 DEG C unlike crystallization temperature, and the time is 108h.Products obtained therefrom is pure SAPO-44 micro porous molecular sieve through XRD diffraction analysis, without dephasign.
embodiment 7
Preparing SAPO-44 according to the method for embodiment 1, is 250 DEG C unlike crystallization temperature, and the time is 48h.Products obtained therefrom is pure SAPO-44 micro porous molecular sieve through XRD diffraction analysis, without dephasign.
embodiment 8
Preparing SAPO-44 according to the method for embodiment 1, is 80 DEG C unlike the crystallization product drying temperature obtained, and the time is 24h.Products obtained therefrom is pure SAPO-44 micro porous molecular sieve through XRD diffraction analysis, without dephasign.
embodiment 9
Preparing SAPO-44 according to the method for embodiment 1, is 120 DEG C unlike the crystallization product drying temperature obtained, and the time is 6h.Products obtained therefrom is pure SAPO-44 micro porous molecular sieve through XRD diffraction analysis, without dephasign.
embodiment 10
Preparing SAPO-44 according to the method for embodiment 1, is 450 DEG C unlike calcining temperature, and the time is 8h.Products obtained therefrom is pure SAPO-44 micro porous molecular sieve through XRD diffraction analysis, without dephasign.
embodiment 11
Preparing SAPO-44 according to the method for embodiment 1, is 650 DEG C unlike calcining temperature, and the time is 4h.Products obtained therefrom is pure SAPO-44 micro porous molecular sieve through XRD diffraction analysis, without dephasign.
embodiment 12
Preparing SAPO-44 according to the method for embodiment 1, is SiO unlike selected mol ratio
2: Al
2o
3: P
2o
5: TEPA:TMHD:H
2o=0.5:1:1:0.54:2.5:30 takes silicon sol, pseudo-boehmite, phosphoric acid, TEPA, TMHD and water.Products obtained therefrom is pure SAPO-44 micro porous molecular sieve through XRD diffraction analysis, without dephasign.
embodiment 13
Preparing SAPO-44 according to the method for embodiment 1, is SiO unlike selected mol ratio
2: Al
2o
3: P
2o
5: TEPA:TMHD:H
2o=1:1:1.5:0.54:2.5:70 takes silicon sol, pseudo-boehmite, phosphoric acid, TEPA, TMHD and water.Products obtained therefrom is pure SAPO-44 micro porous molecular sieve through XRD diffraction analysis, without dephasign.
embodiment 14
Preparing SAPO-44 according to the method for embodiment 1, is SiO unlike selected mol ratio
2: Al
2o
3: P
2o
5: TEPA:TMHD:H
2o=0.75:1:1.25:0.9:2.0:50 takes water glass, boehmite, sodium phosphate, TEPA, TMHD and water.Products obtained therefrom is pure SAPO-44 micro porous molecular sieve through XRD diffraction analysis, without dephasign.
embodiment 15
Preparing SAPO-44 according to the method for embodiment 1, is SiO unlike selected mol ratio
2: Al
2o
3: P
2o
5: TEPA:TMHD:H
2o=0.75:1:1.25:0.27:3.0:50 takes silicon sol, pseudo-boehmite, phosphoric acid, TEPA, TMHD and water.Products obtained therefrom is pure SAPO-44 micro porous molecular sieve through XRD diffraction analysis, without dephasign.
comparative example 1
The method of embodiment 1 is adopted to prepare molecular sieve, unlike: only make template with single R1, when preparing mixture gel, according to mol ratio SiO
2: Al
2o
3: P
2o
5: R1:H
2o=0.75:1:1.25:0.54:50 takes silicon sol, pseudo-boehmite, phosphoric acid, TEPA and water.
As shown in Figure 2, as can be seen from the figure, the SAPO-44 that product is not pure, except SAPO-44, also containing AlPO for the XRD diffractogram of products obtained therefrom
4and SiO
2composition.
comparative example 2
The method of embodiment 1 is adopted to prepare molecular sieve, unlike: only make template with single R2, when preparing mixture gel, according to mol ratio SiO
2: Al
2o
3: P
2o
5: R2:H
2o=0.75:1:1.25:2.5:50 takes silicon sol, pseudo-boehmite, phosphoric acid, TMHD and water.
As shown in Figure 3, as can be seen from the figure, the non-SAPO-44 molecular sieve of products obtained therefrom is SAPO-56 to the XRD diffractogram of products obtained therefrom.
comparative example 3
Molecular sieve is prepared according to the method for embodiment 1, unlike: SiO
2: Al
2o
3: P
2o
5: TEPA:TMHD:H
2o=0.75:1:1.25:0.18:2.5:50.As shown in Figure 5, as can be seen from the figure, products obtained therefrom is non-pure SAPO-44 molecular sieve to the XRD diffractogram of products therefrom, the dephasign containing SAPO-56.
Claims (9)
1. the preparation method of a high purity SAPO-44 micro porous molecular sieve, it is characterized in that: with phosphorus source, aluminium source, silicon source, composite mould plate agent and water for raw material obtains mixture gel, by airtight for mixture gel crystallization, the washing of gained crystallization product, dry, roasting removing composite mould plate agent, obtain SAPO-44 micro porous molecular sieve, composite mould plate agent used is R1 and R2, described R1 is quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine or five ethene hexamines, described R2 is N, N, N ', N '-tetramethyl--1,6-hexanediamine.
2. preparation method according to claim 1, is characterized in that: the Al that composite mould plate agent and aluminium source are brought into
2o
3mol ratio be: Al
2o
3: R1:R2=1:0.27-0.9:2.0-3.0.
3. preparation method according to claim 2, is characterized in that: the Al that composite mould plate agent and aluminium source are brought into
2o
3mol ratio be: Al
2o
3: R1:R2=1:0.5-0.6:2.4-2.6.
4. the preparation method according to any one of claim 1-3, is characterized in that: the consumption of silicon source, aluminium source, phosphorus source and water meets following mol ratio: SiO
2: Al
2o
3: P
2o
5: H
2o=0.5-1.0:1:1.0-1.5:30-70, preferred 0.7-0.8:1:1.2-1.3:35-50.
5. the preparation method according to any one of claim 1-4, is characterized in that: crystallization temperature is 150-250 DEG C, is preferably 190-210 DEG C.
6. the preparation method according to any one of claim 1-5, is characterized in that: crystallization product 450-650 DEG C of roasting, preferably 550 DEG C of roastings.
7. the preparation method according to any one of claim 1-6, is characterized in that: crystallization time is 48-108 hour, is preferably 96 hours; Roasting time is 4-8 hour, is preferably 6 hours.
8. the preparation method according to any one of claim 1-7, is characterized in that: described phosphorus source comes from phosphoric acid, phosphorous acid or phosphoric acid salt; Described aluminium source comes from boehmite, pseudo-boehmite or aluminum oxyhydroxide; Described silicon source comes from tetraethoxy, silicon sol or water glass.
9. the preparation method according to any one of claim 1-8, is characterized in that: crystallization product is dry 6-24 hour at 80-120 DEG C, preferably at 100 DEG C dry 12 hours.
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| US6835363B1 (en) * | 2003-08-06 | 2004-12-28 | Exxonmobil Chemical Patents Inc. | Synthesis of molecular sieves of CHA framework type |
| 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 |
| 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 |
| CN103058208B (en) * | 2011-10-24 | 2015-01-07 | 中国石油化工股份有限公司 | Preparation method of SAPO-56 molecular sieve |
| CN103663489B (en) * | 2012-09-26 | 2015-11-18 | 中国科学院大连化学物理研究所 | A kind of SAPO-44 molecular sieve and synthetic method thereof |
| CN103553073B (en) * | 2013-10-22 | 2015-06-10 | 神华集团有限责任公司 | SAPO-44 molecular sieve with rich Si(4Al) and multistage pore sizes, molecular sieve catalyst thereof and preparation methods thereof |
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| CN110691757A (en) * | 2017-05-31 | 2020-01-14 | Ifp新能源公司 | Direct synthesis of copper-containing SAPO materials with AFX structure and use of the materials |
| JP2020521708A (en) * | 2017-05-31 | 2020-07-27 | イエフペ エネルジ ヌヴェルＩｆｐ Ｅｎｅｒｇｉｅｓ Ｎｏｕｖｅｌｌｅｓ | Direct synthesis of copper containing AFX structure SAPO material and use of this material |
| US11338277B2 (en) * | 2017-05-31 | 2022-05-24 | IFP Energies Nouvelles | Direct synthesis of a SAPO material with AFX structure comprising copper and use of this material |
| CN110691757B (en) * | 2017-05-31 | 2022-09-23 | Ifp新能源公司 | Direct synthesis of copper-containing SAPO materials with AFX structure and use of the materials |
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| CN108557841A (en) * | 2018-07-05 | 2018-09-21 | 天津大学 | The preparation method of CHA molecular sieves is synthesized using tetraethylenepentamine as template |
| CN108557841B (en) * | 2018-07-05 | 2021-07-27 | 天津大学 | Preparation method for synthesizing CHA molecular sieve by using tetraethylenepentamine as template agent |
| CN115231591A (en) * | 2021-04-22 | 2022-10-25 | 中国石油化工股份有限公司 | Pure-phase small-crystal-grain SAPO-44 molecular sieve and preparation method and application thereof |
| CN115231591B (en) * | 2021-04-22 | 2023-08-04 | 中国石油化工股份有限公司 | Pure-phase small-grain SAPO-44 molecular sieve, and preparation method and application thereof |
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