CN115231591B - Pure-phase small-grain SAPO-44 molecular sieve, and preparation method and application thereof - Google Patents
Pure-phase small-grain SAPO-44 molecular sieve, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a pure-phase small-grain SAPO-44 molecular sieve, a preparation method and application thereof. The invention prepares the pure phase small crystal grain SAPO-44 molecular sieve by taking the SAPO-5 molecular sieve as a precursor, and the grain diameter of the molecular sieve is not more than 3 mu m. The preparation method of the pure-phase small-grain SAPO-44 molecular sieve provided by the invention greatly shortens the high-temperature crystallization time and improves the synthesis efficiency; the obtained molecular sieve has pure crystalline phase and smaller crystalline grains, and has good industrial application value in adsorption separation and methanol conversion reaction.
Description
Technical Field
The invention relates to a SAPO-44 molecular sieve, a preparation method and application thereof, in particular to a pure phase small crystal grain SAPO-44 molecular sieve, a preparation method and application thereof.
Background
1982 united statesA new family of molecular sieves- -AlPO-aluminum phosphate- -was successfully developed by combining Wilson S T and Flanigen E M, et al, from carbide corporation 4 N (n is a number), which is also an important milestone in the history of molecular sieve development. The traditional concept that the zeolite molecular sieve consists of silicon oxygen tetrahedra and aluminum oxygen tetrahedra is broken through. AlPO obtained by combining trivalent aluminum ion and trivalent phosphate 4 Molecular sieves are electrically neutral, have very weak surface acidity, have no ion exchange properties, and have no so-called "active sites" required for catalytic reactions. In 1984, lok et al introduced tetravalent Si into AlPO 4 In the molecular sieve framework, a series of silicoaluminophosphate molecular Sieves (SAPO) with certain acidity are synthesized. Wherein SAPO-44 is a chabazite-like structure (structure code CHA). The structure has a three-dimensional eight-membered ring channel structure similar to the SAPO-34 molecular sieve structure, the pore size is also 0.43nm, the catalyst has good catalytic effect in MTO reaction, and the low-carbon olefin can be obtained in high yield. But the crystallization time of the SAPO-44 in the synthesis is relatively long, the impurity phase is easy to appear, and the pure-phase SAPO-44 molecular sieve is not easy to obtain.
In addition, the pore diameter of the SAPO-44 molecular sieve is relatively small, mass transfer and heat transfer of a reaction system are often limited in a catalytic reaction, and the activity and the service life of a catalyst are further influenced, and the defect can be overcome by a method for reducing the crystal size and modulating the crystal pore structure, so that great interest of vast scientific researchers is brought to the synthesis of nano small crystal grains, nano lamellar crystal grains, the synthesis of multi-level pore crystal grains and the like. Therefore, the synthesis of the pure-phase small-grain SAPO-44 has good practical significance.
In example 50 of U.S. Pat. No. 4,4440871 (1984), cyclohexylamine was used as a template, and the sol ratio was 1R:0.6SiO 2 :1Al 2 O 3 :1P 2 O 5 :50H 2 And O, crystallizing at 200 ℃ for 52 hours to obtain the SAPO-44 containing a small amount of impurities. Ursula Lohse et al (chem. Soc. Faraday Trans.91,1155 (1995)) uses cyclohexylamine as a template agent, and reduces the crystallization time (4 h at 200 ℃) under the condition of adding HF to obtain a relatively pure-phase SAPO-44 molecular sieve, but has relatively large crystal grains with the size of about 10-20 mu m. Deep B et al (Colloids and Surfaces A: physicochemical and Engineering A)select 146 (1999) 375-386) with cyclohexylamine as a template, 148 hours at 200 ℃ to produce pure phase SAPO-44 crystals. Chinese patent CN1299775A (2001) uses cyclohexylamine as template, at 0.2<Si/P 2 O 5 Crystallization is carried out for 20h to 160h at the temperature of between 180 and 205 ℃ which is less than or equal to 1.4, and the relatively pure phase SAPO-44 molecular sieve (0) can be obtained<Si/P 2 O 5 The SAPO-17 molecular sieve is prepared when the concentration is less than or equal to 0.1; 0.1<Si/P 2 O 5 And (3) preparing the SAPO-17 and SAPO-44 eutectic molecular sieve at the temperature of less than or equal to 0.2). Yong Huang et Al (J. Phys. Chem. B2004,108,1855-1865) used cyclohexylamine as template, the ratio of each substance in the sol was 1.0Al 2 O 3 /1.0P 2 O 5 /1.0SiO 2 /1.9R/63H 2 And in the process of O, the pure-phase SAPO-44 molecular sieve can be obtained by crystallization for 8 hours at 190 ℃, but the grain size is not reported. Chinese patent CN 103030154B (2015) uses cyclohexylamine as template agent, and the molar ratio of the mixed solution of the raw materials: al (Al) 2 O 3 :P 2 O 5 :SiO 2 :R:H 2 O=1.0:0.6-1.2:0.2-1.2:0.8-2.5:20-100, crystallizing at 150-220 ℃ for 2-160 hours to obtain the intergrowth molecular sieve of SAPO-5 and SAPO-44.
WO9919254A1 (1999) and US 6319487B1 (2001) take cyclohexane or cyclohexane salt as a template agent, crystallize for 72 hours at 200 ℃, age for a period of time at 20-65 ℃ and crystallize for 72 hours at 200 ℃ to obtain a relatively pure-phase SAPO-44 molecular sieve, and the grain size is not reported.
Patent CN103663489a (2014) and WO2014047807A1 (2014) disclose SAPO-44 and a method for synthesizing the same. The expensive hexamethyleneimine is used as a template agent, and is crystallized for 1h to 12h at 195 to 225 ℃ by adding a surfactant of trimethylhexadecyl ammonium bromide (reducing the silicon-rich degree of the surface), so that the SAPO-44 molecular sieve is obtained, and the crystal grain size is about 5 mu m from the SEM result. Chinese patent CN 105347356A (2016) takes benzyl trimethylammonium cation as a template agent, and is crystallized for 5 to 72 hours at the temperature of 150 to 200 ℃ to obtain the SAPO-44 molecular sieve, and SEM shows that the grain size is 5 to 10 mu m. Chinese patent CN 104743574B (2016) takes diethylamine, triethylamine, tetraethylenepentamine and the like and more expensive N, N, N ', N' -tetramethylhexamethylenediamine as composite template agents, and the pure-phase microporous SAPO-44 molecular sieve is obtained by crystallization for 48-108 hours under the conditions that the silicon-aluminum ratio is 0.5-1.0 and the temperature is 150-250 ℃, but the grain size is unknown.
Taken together, it can be seen that there are mainly the following problems in conventional hydrothermal synthesis of SAPO-44: 1. general silicon aluminum (SiO) 2 :Al 2 O 3 ) The ratio is not less than 0.2; 2. generally, a pure-phase SAPO-44 crystalline phase is not easily obtained; 3. the time required for high-temperature crystallization is relatively long; 4. the resulting crystal particles are relatively large, typically greater than 5 μm.
To meet the industrial application requirements, the synthesis of pure-phase, small-grain SAPO-44 and SAPO-44 molecular sieves with lower silicon to aluminum ratio is an important problem to be solved in the prior art.
Disclosure of Invention
In view of the shortcomings of the prior art, the first object of the invention is to provide a pure-phase small-grain SAPO-44 molecular sieve, so as to ensure the relative singleness of the molecular sieve material structure and better exert the shape selectivity of the molecular sieve; the invention also aims to provide a preparation method of the pure-phase small-grain SAPO-44, which is used for simplifying the preparation process, reducing the preparation cost and facilitating the industrialized mass production.
A first aspect of the present invention is to provide a pure phase, small-crystallite SAPO-44 molecular sieve having a crystallite diameter of not greater than 3 μm, preferably not greater than 2.5 μm.
Further, in the molecular sieve, the weight ratio of silicon-aluminum substances is 0.07 less than or equal to SiO 2 /Al 2 O 3 Less than or equal to 1.0, preferably 0.1 less than or equal to SiO 2 /Al 2 O 3 ≤0.4。
The invention further provides a preparation method of the pure-phase small-grain SAPO-44 molecular sieve, which adopts the SAPO-5 molecular sieve as a precursor to synthesize the pure-phase small-grain SAPO-44 molecular sieve.
In the present invention, a pure phase SAPO-44 molecular sieve means that it does not contain other impurity phases.
Further, the synthesis method of the SAPO-44 molecular sieve comprises the following steps:
1) Thoroughly mixing SAPO-5 molecular sieve, water and optional phosphoric acid to obtain a mixed solution I;
2) Adding a template agent into the mixed solution I under stirring, and fully mixing to obtain a mixed solution II;
3) Optionally adding fluoride and/or optionally adding a third template R to the mixture II 3 Fully mixing to obtain a mixed solution III;
4) Crystallizing the mixed solution III to obtain the pure-phase small-grain SAPO-44 molecular sieve.
In the preparation method of the invention, the material which can be selectively added can be added or not.
Further, the template in the step 2) is a first template R 1 And a second templating agent R 2 Wherein the first template R 1 Is cyclohexylamine; second template R 2 One or more of acyclic small molecule amines, preferably ethylamine, diethylamine, triethylamine, propylamine, etc.
Further, the material ratio of each substance in mass ratio in the preparation process of the molecular sieve is as follows: 1SAPO-5 (0-0.2) H 3 PO 4 :(0.1-0.6)R 1 :(0.1-0.4)R 2 :(0-1)R 3 :(0-0.05)F:(2-10)H 2 O。
Further, the feeding amount of phosphoric acid is preferably: 1SAPO-5 (0.05-0.15) H 3 PO 4 。
Further, a first templating agent R 1 The feeding amount of (2) is preferably as follows: 1SAPO-5 (0.3-0.5) R 1 。
Further, a second templating agent R 2 The feeding amount of (2) is preferably as follows: 1SAPO-5 (0.1-0.2) R 2 。
Further, the amount of fluoride to be fed is preferably: 1SAPO-5 (0.01-0.05) F.
Further, the water is preferably fed in an amount of: 1SAPO-5 (3-6) H 2 O。
Further, the weight ratio of the SAPO-5 molecular sieve silica-alumina material in the step 1) (in terms of SiO 2 /Al 2 O 3 As low as 0.06. Preferably, the mass ratio of the silicon aluminum substances is 0.06-SiO 2 /Al 2 O 3 Less than or equal to 0.4, more preferably less than or equal to 0.1 and less than or equal to SiO 2 /Al 2 O 3 ≤0.4。
Further, the fluoride in step 3) is preferably hydrofluoric acid.
Further, the third template R in step 3) 3 Is alcohol template agent, preferably one or more of methanol, ethanol, propanol and ethylene glycol, R is calculated by mass ratio 3 The preferable feed ratio is: 1SAPO-5 (0.2-0.5) R 3 。
Further, the crystallization conditions in step 4) are as follows: crystallizing at 190-210 deg.c for 1-4 hr, preferably at 200-205 deg.c for 1-2 hr. The crystallization is carried out in a crystallization kettle with polytetrafluoroethylene as a lining, and a dynamic crystallization mode is preferably adopted.
Further, the crystallization of step 4) is preferably followed by a drying and firing process, which is performed by conventional operations. The drying conditions are as follows: the temperature is 50-150deg.C, preferably 80-120deg.C, and the drying time is 8-30 h, preferably 12-24 h; the roasting condition is that the roasting temperature is 450-650 ℃, preferably 500-600 ℃, and the roasting time is 3-10 h, preferably 4-6 h.
In a third aspect, the present invention provides the use of a pure phase, small crystallite SAPO-44 molecular sieve as described above as an adsorbent or catalyst component. For example, can be used for carbon dioxide adsorption separation and NH 3 In SCR, MTO, etc.
The invention takes SAPO-5 as a precursor and cheap organic amine as a template agent, well solves the defects of the prior art, and prepares the pure-phase small-grain SAPO-44 molecular sieve. The SAPO-44 molecular sieve has the advantages of simple preparation process, pure crystalline phase, relatively small crystalline grains, and greatly shortened high-temperature crystallization time, and has good economic benefit when being used in industrial production.
Drawings
FIG. 1 shows a silicon aluminum (SiO) 2 :Al 2 O 3 ) XRD pattern of SAPO-5 precursor prepared by the material proportion of 0.4;
FIG. 2 shows a silicon aluminum (SiO) 2 :Al 2 O 3 ) SEM image of SAPO-5 precursor prepared with a feeding ratio of 0.4;
FIG. 3 is an XRD pattern of the molecular sieve prepared in example 1;
FIG. 4 is an SEM image of a molecular sieve prepared according to example 1;
FIG. 5 is an XRD pattern of the molecular sieve prepared in example 2;
FIG. 6 is an SEM image of a molecular sieve prepared according to example 2;
FIG. 7 is an XRD pattern of the molecular sieve prepared in comparative example 1;
FIG. 8 is an SEM image of the molecular sieve prepared in comparative example 1;
FIG. 9 is an XRD pattern of the molecular sieve prepared in comparative example 2;
fig. 10 is an SEM image of the molecular sieve prepared in comparative example 2.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
In the invention, the device and the operation parameters used for performance data or map test are as follows:
XRD: the phase of the sample was analyzed using a PANalytical X' Pert PRO X-ray powder diffractometer from Panalaceae, netherlands, (light pipe: target-rotating Cu target,voltage current: 40kv x 40 ma), 2θ scan range: 2-50 DEG, and the scanning speed is 7 DEG/min.
SEM: the morphology of the crystals was analyzed by Hitachi S-4800 high-resolution scanning electron microscope, FEI Co. Magnification factor: 40-1000000 x and accelerating voltage of 3.0kV.
ICP-AES: the elemental ratios in the samples were analyzed using a Varianalytical 725-ES inductively coupled plasma emission spectrometer from Varianan, inc. of America.
Preparing a precursor:
the silicon-aluminum feeding ratio is 0.4 (namely SiO in terms of mole ratio) 2 :Al 2 O 3 =0.4, the same applies below) to the specific preparation process of SAPO-5: weighing 188g of water, adding 30.2g of pseudo-boehmite under stirring, then adding 46.12g of phosphoric acid, adding in a water bath at 70 ℃ under stirring for 2 hours, adding 13g of Ludox-40wt% under stirring, adding 24.28g of triethylamine after stirring uniformly, continuing stirring for 2 hours, and transferring to crystallizationAnd crystallizing for 30h at 200 ℃. Taking out, quenching, centrifuging, washing (repeating for 2-3 times), and oven drying. XRD patterns and SEM patterns of the prepared SAPO-5 are shown in FIG. 1 and FIG. 2, respectively.
Under the condition that other conditions are unchanged and the content of silicon is only changed, the SAPO-5 molecular sieve with the silicon-aluminum ratio of 0-1.0 is prepared, and the molecular sieve is dried at 80 ℃ for standby.
[ example 1 ]
Weighing 25g of water, adding 0.5g of phosphoric acid and 5g of SAPO-5 (uncaal is an unfired dry matter) with a silicon aluminum feeding ratio of 0.4, and fully mixing to obtain a mixed solution I; then adding 2.5g of cyclohexylamine and 0.9g of diethylamine into the mixed solution I, and stirring at room temperature for 2 hours to obtain a mixed solution II; adding 0.25g of hydrofluoric acid (concentration is 40%, the same shall apply below) and 2.5g of ethanol into the mixed solution II under stirring, and uniformly stirring to obtain a mixed solution III; and transferring the mixed solution III into a crystallization kettle with a polytetrafluoroethylene lining, putting the crystallization kettle into a rotary oven at 200 ℃, crystallizing for 2 hours at the temperature, taking out, quenching, centrifuging, washing and drying to obtain the pure-phase small-grain SAPO-44 molecular sieve. The grain size of the crystal is about 0.5 mu m, siO 2 /Al 2 O 3 ＝0.36。
[ example 2 ]
Weighing 25g of water, adding 0.5g of phosphoric acid, adding 5g of SAPO-5 (cal is a roasting material) with a silicon-aluminum feeding ratio of 0.4, and fully mixing to obtain a mixed solution I; then adding 2g of cyclohexylamine and 0.9g of diethylamine into the mixed solution I, and stirring at room temperature for 2 hours to obtain a mixed solution II; adding 0.25g of hydrofluoric acid and 2.5g of ethanol into the mixed solution II under stirring, and uniformly stirring to obtain a mixed solution III; and transferring the mixed solution III into a crystallization kettle with a polytetrafluoroethylene lining, putting the crystallization kettle into a rotary oven at 200 ℃, crystallizing for 2 hours at the temperature, taking out, quenching, centrifuging, washing and drying to obtain the pure-phase small-grain SAPO-44 molecular sieve. The grain size of the crystal is about 1.0 mu m, siO 2 /Al 2 O 3 ＝0.34。
[ example 3 ]
Weighing 25g of water, adding 0.5g of phosphoric acid and 5g of SAPO-5 (uncal) with a silicon-aluminum feeding ratio of 0.2, and fully mixing to obtain a mixed solution I; then adding 2g of cyclohexylamine and 0.9g of diethylamine into the mixed solution I, and stirring at room temperature for 2 hours to obtain a mixed solution II; adding into the mixed solution II under stirring0.25g of hydrofluoric acid and 2.5g of methanol, and uniformly stirring to obtain a mixed solution III; and transferring the mixed solution III into a crystallization kettle with a polytetrafluoroethylene lining, putting the crystallization kettle into a rotary oven at 200 ℃, crystallizing for 2 hours at the temperature, taking out, quenching, centrifuging, washing and drying to obtain the pure-phase small-grain SAPO-44 molecular sieve. The grain size of the crystal is about 1.2 mu m, siO 2 /Al 2 O 3 ＝0.18。
[ example 4 ]
Weighing 25g of water, adding 0.5g of phosphoric acid and 5g of SAPO-5 (uncal) with a silicon-aluminum feeding ratio of 0.1, and fully mixing to obtain a mixed solution I; then adding 2g of cyclohexylamine and 0.9g of diethylamine into the mixed solution I, and stirring at room temperature for 2 hours to obtain a mixed solution II;0.25g of hydrofluoric acid and 2.5g of isopropanol, and uniformly stirring to obtain a mixed solution III; and transferring the mixed solution III into a crystallization kettle with a polytetrafluoroethylene lining, putting the crystallization kettle into a rotary oven at 200 ℃, crystallizing for 2 hours at the temperature, taking out, quenching, centrifuging, washing and drying to obtain the pure-phase small-grain SAPO-44 molecular sieve. The grain size of the crystal is about 1.4 mu m, siO 2 /Al 2 O 3 ＝0.09。
[ example 5 ]
Weighing 25g of water, adding 0.5g of phosphoric acid and 5g of SAPO-5 (uncal) with a silicon-aluminum feeding ratio of 0.06, and fully mixing to obtain a mixed solution I; then adding 2g of cyclohexylamine and 0.9g of diethylamine into the mixed solution I, and stirring at room temperature for 2 hours to obtain a mixed solution II; adding 0.25g of hydrofluoric acid and 2.5g of ethanol into the mixed solution II under stirring, and uniformly stirring to obtain a mixed solution III; and transferring the mixed solution III into a crystallization kettle with a polytetrafluoroethylene lining, putting the crystallization kettle into a rotary oven at 205 ℃, crystallizing for 2 hours at the temperature, taking out, quenching, centrifuging, washing and drying to obtain the pure-phase small-grain SAPO-44 molecular sieve. The grain size of the crystal is about 2.0 mu m, siO 2 /Al 2 O 3 ＝0.07。
[ example 6 ]
Weighing 25g of water, adding 5g of SAPO-5 (uncal) with a silicon-aluminum feeding ratio of 1.0, and fully mixing to obtain a mixed solution I; then adding 2.5g of cyclohexylamine and 1.25g of triethylamine into the mixed solution I, and stirring for 2 hours at room temperature to obtain a mixed solution II; adding 0.25g of hydrofluoric acid and 2.5g of ethanol into the mixed solution II under stirring, and uniformly stirring to obtain a mixed solution III; however, the method is thatAnd transferring the mixed solution III into a crystallization kettle with a polytetrafluoroethylene lining, putting the crystallization kettle into a rotary oven at 190 ℃, crystallizing for 3 hours at the temperature, taking out, quenching, centrifuging, washing and drying to obtain the pure-phase small-grain SAPO-44 molecular sieve. The grain size of the crystal is about 1.6 mu m, siO 2 /Al 2 O 3 ＝0.88。
[ example 7 ]
Weighing 25g of water, adding 5g of SAPO-5 (uncal) with a silicon-aluminum feeding ratio of 0.4, and fully mixing to obtain a mixed solution I; then adding 2.5g of cyclohexylamine and 1.25g of triethylamine into the mixed solution I, and stirring for 2 hours at room temperature to obtain a mixed solution II; adding 0.25g of hydrofluoric acid and 2.5g of ethanol into the mixed solution II under stirring, and uniformly stirring to obtain a mixed solution III; and transferring the mixed solution III into a crystallization kettle with a polytetrafluoroethylene lining, putting the crystallization kettle into a rotary oven at 190 ℃, crystallizing for 4 hours at the temperature, taking out, quenching, centrifuging, washing and drying to obtain the pure-phase small-grain SAPO-44 molecular sieve. The grain size of the crystal is about 2.4 mu m, siO 2 /Al 2 O 3 ＝0.36。
[ example 8 ]
Weighing 25g of water, adding 5g of SAPO-5 (uncal) with a silicon-aluminum feeding ratio of 0.2, and fully mixing to obtain a mixed solution I; then adding 1g of cyclohexylamine and 1.2g of diethylamine into the mixed solution I, and stirring at room temperature for 2 hours to obtain a mixed solution II; adding 0.25g of hydrofluoric acid and 1g of methanol into the mixed solution II under stirring, and uniformly stirring to obtain a mixed solution III; and transferring the mixed solution III into a crystallization kettle with a polytetrafluoroethylene lining, putting the crystallization kettle into a rotary oven at 210 ℃, crystallizing for 3 hours at the temperature, taking out, quenching, centrifuging, washing and drying to obtain the pure-phase small-grain SAPO-44 molecular sieve. The grain size of the crystal is about 1.8 mu m, siO 2 /Al 2 O 3 ＝0.17。
[ example 9 ]
15g of water is weighed and added, 5g of SAPO-5 (uncal) with the silicon aluminum feeding ratio of 0.4 is fully mixed to obtain a mixed solution I; then adding 2g of cyclohexylamine and 0.4g of diethylamine into the mixed solution I, and stirring at room temperature for 2 hours to obtain a mixed solution II; adding 0.25g of hydrofluoric acid and 2g of isopropanol into the mixed solution II under stirring, and uniformly stirring to obtain a mixed solution III; transferring the mixed solution III into a crystallization kettle with a polytetrafluoroethylene lining, and placing the mixed solution III into a crystallization kettle with a polytetrafluoroethylene lining at 205 DEG CAnd (3) rotating the oven, crystallizing for 2 hours at the temperature, taking out, quenching, centrifuging, washing and drying to obtain the pure-phase small-grain SAPO-44 molecular sieve. The grain size of the crystal is about 1.4 mu m, siO 2 /Al 2 O 3 ＝0.32。
[ example 10 ]
Weighing 25g of water, adding 5g of SAPO-5 (uncal) with a silicon-aluminum feeding ratio of 0.2, and fully mixing to obtain a mixed solution I; then adding 2g of cyclohexylamine and 1.2g of diethylamine into the mixed solution I, and stirring at room temperature for 2 hours to obtain a mixed solution II; adding 2.5g of ethanol into the mixed solution II under stirring, and uniformly stirring to obtain a mixed solution III; and transferring the mixed solution III into a crystallization kettle with a polytetrafluoroethylene lining, putting the crystallization kettle into a rotary oven at 200 ℃, crystallizing for 2 hours at the temperature, taking out, quenching, centrifuging, washing and drying to obtain the pure-phase small-grain SAPO-44 molecular sieve. The grain size of the crystal is about 1.0 mu m, siO 2 /Al 2 O 3 ＝0.15。
[ example 11 ]
Weighing 25g of water, adding 5g of SAPO-5 (uncal) with a silicon-aluminum feeding ratio of 0.2, and fully mixing to obtain a mixed solution I; then adding 2g of cyclohexylamine and 0.7g of propylamine into the mixed solution I, and stirring for 2 hours at room temperature to obtain a mixed solution II; adding 0.25g of HF into the mixed solution II under stirring, and uniformly stirring to obtain a mixed solution III; and transferring the mixed solution III into a crystallization kettle with a polytetrafluoroethylene lining, putting the crystallization kettle into a rotary oven at 205 ℃, crystallizing for 4 hours at the temperature, taking out, quenching, centrifuging, washing and drying to obtain the pure-phase small-grain SAPO-44 molecular sieve. The grain size of the crystal is about 2.0 mu m, siO 2 /Al 2 O 3 ＝0.18。
[ example 12 ]
Weighing 40g of water, adding 5g of SAPO-5 (uncal) with a silicon-aluminum feeding ratio of 0.2, and fully mixing to obtain a mixed solution I; then adding 2g of cyclohexylamine and 1.27g of triethylamine into the mixed solution I, and stirring at room temperature for 2 hours to obtain a mixed solution II; adding 0.25g of HF into the mixed solution II under stirring, and uniformly stirring to obtain a mixed solution III; and transferring the mixed solution III into a crystallization kettle with a polytetrafluoroethylene lining, putting the crystallization kettle into a rotary oven at 205 ℃, crystallizing for 3 hours at the temperature, taking out, quenching, centrifuging, washing and drying to obtain the pure-phase small-grain SAPO-44 molecular sieve. Crystal grainThe diameter is about 1.5 μm, siO 2 /Al 2 O 3 ＝0.17。
Comparative example 1
Weighing 25g of water, adding 0.5g of phosphoric acid and 5g of SAPO-5 (uncal) with a silicon-aluminum feeding ratio of 0.4, and fully mixing to obtain a mixed solution I; then adding 3.8g of cyclohexylamine into the mixed solution I, and stirring for 2 hours at room temperature to obtain a mixed solution II; adding 0.25g of hydrofluoric acid and 2.5g of ethanol into the mixed solution II under stirring, and uniformly stirring to obtain a mixed solution III; and transferring the mixed solution III into a crystallization kettle with a polytetrafluoroethylene lining, putting the crystallization kettle into a rotary oven at 200 ℃, crystallizing for 3 hours at the temperature, taking out, quenching, centrifuging, washing and drying to obtain the pure-phase SAPO-44 molecular sieve. The morphology is twin crystals, the grain diameter of the crystals is about 5 mu m, and SiO 2 /Al 2 O 3 ＝0.35。
Comparative example 2
Weighing 25g of water, adding 0.5g of phosphoric acid and 5g of SAPO-5 (uncal) with a silicon-aluminum feeding ratio of 0.4, and fully mixing to obtain a mixed solution I; then adding 2.7g of diethylamine into the mixed solution I, and stirring for 2 hours at room temperature to obtain a mixed solution II; adding 0.25g of hydrofluoric acid and 2.5g of ethanol into the mixed solution II under stirring, and uniformly stirring to obtain a mixed solution III; and transferring the mixed solution III into a crystallization kettle with a polytetrafluoroethylene lining, putting the crystallization kettle into a rotary oven at 200 ℃, crystallizing for 3 hours at the temperature, taking out, quenching, centrifuging, washing and drying to obtain the pure-phase SAPO-34 molecular sieve with the same CHA framework structure. The grain size of the crystal is about 4 mu m, siO 2 /Al 2 O 3 ＝0.33。
Claims (17)
1. A preparation method of a pure-phase small-grain SAPO-44 molecular sieve is characterized in that the grain diameter of the molecular sieve is not more than 3 mu m, and the mass ratio of silicon to aluminum substances of the molecular sieve is not more than 0.07 and less than or equal to SiO 2 /Al 2 O 3 Less than or equal to 1.0, the preparation method comprises the following steps:
1) Thoroughly mixing SAPO-5 molecular sieve, water and optional phosphoric acid to obtain a mixed solution I;
2) Adding a template agent into the mixed solution I under stirring, and fully mixing to obtain a mixed solution II;
3) Optionally adding fluoride to the mixture IIAnd/or optionally adding a third templating agent R 3 Fully mixing to obtain a mixed solution III;
4) Crystallizing the mixed solution III to obtain a pure-phase small-grain SAPO-44 molecular sieve;
the template agent in the step 2) is a first template agent R 1 And a second templating agent R 2 Wherein the first template R 1 Is cyclohexylamine; second template R 2 Selected from acyclic small molecule amines; the third template R in step 3) 3 Is an alcohol template agent.
2. The method of claim 1, wherein the second template R in step 2) 2 One or more selected from ethylamine, diethylamine, triethylamine and propylamine.
3. The preparation method according to claim 1, wherein the mass ratio of each substance in the molecular sieve preparation process is as follows:
1SAPO-5:(0-0.2)H 3 PO 4 :(0.1-0.6)R 1 :(0.1-0.4)R 2 : (0-1)R 3 : (0-0.05)F:(2-10)H 2 O。
4. a method of preparing as claimed in claim 1 or 3, wherein the phosphoric acid is dosed in an amount of: 1SAPO-5 (0.05-0.15) H 3 PO 4 。
5. A method of preparation according to claim 2 or 3, wherein the first templating agent R 1 The feeding amount of the (2) is as follows: 1SAPO-5 (0.3-0.5) R 1 。
6. A method of preparation according to claim 2 or 3, wherein the second templating agent R 2 The feeding amount of the (2) is as follows: 1SAPO-5 (0.1-0.2) R 2 。
7. The method of claim 1, wherein the SAPO-5 molecular sieve is siliconThe amount ratio of aluminum substances is SiO 2 /Al 2 O 3 SiO is 0.06 ≡ 2 /Al 2 O 3 ≤0.4。
8. The method of claim 1, wherein the ratio of the amounts of the silica alumina materials of the SAPO-5 molecular sieve is based on SiO 2 /Al 2 O 3 SiO is 0.1-0 2 /Al 2 O 3 ≤0.4。
9. The method of claim 1, wherein the fluoride in step 3) is hydrofluoric acid.
10. The method of claim 1, wherein the third template R in step 3) 3 Is one or more of methanol, ethanol, propanol and ethylene glycol.
11. The method according to claim 10, wherein in step 3), R is calculated as a mass ratio 3 The feed ratio is as follows: 1SAPO-5 (0.2-0.5) R 3 。
12. The method according to claim 1, wherein the crystallization conditions in step 4) are as follows: crystallizing at 190-210 deg.c for 1-4 hr.
13. The method according to claim 1, wherein the crystallization conditions in step 4) are as follows: crystallizing for 1-2 h at 200-205 ℃.
14. The pure phase, small crystalline SAPO-44 molecular sieve made by the method of any one of claims 1 to 13.
15. The SAPO-44 molecular sieve of claim 14, wherein the molecular sieve has a grain diameter of not greater than 2.5 μm.
16. Root of Chinese characterThe SAPO-44 molecular sieve according to claim 14, wherein the molecular sieve has a silica to alumina mass ratio of 0.1 to SiO 2 /Al 2 O 3 ≤0.4。
17. Use of the pure phase, small grain SAPO-44 molecular sieve of any one of claims 14 to 16 as an adsorbent or catalyst component.
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