CN100372760C - 12-membered ring macroporous aluminum phosphite molecular sieve and preparation method thereof - Google Patents
12-membered ring macroporous aluminum phosphite molecular sieve and preparation method thereof Download PDFInfo
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Abstract
本发明涉及12元环大微孔亚磷酸铝分子筛(NKX-2)及制备方法。它的化学式是：H6Al4O18P6，具有以下特征衍射峰。分别以二正丙胺、三乙胺、正丙胺、正丁胺和柠檬酸为模板剂，也可以不用任何模板剂，采用水热方法合成。本发明的分子筛是亚磷酸铝分子筛，具有一维12元环孔道结构，12元环孔径为9.7×6.4。本发明是第一个具有12元环大微孔孔道结构的亚磷酸铝分子筛，具有较高的热稳定性。作为具有新性质的分子筛将产生新的广泛应用。The invention relates to a 12-membered ring macroporous aluminum phosphite molecular sieve (NKX-2) and a preparation method. Its chemical formula is: H 6 Al 4 O 18 P 6 , with the following characteristic diffraction peaks. Di-n-propylamine, triethylamine, n-propylamine, n-butylamine and citric acid are respectively used as templates, or can be synthesized by hydrothermal method without any template. The molecular sieve of the present invention is an aluminum phosphite molecular sieve, which has a one-dimensional 12-membered ring channel structure, and the pore diameter of the 12-membered ring is 9.7×6.4. The invention is the first aluminum phosphite molecular sieve with a 12-membered ring macropore structure, and has high thermal stability. Molecular sieves with new properties will generate new and extensive applications.
Description
Technical field
The structure that the present invention relates to molecular sieve specifically is 12 ring large micropore aluminum phosphite molecular sieves (NKX-2) and preparation method with synthetic.
Technical background
The preparation research of micropore phosphite molecular screen material starts from 2000, document Chem.Commun.2000,2385; Inorg.Chem.2001,40,95; J.Solid State Chem.2001,160,4; J.Chem.Soc.Dolton Trans.2001,2459 have reported the study on the synthesis of several micropore zinc phosphites.Because constituting, the orthophosphite ions in phosphite compound have one to be hydrogen atom in the tessarace atom, the distortion tetrahedron that formed tetrahedron, therefore, the structure of phosphite molecular sieve is with the phosphate molecule sieve of broad research is different at present, and the character that the molecular sieve generation is made new advances.
The research of the micropore phosphite material that carries out at present mainly concentrates on the phosphite of main group element phosphorous acid beryllium, subgroup element zinc phosphite and other transition element.Aluminum phosphite molecular sieve only has document J.Chem.Cryst.1994 at present, and an example of 24,155 reports under normal pressure, mild temperature, adopts the method for solvent flashing to make, and contains 8 membered ring channels in the structure.
Summary of the invention
The purpose of this invention is to provide a kind of 12 novel ring large micropore aluminum phosphite molecular sieves (being called for short NKX-2) and preparation method thereof, it is an aluminum phosphite molecular sieve, has one dimension 12 membered ring channel structures, and 12 yuan of annular apertures are 9.7 * 6.4 .The present invention is first aluminum phosphite molecular sieve with 12 yuan of ring large micropore pore passage structures, has higher thermostability (as shown in Figure 1).To produce new widespread use as molecular sieve with new property.
The chemical formula of 12 yuan of rings of the present invention macropore aluminum phosphite molecular sieve NKX-2 is: H
6Al
4O
18P
6
The x ray powder diffraction spectrum of 12 yuan of rings of the present invention macropore aluminum phosphite molecular sieve NKX-2 has following characteristic diffraction peak (as shown in Figure 2):
2θ(°) 12.96 17.99 22.55 25.08 25.86 26.15 28.33 29.05 34.00
I/I
0 100.0 1 23.1 3 100 9 2 35 21
2θ(°) 34.80 36.53 37.11 39.66 41.71 44.67 46.72 47.51 48.10
I/I
0 15 6 6 9 6 5 4 1 3
Described 12 ring large micropore aluminum phosphite molecular sieve NKX-2 belong to hexagonal system, and spacer is P 6
3/ m.Unit cell parameters is a=b=7.876 , c=7.1237 , α=β=90 °, γ=120 °.This crystalline structural unit has polyphyll trifolium shape, and (Fig. 3 a) interconnects along [ab] plane between this structural unit, forms the one-piece construction (Fig. 3 b) of aluminum phosphite molecular sieve NKX-2, wherein includes axial 12 membered ring channels of c.Along with the vertical direction of Fig. 3 b on, the aluminium atom links up with two-layer adjacent aluminium atom up and down respectively by two kinds of different modes: a kind of mode be the aluminium atom that is positioned at certain one deck with the aluminium atom of its top between link to each other with three Al-O-Al, formed three Al
2O
2The little cage of window; This aluminium atom links to each other with three Al-O-P-O-Al with another aluminium atom of its below, forms and contains 4 of three tetra-atomic ring windows
3(tetra-atomic ring is made up of 2 Al atoms and 2 phosphorus atom, does not comprise Sauerstoffatom) cage (Fig. 4).
Preparation method of the present invention comprises the steps:
Aluminium source, phosphorus source, organic formwork agent (perhaps not adding organic formwork agent) are mixed with water (perhaps non-aqueous solvent), under room temperature, stirred 2-4 hour, make uniform mixture, 5-30 days (having in the stainless steel cauldron of tetrafluoroethylene) of hydrothermal crystallizing or solvent thermal crystallization under 100-200 ℃ of autogenous pressure, the gained crystal obtains target product with distilled water wash and suction filtration after 80 ℃ of following dryings.The product of gained is the uniform crystal of well-crystallized's size.
Described aluminium source is 0.5-1.5 with the ratio in phosphorus source, and the mol ratio in organic formwork agent and phosphorus source is 0.3-2.5, and the mol ratio in water and phosphorus source is 20-100.
Described aluminium source is the solubility salt of pseudo-boehmite, aluminium hydroxide, aluminum isopropylate, sodium metaaluminate or aluminium.
Described phosphorus source is phosphorous acid and the phosphorous compound of solubility.
Described organic formwork agent is di-n-propylamine, triethylamine, Tri N-Propyl Amine, n-Butyl Amine 99 and citric acid.
Described non-aqueous solvent is Macrogol 200 or Liquid Macrogol.
Described hydrothermal crystallizing is a hydrothermal crystallizing under 130-200 ℃ of autogenous pressure;
Described solvent thermal crystallization is a crystallization under 160-200 ℃ of autogenous pressure.
The present invention is first aluminum phosphite molecular sieve with 12 yuan of ring large micropore structures, has one dimension 12 membered ring channel structures, and 12 yuan of annular apertures are 9.7 * 6.4 .Has higher thermostability.To produce new widespread use as molecular sieve with new property.
Description of drawings
Fig. 1 is the thermogravimetric-differential thermal analysis curve of 12 yuan of ring large micropore structure aluminum phosphite molecular sieves.
Fig. 2 be molecular sieve of the present invention powder X-ray RD figure (descending) and monocrystalline match spectrogram (on).
Fig. 3 is structural unit and 12 membered ring channels that are positioned in this molecular sieve structure on the ab coordinate axis plane.
Fig. 4 be with ab coordinate axis plane vertical direction on structural unit figure.
Embodiment
Example 1, restrain phosphorous acid at 50 ml beakers with 20 ml waters dissolving 4.59, add pseudo-boehmite 4.13 grams then in one 100 ml beaker, 4.5 milliliters of triethylamines (template) mix, under room temperature, stirred 2 hours, form uniform mixture, change over to then and have in the teflon-lined stainless steel cauldron, obtained target product in 18 days 180 ℃ of crystallization, with distilled water wash and suction filtration, after 80 ℃ of following dryings, obtain target product.Use following instrument and method that product is characterized:
1, uses Japanese Rigaku D/Max-2500 type X-ray diffractometer of science to measure the X-ray powder diffraction spectrogram of product, obtain having the spectrogram (Fig. 2) of the listed characteristic diffraction peak of table 1.
2, select the crystal that is of a size of 0.20 * 0.10 * 0.10mm and be used for the single crystal structure analysis, the single crystal diffraction data are collected on BrukerSmart CCD diffractometer, with the Mok alpha-ray (λ=0.71073 ) of graphite monochromator monochromatization, 5.98 °≤2 θ≤55.04 °.Belong to hexagonal system, spacer P6
3/ m, a=b=7.8762 (11) , c=7.1237 (14) , α=β=90 °, γ=120 °, V=382.71 (11)
3, Z=1, T=293 (2) K, R (F)=0.0444, wR (F
2)=0.1159.Monocrystalline data and parameter see Table 2,3, and crystalline structure is seen Fig. 3-4 (using Ortep III, Diamond2.1 software to draw).By the XRD figure of single crystal diffraction data fitting conform to powder X-ray RD figure (Fig. 2).
3, use the anti-STA409 of the speeding type TG-DSC analyser of Germany that product is carried out thermogravimetric analysis, example weight 8.2mg, temperature range: room temperature～800 ℃ temperature rise rate: 10 ℃/min, reference substance: Al
2O
3, see Fig. 1.This molecular sieve is weightlessness 4.8% (being lattice water) from 21 ℃ to 700 ℃.
The X-ray powder diffraction spectrogram of table 1, NKX-2
| 2θ(°) | 12.96 | 17.99 | 22.55 | 25.08 | 25.86 | 26.15 | 28.33 | 29.05 | 34.00 |
| I/I 02θ(°) I/I 0 | 100.0 34.80 15 | 1 36.53 6 | 23.1 37.11 6 | 3 39.66 9 | 100 41.71 6 | 9 44.67 5 | 2 46.72 4 | 35 47.51 1 | 21 48.10 3 |
Table 2, NKX-2 crystalline structure data
| CSD-number Formula Fomula weight T(K) Wavelength() Crystal system， space group a() | 415615 H 6Al 4O 18P 6(NKX-2) 58779 291(2) 0.71073 Hexagonal P63/m(no.176) 7.8762(11) |
| b() c() α(°) β(°) γ(°) V( 3) Z pcalx(Mg/m 3) μ(mm -1) F(000) Crystal size(mm) θrange(°) Limiting indices Reflections collected/unique Completeness to theta＝26.39 Refinement method Data/restraints/parameters Goodness-of-fitonF 2Final R indices[I>2σ(I)] R indices(alldata) Largest diff.peak and hole(e. -3) | 7.8762(11) 71237(14) 90 90 120 382.71(11) 1 2.550 1.036 292 020×0.10×0.10 2.99to27.52 -8≤h≤10，-10≤k≤0，-9≤1≤9 1464/314[R int＝0.0570] 98.4％ Full-matrix least-squares on F 2314/1/29 1.150 R1＝0.0444，wR2＝0.1159 R1＝0.0504，wR2＝0.1207 0.872and-0568 |
Bond distance () in table 3, the NKX-2 crystalline structure and bond angle (°)
| P(1)-O(1) P(1)-O(1)#1 P(1)-O(2) Al(1)-O(1)#2 Al(1)-O(1)#3 Al(1)-O(1)#4 O(1)-P(1)-O(1)#1 O(1)-P(1)-O(2) O(1)#1-P(1)-O(2) O(1)#2-Al(1)-O(1)#3 O(1)#2-Al(1)-O(1)#4 O(1)#3-Al(1)-O(1)#4 | 1.512(3) 1.512(3) 1.536(4) 1.825(3) 1.825(3) 1.825(3) 114.7(2) 110.81(13) 110.81(13) 98.46(13) 98.46(13) 98.46(13) | Al(1)-O(2)#5 A1(1)-O(2) Al(1)-O(2)#6 Al(1)-Al(1)#1 O(2)-Al(1)#1 O(1)-Al(1)#3 O(1)#3-Al(1)-O(2)#6 O(1)#4-Al(1)-O(2)#6 O(2)#5-Al(1)-O(2)#6 O(2)-Al(1)-O(2)#6 O(1)#2-Al(1)-Al(1)#1 O(1)#3-Al(1)-Al(1)#1 | 1.994(3) 1.994(3) 1.994(3) 2808(4) 1.994(3) 1.825(3) 9145(13) 92.10(13) 75.91(12) 75.91(12) 119.01(10) 119.01(10) |
| O(1)#2-Al(1)-O(2)#5 O(1)#3-Al(1)-O(2)#5 O(1)#4-Al(1)-O(2)#5 O(1)#2-Al(1)-O(2) O(1)#3-Al(1)-O(2) O(1)#4-Al(1)-O(2) O(2)#5-Al(1)-O(2) O(1)#2-Al(1)-O(2)#6 | 92.06(14) 164.23(15) 91.45(13) 91.45(13) 92.10(13) 164.25(14) 75.91(12) 164.25(14) | O(1)#4-Al(1)-Al(1)#1 O(2)#5-Al(1)-Al(1)#1 O(2)-Al(1)-Al(1)#1 O(2)#6-Al(1)-Al(1)#1 P(1)-O(2)-Al(1)#1 P(1)-O(2)-Al(1) Al(1)#1-O(2)-Al(1) P(1)-O(1)-Al(1)#3 | 119.01(10 45.25(8) 45.25(8) 45.25(8) 132，17(11 132.17(11 89.50(16) 144.43(19 |
Form the symmetry operation of atom of equal value:
#1x，y，-z+1/2#2x-y+1，x，-z#3-x+2，-y+1，-z#4y+1，-x+y+1，-z#5-x+y+2，-x+2，z#6-y+2，x-y，z
Example 2 mixes 2.48 gram pseudo-boehmites with 10 ml waters in one 100 milliliters beaker, restrain phosphorous acid at 50 ml beakers with 20 ml waters dissolving 2.75 then, add 2.76 milliliters of Tri N-Propyl Amines, mix, under room temperature, stirred 2 hours, form uniform mixture (gel), change over to then and have in the teflon-lined stainless steel cauldron, at 28 days crystallization products of 160 ℃ of crystallization,, filter through as washing in the example 1, the exsiccant method gets target product.Every sign and result are identical with example 1.
Example 3 mixes 2.48 gram pseudo-boehmites with 10 ml waters in one 100 milliliters beaker, restrain phosphorous acid at 50 ml beakers with 20 ml waters dissolving 2.75 then, add 2.76 milliliters of Di-n-Butyl Amines, mix, under room temperature, stirred 2 hours, form uniform mixture (gel), change over to then and have in the teflon-lined stainless steel cauldron, at 16 days crystallization products of 185 ℃ of crystallization,, filter through as washing in the example 1, the exsiccant method gets target product.Every sign and result are identical with example 1.
Example 4 mixes 2.48 gram aluminium hydroxides with 10 ml waters in one 100 milliliters beaker, restrain phosphorous acid at 50 ml beakers with 20 ml waters dissolving 2.75 then, add 3,5 gram citric acids, mix, under room temperature, stirred 2 hours, form uniform mixture (gel), change over to then and have in the teflon-lined stainless steel cauldron, at 16 days crystallization products of 185 ℃ of crystallization, process is as washing in the example 1, filter, the exsiccant method gets target product.Every sign and result are identical with example 1.
Example 5 mixes 1.25 gram pseudo-boehmites with 10 ml waters in one 100 milliliters beaker, restrain phosphorous acid at 50 ml beakers with 20 ml waters dissolving 1.40 then, add 2.30 milliliters of triethylamines, mix, under room temperature, stirred 2 hours, form uniform mixture (gel), change over to then and have in the teflon-lined stainless steel cauldron, at 8 days crystallization products of 195 ℃ of crystallization,, filter through as washing in the example 1, the exsiccant method gets target product.Every sign and result are identical with example 1.
Example 6, in one 100 milliliters beaker, mix 1.25 gram pseudo-boehmites, restrain phosphorous acid at 50 ml beakers with 20 ml waters dissolving 2.15 then, mix with 10 ml waters, under room temperature, stirred 2 hours, form uniform mixture (gel), change over to then and have in the teflon-lined stainless steel cauldron, at 4 days crystallization products of 180 ℃ of crystallization, process is as washing in the example 1, filter, the exsiccant method gets target product.Every sign and result are identical with example 1.
Example 7 mixes 1.25 gram pseudo-boehmites with 10 milliliters of Liquid Macrogols in one 100 milliliters beaker, mix 2.1 gram phosphorous acid at 50 ml beakers with 20 milliliters of Liquid Macrogols then, add 6.59 milliliters of triethylamines, mix, under room temperature, stirred 2 hours, form uniform mixture, change over to then and have in the teflon-lined stainless steel cauldron, at 11 days crystallization products of 185 ℃ of crystallization,, filter through as washing in the example 1, the exsiccant method gets target product.Every sign and result are identical with example 1.
Example 7 mixes 1.25 gram pseudo-boehmites with 10 milliliters of Liquid Macrogols in one 100 milliliters beaker, mix 1.3 gram phosphorous acid at 50 ml beakers with 20 milliliters of Liquid Macrogols then, add 6.59 milliliters of triethylamines, mix, under room temperature, stirred 2 hours, form uniform mixture, change over to then and have in the teflon-lined stainless steel cauldron, at 11 days crystallization products of 195 ℃ of crystallization,, filter through as washing in the example 1, the exsiccant method gets target product.Every sign and result are identical with example 1.
Example 8 mixes 2.5 gram pseudo-boehmites with 10 milliliters of Liquid Macrogols in one 100 milliliters beaker, mix 4.2 gram phosphorous acid at 50 ml beakers with 20 milliliters of Liquid Macrogols then, add 6.59 milliliters of triethylamines, mix, under room temperature, stirred 2 hours, form uniform mixture, change over to then and have in the teflon-lined stainless steel cauldron, at 11 days crystallization products of 175 ℃ of crystallization,, filter through as washing in the example 1, the exsiccant method gets target product.Every sign and result are identical with example 1.
Example 9 mixes 3.25 gram aluminum isopropylates with 10 milliliters of Macrogol 200s in one 100 milliliters beaker, mix 2.1 gram phosphorous acid at 50 ml beakers with 20 milliliters of Macrogol 200s then, add 3.35 milliliters of triethylamines, mix, under room temperature, stirred 2 hours, form uniform mixture, change over to then and have in the teflon-lined stainless steel cauldron, at 11 days crystallization products of 175 ℃ of crystallization,, filter through as washing in the example 1, the exsiccant method gets target product.Every sign and result are identical with example 1.
Claims (8)
1. a ring large micropore aluminum phosphite molecular sieve is characterized in that its chemical formula is: H
6Al
4O
18P
6, its x ray powder diffraction has following characteristic diffraction peak:
2θ(°) 12.96 17.99 22.55 25.08 25.86 26.15 28.33 29.05 34.00
I/I
0 100.0 1 23.1 3 100 9 2 35 21
2θ(°) 34.80 36.53 37.11 39.66 41.71 44.67 46.72 47.51 48.10
I/I
0 15 6 6 9 6 5 4 1 3
Described 12 ring large micropore aluminum phosphite molecular sieves belong to hexagonal system, and spacer is P6
3/ m; Unit cell parameters is a=b=7.8762 , c=7.1237 , α=β=90 °, γ=120 °; This crystalline structural unit has polyphyll trifolium shape, interconnects along [ab] plane between this structural unit, forms the one-piece construction of aluminum phosphite molecular sieve NKX-2, wherein includes axial 12 membered ring channels of c; The aluminium atom links up with two-layer adjacent aluminium atom up and down respectively by two kinds of different modes: a kind of mode be the aluminium atom that is positioned at certain one deck with the aluminium atom of its top between link to each other with three Al-O-Al, formed three Al
2O
2The little cage of window; This aluminium atom links to each other with three Al-O-P-O-Al with another aluminium atom of its below, forms and contains 4 of three tetra-atomic ring windows
3Cage, tetra-atomic ring is made up of 2 Al atoms and 2 phosphorus atom, does not comprise Sauerstoffatom.
2. the preparation method of described 12 ring large micropore aluminum phosphite molecular sieves of claim 1 is characterized in that it comprises the steps: aluminium source, phosphorus source, organic formwork agent or does not add organic template, mixes with water or non-aqueous solvent; Under room temperature, stirred 1-4 hour, then with this mixture hydrothermal crystallizing or solvent thermal crystallization 5-30 days under 100-200 ℃ of autogenous pressure; The water washing of crystal process, suction filtration, dry under 80 ℃, get target product; Described aluminium source is 0.5-1.5 with the ratio in phosphorus source, and the mol ratio in organic formwork agent and phosphorus source is 0.3-2.5, and the mol ratio in water and phosphorus source is 20-100.
3. according to the preparation method of described 12 ring large micropore aluminum phosphite molecular sieves of claim 2, it is characterized in that described aluminium source is the solubility salt of pseudo-boehmite, aluminium hydroxide, aluminum isopropylate, sodium metaaluminate or aluminium.
4. according to the preparation method of described 12 ring large micropore aluminum phosphite molecular sieves of claim 2, it is characterized in that described phosphorus source is phosphorous acid solid or the phosphorous compound of solubility.
5. according to the preparation method of described 12 ring large micropore aluminum phosphite molecular sieves of claim 2, it is characterized in that described organic formwork agent is di-n-propylamine, triethylamine, Tri N-Propyl Amine, n-Butyl Amine 99 or citric acid.
6. according to the preparation method of described 12 ring large micropore aluminum phosphite molecular sieves of claim 2, it is characterized in that described non-aqueous solvent is Macrogol 200 or Liquid Macrogol.
7. according to the preparation method of described 12 ring large micropore aluminum phosphite molecular sieves of claim 2, it is characterized in that described hydrothermal crystallizing is a hydrothermal crystallizing under 130-200 ℃ of autogenous pressure.
8. according to the preparation method of described 12 ring large micropore aluminum phosphite molecular sieves of claim 2, it is characterized in that described solvent thermal crystallization is a crystallization under 160-200 ℃ of autogenous pressure.
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| CN100429143C (en) * | 2006-06-20 | 2008-10-29 | 南开大学 | Aluminum phosphite molecular sieve for cage type structure unit and preparing method |
| CN101804973B (en) * | 2010-03-15 | 2012-10-03 | 南开大学 | Aluminium phosphite microporous crystal material with organic-inorganic hybrid rings and synthetic method thereof |
| CN102476806A (en) * | 2010-11-30 | 2012-05-30 | 中国科学院大连化学物理研究所 | Method of synthesizing super large micropore aluminium phosphate molecular sieve in eutectic mixture |
| CN103204484B (en) * | 2013-04-09 | 2014-12-17 | 南开大学 | Micropore aluminum orthophosphate with 10-membered ring and 8-membered ring cross pore paths and preparation method thereof |
| CN107082409B (en) * | 2017-04-28 | 2018-09-18 | 南开大学 | A kind of micropore aluminium phosphite [Al2(HPO3)3(H2O)3]·H2The preparation method of O |
| CN109019630A (en) * | 2018-10-15 | 2018-12-18 | 辽宁工程技术大学 | A kind of EDI type molecular sieve and its synthetic method |
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| CN1546376A (en) * | 2003-12-09 | 2004-11-17 | 中国石油化工股份有限公司 | 24-membered ring macroporous zinc aluminum phosphite molecular sieve and preparation method thereof |
| CN1659102A (en) * | 2002-06-12 | 2005-08-24 | 埃克森美孚化学专利公司 | Synthesis of aluminophosphates and silicoaluminophosphates |
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| CN1546376A (en) * | 2003-12-09 | 2004-11-17 | 中国石油化工股份有限公司 | 24-membered ring macroporous zinc aluminum phosphite molecular sieve and preparation method thereof |
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