CN1290766C - Mesoporous aluminium silicophosphate molecular sieve and its prepn - Google Patents
Mesoporous aluminium silicophosphate molecular sieve and its prepn Download PDFInfo
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Abstract
The present invention relates to a mesoporous silicon aluminum phosphate molecular sieve QMPL-1 containing hetero atoms, which is prepared by hydrothermal synthesis at low temperature by using cetyl trimethyl ammonium chloride (CTMAC) as a main template agent. The prepared molecular sieve contains metallic elements with different functions and has a large specific surface area and uniform pore diameters, so that the molecular sieve can provide abundant active centers for reaction. The molecular sieve is an active composition with unique properties for catalysts and is also a favorable carrier used in the field of adsorptive separation.
Description
The present invention relates to a kind of mesopore molecular sieve QMPL-1 (Q represents metallic element) and synthetic method thereof.
The porous inorganic materials has been widely used in catalysis and fractionation by adsorption field.This mainly is because this class material has abundant microporous structure and bigger specific surface area, and a large amount of acid site and adsorption activity positions can be provided.This class material is broadly divided into the pillared material of unformed, crystalline molecular sieve and modification from microtexture.
Amorphous material is an industrial use important catalyst carrier for many years, and most typical is exactly amorphous silicon aluminium, and it is the important carrier of reforming catalyst in a kind of an acidic catalyst and the petrochemical complex.Here the unformed long-range of saying that is meant is unordered, and short distance generally is orderly.Characterizing the most frequently used method of this class material is X-ray powder diffraction.Porous material scope and theory have been enriched in the appearance of molecular sieve greatly, have more brought a revolution to petroleum industry.Particularly zeolite molecular sieve is in industrial application and bring surprising economic benefit, people deepened continuously and perfect to this class novel material research.Zeolite molecular sieve has uniqueness, regular crystalline structure, and wherein each class all has the pore structure of certain size, shape, and all has micropore to link to each other between duct and the duct, constitutes " the huge molecule " in porous road.Because the molecule that such pore passage structure only allows to have certain size passes through, so be called " molecular sieve ", its this character is widely used.No matter this molecular sieve analog is synthetic or natural, and its structure all can be thought by SiO
4And AlO
4Connect the three-dimensional framework structure that constitutes by oxo bridge, prepared a variety of zeolite molecular sieves at present, as A type (U.S.Pat.No.2,882,243); X type zeolite (U.S.Pat.No.2,882,244); Y-type zeolite (U.S.Pat.No.3,130,007); ZSM-5 (U.S.Pat.No.3,702,886) etc., and large quantities of novel non-zeolite molecular sieves, as SAPO series molecular sieve (U.S.Pat.No.4,440,871) etc., SAPO-11 molecular sieve particularly because it has unique activity to the isomerization of long chain alkane, is a kind of ideal composition of isomerization dewaxing catalyst.United States Patent (USP) 4,713,227,4,500,651,4,567,029,4,619,818 have reported the synthetic and application in catalyzed reaction of the molecular sieve MSAPO-n of a series of containing metal elements, but because institute's synthetic molecular sieve is a microvoid structure, the reactant molecule (as heavy oil and residual oil) with big kinetic diameter can not enter in its duct, so its range of application is restricted.
Though people are quite ripe to molecular sieve research, all below 1.0nm, the maximum diameter of hole of bibliographical information is 1.3nm (Davis M E only in the molecular sieve overwhelming majority's who has prepared aperture, SaldarriagaC, et al.Nature, 1991,352:320), still belong to range of micropores.And, be badly in need of developing a series of have ultra-large aperture and the good novel materials of specific surface area, stable in properties, absorption and catalytic performance along with the strictness day by day of development of modern industry and environmental regulation and the appearance of worldwide crude oil poor qualityization and heaviness trend.
United States Patent (USP) 5,057,296 have announced the method for synthetic a kind of big-pore mesoporous molecular sieve M41S, because this molecular sieve analog has the pore distribution of higher surface area and homogeneous, and have adjustable aperture and acidity, its active centre is accessible less diffusional resistance again, can be macromole, especially the heavy oil organic molecule is selected type reaction and is provided between empty profit and effective acid active centre in the petrochemical process, gives the chemical industry worker with great inspiration.But because this molecular sieve analog of preparation generally all is to use the organic formwork agent cetyl trimethylammonium bromide (CTMAB) that costs an arm and a leg, and the thermostability of the molecular sieve that obtains particularly hydrothermal stability is poor, lattice can only keep several hrs even shorter in boiling water, be difficult to have actual using value.Though people give great concern to this molecular sieve, and carried out intensive research, United States Patent (USP) 5,334,368,5,308,602 have also reported mesopore molecular sieve Al-MCM-41, the V-MCM-41 of some containing metal elements, synthetic method and the application of Ga-MCM-41, Ti-HMS, but still do not solve the hydrothermal stability problem of this molecular sieve analog.
The purpose of this invention is to provide a kind of novel QMPL-1 molecular sieve, this molecular sieve has bigger aperture and specific surface area, higher thermostability and hydrothermal stability, and contain various metallic elements to improve it such as performances such as hydrogenation-dehydrogenation, oxidation-reduction and adsorption-desorptions, the object of the invention also is to provide a kind of preparation method of above-mentioned molecular sieve simultaneously.
The anhydrous structural formula of molecular sieve QMPL-1 provided by the present invention can be used m " R " (Q
wSi
xAl
yP
z) O
2Expression, wherein " R " is the organic formwork agent in the microporous molecular sieve, and " Q " is the metallic element in the periodic table of elements, and " w ", " x ", " y ", " z " are respectively the molar fraction of Q, Si, Al, P, and " m " is every mole of (Q
wSi
xAl
yP
z) O
2In the mole number of " R ", the value of " m " is 0～0.5; " w+x ", " y ", " z " generally are limited in the accompanying drawing 1 on the ternary phase diagrams the determined pentagon of F, G, H, J and I point and form in the district, preferably define in accompanying drawing 2 on the ternary phase diagrams the determined tetragon of f, g, h and j point and form in the district.F, G, H, J and I point have following " w+x ", " y " and " z " value in the accompanying drawing 1:
| Molar fraction | |||
| Point F G H I J | w+x 0.02 0.02 0.40 0.98 0.40 | y 0.60 0.38 0.42 0.01 0.18 | z 0.38 0.60 0.18 0.01 0.42 |
F, g, j and h point have following " w+x ", " y " and " z " value in the accompanying drawing 2:
| Molar fraction | |||
| Point f g h j | w+x 0.02 0.02 0.50 0.50 | y 0.52 0.46 0.23 0.27 | z 0.46 0.52 0.27 0.23 |
In the expression formula that above-mentioned reaction is formed, reactant has carried out normalizing, i.e. w+x+y+z=1 according to the sum of " w+x ", " y " and " z ".
Mesoporous molecular sieve QMPL-1 provided by the invention has following characteristics:
1. synthesis of molecular sieve contains various metallic elements, as II in the periodic table of elements
A, VI
BWith VIII family element, particularly Ni, Co, Cr, Ca, Cu, Zn, Mg and/or Fe.
2. the result that records of synthesis of molecular sieve X powder ray diffraction method has mesoporous feature (former powder has at least one diffraction peak at low angle; At least two diffraction peaks are arranged) after the roasting.
3. have higher thermostability and hydrothermal stability, 10 hours lattices of 600 ℃ of roastings keep, and boiling 20 hours degree of crystallinity in the boiling water does not have considerable change.
4. the aperture of synthesis of molecular sieve is: 1.3～10nm is preferably: 2～8nm is preferably: 2.5～6nm.
5. the specific surface area of synthesis of molecular sieve is: 300～1000m
2/ g is preferably: 400～800m
2/ g is preferably: 450～700m
2/ g.
6. the pore volume of synthesis of molecular sieve is: 0.2～1.0ml/g is preferably: 0.3～0.8ml/g is preferably: 0.4～0.6ml/g.
The building-up process of QMPL-1 molecular sieve of the present invention can be expressed as:
(a) template, source metal, silicon source, aluminium source, phosphoric acid and the water with calculated amount mixes in certain sequence, stirs and obtain gel;
(b) gel that (a) made carries out crystallization, and solid in the filtration product obtains molecular screen primary powder through washing, drying;
(c) molecular screen primary powder that roasting (b) makes removes template and obtains molecular sieve.
Wherein the mole proportioning of each material is in the step (a):
0.2～6R: Al
2O
3: 0.7～1.5P
2O
5: 0.01～6.0SiO
2: 0.01～6.0Q: 50～1000H
2O is preferably: 0.4～4R: Al
2O
3: 0.8～1.3P
2O
5: 0.1～4.0SiO
2: 0.1～4.0Q: 100～600H
2O is preferably: 0.5～3R: Al
2O
3: 0.9～1.2P
2O
5: 0.1～2.0SiO
2: 0.1～2.0Q: 150～500H
2O " R " here is a template, and Q is in the respective metal oxide compound.
Preparation MPL-1 molecular sieve is characterised in that template is main organic compounds containing nitrogen group with low-cost palmityl trimethyl ammonium chloride (CTMAC).Other organic compounds containing nitrogens are chain alkyl (C
4～C
18) in amine, cetyl trimethylammonium bromide (CTMAB), Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, cycloalkanes amine or the pyridine one or more, and palmityl trimethyl ammonium chloride (CTMAC) weight in template should be not less than 50%.Crystallization prepares the novel QMPL-1 molecular sieve of a class under the low-temperature hydrothermal condition, and this molecular sieve has bigger aperture and specific surface area, and higher thermostability and hydrothermal stability contain the metallic element with difference in functionality,
Has different purposes.
General compound commonly used is all adopted in the phosphorus source of raw material, silicon source and aluminium source, and source metal adopts the soluble salt of respective metal.
Said crystallization is to adopt hydrothermal reaction at low temperature in the step (b), and crystallization temperature is 50～240 ℃, is preferably 70～200 ℃, is preferably 100～160 ℃; Crystallization time is 10～300 hours, is preferably 15～200 hours, is preferably 20～100 hours.
Said maturing temperature is 400～800 ℃ in the step (c), is preferably 450～700 ℃, is preferably 500～650 ℃; Roasting time is 2～24 hours, is preferably 3～12 hours, is preferably 4～8 hours.
The heteroatom mesopore molecular sieve that contains with larger aperture and specific surface area of the present invention's preparation, can directly be used as the carrier of catalyzer or specific function, can provide a large amount of reaction active site and reaction compartments for reaction, and reduce the diffusional resistance of reactant and product, improve reactive activity and selectivity.Be a kind of catalytic active component and carrier novel material of excellent property, have wide prospect in industrial application and huge potential using value.
Give further instruction below by embodiment to technology of the present invention.
The preparation of embodiment 1 NiMPL-1 molecular sieve
The ortho-phosphoric acid of getting 46 grams 85% mixes with 500 gram deionized waters, adds the pseudo-boehmite and the 18 gram Ni (NO of 28 grams moisture 28% then
3)
2, after 45 ℃ of heating in water bath are stirred to evenly, add 34 gram tetraethoxys successively, 32 gram palmityl trimethyl ammonium chlorides (CTMAC), the Tetramethylammonium hydroxide of 150 grams 10% and 500 gram deionized waters also fully stir and obtain gel, and it consists of:
1.3R∶1.0Al
2O
3∶1.0P
2O
5∶0.8SiO
2∶0.5NiO∶270H
2O。
Above-mentioned gel is enclosed in the autoclave of inner liner polytetrafluoroethylene, be warmed up to 120 ℃ with 25 ℃/minute, thermostatic crystallization 144 hours, filtration product gained solid is through washing, 110 ℃ of dryings are carried out X-ray powder diffraction mensuration after 4 hours, obtain the characteristic diffraction peak (d of central hole structure
100, d
110, d
200, d
210).This result shows that the gained synthetic product is a mesoporous molecular sieve, anhydrous basic composition is: 0.2R (Ni
0.09Si
0.13Al
0.42P
0.36) O
2X-ray diffraction measure to adopt D/MAX-RA type x-ray diffractometer of science, and source of radiation is the copper target, the filtering of graphite monocrystalline, operation tube voltage 35KV, tube current 30～50mA, sweep velocity (2 θ) be 1 degree/minute, sweep limit is 1～10 degree.The specific surface area of gained molecular sieve is 467m
2/ g, pore volume are 0.25ml/g, and mean pore size is 2.7nm.Used instrument is absorption and the desorption isotherm that ASAP2400 adsorbs working sample under the instrument liquid nitrogen temperature automatically, the specific surface area and the pore structure of BET method calculation sample.
The preparation of embodiment 2 CoMPL-1 molecular sieves
The ortho-phosphoric acid of getting 46 grams 85% mixes with 480 gram deionized waters, adds 64 gram aluminum isopropylates and 36 gram Co (NO then
3)
2, after heating in water bath 45 is stirred to evenly, add 17 gram tetraethoxys successively, 14 gram palmityl trimethyl ammonium chlorides (CTMAC), the Tetramethylammonium hydroxide of 100 grams 10% and 500 restrains deionized waters and fully stirs and obtains gel, and it consists of:
1.0R∶1.0Al
2O
3∶1.3P
2O
5∶0.4SiO
2∶1.3CoO∶130H
2O。
Above-mentioned gel is enclosed in the autoclave of inner liner polytetrafluoroethylene, be warmed up to 140 ℃ with 25 ℃/minute, thermostatic crystallization 108 hours, filtration product gained solid is through washing, 110 ℃ of dryings are carried out X-ray powder diffraction measurement result and are shown that the gained synthetic product is a mesoporous molecular sieve after 4 hours, its composition and character see Table 1.
The preparation of embodiment 3 CrMPL-1 molecular sieves
The ortho-phosphoric acid of getting 46 grams 85% mixes with 600 gram deionized waters, adds 82 gram aluminum isopropylates and 3.5 gram Cr (NO then
3)
2, after 45 ℃ of heating in water bath are stirred to evenly, add 68 gram tetraethoxys successively, 64 gram palmityl trimethyl ammonium chlorides (CTMAC), the TBAH of 130 grams 10% and 450 gram deionized waters also fully stir and obtain gel, and it consists of:
2.0R∶1.0Al
2O
3∶1.0P
2O
5∶1.0SiO
2∶0.1CrO∶350H
2O。
Above-mentioned gel is enclosed in the autoclave of inner liner polytetrafluoroethylene, be warmed up to 140 ℃ with 25 ℃/minute, thermostatic crystallization 96 hours, filtration product gained solid is through washing, 110 ℃ of dryings are carried out X-ray powder diffraction measurement result and are shown that the gained synthetic product is a mesoporous molecular sieve after 4 hours, its composition and character see Table 1.
The preparation of embodiment 4 CaMPL-1 molecular sieves
The ortho-phosphoric acid of getting 46 grams 85% mixes with 600 gram deionized waters, adds the pseudo-boehmite and the 65 gram Ca (NO of 28 grams moisture 28% then
3)
2, after 60 ℃ of heating in water bath are stirred to evenly, add 102 gram tetraethoxys successively, 128 gram palmityl trimethyl ammonium chlorides (CTMAC), the TPAOH of 180 grams 10% and 1000 gram deionized waters fully stir and obtain gel, and it consists of:
3.0R∶1.0Al
2O
3∶1.1P
2O
5∶2.5SiO
2∶2.0CaO∶800H
2O。
Above-mentioned gel is enclosed in the autoclave of inner liner polytetrafluoroethylene, be warmed up to 160 ℃ with 25 ℃/minute, thermostatic crystallization 60 hours, filtration product gained solid is through washing, 110 ℃ of dryings are carried out the X-ray powder diffraction and are measured after 4 hours, the result shows that the gained synthetic product is a mesoporous molecular sieve, and its composition and character see Table 1.
The preparation of embodiment 5 CuMPL-1 molecular sieves
The ortho-phosphoric acid of getting 35 grams 85% mixes with 400 gram deionized waters, adds 64 gram aluminum isopropylates and 27 gram CuCl then
2, after 45 ℃ of heating in water bath are stirred to evenly, add 34 gram tetraethoxys successively, 18 gram palmityl trimethyl ammonium chlorides (CTMAC), 15 gram cetyl trimethylammonium bromides (CTMAB) and 450 gram deionized waters also fully stir and obtain gel, and it consists of:
0.7R∶1.0Al
2O
3∶1.0P
2O
5∶1.0SiO
2∶1.0CuO∶315H
2O。
Above-mentioned gel is enclosed in the autoclave of inner liner polytetrafluoroethylene, be warmed up to 180 ℃ with 25 ℃/minute, thermostatic crystallization 24 hours, filtration product gained solid is through washing, 110 ℃ of dryings are carried out X-ray powder diffraction measurement result and are shown that the gained synthetic product is a mesoporous molecular sieve after 4 hours, its composition and character see Table 1.
The preparation of embodiment 6 ZnMPL-1 molecular sieves
The ortho-phosphoric acid of getting 46 grams 85% mixes with 480 gram deionized waters, adds 64 gram aluminum isopropylates and 38 gram Zn (NO then
3)
2, after heating in water bath 45 is stirred to evenly, add 17 gram tetraethoxys successively, 14 gram palmityl trimethyl ammonium chlorides (CTMAC), the Tetramethylammonium hydroxide of 100 grams 10% and 500 restrains deionized waters and fully stirs and obtains gel, and it consists of:
1.0R∶1.0Al
2O
3∶1.3P
2O
5∶0.4SiO
2∶1.3ZnO∶130H
2O。
Above-mentioned gel is enclosed in the autoclave of inner liner polytetrafluoroethylene, be warmed up to 140 ℃ with 25 ℃/minute, thermostatic crystallization 108 hours, filtration product gained solid is through washing, 110 ℃ of dryings are carried out X-ray powder diffraction measurement result and are shown that the gained synthetic product is a mesoporous molecular sieve after 4 hours, its composition and character see Table 1.
The preparation of embodiment 7 MgMPL-1 molecular sieves
The ortho-phosphoric acid of getting 46 grams 85% mixes with 600 gram deionized waters, adds 82 gram aluminum isopropylates and 3.0 gram Mg (NO then
3)
2, after 45 ℃ of heating in water bath are stirred to evenly, add 68 gram tetraethoxys successively, 64 gram palmityl trimethyl ammonium chlorides (CTMAC), the TBAH of 130 grams 10% and 450 gram deionized waters also fully stir and obtain gel, and it consists of:
2.0R∶1.0Al
2O
3∶1.0P
2O
5∶1.0SiO
2∶0.1MgO∶350H
2O。
Above-mentioned gel is enclosed in the autoclave of inner liner polytetrafluoroethylene, be warmed up to 140 ℃ with 25 ℃/minute, thermostatic crystallization 96 hours, filtration product gained solid is through washing, 110 ℃ of dryings are carried out X-ray powder diffraction measurement result and are shown that the gained synthetic product is a mesoporous molecular sieve after 4 hours, its composition and character see Table 1.
The preparation of embodiment 8 FeMPL-1 molecular sieves
The ortho-phosphoric acid of getting 46 grams 85% mixes with 600 gram deionized waters, adds the pseudo-boehmite and the 60 gram FeSO of 28 grams moisture 28% then
4, after 60 ℃ of heating in water bath are stirred to evenly, add 102 gram tetraethoxys successively, 128 gram palmityl trimethyl ammonium chlorides (CTMAC), the TPAOH of 180 grams 10% and 1000 gram deionized waters fully stir and obtain gel, and it consists of:
3.0R∶1.0Al
2O
3∶1.1P
2O
5∶2.5SiO
2∶2.0FeO∶800H
2O。
Above-mentioned gel is enclosed in the autoclave of inner liner polytetrafluoroethylene, be warmed up to 160 ℃ with 25 ℃/minute, thermostatic crystallization 60 hours, filtration product gained solid is through washing, 110 ℃ of dryings are carried out the X-ray powder diffraction and are measured after 4 hours, the result shows that the gained synthetic product is a mesoporous molecular sieve, and its composition and character see Table 1.
The preparation of embodiment 9 Ni-MgMPL-1 molecular sieves
The ortho-phosphoric acid of getting 46 grams 85% mixes with 600 gram deionized waters, adds 82 gram aluminum isopropylates, 9 gram Ni (NO then
3)
2With 3.0 gram Mg (NO
3)
2, after 45 ℃ of heating in water bath are stirred to evenly, add 68 gram tetraethoxys successively, 64 gram palmityl trimethyl ammonium chlorides (CTMAC), the TBAH of 130 grams 10% and 450 gram deionized waters also fully stir and obtain gel, and it consists of:
2.0R∶1.0Al
2O
3∶1.0P
2O
5∶1.0SiO
2∶0.5NiO∶0.1MgO∶350H
2O。
Above-mentioned gel is enclosed in the autoclave of inner liner polytetrafluoroethylene, be warmed up to 165 ℃ with 25 ℃/minute, thermostatic crystallization 60 hours, filtration product gained solid is through washing, 110 ℃ of dryings are carried out X-ray powder diffraction measurement result and are shown that the gained synthetic product is a mesoporous molecular sieve after 4 hours, its composition and character see Table 1.
Get respectively embodiment preparation contain different element molecular sieves a little, put into boiling water and boiled 20 hours, found that its degree of crystallinity does not obviously reduce.In addition, these molecular sieves were 600 ℃ of roastings 10 hours, and degree of crystallinity does not have considerable change, illustrated that this molecular sieve analog has higher thermostability and hydrothermal stability.
The composition of each molecular sieve of table 1 and character
| Numbering | Specific surface area m 2/g | Pore volume ml/g | Mean pore size nm | Form |
| Example 1 example 2 examples 3 examples 4 examples 5 examples 6 examples 7 examples 8 examples 9 | 467 488 514 542 388 435 436 444 452 | 0.25 0.32 0.35 0.33 0.27 0.36 0.37 0.32 0.34 | 2.7 3.6 3.6 3.2 2.8 3.9 3.8 2.8 3.3 | 0.2R·(Ni 0.09·Si 0.13·Al 0.42·P 0.36)O 2 0.15R·(Co 0.2·Si 0.07·Al 0.38·P 0.35)O 2 0.3R·(Cr 0.02·Si 0.20·Al 0.44·P 0.34)O 2 0.4R·(Ca 0.20·Si 0.24·Al 0.31·P 0.25)O 0.1R·(Cu 0.16·Si 0.16·Al 0.41·P 0.27)O 2 0.15R·(Zn 0.20·Si 0.07·Al 0.41·P 0.32)O 2 0.3R·(Mg 0.02·Si 0.23·Al 0.41·P 0.34)O 2 0.4R·(Fe 0.21·Si 0.23·Al 0.31·P 0.25)O 2 0.3R·(Mg 0.02·Ni 0.08·Si 019·Al 0.39·P 0.32)O 2 |
Annotate: saidly consist of anhydrous essentially consist.
Claims (15)
1. mesopore molecular sieve, the anhydrous structural formula that it is characterized in that this molecular sieve is m " R " (Q
wSi
xAl
yP
z) O
2, wherein " R " is the organic formwork agent in the microporous molecular sieve, " Q " is II in the periodic table of elements
A, VI
BWith in the VIII family metallic element one or more; " w ", " x ", " y ", " z " are respectively the molar fraction of Q, Si, Al, P, and " m " is every mole of (Q
wSi
xAl
yP
z) O
2In the mole number of " R ", the value of " m " is 0～0.5, (w+x)+y+z=1, w is not 0; The aperture of said molecular sieve is: 2～10nm; Specific surface area is: 300～1000m
2/ g; Pore volume is: 0.2～1.0ml/g;
Said " w+x ", " y ", " z " form in the district at the determined pentagon of F, G, H, J and I point on the ternary phase diagrams, and wherein F, G, H, J and I point have following " w+x ", " y " and " z " value:
The point Molar fraction
w+x y z
F G H I J 0.02 0.02 0.40 0.98 0.40 0.60 0.38 0.42 0.01 0.18 0.38 0.60 0.18 0.01 0.42
2. according to the described molecular sieve of claim 1, it is characterized in that said " w+x ", " y ", " z " form in the district at the determined tetragon of f, g, h and j point on the ternary phase diagrams, wherein f, g, j and h point have following " w+x ", " y " and " z " value:
The point Molar fraction
w+x y z
f g h j 0.02 0.02 0.50 0.50 0.52 0.46 0.23 0.27 0.46 0.52 0.27 0.23
3. according to the described molecular sieve of claim 1, it is characterized in that said molecular sieve keeps at 10 hours lattices of 600 ℃ of roastings, it is constant to boil 20 hours degree of crystallinity in the boiling water.
4. according to the described molecular sieve of claim 1, it is characterized in that the aperture of said molecular sieve is: 2～8nm; Specific surface area is: 400～800m
2/ g; Pore volume is: 0.3～0.8ml/g.
5. according to the described molecular sieve of claim 1, it is characterized in that the aperture of said molecular sieve is: 2.5～6nm; Specific surface area is: 450～700m
2/ g; Pore volume is: 0.4～0.6ml/g.
6. the synthetic method of the described molecular sieve of claim 1 may further comprise the steps:
(a) template, source metal, silicon source, aluminium source, phosphoric acid and water mixing, stirring are obtained gel;
(b) gel that (a) made carries out crystallization, and solid in the filtration product obtains molecular screen primary powder through washing, drying, and wherein said crystallization is the low-temperature hydrothermal crystallization, and crystallization temperature is 50～240 ℃, and crystallization time is 10～300 hours;
(c) molecular screen primary powder that roasting (b) makes removes template and obtains molecular sieve;
Wherein the mole proportioning of each material is in the step (a):
0.2～6R: Al
2O
3: 0.7～1.5P
2O
5: 0.01～6.0SiO
2: 0.01～6.0Q: 50～1000H
2O, wherein " R " is template, Q is in the respective metal oxide compound; Described template is that palmityl trimethyl ammonium chloride is main organic compounds containing nitrogen group, and palmityl trimethyl ammonium chloride weight should be more than or equal to 50% in template.
7. according to the described synthetic method of claim 6, it is characterized in that the mole proportioning of each material in the step (a) is: 0.4～4R: Al
2O
3: 0.8～1.3P
2O
5: 0.1～4.0SiO
2: 0.1～4.0Q: 100～600H
2O.
8. according to the described synthetic method of claim 6, it is characterized in that the mole proportioning of each material in the step (a) is: 0.5～3.0R: Al
2O
3: 0.9～1.2P
2O
5: 0.1～2.0SiO
2: 0.1～2.0Q: 150～500H
2O.
9. according to the described synthetic method of claim 6, it is characterized in that described metallic element Q is Ni, Co, Cr, Ca, Cu, Zn, Mg and/or Fe.
10. according to the described synthetic method of claim 6, it is characterized in that containing C in the said organic compounds containing nitrogen group
4～C
18In chain alkyl amine, cetyl trimethylammonium bromide, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, cycloalkanes amine or the pyridine one or more.
11. according to the described synthetic method of claim 6, it is characterized in that said crystallization is the low-temperature hydrothermal crystallization in the step (b), crystallization temperature is 70～200 ℃; Crystallization time is 15～200 hours.
12. according to the described synthetic method of claim 6, it is characterized in that said crystallization is the low-temperature hydrothermal crystallization in the step (b), crystallization temperature is 100～160 ℃; Crystallization time is 20～100 hours.
13., it is characterized in that said maturing temperature is 400～800 ℃ in the step (c) according to the described synthetic method of claim 6; Roasting time is 2～24 hours.
14., it is characterized in that said maturing temperature is 450～700 ℃ in the step (c) according to the described synthetic method of claim 6; Roasting time is 3～12 hours.
15., it is characterized in that said maturing temperature is 500～650 ℃ in the step (c) according to the described synthetic method of claim 6; Roasting time is 4～8 hours.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01106007 CN1290766C (en) | 2001-01-05 | 2001-01-05 | Mesoporous aluminium silicophosphate molecular sieve and its prepn |
| CA002359825A CA2359825C (en) | 2000-10-26 | 2001-10-24 | A mesoporous aluminum based molecular sieve and a process for the preparation of the same |
| US09/983,628 US6797248B2 (en) | 2000-10-26 | 2001-10-25 | Mesoporous molecular sieve and a process for the preparation of the same |
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| CN 01106007 CN1290766C (en) | 2001-01-05 | 2001-01-05 | Mesoporous aluminium silicophosphate molecular sieve and its prepn |
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| CN1362365A CN1362365A (en) | 2002-08-07 |
| CN1290766C true CN1290766C (en) | 2006-12-20 |
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| CN101121533B (en) * | 2006-08-08 | 2010-05-19 | 中国科学院大连化学物理研究所 | SAPO-34 molecular sieve with micropore and mesopore structure and synthetic method thereof |
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