CN1111135C - Mesoporous aluminium silicophosphate molecular sieve and its preparing process - Google Patents
Mesoporous aluminium silicophosphate molecular sieve and its preparing process Download PDFInfo
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- CN1111135C CN1111135C CN 00123144 CN00123144A CN1111135C CN 1111135 C CN1111135 C CN 1111135C CN 00123144 CN00123144 CN 00123144 CN 00123144 A CN00123144 A CN 00123144A CN 1111135 C CN1111135 C CN 1111135C
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Abstract
The present invention relates to a mesopore aluminium silicophosphate molecular sieve MPL-1. The present invention uses cetyltrimethylammonium chloride (CTMAC) as main template agents to be synthesized under room temperature. The prepared molecular sieve has large specific surface area, large pore diameter, high thermal stability and high hydrothermal stability, and has large potential application value in the technical field of catalysis and adsorptive separation.
Description
The present invention relates to a kind of mesoporous molecular sieve MPL-1 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.
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 MCM-41, 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, synthesizes this molecular sieve analog of preparation because generally all being hydro-thermal, waste a large amount of energy, the use 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.
The purpose of this invention is to provide a kind of novel MPL-1 molecular sieve, this molecular sieve has bigger aperture and specific surface area, higher thermostability and hydrothermal stability.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 MPL-1 provided by the present invention can be used m " R " (Si
xAl
yP
z) O
2Expression, wherein " R " is at least a organic formwork agent in the microporous molecular sieve, " m " is every mole of (Si
xAl
yP
z) O
2In the mole number of " R ", the value of " m " is 0～0.5; " 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 " x ", " y " and " z " value in the accompanying drawing 1:
Molar fraction
Point x y z
F 0.02 0.60 0.38
G 0.02 0.38 0.60
H 0.40 0.42 0.18
I 0.98 0.01 0.01
J 0.40 0.18 0.42
F, g, j and h point have following " x ", " y " and " z " value in the accompanying drawing 2:
Molar fraction
Point x y z
f 0.02 0.52 0.46
g 0.02 0.46 0.52
h 0.50 0.23 0.27
i 0.50 0.27 0.23
In the expression formula that above-mentioned reaction is formed, reactant has carried out normalizing, i.e. x+y+z=1 according to the sum of " x ", " y " and " z ".
Mesoporous molecular sieve MPL-1 provided by the invention has following characteristics: 1. 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.2. have higher thermostability and hydrothermal stability, 10 hours lattices of 600 ℃ of roastings keep, and boil 20 hours degree of crystallinity in the boiling water and obviously do not reduce.3. the aperture of synthesis of molecular sieve is: 1.3～10nm is preferably: 2～8nm is preferably: 2.5～6nm.4. 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.5. 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 MPL-1 molecular sieve of the present invention can be expressed as: (a) template, 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: 50～1000H
2O is preferably: 0.4～4R: Al
2O
3: 0.8～1.3P
2O
5: 0.1～4.0SiO
2: 100～600H
2O is preferably: 0.5～3.0R: Al
2O
3: 0.9～1.2P
2O
5: 0.1～2.0SiO
2: 150～500H
2O
Here " R " is template.
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 one or more in chain alkyl amine and compound, cetyl trimethylammonium bromide (CTMAB), Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, cycloalkanes amine or the pyridine, and palmityl trimethyl ammonium chloride (CTMAC) weight in template should be not less than 50%.Crystallization prepares a kind of novel MPL-1 molecular sieve under normal temperature condition, and this molecular sieve has bigger aperture and specific surface area, higher thermostability and hydrothermal stability.
General compound commonly used is all adopted in the phosphorus source of raw material, silicon source and aluminium source.
Said crystallization is carried out at normal temperatures in the step (b), and crystallization temperature is 10～70 ℃, is preferably 20～60 ℃, is preferably 25～55 ℃; 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 molecular sieve 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 be for reaction provide a large amount of reaction active site and reaction compartments, 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.Has very high potential using value.
Give further instruction below by embodiment to technology of the present invention.The preparation 1 of embodiment 1 MPL-1 molecular sieve
The ortho-phosphoric acid of getting 46 grams 85% mixes with 500 gram deionized waters, the pseudo-boehmite that adds 28 grams moisture 28% then, 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 and abundant the stirring obtain gel, and it consists of: 1.3R: 1.0Al
2O
3: 1.0P
2O
5: 0.8SiO
2: 270H
2O.
With 35 ℃ of static crystallizations of above-mentioned gel 72 hours, filtration product gained solid was through washing, and 110 ℃ of dryings are carried out the X-ray powder diffraction and measured 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: 0.24R (Si
0.14Al
0.46P
0.40) 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 646m
2/ g, pore volume are 0.48ml/g, and mean pore size is 4.6nm.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 2 of embodiment 2 MPL-1 molecular sieves
The ortho-phosphoric acid of getting 46 grams 85% mixes with 480 gram deionized waters, add 64 gram aluminum isopropylates then, 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 gram deionized waters and abundant the stirring obtain gel, and it consists of: 1.0R: 1.0Al
2O
3: 1.3P
2O
5: 0.4SiO
2: 130H
2O.
With 45 ℃ of static crystallizations of above-mentioned gel 72 hours, filtration product gained solid was through washing, and 110 ℃ of dryings are carried out X-ray powder diffraction measurement result and shown that the gained synthetic product is a mesoporous molecular sieve after 4 hours, and its specific surface area is 588m
2/ g, pore volume are 0.41ml/g, and mean pore size is 3.8nm, anhydrous basic composition is: 0.20R (Si
0.09Al
0.47P
0.44) O
2The preparation 3 of embodiment 3 MPL-1 molecular sieves
The ortho-phosphoric acid of getting 46 grams 85% mixes with 600 gram deionized waters, add 82 gram aluminum isopropylates then, 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 and abundant the stirring obtain gel, and it consists of: 2.0R: 1.0Al
2O
3: 1.0P
2O
5: 1.0SiO
2: 350H
2O.
With 55 ℃ of static crystallizations of above-mentioned gel 48 hours, filtration product gained solid was through washing, and 110 ℃ of dryings are carried out X-ray powder diffraction measurement result and shown that the gained synthetic product is a mesoporous molecular sieve after 4 hours, and its specific surface area is 625m
2/ g, pore volume are 0.46ml/g, and mean pore size is 4.1nm, anhydrous basic composition is: 0.25R (Si
021Al
0.45P
0.34) O
2The preparation 4 of embodiment 4 MPL-1 molecular sieves
The ortho-phosphoric acid of getting 46 grams 85% mixes with 600 gram deionized waters, the pseudo-boehmite that adds 28 grams moisture 28% then, 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: 800H
2O.
With 25 ℃ of crystallization of above-mentioned gel 48 hours, filtration product gained solid was through washing, and 110 ℃ of dryings are carried out the X-ray powder diffraction and measured after 4 hours, and the result shows that the gained synthetic product is a mesoporous molecular sieve, and its specific surface area is 710m
2/ g, pore volume are 0.53ml/g, and mean pore size is 6.0nm, anhydrous basic composition is: 0.40R (Si
0.34Al
0.36P
0.30) O
2The preparation 5 of embodiment 5 MPL-1 molecular sieves
The ortho-phosphoric acid of getting 35 grams 85% mixes with 400 gram deionized waters, add 64 gram aluminum isopropylates then, 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 and abundant the stirring obtain gel, and it consists of: 0.7R: 1.0Al
2O
3: 1.0P
2O
5: 1.0SiO
2: 315H
2O.
With 30 ℃ of crystallization of above-mentioned gel 144 hours, filtration product gained solid was through washing, and 110 ℃ of dryings are carried out X-ray powder diffraction measurement result and shown that the gained synthetic product is a mesoporous molecular sieve after 4 hours, and its specific surface area is 618m
2/ g, pore volume are 0.38ml/g, and mean pore size is 3.2nm, anhydrous basic composition is: 0.11R (Si
0.20Al
0.45P
0.35) O
2The preparation 6 of embodiment 6 MPL-1 molecular sieves
The ortho-phosphoric acid of getting 71 grams 85% mixes with 680 gram deionized waters, add 156 gram aluminum isopropylates then, after 45 ℃ of heating in water bath are stirred to evenly, add 136 gram tetraethoxys successively, 54 gram palmityl trimethyl ammonium chlorides (CTMAC), 15 gram hexahydroaniline and 1200 gram deionized waters and abundant the stirring obtain gel, and it consists of: 1.13R: 1.0Al
2O
3: 1.1P
2O
5: 2.0SiO
2: 365H
2O.
With 50 ℃ of crystallization of above-mentioned gel 144 hours, filtration product gained solid was through washing, and 110 ℃ of dryings are carried out X-ray powder diffraction measurement result and shown that the gained synthetic product is a mesoporous molecular sieve after 4 hours, and its specific surface area is 722m
2/ g, pore volume are 0.41ml/g, and mean pore size is 5.6nm, anhydrous basic composition is: 0.14R (Si
0.31Al
0.40P
0.29) O
2
The molecular sieve of getting in above each example carries out thermostability and hydrothermal stability experiment, and 10 hours lattices of 600 ℃ of roastings of molecular sieve keep in each example as a result, boils 20 hours degree of crystallinity in the boiling water and does not obviously reduce.
Claims (17)
1. mesoporous molecular sieve MPL-1, the anhydrous structural formula that it is characterized in that this molecular sieve is mR (Si
xAl
yP
z) O
2, wherein R is the organic formwork agent in the microporous molecular sieve, m is every mole of (Si
xAl
yP
z) O
2The mole number of middle R, the value of m is 0～0.5; X+y+z=1.
2. according to the described molecular sieve MPL-1 of claim 1, it is characterized in that said x, y, z are at ternary phase diagrams
The determined pentagon of F, G, H, J and I point is formed in the district, and wherein F, G, H, J and I point have following x, y and z value:
Molar fraction
Point x y z
F 0.02 0.60 0.38
G 0.02 0.38 0.60
H 0.40 0.42 0.18
I 0.98 0.01 0.01
J 0.40 0.18 0.42
3. according to the described molecular sieve MPL-1 of claim 1, it is characterized in that said x, y, z are at ternary phase diagrams
The determined tetragon of f, g, h and j point is formed in the district, and wherein f, g, j and h point have following x, y and z value:
Molar fraction
Point x y z
f 0.02 0.52 0.46
g 0.02 0.46 0.52
h 0.50 0.23 0.27
j 0.50 0.27 0.23
4. according to the described molecular sieve MPL-1 of claim 1, it is characterized in that the aperture of said molecular sieve is: 1.3～10nm; Specific surface area is: 300～1000m
2/ g; Pore volume is: 0.2～1.0ml/g.
5. according to the described molecular sieve MPL-1 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.
6. according to the described molecular sieve MPL-1 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.
7. the synthetic method of the described molecular sieve MPL-1 of claim 1 may further comprise the steps: (a) template, 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 through washing, drying
Powder; (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: 50～1000H
2O, wherein R is a template.
8. according to the described synthetic method of claim 7, 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: 100～600H
2O.
9. according to the described synthetic method of claim 7, 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: 150～500H
2O.
10. according to the described synthetic method of claim 7, it is characterized in that 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.
11., it is characterized in that also containing C in the said organic compounds containing nitrogen group according to the described synthetic method of claim 10
4～C
18In alkylamine and compound thereof, cetyl trimethylammonium bromide, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, cycloalkanes amine or the pyridine one or more.
12. according to the described synthetic method of claim 7, it is characterized in that said crystallization is carried out at normal temperatures in the step (b), crystallization temperature is 10～70 ℃; Crystallization time is 10～300 hours.
13. according to the described synthetic method of claim 7, it is characterized in that said crystallization is carried out at normal temperatures in the step (b), crystallization temperature is 20～60 ℃; Crystallization time is 15～200 hours.
14. according to the described synthetic method of claim 7, it is characterized in that said crystallization is carried out at normal temperatures in the step (b), crystallization temperature is 25～55 ℃; Crystallization time is 20～100 hours.
15., it is characterized in that said maturing temperature is 400～800 ℃ in the step (c) according to the described synthetic method of claim 7; Roasting time is 2～24 hours.
16., it is characterized in that said maturing temperature is 450～700 ℃ in the step (c) according to the described synthetic method of claim 7; Roasting time is 3～12 hours.
17., it is characterized in that said maturing temperature is 500～650 ℃ in the step (c) according to the described synthetic method of claim 7; Roasting time is 4～8 hours.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00123144 CN1111135C (en) | 2000-10-26 | 2000-10-26 | Mesoporous aluminium silicophosphate molecular sieve and its preparing process |
| 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 00123144 CN1111135C (en) | 2000-10-26 | 2000-10-26 | Mesoporous aluminium silicophosphate molecular sieve and its preparing process |
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| CN100384729C (en) * | 2005-06-17 | 2008-04-30 | 中国科学院大连化学物理研究所 | Mesoporous Si-Si composite material and its preparing process |
| CN102862955B (en) * | 2011-07-07 | 2015-08-12 | 中国石油化工股份有限公司 | The application of a kind of oxygen carrier in recycle chemistry chain hydrogen production and preparation |
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