CN1362363A - Mesoporous aluminium phosphotitanate molecular sieve and its prepn - Google Patents
Mesoporous aluminium phosphotitanate molecular sieve and its prepn Download PDFInfo
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- CN1362363A CN1362363A CN 01106006 CN01106006A CN1362363A CN 1362363 A CN1362363 A CN 1362363A CN 01106006 CN01106006 CN 01106006 CN 01106006 A CN01106006 A CN 01106006A CN 1362363 A CN1362363 A CN 1362363A
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 71
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000004411 aluminium Substances 0.000 title claims abstract description 7
- 239000011148 porous material Substances 0.000 claims abstract description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 238000002425 crystallisation Methods 0.000 claims description 21
- 230000008025 crystallization Effects 0.000 claims description 21
- 239000010936 titanium Substances 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 238000010189 synthetic method Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 238000010587 phase diagram Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000009415 formwork Methods 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 3
- 150000003973 alkyl amines Chemical class 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- -1 cycloalkanes amine Chemical class 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 13
- 239000003643 water by type Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- 235000011007 phosphoric acid Nutrition 0.000 description 7
- 238000000634 powder X-ray diffraction Methods 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical class Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 241000269350 Anura Species 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 101100493713 Caenorhabditis elegans bath-45 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 102000011759 adducin Human genes 0.000 description 1
- 108010076723 adducin Proteins 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The mesapore aluminium titanophosphate molecular sieve MPL-2 is synthesized by adopting CTMAC as main template agent at normal temp. The prepared molecular sieve possesses large specific surface area and pore size, and contains titanium element with variable valence state. In the field of oxidation, reducing and catalysis or adsorption and separation it possesses high application value.
Description
The present invention relates to a kind of mesopore molecular sieve MPL-2 and synthetic method thereof.Just provide a kind of variable valence state element ti that both contained specifically, have high-specific surface area and wide-aperture non-zeolite molecular sieve and preparation method thereof again.
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 (U.S.Pat.No.2,882,244); Y type (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 sieve 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 the ideal composition that a kind of isomery takes off cured catalyzer.United States Patent (USP) 4,567,029,4,619,818 have reported the synthetic and application in catalyzed reaction of the molecular sieve Ti-SAPO-n that contains titanium elements, but, enough contact area and reaction compartments can not be provided, for heavier petroleum fractions reactant so its range of application is restricted because institute's synthetic molecular sieve is a microvoid structure.
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 along with the appearance of strict day by day and worldwide crude oil poor qualityization and the heaviness trend of development of modern industry and environmental regulation, urgent need is developed a series of novel materials with ultra-large aperture and specific surface area, special catalysis.
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, inspires for the chemical industry worker greatly.But, synthesizes this molecular sieve analog of preparation because generally all being hydro-thermal, waste a large amount of energy, use expensive cetyl trimethylammonium bromide (CTMAB) to be organic formwork agent, 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.People had done a large amount of fruitful work to this molecular sieve analog in recent years, United States Patent (USP) 5,300,277,5,308,602 have reported synthetic method and the application of some titaniferous mesopore molecular sieve Ti-MCM-41, TS-1, Ti-HMS etc., for example making the selective oxidation catalyzer of ethene with TS-1, is oxygenant with hydrogen peroxide, obtains the higher propylene oxide of yield, but the very fast inactivation of catalyzer that is to say that the hydrothermal stability problem of this molecular sieve analog is not still effectively solved.
The purpose of this invention is to provide a kind of novel Ti mesopore molecular sieve MPL-2 that contains, this molecular sieve contains variable valence state element ti, and has bigger aperture and specific surface area, is expected to have good oxidation-reduction performance.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 mesopore molecular sieve MPL-2 of the present invention can be used m " R " (Ti
xAl
yP
z) O
2Expression, wherein " R " is the organic formwork agent in the microporous molecular sieve, " m " is every mole of (Ti
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
j 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 ".
The preparation of above-mentioned MPL-2 molecular sieve is characterised in that phosphorus source in the raw material, titanium source and the general compound commonly used of aluminium source employing, and 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 cetyl trimethylammonium bromide (CTMAB), chain alkyl amine and compound thereof, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, cycloalkanes amine or the pyridine.Crystallization prepares a kind of novel mesopore molecular sieve MPL-2 under normal temperature condition, this molecular sieve has very high thermostability and hydrothermal stability (600 ℃ of roastings lattice maintenance in 10 hours, boiling 20 hours degree of crystallinity in the boiling water does not obviously reduce), contain variable valence state element ti, and have bigger aperture and specific surface area.The building-up process of mesopore molecular sieve MPL-2 of the present invention can be expressed as: (a) template, titanium 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: 0.01～6.0TiO
2: 50～1000H
2O is preferably: 0.4～4R: Al
2O
3: 0.8～1.3P
2O
5: 0.1～4.0TiO
2: 100～600H
2O is preferably: 0.5～3.0R: Al
2O
3: 0.9～1.2P
2O
5: 0.1～2.0TiO
2: 150～500H
2O " R " here is a template.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.
Mesopore molecular sieve MPL-2 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. the aperture of synthesis of molecular sieve is: 1.3～10nm is preferably: 2～8nm is preferably: 2.5～6nm.
3. 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.
4. the pore volume of synthesis of molecular sieve is: 0.2～1.0ml/g is preferably: 0.25～0.8ml/g is preferably: 0.3～0.6ml/g.
The titanium-containing meso-porous molecular sieve of the present invention's preparation not only has the advantage of super macroporous molecular sieve, and have very high thermostability and hydrothermal stability and contain titanium elements with variable valence state, can directly be used as the carrier of catalyzer or specific function, redox catalysis catalysts particularly, can provide abundant active sites and reaction compartment 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.Has sizable potential using value.
Below by embodiment technology of the present invention is given to illustrate further.The preparation 1 of embodiment 1MPL-2 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 the positive titanium ethanolate of 36.5 grams 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: 0.8TiO
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: 0.25R (Ti
0.15Al
0.47P
0.38) 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 character and the composition of gained molecular sieve see Table 1.Measuring 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 2MPL-2 molecular sieve
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 the positive titanium ethanolate of 18.5 grams 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: 0.4TiO
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 character and composition see Table 1.The preparation 3 of embodiment 3MPL-2 molecular sieve
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 the positive titanium ethanolate of 73 grams 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: 1.0TiO
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 character and composition see Table 1.The preparation 4 of embodiment 4MPL-2 molecular sieve
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 95 gram titanium tetrachlorides 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: 2.5TiO
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 character and composition see Table 1.The preparation 5 of embodiment 5MPL-2 molecular sieve
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 38 gram titanium tetrachlorides 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: 1.0TiO
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 character and composition see Table 1.The preparation 6 of embodiment 6MPL-2 molecular sieve
The ortho-phosphoric acid of getting 46 grams 85% mixes with 700 gram deionized waters, add 82 gram aluminum isopropylates then, after 45 ℃ of heating in water bath are stirred to evenly, add the positive titanium ethanolate of 73 grams successively, 64 gram palmityl trimethyl ammonium chlorides (CTMAC), 7.8 gram pyridine and 530 gram deionized waters and abundant the stirring obtain gel, it consists of: 2.0R: 1.0Al
2O
3: 1.0P
2O
5: 1.0TiO
2: 400H
2O.
With 60 ℃ of static crystallizations of above-mentioned gel 50 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 character and composition see Table 1.
Get respectively embodiment preparation molecular sieve containing titanium 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.
Molecular sieve character and composition example specific surface area pore volume mean pore size are formed in each example of table 1
m
2/g ml/g nm?1 687 0.40 4.5 0.25R·(Ti
0.15·Al
0.47·P
0.38)O
2?2 618 0.36 3.6 0.20R·(Ti
0.10·Al
0.48·P
0.42)O
2?3 657 0.44 3.9 0.28R·(Ti
0.21·Al
0.44·P
0.35)O
2?4 682 0.48 4.2 0.35R·(Ti
0.35·Al
0.37·P
0.28)O
2?5 724 0.34 2.8 0.15R·(Ti
0.20·Al
0.43·P
0.37)O
2?6 535 0.38 4.1 0.27R·(Ti
0.20·Al
0.44·P
0.36)O
2
Claims (18)
1. mesopore molecular sieve, the anhydrous structural formula that it is characterized in that this molecular sieve is m " R " (Ti
xAl
yP
z) O
2, wherein " R " is the organic formwork agent in the microporous molecular sieve, " m " is every mole of (Ti
xAl
yP
z) O
2In the mole number of " R ", " x ", " y ", " z " are respectively the molar fraction of Ti, Al, P, the value of " m " is 0～0.5; X+y+z=1.
2. according to the described molecular sieve of claim 1, it is characterized in that said " x ", " y ", " z " form in the district at the determined pentagon of F, G, H, J and I point on the ternary phase diagrams, wherein F, G, H, J and I point have following " x ", " y " and " z " value:
Molar fraction point X y zF 0.02 0.60 0.38G 0.02 0.38 0.60H 0.40 0.42 0.18I 0.98 0.01 0.01J 0.40 0.18 0.42
3. according to the described molecular sieve of claim 1, it is characterized in that said " 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 " x ", " y " and " z " value:
Molar fraction point X y zf 0.02 0.52 0.46g 0.02 0.46 0.52h 0.50 0.23 0.27j 0.50 0.27 0.23
4. according to the described molecular sieve of claim 1, it is characterized in that said molecular sieve has 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 remain unchanged.
5. according to the described molecular sieve 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.
6. 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.
7. 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.
8. according to the synthetic method of the described molecular sieve of claim 1, may further comprise the steps: (a) template, titanium 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; (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: 0.01～6.0TiO
2: 50～1000H
2O, wherein " R " is template.
9. according to the described synthetic method of claim 8, 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: 0.1～4.0TiO
2: 100～600H
2O
10. according to the described synthetic method of claim 8, 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: 0.1～2.0TiO
2: 150～500H
2O.
11. according to the described synthetic method of claim 8, 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.
12., it is characterized in that also containing C in the said organic compounds containing nitrogen group according to the described synthetic method of claim 11
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.
13. according to the described synthetic method of claim 8, 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.
14. according to the described synthetic method of claim 8, 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.
15. according to the described synthetic method of claim 8, 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.
16., it is characterized in that said maturing temperature is 400～800 ℃ in the step (c) according to the described synthetic method of claim 8; Roasting time is 2～24 hours.
17., it is characterized in that said maturing temperature is 450～700 ℃ in the step (c) according to the described synthetic method of claim 8; Roasting time is 3～12 hours.
18., it is characterized in that said maturing temperature is 500～650 ℃ in the step (c) according to the described synthetic method of claim 8; Roasting time is 4～8 hours.
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| CN 01106006 CN1211278C (en) | 2001-01-05 | 2001-01-05 | Mesoporous aluminium phosphotitanate 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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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312037C (en) * | 2004-10-14 | 2007-04-25 | 中国科学院大连化学物理研究所 | Mesopore IIZPA-3 material and preparation method |
| CN100447085C (en) * | 2004-10-16 | 2008-12-31 | 太原理工大学 | A kind of zirconium silicon mesoporous molecular sieve and its synthesis method |
| CN101112994B (en) * | 2006-07-27 | 2010-05-12 | 中国科学院大连化学物理研究所 | A kind of inorganic phosphate and application thereof |
| CN105883845A (en) * | 2016-04-14 | 2016-08-24 | 沈阳理工大学 | Method for preparing molecular sieve with Ti-Ai oxide as framework |
| CN106006659A (en) * | 2016-05-20 | 2016-10-12 | 沈阳理工大学 | Preparation method of titanium-aluminum molecular sieve photocatalyst |
| CN106542549A (en) * | 2016-11-24 | 2017-03-29 | 山西大学 | A kind of fluorine richness titanium phosphate aluminum molecular screen F TAPO 5 and preparation method thereof |
-
2001
- 2001-01-05 CN CN 01106006 patent/CN1211278C/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312037C (en) * | 2004-10-14 | 2007-04-25 | 中国科学院大连化学物理研究所 | Mesopore IIZPA-3 material and preparation method |
| CN100447085C (en) * | 2004-10-16 | 2008-12-31 | 太原理工大学 | A kind of zirconium silicon mesoporous molecular sieve and its synthesis method |
| CN101112994B (en) * | 2006-07-27 | 2010-05-12 | 中国科学院大连化学物理研究所 | A kind of inorganic phosphate and application thereof |
| CN105883845A (en) * | 2016-04-14 | 2016-08-24 | 沈阳理工大学 | Method for preparing molecular sieve with Ti-Ai oxide as framework |
| CN105883845B (en) * | 2016-04-14 | 2017-11-24 | 沈阳理工大学 | A kind of method prepared using Ti Al oxides as the molecular sieve of skeleton |
| CN106006659A (en) * | 2016-05-20 | 2016-10-12 | 沈阳理工大学 | Preparation method of titanium-aluminum molecular sieve photocatalyst |
| CN106542549A (en) * | 2016-11-24 | 2017-03-29 | 山西大学 | A kind of fluorine richness titanium phosphate aluminum molecular screen F TAPO 5 and preparation method thereof |
| CN106542549B (en) * | 2016-11-24 | 2018-10-26 | 山西大学 | A kind of fluorine richness titanium phosphate aluminum molecular screen F-TAPO-5 and preparation method thereof |
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|---|---|
| CN1211278C (en) | 2005-07-20 |
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