CN1211278C - Mesoporous aluminium phosphotitanate molecular sieve and its prepn - Google Patents
Mesoporous aluminium phosphotitanate molecular sieve and its prepn Download PDFInfo
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- CN1211278C CN1211278C CN 01106006 CN01106006A CN1211278C CN 1211278 C CN1211278 C CN 1211278C CN 01106006 CN01106006 CN 01106006 CN 01106006 A CN01106006 A CN 01106006A CN 1211278 C CN1211278 C CN 1211278C
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Abstract
The present invention relates to a mesapore aluminum titanophosphate molecular sieve MPL-2. Cetyltrimethylammonium chloride (CTMAC) is used as a main template agent for synthesizing the molecular sieve MPL-2 at a room temperature. The prepared molecular sieve has large specific surface area and large pore diameter, has titanium elements with variable valence states, and has large potential application value in the field of redox catalysis or adsorptive separation.
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 ME 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 ", " x ", " y ", " z " are respectively the molar fraction of Ti, Al, P, 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 1, 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, template is main organic compounds containing nitrogen group with low-cost palmityl trimethyl ammonium chloride (CTMAC), and palmityl trimethyl ammonium chloride weight should be more than or equal to 50% in template.Other organic compounds containing nitrogens are cetyl trimethylammonium bromide (CTMAB), C
4～C
18In alkylamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, cycloalkanes amine or the pyridine one or more.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 remains unchanged), 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 water mixing, the stirring with calculated amount obtains 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
Be preferably: 0.4～4R: Al
2O
3: 0.8～1.3P
2O
5: 0.1～4.0TiO
2: 100～600H
2O
Be preferably: 0.5～3.0R: Al
2O
3: 0.9～1.2P
2O
5: 0.1～2.0TiO
2: 150～500H
2O
Here " R " is 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: 2～10nm 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: 0.3～0.8ml/g is preferably: 0.4～0.6ml/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 1 MPL-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 2 MPL-2 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 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 3 MPL-2 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 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 4 MPL-2 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 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 5 MPL-2 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 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 6 MPL-2 molecular sieves
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 in each example of table 1
Specific surface area pore volume mean pore size
Example is formed
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 (16)
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; The aperture of said molecular sieve is 2～10nm, and specific surface area is 300～1000m
2/ g, pore volume are 0.2～1.0ml/g;
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, 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
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 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 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
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, boils 20 hours degree of crystallinity and remains unchanged 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. 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; 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: 0.1～4.0TiO
2: 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: 0.1～2.0TiO
2: 150～500H
2O.
9. 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 alkylamine, cetyl trimethylammonium bromide, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH, cycloalkanes amine or the pyridine one or more.
10. according to the described synthetic method of claim 6, 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.
11. 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.
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 20～60 ℃; Crystallization time is 15～200 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 25～55 ℃; Crystallization time is 20～100 hours.
14., 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.
15., 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.
16., 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.
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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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| 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 | Mesoporous Zr-Si molecular sieve and its synthesis |
| CN101112994B (en) * | 2006-07-27 | 2010-05-12 | 中国科学院大连化学物理研究所 | Inorganic phosphate and uses thereof |
| 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 |
| CN106006659B (en) * | 2016-05-20 | 2017-10-27 | 沈阳理工大学 | A kind of method for preparing titanium aluminum molecular screen photochemical catalyst |
| 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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