CN104609440B - TS-1 molecular sieve prepared from amino-terminated polymer as well as preparation method and application thereof - Google Patents
TS-1 molecular sieve prepared from amino-terminated polymer as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a TS-1 molecular sieve prepared from an amino-terminated polymer. During synthesis, the used template agent refers to the amino-terminated polymer. The TS-1 molecular sieve can be prepared by taking the amino-terminated polymer as the template agent, and the range of the template agent used for preparing the TS-1 molecular sieve is widened. Meanwhile, the TS-1 molecular sieve prepared by taking the amino-terminated polymer as the template agent is well-crystallized and regular in morphology, and the propylene epoxidation catalytic performance is superior to that of a TS-1 molecular sieve synthesized by a classic method.
Description
Technical field
The invention belongs to field of preparation of molecular sieve material, it is related to a kind of molecular sieve and its synthetic method, especially one kind makes
It is template synthesis TS-1 molecular sieve with double-end amino polymer, expoxy propane can be produced as propylene and hydrogen peroxide epoxidation
Catalyst.
Background technology
HTS (TS-1 molecular sieve) is the new hetero-atom molecular-sieve material of last century the eighties exploitation.It has
There is MFI topological structure, be the Al that be instead of with Ti in ZSM-5, thus having selective oxidation active center, being widely used in selecting
Select oxidation catalysiss field.Particularly TS-1 is to the epoxidation of Organic substance selective oxidation such as alkene, arene hydroxylation, cyclohexanone-oxime
The reaction such as change, oxidation of alcohol not only has good catalysis activity but also can be prevented effectively from oxidizing process complex process and environment dirt
The problems such as dye, is it is considered to be the milestone of the zeolite catalysis eighties in 20th century.Therefore, in the last thirty years, the system of TS-1 molecular sieve
Standby and application becomes a study hotspot in zeolite catalysis field.
TS-1 molecular sieve is that Taramasso et al. synthesized first in 1981, and academia is referred to as classical synthetic method (US
4410501), but the method not only synthesis condition is harsh, needing using TPAOH organic base expensive in a large number is mould
Plate agent, and material purity is had high demands, the isoionic presence of K+, Na+ in raw material easilys lead to extra-framework titanium (Detitanium-ore-type
TiO2 generation).Subsequently substantial amounts of patent and document report classical approach synthesizes the research situation of TS-1, but because it synthesizes cost
High and limit its commercial Application.
In order to reduce synthesis cost, people have also attempted relatively inexpensive non-TPAOH system synthesis TS-1 and have divided
Son sieve.Chinese patent CN101913620A proposes a kind of synthetic method of TS-1, and its technical characteristic is, with 4-propyl bromide
Divide for alkali source synthesis TS-1 with organic base as titanium source for template, with Ludox as silicon source, with butyl titanate or titanium tetrachloride
Son sieve.In addition, also having a lot of patents and document to synthesize TS-1, such as CN1060411C with non-TPAOH for template
(with tetraethyl ammonium hydroxide and TBAH as template), CN100344375C are (with hexamethylene imine and piperidines
For template), USP5688484 (with cycloheximide as template), CN101767036A and Catalysis today, 74
(2002) 65-75 (with 4-propyl bromide as template), Zeolites, 19 (1997) 246-252 are (with methylamine and tetrapropyl bromine
Change ammonium be template), Material chemistry and physics, 47 (1997) 225-230 (with 4-propyl bromide with
The binary mixture of tetraethylammonium chloride and tetrabutylammonium chloride is template) etc..Although above-mentioned non-TPAOH
System synthesizes the synthesis cost that TS-1 molecular sieve can significantly reduce TS-1 molecular sieve, but the hexa-coordinate in TS-1 zeolite product
Extra-framework titanium content height is so as to catalysis activity substantially reduces.Contain to reduce extra-framework titanium in cheap system synthesis TS-1 product
Amount, improves its catalysis activity, and researchers have carried out the post-modification research for TS-1.As US6103915,
CN101602013A, CN101786638A etc..But post-modification process also makes the technical process of synthesis TS-1 become complexity be increased
Synthesis cost, and modified effect is poor.Double-end amino polymer two ends respectively contain an amino, can be used as molecular sieve crystal grown junction
Structure directed agents, polymer contributes to being formed more nucleus in the crystallization starting stage, generates compared with molecular sieve crystal.
Content of the invention
The present invention overcomes the deficiencies in the prior art, there is provided for solving above-mentioned technical problem, the technical side that the present invention adopts
Case is：
A kind of TS-1 molecular sieve of double-end amino polymer preparation, during its synthesis, template used is polymerized for double-end amino
Thing.
Further, described double-end amino polymer be amino-end peg -600, amino-end peg -800,
Amino-end peg -1200, amino-end peg -2000, double-end amino PolyTHF, double-end amino polyurethane
With one of double-end amino silicone oil or two or more mixture.
The method that another object of the present invention prepares TS-1 molecular sieve in a kind of double-end amino polymer of offer, including as follows
Step：(1) under intense agitation, by silicon source, template, water mix homogeneously, add titanium source, stirring obtains titanium silicon and coagulates
Glue；(2) by titanium Silica hydrogel at 90～130 DEG C pre- crystallization 1～4h, then hydrothermal crystallizing 5～120h at 120～200 DEG C；
(3) be separated by filtration solid-liquid, washing filter cake and dry cake after, at 400～600 DEG C roasting 4～12h with removed template method,
Can get TS-1 molecular sieve.
Preferably, described silicon source：Titanium source：Template：The mol ratio of water is 1.5-3：0.05-0.2：1：80-120.
Further, the process of described step (2) crystallization is to enter in teflon-lined stainless steel cauldron
OK.
Preferably, described step (2) the hydrothermal crystallizing time is 5～96h.
Preferably, the baking temperature of described step (3) is 80～150 DEG C.
In addition, the present invention also provides a kind of double-end amino polymer to prepare the application of TS-1 molecular sieve, described TS-1 molecule
Sieve produces the catalyst of expoxy propane as catalysis propylene and hydrogen peroxide reaction.Further, described catalyst quality concentration is
0.5%-0.4%, preferably 1%-2%.
In reaction, propylene used be polymerization-grade propylene, reactor be batch reactor, reaction temperature at 30～100 DEG C,
Reaction pressure is 0.3～1.0MPa, and solvent for use is methanol, and its content is 6 with the mass ratio of hydrogen peroxide:1～8:1, during reaction
Between be 1.5h, speed of agitator be 800～1000r/min.
The present invention has the advantages and positive effects that：By TS-1 can be prepared for template using double-end amino polymer
Molecular sieve, has widened the scope preparing template used dose of TS-1 molecular sieve.Prepared with double-end amino polymer for template simultaneously
TS-1 molecular sieve not only well-crystallized, regular appearance, and its epoxidation of propylene catalytic performance be better than classical approach synthesis TS-
1 molecular sieve.
Brief description
Fig. 1, Fig. 2 are X-ray diffractogram and and the scanning electron microscope of comparative example gained sieve sample (TS-1-DB)
(SEM) photo.
Fig. 3, Fig. 4 are X-ray diffractogram and the SEM photograph of embodiment 1 gained sieve sample (TS-1-01).
Fig. 5 is the SEM photograph of embodiment 2 gained sieve sample (TS-1-02).
Fig. 6 is the SEM photograph of embodiment 3 gained sieve sample (TS-1-03).
Fig. 7 is the SEM photograph of embodiment 4 gained sieve sample (TS-1-04).
Fig. 8 is the SEM photograph of embodiment 5 gained sieve sample (TS-1-05).
Fig. 9 is the SEM photograph of embodiment 6 gained sieve sample (TS-1-06).
Specific embodiment
Below by embodiment, the present invention is further described, but and is not so limited the present invention.
Comparative example
Comparative example synthesizes TS-1 molecular sieve according to literature method (Zeolites, page 1992, Vol.12,943～950).
Take 12.00g TPAOH to mix with 118.60g deionized water first, be subsequently adding 42.00g tetraethyl orthosilicate
(TEOS), it is stirred vigorously to after uniformly, add 2.40g tetraethyl titanate (TEOT) and be sufficiently stirred for, make uniform titanium silicon and coagulate
Glue；Then above-mentioned glue is transferred in the pressure vessel with inner liner polytetrafluoroethylene, at 110 DEG C pre- crystallization 2h, 160 DEG C
Lower crystallization 36h；End product centrifugation.Solid is scrubbed, obtain final product after air atmosphere roasting 4h at 110 DEG C of dryings and 550 DEG C
Sample.X-ray powder diffraction analysis is carried out to it, as shown in Figure 1.Result shows, gained sample is TS-1 molecular sieve, numbering
For TS-1-DB.Its scanning electron microscope (SEM) photo is as shown in Figure 2.
Embodiment 1
Take 14.80g amino-end peg -600 to mix with 150.00g deionized water, be subsequently adding the positive silicon of 57.25g
Acetoacetic ester (TEOS), is stirred vigorously to after uniformly, adds 47.56g tetraethyl titanate (TEOT) and be sufficiently stirred for, make uniformly
Titanium silicone fluid；Above-mentioned glue is transferred in the pressure vessel with inner liner polytetrafluoroethylene, at 110 DEG C pre- crystallization 2h, 160
Hydrothermal crystallizing 36h at DEG C；Product centrifugation.Solid is scrubbed, after air atmosphere roasting 4h at 110 DEG C of dryings and 550 DEG C i.e.
Obtain sample.X-ray powder diffraction analysis is carried out to it as shown in figure 3, its diffraction maximum is similar to Fig. 1.Result shows, gained sample
Product are TS-1 molecular sieve.Code T S-1-01, its scanning electron microscope (SEM) photo is as shown in Figure 4.
Embodiment 2
Repeat embodiment 1,14.80g amino-end peg -600 therein is changed to the poly- second of 13.98g double-end amino
Glycol -1200, deionized water is changed to 145.00g, and tetraethyl orthosilicate (TEOS) is changed to 54.89g, and TEOT is changed to 44.26g, pre- crystalline substance
The change time is changed to 4h, final score sieve sample.X-ray powder diffraction analysis is carried out to it, its diffraction maximum is similar to Fig. 3.Knot
Fruit shows, gained sample is TS-1 molecular sieve.Code T S-1-02, its scanning electron microscope (SEM) photo is as shown in Figure 5.
Embodiment 3
Repeat embodiment 1,14.80g amino-end peg -600 therein is changed to the poly- second of 15.60g double-end amino
Glycol -2000, deionized water is changed to 148.20g, and TEOS is changed to 56.32g, and TEOT is changed to 45.21g, and crystallization temperature and time divide
It is not changed to 170 DEG C and 40h, final score sieve sample.X-ray powder diffraction analysis is carried out to it, its diffraction maximum and Fig. 3 phase
Seemingly.Result shows, gained sample is TS-1 molecular sieve.Code T S-1-03, its scanning electron microscope (SEM) photo such as Fig. 6 institute
Show.
Embodiment 4
Repeat embodiment 1,14.80g amino-end peg -600 therein is changed to the poly- ammonia of 13.20g double-end amino
Ester, deionized water is changed to 144.00g, and TEOS is changed to 54.25g, and TEOT is changed to 45.10g, and the pre- crystallization temperature time is changed to 4h, brilliant
Change temperature and time and be changed to 170 DEG C and 40h, final score sieve sample respectively.X-ray powder diffraction analysis is carried out to it, its
Diffraction maximum is similar to Fig. 3.Result shows, gained sample is TS-1 molecular sieve.Code T S-1-04, its scanning electron microscope
(SEM) photo is as shown in Figure 7.
Embodiment 5
Repeat embodiment 2,13.98g amino-end peg -1200 therein is changed to 12.13g double-end amino poly- four
Hydrogen furan, deionized water is changed to 143.65g, and TEOS is changed to 52.51g, and TEOT is changed to 44.14g, and pre- crystallization temperature is changed to 120 DEG C,
Crystallization temperature and time are respectively 165 DEG C and 45h, final score sieve sample.X-ray powder diffraction analysis is carried out to it, its
Diffraction maximum is similar to Fig. 3.Result shows, gained sample is TS-1 molecular sieve.Code T S-1-05, its scanning electron microscope
(SEM) photo is as shown in Figure 8.
Embodiment 6
Repeat embodiment 2,13.98g amino-end peg -1200 therein is changed to the poly- second of 8.13g double-end amino
Glycol -1200 and 6.52g double-end amino silicone oil, deionized water is changed to 150.34g, and TEOS is changed to 54.23g, and TEOT is changed to
46.48g, pre- crystallization temperature and time are changed to 120 DEG C and 2h respectively, and crystallization temperature and time are respectively 170 DEG C and 40h, finally
Obtain sieve sample.X-ray powder diffraction analysis is carried out to it, its diffraction maximum is similar to Fig. 3.Result shows, gained sample is
TS-1 molecular sieve.Code T S-1-06, its scanning electron microscope (SEM) photo is as shown in Figure 9.
Embodiment 7
This example demonstrates that the inventive method and TS-1 molecular sieve obtained by comparative example method be used for being catalyzed propylene and pair
The effect of propylene oxide reaction is prepared in oxygen water ring oxidation.
In 250mL batch reactor, it is separately added into TS-1 molecular sieve (TS-1-DB, TS-1- of the above-mentioned preparation of 0.75g
01st, TS-1-02, TS-1-03, TS-1-04, TS-1-05, TS-1-06) and 50g methanol, so that material is mixed all using magnetic agitation
Fall the air in reactor with nitrogen displacement after even；Heating in water bath, elevates the temperature to 55 DEG C, adds 7.5g mass concentration 30%
Hydrogen peroxide, be passed through propylene gas under stirring condition, make system pressure maintain 0.4MPa；Sample analysis after reaction 1.5h,
Reaction result see table 1.
The each embodiment experimental result of table 1
From examples detailed above, the TS-1 molecular sieve prepared for template with double-end amino polymer that the present invention provides is not
Only well-crystallized, regular appearance, and its epoxidation of propylene catalytic performance is better than the TS-1 molecular sieve of classical approach synthesis.Wherein,
Hydrogen peroxide conversion ratio reaches 99.48%, and the yield of expoxy propane and selectivity respectively reach 95.62% and 99.23%.
Above presently preferred embodiments of the present invention is described in detail, but described content has been only the preferable enforcement of the present invention
Example is it is impossible to be considered the practical range for limiting the present invention.All impartial changes made according to the present patent application scope and improvement
Deng all should still belong within the patent covering scope of the present invention.
Claims (6)
1. a kind of double-end amino polymer prepare TS-1 molecular sieve method it is characterised in that：During synthesis, template used is
Double-end amino polymer；
Described double-end amino polymer is amino-end peg -600, amino-end peg -800, double-end amino gather
Ethylene glycol -1200, amino-end peg -2000, double-end amino PolyTHF, double-end amino polyurethane and double-end amino
One of silicone oil or two or more mixture.
2. the method preparing TS-1 molecular sieve according to claim 1 is it is characterised in that comprise the following steps：
(1) under intense agitation, by silicon source, template, water mix homogeneously, add titanium source, stirring obtains titanium Silica hydrogel；
(2) by titanium Silica hydrogel at 90～130 DEG C pre- crystallization 1～4h, then hydrothermal crystallizing 5～120h at 120～200 DEG C；
(3) after filtering, wash, being dried, roasting 4～12h at 400～600 DEG C, you can obtain TS-1 molecular sieve.
3. method according to claim 2 it is characterised in that：Described silicon source：Titanium source：Template：The mol ratio of water is
1.5-3：0.05-0.2：1：80-120.
4. method according to claim 2 it is characterised in that：The process of described step (2) crystallization is with polytetrafluoro
Carry out in the stainless steel cauldron of ethylene liner.
5. method according to claim 2 it is characterised in that：Described step (2) the hydrothermal crystallizing time is 5～96h.
6. method according to claim 2 it is characterised in that：The baking temperature of described step (3) is 80～150 DEG C.
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