CN1167082A - Method for preparing titanium-silicon molecular sieve (TS-1) - Google Patents
Method for preparing titanium-silicon molecular sieve (TS-1) Download PDFInfo
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- CN1167082A CN1167082A CN 96106316 CN96106316A CN1167082A CN 1167082 A CN1167082 A CN 1167082A CN 96106316 CN96106316 CN 96106316 CN 96106316 A CN96106316 A CN 96106316A CN 1167082 A CN1167082 A CN 1167082A
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Abstract
The preparation method of titanium-silicon molecular sieve (TS-1) with MFI structure is as follows: a titanium source is dissolved in ammonium tetrabutyl hydroxide (TBAOH) aqueous solution, then uniformly mixed with solid silica-gel spheres with 60-260 meshes to obtain the reaction mixture whose molar composition is SiO2:(0.0045-0.20), TiO2:(0.03-0.5), TBAOH:(0.6-40)H2O, and then the obtained reaction mixture is crystallized at 130-200 deg.C for 1-6 days in an autoclave, and processed by such processes as filtering, washing, drying and roasting according to the conventional method so as to obtain the invented product.
Description
The present invention relates to the preparation method of HTS, particularly relate to the preparation method of HTS (TS-1) with MFI structure.
HTS is the novel hetero-atom molecular-sieve that early eighties begins to develop.The TS-1 that MFI type structure is arranged that has synthesized at present, the TS-2 of MEL type structure, and have than the TS-48 of macroporous structure etc.This molecular sieve analog is to there being H
2O
2Many organic oxidizing reactions of participating in, for example the reactions such as oxidation of the epoxidation of alkene, aromatic hydrocarbons hydroxylation, pimelinketone oximate, alcohol have excellent catalytic activity and selective paraffin oxidation performance, and they have a good application prospect as redox (redox) type molecular sieve catalyst.
The synthetic method of TS-1 disclosed (GB2071071A, USP4,410,501) first by people such as gondola Marco Taramasso in 1981.This method is to prepare a kind of silicon source, titanium source, organic bases (RN of containing earlier
+) and/or the reaction mixture of basic oxide (Men/2O), with this reaction mixture in autoclave in 130～200 ℃ of hydrothermal crystallizings 6～30 days, separate then, wash, dry, roasting and product.Silicon source wherein can be tetraalkyl silicon ester, colloidal state SiO
2Or alkalimetal silicate, the titanium source can be hydrolyzable titanium compound, preferred Ti (OC2H
5)
4, the preferred TPAOH of organic bases, wherein the mole compositing range of reaction mixture is:
Generally preferred
SiO
2/TiO
2 5～200 35～65
OH
-/SiO
2 0.1～1.0 0.3～0.6
H
2O/SiO
2 20～200 60～100
Me/SiO
2 0～0.5 0
RN
+/SiO
2 0.1～2.0 0.4～1.0
Owing to be incorporated into the TiO of skeleton in the molecular sieve that people's such as M.Taramasso method synthesizes
2Amount seldom, people such as the A.Thangaraj of India disclose in 1992 a kind of be considered at present the method for the most synthetic TS-1 (Zeolites, 1992, Vol.12, P943).This method is that an amount of TPAOH (TPAOH) aqueous solution is joined stirring and dissolving certain hour in the ethyl silicate solution, and the aqueous isopropanol that slowly adds tetrabutyl titanate then under vigorous stirring obtains clarifying liquid mixture and (must slowly drip to prevent that tetrabutyl titanate hydrolysis is too fast and form white TiO
2Precipitation), stirs after 15 minutes, slowly add an amount of TPAOH aqueous solution again, catch up with alcohol to be transferred to after 3～6 hours in the autoclave in 75～80 ℃ reaction mixture then, wherein mole consisting of of reaction mixture: SiO in 170 ℃ of following hydrothermal crystallizings 3～6 days
2: (0.01～0.10) TiO
2: 0.36TPAOH: 35H
2O.The X-ray diffraction crystalline phase figure of the TS-1 molecular sieve that synthesizes and the Silicalite-1 of pure silicon similar (MFI structure), its infrared absorption spectrum (IR) is at 950～970cm
-1The unexistent charateristic avsorption band of Silicalite-1 has appearred in the place, and this is because Ti enters the result who has caused the antisymmetric stretching vibration of Si-O key behind the framework of molecular sieve, is considered to the evidence that Ti enters framework of molecular sieve.
Generally all adopting the more expensive silicon ester of price in the prior art of above-mentioned synthetic TS-1 is the silicon source, and owing to water-content in the synthetic liquid is big, make that the consumption of expensive organic bases (TPAOH) is very big, synthesis step is strict and complicated, therefore the cost of the TS-1 molecular sieve that synthesizes is very high, and its application prospect is restricted.
The objective of the invention is to overcome the shortcoming of prior art, a kind of method of the TS-1 of preparation molecular sieve is provided, make that the TS-1 molecular sieve cost of preparing is lower and preparation process is comparatively simple.
The characteristics of method provided by the present invention are that the cheap solid silicone bead of employing is the silicon source, with TPAOH (TPAOH) the aqueous solution soaking SiO that is dissolved with titanium
2Bead, make crystallization just carry out just can in synthetic system, adding the least possible water so fully on the solid-liquid interface until crystallization, make the organic bases that less input measures just can satisfy required basicity of synthesis of titanium silicon molecular sieve and template dosage, thereby reduce cost and simplify the operation.
The method of the TS-1 of preparation molecular sieve provided by the present invention is that the titanium source is dissolved in TPAOH (TPAOH) aqueous solution, and mix with the solid silicone bead and to obtain reaction mixture, with this reaction mixture in autoclave in 130～200 ℃ of hydrothermal crystallizings 1～6 day, filter according to a conventional method then, wash, drying and roasting, wherein the mole of said reaction mixture consists of:
Scope is preferred
SiO
2/TiO
2 5～220 10～150
TPAOH/SiO
2 0.03～0.5 0.05～0.4
H
2O/SiO
2 0.6～40 1～30
Said titanium source is hydrolyzable titanium compound in the method provided by the present invention, or the α-TiO that is obtained by the titanium compound hydrolysis
2, tetraalkyl titanate Ti (alkoxy) for example
4, TiCl
4, TiOCl
2, Ti (SO
4)
2, TiOSO
4Deng and their hydrolysate.Tetraalkyl titanate Ti (alkoxy) preferably wherein
4, the carbonatoms of alkyl wherein is 1～6.
The granularity of said solid silicone bead is 60～260 orders in the method provided by the present invention, and wherein preferred granularity is 80～200 orders.
The temperature of said hydrothermal crystallizing is 130～200 ℃ in the method provided by the present invention, and wherein preferred crystallization temperature is 150～180 ℃
The method for preparing the TS-1 molecular sieve provided by the present invention compared with prior art, the requirement of its condition control is so not strict complicated, preparation process is simpler, be easy in industrial application, raw material is inexpensive and be easy to get, and the consumption of organic bases reduces greatly, makes product cost reduce greatly, and, make output per single reactor obviously improve because the water consumption in the reaction system is few.
Fig. 1 is according to document Stud.Sci.Surf.Catal., 18,1984, X-ray diffraction (XRD) the crystalline phase figure of the pure silicon molecular sieve (Silicalite-1) that the described method of P159 makes with MFI structure, used instrument is Japanese D/Max-III A type of science, CuK α.
Fig. 2 is the XRD crystalline phase figure of example 1 resulting product.
Fig. 3 is infrared absorption spectrum (IR) figure of five kinds of samples, used instrument is Perkin-Elmer 580 twin-beam infrared spectrometers, wherein a represents Silicalite-1 sample recited above, and b, c, d, e are respectively resulting sample among the embodiment 2,1,3,4.
The following examples will the present invention is described further.In each of the embodiments described below, used solid SiO
2Bead is a Qingdao silica gel factory product, and TPAOH is that the Tokyo changes into product, and all the other reagent are commercially available chemically pure reagent.
Example 1
With 1.63g Ti (OC
4H
9)
4Be dissolved in the TPAOH aqueous solution of 13.29g 22wt% stirring and dissolving 30～50min at room temperature, add 7.83g 80～120 purpose silica gel beads (butt is 92%) then and stir, the mixture mole consists of:
SiO
2/TiO
2＝25，TPAOH/SiO
2＝0.12，H
2O/SiO
2＝5.08。
Said mixture changed over to have in the teflon-lined stainless steel cauldron, in 165 ℃ of crystallization after 3 days, filter according to a conventional method, wash, drying and roasting get zeolite product, its XRD spectra as shown in Figure 2, its crystalline phase and Silicalite-1 similar (Fig. 1), the relative crystallinity of sample are 90.3% (with respect to Silicalite-1, to be according to document Stud.Sci.Surf.Catal.18,1984, the method preparation of P159).The unexistent 960cm of Silicalite-1 has appearred on the IR spectrogram (Fig. 3) of sample
-1Charateristic avsorption band.
Example 2～4
With (2) 4.08g Ti (OC
4H
9)
4, (3) 0.68g Ti (OC
4H
9)
4, (4) 0.34g Ti (OC
4H
9)
4Be dissolved in respectively in the TPAOH aqueous solution of 13.29g 22wt.%, stir about 30min under the room temperature, respectively add 7.83g 80-120 purpose silica gel bead (butt is 92%) then, stir, three kinds of reaction mixture moles compositions are respectively:
TPAOH/SiO
2=0.12, H
2O/SiO
2=5.08, SiO
2/ TiO
2=(2) 10, (3) 60, (4) 120 with these three kinds of reaction mixtures in 165 ℃ of crystallization after 3 days, filter according to a conventional method, wash, drying and roasting, the relative crystallinity of three samples of gained is respectively: (2) 78.8%, 3) 92.8%, 4) 96.3%.960cm has all appearred on the IR of three samples spectrogram (see figure 3)
-1Charateristic avsorption band, this peak relative intensity increases along with the increase of product titanium content.
Example 5～7
With three parts of each 1.63g Ti (OC
4H
9)
4Be dissolved in respectively in the TPAOH aqueous solution of 7.31g40wt.%, stir 20min～40min under the room temperature, in these three parts of mixtures, respectively add 7.83g 80～120 purpose SiO
2Bead after stirring, adds (5) 0.0g distilled water respectively again, (6) 12.28g distilled water and (7) 25.24g distilled water, and the mole composition of three kinds of reaction mixtures is respectively:
SiO
2/TiO
2＝25，TPAOH/SiO
2＝0.12，H
2O/SiO
2＝(5)2.3、(6)8、(7)14
These three kinds of reaction mixtures in 170 ℃ of crystallization after 3 days, are filtered according to a conventional method, wash, drying and roasting, and the relative crystallinity of three kinds of samples of gained is respectively (5) 88.4%, and (6) 91.2%, (7) 80.4%.960cm has all appearred on the IR spectrogram of three kinds of samples
-1Charateristic avsorption band.
Example 8～10
With three parts of each 1.63g Ti (OC
4H
9)
4Be dissolved in (8) 3.65g 40%TPAOH respectively, (9) 10.96g 40%TPAOH in the aqueous solution of (10) 17.05g 40%TPAOH, stirs 20～30min in about 38 ℃, respectively adds 7.83g80～120 order SiO in three kinds of mixtures
2Bead (butt is 92%) stirs, and the mole of three kinds of reaction mixtures forms and crystallization condition is respectively: (8) SiO
2/ TiO
2=25, TPAOH/SiO
2=0.06, H
2O/SiO
2=1.3, in 4 days (9) SiO of 168 ℃ of crystallization
2/ TiO
2=25, TPAOH/SiO
2=0.18, H
2O/SiO
2=3.3, in 3 days (10) SiO of 150 ℃ of crystallization
2/ TiO
2=25, TPAOH/SiO
2=0.28, H
2O/SiO
2=5.03, in the product after 3 days crystallization of 160 ℃ of crystallization filter according to a conventional method, wash, after drying and the roasting, the relative crystallinity of three kinds of samples of gained is respectively: (8) 76.5%, (9) 91.7%, (10) 90.2%.960cm has all appearred on the IR spectrogram of three kinds of samples
-1Charateristic avsorption band.
Example 11
With 1.09g tetraethyl titanate Ti (OC
2H
4)
4Be dissolved in the 13.29g 22%TPAOH solution,, add 9.47g 100～200 order SiO then in 25 ℃ of stirring 40min
2Bead (butt is 76%) stirs, and the mole of gained reaction mixture consists of:
SiO
2/TiO
2＝25，TPAOH/SiO
2＝0.12，H
2O/SiO
2＝5.84。This mixture in 175 ℃ of crystallization after 2 days, is filtered according to a conventional method, washs, drying and roasting, and the relative crystallinity of gained sample is 89.6%.960cm has appearred on its IR spectrogram
-1Charateristic avsorption band.
Example 12～14
Respectively with (12) 0.65g TiOCl
2, (13) 0.91g TiCl
4, (14) 0.38g α-TiO
2(by Ti (SO
4)
2At NH
3.H
2In the O system after the hydrolysis after filtration, washing and dry and make) be dissolved in the TPAOH aqueous solution of three parts of each 10.96g40%, stir about 50min in 28 ℃, respectively add 7.83g 80-120 purpose silica gel bead (butt is 92%) then, add 4.02g water again, stir, the mole of three kinds of reaction mixtures is formed identical, for:
SiO
2/TiO
2＝25，TPAOH/SiO
2＝0.18，H
2O/SiO
2＝5.2，
Three kinds of reaction mixtures in 168 ℃ of crystallization after 5 days, are filtered according to a conventional method, wash, drying and roasting, and the relative crystallinity of three kinds of samples of gained is respectively (12) 90.8%, and (13) 89.3%, (14) 91.7%.960cm has all appearred on its IR spectrogram
-1Charateristic avsorption band.
Claims (8)
1. preparation method with HTS of MFI structure, it is characterized in that this method is that the titanium source is dissolved in TPAOH (TPAOH) aqueous solution, and mix with the solid silicone bead and to obtain reaction mixture, with this reaction mixture in autoclave in 130～200 ℃ of hydrothermal crystallizings 1～6 day, filter according to a conventional method then, wash, drying and roasting, wherein the mole of said reaction mixture consists of:
SiO
2/TiO
2＝5～220，
TPAOH/SiO
2＝0.03～0.5
H
2O/SiO
2＝0.6～40。
2. according to the preparation method of claim 1, wherein said titanium source is hydrolyzable titanium compound, or the α-TiO that is obtained by hydrolyzable titanium compound hydrolysis
2
3. according to the preparation method of claim 2, wherein said hydrolyzable titanium compound is tetraalkyl titanate Ti (alkoxy)
4, TiCl
4, TiOCl
2, Ti (SO
4)
2Or TiOSO
4
4. according to the preparation method of claim 3, the carbonatoms of the alkyl in the wherein said tetraalkyl titanate is 1～6.
5. according to the preparation method of claim 1, the granularity of wherein said solid silicone bead is 60～260 orders.
6. according to the preparation method of claim 5, the granularity of wherein said solid silicone bead is 80～200 orders.
7. according to the preparation method of claim 1, wherein the temperature of said crystallization is 150～180 ℃.
8. according to the preparation method of claim 1, wherein the mole of said reaction mixture consists of:
SiO
2/TiO
2＝10～150，
TPAOH/SiO
2＝0.05～0.4
H
2O/SiO
2＝1～30。
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Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0292363B1 (en) * | 1987-05-22 | 1993-04-21 | Rhone-Poulenc Chimie | Zeolites having an mfi-structure, based on silica and titanium oxide, and method for their synthesis |
| RU2140819C1 (en) * | 1993-12-23 | 1999-11-10 | Арко Кемикал Текнолоджи, Л.П. | TITANIUM-CONTAINING ZEOLITE, METHOD OF ITS PRODUCTION (Versions), METHOD OF EPOXIDATION OF OLEFINS AND DIQUATERNARY AMMONIUM COMPOUND FOR PRODUCTION OF TITANIUM-CONTAINING ZEOLITE |
| FR2715647B1 (en) * | 1994-01-28 | 1996-04-05 | Elf Aquitaine | Process for obtaining zeolites containing titanium. |
-
1996
- 1996-06-05 CN CN96106316A patent/CN1050584C/en not_active Expired - Lifetime
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