CN104843733A - Preparation method of titanium silicalite molecular sieve in alkali metal ion coexistence system - Google Patents

Abstract

The invention provides a highly active titanium silicalite molecular sieve (TS-1) and its preparation method in an alkali metal ion coexistence system. The method mainly solves the problem of difficult preparation of highly active titanium silicalite molecular sieve catalysts in the alkali metal ion coexistence system through existing preparation technologies, and also solves the problems of low yield, low repeatability and low titanium content of the catalysts obtained through previous technologies. An anionic polymer is added to the titanium silicalite molecular sieve synthesis system to eliminate unfavorable influences of alkali metal ions in the system on the catalyst in order to realize high yield preparation of the highly active titanium silicalite molecular sieve. The method adopts industrial raw materials with low price effectively reduces the production cost of the titanium silicalite molecular sieve, and can be used for industrial production.

Description

The preparation method that a kind of HTS coexists in system at alkalimetal ion

Technical field

The invention belongs to material science, be specifically related to a kind of micropore titanium silicon molecular sieve with MFI structure and preparation method thereof.

Background technology

TS-1 HTS is Italian EniChem company in nineteen eighty-three research and develop a kind of have MFI skeleton structure, the heteroatomic micro porous molecular sieve of titaniferous (US 4,410,501).Based on the titanium center (Catal. Today, the 1993,18th volume, the 163rd page) of skeleton structure, TS-1 is to H ₂o ₂there is unique adsorption activity, selective catalytic oxidation can be carried out to multiple organic compound, preparation petrochemical complex and the very important oxygenatedchemicals of field of fine chemical (alcohol, ketone, aldehyde, acid, phenol, epoxy alkane etc.), pollution is not produced, therefore TS-1/H because its by product is water ₂o ₂oxidation system opens new era of green oxidation manufacture, and TS-1 HTS also becomes a milestone of molecular sieve and heterogeneous catalysis field.Because this catalytic oxidation system has important theory significance and industrial application value, therefore, since self-discovery, be one of study hotspot in molecular sieve and catalytic field about the research of HTS always.

Although TS-1 HTS has great potentiality in green catalysis oxidation, but the preparation of TS-1 is but difficult to control, synthesis condition is very harsh, and the TS-1 catalytic activity prepared by different experiments room greatly differs from each other, only have several companies such as Enichem technology and Sinopec to have the ability this catalyzer of stably manufactured, and the production cost of two technology is all high.The production cost of production technology rambunctious like this and superelevation, causes the widespread use of this new catalyst of TS-1 to be greatly limited.Therefore, in TS-1 synthesis, the research of influence factor and the scheme of effective reduction TS-1 production cost, be still the problem that this field is challenging and very popular so far.

The catalytic activity of HTS, depend on content (the J. Am. Chem. Soc. of framework titania to a great extent, 2008,130th volume, 10150th page), why difficult the synthesis of TS-1 HTS is controls, and is because titanium ion radius ratio silicon ion radius is large, causes titanium to be difficult to enter in the skeleton of silicon-dioxide.Affect a lot (petroleum journal (refining of petroleum) of factor that titanium enters skeleton, 1994,10th volume, the 37th page), comprise titanium source category, silicon source category, template consumption (TPAOH), alkali metal ion content measured (sodium ion, potassium ion etc.), the content of alcohol, pH value, crystallization temperature, stirs.Wherein topmost two disadvantageous effect factors are: the hydrolysis in (1) titanium source inevitably forms TiO ₂precipitation, stops Ti to enter skeleton; (2) existence of alkalimetal ion (sodium, potassium ion etc.) is unfavorable for that Ti enters skeleton and easily becomes anatase octahedrite.

For (1) individual influence factor, avoiding the formation of TiO ₂precipitation aspect, it is crucial that prevent from forming TiO in liquid preparation before crystallization ₂precipitation, for this problem, the US Patent No. 4 that Taramasso etc. reported for work first in nineteen eighty-three, 410, propose two kinds of main solutions in 501, one is the hydrolysis rate controlling titanium source (tetraethyl titanate) and silicon source (tetraethoxy), avoids TiO ₂the formation of precipitation; Another is by stoping titanium to aggregate into TiO with the complexing of hydrogen peroxide and titanium species ₂precipitation.Subsequently, more mate to make the hydrolysis rate in titanium source and silicon source, the people such as Thangaraj (J. Chem. Soc., Chem. Commun., 1992,123rd page) adopt the slower tetrabutyl titanate of hydrolysis rate to be distributed to inside Virahol, replace hydrolysis rate tetraethyl titanate faster, by the method for this improvement, the TS-1 that titanium content is higher can be obtained.High shining newly waits people (CN1084294C) to adopt TiCl ₃do titanium source, can TiO be avoided ₂formation.The people such as Jorda (Zeolites, the 1997,19th volume, the 238th page) and Chinese patent CN1245089A adopt TiF ₄do titanium source, effectively can avoid TiO equally ₂formation.

For the disadvantageous effect that (2) individual alkalimetal ion exists, the high purity reagent using alkali-free metal ion is terms of settlement main at present, but the existence of alkalimetal ion is difficult to avoid, especially in template TPAOH, some sodium potassium ion impurity of existence more or less.There is report to show (Stud. Surf. Sci. Catal., the 1991,69th volume, the 79th page), even if there is trace alkalimetal ion, titanium also can be hindered to enter framework of molecular sieve, even cause HTS complete deactivation.The people such as Davis (J. Catal., 1995, 151st volume, 77th page) do systematic research at alkalimetal ion in the affecting of HTS, find that alkalimetal ion can enter the finished product, catalyst activity is caused to reduce or complete deactivation, by the post-treating method of pickling, most alkalimetal ion can be removed, the catalytic activity of TS-1 can be recovered simultaneously, but, activity recovery is also the TS-1 catalyzer prepared for those under ultra-low-alkali concentration of metal ions (mol ratio Na/Si<0.01), to the TS-1 prepared under (mol ratio Na/Si>0.02) condition that alkalimetal ion concentration is slightly high, can only recuperation section active, therefore, the method of pickling can not meet the requirement of technical grade reagent, and repeatability is very poor.Chinese patent literature CN102320619A discloses a kind of synthetic method of titanium-silicon molecular sieve TS-1, matched by the control hydrolysis rate in silicon source and the hydrolysis rate in titanium source, the TS-1 molecular sieve prepared in case and there is certain catalytic activity can be deposited at alkalimetal ion, method is by silicon source, titanium source, template, alkalescence mineralizer and water prepare titanium Silica hydrogel in proportion, direct method or indirect method is adopted to introduce appropriate an alkali metal salt joining in glue process, then at 160 ~ 180 degree of lower hydrothermal crystallizings, again after filtration, washing, drying and roasting, obtain TS-1 molecular sieve.This method can join the depolymerization promoting silicon source in glue process, thus is conducive to titanium and enters skeleton and suppress the generation of amorphous hexa-coordinate extra-framework titanium, but still there is a large amount of extra-framework titaniums in the TS-1 molecular sieve prepared of this method.Patent documentation CN104229820A discloses using the composite organic bases aqueous solution as alkali source and template, and containing alkalimetal ion in alkali source, the composite organic bases aqueous solution is the aqueous solution of TPAOH and an alkali metal salt or alkali; In Ti-Si sol preparation process, add silicon sol, molar ratio of material is silicon source (a): titanium source (b): TPAOH (c): alkalimetal ion (d): water (e): Virahol (f): silicon sol (g)=1: 0.01 ~ 0.1: 0.05 ~ 0.5: 0.002 ~ 0.009: 40 ~ 90: 0.5 ~ 2: 0.01 ~ 0.2.Zeolite crystal obtained is in this way comparatively large and even, and certainly piles up for single-column shape, prepares in the application of propylene oxide have good catalytic activity and selectivity at catalyzing hydrogen peroxide propylene oxide.The basic metal introduction volume that this method limits is very low, is difficult to the requirement meeting other reagent of technical grade.

Be not difficult to find out, containing in the system of alkalimetal ion, be difficult to prepare highly active TS-1 molecular sieve, avoid using the raw material containing alkalimetal ion impurity to be current main terms of settlement, because template TPAOH (TPAOH) is containing more sodium, the alkalimetal ions such as potassium, the significant contributor bringing alkalimetal ion impurity into, therefore, a lot of scientist 4-propyl bromide (TPABr) replaces TPAOH to prepare TS-1, regulate basicity with ammoniacal liquor or organic amine simultaneously, develop the synthetic system (Journal of Molecular Catalysis of many alkali-free metal ions, 1998, 12nd volume, 436th page).Although TPABr and TPAOH has identical TPA positively charged ion, but it is often larger with the TS-1 crystalline size of TPABr synthesized by template, and the catalytic performance of TS-1 HTS can decline rapidly along with the increase of size, therefore, the TS-1 HTS poor activity prepared with TS-1 ratio TPAOH prepared by TPABr is a lot.

At present, about the disadvantageous effect of alkalimetal ion, there is no better terms of settlement, can only adopt not containing the high purity TPAOH template reagent of sodium potassium ion, even if industrial production is also like this, industrially prepare TPAOH by 4-propyl bromide by ion exchange method, the TPAOH obtaining alkali-free metal ion is more difficult, loaded down with trivial details purification & isolation step causes the expensive of TPAOH, it occupies high proportion (the Microporous Mesoporous Mater. of 96% in the synthesis material cost of TS-1, 2002, 150th volume, page 1), this is also the major cause that the TS-1 HTS adopting this high purity template to prepare holds at high price.

Document (ChemCatChem, the 2014,6th volume, the 2719th page) is reported for work, and introduces polyacrylic acid to regulate the mechanism of crystal growth of HTS, synthesized the high-activity titanium si molecular sieves of rich titanium in the preparation of HTS.But synthetic system is alkali-free metal ion, and polyacrylic Main Function uses as gel reagents.The present invention has expanded the kind of polymkeric substance further, and reaction system is expanded in the synthetic system containing alkalimetal ion.

summary of the invention:

The preparation method that the object of the invention there are provided a kind of high-activity titanium si molecular sieves (TS-1) and coexists in system at alkalimetal ion, the method mainly solves in existing technology of preparing the problem being difficult to obtain high-activity titanium silicalite molecular sieve catalyst in alkalimetal ion coexists system.Meanwhile, the present invention also solves the low-yield in conventional art in the lump, the problem of low repeatability and low titanium content.Significantly reduce the production cost of TS-1 molecular sieve from many aspects.

Key of the present invention is, by adding anionic polymer in Synthetic Systems of Titanium Silicalite, to carry out in elimination system alkalimetal ion to the disadvantageous effect of catalyzer, thus " one kettle way " realizes the preparation that high productivity prepares high-activity titanium si molecular sieves.

Method of the present invention comprises following steps:

1) under room temperature, titanium source is hydrolyzed in hydrogen peroxide, obtains stable titanium species, then, under constantly stirring, add the template TPAOH containing alkalimetal ion, stir after 10-30 minute, add silicon source, after By Hydrolysis At Room Temperature 4-12 hour, the alcohol volatilized in 60-80 degree water-bath, constantly supplements the moisture volatilizing and take away simultaneously, after alcohol is all evaporated completely, obtain settled solution;

2) in as above settled solution, add anionic polymer, after stirring, obtain reaction mixture;

3) transferred to by above-mentioned reaction mixture in band teflon-lined stainless steel cauldron, hydro-thermal reaction 0.5-7 days in 120-250 degree reaction baking oven, in reactor, solid is through being separated, washing, drying, then roasting, after 6 hours, obtains TS-1 HTS in 400-550 degree retort furnace.

In step 1), silicon source is tetraethyl orthosilicate or silicon sol; Titanium source is tetrabutyl titanate, tetraethyl titanate, titanium isopropylate, titanium tetrachloride or titanyl sulfate; Alkalimetal ion is lithium, sodium, potassium or cesium ion; The time of volatilization alcohol is 4-5 hour.

Step 2) in anionic polymer for containing carboxyl (-COOH), sulfonic acid (-SO ₃h),-sulfinic acid (-SOOH), thionothiolic acid (-COSH) functional group one or more polymkeric substance, or their salt, or their two kinds or more of mixture.Described anionic polymer comprises polyacrylic acid, polymethyl acrylic acid, polymaleic acid, polystyrolsulfon acid, acid-co-maleic acid, Styrene-acrylic copolymer, sodium polyacrylate, polyphenyl ammonium sulphonate, and the polymaleic anhydride that can be hydrolyzed the anionic polymer described in being formed in synthetic system, polymethyl acrylate, polyethyl acrylate, polyacrylamide, polymethylmethacrylate, and mixture Zeo-karb.

Step 2) described in the mol ratio of each component of reaction mixture be: alkalimetal ion/SiO ₂=0-0.6; SiO ₂/ TiO ₂=10-200; Template/SiO ₂=0.05-0.6; H ₂o/SiO ₂=5-80; Anionic polymer (number of monomers)/SiO ₂=0.02-1.0.

In step 3), hydro-thermal reaction can be static reaction, also can be the dynamic responses such as stirring, rotation.

The present invention is by adopting the method for anionic polymer additive, and eliminate the disadvantageous effect of alkalimetal ion, " one pot " method obtains highly active TS-1 molecular sieve, and in product, framework titania content is high, and almost do not have the outer titanium species of skeleton, productive rate is close to 100%; Preparation process is without the need to accurately controlling titanium source and silicon source hydrolysis matching problem, and technique is simple, reproducible.

Accompanying drawing explanation

The XRD figure of TS-1 HTS prepared by Fig. 1 embodiment 7 of the present invention.

The infrared spectrum (IR) of TS-1 HTS prepared by Fig. 2 embodiment 7 of the present invention.

The infrared spectrum (IR) of TS-1 HTS prepared by Fig. 3 embodiment 6 of the present invention.

The ultraviolet-visible spectrogram of TS-1 HTS prepared by Fig. 4 embodiment 7 of the present invention.

Embodiment

Further describe feature of the present invention below by example, but the present invention is not limited to following example.

Embodiment 1

First, tetrabutyl titanate (TBOT) is hydrolyzed in hydrogen peroxide, obtain stable titanium species, then under constantly stirring, add the template TPAOH solution of alkali-free metal ion, stir after 30 minutes, add silicon source TEOS, By Hydrolysis At Room Temperature is after 12 hours, TEOS and TBOT that volatilize in 80 degree of water-baths is hydrolyzed the alcohol generated, constantly supplement the moisture volatilizing and take away simultaneously, after alcohol is all evaporated completely (4 hours), the settled solution cool to room temperature obtained, the mol ratio of each component of gained reaction solution is: 1SiO ₂: 0.025TiO ₂: 0.45TPAOH:35H ₂o.After stirring, transfer in band teflon-lined stainless steel cauldron, stationary water thermal response 2 days in 170 degree of reaction baking ovens, in reactor, solid is through centrifugation, washing, and 100 degree dry, in 550 degree of retort furnaces, roasting, after 6 hours, obtains TS-1 HTS again.Figure and Fig. 1 is similar for its XRD crystalline phase, is MFI structure; Infrared spectrum and Fig. 2 similar, at 960 cm ^-1there is charateristic avsorption band, show that titanium enters framework of molecular sieve.

Embodiment 2

First, tetrabutyl titanate (TBOT) is hydrolyzed in hydrogen peroxide, obtain stable titanium species, then under constantly stirring, add the template TPAOH solution of alkali-free metal ion, stir after 30 minutes, add silicon source TEOS, By Hydrolysis At Room Temperature is after 12 hours, TEOS and TBOT that volatilize in 80 degree of water-baths is hydrolyzed the alcohol generated, constantly supplement the moisture volatilizing and take away simultaneously, after alcohol is all evaporated completely (4 hours), the settled solution cool to room temperature obtained, the mol ratio of each component of gained reaction solution is: 1SiO ₂: 0.05TiO ₂: 0.45TPAOH:35H ₂o.Then, add polyacrylic acid (PAA) toward this settled solution, addition is, PAA(number of monomers)/SiO ₂(mol ratio)=0.25.After stirring, transfer in band teflon-lined stainless steel cauldron, stationary water thermal response 2 days in 170 degree of reaction baking ovens, in reactor, solid is through centrifugation, washing, and 100 degree dry, in 550 degree of retort furnaces, roasting, after 6 hours, obtains TS-1 HTS again.Figure and Fig. 1 is similar for its XRD crystalline phase, is MFI structure; Infrared spectrum and Fig. 2 similar, at 960 cm ^-1there is charateristic avsorption band, show that titanium enters framework of molecular sieve.

Embodiment 3

PAA addition is, PAA(number of monomers)/SiO ₂(mol ratio)=0.45, the other the same as in Example 2, XRD crystalline phase figure and the Fig. 1 obtaining TS-1 molecular sieve is similar, is MFI structure; Infrared spectrum and Fig. 2 similar, at 960 cm ^-1there is charateristic avsorption band, show that titanium enters framework of molecular sieve.

Embodiment 4

Polyacrylic acid PAA is replaced to polystyrolsulfon acid, the other the same as in Example 3, XRD crystalline phase figure and the Fig. 1 obtaining TS-1 molecular sieve is similar, is MFI structure; Infrared spectrum and Fig. 2 similar, at 960 cm ^-1there is charateristic avsorption band, show that titanium enters framework of molecular sieve.

Embodiment 5

Polyacrylic acid PAA is replaced to maleic acid-acrylic acid copolymer, the other the same as in Example 3, XRD crystalline phase figure and the Fig. 1 obtaining TS-1 molecular sieve is similar, is MFI structure; Infrared spectrum and Fig. 2 similar, at 960 cm ^-1there is charateristic avsorption band, show that titanium enters framework of molecular sieve.

Embodiment 6

First, tetrabutyl titanate (TBOT) is hydrolyzed in hydrogen peroxide, obtain stable titanium species, then under constantly stirring, add the template TPAOH solution containing potassium ion, stir after 30 minutes, add silicon source TEOS, By Hydrolysis At Room Temperature is after 12 hours, TEOS and TBOT that volatilize in 80 degree of water-baths is hydrolyzed the alcohol generated, constantly supplement the moisture volatilizing and take away simultaneously, after alcohol is all evaporated completely (4 hours), the settled solution cool to room temperature obtained, the mol ratio of each component of gained reaction solution is: 1SiO ₂: 0.025TiO ₂: 0.45TPAOH:35H ₂o:0.05K ₂sO ₄.After stirring, transfer in band teflon-lined stainless steel cauldron, stationary water thermal response 2 days in 170 degree of reaction baking ovens, in reactor, solid is through centrifugation, washing, and 100 degree dry, in 550 degree of retort furnaces, roasting, after 6 hours, obtains TS-1 HTS again.Figure and Fig. 1 is similar for its XRD crystalline phase, is MFI structure; Infrared spectrum as shown in Figure 3, at 960 cm ^-1charateristic avsorption band almost disappear, show that framework titania content is very low, titanium does not enter framework of molecular sieve.

Embodiment 7

Add polyacrylic acid (PAA) toward the settled solution before hydro-thermal reaction, addition is, PAA(number of monomers)/SiO ₂(mol ratio)=0.45.Other is with embodiment 6, and the XRD phasor obtaining TS-1 molecular sieve as shown in Figure 1, is MFI structure; Infrared spectrum as shown in Figure 2, at 960 cm ^-1there is charateristic avsorption band, shown that titanium enters framework of molecular sieve.As shown in Figure 4, the absorption peak at 210 nm places is characteristic peaks of framework titania to uv-vis spectra, and the peak at the peak at 260 nm places and 330 nm places, be the outer titanium of skeleton and TiO respectively ₂characteristic peak, spectrogram shows, and the titanium species in gained TS-1 is mainly framework titania, does not almost have the formation of the outer titanium of skeleton and titanium dioxide.

Embodiment 8

Template TPAOH solution containing potassium ion is replaced to the template TPAOH solution containing sodium ion, and sodium ions content is, Na ₂sO ₄/ SiO ₂(mol ratio)=0.05.Other is with embodiment 7, and XRD phasor and Fig. 1 of obtaining TS-1 molecular sieve are similar, are MFI structure; Infrared spectrum (IR) is similar with Fig. 2, at 960 cm ^-1there is charateristic avsorption band, shown that titanium enters framework of molecular sieve, uv-vis spectra and Fig. 4 similar, illustrate that the titanium species in gained TS-1 is mainly framework titania, almost there is no the formation of the outer titanium of skeleton and titanium dioxide.

Embodiment 9

Sodium ions content is, Na ₂sO ₄/ SiO ₂(mol ratio)=0.2.Other is with embodiment 7, and XRD phasor and Fig. 1 of obtaining TS-1 molecular sieve are similar, are MFI structure; Infrared spectrum (IR) is similar with Fig. 2, at 960 cm ^-1there is charateristic avsorption band, shown that titanium enters framework of molecular sieve, uv-vis spectra and Fig. 4 similar, illustrate that the titanium species in gained TS-1 is mainly framework titania, almost there is no the formation of the outer titanium of skeleton and titanium dioxide.

Embodiment 10

Polyacrylic acid is replaced to Zeo-karb.Other is with embodiment 7, and XRD phasor and Fig. 1 of obtaining TS-1 molecular sieve are similar, are MFI structure; Infrared spectrum (IR) is similar with Fig. 2, at 960 cm ^-1there is charateristic avsorption band, shown that titanium enters framework of molecular sieve, uv-vis spectra and Fig. 4 similar, illustrate that the titanium species in gained TS-1 is mainly framework titania, almost there is no the formation of the outer titanium of skeleton and titanium dioxide.

Embodiment 11

The addition of PAA is, PAA(number of monomers)/SiO ₂(mol ratio)=0.35, other is with embodiment 7, and XRD phasor and Fig. 1 of obtaining TS-1 molecular sieve are similar, are MFI structure; Infrared spectrum (IR) is similar with Fig. 2, at 960 cm ^-1there is charateristic avsorption band, shown that titanium enters framework of molecular sieve, uv-vis spectra and Fig. 4 similar, illustrate that the titanium species in gained TS-1 is mainly framework titania, almost there is no the formation of the outer titanium of skeleton and titanium dioxide.

Embodiment 12

First, tetrabutyl titanate (TBOT) is hydrolyzed in hydrogen peroxide, obtain stable titanium species, then under constantly stirring, add the template TPAOH solution containing sodium, potassium ion, stir after 30 minutes, add the silicon sol of 30 wt.%, add PAA subsequently, stir, the mol ratio of each component of gained reaction solution is: 1SiO ₂: 0.025TiO ₂: 0.36TPAOH:35H ₂o:0.08KOH:0.03NaOH:0.45PAA (monomer).Gained reaction mixture is transferred in band teflon-lined stainless steel cauldron, stationary water thermal response 2 days in 170 degree of reaction baking ovens, and in reactor, solid is through centrifugation, washing, 100 degree dry, then roasting, after 6 hours, obtains TS-1 HTS in 550 degree of retort furnaces.Figure and Fig. 1 is similar for its XRD crystalline phase, is MFI structure; Infrared spectrum (IR) is similar with Fig. 2, at 960 cm ^-1there is charateristic avsorption band, shown that titanium enters framework of molecular sieve, uv-vis spectra and Fig. 4 similar, illustrate that the titanium species in gained TS-1 is mainly framework titania, almost there is no the formation of the outer titanium of skeleton and titanium dioxide.

Embodiment 13

Polyacrylic acid is replaced to polyacrylamide.Other is with embodiment 7, and XRD phasor and Fig. 1 of obtaining TS-1 molecular sieve are similar, are MFI structure; Infrared spectrum (IR) is similar with Fig. 2, at 960 cm ^-1there is charateristic avsorption band, shown that titanium enters framework of molecular sieve, uv-vis spectra and Fig. 4 similar, illustrate that the titanium species in gained TS-1 is mainly framework titania, almost there is no the formation of the outer titanium of skeleton and titanium dioxide.

Embodiment 14

Catalyzed reaction: by the TS-1 HTS 25 milligrams prepared in above-described embodiment, methyl alcohol 5 milliliters, n-hexylene 5 mmole, hydrogen peroxide 5 mmole of 30 wt.% 20 milliliters sealed reactor in, under constantly stirring, be heated to 60 degree, and maintain this thermotonus 2 hours.Products therefrom gas-chromatography characterizes its content.The results are shown in Table 1, in the synthetic system (embodiment 1-5) not containing alkalimetal ion, introduce anionic polymer of the present invention, effectively can improve the catalytic activity of TS-1, catalytic activity can improve more than twice.The synthetic system existed when there being alkalimetal ion, the TS-1 molecule prepared of traditional method (embodiment 6) substantially work does not have catalytic activity, and in anionic polymer system in the present invention (embodiment 7-12), catalytic activity hardly by the impact of alkalimetal ion in solution, can effectively can eliminate the disadvantageous effect of alkalimetal ion to molecular sieve.

Claims (8)

1. one kind has the preparation method of the HTS of MFI structure, it is characterized in that the method is mixed silicon source, titanium source, compound, template and water containing alkalimetal ion (Me), add anionic polymer wherein, obtain reaction mixture, by this reaction mixture in 120 ~ 250 DEG C water thermal crystallisation 0.5 ~ 7 day, reclaim product, wherein the mol ratio of each component of said reaction mixture is: Me/SiO ₂=0 ~ 0.6; SiO ₂/ TiO ₂=10 ~ 200; Template/SiO ₂=0.05 ~ 0.6; H ₂o/SiO ₂=5 ~ 80; Anionic polymer (number of monomers)/SiO ₂=0.02 ~ 0.1.

2. anionic polymer as claimed in claim 1, for containing carboxyl (-COOH), sulfonic acid (-SO ₃h), one or more polymkeric substance of-sulfinic acid (-SOOH), thionothiolic acid (-COSH) functional group, or comprise the multipolymer of other monomers, polyacrylic acid, polymaleic acid, polystyrolsulfon acid, acid-co-maleic acid, Styrene-acrylic copolymer, sodium polyacrylate, polyphenyl ammonium sulphonate.

3. anionic polymer as claimed in claim 1, comprise the anionic polymer (polymaleic anhydride, polymethyl acrylate, polyethyl acrylate, polyacrylamide, polymethylmethacrylate) generated by hydrolysis reaction, the polymkeric substance (liquid, solid-state, mixture) of various existence, the aqueous solution of anionic polymer and Zeo-karb.

4. the preferred tetraethyl orthosilicate in silicon source as claimed in claim 1 and silicon sol, optimum is tetraethyl orthosilicate.

5. titanium source as claimed in claim 1 is tetrabutyl titanate, tetraethyl titanate, titanium isopropylate, titanium tetrachloride and titanyl sulfate.

6. template as claimed in claim 1 is TPAOH.

7. alkalimetal ion as claimed in claim 1 is lithium, sodium, potassium, cesium ion, and the compound containing alkalimetal ion (Me) is the vitriol of alkalimetal ion, phosphoric acid salt, nitrate, oxyhydroxide, carbonate, supercarbonate, oxalate, one or more mixture muriatic.

8. crystallization condition as claimed in claim 1 is 120 ~ 150 degrees Celsius, static or Dynamic Hydrothermal crystallization 0.5 ~ 7 day.