CN101935052A - Method for synthesizing titanium silicon zeolite material - Google Patents
Method for synthesizing titanium silicon zeolite material Download PDFInfo
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- CN101935052A CN101935052A CN2009101484627A CN200910148462A CN101935052A CN 101935052 A CN101935052 A CN 101935052A CN 2009101484627 A CN2009101484627 A CN 2009101484627A CN 200910148462 A CN200910148462 A CN 200910148462A CN 101935052 A CN101935052 A CN 101935052A
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Abstract
The invention relates to a method for synthesizing a titanium silicon zeolite material, which comprises the following steps of: adding all silicone zeolite and/or boron silicon zeolite in an alkaline aqueous solution, mixing uniformly, adding a titanium source, mixing uniformly, treating under hydro-thermal treatment conditions, and recovering the products to obtain the titanium silicon zeolite material. The method has the characteristics of low cost and good repeatability. Compared with the prior art, the obtained zeolite material has high oxidative activity in an oxidizing reaction and good selectivity of the target product.
Description
Technical field
The present invention relates to a kind of method of synthesis of titanium silicon zeolitic material.
Background technology
Ti-Si zeolite is the novel heteroatom zeolite that last century, early eighties began to develop.The TS-1 that MFI type structure is arranged that has synthesized at present, the TS-2 of MEL type structure, the MCM-22 of MWW type structure and have than the TS-48 of macroporous structure etc.The wherein Italian Enichem exploitation synthetic Ti-Si zeolite TS-1 of company is that the transition metal titanium is introduced formed a kind of new titanium-silicone zeolite with good catalytic selectivity oxidation susceptibility in the zeolite framework with ZSM-5 structure.TS-1 not only has the catalysed oxidn of titanium, but also has the shape effect selected and the advantages of excellent stability of ZSM-5 zeolite.Adopt Ti-Si zeolite as catalyzer, can the polytype organic oxidizing reaction of catalysis, as the epoxidation of alkene, the partial oxidation of alkane, the oxidation of alcohols, the hydroxylation of phenols, the ammonia oxidation of cyclic ketones etc.Because the TS-1 zeolite is in organic oxidizing reaction, can adopt free of contamination lower concentration hydrogen peroxide as oxygenant, oxidising process complex process and problem of environment pollution caused have been avoided, have unrivaled energy-conservation, economy of conventional oxidation system and advantages of environment protection, and have good reaction preference, therefore have great prospects for commercial application.Ti-Si zeolite is considered to a milestone in zeolite catalysis field as the organism catalyst for selective oxidation.
But at present the Ti-Si zeolite that obtains of synthetic method all exists active low, activity stability difference and easy problem such as inactivation.So, improving correlation method to improve the transformation efficiency of reaction, activity stability and anti-inactivation performance are the keys of titanium-silicon zeolite material research and development.
Summary of the invention
The present invention is directed to the deficiency that existing titanium-silicon zeolite material synthetic method exists, a kind of method of new synthesis of titanium silicon zeolitic material is provided.
Synthetic method provided by the invention is earlier zeolite to be joined mixing in the alkaline aqueous solution, adds titanium source mixing then and changes hydrothermal treatment consists in the reactor over to, filters, washs, is drying to obtain.
More particularly, method provided by the invention comprises: (1) joins in the alkaline aqueous solution zeolite evenly mixed, add titanium source and mixing then, obtain consisting of zeolite: titanium source: alkali source: water=100: (0.005～5.0): (0.005～2.0): the mixture of (200～10000), its mesolite and water are in gram, and alkali source and titanium source are in mole; (2) step (1) gained mixture is changed in the reactor, react under the hydrothermal treatment consists condition, reclaim product and promptly get titanium-silicon zeolite material.
Form in the step (1) and be preferably zeolite (gram): titanium source (mole): alkali source (mole): water (gram)=100: (0.01～5.0): (0.01～2.0): (500～5000).
Said zeolite is for being total silicon zeolite or borosilicate zeolite in the step (1), wherein the total silicon zeolite can be that Si-Al zeolite obtains through dealuminzation, benefit silicon, also can directly synthesize and obtain, the total silicon zeolite or the borosilicate zeolite that comprise all kinds structure, as S-1, S-2, BETA, MOR, MCM-22, MCM-41, SBA-15, MCM-48 etc., wherein be preferably S-1.
Said alkali source can be mineral alkali source and/or organic alkali source in the step (1).Wherein, the inorganic alkali source mixture that is selected from ammoniacal liquor, sodium hydroxide, potassium hydroxide, hydrated barta etc. or forms by them; The mixture that organic alkali source is selected from urea, quaternary ammonium hydroxide compounds, fat amine compound, alcamine compound or is made up of them.
The general formula of said quaternary ammonium hydroxide compounds is (R
1)
4NOH, R
1For having the alkyl of 1～4 carbon atom, preferred R
1Be propyl group.
The general formula of said fat amine compound is R
2(NH
2)
n, R
2Be selected from alkyl or alkylidene group, n=1 or 2 with 1～6 carbon atom; Said fat amine compound is ethamine, n-Butyl Amine 99, butanediamine or hexanediamine.
The general formula of said alcamine compound is (HOR
3)
mNH
(3-m), R wherein
3Be selected from alkyl with 1～4 carbon atom; M=1,2 or 3; Said alcamine compound is monoethanolamine, diethanolamine or trolamine.
Said titanium source is inorganic titanium salt or organic titanate, and preferred titanium source is an organic titanate.Inorganic titanium salt can be TiCl
4, Ti (SO
4)
2Perhaps TiOCl
2The general formula of organic titanate is Ti (OR
4)
4, R
4For having the alkyl of 1-6 carbon atom, preferably has the alkyl of 2～4 carbon atoms.
In method provided by the invention, the said hydrothermal treatment consists condition of step (2) is a hydrothermal treatment consists 2～360 hours under 80～200 ℃ of temperature and autogenous pressure, the process of said recovery product is well known to those skilled in the art, there is no special feature, generally include processes such as product washing, drying, roastings.
Method provided by the invention, template agent can reduce greatly, thereby the preparation cost of Ti-Si zeolite is reduced, and the preparation good reproducibility.In addition, present method can also prepare those and utilize direct synthetic method to be difficult to the Ti-Si zeolite for preparing, as BETA, ITQ-13, MCM-22 etc.
Simultaneously, method gained Ti-Si zeolite provided by the invention, effectively skeleton titanium amount increases.By investigating the infrared spectra of HTS, adopt 960cm
-1Place's absorption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550The relative titanium content that characterizes in the HTS skeleton is effective skeleton titanium amount, and the size that can be worth is in view of the above judged the relative titanium content in the skeleton, and value is big more to show that titanium content is high more relatively in the skeleton, the sample that the inventive method obtains, its I
960/ I
550Value is than the I of Comparative Examples
960/ I
550Value big (table 1) illustrates relative titanium content height.In oxidizing reaction, the selectivity of its catalytic oxidation activity, reaction product compared with prior art obviously improves, and has stability of catalytic activity (seeing embodiment 12,13) preferably simultaneously.
Description of drawings
(A) is X-ray diffraction (XRD) the crystalline phase figure of Comparative Examples 1 synthetic TS-1 sample among Fig. 1.
(B) is X-ray diffraction (XRD) the crystalline phase figure of embodiment 1 gained sample among Fig. 1.
(C) is X-ray diffraction (XRD) the crystalline phase figure of embodiment 2 gained samples among Fig. 1.
(a) is fourier infrared (FT-IR) spectrogram of Comparative Examples 1 synthetic gained TS-1 sample among Fig. 2.
(b) is fourier infrared (FT-IR) spectrogram of embodiment 1 gained sample among Fig. 2.
(c) is fourier infrared (FT-IR) spectrogram of embodiment 2 gained samples among Fig. 2.
(i) is ultraviolet-visible spectrum (UV-vis) spectrogram of Comparative Examples 1 synthetic gained TS-1 sample among Fig. 3.
(ii) ultraviolet-visible spectrum (UV-vis) spectrogram of embodiment 1 gained sample among Fig. 3.
(iii) ultraviolet-visible spectrum (UV-vis) spectrogram of embodiment 2 gained samples among Fig. 3.
Embodiment
Following embodiment will be further described the present invention, but therefore not limit the present invention.
Used reagent is commercially available analytical reagent among Comparative Examples and the embodiment.Used total silicon zeolite is by prior art Nature among the embodiment, 1978, and the method synthetic Silicalite described in the 512nd page of the Vol.271, i.e. S-1 zeolite sample.X-ray diffraction (XRD) the crystalline phase figure that carries out sample on Siemens D5005 type x-ray diffractometer measures, and gamma ray source is CuK α
0.5 °/min of sweep velocity, sweep limit 2 θ=4 °～40 °.The fourier infrared of sample (FT-IR) spectrogram is measured on Nicolet 8210 type Fourier infrared spectrographs, adopts KBr compressing tablet, test specification 400～1800cm under the vacuum
-1Sample solid ultraviolet-visible diffuse reflection spectrum (UV-vis) records test specification 200～800nm on Japanese SHIMADZU UV-3100 type ultraviolet-visual spectrometer.
Comparative Examples 1
The explanation of this Comparative Examples is according to the process of conventional synthesis of titanium silicon zeolite.By prior art Zeolites, 1992, the TS-1 sieve sample of the method preparation described in the 943rd～950 page of the Vol.12.
The positive tetraethyl orthosilicate of 22.5 grams is mixed with 7.0 gram TPAOH, and add 59.8 the gram distilled water, mix the back in normal pressure and 60 ℃ of following hydrolysis 1.0 hours, obtain the hydrating solution of positive tetraethyl orthosilicate, under vigorous stirring, add the solution of forming by 1.1 gram tetrabutyl titanates and 5.0 gram anhydrous isopropyl alcohols lentamente, the gained mixture was stirred 3 hours down at 75 ℃, obtain the clear colloid.This colloid is put into stainless steel cauldron, and constant temperature was placed 3 days under 170 ℃ temperature, obtained the mixture of crystallization product; This mixture is filtered, is washed with water to pH is 6～8, and in 110 ℃ of dryings 60 minutes, obtains the former powder of TS-1.With the former powder of this TS-1 in 550 ℃ of roasting temperatures 3 hours, the TS-1 molecular sieve.Its XRD crystalline phase figure is shown in Fig. 1 (A); The fourier infrared spectrogram shown in Fig. 2 (a), 960cm
-1Place's absorption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1; The ultraviolet-visible light spectrogram has stronger absorption band, and near 340nm absorption is arranged also shown in Fig. 3 (i) near wavelength is 210nm, illustrate that titanium has just partly entered skeleton, exists the part extra-framework titanium.
Embodiment 1
20 gram total silicon zeolite S-1 are joined in the TPAOH aqueous solution mix, add tetrabutyl titanate and mixing then, obtain mixture and consist of: total silicon zeolite (gram): titanium source (mole): alkali source (mole): water (gram)=100: 0.2: 0.2: 600.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 48 hours under 150 ℃ temperature and autogenous pressure, and gains are filtered, wash with water, after the seasoning, and 550 ℃ of following roastings 5 hours, promptly gets titanium-silicon zeolite material A.Its XRD crystalline phase figure is shown in Fig. 1 (B), and is similar with Comparative Examples; The fourier infrared spectrogram is shown in Fig. 2 (b), and is also similar with Comparative Examples, at 960cm
-1Near the unexistent infrared absorption peak of total silicon molecular sieve appears, show that titanium has entered framework of molecular sieve, 960cm
-1Place's absorption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1; The ultraviolet-visible light spectrogram as Fig. 3 (ii) shown in, near wavelength is 210nm, stronger absorption band is arranged in the ultraviolet-visible spectrum, and do not have to absorb near the 340nm, illustrate that titanium all enters skeleton, do not have the extra-framework titanium generation.
Embodiment 2
20 gram total silicon zeolite S-1 are joined in the aqueous sodium hydroxide solution mix, add metatitanic acid orthocarbonate and mixing then, obtain mixture and consist of: total silicon zeolite (gram): titanium source (mole): alkali source (mole): water (gram)=100: 5.0: 1.2: 3500.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 24 hours under 180 ℃ temperature and autogenous pressure, and gains are filtered, wash with water, after the seasoning, and 550 ℃ of following roastings 5 hours, promptly gets titanium-silicon zeolite material B.Its XRD crystalline phase figure is shown in Fig. 1 (C), and is similar with Comparative Examples; The fourier infrared spectrogram is shown in Fig. 2 (c), and is also similar with Comparative Examples, in the infrared spectrum at 960cm
-1Near the unexistent infrared absorption peak of total silicon molecular sieve appears, show that titanium has entered molecule screen frame (unit), 960cm
-1Place's absorption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1; The ultraviolet-visible light spectrogram as Fig. 3 (iii) shown in, near wavelength is 210nm, stronger absorption band is arranged in the ultraviolet-visible spectrum, and does not absorb near the 340nm, illustrate that titanium all enters skeleton, do not have the extra-framework titanium generation.
Embodiment 3
20 gram total silicon zeolite S-1 are joined in the TPAOH aqueous solution mix, add tetraethyl titanate and mixing then, obtain mixture and consist of: total silicon zeolite (gram): titanium source (mole): alkali source (mole): water (gram)=100: 2.0: 1.0: 1200.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 48 hours under 150 ℃ temperature and autogenous pressure, and gains are filtered, wash with water, after the seasoning, and 550 ℃ of following roastings 5 hours, promptly gets titanium-silicon zeolite material C.Near wavelength is 210nm, stronger absorption band is arranged in its ultraviolet-visible spectrum, and do not absorb near the 340nm, illustrate that titanium all enters skeleton, do not have extra-framework titanium to produce.Its infrared spectra 960cm
-1Place's absorption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1.
20 gram total silicon zeolite S-1 are joined in the potassium hydroxide aqueous solution mix, add tetrabutyl titanate and mixing then, obtain mixture and consist of: total silicon zeolite (gram): titanium source (mole): alkali source (mole): water (gram)=100: 3.0: 0.1: 4600.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 24 hours under 180 ℃ temperature and autogenous pressure, and gains are filtered, wash with water, after the seasoning, and 550 ℃ of following roastings 5 hours, promptly gets titanium-silicon zeolite material D.Near wavelength is 210nm, stronger absorption band is arranged in its ultraviolet-visible spectrum, and do not absorb near the 340nm, illustrate that titanium all enters skeleton, do not have extra-framework titanium to produce.Its infrared spectra 960cm
-1Place's absorption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1.
Embodiment 5
20 gram total silicon zeolite S-1 are joined in the butanediamine aqueous solution mix, add tetrabutyl titanate and mixing then, obtain mixture and consist of: total silicon zeolite (gram): titanium source (mole): alkali source (mole): water (gram)=100: 0.4: 1.5: 2000.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 120 hours under 120 ℃ temperature and autogenous pressure, and gains are filtered, wash with water, after the seasoning, and 550 ℃ of following roastings 5 hours, promptly gets titanium-silicon zeolite material E.Near wavelength is 210nm, stronger absorption band is arranged in its ultraviolet-visible spectrum, and do not absorb near the 340nm, illustrate that titanium all enters skeleton, do not have extra-framework titanium to produce.Its infrared spectra 960cm
-1Place's absorption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1.
Embodiment 6
20 gram total silicon zeolite SBA-3 are joined in the TPAOH aqueous solution mix, add TiCl then
4And mixing, obtain mixture and consist of: total silicon zeolite (gram): titanium source (mole): alkali source (mole): water (gram)=100: 2.5: 0.5: 2000.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 240 hours under 90 ℃ temperature and autogenous pressure, and gains are filtered, wash with water, after the seasoning, and 600 ℃ of following roastings 5 hours, promptly gets titanium-silicon zeolite material F.Near wavelength is 220nm, stronger absorption band is arranged in its ultraviolet-visible spectrum, and do not absorb near the 340nm, illustrate that titanium all enters skeleton, do not have extra-framework titanium to produce.Its infrared spectra 960cm
-1Place's absorption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1.
Embodiment 7
20 gram total silicon zeolite MCM-41 are joined in the n-Butyl Amine 99 aqueous solution mix, add tetrabutyl titanate and mixing then, obtain mixture and consist of: total silicon zeolite (gram): titanium source (mole): alkali source (mole): water (gram)=100: 2.0: 0.4: 1000.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 120 hours under 120 ℃ temperature and autogenous pressure, and gains are filtered, wash with water, after the seasoning, and 550 ℃ of following roastings 5 hours, promptly gets titanium-silicon zeolite material G.Near wavelength is 220nm, stronger absorption band is arranged in its ultraviolet-visible spectrum, and do not absorb near the 340nm, illustrate that titanium all enters skeleton, do not have extra-framework titanium to produce.Its infrared spectra 960cm
-1Place's absorption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1.
20 gram total silicon zeolite SBA-15 are joined in the TPAOH aqueous solution mix, add TiOCl then
2And mixing, obtain mixture and consist of: total silicon zeolite (gram): titanium source (mole): alkali source (mole): water (gram)=100: 0.1: 0.6: 1500.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 240 hours under 90 ℃ temperature and autogenous pressure, and gains are filtered, wash with water, after the seasoning, and 550 ℃ of following roastings 5 hours, promptly gets titanium-silicon zeolite material H.Near wavelength is 210nm, stronger absorption band is arranged in its ultraviolet-visible spectrum, and do not absorb near the 340nm, illustrate that titanium all enters skeleton, do not have extra-framework titanium to produce.Its infrared spectra 960cm
-1Place's absorption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1.
Embodiment 9
20 gram total silicon zeolite S-1 are joined in the trolamine aqueous solution mix, add Ti (SO then
4)
2And mixing, obtain mixture and consist of: total silicon zeolite (gram): titanium source (mole): alkali source (mole): water (gram)=100: 0.08: 0.05: 800.Put into reactor then, hydrothermal treatment consists is 320 hours under 130 ℃ temperature and autogenous pressure, and gains are filtered, wash with water, after the seasoning, and 550 ℃ of following roastings 5 hours, promptly gets titanium-silicon zeolite material I.Near wavelength is 210nm, stronger absorption band is arranged in its ultraviolet-visible spectrum, and do not absorb near the 340nm, illustrate that titanium all enters skeleton, do not have extra-framework titanium to produce.Its infrared spectra 960cm
-1Place's absorption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1.
Embodiment 10
20 gram total silicon zeolite BETA are joined in the diethanolamine aqueous solution mix, add tetrabutyl titanate and mixing then, obtain mixture and consist of: total silicon zeolite (gram): titanium source (mole): alkali source (mole): water (gram)=100: 0.05: 0.01: 520.Put into reactor then, hydrothermal treatment consists is 320 hours under 130 ℃ temperature and autogenous pressure, and gains are filtered, wash with water, after the seasoning, and 550 ℃ of following roastings 5 hours, promptly gets titanium-silicon zeolite material J.Near wavelength is 210nm, stronger absorption band is arranged in its ultraviolet-visible spectrum, and do not absorb near the 340nm, illustrate that titanium all enters skeleton, do not have extra-framework titanium to produce.Its infrared spectra 960cm
-1Place's absorption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1.
Embodiment 11
20 gram total silicon zeolite S-1 are joined in the tetraethyl ammonium hydroxide aqueous solution mix, add tetrabutyl titanate and mixing then, obtain mixture and consist of: total silicon zeolite (gram): titanium source (mole): alkali source (mole): water (gram)=100: 1.8: 1.8: 1800.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 72 hours under 180 ℃ temperature and autogenous pressure, and gains are filtered, wash with water, after the seasoning, and 550 ℃ of following roastings 5 hours, promptly gets titanium-silicon zeolite material K.Near wavelength is 210nm, stronger absorption band is arranged in its ultraviolet-visible spectrum, and do not absorb near the 340nm, illustrate that titanium all enters skeleton, do not have extra-framework titanium to produce.Its infrared spectra 960cm
-1Place's absorption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1.
Comparative Examples 2
The explanation of this Comparative Examples prepares the process of borosilicate zeolite according to routine.
The positive tetraethyl orthosilicate of 22.5 grams is mixed with 7.0 gram TPAOH, and add 59.8 the gram distilled water, mix the back in normal pressure and 60 ℃ of following hydrolysis 1.0 hours, obtain the hydrating solution of positive tetraethyl orthosilicate, under vigorous stirring, add lentamente by 0.8 gram boric acid, after treating to mix fully, continuation was stirred 1 hour down at 60 ℃, put it into stainless steel cauldron then, constant temperature was placed 3 days under 170 ℃ temperature, obtained crystallization product, filtered, washed with water, and, obtain the borosilicate zeolite powder in 110 ℃ of dryings 60 minutes.With this former powder in 550 ℃ of roasting temperatures 3 hours, borosilicate zeolite DB-2.Its infrared spectra 960cm
-1Place's absorption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1.
20 gram borosilicate zeolites are joined in the tetraethyl ammonium hydroxide aqueous solution mix, add tetrabutyl titanate and mixing then, obtain mixture and consist of: borosilicate zeolite (gram): titanium source (mole): alkali source (mole): water (gram)=100: 2.0: 1.5: 1000.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 48 hours under 170 ℃ temperature and autogenous pressure, and gains are filtered, wash with water, after the seasoning, and 550 ℃ of following roastings 5 hours, promptly gets titanium-silicon zeolite material L.Near wavelength is 210nm, stronger absorption band is arranged in its ultraviolet-visible spectrum, and do not absorb near the 340nm, illustrate that titanium all enters skeleton, do not have extra-framework titanium to produce.Its infrared spectra 960cm
-1Place's absorption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1.
Embodiment 13
20 gram borosilicate zeolites are joined in the diethanolamine aqueous solution mix, splash into an amount of TiCl then
4And mixing, obtain mixture and consist of: borosilicate zeolite (gram): titanium source (mole): alkali source (mole): water (gram)=100: 0.5: 0.1: 500.Put into reactor then, hydrothermal treatment consists is 96 hours under 140 ℃ temperature and autogenous pressure, and gains are filtered, wash with water, after the seasoning, and 550 ℃ of following roastings 5 hours, promptly gets titanium-silicon zeolite material M.Near wavelength is 210nm, stronger absorption band is arranged in its ultraviolet-visible spectrum, and do not absorb near the 340nm, illustrate that titanium all enters skeleton, do not have extra-framework titanium to produce.Its infrared spectra 960cm
-1Place's absorption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1.
Table 1
| Sample source | Sample number into spectrum | I 960/I 550 |
| Embodiment 1 | A | 0.727 |
| Embodiment 2 | B | 0.724 |
| Embodiment 3 | C | 0.721 |
| Embodiment 4 | D | 0.726 |
| Embodiment 5 | E | 0.722 |
| Embodiment 6 | F | 0.716 |
| Embodiment 7 | G | 0.724 |
| Embodiment 8 | H | 0.718 |
| Embodiment 9 | I | 0.719 |
| Embodiment 10 | J | 0.717 |
| Embodiment 11 | K | 0.723 |
| Embodiment 12 | L | 0.704 |
| Embodiment 13 | M | 0.692 |
| Comparative Examples 1 | DB-1 | 0.678 |
| Comparative Examples 2 | DB-2 | 0.634 |
By table 1 as seen, the sample I of the inventive method preparation
960/ I
550Value is than the I of Comparative Examples
960/ I
550Value is big, and the relative titanium content height of sample of the inventive method preparation is described.
Embodiment 14
Present embodiment explanation TS-1 sieve sample is used for the effect of the catalytic oxidation of phenol hydroxylation.
With the foregoing description 1-13 and 1,2 synthetic samples of Comparative Examples according to sample: phenol: the weight ratio of acetone=1: 20.0: 16.0 mixes in a there-necked flask that has a prolong, be warming up to 80 ℃, then under whipped state according to phenol: it is 27.5% hydrogen peroxide that the weight ratio of hydrogen peroxide=1: 0.39 adds concentration, reaction is 2 hours under this temperature, the product of gained reaction product distributes and measures through the Varian3400 chromatographic instrument, and (30m * 0.25mm) is OV-101 to capillary column.The results are shown in Table 2.
Table 2
| Sample source | Sample number into spectrum | Phenol conversion % | Dihydroxy-benzene selectivity % |
| Embodiment 1 | A | 20.4 | 92.8 |
| Embodiment 2 | B | 19.3 | 92.4 |
| Embodiment 3 | C | 18.8 | 92.2 |
| Embodiment 4 | D | 19.5 | 93.5 |
| Embodiment 5 | E | 19.5 | 91.7 |
| Embodiment 6 | F | 18.3 | 92.4 |
| Embodiment 7 | G | 19.8 | 91.9 |
| Embodiment 8 | H | 20.2 | 92.2 |
| Embodiment 9 | I | 18.5 | 92.5 |
| Embodiment 10 | J | 18.3 | 91.6 |
| Embodiment 11 | K | 21.0 | 93.4 |
| Embodiment 12 | L | 16.1 | 91.1 |
| Embodiment 13 | M | 17.6 | 90.2 |
| Comparative Examples 1 | DB-1 | 8.6 | 84.8 |
| Comparative Examples 2 | DB-2 | 1.4 | 91.3 |
As can be seen from Table 2: the inventive method synthetic sample, its phenol hydroxylation activity is apparently higher than the sample of Comparative Examples, selectivity also increases to some extent, illustrates that its catalytic oxidation activity of sample of synthetic method gained provided by the invention and selectivity compared with prior art obviously improve.
Embodiment 15
Present embodiment explanation TS-1 sieve sample is used for the effect of the catalytic oxidation of ammoxidation of cyclohexanone.
With the TS-1 molecular sieve of gained among the embodiment 1 according to TS-1: the trimethyl carbinol: the weight ratio of 25% ammoniacal liquor=1: 7.5: 7.5 mixes in slurry bed, be warming up to 80 ℃ and under whipped state, add the mixture (volume ratio of water and hydrogen peroxide is 10: 9) of the hydrogen peroxide of entry and 30% with 5.7 milliliters/hour speed, the mixture (volume ratio of the pimelinketone and the trimethyl carbinol is 1: 2.5) that adds the pimelinketone and the trimethyl carbinol with 10.5 milliliters/hour speed, adding the quality percentage composition with 5.7 milliliters/hour speed is 25% ammoniacal liquor, above-mentioned three bursts of streams are for adding simultaneously, simultaneously with the continuous discharging of corresponding speed, every 2 hours product sampling is analyzed with chromatogram after the stable reaction, the production rate gained of cyclohexanone-oxime the results are shown in Table 3.
Table 3
| First day average | Second day average | The 3rd day average | The 4th day average | |
| The production rate % of cyclohexanone-oxime | 83.7 | 86.1 | 91.5 | 90.8 |
The TS-1 molecular sieve through roasting of Comparative Examples 1 gained is carried out the ammoxidation of cyclohexanone reaction evaluating by above-mentioned identical method, every 1 hour product is carried out sampling analysis, the results are shown in Table 4 for gained.
Table 4
| The 2nd hour | The 6th hour | The 10th hour | |
| The production rate % of cyclohexanone-oxime | 58.7 | 38.5 | 31.9 |
Comparing result by table 3 and table 4 shows that the inventive method gained TS-1 molecular sieve has catalytic activity and activity stability preferably.
Claims (17)
1. the method for a synthesis of titanium silicon zeolitic material is characterized in that this method comprises the following steps:
(1) join in the alkaline aqueous solution total silicon zeolite and/or borosilicate zeolite evenly mixed, add titanium source and mixing then, obtain consisting of zeolite: titanium source: alkali source: water=100: (0.005～5.0): (0.005～2.0): the mixture of (200～10000), its mesolite and water are in gram, and alkali source and titanium source are in mole;
(2) mixture with step (1) gained changes in the reactor, handles and reclaims product under the hydrothermal treatment consists condition and obtain titanium-silicon zeolite material.
2. according to the process of claim 1 wherein that the said zeolite of step (1) is selected from one or more the mixture among S-1, S-2, BETA, MOR, MCM-22, MCM-41, SBA-15 and the MCM-48.
3. according to the process of claim 1 wherein that the said zeolite of step (1) is S-1.
4. according to the process of claim 1 wherein that the said alkali source of step (1) is inorganic alkali source and/or organic alkali source.
5. according to the method for claim 4, wherein inorganic alkali source is ammoniacal liquor, sodium hydroxide, potassium hydroxide, hydrated barta or the mixture be made up of them; Organic alkali source is urea, quaternary ammonium hydroxide compounds, fat amine compound, alcamine compound or the mixture be made up of them.
6. according to the method for claim 5, the general formula of wherein said quaternary ammonium hydroxide compounds is (R
1)
4NOH, R
1For having the alkyl of 1～4 carbon atom.
7. according to the method for claim 6, wherein said R
1Be propyl group.
8. according to the method for claim 5, wherein the general formula of said fat amine compound is R
2(NH
2)
n, R
2Be selected from alkyl or alkylidene group, n=1 or 2 with 1～6 carbon atom.
9. according to the method for claim 8, wherein said fat amine compound is ethamine, n-Butyl Amine 99, butanediamine or hexanediamine.
10. according to the method for claim 5, wherein the general formula of said alcamine compound is (HOR
3)
mNH
(3-m), R
3Be selected from alkyl, m=1,2 or 3 with 1～4 carbon atom.
11. according to the method for claim 10, wherein said alcamine compound is monoethanolamine, diethanolamine or trolamine.
12. according to the process of claim 1 wherein that the said titanium of step (1) source is inorganic titanium salt or organic titanate.
13. according to the method for claim 12, inorganic titanium salt wherein is TiCl
4, Ti (SO
4)
2Perhaps TiOCl
2
14. according to the method for claim 12, the general formula of organic titanate wherein is Ti (OR
4)
4, R
4Be selected from alkyl with 1-6 carbon atom.
15. according to the method for claim 14, wherein R
4Be selected from alkyl with 2～4 carbon atoms.
16. according to the process of claim 1 wherein that the said mixture of step (1) consists of zeolite: titanium source: alkali source: water=100: (0.01～5.0): (0.01～2.0): (500～5000).
17. according to the process of claim 1 wherein in the step (2) that said hydrothermal treatment consists condition is a hydrothermal treatment consists 2～360 hours under 80～200 ℃ of temperature and autogenous pressure.
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