CN101190793A - Method for synthesizing TS-1 molecular screen - Google Patents
Method for synthesizing TS-1 molecular screen Download PDFInfo
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- CN101190793A CN101190793A CNA2006101442141A CN200610144214A CN101190793A CN 101190793 A CN101190793 A CN 101190793A CN A2006101442141 A CNA2006101442141 A CN A2006101442141A CN 200610144214 A CN200610144214 A CN 200610144214A CN 101190793 A CN101190793 A CN 101190793A
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Abstract
A synthetic method of TS-1 molecular sieve is characterized in that: first mixing silicon source with titanium source, then mixing thereof with organo-alkali compound solution; under the ultrasonic agitation, the hydrolytic solution of silicon and titanium is acquired; then hydrothermally crystallizing the mixture in a reaction vessel and recycling to get TS-1 molecular sieve. The synthetic method can eliminate partial uneven concentration, leads the amount of TiO2 generated by self agglomeration after the hydrolysis of titanium source to be as little as possible and reduces the production of extra framework titanium. Compared with the prior art, the TS-1 molecular sieve synthesized by the method not only has better catalytic oxidation activity and selectivity but also has better stability of catalytic activity.
Description
Technical field
The present invention relates to a kind of synthetic method of HTS (TS-1) of the MFI of having structure.
Background technology
HTS is the novel hetero-atom molecular-sieve 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, and have than the TS-48 of macroporous structure etc.Wherein the TS-1 molecular sieve is that the transition metal titanium is introduced formed a kind of new titanium-silicone molecular sieve with good catalytic selectivity oxidation susceptibility in the framework of molecular sieve 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 molecular sieve.Because the TS-1 molecular sieve 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.
The synthetic method of TS-1 disclosed (GB 2071071A, USP 4410501) first by people such as gondola Marco Taramasso in 1981.This method is earlier synthetic a kind of silicon source, titanium source, organic bases (RN of containing
+) and/or basic oxide (Me
N/2O) reaction mixture, with this reaction mixture in autoclave in 130～200 ℃ of hydrothermal crystallizings 6～30 days, separate then, wash, dry, roasting and product.In becoming the glue process, the mixing solutions hydrolysising condition of estersil and titanium ester is very harsh, because the hydrolysis rate of the two does not match, the latter is higher than the former, and the speed that adds organic bases will produce the polymer of irreversible titanium slightly soon, and the polymer of these titaniums is difficult to enter skeleton in crystallization process, and be entrained in the middle of the molecular sieve with the form of extra-framework titanium, this part titanium both may stop up the duct, again can the catalytic decomposition hydrogen peroxide, and the waste starting material.
People such as Thangaraj think enter skeleton in the TS-1 molecular sieve that aforesaid method synthesizes effective titanium content seldom, so they disclose a kind of method (Zeolites that can effectively increase the synthetic TS-1 molecular sieve of titanium content in the skeleton in 1992,1992, Vol.12:943), it is said that the Si/Ti of the method gained molecular sieve that people such as Taramasso can be proposed is than dropping to 20 from 39.Promptly prior art has been done the improvement of three aspects: the one, adopting the slower butyl (tetra) titanate of hydrolysis rate is the titanium source, the 2nd, the titanium source is dissolved in the anhydrous isopropyl alcohol, the 3rd, adjust order of addition(of ingredients), the aqueous isopropanol in titanium source is joined in the estersil solution of hydrolysis.In the technology of existing synthesis of titanium silicon molecular sieve (as Zeolites, 1992, Vol.12:943) in, though the content that adopting improves one's methods can make the skeleton titanium improves, but fundamentally do not solve into the aggregation problem of titanium in the glue process, Same Way of different experiments chamber employing so far synthetic TS-1 of institute difference in quality is big just for this, even the performance of the synthetic different batches of same operator is also unstable, the major cause of poor repeatability.
Under the ultrasonic wave radiation, produce the collapse moment of countless small cavity bubbles in the medium, can emit great energy and huge pressure, promptly in medium, produce a series of extreme conditions that approach, as the high temperature of moment, high pressure etc., these energy have played light, electricity, the by the use of thermal means effect of being beyond one's reach in material is synthetic.Ultransonic cavatition is seen uniform mixing with the synthetic technology that the stirring of machinery is merged mutually with desired Jie of the narrow distribution nano-powder of easier realization particle, eliminates the partial concn inequality, can also play shearing action to coacervate simultaneously.In recent years; ultrasonic technology is as a kind of novel synthetic technology; being subjected to people just day by day pays close attention to; it has demonstrated great potential at chemistry and material aspect synthetic; for example; the report of the nano material of being applied on synthetic arranged, and (the big woods of state etc., " SCI " in August, 2002,1592～1594 pages are used for synthesis of nano TiO
2Ren Zhen etc., " chemical industry journal " in January, 2006,210～213 pages are used for synthesis of nano SiO
2Deng), have to be applied in the report (Wu Jianmei etc., " catalysis journal " in May, 2006,375～377 pages) that the MCM-49 Si-Al molecular sieve synthesizes; The report (intercalation bright great waves etc., " Chinese Journal of Inorganic Chemistry " in February, 2004,219～224 pages) that is applied in synthetic pure silicon mesopore molecular sieve is arranged.
Summary of the invention
In the process of synthetic TS-1 HTS, be with pure silicon molecular sieve or Si-Al molecular sieve difference, prevent the polymerization of titanium in becoming the glue process, prevent that promptly titanium is derived from the irreversible TiO of generation that reunites
2Be crucial.
Also do not find up to now ultrasonic technique be used for HTS, especially for the report of synthetic TS-1 molecular sieve.The inventor finds through a large amount of compound experiments, ultrasonic technique is introduced in the building-up process of TS-1, and the minimizing titaniums are derived to reunite and generate irreversible TiO in a large number
2, reduce the generation of extra-framework titanium.
Therefore, the objective of the invention is on the basis of existing technology, a kind of polymerization of titanium in becoming the glue process that prevent is provided, reduce the synthetic method of the TS-1 molecular sieve of extra-framework titanium generation.
The invention provides the synthetic method of TS-1 molecular sieve, it is characterized in that aqueous solution with silicon source, titanium source and organo-alkali compound, utilize the ultrasonic agitation technology to make it mixing, obtain the hydrating solution of silicon, titanium, then with gained mixture hydrothermal crystallizing in reactor, and reclaim the TS-1 molecular sieve that obtains.
In the method provided by the invention, the process of said aqueous solution with silicon source, titanium source and organo-alkali compound can preferably following step, after earlier silicon source and titanium source being mixed, with the aqueous solution of organo-alkali compound, ultrasonic agitation obtains then again.
In the method provided by the invention, the hydrating solution of said silicon titanium, its mole consists of the silicon source: titanium source: organic bases: water=1: (0.001～0.5): (0.001～0.80): (5～150), preferred 1: (0.005～0.5): (0.05～0.5): (10～100), wherein, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter.
In the method provided by the invention, said ultrasonic agitation is meant utilizes ultrasonic wave and mechanical stirring to make it mixing, promptly utilizes synthetic technology that ultransonic cavatition and mechanical stirring merge mutually to make it the technology of mixing.
In the method provided by the invention, said silicon source is silica gel, silicon sol or organosilicon acid esters, wherein preferred organic silicon ester.Its general formula of organosilicon acid esters is R
1 4SiO
4, R wherein
1Be preferably alkyl, be more preferably ethyl with 1～4 carbon atom.
In the method provided by the invention, said titanium source is inorganic titanium salt or organic titanate, wherein preferably has organic titanate.Said inorganic titanium salt can be TiCl
4, Ti (SO
4)
2Perhaps TiOCl
2Its general formula of said organic titanate is Ti (OR
2)
4, R wherein
2For having the alkyl of 1～6 carbon atom, preferably has the alkyl of 2～4 carbon atoms.
In the method provided by the invention, said organo-alkali compound is a TPAOH, perhaps the mixture formed of TPAOH and fat amine compound or alcamine compound.
Its general formula of said fat amine compound is R
3(NH
2)
n, R wherein
3Be alkyl or alkylidene group with 1～4 carbon atom, n=1 or 2, wherein preferred fat amine compound is ethamine, n-Butyl Amine 99, butanediamine or hexanediamine.
Its general formula of said alcamine compound is (HOR
4)
mNH
(3-m)R wherein
4For having the alkyl of 1～4 carbon atom, m=1,2 or 3, wherein preferred alcamine compound is monoethanolamine, diethanolamine or trolamine.
In the method provided by the invention, said hydrothermal crystallization process is known by those of ordinary skill in the art, normally mixture is handled 2～360 hours, preferred 10～240 hours under 80～200 ℃, preferred 80～180 ℃ of autogenous pressures in sealed reactor.
The synthetic method of TS-1 molecular sieve provided by the invention has following advantage:
1, earlier silicon source and titanium source are mixed, utilize the silicon source with the titanium source diluting on the one hand, without materials such as other unnecessary solvents, reduce cost and environmental pressure, on the other hand, earlier with silicon source and titanium source mixing, can make in the hydrolyzed solution that obtains after the hydrolysis titanium, the silicon more homogeneous that distributes, make organic bases better play the effect of template, reduced expensive organic bases template agent, reduced synthetic cost.
2, utilize the ultrasonic agitation technology to eliminate partial concn inequality in the building-up process, the TiO that makes the titanium source reunite and generate
2As far as possible few, reduce the generation of extra-framework titanium, also impel silicon source and titanium source to combine with the organic bases template is better, (quality that is the TS-1 molecular sieve that obtains after the roasting accounts for the silicon source of input (with SiO to product yield by 72% bringing up to more than 88%
2The meter) and the titanium source (with TiO
2The per-cent of total mass meter)).
3, extra-framework titanium content obviously reduces in institute's synthetic molecular sieve, thereby its catalytic oxidation activity and selectivity are compared with prior art obviously improved, and has stability of catalytic activity preferably simultaneously.
Description of drawings
Fig. 1 (A) be Comparative Examples 1 by prior art (Zeolites, 1992, the Vol.12:943) X-ray diffraction of synthetic TS-1 sieve sample (XRD) crystalline phase figure.
Fig. 1 (B) is X-ray diffraction (XRD) the crystalline phase figure of embodiment 1 gained sample.
Fig. 1 (C) is X-ray diffraction (XRD) the crystalline phase figure of embodiment 2 gained samples.
Fig. 2 (a) be Comparative Examples 1 by prior art (Zeolites, 1992, Vol.12:943) fourier infrared (FT-IR) spectrogram of synthetic gained TS-1 sieve sample.
Fig. 2 (b) is fourier infrared (FT-IR) spectrogram of embodiment 1 gained sample.
Fig. 2 (c) is fourier infrared (FT-IR) spectrogram of embodiment 2 gained samples.
Fig. 3 (i) be Comparative Examples 1 by prior art (Zeolites, 1992, Vol.12:943) ultraviolet-visible spectrum (UV-vis) spectrogram of synthetic gained TS-1 sieve sample.
Fig. 3 (ii) is ultraviolet-visible spectrum (UV-vis) spectrogram of embodiment 1 gained sample.
Fig. 3 (iii) is ultraviolet-visible spectrum (UV-vis) spectrogram of embodiment 2 gained samples.
Embodiment
Following embodiment will be further described the present invention, but therefore not limit content of the present invention.
Used reagent is commercially available chemically pure reagent in embodiment and the Comparative Examples.
Used ultrasonic wave is KQ-100DE type numerical control supersonic cleanser (220 volts of operating voltage, 50 hertz that Kunshan Ultrasonic Instruments Co., Ltd. produces; 40 kilo hertzs of operating frequencies; 100 watts of ultrasonic electric power).
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 (λ=1.5418
), tube voltage 40kV, tube current 40mA, 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 (sample accounts for 1wt%), test specification 400～1400cm under the vacuum
-1
Sample solid ultraviolet-visible diffuse reflection spectrum (UV-vis) records on Japanese SHIMADZU UV-3100 type ultraviolet-visual spectrometer, with BaSO
4Be reference substance, test specification 200～1000nm.
Comparative Examples 1
This Comparative Examples is for pressing prior art Zeolites, 1992, method synthetic TS-1 sieve sample described in the 943rd～950 page of the Vol.12, being about to the positive tetraethyl orthosilicate of 22.5 grams mixes 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 the stainless steel sealed reactor, and constant temperature was placed 3 days under 170 ℃ temperature, obtained the mixture of crystallization product; This mixture is filtered, washes with water, and, obtain the former powder of TS-1 in 110 ℃ of dryings 60 minutes.With the former powder of this TS-1 in 550 ℃ of roasting temperatures 3 hours, the TS-1 molecular sieve.Yield is about 72%, and (quality that is the TS-1 molecular sieve that obtains after the roasting accounts for the silicon source of input (with SiO
2The meter) and the titanium source (with TiO
2The per-cent of total mass meter)).Its XRD crystalline phase figure is shown in Fig. 1 (A), and the fourier infrared spectrogram is shown in Fig. 2 (a), and the ultraviolet-visible light spectrogram is shown in Fig. 3 (i).Fig. 3 (i) has stronger absorption band near wavelength is 220nm, and near 340nm absorption is arranged also, illustrates that titanium has just partly entered skeleton, exists the part extra-framework titanium.
Embodiment 1
Join after earlier positive tetraethyl orthosilicate and tetrabutyl titanate being mixed that ultrasonic agitation mixes in the aqueous solution of TPAOH, the mol ratio of wherein positive tetraethyl orthosilicate, tetrabutyl titanate, TPAOH and water is 1: 0.04: 0.1: 15, obtained titanium, silicon hydrating solution in 2 hours at normal pressure and 40 ℃ of following ultrasonic agitation hydrolysis.This titanium, silicon hydrolyzed solution are put into the stainless steel sealed reactor, crystallization is 24 hours under 170 ℃ temperature and autogenous pressure, and the gained crystallization product is filtered, washes with water, and in 110 ℃ of oven dry 120 minutes, 550 ℃ of roasting temperatures 3 hours, obtain the TS-1 molecular sieve then.Yield is about 92%.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; The ultraviolet-visible light spectrogram as Fig. 3 (ii) shown in, near wavelength is 220nm, 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 2
Joining in the aqueous solution of TPAOH ultrasonic agitation after positive tetraethyl orthosilicate and tetrabutyl titanate mixed mixes and obtains titanium, silicon hydrating solution, the mol ratio of wherein positive tetraethyl orthosilicate, tetrabutyl titanate, TPAOH and water is 1: 0.1: 0.15: 75, this titanium, silicon hydrolyzed solution are put into the stainless steel sealed reactor, crystallization is 96 hours under 150 ℃ temperature and autogenous pressure, the gained crystallization product is filtered, washes with water, and in 110 ℃ of oven dry 120 minutes, 550 ℃ of roasting temperatures 3 hours, obtain the TS-1 molecular sieve then.Yield is about 90%.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 framework of molecular sieve; The ultraviolet-visible light spectrogram as Fig. 3 (iii) shown in, near wavelength is 220nm, 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
Joining in the aqueous solution of TPAOH and trolamine ultrasonic agitation after positive tetraethyl orthosilicate and tetrabutyl titanate mixed mixes and obtains titanium, the silicon hydrating solution, wherein positive tetraethyl orthosilicate, tetrabutyl titanate, TPAOH, the mol ratio of trolamine and water is 1: 0.05: 0.15: 0.15: 35, with this titanium, the silicon hydrolyzed solution is put into the stainless steel sealed reactor, crystallization is 48 hours under 170 ℃ temperature and autogenous pressure, the gained crystallization product is filtered, wash with water, and in 110 ℃ of oven dry 120 minutes, 550 ℃ of roasting temperatures 3 hours, obtain product then.Yield is about 89%.Through X-ray diffraction (XRD) and infrared spectra (IR) sign proof gained sample is the TS-1 molecular sieve, 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, there is not extra-framework titanium to produce.
Embodiment 4
Joining in the aqueous solution of TPAOH ultrasonic agitation after positive tetraethyl orthosilicate and tetraethyl titanate mixed mixes and obtains titanium, silicon hydrating solution, the mol ratio of wherein positive tetraethyl orthosilicate, tetraethyl titanate, TPAOH and water is 1: 0.04: 0.35: 55, this titanium, silicon hydrolyzed solution are put into the stainless steel sealed reactor, crystallization is 72 hours under 110 ℃ temperature and autogenous pressure, the gained crystallization product is filtered, washes with water, and in 110 ℃ of oven dry 120 minutes, 550 ℃ of roasting temperatures 3 hours, obtain product then.Yield is about 89%.Through X-ray diffraction (XRD) and infrared spectra (IR) sign proof gained sample is the TS-1 molecular sieve, 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, there is not extra-framework titanium to produce.
Embodiment 5
Joining in the aqueous solution of TPAOH and quadrol ultrasonic agitation after positive tetraethyl orthosilicate and tetrabutyl titanate mixed mixes and obtains titanium, the silicon hydrating solution, wherein positive tetraethyl orthosilicate, tetrabutyl titanate, TPAOH, the mol ratio of quadrol and water is 1: 0.1: 0.25: 0.4: 75, with this titanium, the silicon hydrolyzed solution is put into the stainless steel sealed reactor, crystallization is 24 hours under 190 ℃ temperature and autogenous pressure, the gained crystallization product is filtered, wash with water, and in 110 ℃ of oven dry 120 minutes, 550 ℃ of roasting temperatures 3 hours, obtain product then.Yield is about 88%.Through X-ray diffraction (XRD) and infrared spectra (IR) sign proof gained sample is the TS-1 molecular sieve, 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, there is not extra-framework titanium to produce.
Embodiment 6
Joining in the aqueous solution of TPAOH ultrasonic agitation after positive tetraethyl orthosilicate and tetraethyl titanate mixed mixes and obtains titanium, the silicon hydrating solution, add small cations tensio-active agent cetyl trimethylammonium bromide therebetween to promote hydrolysis, wherein positive tetraethyl orthosilicate, tetraethyl titanate, the mol ratio of TPAOH and water is 1: 0.4: 0.35: 95, with this titanium, the silicon hydrolyzed solution is put into the stainless steel sealed reactor, crystallization is 48 hours under 170 ℃ temperature and autogenous pressure, the gained crystallization product is filtered, wash with water, and in 110 ℃ of oven dry 120 minutes, 550 ℃ of roasting temperatures 3 hours, obtain product then.Yield is about 89%.Through X-ray diffraction (XRD) and infrared spectra (IR) sign proof gained sample is the TS-1 molecular sieve, 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, there is not extra-framework titanium to produce.
Embodiment 7
Joining in the aqueous solution of TPAOH and trolamine ultrasonic agitation after positive tetraethyl orthosilicate and tetraethyl titanate mixed mixes and obtains titanium, the silicon hydrating solution, wherein positive tetraethyl orthosilicate, tetraethyl titanate, TPAOH, the mol ratio of trolamine and water is 1: 0.05: 0.25: 0.35: 55, with this titanium, the silicon hydrolyzed solution is put into the stainless steel sealed reactor, crystallization is 48 hours under 160 ℃ temperature and autogenous pressure, the gained crystallization product is filtered, wash with water, and in 110 ℃ of oven dry 120 minutes, 550 ℃ of roasting temperatures 3 hours, obtain product then.Yield is about 88%.Through X-ray diffraction (XRD) and infrared spectra (IR) sign proof gained sample is the TS-1 molecular sieve, 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, there is not extra-framework titanium to produce.
Embodiment 8
Present embodiment explanation TS-1 sieve sample is used for the effect of the catalytic oxidation of phenol hydroxylation.
With the foregoing description 1-7 and 1 synthetic sample 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: the weight ratio of hydrogen peroxide=1: 0.39 adds the hydrogen peroxide that concentration is 27.5 heavy %, reaction is 3 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 1.
In table 1:
Table 1
From table 1 we as can be seen: the inventive method synthetic sample, its phenol hydroxylation activity is apparently higher than the sample of Comparative Examples 1, 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 9
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 heavy % 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 heavy % 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 of cyclohexanone-oxime is defined as follows, and gained the results are shown in Table 2.
Table 2
| First day average | Second day average | The 3rd day average | The 4th day average | |
| The production rate % of cyclohexanone-oxime | 85.96 | 87.31 | 91.22 | 90.73 |
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 3 for gained.
Table 3
| The 2nd hour | The 6th hour | The 10th hour | |
| The production rate % of cyclohexanone-oxime | 58.72 | 38.46 | 31.95 |
Comparing result by table 2 and table 3 shows that the inventive method gained TS-1 molecular sieve has catalytic activity and activity stability preferably.
Claims (15)
1. the synthetic method of a TS-1 molecular sieve, it is characterized in that ultrasonic agitation makes it mixing with the aqueous solution of silicon source, titanium source and organo-alkali compound, obtain the hydrating solution of silicon, titanium, then with gained mixture hydrothermal crystallizing in reactor, and reclaim the TS-1 molecular sieve that obtains.
2. according to the method for claim 1, the hydrating solution that it is characterized in that said silicon, titanium is after earlier silicon source and titanium source being mixed, and with the aqueous solution of organo-alkali compound, ultrasonic agitation obtains then again.
3. according to the method for claim 1, it is characterized in that the hydrating solution of said silicon, titanium, its mole consists of the silicon source: titanium source: organic bases: water=1: (0.001～0.5): (0.001～0.80): (5～150); Wherein, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter.
4. according to the method for one of claim 1～3, wherein said silicon source is silica gel, silicon sol or organosilicon acid esters.
5. according to the method for claim 4, wherein said organosilicon acid esters, its general formula are R
1 4SiO
4, R
1Be selected from alkyl with 1～4 carbon atom.
6. according to the method for one of claim 1～3, wherein said titanium source is inorganic titanium salt or organic titanate.
7. according to the method for claim 6, wherein said inorganic titanium salt is TiCl
4, Ti (SO
4)
2Perhaps TiOCl
2
8. according to the method for claim 6, wherein said its general formula of organic titanate is Ti (OR
2)
4, R
2Be selected from alkyl with 1～6 carbon atom.
9. according to the method for claim 8, wherein said R
2Be selected from alkyl with 2～4 carbon atoms.
10. according to the method for claim 3, the hydrating solution of wherein said titanium, silicon, its mole consists of the silicon source: titanium source: organic bases: water=1: (0.005～0.5): (0.05～0.5): (10～100).
11. according to the method for one of claim 1～3, wherein said organo-alkali compound is a TPAOH, perhaps the mixture of forming for TPAOH and fat amine compound or alcamine compound.
12. according to the method for claim 11, wherein said its general formula of fat amine compound is R
3(NH
2)
n, R
3Be selected from alkyl or alkylidene group, n=1 or 2 with 1～4 carbon atom.
13. according to the method for claim 12, wherein said fat amine compound is selected from ethamine, n-Butyl Amine 99, butanediamine or hexanediamine.
14. according to the method for claim 11, wherein said its general formula of alcamine compound is (HOR
4)
mNH
(3-m), R
4Be selected from alkyl, m=1,2 or 3 with 1～4 carbon atom.
15. according to the method for claim 14, wherein said alcamine compound is monoethanolamine, diethanolamine or trolamine.
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| CN102627293A (en) * | 2012-04-09 | 2012-08-08 | 华东师范大学 | Synthetic method of titanium-silicon molecular sieve TS-1 |
| CN102627292A (en) * | 2012-04-09 | 2012-08-08 | 华东师范大学 | Preparation method of TS-1 molecular sieve |
| CN103201030A (en) * | 2010-11-08 | 2013-07-10 | 国际壳牌研究有限公司 | Improvements relating to Fischer-Tropsch catalysts |
| CN103420392A (en) * | 2012-05-23 | 2013-12-04 | 中国石油化工股份有限公司 | Rare earth-containing titanium silicalite and preparation method and applications thereof |
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| CN1050584C (en) * | 1996-06-05 | 2000-03-22 | 中国石油化工总公司 | Method for preparing titanium-silicon molecular sieve (TS-1) |
| CN1245089A (en) * | 1998-08-18 | 2000-02-23 | 中国石油化工集团公司 | Process for preparing Ti-Si molecular sieve |
| CN1089279C (en) * | 1998-09-17 | 2002-08-21 | 中国石油化工集团公司 | Synthesis of titania-silica molecular sieve |
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Correction item: Patentee|Address|Co-patentee Correct: Sinopec Corp.|100029 Beijing City, Chaoyang District Hui Street No. 6|SINOPEC Research Institute of Petroleum Processin False: SINOPEC Research Institute of Petroleum Processin|100083 No. 18, Haidian District, Beijing, Xueyuan Road Number: 03 Volume: 27 |
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Correction item: Patentee|Address|Co-patentee Correct: Sinopec Corp.|100029 Beijing City, Chaoyang District Hui Street No. 6|SINOPEC Research Institute of Petroleum Processin False: SINOPEC Research Institute of Petroleum Processin|100083 No. 18, Haidian District, Beijing, Xueyuan Road Number: 03 Page: The title page Volume: 27 |
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Free format text: CORRECT: PATENTEE; ADDRESS; CO-PATENTEE; FROM: SINOPEC CORP. RESEARCH INSTITUTE OF PETROLEUM PROCESSING;100083 NO. 18, XUEYUAN ROAD, HAIDIAN DISTRICT, BEIJING TO: CHINA PETROCHEMICAL CO., LTD.;100029 NO. 6-A, HUIXIN EAST STREET, CHAOYANG DISTRICT, BEIJING; SINOPEC CORP. RESEARCH INSTITUTE OF PETROLEUM PROCESSING |