KR100978488B1 - Methods for Rapid Synthesis of High?Quality Titanosilicate Molecular Sieve - Google Patents

Abstract

The present invention comprises the steps of (a) preparing a reaction mixture comprising a silicon source (Si source), a titanium source (Ti source), a base, a source of alkalinity and water; And (b) hydrothermal reaction by adding heat to the reaction mixture to obtain a titanium-silicon-containing molecular sieve, and a high-quality titanium-silicon-containing molecular sieve. According to the process of the invention, it is possible to produce titanium-silicon-containing molecular sieves, in particular ETS-10, very quickly and economically. Titanium-silicon-containing molecular sieves prepared by the present invention have perfectly uniform size and smooth surface. The quality of titanate quantum wires in the titanium-silicon-containing molecular sieves of the present invention is very good.

Titanium-silicon-containing molecular sieve, ETS, silicon, titanium, zeolite, molecular sieve, hydrothermal reaction, organosilicon compound, TEOS, TMOS, titanate, quantum wire

Description

Methods for Rapid Synthesis of High-Quality Titanosilicate Molecular Sieve

The present invention relates to a process for the production of titanium-silicon containing molecular sieves and to high quality titanium-silicon containing molecular sieves.

ETS-10 is a unique zeolitic material with ~ 0.67 nm thick semiconductor titanate quantum wires [-O-Ti (O-) ₄ -O-] surrounded by nanoporous silica of 8 Å x 5 Å size [1- 4]. TiO ₃ ^{2 -} quantum wires exhibit length-dependent quantum confinement effects along the chain direction even at lengths greater than 50 nm. In addition, the exciton mass in the quantum wire chain direction (μ _z ) is calculated to be much smaller than the known InSb (0.014 m _e ) [6] and single-walled carbon nanotubes (0.019 m _e ) [7]. [5] This means that although titanate is an oxide, it has the potential that electron mobility is faster than single-walled carbon nanotubes as it becomes a quantum line.

Titanates of the above ETS-10 proton beam, in addition to the physical properties of interest, such as the ^{semiconductor, Pb 2 +, Cd 2+,} Cu 2 + , and selectively removing the metal ions harmful to the environment, with high affinity for Hg ^{2 +} [8-13], dehydration of t-butanol to isobutene [14], aldol condensation of acetone [15], oxidative dehydrogenation of cyclohexanol [16], carbon dioxide and propylene oxide It is used as a catalyst for various reactions such as carbonate formation [17] and n-hexane aromatization [18]. ETS-10 can also be used as a thin film material for solar cells [19] and fuel cells [20].

The above mentioned applications and important properties of ETS-10 are attributable to titanate quantum wires in molecular sieve structures. But still with high quality TiO ₃ ^{2 -} quantum wire Synthesis of ETS-10 has not been easy, and all the synthesis procedures known to date [2,4,5,21-43] require long crystallization times (> 24 h). Thus, a new method of synthesizing ETS-10 with high quality TiO ₃ ^{2 -} quantum wires in a short time has revealed important physical properties of TiO ₃ ^{2 -} quantum wires that have not yet been identified and contributed greatly to the application of ETS-10. Seems to do.

Numerous papers and patent documents are referenced and cited throughout this specification. The contents of cited papers and patent documents are incorporated herein by reference to more clearly explain the level of the technical field to which the present invention belongs and the content of the present invention.

The inventors have sought to develop a new method for economically synthesizing crystals of titanium-silicon containing molecular sieves of uniform size and shape with high quality TiO ₃ ^2- quantum wires. As a result, the present invention is completed by economically synthesizing high quality titanium-silicon-containing molecular sieves by using TiO ₂ nanoparticles as a titanium source, using an organosilicon compound as a silicon source, and controlling other reaction conditions. It became.

Accordingly, an object of the present invention is to provide a method for producing a titanium-silicon-containing molecular sieve.

Another object of the present invention is to provide a titanium-silicon-containing molecular sieve.

Other objects and advantages of the present invention will become more apparent from the following detailed description of the invention, claims and drawings.

According to one aspect of the present invention, the present invention provides a method for producing a titanium-silicon containing molecular sieve comprising the following steps:

(a) preparing a reaction mixture comprising a Si source, a Ti source, a source of alkalinity, a salt and water; And

(b) adding hydrothermal reaction to the reaction mixture to obtain a titanium-silicon containing molecular sieve.

According to another aspect of the present invention, the present invention provides a titanium-silicon-containing molecular sieve represented by the following general formula (1):

Formula 1

( M ^{n +} ) _x Ti _y Si _z O _{3y + 2z}

In the above general formula, M is at least one cation having a valence of n (preferably an alkali metal, alkaline earth metal or transition metal), x is 0.01-100 as the number content per unit cell of such cation, and y is per unit cell of titanium It is 0.01-100 as number content, and z is 0.01-100 as number content per unit cell of silicon.

The inventors have sought to develop a new method for economically synthesizing crystals of titanium-silicon containing molecular sieves of uniform size and shape with high quality TiO ₃ ^{2 -} quantum wires. As a result, the present invention is completed by economically synthesizing high quality titanium-silicon-containing molecular sieves by using TiO ₂ nanoparticles as a titanium source, using an organosilicon compound as a silicon source, and controlling other reaction conditions. It was.

The method of the present invention is described in detail by dividing each step as follows:

(a) Preparation of reaction mixture for the synthesis of titanium-silicon-containing molecular sieves

First, a reaction mixture is prepared for the synthesis of titanium-silicon-containing molecular sieves from a Si source, a Ti source, a source of alkalinity, a salt and water.

The silicon source used in the present invention is preferably an organosilicon compound, more preferably an organosilicon compound represented by the following general formula (1):

Formula 1

In the formula, R ₁ -R ₄ independently represent hydrogen, a halogen group, a C ₁ -C ₂₂ alkyl group or an alkoxy group, an aralkyl or an aryl group, and R ₁ -R ₄ represents one or more oxygen, nitrogen, sulfur or metal It may contain atoms.

Even more preferably the silicon source is an alkoxide or silicate of silicon, most preferably tetraethyl orthosilicate (TEOS).

One of the greatest features of the present invention is the use of TiO ₂ nanoparticles as the titanium source.

The term “nanoparticle” as used herein referring to TiO ₂ as the titanium source is 0.5-1000 nm, preferably 1-300 nm, more preferably 1-100 nm, even more preferably 1- 50 nm, even more preferably 1-20 nm, most preferably 1-10 nm. In addition, such titanium nanoparticles preferably have crystallinity of amorphous, anatase, rutile or brukite, and most preferably the titanium nanoparticles used in the present invention are anatase nanoparticles. to be. Since the rate of decomposition of TiO ₂ nanocrystals as a titanium source is a rate determining step in the synthesis of titanium-silica-based molecular sieves, smaller TiO ₂ nanoparticles cause shorter synthesis rates and higher quality titanium-silica-based molecular sieves Are manufactured.

The alkali source used in the present invention is preferably a metal hydroxide or ammonium hydroxide, and the ammonium hydroxide is represented by the following formula (2):

Formula 2

In the formula, R ₁ -R ₄ independently represent hydrogen, a halogen group, a C ₁ -C ₂₂ alkyl group or an alkoxy group, an aralkyl or an aryl group, and R ₁ -R ₄ represents one or more oxygen, nitrogen, sulfur or metal It may contain atoms.

More preferably, the alkali source used in the present invention is a hydroxide of alkali metal, most preferably sodium or potassium hydroxide. In the following specific examples sodium hydroxide was used. This alkali source maintains electrovalent neutrality in the reaction mixture and allows the pH to be adjusted in the basic range.

Salts used in the present invention are preferably compounds in which metal cations are paired with anions. In the examples below, potassium fluoride (KF), which is one of the halogen compounds of alkali metals, was used.

According to a preferred embodiment of the present invention, the molar ratio of reactants in the reaction mixture is a silicon source of 0.01-9.99, a salt of 0.01-9.99, an alkali of 0.01-9.99 and water of 50-1200 when the titanium source is 1. More preferably, the molar ratio of titanium source: silicone source: salt: alkaline source: water is 5-6: 0.5-2: 6-10: 0.5-2: 300-400.

(b) Hydrothermal Reactions for the Synthesis of Titanium-Silica Molecular Sieves

Heat is applied to the reaction mixture for a suitable time to obtain a titanium-silica-based molecular sieve.

The reaction of step (b) is typically hydrothermal.

In step (b) the reaction temperature and reaction time are not particularly limited. However, according to the present invention, titanium-silica-based molecular sieves can be produced for a short time even under mild conditions. Therefore, in the present invention, the hydrothermal reaction of step (b) is preferably at a temperature of 130-300 ° C, more preferably 180-230 ° C, even more preferably 190-220 ° C, most preferably about 200 ° C. Preferably 0.1-200 hours, more preferably 1-50 hours, most preferably 1-10 hours.

According to the present invention, high quality titanium-silica-based molecular sieves can be obtained even by such a shortened reaction time.

According to the method of the present invention, titanium-silicon-containing molecular sieves can be produced very quickly and economically. In addition, the titanium-silicon-containing molecular sieve prepared by the present invention has a perfectly uniform size and smooth surface of crystals, and the quality of the titanate quantum wire contained in the titanium-silicon-containing molecular sieve is excellent. .

According to a preferred embodiment of the invention, the finally obtained titanium titanium sieve zeolite is an ETS series molecular sieve, more preferably ETS-1, ETS-2, ETS-4, ETS-10 or ETS-14 And most preferably ETS-10.

Titanium-silicon-containing molecular sieve zeolites prepared by the present invention have perfectly uniform size and smooth surface.

In the titanium-silicon-containing molecular sieve of the present invention represented by the general formula (1), M is preferably an alkali metal, more preferably sodium, potassium, lithium or a mixture thereof, most preferably sodium, potassium or Mixtures thereof.

Generally, the titanium-silica-based molecular sieves of the ETS-10 series have a 724-840 cm ⁻¹ Raman band frequency and a Raman band width of 23-100 cm ⁻¹ , according to an embodiment of the present invention. The result has a 724 cm ⁻¹ Raman band frequency and a Raman band width of 23 cm ⁻¹ .

As described above, the relatively small Raman band frequency and Raman band width indicate that the quality of the titanate quantum wire contained in the titanium-silica-based molecular sieve of the present invention is very good.

The features and advantages of the present invention are summarized as follows:

(i) According to the method of the present invention, titanium-silica-based molecular sieves can be produced very quickly and economically.

(Ii) Titanium-silica-based molecular sieves produced by the present invention have perfect uniformity in size and smooth surface of crystals.

(Iii) The quality of the titanate quantum wire contained in the titanium-silica-based molecular sieve of the present invention is very excellent.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for describing the present invention in more detail and that the scope of the present invention is not limited by these embodiments in accordance with the gist of the present invention .

Example

Experiment method

Synthesis process

Tetraethyl orthosilicate (TEOS, source Si), 2-5 nm TiO ₂ nanoparticles, H ₂ SO ₄ , NaOH, KF, and H ₂ O each have a molar ratio of 5.5: 1: 2.2: 8.4: 1.43: 350 Gel consisting of was prepared according to the following procedure.

First, very small anatase nanoparticles (2-5 nm) were prepared from titanium isopropoxide [Ti (iPrO) ₄ ] and sulfuric acid (H ₂ SO ₄ ). To this end, concentrated H ₂ SO ₄ (36.0 g) and deionized distilled water (280.0 g) were added to a round-bottom flask containing Ti (iPrO) ₄ (45.6 g, Aldrich) at room temperature. As soon as the addition of concentrated H ₂ SO ₄ to Ti (iPrO) ₄ is a white solid sludge it was formed ttuin the yellow light from a Ti (iPrO) _4. After addition of water (280.0 g) the mixture turned into a clear pink solution. While the bright pink solution was boiled and refluxed for 60 minutes, the pink color faded and the solution gradually became cloudy. The turbidity is due to the formation of TiO ₂ anatase nanoparticles, in order to increase the yield of the nanoparticles, 70 mL of deionized distilled water was added to the solution, and the solution was further boiled and refluxed for 30 minutes. After the reaction, it was left to cool, and the white powder slowly precipitated. The white powder was separated using a centrifuge (yield = 3.8 g) and washed by centrifugation with deionized distilled water until the powder was neutral. X-ray powder diffraction pattern of the white powder was confirmed that the particles have a crystallinity of TiO ₂ anatase [5]. In addition, the size of the TiO ₂ anatase particles was 2-5 nm can be measured by transmission electron microscopy (TEM) [5].

To make the silicon source solution, add TEOS (Acros) to a solution consisting of NaOH (13.6 g), KF (3.5 g) and water (220.0 g) at room temperature and stir for 15-30 minutes to hydrolyze TEOS (46.8 A basic solution comprising g) was prepared.

To make a titanium source solution, TiO ₂ anatase nanoparticles (3.1 g) were added to a solution consisting of H ₂ SO ₄ (9.1 g) and deionized distilled water (35.0 g) at room temperature to disperse the acidic solution dispersed with the nanoparticles. Prepare and continue stirring the solution to maintain dispersion of the particles.

While stirring the silicon source solution vigorously, an acidic titanium source solution was slowly added dropwise using a glass dropper at room temperature. By the time most of the titanium source solution was added to the silicon source solution, a white gummy solid suddenly formed, with the remainder being a transparent solution. The rubbery solids and clear solution were placed in a Teflon-line autoclave and allowed to react at 200 ° C. for various times (5-48 h).

Measure

SEM images were obtained from FE-SEM (Hitachi S-4300) operated with an acceleration voltage of 20 kV. TEM images were obtained from JEOL JEM (4010) operated with an accelerating voltage of 400 kV. X-ray powder diffraction pattern was obtained from Rigaku D / MAX-2500 / pc. CP-MAS Solid ²⁹ Si using a solid state FT-NMR spectrometer (DSX 400 MHz, Bruker Analytische GmbH) owned by the Korea Basic Science Institute at Kyungpook National University. NMR spectra (magic angle spinning solid-state ²⁹ Si NMR spectra) were obtained. Record Raman spectra of titanium-silica-based molecular sieves obtained as a result of Raman measurement instrument consisting of Ar ⁺ ion laser (Spectra-Physics Stabilite 2017), Spectrometer (Horiba Jobin Yvon TRIAX 550) and CCD detector (Horiba Jobin Yvon Symphony) It was. At this time, the wavelength of light as an excitation energy was 514.5 nm. A Varian Cary 5000 UV-VIS-NIR spectrometer with an integrating sphere was used to record the Diffuse Reflectance UV-vis spectrum of the sample.

Experiment Results and Discussion

Scanning electron microscopy (SEM) images showed that the synthesized crystals all had a tetragonal pyramid structure with a size of ˜500 nm, and the surface of the crystal was observed to be smooth. (FIG. 1A). In addition, transmission electron microscopy (TEM) images showed that the crystal had a typical structure [2] of EST-10 (FIG. 1B). The X-ray powder diffraction pattern of the crystal (Fig. 1c) and CP-MAS solid ²⁹ Si NMR (Fig. 2a) also further confirmed that the crystal was a typical ETS-10 crystal. The Raman spectrum of the crystal (λ _ext = 514.5 nm) has a band width between 724 cm ^-1 and 23 cm ^-1 (the maximum width of the ring point at maximum, fwhm), which is the interatomic along the chain direction of Ti-O-Ti. Vibration patterns were shown (FIG. 2B). The UV-vis spectrum of the powder showed a band gap energy ( E _g ) of 4.00 eV, which was previously reported with a band gap energy of 300 nm size ETS-10 (4.03 eV) and a band gap energy of 2000 nm size ETS-10. (3.98 eV) [5]. This means that the average length of the titanate quantum wires embedded in the crystal of ETS-10 obtained as a result of the invention is longer than that of the 300-nm size ETS-10 but shorter than that of the 2000-nm size ETS-10. (FIG. 2C).

The experimental results thus clearly demonstrate that despite the short crystallization period (7 hr), the process described above can easily produce high quality ETS-10 crystals.

As the quality of titanate quantum wires decreases, it is known that the Raman band frequency shifts to the high frequency region and the band width (fwhm) widens [25, 45]. Conversely, as the quality of titanate quantum wires increases, the Raman band frequency shifts to the low frequency region and the band width fwhm narrows. By the way, it has been reported in the art so far, titanate proton in the ETS-10 ETS-10 has a frequency of a Raman band in the region of 724-800 cm ^-1, depending on its quality, 23-100 cm ^{- It} has been reported to have a band width in the region of ¹ [45, 49]. Thus, the lowest frequency and narrowest bandwidths observed so far are 724 and 24 cm ^−1, respectively (Table 1). In this regard, the 724 cm observed from the results of the present ^invention frequency and 23 (± 1) cm of the ^1-band width of ¹ means that there is not very good quality titanate both lines in the ETS-10 crystals synthesized by the present invention do. Table 1 summarizes the Raman frequency and the band width of the ETS-10 crystals observed in the prior art and the present invention.

In order to elucidate the relationship between the bandwidth and frequency of the Raman band, the inventors of the present inventors have performed a full , The band width of the Raman band was plotted against the frequency v of the Raman band (FIG. 3). For ETS-10 samples without significant damage (frequency below 780 cm −1), the plot shows a significant linear relationship between frequency and band width (FIG. 3). The results of the present invention, located in the plot, show that the frequency and band width are the smallest of those produced so far, indicating that the quality of the titanate quantum lines in the crystal is very high.

As listed in Table 2, titanium halides (TiCl ₃ , TiCl ₄ and TiF ₄ ) [2, 21-33, 41-42], sodium or ammonium hexafluorotitanate (M ₂ F ₆ Ti, M = Na or NH ₄ ) [4,39,51], titanium sulfate [34-38], titanyl sulfate [36], titanium tetraisopropoxide [5], and commercially available titanium dioxide (TiO ₂ ) [28, 33, 39-40, 43] have been used as a titanium source for the synthesis of ETS-10. Table 2 summarizes the silicon source, titanium source, reaction temperature and time used in the synthesis of ETS-10 crystals in the prior art and the present invention.

Of these, Ti0 ₂ is the most preferred because it is the least expensive, the most stable and the most manageable. In addition, when Ti0 ₂ is used as a titanium source, it is known that the production rate of ETS-10 is faster than that of other titanium sources [39,51], and the purity of the produced ETS-10 is relatively high. Widely used TiO ₂ sources include Degussa P25 (a mixture of 76% Ti0 ₂ anatase crystals with ~ 25 nm size and 24% Ti0 ₂ rutile crystals), commercial Ti0 ₂ pure anatase (~ 600 nm), and pure ruta There is one (~ 1 μm).

Liu and Thomas reported for the _{first time} that TiO ₂ is a good source of titanium for the synthesis of ETS-10, and that PTS can be used to synthesize ETS-10 perfectly [52]. Anderson and colleagues found that when Ti0 ₂ anatase crystals were used as the titanium source, the rate of decomposition of Ti0 ₂ anatase crystals was a rate determining step in the synthesis of ETS-10 [28]. Nevertheless, the quality of the titanate quantum wires contained in the ETS-10 synthesized by them was relatively low quality. Zhao and coworkers reported that using only anatase with a size of -600 nm, quartz as an impurity was synthesized in a mixture, while P25 was used to synthesize high-purity ETS-10 crystals [33, 39, 51]. They also reported that P25 is better than TiF ₄ , TiCl ₃ , (NH ₄ ) ₂ F ₆ Ti and ˜600 nm anatase to synthesize pure ETS-10 faster. The reaction time and temperature required for the synthesis were reported to be 42 hr [33] and 48 hr [52] at 200 ° C. for P25 and 24 hr at 230 ° C. for anatase of unspecified size [28,39,51].

Therefore, compared with the existing reports, the conditions of the present invention is very economical, because it is a very short time (7 hr) at a relatively low temperature (200 ℃). Since the degradation rate of the anatase crystals is the rate determining step of the synthesis of ETS-10 [28], the significantly short reaction time in the present invention is believed to be due to the use of small anatase nanoparticles (2-5 nm). Another prominent feature of the method developed by the inventors is that the size of the synthesized ETS-10 crystals is very uniform while the surface of the crystals is very smooth.

As the silicon source, silica silica (Ludox) [36, 41-43] such as sodium silicate [2, 4, 5, 21-40] and colloid is widely used, which is unique in that the present invention uses TEOS. The hydrolysis time of TEOS is important for the production of pure ETS-10 crystals, which is very economical and efficient in that high quality titanium-silica-based molecular sieves are synthesized even with some hydrolysis (FIG. 4).

The minimum hydrothermal reaction time required for pure ETS-10 synthesis is 7 hr. When the reaction time was reduced to 6 hr, only a small amount of ETS-10 crystals were synthesized. (FIG. 5). This rapid change from 0% to 100% yield in such a short time is an unprecedented and interesting phenomenon for ETS-10 synthesis.

As described above, specific parts of the present invention have been described in detail, and it is apparent to those skilled in the art that these specific technologies are merely preferred embodiments, and thus the scope of the present invention is not limited thereto. Therefore, the substantial scope of the present invention will be defined by the appended claims and equivalents thereof.

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1 is an SEM image (a), a TEM image (b) and an X-ray powder diffraction pattern of an ETS-10 crystal prepared by the method of the present invention.

2 is a MAS solid-state ²⁹ Si NMR spectrum (a), a Raman spectrum (λ _ext = 514.5 nm) (b) and a diffuse-reflective UV-vis spectrum (c) of an ETS-10 crystal prepared by the method of the present invention .

FIG. 3 is a plot of Raman band width (full width at half maximum, fwhm) versus Ti-O-Ti Raman frequency of a chain of ETS-10 samples of the literature described in Table 1. FIG. The number in the circle is the reference number.

4 is an X-ray powder diffraction pattern of the product obtained from gels of different hydrolysis times of TEOS.

5 is an X-ray powder diffraction pattern of the product obtained from gels of different reaction times.

Claims (10)

Method for preparing a titanium-silicon-containing molecular sieve comprising the following steps: (a) a reaction mixture comprising a silicon source represented by Formula 1, a Ti source having a particle size of 1-20 nm, a source of alkalinity, a salt, and water; Manufacturing; And (b) adding hydrothermal reaction to the reaction mixture to obtain a titanium-silicon containing molecular sieve: Formula 1

R ₁ -R ₄ in the above formula are independently of each other a C ₁ -C ₂₂ alkoxy group. delete The method of claim 1, wherein the titanium source is amorphous TiO ₂ nanoparticles, anatase TiO ₂ nanoparticles, rutile TiO ₂ nanoparticles, or Brukite TiO ₂ nanoparticles. . The method of claim 1, wherein the alkali source is a hydroxide of a metal or an ammonium hydroxide represented by the following Chemical Formula 2: Formula 2

In the formula, R ₁ -R ₄ independently represent hydrogen, a halogen group, a C ₁ -C ₂₂ alkyl group or an alkoxy group, an aralkyl or an aryl group, and R ₁ -R ₄ represents one or more oxygen, nitrogen, sulfur or metal It may contain atoms. The method of claim 1 wherein the salt is a compound wherein the metal cation is paired with an anion. The method of claim 1, wherein the molar ratio of the reactants in the reaction mixture is a silicon source of 0.01-9.99, a salt of 0.01-9.99, an alkali of 0.01-9.99, and water of 50-1200 with a titanium source of 1. The method of claim 1, wherein the hydrothermal reaction of step (b) is carried out for 0.1-200 hours at a temperature of 130-300 ℃. delete A titanium-silicon-containing molecular sieve represented by the following general formula (1) prepared by the method of any one of claims 1 or 3-7: Formula 1 (M ^{n +} ) _x Ti _y Si _z O _{3y + 2z} In the above general formula, M is at least one cation having a valence of n, x is 0.01-100 as the number content per unit cell of such cation, y is 0.01-100 as the number content per unit cell of titanium, and z is a unit of silicon The number content per cell is 0.01-100. delete

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