KR900009149B1 - Catalyst based on silicon titanium and gallium - Google Patents

Abstract

No content.

Description

Catalysts based on silicon, tartans and gallium and methods for their preparation

Figure 1 shows the I.R. spectrum.

2 is the I.R spectrum of ZSM-5.

3 shows I.R. of gallium-titanium-silicalite of Examples 1, 3, 4-7. spectrum.

4 is a graph showing the relationship between the SiO ₂ / TiO ₂ ratio and the SiO ₂ / Ga ₂ O ₃ ratio of the product obtained in Example 7.

6 is a relationship between gallium and zeolite replacement amounts in Example 7.

원자가의 양이온)를 사용하여 소성 무수물 형태로 구성한다.The present invention relates to a composite material comprising silicon, titanium and gallium oxide having a zeolite porous crystal structure and a method for producing the same. This material is structurally similar to the zeolite ZSM-5 published in U.S. Patent No. 3,702,886, with M _1n / O, SiO ₂ , Al ₂ O ₃ ie metal oxides, silica and alumina (where M =

Valent cations) in the form of calcined anhydride.

Other composites that are structurally interrelated with the Zeolite ZSM-5 are composed of calcined anhydride by SiO ₂ as disclosed in US Pat. No. 4,061,724 and also contain SiO ₂ and TiO ₂ as disclosed in BE-886,812. It is known to construct in the form of calcined anhydrides.

The findings of this time are the new synthetic geolites called titanium-gallium-silicalite, which are similar to silicalite and can be used as molecular sieves or as ion-exchange materials or as catalysts in the reactions below. . Cracking, selective formation, hydrogenation and dehydrogenation, oligomerization, alkylation, isomerization, dehydration from oxygen-containing organic compounds, selective oxidation and hydroxylation of organic substrates using H ₂ O ₂ (eg olefins, diolefins, alcohols) Hydroxylation of oxidation, aromatics, etc.).

The synthetic crystalline porous material of the present invention, including oxides of silicon, titanium and gallium, is represented by the following empirical formula when in the form of calcined anhydride:

pHGaO ₂ · qTiO ₂ · SiO ₂

는 0보다 크고 0.050과 같거나 이보다 작은 값이며,

는 0보다 크고 0.025와 같거나 이보다 작은 값이며 ; HGaO₂의 H⁺는 양이온으로 대체할 수 있다.here

Is a value greater than 0 and less than or equal to 0.050.

Is a value greater than 0 and less than or equal to 0.025; H ⁺ of HGaO ₂ can be replaced with a cation.

The transition from the cationic form to another cationic form is carried out according to conventional substitution methods known in the prior art.

The synthetic material of the present invention exhibits crystals when tested by X-rays.

This test is carried out with a powder-diffraction system equipped with an electronic pulse, calculation system using CuK-alpha radiation. To calculate the intensity, the height of the peak is measured and expressed as a percentage of the strongest peak.

의 아래의 값을 특징으로 한다(여기서

는 내측평면 거리임) :The main reflectance for the calcined anhydrous product is

It is characterized by the following values of

Is the inner plane distance):

(Where vs is very strong; s = strong; m = medium; mw = medium).

This diffraction spectrum is essentially similar to that of ZSM-5 and thus similar to other Zeolites that are structurally interrelated with ZSM-5 discussed at the beginning of this document.

(여기서

는 파장값)의 가장 대표적인 값을 특징으로 하는 I.R. 스펙트럼을 보여준다) .The material of the present invention is

(here

Shows the IR spectrum characterized by the most representative value of wavelength).

wn (㎝ ^-1 ) relative strength

1220-1230 w

1080-1110 s

965- 975 mw

795- 805 mw

550- 560 m

450-470 ms

Where s = strong; ms = medium-strong; m = medium; mw = medium-weak; w = weak.

In Fig. 1, the IR spectrum is released, where the abscissa represents the wavelength in cm ⁻¹ , and the ordinate represents the transmittance (%).

Such I.R. The spectra are similar to those of Zeolite published in BE-886, 812 and differ markedly from ZSM-5 (or similar structures) shown in FIG.

What can be observed in the spectra is that there is no band at 965-975 cm ⁻¹ , which is characteristic of the titanium-silicalite and titanium-gallium-dicalite of BE-886,812. In summary, the material presented here differs from ZSM-5 in US Pat. No. 3,702,586 due to both the empirical formula and the 1.R spectrum, and also the zeolite of BE-886, 812 because of the empirical formula.

In fact, ZSM-5 of US Pat. No. 3,702,886 can be used as a catalyst in reactions such as dehydration, cracking, selective formation, hydrogenation and dehydrogenation, oligomerization, alkylation, and isomerization from oxygen-containing organic compounds, but with organic matter and H ₂ O Reaction with ₂ (oxidation of hydroxylated olefins to make phenol diphenols) is inactive, while Zeolites BE-886, 812 are inactive in the first reaction and active in the final reaction; On the other hand, the Zeolites presented here are active in all the reactions discussed above.

A second object of the present invention is a preparation method for obtaining the synthetic crystalline porous material disclosed above.

This method is characterized by reacting silicon derivatives, titanium derivatives, gallium derivatives and nitrogenous organic bases in an aqueous environment and at least from room temperature to 200 ° C., wherein the reactant SiO ₂ / Ga ₂ O ₂ molar ratio is at least 100, in particular The molar ratio of SiO ₂ / TiO ₂ of the reactants is at least 5, in particular in the range of 15 to 25, and the molar ratio of H ₂ O / SiO _{2 in the} reactants is in the range of 10 to 100 and in particular in the range of 30 to 50. When there is one or more alkali- and / or alkaline-earth metal salts and / or hydroxides, the M / SiO ₂ molar ratio of the reactants, where M is an alkali and / or alkaline-earth metal cation, is 0.1 or less, in particular 0.01 or less Or equal to zero.

In the empirical formula of this material, gallium is represented in the form of HGaO ₂ , emphasizing that the material is in H ⁺ form. When discussing the ratio between the various reactants, the Ga ₂ O ₃ form is used for gallium, which is more useful.

The silicone derivative is selected from silica gel, silica sol and alkyl silicates, of which tetraethyl silicate is most preferred, and titanium derivatives are organic such as, for example, titanium halides, and also organic such as alkyl-titanic acids, in particular tetraethyl-titanic acid, for example titanium halides. Selected from titanic acid derivatives; Gallium derivatives are selected from, for example, salts thereof such as gallium halides, gallium nitrate and gallium hydroxide.

Nitrogen-based organic bases include alkylammonium hydroxides, in particular tetrapropyl-ammonium hydroxide.

When using tetrapropyl-ammonium hydroxide, the TPA ⁺ / SiO ₂ ratio of the reactants, where TPA is tetrapropyl-ammonium, ranges from 0.1 to 1, in particular from 0.2 to 0.4. This reactant is reacted by operation at a temperature in the range of 100 to 200 ° C. The reaction is carried out for a period of 1 hour to 5 days in the range of pH 9 to 14, especially in the range of pH 10 to 12.

According to another embodiment of the present invention, titanium-gallium-silicalite is in combination with amorphous oligomeric silica and has a molar ratio of amorphous oligomeric silica / titanium-gallium-silicalite in the range of 0.05 to 0.2. Titanium-gallium-silicalite crystals are bonded by crosslinking of Si-O-Si, and titanium-gallium-silicalite crystals containing microspherical silica have a diameter of 5 to 1000 µm. The process for the preparation of catalysts comprising binders is based on the use of aqueous tetraalkyl-ammonium hydroxides and aqueous silica solutions obtained by hydrolysis of tetraethyl-ortho-acid salts in aqueous solutions of tetraalkyl-acid salts, in particular tetraalkylammonium hydroxide.

The alkyl group in the tetraalkyl-ammonium moiety contains carbon atoms in the range of 1-5.

Hydrolysis is carried out in a liquid state at room temperature to 200 ° C. and 0.2 hours for 10 hours.

＞10과 같은 충분히 높은 pH값으로 존재한다. 매우 미세한 결정체가 있는 결정형의 티탄-갈륨-실리카라이트를 이 용액에 분산시킬때 결정체 표면은 매질의 알칼리성 때문에 부분적으로 부식되고 ; 이러한 상태는 용액속의 결정체의 표면과 올리고머 규산염 사이에 안정한 화학결합이 형성될때 도움을 준다. 분무 건조기로 이 현탁액을 급속히 건조하면, 물이 제거되고 동시에 올리고머에 가교결합이 생겨서 삼차원 격자로 형성된 미세구가 생기고 여기서 지얼라이트 결정체는 Si-O-Si-가교에 의해서 정밀하게 결합한다.In such solutions, the silica is in oligomeric form, for example

It is present at a sufficiently high pH value such as> 10. When dispersing the crystalline titanium-gallium-silicalite with very fine crystals in this solution, the crystal surface is partially corroded due to the alkalinity of the medium; This condition helps when a stable chemical bond is formed between the surface of the crystal in the solution and the oligomeric silicate. Rapid drying of this suspension with a spray drier removes water and at the same time crosslinks to the oligomer, resulting in microspheres formed into three-dimensional lattice, where the zeolite crystals are precisely bound by Si-O-Si-crosslinking.

Prior to use, the microspheres are first calcined under an inert medium (H ₂ , N _2, etc.) and then oxidized at a temperature between 150 and 700 ° C., in particular between 500 and 600 ° C.

The optimal concentration of the total solids (SiO ₂ , titanium-gallium-silicalite, TAA-OH) of the suspension to be sprayed is 10 to 40% by weight. By varying the solid concentration of this suspension and the size of the nebulizer, the average diameter of the resulting particles can be varied. As such, the diameter of the catalyst microspheres is varied within the range of 5 to 1000 μm to select the size that is most suitable for the specific use.

In order to better explain the present invention, the production method and application examples are disclosed as follows, but the present invention is not limited thereto.

Example 1

A solution consisting of 22.7 g of tetraethyl-titanate and 416 g of tetraethyl-mycotic acid, dissolving 6.1 g of Ga (NO ₃ ) ₃ .8H ₃ O in 70 g of C ₂ H ₅ OH and gently stirring the resulting solution. Add to

The clear alcoholic solution thus obtained is added with moderate stirring to 870 g of an aqueous solution of 14% tetrapropione-ammonium hydroxide. The mixture is kept stirring while heating until a clear solution of single phase is obtained. In addition, 700 g of demineralized water is added while stirring the mixture again for an hour. The mixture obtained here is placed in a stirring stainless steel pressure cooker and heated to a temperature of up to 170 ° C. under autogenous pressure. After maintaining this condition for 15 hours, the autoclave is cooled and the reaction mixture is drained. The resulting suspension is centrifuged and the solid is washed by re-dispersion and centrifugation, dried at 120 ° C. and calcined at 550 ° C. for 4 hours.

The product obtained is substituted in proton form according to known methods.

Chemical analysis shows that the anhydride product is of the composition: SiO ₂ / Ga ₂ O ₃ = 195.5, SiO ₂ / TiO ₂ = 54.2.

Powder X-ray diffraction analysis shows that this product is crystalline and has a ZSM-5 form structure. I.R. of this. The spectrum is shown in FIG.

Example 2-6

Five kinds were prepared in the same manner as in Example 1, in which the molecular analysis of the reaction mixture and the molecular composition of the obtained product are shown in Table 1 as shown in Table 1.

The crystallization time and temperature were changed in Examples 3 and 6. In particular, in Example 3, the crystallization reaction was performed at 190 ° C. for 3 hours, and in Example 6, it was performed at 100 ° C. for 5 days.

The reaction mixture prepared under the conditions described as disclosed in Example 2 did not crystallize but remained as an amorphous product in a jellyous concentration.

The products taken in Examples 3-6 are crystalline and show to be ZSM-5 type structures in X-ray diffraction analysis.

I.R. The spectrum is shown in FIG.

Example 7

A reaction mixture was prepared in the same manner as in Example 1 and the molar ratio thereof was as follows: SiO ₂ / TiO ₂ = 20; SiO ₂ / Ga ₂ O ₃ = 200; TPA / SiO ₂ = 0.3; H ₂ O / SiO ₂ = 40.

The only difference is that gallium nitrate is directly dissolved in 14% tetrapropyl-ammonium hydroxide solution and not in ethyl alcohol. The reaction mixture is placed in an autoclave and left for 15 hours at 170 ° C. under autogenous pressure. The discharged product is centrifuged, washed twice by re-dispersion and centrifugation, which is then dried at 120 ° C. for 1 hour and then calcined at 550 ° C. for 4 hours in known batches.

The product obtained in the form of calcined anhydride has the following chemical composition: SiO ₂ / TiO ₂ = 38.2; SiO ₂ / Ga ₂ O ₃ = 140.

In powder X-ray diffraction analysis, it can be seen that there is a ZSM-5 form of crystal structure and a small amount of crystal TiO ₂ (anatas type).

In Figure 3 I.R. The spectrum shows the gallium-titanium-silicalite of Examples 1 and 3-7.

In FIG. 4, the obtained product decreases with increasing SiO ₂ / Ga ₂ O ₃ ratio until the SiO ₂ / TiO ₂ ratio stabilizes at about 40-50 with respect to the SiO ₂ / Ga ₂ O ₃ ratio of 200 or more. I can see that.

5 shows how the relative intensity ratio varies between the bond band at 970 cm ⁻¹ (I ₁ ) and also at 550 cm ⁻¹ , which contributes to the structural titanium in the IR spectrum.

This strength ratio increases as the SiO ₂ / Ga ₂ O ₃ ratio increases and this fact shows that the titanium in the crystal lattice actually decreases as the gallium decreases.

FIG. 6 shows that the substitution amount of zeolite obtained is increased with increasing gallium value shown in chemical analysis; This indicates that the gallium found in chemical analysis is actually structural gallium.

Example 8

In this example, the catalyst of Example 1 with a binder is prepared.

Dissolved in 100 g of Ga (NO ₃ ) _{3 8} H ₂ O 1,050 C ₂ H ₅ OH and the solution so obtained was stirred in a solution consisting of 340.5 g of tetraethyl-tercarbonate and 6,240 g of tetraethyl-silicate with gentle stirring. Add.

The clear alcoholic solution thus obtained is added to 13,000 g of 14% aqueous tetrapropyl-ammonium hydroxide solution with moderate stirring. The mixture is kept stirring while heating until a clear solution of single phase is obtained. Also 10,500 g of demineralized water is added and the mixture is kept stirring for an hour. The resulting mixture is poured into a stirring stainless steel autoclave and heated up to 170 ° C. under autogenous pressure. Maintain this condition for 15 hours, then cool the autoclave and drain the reaction mixture. The suspension obtained is centrifuged and the solid is washed by re-dispersion and centrifugation.

550 g of tetraethyl-silicate is added to 590 g of 12% aqueous solution of tetrapropyl ammonium hydroxide with stirring and the resulting mixture is stirred at approximately 60 ° C. for 1 hour, then 2400 g of demineralized water is added, and the solution is then added for another hour. Stir and cool to approximately 25 ° C on the one hand.

Carefully disperse the 2050 g washed centrifuge cake as disclosed above for the clear solution thus obtained. This centrifugal cake contains approximately 70% zeolite by weight.

The resulting milky suspension is spray-dried (NIRO-ATOMIZER; disk-atomized; inlet air temperature 300 ° C; outlet air temperature 120 ° C; chamber diameter 1.5 m) to obtain dense microspheres. The average diameter is close.

The sprayed competitor is heated to 550 ° C. in the N ₂ band; Gradually change this zone from N ₂ to air; This product is further maintained at 550 ° C. for 2 hours in air.

The obtained solid has the following composition and molar ratio: SiO ₂ / Ga ₂ O ₃ = 217; SiO ₂ / TiO ₂ = 60.

Example 9

4 g of catalyst according to Example 4 and 60 ml of 1-octane in 1 ml octane are injected into a maintained pressure cooker and heated to 200 ° C. for 5 hours with stirring. After cooling, the suspension was filtered and the product analyzed by gas chromatography and mass spectrometry.

1-octene conversion: 18%

95% selectivity for dimers

Selectivity to trimers: 5%

Example 10

In a 1 liter steel autoclave equipped with a mechanical stirrer and temperature control system, 373 g of methanol, 4 g of catalyst according to Example 8, 5.0 g of benzene (as internal standard for gas-chromatographic analysis) and 45 g of 1-butene Inject. After adjusting the temperature to the reference value of 22 ° C, 20 ml of 33% (w / v) hydrogen peroxide was added to this suspension with vigorous stirring. This reaction is observed by taking a sample for analysis and filtering. Hydrogen peroxide is measured by iodine titration and the reaction product is measured in GLC equipped with a 1.8 m long column filled with Porcpak PS. After 45 minutes, the situation is as follows:

Converted H ₂ O ₂ 85%

1,2-epoxybutane: 0.0326 moles

1-methoxy-2-hydroxybutane: 0.0795 mol

2-Methodi-1-hydroxybutane: 0.0517 mol

Example 11

193 g of methanol and 4.0 g of the catalyst according to example 4 are injected into a pressure cooker of 1 liter of capacity and equipped with a mechanical stirrer temperature control system and a constant pressure control system. Add 11.2 g of 32% (w / w) H ₂ O ₂ to the vessel connected to the autoclave. Adjust the temperature to the reference value of 22 ° C, add propylene while stirring and raise the pressure to 300 KPa (this pressure is kept constant during the entire reaction time). Hydrogen peroxide is added all at once to this suspension of the pressure cooker.

This reaction is observed by taking a sample of the suspension, filtering and analyzing. Hydrogen peroxide is measured by iodine titration and the reaction product is measured by gas-chromatography on a 1.8 meter long column filled with Poropak PS. After 45 minutes, the situation is as follows:

Converted H ₂ O ₂ 88%

Propylene Oxide 6.02 × 10 ^-3 Mole

1-methoxy-2-hydroxy propane: 52.0 × 10 ^-3 moles

2-methoxy-1-hydroxy propane: 34.6 × 10 ^-3 moles

Example 12

99.8 g of phenol in a 250 cc small glass flask; Water 24.2 g; 18.5 g of acetone. The catalyst is also injected in sequence as in Example 5.

The reaction mixture is heated to 100 ° C. with stirring and refluxed, and then 15.4 g of H ₂ O _{2 at} 60% w / w is added dropwise within 45 minutes under the same conditions.

After 60 minutes of addition all H ₂ O ₂ was converted and the reaction product was analyzed by gas chromatography.

The residual amount of H ₂ O ₂ is converted to pitch and O ₂ . The ratio of ortho / para in the diphenol obtained is 1.26.

TABLE 1

Claims (7)

Formed of microspheres and composed of oligomeric silica and crystals of the material according to claim 1, i.e., titanium-gallium-acid salt, while the molar ratio of oligomeric silica / titanium-gallium-silicate ranges from 0.05 to 0.2, and also titanium-gallium-silicate A catalyst based on silicon, titanium and gallium, characterized in that the crystals of are bonded by means of Si-O-Si crosslinking. The catalyst of claim 1 wherein the microspheres have a diameter size of 5 to 1,000 μm. In an aqueous solution of silica and tetraalkyl-ammonium hydroxide, tetraalkyl-orthopolar acid salt in an aqueous solution of tetraalkyl-ammonium hydroxide at a temperature of room temperature to 200 ° C. for 0.2 to 10 hours was obtained by hydrolysis in a liquid phase, and titanium-gallium- The method for producing a catalyst according to claim 16, characterized in that the silicate crystals are dispersed, a suspension of titanium-gallium-cronate or oligomeric silica is obtained, and the obtained suspension is also rapidly dried. 4. The process of claim 3, which is tetraethyl-orthosilicate of tetraalkyl-orthosilicate. The method of claim 3 wherein the hydrolysis is hydrolyzed at a temperature in the range from 40 to 100 ° C. 5. The method of claim 3 wherein the alkyl moiety of the tetraalkyl-ammonium contains 1 to 5 carbon atoms. The method of claim 6 wherein the tetraalkyl-ammonium is tetrapropyl-ammonium.

Images