DD209795A5 - PROCESS FOR THE PRODUCTION OF SYNTHETIC, CRYSTALLINES, POROESEN BOROSILICATES WITH ZEOLITE FUEGE - Google Patents

Abstract

The invention relates to a process for the preparation of synthetic, crystalline, porous borosilicates with zeolite structures. The aim of the invention is to provide a new class of synthetic, crystalline, porous borosilicates. According to the invention, boron E, i. synthetic, crystalline, porous, zeolitic borosilicates prepared by hydrothermal reaction of a silicon and a boron compound and a mixture of tetramethyl- and tetrabutylammonium hydroxide or a mixed quaternary methylbutylammonium hydroxide, optionally in the presence of an alkali hydroxide or ammonium hydroxide.

Description

Berlin, 24.9.1983 APC 01B250 710/7 (62 413/18)

Process for the preparation of synthetic, crystalline, porous borosilicates

Field of application of the invention

The invention relates to synthetic materials based on SiO 2 and ^B 2 O 3 ^with P * ^ro * s crystalline structure of a zeolite and a process for their preparation and their use,

Characteristic of the known technical solutions

Synthetic borosilicates are known. "Thus, borosilicate, which is known from BI-PS877 205, has a crystalline, porous structure. There are four known products synthesized therefrom, namely Boralith A ^M , Boralith B, Boralith C and Boralith D which have been synthesized with the aid of organic substances, preferably tetraalkylammonium ions Synthesis to the desired microstructure * For Boralith A, tetramethylammonium was used, for Botalith B tetraethylammonium, for Boralith C tetraethylammonium or tetrapropylammonium ion or an ethylenediamine-derived cation and for Boralith D letrabutylammonium ion.

Object of the invention

The aim of the invention is to provide a new class of synthetic, crystalline, porous borosilicates.

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Explanation of the essence of the invention

It is the object of the invention to find a new synthesis process and suitable reaction components.

According to the invention, a new class of "Boralites", hereinafter referred to as "Boralites E ^M , which can be synthesized by means of a mixture of tetraalkylammonium bases or mixed tetraalkylammonium bases." The ammonium bases for the preparation of Boralith E. are mixtures of Tetramethyl- and tetrabutylaramonium hydroxide in various mixing ratios or mixed bases such as tributylmethylammonium hydroxide, dimethyldibutylammonium hydroxide and butyltrimethylammonium hydroxide

Boralites E can be characterized in the anhydrous state by the molar ratio of the oxides contained by means of the following formulas:

where a between 0 and 1 χ can be between 30 and 120, and R can be quaternary ammonium cation (s), while a cation is H ⁺ , MHt, or an alkali ion.

The products according to the invention are X-ray crystalline. The X-ray analysis is carried out for this determination with the aid of a powder diffractometer equipped with an electronic pulse counter using the CuK O.sub.1 radiation. For the calculation of the intensities, the

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Height of the peaks, they are given as a percentage of the height of the peak or the highest intensity band ·

The Röntgenbeugangsspektrum of Boralith E is similar to that of Boralith C, in terms of the lattice spacings d, however, considerable variation in the intensity ratios against Boralith C. showed it can be observed that in the spectrum of Boralithe E the intensity of a certain number of typical reflections of Boralith C is lower than others, which retain their characteristic intensities. a single sample of Boralith ü gives a hint of a complete disappearance of such reflections (bands) ·

Due to the difference in the X-ray diffraction spectrum, a Boralith is rather a Boralith group than a single compound. The bands or major reflections that occur in the above-noted phenomenon can be characterized by the following values of the lattice spacings d;

0.965 + 0.010 nm

0.632 + 0.007 nm

0.567 + 0.007 nm

0.424 + 0.0005 nm

0.388 + 0.005 nm

0.373 + 0.005 nm

0.363 + 0.005 nm

0.342 + 0.005 nm

0.293 ± 0.005 nm

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To give a quantitative idea of the phenomena, the ratio of the intensity of the reflection at d "0.363 + 0.005 nm (I ₁ ) to the reflection with unchanged intensity at d" 0.383 ± 0.005 nm (I _g ) was selected The ratio I ₁ to "L about 0.40 · For Boralithen £ this ratio is lower and can fall down to values in the order of 0.1" In each Boralith ϋ is the reduction in intensity - in % - for all reflections above, while the extent of this phenomenon varies from product to product.

Figure 1 shows a comparison of the X-ray diffraction spectra of a Boralith E - prepared according to Example 4 - and the spectrum of a typical Boralith C - prepared by BJi-PS 877 205. Both spectra were taken from products in the hydrogen form, i. h, they were 6 h at 550 ⁰ C calcined with ammonium acetate, subjected to ion exchange and then held again at 550 ⁰ C for 6 h.

Slight variations in the spectrum of Table 1 may be due to variations in the Si / B ratio of the firing temperature or the presence of cations. "

00 Boralith C (Nm) table 1 2 S d 1 Boralith e , 89 d 105 7 99 0 (Nm) ReI.Int · 17 1, 995 ReI · Int · 8th , 87 0 , 106 100 8th 0 964 100 9 15 , 997 48 θ ο, 47 , 966 5 9 16

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(62 413/18)

Table I (JPortsetzung)

9.93 0.891 1.2 9.91 0,893 0.7 12,00 0.738 1.1 11.98 0.739 0.8 12.61 0.702 0.7 12.59 0.703 0.3 13.31 0,665 3.7 13.29 0.666 3.7 14.03 0.631 9 14.00 0.632 2.5 14,89 0.595 11 14.86 0.596 11 15.65 0.566 6.6 15.63 0.567 2 16,01 0.554 6.9 15.99 0.554 6.6 16.65 0.532 1.4 16,63 0.533 0.5 17.40 0,510 1 17,37 0.511 0.7 17.78 .4988 2.6 17.75 .4997 2.6 17.93 .4947 3.3 17,89 .4957 2.8 13.33 .4340 0.4 18.29 .4850 0.2 19.39 .4578 2.7 19.34 .4589 2.5 20.07 0.4424 0.6 19.99 .4442 0.5 20.51 .4330 3.3 20.46 .4341 3.5 20.98 .4234 6.7 20.93 .4244 1.6 21,90 .4058 0.8 21.82 .4073 0.5 22.33 0.3981 2.6 22.32 .3983 1.2 23.23 .3829 40 23.19 .3835 36 23.44 .3795 31 23.38 .3805 26 23.86 .3729 14 23.82 .3735 7 24.07 .3697 20 24,03 .3703 19 24.57 .3623 16 24.52 .3630 6 24.93 .3572 1.3 24.85 .3583 1.8 25.74 .3461 2.2 25.69 .3468 2.3 26.05 0.3420 4.2 26.00 .3427 1.4 26.41 0.3375 1.4 26.34 .3383 1.5 26.79 .3328 3.1 26.72 .3336 2.7 27.11 .3289 4.2 27.00 0.3302 2.4

1 (continued) 1.4 -6- 24.9 .1983 .3238 0.8 .3224 0.8 AP 250 710/7 .3168 0.7 .3158 1.2 (62 413/18) 0.3125 0.5 table .3118 5 .3039 4 27.67 .3031 4.5 27,55 .2973 4.2 28.26 .2965 3.1 28.17 .2931 1.1 28.63 .2924 0.9 28,56 .2852 0.7 29,47, .2847 0.5 29.39 .2775 0.4 30.14 .2767 1.9 30,06 .2722 0.4 30.57 .2717 0.4 30.50 .2672 0.1 31.42 0.2666 0.4 31.36 .2647 0.3 32.35 .2541 2 32.26 .2599 1.4 32,97 .2592 0.9 32.90 .2579 0.2 33.62 0.2574 0.8 33.54 .2561 0.3 33.94 .2555 0.5 33 * 86 .2541 0.5 34.61 .2536 1.2 34.51 .2504 0.9 34.86 0.2500 1.9 34.78 .2479 M 35.12 0.2475 1.1 35.04 0.2407 0.8 35.40 .2403 1.4 35.32 .2387 0.8 35.92 .2382 3.5 35.86 .2005 3 36,30 0.2000 3.6 36.24 .1987 2.4 37.42 .1982 0.8 37.36 .1946 0.3 37.77 .1941 0.9 37.68 .1910 0.5 43.35 .1904 1 45.23 .1866 0.8 45.79 .1862 45.65 46.79 46.67 47.77 47.61 48.92 48,80

Boralites E according to the invention are prepared by hydrothermal reaction of a silicon-supplying substance, a boron-providing substance and a mixture of tetramethylammonium and tetrabutylammonium hydroxide

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certain proportions or of a mixed methylbutylammonium hydroxide, if appropriate in the presence of an alkali metal hydroxide or ammonium hydroxide at a pH of between 9 and 14 at a temperature between 100 and 220 ⁰ C for 2 to 30 days,

Table 2 shows the molar ratios of the reactants used.

table

O , 5 to 30 1 prefers SiO ₂ / B ₂ O ₃ O , 05 to 5 O to 15 R / SiO ₂ 10 to 50 20 , 1 to 0.3 H ₂ 0 / Si0 ₂ O to 0.5 O to 40 lie / SiOg , 01 to 0.4

The molar ratio tetramethylammonium to tetrabutylammonium in the case of a mixture is preferably between 0.3 and 3.

The silioium-donating compound may be a tetraalkylorthosilicate such as tetraethylorthosilicate or tetramethylorthosilicate or colloidal silica, silica gel, sodium silicate, Aerosil (SiO ₂ prepared by the hydrolysis of plams) or the like.

The boron-providing compound may be a trialkyl borate, tetraalkyl borate or boric acid, sodium borate or borax.

The selection of silicon and boron-providing compounds

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generally depends on the greater or lesser purity of the product to be produced.

Boralites E can be used for catalytic purposes or for adsorption processes, as such or applied to a more or less inert substrate, preferably a silica / clay or a clay-like material.

Boralites B can also be used as catalysts for a wide variety of reactions, as also mentioned, for example, in Belgian Pat. No. 877,205.

Ausfuhrungabeiapiel

The invention will be further illustrated by the following examples.

example 1

400 g of distilled water, 90.6 g of tributylmethylammonium hydroxide in 40% strength by weight aqueous solution, 8.3 g of boric acid and 0.26 g of sodium hydroxide were stirred into a Pyrex glass vessel in a CO ₂ -free atmosphere with stirring. After complete dissolution, 138.6 g of tetraethylorthosilicate were stirred in.

The reaction mixture was maintained at 70 ^° C. with stirring for 5 hours, whereby ethanol, which formed by hydrolysis of tetraethyl orthosilicate, was driven off.

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The milky gel was filled with distilled water to 400 cm- *, then to convert it into an autoclave with a stirrer and is maintained at 160 ⁰ C, 60 h under the pressure which is established automatically as a result of reactions. After cooling to room temperature, the resulting solid was centrifuged from the mother liquor, washed with distilled water to remove soluble impurities, and finally dried at 120 ^° C..

A portion of this product was held for 6 hours at 550 ⁰ C, subjected to ion exchange with Amraoniumacetat 6 h and then again fired at 550 G ⁰ ·

The ratio SiOg / BgO., In the product obtained was 60. The Boralith E thus obtained is not only characterized by an X-ray diffraction spectrum similar to that of the table, but also has an intensity ratio I ₁ : I ₂ of 0.34, where I ₁ the intensity in the X-ray diffraction spectrum at a grating pitch d is 0.363 ± 0.005 nm and for I _{2 is} 0.383 + 0.005 nm.

Examples 2 to 9

According to Example 1 further Boralithe were prepared, the ratios of the reactants are summarized in Table 3. In Example 6 kolHdale silica ("Ludox AS") with 40 wt -% SiO _{2 was} used as Silioium-supplying compound. In all other examples, however, tetraethylorthosilicate was used.

The boron heel thus obtained are characterized by the g ratio and the ratio of the intensities of the stated lattice spacings.

2 3 Table 3 5 30 6 7 8th 9 CTk ro 15 ι Example Hr, 3B1M 2B2M 4 I ¹ MA _- . 3 TMA ₌ J TMA _{= 1} TMA TMA _-1 T RN ⁺ TMA _-1 TBA ' 165 IBA "3 TBA TBa " TBA 10 10 tba " 10 10 10 10 2 V ») ro SiO ₂ / B ₂ O ₃ 0.25 0.25 10 0.25 6 0.25 0,125 0.25 0.17 / IU) VJl 0 -3 H / SiO ₂ 0.10 ^ ^a) 0.01 0.25 ^(a) 0.0i ^(a) tf, 01 48 (a) _{0> 01} (a) 0.01 ^Ca) 0.20 ^Cb) O, 35 ^(b) MeZSiO ₂ 30 30 30 0.18 30 30 30 39 ro H ₂ OZSiO ₂ VD crystallization 165 160 165 160 I6O 160 170 Ik temperature, oc VD crystallization 6 6 .6 6 9 6 15 Φ time, days 110 95 57 44 41 60 39 SiO ₂ ZB ₂ O ₃ 0.30 0.35 0.18 0.13 0.16 0.19 0.17 I ₁ Zi ₂ (a) Me - Na ⁺ (b) Me «ΝΗΪ

Claims (2)

AP 250 710/7 (62 413 / i) 1. A process for the preparation of synthetic, crystalline, porous, zeolitic boron silicates, which in the anhydrous state of the empirical formula wherein a is 0 to 1 and χ is 30 to 120, and Me is a hydrogen, ammonium or alkali ion and R is one or more tetraalkylammonium group (s) and in the hydrogen form has the X-ray diffraction spectrum given in Table 1 in that a silioium-supplying and a boron-providing compound in the presence of a mixture of ietramethyl- and tetrabutylammonium hydroxide or a quaternary Methylbutylammoniumhydroxide and optionally an alkali metal hydroxide or ammonium hydroxide at 100 to 220 ⁰ G and a pH between 9 and 14 during 2 hydrothermal reaction until 30 days, wherein in the output sgemi sch the molar ratio of SiO ₂ ZBpO., 0.5 to 30, of H ₂ dysi0 ₂ 10 to 50, of R / SiO ₂ 0.05 to 5 and of Me ⁺ / SiO _{2 is} 0 to 0.5 » Method according to item 1, characterized in that in the starting mixture a molar ratio of SiOg / BgO, -1 to Ί5 »of H ₂ OZSiO ₂ 20 to 40, of S / SiO ₂ 0.1 to 0.3 and of Me / SiO ₂ 0.01 to 0.4. 3. The method according to item 1 and 2, characterized in that in the starting mixture, a ratio of the ions -13- 24 · 9,1983 AP 250 710/7 (62 413/18) j Tetramethylammonium to .Tetrabutylammonium 0.3 to 3. ; '·; "· .- ;:"; /C^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^. 4 Process according to items 1 to 3, characterized in that tetraalkyl orthosilicate, colloidal silica, silica gel, sodium silicate or silica prepared by flame hydrolysis are used as the silicon-yielding compound. : '.': ':''' ^: ^ / ^v : "- ''. ν ': ·: ^ to items 1 to 4, characterized in that the boron-yielding compound used is a trialkyl borate or tetraalkyl borate, boric acid, sodium borate or borax. 6, method according to item 1 to 5 », characterized in that one uses as the quaternary Aounoniumbase Dirnethyldibutylammoniumhydroxid, Butyltrimethylammoniumhydroxid or iributylmethylammoniumhydroxid. '-10- 24.9.1983 AP 250 710/7 (62 413/18) The cation Me was sodium, only in Examples 8 and 9 Ammonium, The quaternary ammonium base was different in the individual examples, namely Example 2 Iributylmethylajanioniumhydroxid (3B1M), in Example 3 dibutyldimethylammonium hydroxide (2B2M) and in the following examples a mixture of different ratios of tetramethylammonium hydroxide (TMA) and tetrabutylammonium hydroxide (ΪΒΑ). "