LU84790A1 - SYNTHETIC AND POROUS SYNTHETIC MATERIALS CONSISTING OF SILICON AND BORUS OXIDES, THEIR PREPARATION PROCESS AND THEIR USE - Google Patents

Description

If ii; |

P

the ,

Crystalline and porous synthetic materials constituted by oxides of silicon and boron, their process of preparation and their use.

The present invention relates to plastics consisting of oxides of silicon and boron having a porous and crystalline structure of a zeolitic nature, their process of preparation and their use.

J Synthetic materials based on silicon oxide and boron oxide are known.

] 10 Belgian patent n ° 877.205 describes four synthetic materials constituted by oxides of silicon and boron having a crystalline and porous structure, their process of preparation and their use.

These materials called Boralite A, Boralite B, Boralite C} Boralite D have been synthesized with organic substances present, preferably with t-traalkylammonium ions, having the effect of driving the synthesis to the desired structure.

The cations of this kind are tetramethylammonium for Boralite A, tetraethylammonium for Boralite B, 2o tetraethylammonium or tetrapropylammonium or a cation derived from ethylenediamine for Boralite C, and tetrabutylammonium for Boralite D.

Surprisingly, a new family of Boralites has been discovered which have been designated by Boralites E 25 which are prepared using for the synthesis a mixture of tetraalkylammonium bases or mixed tetraalkylammonium bases.

The ammonium bases to be used to obtain Boralites E are mixtures of tetramethyl- and tetrabutyl-A ammonium hydroxides in variable ratios, or mixed bases such as i / ο it.

tributylethyl ammonium hydroxide, dimetbyldihu-tylammonium hydroxide and butyltrimethylammonium hydroxide.

The Boralites of the family E can be represented in the anhydrous state in terms of molar ratio of the oxides, by the following formula:

aR20. (l-a) Me20.B2O xSiO

in which a_ is a value between O and 1; x is a value between 30 and 120; R is the quaternary ammonium cation (s) - i mentioned above; Me is a cation such as H or ^ t! H + ^ or an alkali metal ion.

The synthetic materials according to the present invention are crystalline on X-ray analysis. This analysis is carried out by means of a diffractometer of the type suitable for powders and equipped with an electronic pulse counting device, the CuRa radiation being used. To calculate the intensities, the peak heights were measured and reported as a percentage of the height of the most intense peak.

The X-ray diffraction spectrum of Boralites E 20 is similar to that of Boralites C as far as the values of the interplanar distances are concerned, but significant variations are noted in the intensity ratios compared to Boralites C. More particularly, it is necessary to note that in the spectrum of Boralites E the intensity of a certain number of typical reflections of Boralites C is reduced compared to those which retain their characteristic intensity. No sample of Boralites E shows a total weakening of these reflections.

It is because of the variability found in the X-ray diffraction spectrum that a family of Boralites is involved rather than a single compound.

The main reflections involved in the aforementioned phenomenon are characterized by the following values for d j fj, that is to say:

AT

U

* 2

9.65 + 0.10 A

6.32 + 0.07 A

5.67 + 0.07 A

| 4.24 + 0.05 A

5 3.98 + 0.05 A

3.73 + 0.05 A

3.63 + 0.05 A

3.42 + 0.05 A

2.93 + 0.05 A

10 To get a quantitative idea of the phenomenon, we chose the ratio of the intensity of the reflection at d = 3.63 - 0; 05'Â (ï,) to that of the reflection with the intensity not varying at d = 3.83 - 0.05 A (l2). In βoralite C, the ratio 1 ^ to I is typically quite close to 0.40. In Boralite 15 E this ratio is reduced and can fall to values of the order of 0.1.

In any of the Boralites E, the decrease in intensity is similar, expressed as a percentage ^ for all the reflections mentioned above, while the amplitude of the phenomenon varies from one product to another.

Table 1 shows a comparison between the X-ray diffraction spectrum of a Boralite E (as obtained according to the method of Example 4 described below) and the corresponding spectrum of a typical Boralite C (prepared according to the Belgian patent n ° 877.205).

+ 25 The two spectra relate to products of form H, that is to say products which have been calcined for six hours at 550 ° C., have undergone an ion exchange with ammonium acetate and have were calcined again at 550 ° C for six hours.

Small variations in the spectrum of Table I may be due to variations in the Si / B ratio, the calcination temperature or the presence of cations.

/ '4; TABLE_____1

; - Boralite C?, Orality E

! 2 Θ "d (Â) Relative intensity 2 ^ d (A) Relative intensity 8 d 00 11.05 100 7.99 H, 06 100 5 8.89 9.95 47 8.87 9.97 48 9.17 9.64 16 9.15 9.66 5 9.93 8.91 1.2 9.91 8.93 0.7 12.00 7.37 1.1 11.98 7.39 0.8 12.61 7, 02 0.7 12.59 7.03 0.3 10 13.31 6.65 3.7 13.29 6.66 3.7 14.03 6.31. 9 14.00 6.32 2.5 14.89 5.95 11 14.86 5.96 11 15.65 5.66 6.6 15.63 5.67 2 16.01 5.54 6.9 15.99 5.54 6.6 15 16.65 5.32 1.4 16.63 5.33 0.5 17.40 5.10 1 17.37 5.11 0.7 17.78 4.988 2.6 17.75 4.997 2.6 17.93 4.947 3.3 17.89 4.957 2 , 8 18.33 4.840 0.4 18.29 4.850 0.2 20 19.39 4.578 2.7 19.34 4.589 2.5 20.07 4.424 0.6 19.99 4.442 0.5 20.51 4.330 3.8 20.46 4.341 3.5 20.98 4.234 6.7 20.93 4.244 1.6 21.90 4.058 0.8 21.82 4.073 0.5 25 22.33 3.981 2.6 22.32 3.983 1.2 23, 23 3.829 40 23.19 3.835 36 23.44 3.795 31 23.38 3.805 26 23.86 3.729 14 23.82 3.735 7 24.07 3.697 20 24.03 3.703 19 30 24.57 3.623 16 24.52 3.630 6 24.93 3.572 1 , 3 24.85 3.583 lj8 25.74 3.461 2.2 25.69 3.468 2.3 26.05 3.420 4.2 26.00 3.427 1.4 26.41 3.375 1.4 2 6.34 3.383 1.5 35, 26.79 3.328 3.1 26.72 3.336 2.7>

. J

π; _>

! 27 d11 3,289 4.2 27.00 3.302 2, A

I 27.67 3.22A 1, A 27.35 3.238 0.8 28.26 3.158 0.8 28.17 3.168 0.7 28.67 3.118 1.2 28.56 3.125 0.5

5 29, A7 3.031 5 29.39 3.039 A

30, IA 2.965 A, 5 30.06 2.973 A, 2 30.57 2.92A 3.1 30.50 2.931 1.1 31, A2 2.8A7 0.9 31.36 2.852 0.7

32.35 2.677 0.5 32.26 2.775 0, A

10 32.97 2.717 1.9 32.90 2.722 0, A

33.62 2.666 0, A 33.5A 2.672 0.1 33.9A 2.6A1 '0, A 33.86 2.6A7 0.3

3A, 61 2.592 2 3A, 5l 2.599 1, A

3A, 86 2.57A 0.9 3A, 78 2.579 0.2 15 35.12 2.555 0.8 35, OA 2.561 0.3 35, AO 2.536 0.5 35.32 2.5Al 0.5 35.92 2,500 1.2 35.86 2.50A 0.9 36.30 2, A75 1.9 36.2A 2, A79 1.4 37, A2 2, A03 1.1 37.36 2, A07 0.8 20 37.77 2.382 1, A 37.68 2.387 0.8 A3.35 2,000 3.5 A5.23 2.005 3

45.79 1.982 3.6 A5.65 1.987 2, A

A6.79 1.9A1 0.8 A6.67 1.9A6 0.3 A7.77 1.904 0.9 47.61 1.910 0.5 25 48.92 1.862 1 48.80 1.866 0.8

The process for the preparation of Boralites E consists in reacting, under hydrothermal conditions, a silicon derivative, a boron derivative, a mixture of tetramethylammonium and tetrabutylammonium hydroxides in determined ratios, or alternatively a mixed quaternary base of 'methylhutylammonium hydroxide as defined above, optionally an alkali metal hydioxide or an ammonium hydroxide being present, to work at a pH between 9 and 14, at a temperature between 100 ° C and 220 ° C and for a period varying from 2 days to 30 days.

35 A Table 2 shows the molar ratios between the reactants.

Λ <1 6 I · TABLE 2 I extended range preferred range t

Molar ratio Si ° 2 / B2 ° 3 0.5: 30 1:15 R / Si02 0.05: 5 0.1: 0.3 5 "" H20 / Si02 10:50 20:40 "Me / Si02 0: 0.5 0.01: 0.4

The molar ratio of the tetramethylammonium cation to the tetramethylammonium cation in the case where this mixture is used is preferably chosen between 0.3 and 3.

The silicon derivative can be chosen either from tetraelkylorthosilicates such as tetraethylorthosilicate and tetramethylorthosilicate, or from colloidal silica, silica gel, sodium silicate, aerosil and other products.

The boron derivatives can be chosen from trialkyl-15 borates, tetraalkylborates, boric acid, sodium borate and b orax.

I The choice of silicon and boron derivatives mainly depends on | of the greater or lesser purity of the material which it is proposed to obtain.

! The Boralites E can be used for catalytic purposes or in absorption applications, as such, or dispersed on a more or less inert substrate, preferably chosen from silica, alumina and clay materials.

These Boralites can be used as catalysts in a large number of reactions such as those illustrated in Belgian Patent No. 6,877,205 mentioned above.

The present invention is illustrated by the descriptive and nonlimiting examples below.

EXAMPLE 1 2Q This example illustrates the preparation of Boralite E.

400 g of distilled water, 90.6 g of tributylmethylammonium hydroxide in aqueous solution at 40Z by weight, 8.3 g of water, are successively introduced into a Pyrex glass container maintained in an atmosphere deprived of CO 2. boric acid and 0.26 g of sodium hydroxide. Once the dissolution is complete, we add, always under

AT

/ stirring, 138.6 g of tetraethylorthosilicate. j. Maintaining the reaction mixture at 70cC for 5 hours still with stirring to remove the ethanol produced by the hydrolysis I · tetraethylorthosilicate.

5 To the milky gel thus obtained, distilled water is added to make up to 400 inl; the reaction mixture is transferred to an autoclave equipped with a stirring mechanism and kept there at 160 ° C. for 60 hours under the pressure which is spontaneously generated in the autoclave by the reactions.

After cooling to room temperature, the product / obtained is separated from its mother liquor by centrifugation, washed with running distilled water to remove any soluble impurities, and then dried at 120 ° C.

A part of the product is calcined for 6 hours at 550 ° C., it is subjected to an ion exchange with ammonium acetate and it is calcined again at 550 ° C. for 6 hours.

The S1O2 / B2O2 ratio in the material thus obtained is 60.

The Boralite E thus obtained can be characterized not only by the X-ray diffraction spectrum similar to that of table 1, 20 but also by a ratio I ^: I2 0.34, 1 ^ and being * as explained above, the intensities of the reflections characteristic of the X-ray diffraction spectrum corresponding to the distance + 0 + 0 interplanar equal to 3.63 - 0.05 A for 1 ^ and 3.83 - 0.05 A for I respectively EXAMPLES 2 to 9 Other Boralites of family E can be prepared according to Example 1, but with the ratios between the reagents indicated in Table 3 below.

As the source of silicon for Example 8, colloidal silica Ludox A.s! (registered trademark) containing 40% of silica by weight, while all the other examples are carried out using tetraethylorthosilicate as the source of silicon.

The cation Me used is sodium except for Examples 8 and 9 in which ammonium is used.

* 35 I The quaternary ammonium base used varies in the various> δ 1 preparations: in example 2 ron uses the hydroxide of tributyimethylammonium (3B1M), in example 3 one uses the hydroxide of i dibutyldimethylammoniura (2B2M ) and in the following examples, a mixture of tetramethylammonium hydroxide (ΤΜΑ) and 5-tetrabutylarimonium hydroxide (TEA) is used in different ratios.

The Boralit.es of family E thus obtained are characterized above all by the Si00 ratio and by the I ^ T ratio of the interplanar distances.

9 t - y

M rQ

It w D- m rv <5 <μ co ο Γ- »_Γ Z 'θ'. r- ~ m σν ^

H H ol O O co "—i ^ nO

, -.

- <D2

Il '' - 'u'1 O ov <5 <1 ol ΟΙ Ο —l

"5 p H O" - O \ D O

H H M O O co r-i vD vD O

/ -.

CB

i — i in

I CM M VO

_ M "O O t — t Γ'-ΛΡΡΟ • '-O VD t-C"

HH' — I O O co .—! ov <j- O

1-11 CO CB

'w' 1 m t — i „<S <5„ CNl O O r ~ l VDgiwpqO ^ ^ O VD ·%

H H O O Cî t — t o <j- O

CD

CO V- / 1 LO r — i 00 n O m h ^ OçîjPQO · »Λ O vD o0 **

^ H H M O O CO M V0 <| - O

^ / -N

FQ CQ

<ö r — I vy H I ΙΠ r-i oo * <! <_ cn O m. — i öl "S PQ Ο ·» · * O VD jv. »H H μ o O co m voino

/ ^ N

CD

Nw 'S ΙΛ> - <IP,

Su (NO O CO

H O - - O VD LO "

<M c-lOOcn r-J vD Ον O

/ —S

CB

S ΙΟ Ο ο

rî _ DI> -1 LO O CO

CN fl O - "O vo r ^ i η μ o o co <-i vo i — i o i r ~ i

O CO

O AJ

"CD

ß -H

had O U CD

Ό -H U IJ

DD 3 + + vJ-

. had co had o cb M

%, _ J-l CD -c-, S g ° Di jj ”—i eu d ο η h fy d) c-iocu'-joo oj

f-J CQ cv | O -I-I ü CB -1-1 cq G) CD

Ci ^ ° • 'J CO 1 "J U OJJJ \ (VJ“ a

fi. D! 'M W> 5 <C0 Ό m OIM

0 +, -, Ç CO -v- O B -A MCO o -V. ^ v, -v G 5 ^ 0 û> ojcujj 3 H .m mcbjs iWPa CD Pi pi MO G1- * CP M v— ^ v_4-

AT

Claims (7)

1. Synthetic and porous synthetic materials of a zeolitic nature constituted by oxides of silicon and boron corresponding in anhydrous state to the following empirical formula: i 5 a ^ O. (l-a) Me20.B203.xSi02 il S in which a varies from 0 to 1; x varies from 30 to 120; Me is an f + + I cation H or a cation NH, or a cation of an alkali metal: R is one or more tetraa lkylammonium cation (s), characterized in that they are prepared by reacting under conditions Hydrothermal a silicon derivative, a boron derivative, a mixture of tetramethylammonium hydroxides and tetrabutylammonium ^ or alternatively, a mixed quaternary base of methylbutylammonium hydroxide, an alkali metal hydroxide or an ammonium hydroxide possibly being present, with a molar ratio Si02: B203 of the 15 reactants chosen between 0.5 and 30, a molar ratio of the reactants iH ^ OrSiO chosen between 10 and 50, a molar ratio R: SiO? of reagents 2 2 + 2 chosen between 0.05 and 5 and a Me: Si02 molar ratio of the reagents chosen between 0 and 0.5. 2. Crystalline and porous synthetic materials according to! 20 claim 1, characterized in that they have an X-ray diffraction spectrum of the H form corresponding to the following results: ^ ^ ^ π I; e J '2 P "d (A) InfenFifé relative to 7.99 Π, 06 100 a 8.87 9.97 48 5 9.15 9.66 5 9.91 8.93 0.7 11.98 7.39 0.8 12.59 7.03 0.3 13.29 6.66 3.7 10 Ι ^ -ι, ΟΟ 6.32 2.5 - 14.865.96 11 15.63 5.67 2 15.99 5.54 6.6 16.63 5.33 0.5 | 15 17.37 5.11 0.7] 17.75 4.997 2.6 1 17.89 4.957 2.8 18.29 4.850 0.2 19.34 4.589 2.5 20 19.99 4.442 0.5 20.46 4.341 3.5 20.93 4.244 1.6 21.82 4.073 0.5 22.32 3.983 1.2 25 23.19 3.835 36 23.38 3.805 26 23.82 3.735 7 24, 03 3.703 19 24.52 3.630 6 30 24.85 3.583 1.8 25.69 3.468 2.3 26.00 3.427 1.4 26.34 3 ', 383 1.5 ^ 26.72 3.336 2.7 9 P η 27 .00 3.302 2.4 il 27> 55 3.238 0.8 '28.17 3, H8 ο, 7 28.56 3.125 0.5 5 29.39 3.039 4 30.06 2.973 4.2 30.50 2.931 1.1 31.36 2.852 0.7 32.26 2.755 0.4 10 32.90 2.722 0.4 33.54 2.672 0.1 33.86 2.647 0.3 34.51 2.599 1.4! 34.78 2.579 0.2 d 15 35, 04 2.561 0.3; 35.32 2.541 o, 5 d 35.86 2.504 0.9 | 36.24 2.479 1.4 37.36 2.407 0.8 20 37.68 2.387 0.8 45.23 2.005 3 45.65 1,987 2.4 46.67 1.946 0.3 1.910 0.5 25 48.80 1.866 0.8 3. crystalline and porous synthetic materials according to claim 1, characterized in that they are prepared starting from a molar ratio c ^ lo ^ s ^ · between 1 and 15, a molar ratio H20: Si02 chosen between 20 and 40, a molar ratio 30 R: Si02 chosen between 0.1 and 0.3 ^ and a molar ratio Me: Si02 chosen | between 0.01 and 0.4. Crystalline and porous plastics according to claim 1, characterized in that they are prepared with a tetramethylammonium cation to tetrabutylammonium cation ratio 35 Λ chosen between 0.3 and 3. ev 13 "5. Crystalline and porous plastics according to claim 1, characterized by the fact that they are prepared! operating at a temperature between 100cC and 220cC, at ur. | · PH between 9 and 14 and for a period varying from 2 days to '! 5 30 days. i {6. Crystalline and porous synthetic materials according to the. | claim 1, characterized in that the silicon derivative is chosen from tetr & alkvlorthosilicates or from silica | colloidal, silica gel, sodium silicate or aerosil. | 7. My crystalline and porous synthetic titles according to claim 1, characterized in that the boron derivatives are chosen from trialkylborates, tetraalkylborates, boric acid, sodium borate and borax. 8. Crystalline and porous synthetic materials according to claim 1, characterized in that the mixed quaternary base of methylbutylammonium is dimethyldibutylammonium hydroxide. 9. crystalline and porous synthetic materials according to claim 1, characterized in that the mixed base of methylbutylammonium is butyltrimethylammonium hydroxide. 10. crystalline and porous synthetic materials according to claim 1, characterized in that the mixed quaternary base of methylbutylammonium is tributylmethyl- * __ ammonium hydroxide.