FR2526414A1 - CRYSTALLINE AND POROUS SYNTHETIC MATERIALS CONSISTING OF SILICON AND BORON OXIDES, PROCESS FOR THE PREPARATION THEREOF AND USE THEREOF - Google Patents

Abstract

THESE CRYSTALLINE AND POROUS SYNTHETIC MATERIALS, OF THE ZEOLITIC TYPE, ARE CONSTITUTED BY OXIDES OF SILICON AND OF BORON, AND ARE PREPARED BY REACTING IN HYDROTHMIC CONDITIONS A DERIVATIVE OF SILICON, A DERIVATIVE OF BORON AND BORON, AND TAMLETRAMDHANGE MELANGE OF TETRABUTYLAMMONIUM OR AS A VARIANT, A MIXED QUATERNARY BASE OF METHYLBUTYLAMMONIUM HYDROXIDE, A METAL ALKALINE HYDROXIDE OR AN AMMONIUM HYDROXIDE IS POSSIBLE PRESENT. USE OF THESE MATERIALS AS CATALYSTS, ABSORBENT PRODUCTS, FOR EXAMPLE.

Description

Crystalline and porous synthetic materials consisting of oxides

  silicon and boron, their process of preparation and

their usage.

  The present invention relates to synthetic materials consisting of oxides of silicon and boron having a structure

  porous and crystalline zeolites, their process for the preparation

and their use.

  Synthetic materials based on aluminum oxide are known

silicon and boron oxide.

  Belgian Patent No. 877,205 describes four synthetic materials.

  consisting of silicon and boron oxides having a crystalline and porous structure, their process of preparation and

their usage.

  These materials are Boralite A, Boralite B, Boralite C,

  Boralite D have been synthesized with organic substances

  preferably with tetraalkylammonium ions,

  effect of driving the synthesis to the desired structure.

  Cations of this type are tetramethylammonium for Boralite A, tetraethylammonium for Boralite B, tetraethylammonium or tetrapropylammonium or a cation derived from ethylenediamine for Boralite Ce tetrabutylammonium for Boralite D. surprisingly, a new family of Boralites has been discovered that have been designated by Boralites E and which are prepared using for the synthesis a mixture of bases

  tetraalkylammonium or mixed tetraalkylammonium bases.

  Ammonium bases & use to obtain Boralis

  E is a mixture of tetramethyl and tetrabutyl hydroxides

  ammonium in varying ratios, or mixed bases such as

  tributylmethylammonium hydroxide, dimethyldibu-

  tylammonium and butyltrimethylammonium hydroxide.

  The Boralites of the family E can be represented in the anhydrous state in terms of the molar ratio of the oxides, by the following formula: ## STR3 ## in which a is a value between 0 and 1; x is a value between 30 and 120; R is the quaternary ammonium compound (s) mentioned above; Me is a cation such as H + or

NH + 4 or an alkali metal ion.

  The synthetic materials according to the present invention are crystalline by X-ray analysis. This analysis is carried out using a diffractometer of the type suitable for powders and equipped with an electronic pulse counting device, where Cu Ka radiation is used. To calculate the intensities the heights of the peaks were measured and reported in terms of percentage with respect to the height of the most intense peak. The X-ray diffraction pattern of Boralites E is similar to that of Boralites C in that the values of interplanar distances d are concerned but variations

  important are noted in the comparative intensity ratios.

  Boralites C More particularly it should be noted that in

  the spectrum of Boralites E the intensity of a certain number of

  Typical types of Boralites C are lower than those that retain their characteristic intensity.

  Boralites E does not show a complete weakening of these reflections.

  It is precisely because of the variability observed in the X-ray diffraction spectrum that we are talking about a family

  Boralites rather than a single compound.

  The main reflections involved in the aforementioned phenomenon are characterized by the following values for d y ie:

9.65 + 0.10 AO

6.32 + 0.07 A

5167 + 0.07 A

4.24 + 0105 A

3.98 + 0105 A

3.73 0105 A

3.63 + 0.05 A

3.42 + 0105 A

2.93 + 0.05 A

  To obtain a quantitative idea of the phenomenon, we have chosen the ratio of the intensity of reflection at d = 3.63 0.05 A (II) to that of reflection with intensity not varying at d = 3.83 0.05 A (I 2) In Boralite C, the ratio II to 12 is typically quite close to 0.40 In Boralite E this ratio is decreased and can fall to values of the order of 0, 1. In any of the Boralites the decrease in intensity is similar, expressed as a percentage for all the reflexions mentioned above, while the magnitude of the phenomenon

  varies from any product to any other.

  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.

  Boralite C type (prepared according to Belgian Patent No. 877,205).

  Both spectra relate to products of the H + form, that is to say products which have been calcined for six hours at 550 ° C., have undergone ion exchange with ammonium acetate and have been calcined.

  again at 550 C for six hours.

  The small variations in the spectrum of Table I may be due to variations in the Si / B ratio, h the temperature of

  calcination or present cation.

TABILEAU 1

Boralite C 2 r d G)

8.00 11.05

8.89 9.95

9.17 9.64

9.93 8.91

12.00 7.37

12.61 7.02

13,31 6 i 65

14.03 6.31

14.89 5.95

, 65 5.66

16.01 5.54

16.65 5.32

17.40 5.10

17.78 4.988

17.93 4.947

18.33 4.840

19.39 4.578

, 07.4424

51.4330

, 98 4,234

21.90 4.058

22.33 3.981

23.23 3.829

23.44 3.795

23.86 to 3.729

24.07 3.677

24.57 3.623

24.93 3.572

74, 3,461

26.05, 3.420

26.41 3.375

26.79 3.328

  Relative intensity 1,2 1,1 0,7 3,7 6,6 6,9 1,4 2,6 3,3 0,4 2,7 0.6 3.8 6, 7 0.8 2.6 1,3 2,2 4,2 1,4 3,1 7,99 8,87 9,15 9,91 11,98 12,59 13,29 14,00 14,86, 63, 99 16,63 17 , 37 17.75 17.89 18.29 19.34 19.99, 46, 93 21.82 22, 32 23.19 23.38 23.82 24.03 24.52 24.85, 69 26.00 26.34 26.72 Boralite E gold

d (A) Intensity relative to

tive

11.06 100

9.97 48

9.66 5

8.93 0.7

7.39 0.8

7.03 0.3

6.66 3.7

6.32 2.5

, 96 11

, 67 2

, 6.6

, 33 0.5

, 11 0.7

4.997 2.6

4.957 2.8

4,850 0,2

4,589 2.5

4,442 0.5

4,341 3.5

4,244 1.6

4.073 0.5

3.983 1.2

3.835 36

3.805 26

3,735 7

3,703 19

3,630 6

3.583 148

3,468 2.3

3,427 1.4

3,383 1.5

3,336 2.7

27.11 3.299 4.2 27.00 3.302 2.4

27.67 3.224 1.4 27.55 3.238 0.8

28.26 3.158 0.8 28.17 3.168 0.7

28.63 3.118 1.2 28.56 3.125 0.5

29.47 3.031 5 29.39 3.039 4

, 14 2.965 4.5 30.06 2.973 4.2

, 57 2.924 3.1 30.50 2.931 1.1

31.42 2.847 0.9 31.36 2.852 0.7

32.35 2.767 0.5 32.26 2.775 0.4

32.97 2.717 1.9 32.90 2.722 0.4

33.62 2.666 0.4 33.54 2.672 0.1

33.94 2.64 t 0.4 33.86 2.647 0.3

34.61 2.592 2 34.51 2.599 1.4

34.86 2.574 0.9 34.78 2.579 0.2

35.12 2.555 0.8 35.04 2.561 0.3

, 40 2.536 0.5 35.32 2.541 0.5

, 92 2,500 1,2 35.86 2.504 0.9

36.30 2,475 1.9 36.24 2,479 1.4

37.42 2.403 1.1 37.36 2.407 0.8

37.77 2,382 1.4 37.68 2,387 0.8

43.35 2,000 3.5 45.23 2,005 3

, 79 1,982 3.6 45.65 1,987 2,4

46.79 1.941 0.8 46.67 1.946 0.3

47.77 1.904 0.9 47.61 1.910 0.5

48.92 1.862 1 48.80 1.866 0.8

  The process for the preparation of Boralites E is designed to react under hydrothermal conditions a silicon derivative, a boron derivative, a mixture of tetramethylammonium hydroxide and tetrabutylammonium in specific ratios or alternatively a mixed quaternary base. methylbutylammonium hydroxide as defined above, optionally an alkali metal hydroxide or an ammonium hydroxide being present, to work a p H between 9 and 14, at a temperature between 1000 C

  and 220 C and for a period ranging from 2 days to 30 days.

  Table 2 shows the molar ratios between the reagents.

TAB LEAU 2

  extended range preferred range Si O 2 / B 203 molar ratio 0.5: 30 1:15 "" R / Si O 2 0.05: 5 0.1: 0.3 "" 20 / SiO 02 10:50 20: The molar ratio of the tetramethylammonium cation to the tetramethylammonium cation in the case where this mixture is used is chosen.

preferably between 0.3 and 3.

  The silicon derivative may be chosen from among tetraalkylorthosilicates such as tetraethylorthosilicate and tetramethylorthosilicate, or from colloidal silica,

  silica, sodium silicate, aerosil and other products.

  The boron derivatives may be chosen from trialkyl-

  borates, tetraalkyl borates, boric acid, sodium borate and borax. The choice of derivatives of silicon and boron depends mainly on the purity more or less of the material that is proposed to obtain.

  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

  among silica, alumina and clay materials.

  These Boralites can be used as catalysts in a large number of reactions such as those illustrated in FIG.

  Belgian Patent No. 877,205 recalled above.

  The present invention is illustrated by the descriptive examples

and not limiting thereafter.

EXAMPLE 1

  This example illustrates the preparation of Boralite E. In a Pyrex glass container maintained in a Co 2 ton-free atmosphere introduced successively with stirring, 400 g of distilled water, 90.6 g of tributylmethylammonium hydroxide in aqueous solution. at 40% by weight, 8.3 g of boric acid and 0.26 g of sodium hydroxide. Once the dissolution is complete, it is added, still under

  stirring, 138.6 g of tetraethylorthosilicate.

  The reaction mixture is kept at 70 ° C. for 5 hours, still stirring, in order to expel the ethanol produced by the hydrolysis.

tetraethylorthosilicate.

  To the milky gel thus obtained, distilled water is added to make up to 400 ml; the reaction mixture is transferred into an autoclave equipped with a stirring mechanism and kept at 1600 ° 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 standard distilled water to remove all soluble impurities,

then it is dried at 120 ° C.

  Part of the product is calcined for 6 hours at 550 ° C., ion-exchanged with ammonium acetate and

  calcine again at 5500 C for 6 hours.

  The SiO 2 / B 203 ratio in the material thus obtained is 60.

  The Boralite E thus obtained can be characterized not only by the X-ray diffraction pattern similar to that of Table 1, but also by a ratio of I 1: I 2 of 0.34, I 1 and I 2 being as it was explained above the intensities of the characteristic reflections of the X-ray diffraction spectrum corresponding to the interplenial distance d equal to 3.63 0.05 A for I and 3.83 + 0.05 A for I 2 respectively.

EXAMPLES 2 to 9

  Other Boralites of the E family can be prepared according to Example 1, but with the ratios between the indicated reagents

in Table 3 below.

  As a silicon source for Example 81, Ludox A S (registered trademark) silica colloidal silica containing 40% of silica is used.

  by weight, while all other examples are made using

  tetraethylorthosilicate as the source of silicon.

  The cation Me used is sodium except for the examples 8

  and 9 in which ammonium is used.

  The quaternary ammonium base used varies in the various

  In Example 2, tributylhydroxide is used.

  methylammonium (3 BIM), in Example 3 the hydroxide of

  dibutyldimethylammonium (2 B 2 M) and in the following examples it is

  read a mixture of tetramethylammonium hydroxide (TMA) and hydro-

  tetrabutylammonium hydroxide (TBA) in different ratios.

  The Boralites of the E family thus obtained are characterized

  especially by the ratio Si O 2: B 203 and the ratio I 1: I 2 of

interplanar distances.

EXMPLOE No RN +

RS ú 02 23

Me / S ú 02

H 20 ISI-02

  Crystallization temperature, O C

Duration of the crystal

lisation, days

S'2 / 203

11/12

(a) Me = Na + (b) Me = N * 14

3 E 1 M

0.25 0.10 (a)

2 B 2 M

0.25

160

0.30 0.35

TA.BIZAU 3

4 5

TBA TEA

10

0.25 0.25

0.01 (to) 0.01 (at)

30

  0.18 0.18 TBA 3 0.25 0.13 TEA 0.125 0, 16

TIIA = 1

  TEA 0.25 0, 19 0.17 0.35 <(b) 0.17 J>.

Claims (6)

  1 Crystalline and Porous Synthetic Synthetic Materials   zeolite composed of corresponding silicon and boron oxides   in an anhydrous state having the following empirical formula: R 20 (1-a) Me 20 B 203 x Si O 2 where a is from 0 to 1; x varies from 30 to 120; Me is an H + cation or an NH 4 cation or an alkali metal cation; R is one or more tetraalkylammonium cation (s), characterized in that they are prepared by reacting under hydrothermal conditions a silicon derivative, a boron derivative, a mixture of tetramethylammonium hydroxide and tetrabutylammonium hydroxide, or   Alternatively, a mixed quaternary base of methylbutylhydroxide   ammonium, an alkali metal hydroxide or an ammonium hydroxide being optionally present, with a SiO 2: B 203 molar ratio of reactants selected between 0.5 and 30, a molar ratio of the reactants H 20: Si O 2 selected between 10 and 50, a molar ratio R: Si O 2 of the reactants chosen between 0.05 and 5 and a molar ratio Me +: Si O 2 of the reactants chosen between 0 and 0.5.   2 crystalline and porous synthetic materials according to claim 1, characterized in that they have an X-ray diffraction spectrum of the form H + corresponding to the following results: 2 e d (A) 7.99 11.06 8.87 9.97 9.15 9.66 9.91 8.93 11.98 7.39 12.59 7.03 13.29 6.66 14.00 6.32 14.86 6.96 63.67 , 99 5.54 16.63 5.33 17.37 5.11 17.75 4.997 17.89 4.957 18.29 4.850 19.44 4.589 19.99 4,442 46.4,341 , 4.224 21.82 4.073 22.32 3.983 23.19 3.835 23.38 3.805 23.82 3.735 24.03 3.703 24.52 3.630 24.85 3.583 , 69, 3,468 26.00 3.427 26.34 3.333 26.72 3,336 Intensity   t ive 0.7 0.8 0.3 3.7 2.5 6.6 0.5 0.7 2.6 2.8 0.2 2.5 0.5 3.5 1.6 0.5 1.2 1 Y 8 2.3 1.4 1.5 2.7 27.00 3.302 2.4 27.55 3,238 0.8 28.17, 3.168 0.7 28.56 3.125 0.5 29.39 3.039 4 , 06 2.973 4.2 , 50 2.931 1.1 31.36 2.852 0.7 32.26 2.775 0.4 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 35.04 2.561 0.3 , 32 2.541 0.5 , 86 2.504 0.9 36.24 2,479 1.4 37.36 2; 407 0.8 37.68 2.388 0.8 , 23 2.005 3 , 65 1,987 2,4 46.67 1.946 0.3 47.61 1.910 0.5 48.80 1.866 0.8   3 crystalline and porous synthetic materials according to claim 1, characterized in that they are prepared starting from an Si O 2: B 203 molar ratio chosen between 1 and 15, a molar ratio H 20: Si O 2 chosen between 20 and 40, a molar ratio R: Si O 2 chosen between 0.1 and 0.3 and a molar ratio Me: Si O 2 chosen between 0.01 and 0.4.   4 crystalline and porous synthetic materials according to claim 1, characterized in that they are prepared with a tetrabutylammonium cation tetramethylammonium cation ratio chosen between 0.3 and 3.   Crystalline and porous synthetic materials according to claim 1, characterized in that they are prepared by operating at a temperature of between 1000 ° C. and 220 ° C., at a pH of between 9 and 14 and for a duration varying from 2 days to 30 days. 6 crystalline and porous synthetic materials according to claim 1, characterized in that the silicon derivative is chosen from tetramylkylorthosilicates or from silica   Tdale collo, silica gel, sodium silicate or aerosil.   7 crystalline and porous synthetic materials according to claim 1, characterized in that the boron derivatives are chosen from trialkylborates and tetraalkylborates,   boric acid, sodium borate and borax.   8 crystalline and porous synthetic materials according to claim 1, characterized in that the quaternary base   methyl butylammonium compound is dimethyldibutyl   ammonium. 9 crystalline and porous synthetic materials according to claim 1, characterized in that the mixed base of   methylbutylammonium is butyltrimethylammonium hydroxide.   Crystalline and porous synthetic material according to Claim 1, characterized in that the quaternary base   mixture of methylbutylammonium is tributylmethylhydroxide ammonium.