NL8104347A - SILICON DIOXIDE POLYMORF. - Google Patents

Description

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Silicon dioxide polymorph.

The invention relates to crystalline silicon dioxide polymorphs having a zeolite crystal structure equal to that of zeolite ZSM-5.

Numerous articles and patents on molecular, shape-selective catalysis have been published in the literature since the first article was published about 20 years ago by Weisz and Frilette. (J. Phys.

Chem., 64, 382 (1960)).

Recently, a group of crystalline aluminosilicates designated as those of the ZSM-5 type has been found to be formally selective. This group of zeolites is described in particular in U.S. Pat. No. 3,702,886. These zeolites are, for example, synthesized from a solution containing an oxide of aluminum or gallium, an oxide of silicon or germanium, an oxide of sodium, a tetraalkylammonium hydroxide and water. This group of zeolites is characterized by a specific X-ray deflection pattern.

Another group of crystalline compounds, which are mostly silicon dioxide, have been shown to have a ZSM-5 type X-ray pattern. Examples are silicalite and a silicon dioxide polymorph, which are described in U.S. Pat. Nos. 4,061,724 and 4,073,865, respectively.

The present invention relates to the synthesis of new silicon dioxide-containing crystalline compounds, which are in principle aluminum-free and have surprisingly been found to have an X-ray diffraction pattern equal to that of the crystalline aluminosilicates of the ZSM-5 type. These materials are synthesized from a mixture containing an oxide of sodium (or potassium), an oxide of silicon, tetraalkyl or tetraarylammonium cation, sulfuric acid or a salt thereof, phosphoric acid or a salt thereof, and water.

8104347 - 2 _

The products of the invention, when prepared under autogenous pressure and using an acid (or a salt thereof) in the mixture, are extremely resistant to heating. They consist of well-separated, twisting, rectangular prismatic crystals of extremely uniform size and shape. Crystal size and thermal stability can be controlled with the nature of the acid and the pressure at which the synthesis is carried out.

The absence of the acid results in a mixture of relatively high pH. This mixture, when crystallized under autogenous pressure, results in yet another product composed of relatively large crystalline nests. These nests consist of rectangular prism-like crystals, which grow together.

The above-mentioned products contain SiO2, (TPA) 21

Na20 and anything but the last trapped phosphorus or sulfur. The product could also contain very small amounts of aluminum oxide, which is mainly due to aluminum oxide impurities in the starting materials used.

The sodium can be removed by first annealing the material in air at 537 ° C, followed by treatment with +41, H or NH2 -containing solution. The treated product is then calcined in air.

The materials of the invention are useful as catalysts for the conversion of organic compounds and as selective sorbents.

Specific preferred examples of the invention.

Example I

a. A reaction mixture was prepared by dissolving 650 g NaOH in 11000 ml H 2 O, followed by addition of 872 g H 3 PO 4 and 851 g (C 3 H 3) NBr (TPABr). To the resulting solution was added 3375 g of silica sol - 35 (40 wt% SiO 2) with continuous stirring. The overall reaction mixture, which had a pH of 8104347-3.8), had the following oxide mol ratios: EO '/ SiO = 0.20

Na 2 O / SiO 2 = 0.36 (TPA) 20 / SiO 2 = 0.07 H 2 O / SiO 2 = 33.10.

The synthesis mixture was placed in a 19 liter jacketed autoclave equipped with a screw stirrer and an oil heating unit and the mixture was allowed to crystallize at 145 ° C. The mixture was kept at this temperature for 52 hours, during which time intermediate samples were taken, filtered, washed with water and then dried overnight at 110 ° C.

b. Portions of the solids obtained in Example 1a were subjected to X-ray analysis. The data are summarized in Table A.

The X-ray powder diagrams of the samples listed in Table A were obtained by standard methods.

The radiation source was the K-alpha doublet of copper and a scintillation counter spectrometer connected to a strip chart pen recorder was used. The peak heights and their positions as a function of 2 times the Braggh angle (teta) were read from the spectrometer map. The relative intensities, 100 I / I, where I is the intensity of the strongest angle and o the observed interplanar space in A units (d) corresponding to the recorded lines, were then determined.

The samples listed in Table A all showed the same X-ray pattern. Table B shows a typical X-ray deflection pattern.

Portions of samples a and g of Table A were examined by scanning electron microscopy (SEM).

Both samples were highly crystalline and consisted of well-separated, highly uniformly-dispersed, rectangular prismatic crystals of extremely uniform size with curved edges. Sample a (autoclaved for 6 hours) showed extremely small amounts of amorphous material. The sides of the individual crystals were about 5.5 x 9 x 3.5 µm. SEM of sample g after calcination in air at 537 ° C for 4 hours was completely the same as without calcination.

The composition of sample g of Table A 5 was 8.66 wt% C, 0.68 wt% N, 80.21 wt% SiO 2, 0.12 wt% ^ 0 and 0.08 wt% P ^ 0, , which level remained the same after the sample had been annealed in air at 537 ° C for 4 hours.

Example II

The DTA of samples a through g of Table A were measured. All samples showed the same DTA, different intense walls at 350-500 ° C and a lower intensity symmetrical exotherm at 1093 + 7 ° C.

Example III

This is a duplicate of Example I except that the intermediate samples were taken at slightly different times, namely after 2, 4, 5.5, 12, 30, 46 and 54 hours. As in Example I, the collected washed and dried solids were analyzed by X-rays. The lines at 10.78, 9.82 and 3.80 A ° began to develop in the 20 2-hour samples. Between a crystallization time of 4 and 5.5 hours, the X-ray pattern shown in Table B was fully developed.

Example IV

Portions of samples a, e and g of Table A 25 were calcined in air at 537 ° C for 4 hours. The resulting products were then X-rayed. The deflection patterns were all the same.

Table C shows a typical X-ray diffraction pattern. The technique used in collecting the data from Table C is described in Example Ib.

Example V

Portions of samples a, e and g of Table A were calcined in air at 537 ° C for 4 hours. The thermogram (DTA) of the resulting products was then measured. The 350-500 ° C tires of Example II disappeared. The high temperature exotherm was still present, but had shifted slightly to a lower temperature (1076 ± 4 ° C). A broad weak endotherm also appeared, centered at about 115 ° C.

Example VI

5 aliquots of the calcined samples e and g of Example V were heated at reflux for 2 hours with 17% ammonium acetate solution. The solution to powder weight ratio was 10: 1. The DTA of the isolated washed and dried (110 °) solids showed that the 350-500 ° C bands and the high temperature exotherm were gone.

Example VII

a. A solution of 410 g NaOH and 455 g 96% SO 2 in 1 1222 ml H 2 O was prepared. While the solution was stirred, 851 g of tetra-n-propylammonium bromide (TPABr) were added. To the resulting solution was added 3375 g of silica sol (40 wt% SiO2) with continuous stirring. The mixture had a pH of 10.95 after stirring for 15 minutes. The composition was in moloxide ratios: 20 SO3 / SiO2 = 0.20

Na 2 O / SiO 2 = 0.23 (TPA) 20 / SiO 2 = 0.07 H 2 O / SiO 2 = 32.97

The reaction mixture was heated in an autoclave at 145 ° C for 69 hours. As in Example 1a, intermediate samples were taken, filtered, washed and then dried at 110 ° C.

b. Samples of the solids collected in Example Vila were analyzed by X-rays.

30 The data are summarized in Table D.

Samples c through h all had the same x-ray gene pattern, which is described in Table B. Only the strongest bands were about 25-30% developed in sample b.

SEM examination of sample 1 shows the same type of crystal morphology as in the phosphorus based product 8104347-6 of Example I. However, there are some differences. In this example, the crystals are larger (12.5 x 11 x 5 µm) and the twin contains more than 2 crystals. Crystal size and morphology did not change when the sample was calcined in air 5 at 537 ° C for 4 hours. Sample c (autoclaved for 12 hours) showed some amorphous materials when tested with SEM.

Chemical analysis of sample i showed the following composition: 8.85 wt% C, 0.79 wt% N, 77.41 wt% SiOg, 0.085 wt% Na 2 O, 0.04 wt% SO 2.

The SO 2 content remained at 0.04 wt% after annealing the sample in air at 537 ° C for 4 hours.

Example VIII

15 portions of the sulfuric acid (or sodium sulfate) samples c through i of Table D were calcined in air at 537 ° C for 4 hours and then subjected to X-ray analysis. All samples showed the same X-ray pattern as described in Table C.

Example IX

Samples c through i (prepared with sulfuric acid) from Table D were analyzed with DTA. All samples showed the same thermograms as described in Example II except that the high temperature exotherm (1094 ± 7 ° C) was absent. Actually, no bands were seen in the 500-1110 ° C temperature range. When calcining these samples at 537 ° C for 4 hours in air, the 350-500 ° C bands disappeared.

Comparative Examples A and B

Samples of silicalite and a silicon dioxide polymorph were prepared in accordance with U.S. Pat. No. 3,702,886 and U.S. Pat. No. 4,073,865, respectively. The silicalite was prepared by adding a solution of 14.2 g (C 2 H 4) NBr in 68 ml H 2 O by hand stirring 3 7 4 2 - 35 to 160.7 g Ludox HS-40 silica sol ( 40% SiO4). This mixture was mixed by hand with another solution containing 6.1 g NaOH in 101 ml H 2 O with stirring. The overall mixture thus had a moloxide composition of 2.0 (TPA) 20, 6.5 Na 2 O, 80 SiO 2, 1105 Η 0 0 (Na 2 O / SiO 2 = 0.081; (TPA) 20 / SiO 2 = 5 0.025; H 2 O / SiO 2 = 13 81). The mixture was placed in a stainless steel bomb, sealed and heated at 200 ° C for 43 hours. The product was then recovered by filtration, followed by washing and drying at 110 ° C, and from X-ray analysis, the product was free of quartz and was identified as silica-10. This mixture was used for further investigation. (Another mixture was autoclaved at 200 ° C for 72 hours.

This product showed quartz).

The silica polymer was prepared by adding a solution of 8.0 g NH 2 F dissolved in 39 ml H 2 O to 154 g Ludox HS-40 silica sol (40% SiO 2) diluted with 71 ml H 2 O. To this was added a solution of 5.7 g of NaOH in 20 ml of H 2 O, followed by the addition of another solution containing 13.8 g of (C 1 H 2 H 2 NBr in 39.2 ml H 2 O. The overall mixture thus had a mole composition of 0.791 SiO2 · 0.063 20 Na 2 O.0.166 NH 2 F, 0.02 (TPA) 20. 11.2 H 2 O (Na 2 O / SiO 2 = 0.080; NH 4 F / SiO 2 = 0.210; (TPA) 20 / Si 2 O = 0.025; H 2 O / SiO2 = 14.159).

The mixture was then placed in a stainless steel bomb, sealed and heated at 200 ° C for 92 hours. The product was filtered off, washed and then dried at 110 ° C. By X-ray analysis, the product was identified as a silica polymer polymorph, described in U.S. Pat. No. 4,073,865 (the pattern showed no quartz).

Portions of the silicalite and the silicon dioxide polymorph were analyzed by TDA. Both sample 30 showed the previously seen 350-500 ° C bands. The silicalite exhibited an exotherm at 960 ° C (including the one exhibiting quartz). The silica polymorph showed none in the 500-1100 ° C temperature range.

Samples of the silicalite (quartz free) and the silica polymer polymorph were also tested with SEM. The 810 43 4 7 - 8 - silicalite material consists of twirling crystals in which the surface is streaked (layered structure). The silicon dioxide polymer morph consists of fairly large rod-shaped crystals.

5 Example X

One-tenth of the weight of the reaction mixture described in Example 1a was placed in a 3-liter flask equipped with a cooler and mechanical stirrer. The mixture was heated under reflux for 700 hours under atmospheric pressure. Intermediate samples were collected, filtered, washed and then dried at 110 ° C. The collected solids were analyzed by DTA and X-rays. The data are summarized in Table E.

SEM of sample j shows that the crystals have the same morphology as that of example I except that they are more twirling and smaller in crystal size (3.5 x 5 x 1.75 µm).

Example XI

One-tenth of the weight of the reaction mixture described in Example 20 was placed in a 3-liter flask fitted with a cooler and mechanical stirrer. The mixture was heated under reflux for 700 hours under atmospheric pressure. Intermediate samples were collected, filtered and then dried at 110 ° C. The collected solids were analyzed by DTA and X-rays. The data is summarized in Table G.

For convenience, the high temperature (500-1100 ° C) DTA bands of the products of the present invention, silicalite and silica polymer polymorph are listed in Table F.

Again, the same twinning was obtained, but the crystal size was much smaller than that of Example X.

Example XII

The infrared (IR) of sample b of table Aj 8104347% 9 sample h of table D, sample f of table E and sample k of table G were measured on wafers containing 2 mg sample and 200 mg KBr. Also, the IR of silicalite and silicon dioxide polymer form of Comparative Examples A and B were included.

5 Silicalite and silicon dioxide polymorph vert -1.

and a weak, well-defined band at 700 cm as opposed to no band in the samples of the present invention (acid-based products).

Example XIII

10 portions of sample g of table A, sample i of table D, sample j of table E and sample k of table G were simultaneously fired at 537 ° C in air for 4 hours. The silicalite and the silicon dioxide polymorph of the comparative examples were calcined in air at 600 ° C for 2 hours. This is 15 according to U.S. Pat. Nos. 4,061,724 and 4,073.

865 recommended temperature. All samples were then refluxed with 17 wt% ammonium acetate solution for 2 hours. The solution to sample weight ratio was 10: 1. The samples were then filtered and then washed thoroughly with water. This step was repeated once followed by drying at 110 ° C overnight.

Portions of the above samples were simultaneously fired in air at 537 ° C in shallow beds for 4 hours. Using fresh samples, more anneals were performed at 1200, 1250, 1300, and 1350 ° C for different times. All samples were then X-rayed. In addition to these samples, a commercially available hydrogen mordenite powder from the Norton Company was calcined in air at 1150 ° C for 2 hours and then analyzed by X-ray.

No decrease in crystallinity was observed at 537 ° C (the same as in Table C). The crystallinity of these substances was considered as a reference. The crystallinity of the samples annealed at 1200-1350 ° C was calculated using the following formula: 8104347 - 10 - (i - o

Sum x-ray line intensity at 11.05 A, 9.94 A °, 3.83 A ° and 3.71 A ° of material a, annealed at T ° C x 100. __% crystallinity = _. . . . .. ..... , ..

Sum x-ray intensity at d = 11.05 A °, 9.94 A °, 3.83 A ° and 3.71 A ° of material a, annealed at 537 ° C.

The data are shown in Table G.

The table also includes one or more other phases that developed at a given annealing temperature / time. Only one X-ray crystalline phase could be observed, namely alpha crystalline, which is a form of silicon dioxide.

The hydrogen mordenite sample was completely decomposed (amorphous) at 1150 ° C.

Example XIV

15 portions of autoclaved and refluxed H 2 PO 3 and H 2 SO 2 product, silicalite and silica polymer of Example XIII were tested for absorption. The data was collected at liquid nitrogen temperature and a partial nitrogen pressure of 0.20. Furthermore, the BET internal surface was also measured. Both data are shown in Table I.

Summary of Examples I to XIV

Example I

This example simply describes the synthesis of the crystalline organosilicate using phosphoric acid in the composition. It also shows that the product reaches maximum crystallinity after about 6 hours of crystallization. The fact that the X-ray pattern remained unchanged for 52 hours indicates that the product is highly stable under the synthesis conditions.

It also shows that the product contains an organic component, namely a tetrapropylammonium compound and a phosphorus-containing component. The fact that the phosphorus content remained the same after calcination of the material at 537 ° C for 48104347 hours for 11 hours suggests that the phosphorus is in a non-volatile form.

Another important observation is the extremely uniform crystal shape, which was maintained throughout the autoclave treatment period. Also, no crystal distortion or shrinkage occurred when the product was calcined in air at 537 ° C.

Example II

Here the thermal behavior of the product is shown on calcination in air. The 350-500 ° C DTA bands are due to the decomposition of the tetrapropyl ammonium component. The exotherm at 1093 ° C indicates a phase transformation.

Example III

This is a duplicate of Example I, which shows that the synthesis procedure is reproducible.

Example IV

This example shows that calcination of the product in air at 537 ° C results in a change in composition and / or crystal structure as indicated by the change in X-ray deflection.

Example V

Here, more evidence is shown of the presence of the tetrapropylammonium (TPA) component in the product as indicated by the disappearance of the 350-500 ° C

DTA bands when the material was pre-calcined. The 1076 ± 4 ° C DTA exotherm indicates that the product retains its high temperature phase transformation when the TPA component is removed. The weak 115 ° C endotherm is attributed to water.

Example VI

This example shows that the transformation that occurs at 1076 ° C in the calcined product (prepared from the H 2 PO 2 mixture) does not occur when the sample is treated with ammonium acetate. This indicates that the product before treatment with ammonium contains sodium, the presence of which destabilizes the structure.

Example VII

It is shown that using sulfuric acid in the mixture results in a product with the same X-ray diffraction pattern as the phosphoric acid-based product. The product also contains the PTA component and sulfur. As in the phosphoric acid based product, the sulfur occurs in a non-volatile form as evidenced by the composition (same sulfur content) of the sample annealed at 537 ° C.

The SEM study indicates that the H 2 SO 4 based product crystallizes somewhat more slowly than the H 2 PO 3 derivative. Another observation is the exceptionally uniform crystal size. Neither the crystal size nor its uniformity changes to an autoclave even after 69 hours of treatment.

This was also evident with the H 2 PO 4 based products. Also note that the crystals of the SO 2 product are larger than the HOPO. material. This shows that the nature or strength of the acid determines the crystal size. Another difference between the two products (SO 2 and H 2 PO 3) is that the twinning in the SO 2 based product consists of more than 2 crystals.

Example VIII

This example shows that calcination of the H 2 SO 4 based product gives an X-ray pattern similar to that of the calcined H 2 PO 3 based material.

Example IX

It is shown here that the product (calcined or uncalcined) prepared from a sulfuric acid-based mixture does not behave the same as that produced with H 2 PO 4 when heated in air at 500-1100 ° C. This is evidenced by the absence of the 1093 ° C exotherm, which appeared in the phosphor case. The 350-500 ° C DTA bands indicate that the uncalcined product contains, as well as prepared with H 2 PO 4, the 8104347-13 TPA component.

Comparative examples A and B.

It is shown herein that the DTAs of silicalite and silicon dioxide polymorph which have the same X-ray patterns are different from the H 2 PO 4 based product. The silicalite has an exotherm at 960 ° C as opposed to 1093 ° C in the H 2 PO 4 product. The silica polymer polymorph showed none in the 500-1100 ° C temperature range.

The crystal morphology of silicalite and silicon dioxide polymorph are different from all species of the present invention. The silicalite shows the same twist, but the individual crystals do not show sharp boundaries as with the others. The crystal surfaces are also striped (layered structure).

Example X.

This example shows that refluxing the H 2 PO 4 based mixture results in a crystalline product having the same X-ray pattern as in the product prepared by autoclaving (autogenous pressure). However, the crystallization rate is slow. The product of this example still contains the TPA component (the 350-500 ° C TDA bands). However, it differs from the autoclaved product when heated in air at 500-1100 ° C. This is evidenced by the absence of any TDA band in this temperature range.

Another difference between the product of this example and the product prepared by autoclaving is in the morphology and size of the crystals.

The product produced by reflux appears to have more twinning and most importantly, the size of the crystals is much smaller than that of the autoclaved material. This small crystal size may be desirable in certain catalytic applications. Crystals of both products (heated under reflux or in an autoclave) exhibit the same strong uniformity.

8104347 - 14 -

Example XI

It is shown here that reflux heating of the containing mixture results in a crystalline product having the same X-ray pattern as the product prepared by autoclaving. The product still contains the TPA component as indicated by the 350-500 ° C DTA bands. However, it differs in behavior of the product prepared by autoclaving by the presence of a DTA exotherm at 950-1005 ° C when heated in air. Like the refluxed H 2 PO 4 based product, the crystallization rate is slow.

For comparison, Table F shows the 500-1100 ° C portion of the DTA of products of the present invention, silicalite and silicon dioxide polymorph.

Crystals of this example still have the same great uniformity and twinning as shown in the preceding examples. However, the crystals are much smaller in size (1-2.5 µm) than any other product (H 2 PO 4 and H 2 S0 autoclaved and H 2 PO 2 heated under reflux).

The crystal size decreases in the following order: autoclaved H ^ SO ^ material ^ autoclaved H ^ PO ^ material ^ heated to reflux H ^ PO ^ pounder reflux heated ^ SO ^ material.

Example XII

This example shows that the products of the present invention (prepared in the presence of acid by autoclaving or refluxing) are structurally different from silicalite and the silicon dioxide polymorph.

This is because silicalite and thus silicon dioxide polymorphic IR bands have -1 at 700 cm m as opposed to no bands in the products of the present invention. Bands in the middle infrared region (200-1300 cm) represent structural features of zeolite lattices. (Breek, D.W., "Zeolite Molecular 8104347-15 -

Sieves, "John Wiley and Sons, N.Y. (1974), page 415).

Example XIII

This example shows that incorporation of an acid into the mixture (eg H 2 SO 2) and carrying out the reaction under autogenous pressure results in products of extremely high thermal stability. This thermal stability is much greater than that of silicalite, silicon dioxide polyphenorph and H-mordenite. The data of this example was collected on ammonium salt treated material, i.e., sodium 10 oxide had been removed (the mordenite was in hydrogen form). In almost all catalytic applications, it is desirable that the catalyst contain little or no sodium oxide.

Based on the results of this example, the thermal stability decreases in the following order: autoclaved H ^ PO ^ based product} autoclaved based product / silicalite ^ refluxed, H ^ PO silicon dioxide depolymorph based product heated to reflux based on H-mordenite based product. ! This example also shows that the thermal stability can be varied with the nature of the acid used and the pressure at which the synthesis is performed.

Example XIV

This example shows that the products based on H 2 O 2 and H 4 PO 2 (autoclaved and refluxed) have porous structures as evidenced by their high affinity for adsorbing nitrogen and their large internal properties. surface. These properties make these products valuable as catalysts for the conversion of organic compounds and as adsorbents.

Example XV - Catalysis.

A portion of sample g of Table A (autoclaved H 2 PO 4 product - 52 hours) was calcined in air at 537 ° C for 4 hours. This was followed by 2 treatments - 35 with NH 4 OAc solution as described in Example VI. The resulting powder was extruded into 1/16 "pellets using 20% Al 2 O 3 (Al 2 O 3 source was boehmite). The pellets were dried at 110 ° C and then 5 hours calcined in air at 537 ° C.

The pellets, 20 ml, were placed in a tube reactor and subjected to a feed of normal pentane and E at a temperature range of 254-374 ° C. The n-pentane was converted to other hydrocarbons, which are listed in Table K. The table also shows detailed operating conditions under which the catalyst was tested.

This example shows that the autoclaved H 2 PO 4 product is active for the conversion of n-pentane to other hydrocarbons. The total conversion and selectivity for cracked products increased with increasing temperature. Total conversion increased exponentially with temperature.

Close examination of these data reveals that at low temperature (254-316 ° C) isomerization activity predominates over hydrocracking, while at high temperatures (316-375 ° C) hydrocracking activity is preferred.

It is interesting to note that COH0 is the main component of the cracked products. The relative amounts of cracked products decrease in the following order: C 1 Hg> 1 C 4 H 10 * n "4H 10> C 2 H 6" CH 4 "Example XVI - Catalysis.

Some ammonium acetate-treated powder of Example XV was extruded into 1/16 "pellets using 5% Al 2 O 4. The pellets were dried at 110 ° C and then air-calcined at 537 ° C for 5 hours.

The resulting catalyst was then subjected to n-pentane conversion using the same conditions as in Example XV, but the liquid flow rate per hour was increased from 1.00 to 1.25 per hour. Results and detailed operating conditions are shown in - 35 table L.

8104347 - 17 -

This example further shows that the autoclaved H 2 PO 4 based product can be used as a catalyst for the conversion of n-pentane into other hydrocarbons of different molecular weights as shown in Example XV. The fact that the activity was less than shown in Example XV is due to the larger spatial flow rate, which means a shorter contact time between the feed and the catalyst.

Example XVII - methanol conversion.

At the end of the test of Example XVI

the catalyst was kept in the reactor and subjected to a methanol feed. The test was performed at 1 atmosphere, a flow rate of 1.25 per hour and a temperature of 429-447 ° C. The results are summarized in Table M.

It is shown here that the autoclaved H 2 PO 4 based material is active for the conversion of methanol to other hydrocarbons. Some products have been identified as being hydrocarbons. The others are high molecular weight hydrocarbons, which could be either aliphatic or aromatic in nature.

The results of this example confirm that the product is a molar-selective zeolite.

Example XVIII

The nitrogen absorption and the BET internal surface of autoclaved, H 2 PO 4 based products, silicalite and refluxed H 2 PO 3 product, which had been annealed at 1300 ° C for 2 hours (see Table H - example XIII) were measured. The data are shown in Table J. The table also shows data of substances which have been calcined in air at 537 ° C for 4 hours. As in Example XVI, the data of the product calcined at 1300 ° C was collected at the liquid nitrogen temperature and a nitrogen pressure of 0.20.

In this example, more support is given for the fact claimed in Example XIII, that the thermal stability of autoclaved acid-based products is much higher than that of silicalite. For example, with the H 2 PO 4 based product, about 21% of the nitrogen absorption capacity of the interior surface is retained after calcination at 1300 ° C for 2 hours, with the silicate retaining only 7.4%. The retained sorption and internal surface area of the I 2 SO 2 derivative (12.6-13.2%) were also higher than that of silicalite.

10 8104347 - 19 -

Table A

Crystalline resistance to crystallization time of uncalcined products.

! ί i (H ^ PO ^ based mixture, Example Ib) ί

Sample crystallization time, hour X-ray deflection a 6.0 strong crystalline b 12.6 strong crystalline c 22.0 strong crystalline d 30.0 strong crystalline e 36.0 strong crystalline f i + 6.0 strong crystalline g 52.0 strong crystalline! J! | ί i | I | r: ................................................ ................._ _................... j 8104347 ψ - 20 -

Table Ε i

Characteristic X-ray pattern of de-calcined products. (H ^ PO ^ based formulation, Example Ib) d (a) _ Relative Intensity 10.78 moderate-strong 9382 moderate-strong 9361 moderate-weak 8.85 weak 7338 moderate-weak 6.97 weak 6.61 weak 6.28 moderate-weak 5s99 moderate-weak 5.91 moderate-weak 5.64 moderate-weak 5350 moderate-weak 4.93 weak 4.55 moderate-weak 4.33 moderate-weak 4.23 moderate-weak 3.97 moderate-weak 3.80 very strong 3.72 strong 3, 69 strong 3.62 strong 3.43 moderate-weak 3.33 moderate-weak 3.29 moderate-weak 3.03 moderate-weak 2.97 matte weak 2.92 weak 2.71 weak 2.59 weak 2.48 weak 2.39 weak 2, 00 moderate-weak 1.99 moderate-weak 1.95 weak 1.91 weak 1 387 weak 1.65 weak 1.48 weak | j | 8104347 * - - 21 -

Table C

X-ray deformation pattern of calcined product (Based on preparation, example IV) d (A) _; _ Relative intensity j 11.0 very strong j 9.97 very strong 9.72 moderate-weak (bending)! 6.61 weak 6.33 moderate-weak 5.95 moderate-strong 5.6U moderate-strong 5.57 moderate-strong 5.31 weak 7.96 weak 1 +, 58 weak 1 +, 35 weak 1 +, 23 moderate-weak 3.97 weak 3 .83 very strong 3.82 strong (bend) 3.77 strong (bend) 3.71 strong 3.62 moderate-weak 3.73 weak 3.29 weak 3.01 + 1 weak 2.98 moderate-weak 2.97 weak 2.73 weak 2, 61 weak 2.1 + 7 weak 2.38 weak 2.01 moderate-weak 1.99 moderate-weak 1.95 weak 1.91 weak 1.87 weak 1.66 weak 8 104 347 - 22 -

Table D

Crystallinity against crystallization time of non-calcined products.

(HSO4 based mixture, example IIIb) "i. .

Sample _ Crystallization time, hour_ X-ray diffraction a 2.5 mostly amorphous b 5 crystalline c 12 strong crystalline d 21 strong crystalline e 29 strong crystalline f 36 strong crystalline g i + 5 strong crystalline h 53 strong crystalline i 69 strong crystalline iiii i ... ..

j _________________________ _ _ _ | 8104347 - 23 - i

Table E

DTA 1 crystallinity against crystallization, of uncalcined products (H 2 PO 4 based mixture / reflux, Example X)

Sample_Crystallizes, hour, X-ray radiation ^ DTA ^ a 2k amorphous b 1 | 8 amorphous c 72 crystalline d 96 crystalline e 168 strong crystalline 350-500 ^ 0 f 1 <j2 π - 11 bands |

g 216 "" 350-500 ° C

tires

h 267 "" 350-500 ° C

tires

578 "350-500 ° C

tires

700-700 ° C

bands o 1. Samples e through j showed the same X-ray pattern as m table B of example Ib. The band intensities of samples c and d were U5 and 80%, respectively, compared to the other highly crystalline samples.

2. No bands appeared between 500 and 1110 ° C.

j ί 1 i

. I

j 8104347 - 24 -

Table F

DTA of different crystalline silicon dioxide! containing preparations.

300-1100 ° C range (Example XI) o

Material_Exothermic temperature, C

Product based on autoclave (Example 1) 1093 + 7 °

HSO-based product (autoclave) (example / Vil) none

Acid-free product (autoclave) (example X) 915 - 1035

H ^ PO ^ based product reflux (Example XXII) none

H 2 SO 4 based product reflux (Example XIII) 959 qO3

Silicalite (Example XI) 9gg

Silica polymorph none * All material showed 350-500 ° C. ρτΑ tires.

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Table I

N ^ absorption and internal. surface of various silicon dioxide containing substances.

(example XXV)

Material N ^ absorption Internal

Scc N ^ / g surface

Product based (autoclave) 110.5 3.78.5!

Based on H ^ SO ^; product (autoclave) 113.7 196.9!

H PO ^ based I

product (reflux) 119.3 U21.9

H 2 SO 4 based product (reflux) 96.6 330.0

Silicalite 97.7 ^ 330.5

Silicon Dioxide Polymorph 121.0 × 13 ^ 7 i j

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rH

a 33 * Ο Ο Ο a η Λ Ρ ο ο ο

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3! -Ι P

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ft O.

p o cd μ Ρ Ρ μ o!> * 0 ft & o ft μ 6 ^ Ό • i-l ft CC ft

(1) <D O P

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ft O H ft S H

| > ft Η p O

ί · η co> i-i ö ai m

ft 33> <> P O 'O'> - I

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M ft P ft 50 OP

<1 ft Ρ μ 50 h É H -O ft! O P ftp P P O μ ra r-l

N ft> CU S-ι O

g ^ H O> o ft - • Oh

r-l Ρ Ό O

AT Β ft ft

P ft ft O P

po p ft ra ft O ra ft ft «· ft ft

PP ft P P

SP l p o ft

μ μ ft P

o μ p l> ft ft P μ

P P P

ra Ό p co | f>% ra c ·· co ··

ft p ft ·· ** P

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; ft ft

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ft ft B ft 50

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p

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Claims (2)

Silicon dioxide polymorph characterized in that it has an X-ray powder deflection pattern with the d distances shown in Table C and retains more than 50% of its crystallinity after calcining at 1300 ° C for 2 hours. 5 Silicon dioxide polymorph according to claim 1, characterized in that it has no infrared adsorption band at -1 700 cm. 10 8104347