Crystalline silicates

Abstract: Silicates having in the as-synthesized form the formula (M 2/n O) p :(TMA₂O) q :SiO₂:(Al₂O₃) r :(H₂O) s wherein M represents an alkali metal or alkaline earth metal of valency n and TMA represents a tetramethylammonium cation and wherein 0 ≦ p < 0.3; 0.01 < q < 0.4; 0 ≦ r < 0.01 and 0 ≦ s < 4. They can be prepared from a forming solution comprising a mixture having the molar composition a (M 2/n O):bTMA₂O:SiO₂:cAl₂O₃:dH₂O wherein 0 ≦ a < 0.5; 0.05 < b < 10; 0 ≦ c < 0.01 and 5 < d < 100 wherein the OH-/SiO₂ molar ratio is at least 0.3, which mixture is kept at elevated temperature for a time sufficient to produce crystalline material followed by separating off the crystalline material produced.

Description: The present invention relates to novel crystalline silicates and their preparation as well as to novel silicates thus prepared. The present invention also relates to the use of the novel silicates as molecular sieves and as catalyst carriers. Synthetic crystalline materials are of general interest. Much attention has been and is paid to the synthesis of crystalline aluminosilicates, often referred to as synthetic zeolites since they find wide application in industry as molecular sieves, catalyst carriers as well as catalysts, e.g. in catalytic cracking and hydrocracking. Apart from the almost classical zeolites also crystalline silicates have been reported in the art. Examples of this class of materials comprise silicalite and structures designated as ZSM-11, ZSM-12 and ZSM-39. It has now been found that novel synthetic crystalline silicates can be prepared from crystalline forming solutions when use is made of specific molar ratios of the forming components and using a specific organic nitrogen-containing cation. United States patent specification n o 4060 590 describes a zeolite NU-1 having a specified as synthesized chemical composition and prepared by a process using a methylated quarternary ammonium compound. The present invention relates to silicates having in the as-synthesized form the formula: (M 2/n O) p : (TMA₂0) q :SiO₂:(Al₂O₃) r : (H₂O) s wherein M represents an alkali metal or alkaline earth metal of valency n and TMA represents a tetramethylammonium cation and wherein O ≦ p < 0.3; 0.025 < q < 0.4; 0 ≦ r < 0.01 and 0 ≦ s < 4. The present invention relates in particular to synthetic crystalline silicates which do not contain alumina in their structure or only to a limited amount, i.e. silicates having a SiO₂:Al₂O₃ molar ratio larger than 100, in particular larger than 200. In particular, the present invention relates to silicates according to the formula as described hereinabove wherein M represents an alkali metal cation and p < 0.15; 0.025 < q < 0.35; r < 0.01 and 0.1 < s < 2. Preference is given to silicates having also a rather low amount of alkaline (earth) metal moieties in the structure, i.e. to silicates wherein p < 0.1; 0.04 < q < 0.3; r < 0.005 and 0.3 < s < 1.75. An example of a novel synthetic crystalline silicate according to the present invention comprises the structure indicated as SCS-1 having in the as-synthesized form the formula (0.10-0.20)TMA₂O:SiO₂:(Al₂O₃) r :(0.5 - 1.5)H₂O wherein r < 0.005 and having an X-ray diffraction pattern as given in Table I. A further example comprises the structure indicated as SCS-2 having in the as-synthesized form the formula (0-0.1)Na₂O:(0.025-0.20)TMA₂O:SiO₂:(Al₂O₃) r :(0.1-1.5)H₂O wherein r < 0.01 and having an X-ray diffraction pattern as given in Table II. The crystalline silicate SCS-2 can be suitably subjected to drying and calcining to remove at least part of the water from the as-synthesized product together with at least part of the tetramethylammonium cation. This can be carried out at temperatures up to around 470 °C whilst maintaining a substantial part of the crystallinity of the product. It is preferred to carry out the calcination at a temperature between 400 and 465 °C. A further example comprises the structure indicated as SCS-4 having in the as-synthesized form the formula (0-0.1)Na₂O:(0.05-0.25)TMA₂O:SiO₂:(Al₂O₃) r :(0.3-1.5)H₂O wherein r < 0.01 and having an X-ray diffraction pattern as given in Table III. The present invention also relates to a process for synthesizing silicates of the general formula (M 2/n O) p :(TMA₂O) q :SiO₂:(Al₂O₃) r :(H₂O) s from a forming solution having a molar composition of a(M 2/n O) :bTMA₂O:SiO₂:cAl₂O₃:dH₂O wherein M represents an alkali metal or alkaline earth metal of valency n and TMA represents a tetramethylammonium cation and wherein 0 ≦ a < 0.5; 0.05 < b < 10; 0 ≦ c < 0.01 and 5 < d < 100 and wherein the OH-/SiO₂ molar ratio is at least 0.4, which mixture is kept at elevated temperature for a time sufficient to produce crystalline material followed by separating off the crystalline material produced. The expression OH⁻ as used herein comprises hydroxyl ions added to the forming solution originating from both tetramethyl anmonium hydroxide and the appropriate metal hydroxide (s). It should he noted that the products obtained may contain alumina. Alumina can be introduced into the structure when use is made of a forming solution containing (optionally) an alkaline (earth) cation, a tetramethylammonium cation, a source of silica, a source of alumina and water within the molar ranges as specified hereinabove. A preferred process for producing the crystalline silicates, optionally containing small amounts of alumina in their structure comprises using a mixture having the following molar relationship between the various constituents 0 ≦ a < 0.25; 0.1 < b < 2; 0 ≦ c < 0.005 and 8 < d < 50 and wherein the OH-/SiO₂ molar ratio is between 0.4 and 1.5. It is also possible to synthesize the crystalline silicates according to the present invention by using one or more compounds of the general formula R₁R₂O wherein R₁ and R₂ represent a (substituted) hydrocarbyl moiety and one of R₁ and R₂ may represent a hydrogen atom in the forming solution provided a molar ratio R₁R₂O:SiO₂ not above 10 is applied. Preferably, when using a compound according to the general formula R₁R₂O, a R₁R₂O:SiO₂ molar ratio at most 2 is applied. Examples of compounds according to the general formula R₁R₂O comprise alcohols such as methanol, ethanol and mixtures thereof, and ethers such as methoxymethane, ethoxyethane as well as mixtures thereof and low molecular weight cyclic ethers. It should he noted that the alkali and alkaline earth ions as well as the nitrogen containing cations can be added in the form of the hydroxides and/or suitable salts. The process according to the present invention is normally carried out at temperatures between 75 °C and 250 °C, in particular between 125 °C and 225 °C. Normally the novel crystalline structures will be produced when the forming solution has been kept under the appropriate conditions for a period of time ranging between 12 and 750 hours allowing for the proper structure to be formed and in reasonable amounts. Preferably the process according to the present invention is carried out for a period of time ranging between 24 and 500 hours. It has been found that sometimes agitation is advantageously applied to produce the desired synthetic crystalline silicate from the forming solution. The structures SCS-1 and SCS-4 can be suitably produced when the forming mixture is kept for a sufficient period of time at about 150 °C under continuous stirring. It is possible to subject the crystalline silicates according to the present invention to a metallating procedure in order to increase the amount of the appropriate metal(s) present in or to be incorporated into the system. Preferred metallation procedures comprise the incorporation of aluminium and/or gallium moieties into the crystalline silicates according to the present invention. In particular, the incorporation of aluminium moieties is of interest in order to increase the number of acid sites in the system. The metallation can be carried out by methods known in the art. The novel compounds according to the present invention can be used as molecular sieves, optionally after (partial) drying and/or calcining, as well as catalyst carriers. In particular alumina-containing crystalline silicates can be used as carriers in the production of catalytically active species, e.g. by incorporating therein one or more metals with catalytic activity. The invention will now be illustrated by means of the following Examples. Example 1 - Preparation of SCS-1 364 Grammes of a 25% tetramethylammoniumhydroxide solution (ex Fluka) and 60 grammes of silica (ex Baker, dehydrated at 350 °C) were mixed together to form a mixture having a molar composition 1 tetramethylammonium hydroxide:1 SiO₂:15H₂O. This mixture was kept under stirring at 150 °C for 72 hours. After cooling, a crystalline compound was obtained having the molar composition 0.16 TMA₂O:SiO₂:(Al₂O₃) r :0.9H₂O wherein r < 0.01 and having an X-ray diffraction pattern as given in Table I below. D spacing (Å) Intensity 13.8 ± 0.2 VS 4.8 ± 0.1 M 3.8 ± 0.1 M 3.40 ± 0.05 M 2.70 ± 0.05 M The yield of the compound SCS-1 amounted to 44 %wt (calculated on the amount of SiO₂ present in the forming solution). The crystallinity of the product obtained was 100%. The experiment described hereinabove was repeated with similar starting materials but using a more concentrated tetramethylammonium hydroxide solution giving a SiO₂:H₂O molar ratio of 12.5. The mixture was kept under static conditions for 168 hours at 150 °C without any detectable product being formed. The mixture was held under static conditions for another 168 hours at the same temperature. SCS-1 together with some amorphous material was formed. The experiment described hereinabove was repeated using tetramethylammonium hydroxide, SiO₂ and H₂O in a molar ratio 0.5 tetramethylammonium hydroxide:SiO₂:12.5 H₂O. Tetramethylammonium chloride was added to give a Cl-/SiO₂ ratio of 0.5. This mixture was kept under static conditions at 150 °C for 168 hours to yield SCS-1 together with amorphous material. Example 2 - Preparation of SCS-2 364 Grammes of a 25 %wt solution of tetramethylammonium hydroxide (ex Fluka) and 60 grammes of silica (ex Baker, dehydrated at 350 °C) were mixed together to form a mixture having a molar composition 1 tetramethylammonium hydroxide:1 SiO₂:15 H₂O. This mixture was kept under static conditions at 150 °C for a period of 168 hours. After this time a small amount of the novel silicate SCS-2 could be isolated. The mixture was kept under the same conditions for another 168 hours yielding SCS-2 together with amorphous material. The molar composition of the crystalline compound as-synthesized was: 0.05 TMA₂O:SiO₂:(Al₂O₃) r :0.6H₂O wherein r < 0.01, and it has an X-ray diffraction pattern as given in Table II. D spacing (Å) Intensity 9.0 ± 0.1 M 8.3 ± 0.1 M 6.6 ± 0.1 M 6.3 ± 0.1 M 4.5 ± 0.1 M 4.3 ± 0.1 M 4.2 ± 0.1 M 4.0 ± 0.1 VS The amount of SCS-2 obtained was 15 %wt. Another form of the crystalline compound SCS-2 could be prepared as follows: A clear solution of 45 grammes of tetramethylammonium hydroxide (25% ex Fluka), 15 grammes of silica (ex Baker and dehydrated at 350 °C) and 22 grammes of water were subjected to evaporation to yield a forming solution containing a molar composition 0.25 TMA₂O:SiO₂:12.5 H₂O. This mixture was kept under static conditions at 150 °C for a period of at least 168 hours, after which the crystalline silicate SCS-2 could be isolated. The molar composition of the silicate as-synthesized was 0.07 TMA₂O:SiO₂:0.29 H₂O. The SCS-2 compound was obtained in 100% crystallinity. Example 3 - Preparation of SCS-4 30 Grammes of a clear solution of tetramethylammonium hydroxide and water also containing 0.4 grammes of sodium chloride was prepared to give a forming solution having a molar composition 0.05 Na₂O:1 tetramethylammonium hydroxide:SiO₂:15 H₂O. When this mixture was stirred for 72 hours at 150 °C no product was obtained. When the mixture was kept under the same conditions for a further 96 hours the novel silicate SCS-4 had been formed with 100% crystallinity in a yield of 35 %wt. The molar composition of the compound SCS-4 as-synthesized was 0.07 Na₂O:0.1 TMA₂O:SiO₂:0.6 H₂O, and it has an X-ray diffraction pattern as given in Table III. D spacing (Å) Intensity 11.3 ± 0.2 M 5.7 ± 0.1 VS 4.2 ± 0.1 M 3.8 ± 0.1 S 3.25 ± 0.05 M 3.10 ± 0.05 M 2.85 ± 0.05 M

Claims: Silicates with the exception of NU-1 zeolite having in the as-synthesized form the formula: (M 2/n O)p:(TMA₂0) q :SiO₂:(Al₂O₃) r :(H₂O) s wherein M represents an alkali metal or alkaline earth metal of valency n and TMA represents a tetramethylammonium cation and wherein O ≦ p < 0.3; 0.025 < q < 0.4; 0 ≦ r < 0.01 and 0 ≦ s < 4. Silicates according to claim 1 wherein M represents an alkali metal cation and p < 0.15; 0.025 < q < 0.35; r < 0.01 and 0.1 < s < 2. Silicates according to claim 2, wherein p < 0.1; 0.04 < q < 0.3; r < 0.005 and 0.3 < s < 1.75. Silicate having in the as-synthesized form, the formula (0.10 - 0.20)TMA₂O:SiO₂:(Al₂O₃) r :(0.5-1.5) H₂O wherein r < 0.01 and having an X-ray diffraction pattern containing at least the lines given hereinbelow: D spacing (Å) Intensity 13.8 ± 0.2 VS 4.8 ± 0.1 M 3.8 ± 0.1 M 3.40 ± 0.05 M 2.70 ± 0.05 M Silicate having in the as-synthesized form the formula (0-0.1)Na₂O:(0.025-0.20)TMA₂O:SiO₂:(Al₂O₃) r :(0.1-1.5)H₂O wherein r < 0.01 and having an X-ray diffraction pattern containing at least the lines as given hereinbelow: D spacing (Å) Intensity 9.0 ± 0.1 M 8.3 ± 0.1 M 6.6 ± 0.1 M 6.3 ± 0.1 M 4.5 ± 0.1 M 4.3 ± 0.1 M 4.2 ± 0.1 M 4.0 ± 0.1 VS Silicate having in the as-synthesized form the formula (0-0.1)Na₂O:(0.05-0.25)TMA₂O:SiO₂:(Al₂O₃) r :(0.3-1.5)H₂O wherein r < 0.01 and having an X-ray pattern containing at least the lines as given hereinbelow: D spacing (Å) Intensity 11.3 ± 0.2 M 5.7 ± 0.1 VS 4.2 ± 0.1 M 3.8 ± 0.1 S 3.25 ± 0.05 M 3.10 ± 0.05 M 2.85 ± 0.05 M Process for synthesizing silicates of the general formula according to claim 1 from a forming solution comprising a mixture having the molar composition a (M 2/n O):bTMA₂O:SiO₂:cAl₂O₃:dH₂O wherein 0 ≦ a < 0.5; 0.05 < b < 10; 0 ≦ c < 0.01 and 5 < d < 100 and wherein the OH-/SiO₂ molar ratio is at least 0.4 which mixture is kept at elevated temperature for a time sufficient to produce crystalline material followed by separating off the crystalline material produced. Process according to claim 7 wherein a mixture having a molar composition wherein 0 ≦ a < 0.25, 0.1 < b < 2; 0 ≦ c < 0.005 and 3 < d < 50 and wherein the OH-/SiO₂ molar ratio is between 0.4 and 1.5 is kept at elevated temperature for a time sufficient to produce crystalline material followed by separating off the crystalline material produced. Process according to claim 7 or 8 wherein the forming solution also contains one or more compounds of the formula R₁R₂O wherein R₁ and R₂ represent a (substituted) hydrocarbyl moiety and one of R₁ and R₂ may represent a hydrogen atom and wherein the molar ratio R₁R₂O:SiO₂ is not above 10. Process according to claim 9 wherein use is made of a forming solution having a R₁R₂O:SiO₂ ratio of at most 2. Process according to any one of claims 7-10 wherein the temperature is kept between 75 °C and 250 °C, in particular between 125 °C and 225 °C. Process according to any one of claims 7-11 wherein the forming solution is kept for a period between 12 and 750 hours under crystal-forming conditions, in particular between 24 and 500 hours. Process for the preparation of crystalline silicates as defined in claims 4 and 6 according to a process according to one or more of claims 7-10 whilst applying agitation to the forming mixture. Use of silicates according to one or more of claims 1-6, which may have been subjected to a drying and/or calcining treatment, as molecular sieves. Use of silicates according to one or more of claims 1-6, which may have been subjected to a drying and/or calcining treatment as catalyst carriers.

Inventors: DE JONG-VERSLOOT PETERINA CORN, KORTBEEK ANDRAS GUUS THEODORUS, POST MARTIN FRANCISCUS MARIA, VAN DEN BERG JOHANNES PETRUS, DE JONG-VERSLOOT, PETERINA CORNELIA, KORTBEEK, ANDRAS GUUS THEODORUS GEORGE, POST, MARTIN FRANCISCUS MARIA, VAN DEN BERG, JOHANNES PETRUS
Applicants: SHELL INT RESEARCH, SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1988
Main classification: C01B33
IPC codes: C01B39, C10G11, C01B37, C10G35, B01J29, C10G47