Patent EA-000242-B1 (EA)
Title: Ers-10 zeolite and process for its preparation
Inventor: CARLUCCIO LUCIANO
IPC: C01B39/48
Filed: 1997-03-20
Abstract: 1. A porous crystalline material designated ERS-10 zeolite having in its calcined and anhydrous form a molar composition of oxides corresponding to the general formula (I) mM2/nOxzX2O3xYO2 (I), wherein: m is a number of between 0.01 and 10, M is H<+> and/or a cation of an alkaline or earth-alkaline metal with valence n, z is a number between 0 and 0.02, X represents one or more elements selected from aluminum, iron, gallium, boron, vanadium, arsenic, antimony, chromium and manganese and Y represents one or more elements selected from silicon, germanium, titanium, zirconium, characterized by an X-ray diffraction spectrum of the powders shown in table 1. 2. The porous crystalline material according to Claim 1, wherein M is selected from sodium, potassium, hydrogen or their mixtures. 3. The porous crystalline material according to Claim 1, wherein X is aluminum or aluminum partially substituted with an element selected from iron, gallium, boron, vanadium, arsenic, antimony, chromium and manganese. 4. The porous crystalline material according to Claim 1, wherein Y is silicon or silicon partially substituted with an element selected from germanium, titanium and zirconium. 5. A process for the preparation of the porous crystalline material ERS-10 according to Claim 1, which comprises: (a) preparing an aqueous solution optionally containing at least one compound capable of hydrolyzing to X2O3, at least one compound capable of hydrolyzing to YO2 a cation source of an alkaline or earth-alkaline metal and an organic templating agent (Q) characterized in that said templating agent is an azo spiro compound having general formula (II)   wherein: n and n', the same or different, represent an integer between 3 and 6 and X<-> is an anion selected from OH<->, chloride, bromide, fluoride and iodide-ion, and wherein the quantity of reagents is such as to respect the following molar ratios:  YO2/X2O3 from 50/1 to  infinity   OH<->/YO2, from 0.15/1 to 0.7/1  Q/YO2, from 0.1/1 to 0.5/1  H2O/YO2, from 20/1 to 60/1  M<+/>Y2 from 0.05/1 to 0.20/1 (b) maintaining the solution obtained in (a) under sufficient conditions to form a solid crystalline material; (c) drying the solid crystalline material which in its anhydrous form has a molar composition of oxides, corresponding to the general formula (III) YQ2OxmM2/nOxZX2O3xYO2 (III), wherein: y has a value of between 0.1 and 1, Q is the organic templating agent having general formula (II), M is a cation of an alkaline and/or alkaline earth metal and m, n, z, X and Y have the same meaning defined above; (d) calcining the crystalline material (III) obtained in step (c); and finally (e) at least partly substituting the cation M with H to obtain the ERS-10 zeolite having general formula (I) in acid form. 6. The process according to Claim 5, characterized in that in step a) the compound capable of hydrolyzing to X2O3 is selected from aluminum isopropylate, aluminum sulfate, NaAlO2. 7. The process according to Claim 6, wherein the aluminum compound is selected from aluminum isopropylate and aluminum sulfate. 8. The process according to Claim 5, characterized in that in step a) the compound capable of hydrolyzing to YO2 is a silicon compound selected from tetraethylorthosilicate, colloidal silica, sodium silicate, pyrophoric silica. 9. The process according to Claim 8, characterized in that the silicon compound is selected from tetraethylorthosilicate, colloidal silica. 10. The process according to Claim 5, characterized in that the sources of cations are sodium or potassium hydroxide. 11. The process according to Claim 5, characterized in that the organic templating agent (Q) is a compound having formula (II) wherein n and n', the same as each other, have a value equal to 5 and X<-> is OH<-> 12. The process according to Claim 5, characterized in that the quantity of constituents of the solution is such as to respect the following molar ratios: SiO2 /X2O3 from 80/1 to  infinity  OH<->SiO2, from 0.2/1 to 0.45/1 Q/SiO2 from 0.2/1 to 0.3/1 H2O/SiO2 from 40/1 to 50/1 M<+> SiO2 from 0.09/1 to 0.15/1. 13. The process according to Claim 5, characterized in that in step b) the reaction is carried out at a temperature of between 150 degree C and 180 degree C and for a time of from 3 to 28 days. 14. The process according to Claim 13, characterized in that the temperature is about 170  degree C and the reaction time is between 7 and 14 days. 15. The process according to Claim 5, characterized in that in step c) the drying is carried out at temperatures up to 170 degree C. 16. The process according to Claim 15, characterized in that said drying is carried out at temperatures of between 90 to 120 degree C. 17. The process according to Claim 5, characterized in that in step (d) the calcination is carried out at a temperature of between 500 and 700 degree C and for a time of between 4 and 20 hours. 18. The process according to Claim 17, characterized in that the calcination is carried out at a temperature of between 550 and 650 degree C and for a time of from 6 to 15 hours. 19. The process according to Claim 5, characterized in that in step (e), the substitution is carried out by ion exchange using a mineral acid such as hydrochloric acid or an ammonium salt such as ammonium acetate. 20. Zeolitic precursor having in its anhydrous form a molar composition of oxides corresponding to general formula (III) YQ2 OxmM2/h O.zX2O3xYO2  (III) wherein: Y has a value of between 0.1 and 1, Q is the organic templating agent having general formula (II)   wherein: n and n', the same or different, represent an integer between 3 and 6 and X<-> is an anion selected from OH<->, chloride, bromide, fluorlde and iodide, M is a cation of an alkaline or alkaline earth metal with valence n, z is a number between 0 and 0.02, X represents one or more elements selected from aluminum, iron, gallium, boron, vanadium, arsenic, antimony chromium and manganese and Y represents one or more elements selected from silicon, germanium, titanium, zirconium, characterized by an X-ray diffraction spectrum of the powders shown in table 2. 21. Use of the porous crystalline material ERS-10 according to Claims 1 to 19 as molecular sieve, ion exchanger and in a catalytic process for the conversion of hydrocarbons.