Patent EA-002220-B1 (EA)
Title: Zeolite catalyst and its use in hydrocarbon conversion
Inventor: VERDUIJN JOHANNES P
IPC: C10G29/20
Filed: 1997-05-29
Abstract: 1. A zeolite bound zeolite catalyst comprising: (a) first crystals of a first zeolite, and (b) a binder comprising second crystals of a second zeolite which has a structure type that is different from the structure type of the first zeolite. 2. The catalyst recited in Claim 1, wherein the second crystals are intergrown and form at least a partial coating on the first crystals. 3. The catalyst recited in Claim 2, wherein the coating is resistant to attrition. 4. The catalyst recited in Claim 1, 2 or 3 that does not contain significant amounts of non-zeolitic binder. 5. The catalyst recited in Claim 4 that contains less than 5% by weight of non-zeolitic binder based on the combined weight of first zeolite and second zeolite. 6. The catalyst recited in any preceding Claim wherein the first crystals have an average particle size greater than 0.1 micron. 7. The catalyst recited in Claim 6 wherein the first crystals have an average particle size of from 1 to 6 microns. 8. The catalyst recited in any preceding Claim wherein the second crystals have an average particle size less than that of the first crystals. 9. The catalyst recited in any preceding Claim wherein the second crystals have an average particle size of from 0.1 to 0.5 micron. 10. The catalyst recited in any preceding Claim wherein the first zeolite and the second zeolite are independently a composition having the following molar relationship: X2O3:(n)YO2 wherein X is aluminum, boron, titanium, and/or gallium, Y is silicon, tin, and/or n is at least 2. 11. The catalyst recited in Claim 10 wherein the first zeolite is an aluminosilicate and has a silica to alumina mole ratio of from 20:1 to about 200:1. 12. The catalyst recited in Claim 10 wherein the second zeolite is and aluminosilicate and has a silica to alumina mole ratio greater than 200:1, preferably greater than 500:1. 13. The catalyst recited in any preceding Claim wherein the second zeolite has lower acidity than the first zeolite. 14. The catalyst recited in any of Claims 1 to 12 wherein the second zeolite has higher acidity than the first zeolite. 15. The catalyst recited in any preceding Claim wherein the pore size of the first zeolite is larger than the pore size of the second zeolite. 16. The catalyst recited in any of Claims 1 to 14 wherein the pore size of the second zeolite is larger than the pore size of the first zeolite. 17. The catalyst recited in any preceding Claim wherein the first zeolite and the second zeolite independently have a large pore size or an intermediate pore size. 18. The catalyst recited in Claims 1 to 16 wherein the first zeolite and the second zeolite independently have an intermediate pore size or small pore size. 19. The catalyst recited in any preceding Claim wherein the first zeolite and the second zeolite are independently of a structure type selected from the group consisting of OFF, BEA, MAZ, MEI, FAU, EMT, LTL, VFI, MOR, MFI, MFS, MEL, MTW, MTT, FER, EUO, HEU, TON, CHA, ERI, KFI, LEV, and LTA. 20. The catalyst recited in Claim 19 wherein the first zeolite and the second zeolite are independently of a structure type selected from the group consisting of MAZ, MEI, OFF, BEA, MFI, MEL, MTW, EMT, MTT, HEU, FER, TON, EUO, and LTL. 21. The catalyst recited in Claim 20 wherein the structure type of the second zeolite is MFI, MEL, EMT or OFF. 22. The catalyst recited in Claim 19 or 21 wherein the structure type of the first zeolite is LTL, FAU, MFI, or CHA. 23. The catalyst recited in any preceding Claim which is preparable by aging at elevated temperature a silica-bound aggregate containing first crystals of the first zeolite in an aqueous ionic solution containing a source of hydroxy ions sufficient to convert the silica in the aggregate to the second zeolite. 24. The catalyst recited in any preceding Claim which further comprises a catalytically active metal. 25. A process for converting hydrocarbons comprising contacting a hydrocarbon feedstre am under hydrocarbon conversion conditions with a zeolite bound zeolite catalyst according to any of the preceding claims. 26. The process recited in Claim 25 wherein the first zeolite and second zeolite of the catalyst are intermediate pore size zeolites. 27. The process of Claim 25 or 26 wherein the hydrocarbon conversion is carried out at conditions comprising a temperature of from 100 degree C to 760 degree C and/or a pressure of from 10.1 kPag to 10.1 MPag (0.1 to 100 atmospheres) and/or a weight hourly space velocity of from 0.08 hr 1 to 200 hr<-1>. 28. The process recited in any of Claims 25 to 27 wherein the hydrocarbon conversion is selected from the group consisting of cracking of hydrocarbons, isomerization of alkyl aromatics, disproportionation of toluene, transalkylation of aromatic, alkylation of aromatics, reforming of naphtha to aromatics, conversion of paraffins and/or olefins to aromatics, conversion of oxygenates to hydrocarbon products, cracking of naphtha to light olefins, and dewaxing of hydrocarbons. 29. The process recited in Claim 28 which comprises isomerizing a hydrocarbon feed containing an aromatic C8 stream comprising xylene isomers or a mixture of xylene isomers and ethylbenzene, comprising contacting said feed under isomerization conversion conditions with the zeolite bound zeolite catalyst, the first zeolite of which a large or intermediate pore size zeolite. 30. The process recited in Claim 29 wherein the catalyst contains a catalytically active metal. 31. The process recited in Claim 29 or 30 wherein the first zeolite is a structure type selected from the group consisting of MFI, MEL, MTW, EUO, MTT, FER, TON and MOR, and/or the second zeolite is a structure type selected from the group consisting of MFI, MEL, MTW, EUO, MTT, FER, and TON, with the first or second zeolite preferably being of MFI structure type. 32. The process recited in Claim 29, 30 or 31 wherein the catalyst has first crystals of an average particle size of from 1 to 6 microns and second crystals of an average particle size of from 0.1 to less than 0.5 microns. 33. The process recited in Claim 29, 30, 31 or 32 wherein the second zeolite of the catalyst is an aluminosilicate and has a silica to alumina mole ratio of from 20:1 to 150:1. 34. The process recited in Claim 28 which comprises cracking hydrocarbon compounds by contacting a hydrocarbon feed under catalytic cracking conditions with the zeolite bound zeolite catalyst, the first zeolite of which is acidic. 35. The process recited in Claim 34 wherein the catalyst has first crystals that are larger than the second crystals and have an average particle size of at least 0.1 microns. 36. The process recited in Claim 35 wherein the first crystals have an average particle size of from 0.1 to 3 microns. 37. The process recited in Claims 34, 35 or 36 wherein the second crystals have an average particle size of from 0.1 to less than 0.5 microns. 38. The process recited in any of Claims 34 to 37 wherein the first zeolite is a structure type selected from the group consisting of OFF, BEA, MAZ, MEI, FAU, VFI, MOR, MFI, MFS, MEL, MTW, MTT, FER, EUO, HEU, TON, CHA, ERI, KFI, LEV, and LTA, and/or the second zeolite is a structure type selected from the group consisting of OFF, BEA, MAZ, MEI, FAU, EMT, LTL, VFI, MOR, MFI, MFS, MEL, MTW, MTT, FER, EUO, HEU, TON, CHA, ERI, KFI, LEV, and LTA. 39. The process recited in any of Claims 34 to 38 wherein the hydrocarbon feed comprises a C4+ naphtha feed. 40. The process recited in Claim 28 which comprises disproportionation of toluene by contacting a toluene stream under toluene disproportionation conditions with the zeolite bound zeolite catalyst wherein the first zeolite is acidic and of intermediate pore size, and the second zeolite is of lower acidity than the first zeolite. 41. The process recited in Claim 40 wherein the catalyst has first crystals with average particle size of from 1 to 6 microns and/or second crystals with average particle size of from 0.1 to less than 0.5 microns. 42. The process recited in Claim 40 or 41 wherein the first zeolite and the second zeolite are independently of a structure type selected from the group consisting of MFI, MEL, MEI, MFS, MTW, EUO, MTT, and TON. 43. The process recited in Claim 40, 41 or 42 wherein the first zeolite is an aluminosilicate zeolite having a silica to alumina mole ratio of from 20:1 to 150:1 and/or the second zeolite is an aluminosilicate zeolite having a silica to alumina mole ratio greater than 200:1. 44. The process recited in any of Claims 40 to 43 wherein the second zeolite is silicalite or silicalite 2. 45. The process recited in any of Claims 40 to 44 wherein the catalyst is in the acidic hydrogen form. 46. The process recited in any of Claims 40 to 45 wherein the catalyst is preparable by aging at elevated temperature a silica bound aggregate containing first crystals of the first zeolite in an aqueous ionic solution containing a source of hydroxy ions sufficient to convert the silica in the aggregate to the second zeolite. 47. The process recited in any of Claims 40 to 46 wherein the catalyst is preselectivated. 48. The process of Claim 47 wherein the catalyst is a preselectivated catalyst containing from 2 to 40% by weight of coke. 49. The process recited in Claim 47 or 48 wherein the catalyst is preselectivated by contacting the catalyst with a hydrocarbon stream at a temperature of from 480 degree C to 650 degree C, at a pressure of from 101 kPag to 10.1 MPag (1 to 100 atmospheres), and a weight hourly space velocity of 0.1 to 20. 50. The process recited in Claim 49 wherein the hydrocarbon stream further contains hydrogen, preferably at a hydrogen/ hydrocarbon ratio of up to 2. 51. The process recited in any of Claims 40 to 45 wherein the toluene disproportionation conditions comprise a temperature of from 400 degree C to 550 degree C or and/or a pressure from 101 kPag to 10.1 MPag (1 to 100 atmospheres) and/or a weight hourly space velocity from 0.5 to 50. 52. The