Process to make small crystallites of ZSM-5

Claim 2

A process to make the ZSM-5 zeolite a) having a Sio 2 to A1 2 0 3 mole ratio R greater than 5, b) having crystallites with their smallest dimension below about 0.3 micrometer, and c) having an average unit cell represented by the formula where M represents monovalent cations, represents the intersections of the channels inside the ZSM-5 porous framework free of tetrapropyl ammonium ions, and represents the intersections of the channels inside the ZSM-5 porous framework having occluded tetrapropyl ammonium ions; comprising reacting a mixture containing a source of silica, a source of alumina, a source of alkali metal hydroxide, water, a polyol, and a small amount of tetrapropyl ammonium ions, said tetrapropyl ammonium ions being present in the reaction mixture in an effective amount and in an amount less than that which corresponds to y = 0.8 in the formula, and recovering the ZSM-5 zeolite product.

Claim 3

A process according to Claim 1, wherein the amount of tetrapropyl ammonium ions being present in the reaction mixture is an amount less than that which corresponds to y = 0.6 in the formula.

Claim 4

A process according to Claim 1, wherein the amount of tetrapropyl ammonium ions being present in the reaction mixture is an amount lees than that which corresponds to y = 0.4 in the formula.

Claim 5

A process according to Claim 1, wherein the mother liquor from a previous synthesis is recycled to supply part of the reaction mixture.

Claim 6

A process according to Claim 1, wherein the polyol is ethylene glycol.

Claim 7

A process according to Claim 1, wherein there is essentially no alumina present and the product produced is silicalite.

Claim 8

Small crystallites of Z SM-5 having crystallites with their smallest dimension below about 0.3 micrometer made by the process of Claim 1.

Claim 9

Small crystallites of silicalite having crystallites with their smallest dimension below about 0.3 micrometer made by the process of Claim 1.

Claim 10

A process to make the ZSM-5 zeolite a) having a 5i0 2 to A1 2 0 3 ratio R greater than 5, and b) having crystallites with their smallest dimension below about 0.3 micrometer, comprising reacting a mixture containing a source of silica, a source of alumina, a source of alkali metal hydroxide, water, a polyol, and a small amount of tetrapropyl ammonium ions, said tetrapropyl ammonium ions being present in the reaction mixture in an effective amount and in an amount less than 0.8U in which U is 1/96 of the sum of the number of moles of S i in the reacting mixture multiplied by 0.8 plus the number of moles of Al in the resulting mixture, and recovering the ZSM-5 zeolite product. 10. A process according to Claim 9, wherein the amount of tetrapropyl ammonium ions being present in the reaction mixture is an amount less than 0.6U. 11. A process according to Claim 9, wherein the amount of tetrapropyl ammonium ions being present in the reaction mixture is an amount less than 0.4U. 12. A process according to claim 9, wherein the mother liquor from a previous synthesis is recycled to supply part of the reaction mixture. 13. A process according to Claim 9, wherein the polyol is ethylene glycol. 14. A process according to Claim 9, wherein there is essentially no alumina present and the product produced is silicalite. 15. A process according to Claim 9, wherein the reaction mixture contains no source of Z SM-5 crystallites which are discernible by powder x-ray diffraction. 16. A process according to Claim 9, wherein the reaction slurry mixture has the following molar ratios of inqredients Si0 2 to A1 2 0 3 greater than 6 H 2 0 to OH - 20-120 Polyol to (SiO 2 +Al 2 O 3 ) less than 1.0 (Si+Al) to H 2 0 0.03-0.15 Q to U less than 0.8 wherein essentially all of the Q charged to the reaction slurry becomes occluded in the reaction product; wherein essentially all of the A1 2 0 3 charged to the reaction slurry becomes a part of the covalent network of the reaction product; and wherein the reaction temperature is from 150-200°C and the reaction time is less than 24 hours. 17. A process according to Claim 16, wherein molar ratios of ingredients are SiO 2 to Al 2 O 3 20-120 H 2 O to OH - 30-100 Polyol to (SiO 2 +Al 2 O 3 ) less than 0.50 (Si+Al) to H 2 O 0.05=0.12 Q to U less than 0.6 and wherein the reaction temperature is from 160-190°C and the reaction time is less than 12 hours. 18. A process according to Claim 17, wherein the molar ratios of ingredients are SiO 2 to Al 2 O 3 40-80, H 2 0 to OH - 50-70 Polyol to (SiO 2 +Al 2 O 3 ) less than 0.20 (Si+Al) to H 2 0 0.06-0.09 Q to U less than 0.4 and wherein the reaction temperature is from 170-180°C and the reaction time is less than 8 hours. 19. A process according to Claim 9 wherein said Z SM-5 produced has a high degree of crystallinity; an occluded carbon content as prepared and water washed of less than 0.1 mole of carbon per mole of total silicon and aluminum contained in said ZSM-5; a zeolitic alkali metal content as prepared and water washed of less than one mole per mole of contained aluminum; a high degree of crystalline purity exhibiting a single phase crystalline material; an aluminosilicate or silicalite structure; the capacity to be readily exchangeable without prior removal of Q ions; and containing as prepared and water washed less than 1/120 mole of nitrogen per mole of total silicon and aluminum contained in said Z SM-5. 20. Small crystallites of ZSM-5 having crystallites with their smallest dimension below about 0.3 micrometer made by the process of Claim 9. 21. Small crystallites of silicalite having crystallites with their smallest dimension below about 0.3 micrometer made by the process of Claim 9. 22. A nonpolluting process to make the ZS M-5 zeolite a) having a Sio 2 to A1 2 0 3 mole ratio R greater than 5, and b) having an average unit cell represented by the formula where M represents monovalent cations, represents the intersections of the channels inside the ZSM-5 porous framework free of tetrapropyl ammonium ions, and represents the intersections of the channels inside the ZSM-5 porous framework having occluded tetrapropyl ammonium ions; comprising (i) reacting a mixture containing a source of silica, a source of alumina, a source of alkali metal hydroxide, water, a polyol, and a small amount of tetrapropyl ammonium ions, said tetrapropyl ammonium ions being present in the reaction mixture in an effective amount and in an amount less than that which corresponds to y = 0.8 in the formula, said mixture having an equivalent product concentration of greater than 12%, at a rate corresponding to a throughput greater than 400 K g/m 3 /day, and (ii) recovering the ZSM-5 zeolite product. 23. A process according to Claim 22, wherein the equivalent product concentration is greater than 14% and the throughput is greater than 500 K g/m 2 /day. 24. Small crystallites of Z SM-5 a) having a Sio 2 to Al 2 O 3 mole ratio R greater than 5, b) having crystallites with their smallest dimension below about 0.3 micrometer, and c) having an average unit cell as synthesized and water washed represented by the formula where M represents an alkali metal cation, y is less than 0.8, channels inside the ZSM-5 porous framework having occluded tetrapropyl ammonium ions, said crystallites being ion-exchangeable without requiring a preliminary calcination step. 25. The composition of Claim 24, wherein M in the formula is Na. 26. The composition of Claim 24, which has been further ammonium ion exchanged and where M in the formula is NH 4. 27. The composition of Claim 24, wherein M in the formula is H. 28. The composition of Claim 27, wherein the cation M has been at least partially replaced by the equivalent amount of lanthanide ion. 29. The composition of Claim 26 after subsequent removal of the Q. 30. The composition of Claim 27 after subsequent removal of the Q. 31. The composition of Claim 28 after subsequent removal of the Q. 32. A process for making a catalyst comprising a) mixing together a reaction slurry as defined in Claim 1; b) heating the reaction slurry at a temperature of from about 150-200°C for less than 24 hours to produce a Z SM-5 zeolite and a mother liquor; c) cooling the reaction materials from step (b); d) filtering the cooled reaction materials to obtain the zeolite reaction product; e) washing the filtered zeolite; f) cation exchanging the washed zeolite; g) blending the exchanged zeolite with a matrix material; h) forming the blended material into a formed particle; i) drying the formed particle; and j) calcining the dried particle to yield a ZSM-5 zeolite containing catalyst. 33. A process according to Claim 32, wherein the cation exchange is made with NH4 ions. 34. A process according to Claim 32, wherein the cation exchange is made with NH + 4 ions and lanthanide ions. 35. A process according to Claim 32, wherein the cation exchange is made with H + ions. 36. A process according to Claim 32, wherein the cations exchange is made with H ions and lanthanide ions. 37. A ZSM-5 zeolite containing catalyst made by the process of Claim 32. 38. A process for making a catalyst comprising a) mixing together a reaction slurry as defined in Claim 9; b) heating the reaction slurry at a temperature of from about 150-200°C for less than 24 hours to produce a ZSM-5 zeolite and a mother liquor; c) cooling the reaction materials from step (b); d) filtering the cooled reaction materials to obtain the zeolite reaction product; e) washing the filtered zeolite; f) cation exchanging the washed zeolite; g) blending the exchanged zeolite with a matrix material; h) forming the blended material into a formed particle; i) drying the formed particle; and j) calcining the dried particle to yield a ZSM-5 zeolite containing catalyst. 39. A process according to Claim 38, wherein the cation exchange is made with NH + 4 ions. 40. A process according to Claim 38, wherein the cation exchange is made with NH + 4 ions and lanthanide ions. 41. A process according to Claim 38, wherein the cation exchange is made with H + ions. 42. A process according to Claim 38, wherein the cations exchange is made with H + ions and lanthanide ions. 43. A ZSM-5 zeolite containing catalyst made by the process of Claim 35.