Process for making crystalline siliceous materials

Claim 2

Small crystallites of ZSM-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, (c) having a crystallinity of greater than 71% as measured by X-ray diffraction, (d) having an average unit cell as synthesized and water washed represented by the formula ##STR16## where ##EQU3## x is the average number of Al atoms in the unit cell, M represents an alkali metal cation, y is less than 0.8 but greater than zero, □ represents the intersections of the channels inside the ZSM-5 porous framework free of tetrapropyl ammonium ions, and Q represents the intersections of the channels inside the ZSM-5 porous framework having occluded tetrapropyl ammonium ions, said crystallites being ion-exchangeable without requiring a preliminary calcination step and without prior removal of the occluded tetrapropyl ammonium ions.

Claim 3

The small crystallites of ZSM-5 of claim 1, wherein M in the formula is Na.

Claim 4

The small crystallites of ZSM-5 of claim 1, which has been ammonium ion exchanged and where M in the formula is NH 4 .

Claim 5

The small crystallites of ZSM-5 of claim 1, wherein M in the formula is H.

Claim 6

The small crystallites of ZSM-5 of claim 4, wherein the cation M has been at least partially replaced by the equivalent amount of lanthanide ion.

Claim 7

A process to make a ZSM-5 zeolite (a) having a SiO 2 to Al 2 O 3 mole ratio R between about 20 and 120, (b) having crystallites with their smallest dimension below about 0.3 micrometer, and (c) having a crystallinity of greater than 71% as measured by X-ray diffraction, (d) having an average unit cell represented by the formula ##STR17## where ##EQU4## M represents monovalent cations, x is the average number of Al atoms in the unit cell, □ represents the intersections of the channels inside the ZSM-5 porous framework free of tetrapropyl ammonium ions, and Q 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, and an organic template consisting essentially of tetrapropyl ammonium ions in the reaction mixture in an effective amount but less than that which corresponds to y=0.8 and in an amount such that the mole ratio of tetraproyl ammonium ions to SiO 2 in said reaction mixture is 0.0087 or less, and recovering ZSM-5 zeolite product which is ion-exchangeable without requiring a preliminary calcination step.

Claim 8

A process to make a ZSM-5 zeolite (a) having a SiO 2 to Al 2 O 3 mole ratio R between about 20 and 120, (b) having crystallites with their smallest dimension below about 0.3 micrometer, and (c) having a crystallinity of greater than 71% as measured by X-ray diffraction, (d) having an average unit cell represented by the formula ##STR17## where ##EQU4## M represents monovalent cations, x is the average number of Al atoms in the unit cell, □ represents the intersections of the channels inside the ZSM-5 porous framework free of tetrapropyl ammonium ions, and Q 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, and an organic template consisting essentially of tetrapropyl ammonium ions in the reaction mixture in an effective amount but less than that which corresponds to y=0.8 and in an amount such that the mole ratio of tetraproyl ammonium ions to SiO 2 in said reaction mixture is 0.0087 or less, and recovering ZSM-5 zeolite product which is ion-exchangeable without requiring a preliminary calcination step.

Claim 9

A process according to claim 6, 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 10

A process according to claim 6, wherein the amount of tetrapropyl ammonium ions being present in the reaction mixture is an amount less than that which corresponds to y=0.4 in the formula.

Claim 11

A process according to claim 6, wherein the mother liquor from a previous synthesis is recycled to supply part of the reaction mixture.

Claim 12

The uncalcined ZSM-5 zeolite made by the process of claim 6.

Claim 13

A process according to claim 6, wherein the mole ratio of the tetrapropyl ammonium ions to the SiO 2 in the reaction mixture is 0.0052 or less.

Claim 14

A process according to claim 6, wherein the mole ratio of the tetrapropyl ammonium ions to the SiO 2 in the reaction mixture is 0.0026 or less.

Claim 15

A process according to claim 6, wherein the mole ratio of the tetrapropyl ammonium ions to the SiO 2 in the reaction mixture is 0.0013 or less.

Claim 16

A process according to claim 6, wherein the mole ratio of the tetrapropyl ammonium ions to the SiO 2 in the reaction mixture is 0.00087 or less.

Claim 17

A process according to claim 6, wherein the mole ratio of the tetrapropyl ammonium ions to the SiO 2 in the reaction mixture is 0.00052 or less.

Claim 18

A process according to claim 6, wherein the mole ratio of the tetrapropyl ammonium ions to the SiO 2 in the reaction mixture is 0.00017 or less.

Claim 19

A process to make a ZSM-5 zeolite having a SiO 2 to Al 2 O 3 mole ratio R greater than 5, having crystallites with their smallest dimension below about 0.3 micrometer and having a crystallinity of greater than 71% as measured by X-ray diffraction comprising reacting a mixture containing a source of silica, a source of alumina, a source of alkali metal hydroxide, water, and an organic template consisting essentially of tetrapropyl ammonium ions in the reaction mixture in an effective amount but less than 0.8U in which U is 1/96 of the sum of (1) the number of moles of Si in the reacting mixture multiplied by 0.8 plus (2) the number of moles of Al in the reacting mixture, and recovering ZSM-5 zeolite product which is ion-exchangeable without requiring a preliminary calcination step and without prior removal of the occluded tetrapropyl ammonium ions.

Claim 20

A process to make a ZSM-5 zeolite having a SiO 2 to Al 2 O 3 mole ratio R greater than 5, having crystallites with their smallest dimension below about 0.3 micrometer and having a crystallinity of greater than 71% as measured by X-ray diffraction comprising reacting a mixture containing a source of silica, a source of alumina, a source of alkali metal hydroxide, water, and an organic template consisting essentially of tetrapropyl ammonium ions in the reaction mixture in an effective amount but less than 0.8U in which U is 1/96 of the sum of (1) the number of moles of Si in the reacting mixture multiplied by 0.8 plus (2) the number of moles of Al in the reacting mixture, and recovering ZSM-5 zeolite product which is ion-exchangeable without requiring a preliminary calcination step and without prior removal of the occluded tetrapropyl ammonium ions.

Claim 21

A process according to claim 17 wherein the amount of tetrapropyl ammonium ions being present in the reaction mixture is an amount less than 0.6U.

Claim 22

A process according to claim 17, wherein the amount of tetrapropyl ammonium ions being present in the reaction mixture is an amount less than 0.4U.

Claim 23

A process according to claim 17, wherein the mother liquor from a previous synthesis is recycled to supply part of the reaction mixture.

Claim 24

A process according to claim 17, wherein the reaction mixture at the onset of the reaction contains no source of ZSM-5 crystallites which are discernible by powder x-ray diffraction.

Claim 25

A process according to claim 17, wherein the reaction slurry mixture has the following molar ratios of ingredients ______________________________________ SiO.sub.2 to Al.sub.2 O.sub.3 greater than 6 H.sub.2 O to OH.sup.- 20-120 (Si + Al) to H.sub.2 O 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 Al 2 O 3 charged to the reaction slurry becomes a part of the covalent network of the reaction product; and wherein the reaction temperature is from 100°-280° C. and the reaction time is less than 24 hours.

Claim 26

A process according to claim 22, wherein molar ratios of ingredients are ______________________________________ SiO.sub.2 to Al.sub.2 O.sub.3 20-120 H.sub.2 O to OH.sup.- 30-100 (Si + Al) to H.sub.2 O 0.05-0.12 Q to U less than 0.6 ______________________________________ and wherein the reaction temperature is from 140°-230° C. and the reaction time is less than 12 hours.

Claim 27

A process according to claim 23, wherein the molar ratios of ingredients are ______________________________________ SiO.sub.2 to Al.sub.2 O.sub.3 40-80 H.sub.2 O to OH.sup.- 50-70 (Si + Al) to H.sub.2 O 0.06-0.09 Q to U less than 0.4 ______________________________________ and wherein the reaction temperature is from 170°-190° C. and the reaction time is less than 8 hours.

Claim 28

A process according to claim 17 wherein said ZSM-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; 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 ZSM-5.

Claim 29

The uncalcined ZSM-5 zeolite made by the process of claim 17.

Claim 30

A process to produce silicalite wherein there is essentially no alumina present having crystallites with their smallest dimension below about 0.3 micrometer and having a crystallinity of greater than 71% as measured by X-ray diffraction comprising reacting a mixture containing a source of silica, a source of alkali metal hydroxide, essentially no alumina except as impurity, water, and an organic template consisting essentially of tetrapropyl ammonium ions in the reaction mixture in an effective amount but less than 0.8U in which U is 1/96 of the sum of (1) the number of moles of Si in the reacting mixture multiplied by 0.8 plus (2) the number of moles of Al in the reacting mixture, and recovering silicalite product which is ion-exchangeable without requiring a preliminary calcination step and without prior removal of the occluded tetrapropyl ammonium ions.

Claim 31

A process to produce silicalite wherein there is essentially no alumina present having crystallites with their smallest dimension below about 0.3 micrometer and having a crystallinity of greater than 71% as measured by X-ray diffraction comprising reacting a mixture containing a source of silica, a source of alkali metal hydroxide, essentially no alumina except as impurity, water, and an organic template consisting essentially of tetrapropyl ammonium ions in the reaction mixture in an effective amount but less than 0.8U in which U is 1/96 of the sum of (1) the number of moles of Si in the reacting mixture multiplied by 0.8 plus (2) the number of moles of Al in the reacting mixture, and recovering silicalite product which is ion-exchangeable without requiring a preliminary calcination step and without prior removal of the occluded tetrapropyl ammonium ions.

Claim 32

Uncalcined silicalite made by the process of claim 27.

Claim 33

A nonpolluting process to make a ZSM-5 zeolite (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, (c) having a crystallinity of greater than 71% as measured by X-ray diffraction, and (d) having an average unit cell represented by the formula ##STR18## where ##EQU5## M represents monovalent cations, x is the average number of Al atoms in the unit cell, □ represents the intersections of the channels inside the ZSM-5 porous framework free of tetrapropyl ammonium ions, and Q 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, and an organic template consisting essentially of tetrapropyl ammonium ions in the reaction mixture in an effective amount but less than that which corresponds to y=0.8 in the formula and in an amount such that the mole ratio of tetrapropyl ammonium ions to SiO 2 in said reaction mixture is less than 0.01108, said mixture having an equivalent product concentration greater than 12%, at a rate corresponding to a throughput greater than 400 Kg/m 3 /day, and (ii) recovering ZSM-5 zeolite product which is ion-exchangeable without requiring a preliminary calcination step and without prior removal of the occluded tetrapropyl ammonium ions.

Claim 34

A nonpolluting process to make a ZSM-5 zeolite (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, (c) having a crystallinity of greater than 71% as measured by X-ray diffraction, and (d) having an average unit cell represented by the formula ##STR18## where ##EQU5## M represents monovalent cations, x is the average number of Al atoms in the unit cell, □ represents the intersections of the channels inside the ZSM-5 porous framework free of tetrapropyl ammonium ions, and Q 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, and an organic template consisting essentially of tetrapropyl ammonium ions in the reaction mixture in an effective amount but less than that which corresponds to y=0.8 in the formula and in an amount such that the mole ratio of tetrapropyl ammonium ions to SiO 2 in said reaction mixture is less than 0.01108, said mixture having an equivalent product concentration greater than 12%, at a rate corresponding to a throughput greater than 400 Kg/m 3 /day, and (ii) recovering ZSM-5 zeolite product which is ion-exchangeable without requiring a preliminary calcination step and without prior removal of the occluded tetrapropyl ammonium ions.

Claim 35

A process according to claim 29 wherein the equivalent product concentration is greater than 14% and the throughput is greater than 500 Kg/m 3 /day.

Claim 36

A process for making a catalyst comprising (a) mixing together a reaction slurry as defined in claim 6; (b) heating the reaction slurry at a temperature of from about 100°-280° 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 materials to obtain the zeolite reaction product; (e) washing the filtered zeolite; (f) cation exchanging the washed zeolite; (g) blending the exchanged zeolite with catalyst forming materials; (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.

Claim 37

A process according to claim 31, wherein the catalyst forming material is at least a matrix material.

Claim 38

A process according to claim 31, wherein the cation exchange is made with NH 4 + ions

Claim 39

A process according to claim 31 wherein the cation exchange is made with NH 4 + ions and lanthanide ions.

Claim 40

A process according to claim 31, wherein the cation exchange is made with H + ions.

Claim 41

A process according to claim 31, wherein the cation exchange is made with H + ions and lanthanide ions.

Claim 42

A process for making a catalyst comprising (a) mixing together a reaction slurry as defined in claim 17; (b) heating the reaction slurry at a temperature of from about 100°-280° 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 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.

Claim 43

A process according to claim 37, wherein the cation exchange is made with NH 4 + 0 ions.

Claim 44

A process according to claim 37, wherein the cation exchange is made with NH 4 + ions and lanthanide ions.

Claim 45

A process according to claim 37, wherein the exchange is made with H + ions.

Claim 46

A process according to claim 37, wherein the cation exchange is made with H + ions and lanthanide ions.

Claim 47

A process to produce silicalite (a) having crystallites with their smallest dimension below about 0.3 micrometer, and (b) having an average unit cell represented by the formula ##STR19## where □ represents the intersections of the channels inside the ZSM-5 porous framework free of tetrapropyl ammonium ions, and Q 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 alkali metal hydroxide, essentially no alumina except as impurity, water, and an organic template consisting essentially of tetrapropyl ammonium ions in the reaction mixture in an effective amount but less than that which corresponds to y=0.8 and in an amount such that the mole ratio of tetrapropyl ammonium ions to SiO 2 in the reaction slurry is 0.00792 or less, and recovering the silicalite product which is water washable without requiring a preliminary calcination step.

Claim 48

A process to produce silicalite (a) having crystallites with their smallest dimension below about 0.3 micrometer, and (b) having an average unit cell represented by the formula ##STR19## where □ represents the intersections of the channels inside the ZSM-5 porous framework free of tetrapropyl ammonium ions, and Q 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 alkali metal hydroxide, essentially no alumina except as impurity, water, and an organic template consisting essentially of tetrapropyl ammonium ions in the reaction mixture in an effective amount but less than that which corresponds to y=0.8 and in an amount such that the mole ratio of tetrapropyl ammonium ions to SiO 2 in the reaction slurry is 0.00792 or less, and recovering the silicalite product which is water washable without requiring a preliminary calcination step.

Claim 49

Uncalcined silicalite made by the process of claim 42.