EP0173895A2
Expired / Lapsed
EP
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A process for making crystalline siliceous materials
Assignee: WR Grace and Co Conn
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Filing: 1985-08-14
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Granted: —
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Expires: 2005-08-14
Abstract
Abstract ZSM-5 crystallites are produced in the as-synthesized form with very low levels of blocking tetrapropyl ammonium (Q) ions. The reaction mixture contains sources of silica, soda, alumina and trace amounts of Q ions as nucleation agents. Because the crystallites as synthesized from the aqueous medium exhibit only a very small fraction of blocking cations, there is always a diffusion path for the hydrated sodium ions to be exchanged without the need of prior removal of the blocking cations by calcination or otherwise. The small size crystallites can be exchanged. blended with matrix material, and formed into catalyst particles. The silcia to alumina ratio can be varied and when no aluminium is added, silicalite may be formed. The synthesis can be done in 24 hours or less.
Inventors
- 👤 Charles Chingren Chang
- 👤 Sandra Mary Waters
- 👤 Moises Gali Sanchez
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-11-05 14:59
CPC Classifications
B; B01; B01J; B01J29/00; B01J29/03; B01J29/035; B01J29/04; B01J29/06; B01J29/40; C; C01; C01B; C01B37/00; C01B37/02; C01B39/00; C01B39/02; C01B39/36; C01B39/38; C01B39/40; B01J2229/00; B01J2229/10; B01J2229/20; B01J2229/26; B01J2229/30; B01J2229/42
Claims Analysis
Total Claims: 45
Claim 1
Independent Claim
136 words
A process to make the ZSM-5 zeolite a) having a Sio 2 to Al 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 Z SM-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, 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 2
Dependent Claim
136 words
A process to make the ZSM-5 zeolite a) having a Sio 2 to Al 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 Z SM-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, 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
Dependent Claim
35 words
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
Dependent Claim
34 words
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 = 0.4 in the formula.
Claim 5
Dependent Claim
23 words
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
Dependent Claim
19 words
A process according to Claim 1, wherein there is essentially no alumina present and the product produced is silicalite.
Claim 7
Dependent Claim
10 words
The ZSM-5 zeolite made by the process of Claim 1.
Claim 8
Dependent Claim
8 words
Silicalite made by the process of Claim 1.
Claim 9
Dependent Claim
110 words
A process to make the ZSM-5 zeolite having a sio 2 to Al 2 0 3 mole ratio R greater than 5 comprising reacting a mixture containing a source of silica, a source of alumina, a source of alkali metal hydroxide, water, 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 Si 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.
Claim 10
Dependent Claim
110 words
A process to make the ZSM-5 zeolite having a sio 2 to Al 2 0 3 mole ratio R greater than 5 comprising reacting a mixture containing a source of silica, a source of alumina, a source of alkali metal hydroxide, water, 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 Si 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.
Claim 11
Dependent Claim
25 words
A process according to Claim 8, wherein the amount of tetrapropyl ammonium ions being present in the reaction mixture is an amount less than 0.6U.
Claim 12
Dependent Claim
25 words
A process according to Claim 8, wherein the amount of tetrapropyl ammonium ions being present in the reaction mixture is an amount less than 0.4U.
Claim 13
Dependent Claim
23 words
A process according to Claim 8, wherein the mother liquor from a previous synthesis is recycled to supply part of the reaction mixture.
Claim 14
Dependent Claim
19 words
A process according to Claim 8, wherein there is essentially no alumina present and the product produced is silicalite.
Claim 15
Dependent Claim
23 words
A process according to Claim 8, wherein the reaction mixture contains no source of ZSM-5 crystallites which are discernible by powder x-ray diffraction.
Claim 16
Dependent Claim
77 words
A process according to Claim 8, wherein the reaction slurry mixture has the following molar ratios of ingredients 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 100-280°C and the reaction time is less than 24 hours.
Claim 17
Dependent Claim
29 words
A process according to Claim 14, wherein molar ratios of ingredients are and wherein the reaction temperature is from 140-230°C and the reaction time is less than 12 hours.
Claim 18
Dependent Claim
30 words
A process according to Claim 15, wherein the molar ratios of ingredients are and wherein the reaction temperature is from 170-190°C and the reaction time is less than 8 hours.
Claim 19
Dependent Claim
116 words
A process according to Claim 8 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; 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 ZSM-5.
Claim 20
Dependent Claim
10 words
The ZSM-5 zeolite made by the process of Claim 8.
Claim 21
Dependent Claim
8 words
Silicalite made by the process of Claim 8.
Claim 22
Dependent Claim
166 words
A nonpolluting process to make the ZSM-5 zeolite a) having a SiO 2 to Al 2 O 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, 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 greater than 12%, at a rate corresponding to a throughput greater than 400 K g/ m 3 /day, and (ii) recovering the Z SM -5 zeolite product.
Claim 23
Dependent Claim
166 words
A nonpolluting process to make the ZSM-5 zeolite a) having a SiO 2 to Al 2 O 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, 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 greater than 12%, at a rate corresponding to a throughput greater than 400 K g/ m 3 /day, and (ii) recovering the Z SM -5 zeolite product.
Claim 24
Dependent Claim
25 words
A process according to Claim 20, wherein the equivalent product concentration is greater than 14% and the throughput is greater than 500 Kg/m 3 /day.
Claim 25
Dependent Claim
101 words
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 above 0.3 micrometer, 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, 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, said crystallites being ion-exchangeable without requiring a preliminary calcination step.
Claim 26
Dependent Claim
101 words
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 above 0.3 micrometer, 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, 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, said crystallites being ion-exchangeable without requiring a preliminary calcination step.
Claim 27
Dependent Claim
12 words
The composition of Claim 22, wherein M in the formula is Na.
Claim 28
Dependent Claim
22 words
The composition of Claim 22, which has been further ammonium ion exchanged and where M in the formula is N H 4.
Claim 29
Dependent Claim
13 words
The composition of Claim 22, wherein M in the formula is H .
Claim 30
Dependent Claim
22 words
The composition of Claim 25, wherein the cation M has been at least partially replaced by the equivalent amount of lanthanide ion.
Claim 31
Dependent Claim
11 words
The composition of Claim 24 after subsequent removal of the Q.
Claim 32
Dependent Claim
11 words
The composition of Claim 25 after subsequent removal of the Q.
Claim 33
Dependent Claim
11 words
The composition of Claim 26 after subsequent removal of the Q.
Claim 34
Dependent Claim
112 words
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 100-280°C for less than 24 hours to produce a ZS M-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.
Claim 35
Dependent Claim
15 words
A process according to Claim 30, wherein the cation exchange is made with NH4 ions.
Claim 36
Dependent Claim
20 words
A process according to Claim 30, wherein the cation exchange is made with NH + 4 ions and lanthanide ions.
Claim 37
Dependent Claim
16 words
A process according to Claim 30, wherein the cation exchange is made with H + ions.
Claim 38
Dependent Claim
19 words
A process according to Claim 30, wherein the cations exchange is made with H + ions and lanthanide ions.
Claim 39
Dependent Claim
12 words
A ZSM-5 zeolite containing catalyst made by the process of Claim 30.
Claim 40
Dependent Claim
113 words
A process for making a catalyst comprising a) mixing together a reaction slurry as defined in Claim 8; b) heating the reaction slurry at a temperature of from about 100-280 o 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.
Claim 41
Dependent Claim
15 words
A process according to Claim 36, wherein the cation exchange is made with NH4 ions.
Claim 42
Dependent Claim
20 words
A process according to Claim 36, wherein the cation exchange is made with NH + 4 ions and lanthanide ions.
Claim 43
Dependent Claim
16 words
A process according to Claim 36, wherein the cation exchange is made with H + ions.
Claim 44
Dependent Claim
19 words
A process according to Claim 36, wherein the cations exchange is made with H + ions and lanthanide ions.
Claim 45
Dependent Claim
12 words
A ZSM-5 zeolite containing catalyst made by the process of Claim 36.
References Cited (Backward Citations)
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