US4377502A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Synthesis of crystalline aluminosilicate molecular sieves
Assignee: BP Corp North America Inc
•
Filing: 1980-12-19
•
Granted: 1983-03-22
•
Expires: 2000-12-19
Abstract
Abstract Crystalline aluminosilicate molecular sieves are prepared by (1) forming an aqueous mixture of an oxide of aluminum, an oxide of silicon, a metal or ammonium cation and a suitable oxygen-containing monomeric organic template compound, (2) maintaining the pH of such mixture between 9 and 14, and (3) crystallizing the mixture. The organic templates include ethanolamine, diethanolamine, triethanolamine, ethylethanolamine, ethyldiethanolamine, 2-amino-2-ethyl-1,3-propanediol, morpholine, and alkali metal complexed tetrahydrofuran, dioxane, dioxolane, and crown ethers. Crystalline aluminosilicates prepared include mordenite, ferrierite, ZSM-4, and ZSM-5.
Inventors
- 👤 Marvin R. Klotz
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 11:37
CPC Classifications
C; C01; C01B; C01B39/00; C01B39/02; C01B39/44; C01B39/445; B; B01; B01J; B01J29/00; B01J29/04; B01J29/06; B01J29/18; B01J29/40; B01J29/65; B01J29/80; C01B39/26; C01B39/265; C01B39/34; C01B39/36; C01B39/38; C01B39/40; C07; C07C; C07C5/00; C07C5/22; C07C5/27; C07C5/2767; C07C5/277; C07C5/2775; B01J2229/00; B01J2229/10; B01J2229/26; B01J2229/30; B01J2229/42; B01J29/70; B01J29/7011; Y; Y02; Y02P; Y02P20/00; Y02P20/50; Y02P20/52
Claims Analysis
Total Claims: 29
Claim 1
Independent Claim
138 words
A method to prepare a mordenite, ferrierite, ZSM-4 or ZSM-5 crystalline aluminosilicate molecular sieve comprising (1) forming an aqueous mixture of sources for an oxide of aluminum and an oxide of silicon, a cation and an alkali metal cation-complexed ether wherein the composition of the mixture of initial reactants in terms of mole ratios of oxides is: ______________________________________
SiO.sub.2 /Al.sub.2 O.sub.3
8-80
R.sub.2 O.sup.+ (R.sub.2 O.sup.+ + M.sub.2/n O)
0.2-0.95
OH.sup.- /SiO.sub.2
0.01-3
H.sub.2 O/OH.sup.- 10-500
______________________________________ where R is an alkali metal cation-complexed ether and M is at least one cation having a valence n, (2) maintaining the pH of such mixture between about 9 and about 14 and (3) crystallizing such mixture at a pressure at least the vapor pressure of water for about 0.25 to about 20 days at about 125° to about 200° C.
Claim 2
Independent Claim
138 words
A method to prepare a mordenite, ferrierite, ZSM-4 or ZSM-5 crystalline aluminosilicate molecular sieve comprising (1) forming an aqueous mixture of sources for an oxide of aluminum and an oxide of silicon, a cation and an alkali metal cation-complexed ether wherein the composition of the mixture of initial reactants in terms of mole ratios of oxides is: ______________________________________
SiO.sub.2 /Al.sub.2 O.sub.3
8-80
R.sub.2 O.sup.+ (R.sub.2 O.sup.+ + M.sub.2/n O)
0.2-0.95
OH.sup.- /SiO.sub.2
0.01-3
H.sub.2 O/OH.sup.- 10-500
______________________________________ where R is an alkali metal cation-complexed ether and M is at least one cation having a valence n, (2) maintaining the pH of such mixture between about 9 and about 14 and (3) crystallizing such mixture at a pressure at least the vapor pressure of water for about 0.25 to about 20 days at about 125° to about 200° C.
Claim 3
Dependent Claim
15 words
The method of claim 1 wherein source for the oxide of aluminum is sodium aluminate.
Claim 4
Dependent Claim
58 words
The method of claim 1 wherein the composition of the mixture of initial reactants in terms of mole ratios of oxides is: ______________________________________
SiO.sub.2 /Al.sub.2 O.sub.3
15-80
R.sub.2 O+/[R.sub.2 O+ + M.sub.2/n O]
0.2-0.95
OH-/SiO.sub.2 0.01-3
H.sub.2 O/OH- 10-500
______________________________________ where R is an alkali metal cation-complexed ether and M is at least one cation of valence n.
Claim 5
Dependent Claim
11 words
The method of claim 1 wherein the crystalline aluminosilicate is mordenite-like.
Claim 6
Dependent Claim
11 words
The method of claim 1 wherein the crystalline aluminosilicate is ferrierite-like.
Claim 7
Dependent Claim
11 words
The method of claim 1 wherein the crystalline aluminosilicate is mordenite-like.
Claim 8
Dependent Claim
11 words
The method of claim 3 wherein the crystalline aluminosilicate is ferrierite-like.
Claim 9
Dependent Claim
15 words
The method of claim 1 wherein the silica/alumina ratio of initial reactants is about 16.
Claim 10
Dependent Claim
15 words
The method of claim 3 wherein the silica/alumina ratio of initial reactants is about 32.
Claim 11
Dependent Claim
14 words
The method of claim 1 wherein the cation-complexed ether is dioxane complexed sodium ion.
Claim 12
Dependent Claim
19 words
The method of claim 1 wherein the pH of the mixture is maintained between about 10.5 and about 13.
Claim 13
Dependent Claim
26 words
The method of claim 1 wherein the crystallizing mixture is maintained at about 125° C. to about 200° C. for about one to about seven days.
Claim 14
Dependent Claim
16 words
The method of claim 1 wherein M is an alkali metal or alkaline earth metal cation.
Claim 15
Dependent Claim
17 words
The method of claim 1 wherein source for the oxide of silicon is a silicic acid polymer.
Claim 16
Dependent Claim
16 words
The method of claim 1 wherein a catalytically active material is placed onto the crystalline aluminosilicate.
Claim 17
Dependent Claim
17 words
The method of claim 15 wherein the catalytically active material is ion exchanged onto the crystalline aluminosilicate.
Claim 18
Dependent Claim
31 words
The method of claim 16 wherein the catalytically active material is hydrogen, metal ions of Groups IB, IIB, IIIA or VIII or of manganese, vanadium, chromium, uranium or rare earth elements.
Claim 19
Dependent Claim
11 words
The method of claim 25 wherein the ion is nickel ion.
Claim 20
Dependent Claim
17 words
The method of claim 17 wherein a catalytically active compound is impregnated onto the mordenite crystalline aluminosilicate.
Claim 21
Dependent Claim
32 words
The method of claim 19 wherein the catalytically active compound is a water soluble salt of metals of Groups IB, IIB, IIIA, IVB, VB, VIB, VIIB, or VIII, or rare earth elements.
Claim 22
Dependent Claim
15 words
The method of claim 20 wherein the catalytically active compound is a salt of molybdenum.
Claim 23
Dependent Claim
17 words
The method of claim 1 wherein the prepared molecular sieve is incorporated within a suitable matrix material.
Claim 24
Dependent Claim
14 words
The method of claim 22 wherein the matrix material is silica, silica-alumina or alumina.
Claim 25
Dependent Claim
22 words
The method of claim 1 wherein the prepared crystalline aluminosilicate shows the X-ray diffraction lines contained in Table IV of the specification.
Claim 26
Dependent Claim
22 words
The method of claim 1 wherein the prepared crystalline aluminosilicate shows the X-ray diffraction lines contained in Table V of the specification.
Claim 27
Dependent Claim
28 words
The method of claim 1 wherein the alkali metal cation-complexed ether is an ether containing up to about twelve carbon atoms complexed with a Group IA metal cation.
Claim 28
Dependent Claim
12 words
The method of claim 26 wherein the ether is a cyclic ether.
Claim 29
Dependent Claim
16 words
The method of claim 26 wherein the ether is tetrahydroxyfuran, dioxane, dioxolane or a crown ether.
References Cited (Backward Citations)
US3130007A
Cited
US3271418A
Cited
US3578723A
Cited
US3702886A
Cited
GB1365318A
Cited
US4199556A
Cited
US4000248A
Cited
US4046859A
Cited
US4242233A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1986-03-21 | 1986-09-20 | 1987-03-22 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-03-21 | 1990-09-20 | 1991-03-22 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-03-21 | 1994-09-20 | 1995-03-22 | $7700.00 | Window Closed / Lapsed |