US5167942A
Expired / Lapsed
US
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Methods for the preparation of molecular sieves, including zeolites, using metal chelate complexes
Assignee: The University of Texas System
•
Filing: 1990-11-21
•
Granted: 1992-12-01
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Expires: 2010-11-21
Abstract
Abstract The present disclosure relates to improved methods for the preparation of aluminum phosphate molecular sieves and faujasite-type zeolites having stably encapsulated multidentate metal chelate complexes. This is achieved through direct incorporation of a selected multidentate chelate complex into the molecular sieve or zeolite reaction admixture prior to crystallization, allowing the admixture to react under conditions appropriate for the selected molecular sieve or zeolite, followed by preparation of the resultant molecular sieve-metal chelate complex in a highly crystalline form.
Inventors
- 👤 Kenneth J. Balkus
- 👤 Stanislaw Kowalak
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-23 18:50
CPC Classifications
B; B01; B01J; B01J45/00; B01J20/00; B01J20/02; B01J20/10; B01J20/16; B01J20/18; B01J29/00; B01J29/04; B01J29/06; B01J29/08; B01J29/70; B01J29/82; B01J29/84; C; C01; C01B; C01B33/00; C01B33/20; C01B33/26; C01B33/28; C01B33/2807; C01B33/2892; C01B37/00; C01B37/04; Y; Y10; Y10S; Y10S423/00; Y10S423/21
Claims Analysis
Total Claims: 46
Claim 1
Independent Claim
112 words
A process for the preparation of zeolites of the faujasite group which includes an encapsulated multidentate metal chelate complex, the process comprising the steps of: preparing an aqueous alkaline admixture of aluminate and silicate anions and an alkaline or alkaline earth hydroxide, in molar ratios and a pH appropriate for the formation of a zeolite of the faujasite group; introducing a multidentate metal chelate complex larger than nominal pore size of the faujasite zeolite into the admixture; reacting the admixture under conditions appropriate for the formation of a crystalline zeolite of the faujasite group; and preparing from the reacted admixture a crystalline zeolite having the multidentate metal complex encapsulated within the zeolite.
Claim 2
Dependent Claim
112 words
A process for the preparation of zeolites of the faujasite group which includes an encapsulated multidentate metal chelate complex, the process comprising the steps of: preparing an aqueous alkaline admixture of aluminate and silicate anions and an alkaline or alkaline earth hydroxide, in molar ratios and a pH appropriate for the formation of a zeolite of the faujasite group; introducing a multidentate metal chelate complex larger than nominal pore size of the faujasite zeolite into the admixture; reacting the admixture under conditions appropriate for the formation of a crystalline zeolite of the faujasite group; and preparing from the reacted admixture a crystalline zeolite having the multidentate metal complex encapsulated within the zeolite.
Claim 3
Dependent Claim
15 words
The process of claim 1, wherein the zeolite comprises an FAU or LTA type zeolite.
Claim 4
Dependent Claim
13 words
The process of claim 2, wherein the zeolite comprises and FAU type zeolite.
Claim 5
Dependent Claim
14 words
The process of claim 1, wherein the crystalline zeolite is at least 80% crystalline.
Claim 6
Dependent Claim
13 words
The process of claim 4, wherein the crystalline zeolite is about 100% crystalline.
Claim 7
Dependent Claim
19 words
The process of claim 1, wherein the aqueous alkaline admixture has a pH of from about 11 to 14.
Claim 8
Dependent Claim
23 words
The process of claim 1, wherein the aqueous alkaline admixture comprises a molar ratio of aluminate/silicate/water in a range of about 1/1-10/17-100, respectively.
Claim 9
Dependent Claim
30 words
The process of claim 7, wherein an FAU type zeolite is prepared and the aqueous alkaline admixture comprises a molar ratio of aluminate/silicate/water in a range of about 1/1-10/50-160, respectively.
Claim 10
Dependent Claim
25 words
The process of claim 8, wherein the admixture is reacted at between about 20 and 175 degrees C., for between about 2 and 144 hours.
Claim 11
Dependent Claim
15 words
The process of claim 9, wherein the admixture is reacted until crystallization is essentially complete.
Claim 12
Dependent Claim
30 words
The process of claim 7, wherein an LTA type zeolite is prepared and the aqueous alkaline admixture comprises a molar ratio of aluminate/silicate/water in a range of about 1/1-3/17-100, respectively.
Claim 13
Dependent Claim
25 words
The process of claim 11, wherein the admixture is reacted at between about 20 and 175 degrees C., for between about 2 and 144 hours.
Claim 14
Dependent Claim
15 words
The process of claim 12, wherein the admixture is reacted until crystallization is essentially complete.
Claim 15
Dependent Claim
15 words
The process of claim 1, wherein the prepared crystalline zeolite is at least 80% pure.
Claim 16
Dependent Claim
13 words
The process of claim 14, wherein the prepared crystalline zeolite is essentially pure.
Claim 17
Dependent Claim
17 words
A faujasite zeolite encapsulating a homogeneously distributed multidentate metal chelate prepared by the process of claim 1.
Claim 18
Dependent Claim
108 words
A process for the preparation of a crystalline aluminum phosphate molecular sieve which includes an encapsulated multidentate metal chelate complex, the process comprising the steps of: a) preparing an aqueous acidic admixture of aluminate and phosphate anions in molar ratios appropriate for the formation of an aluminum phosphate molecular sieve; b) introducing a multidentate metal chelate complex larger than nominal pore size of the crystalline aluminophosphate molecular sieve into the admixture; c) reacting the admixture under conditions appropriate for the formation of an aluminum phosphate molecular sieve; and d) preparing from the reacted admixture the molecular sieve having the multidentate metal chelate complex encapsulated within the molecular sieve.
Claim 19
Dependent Claim
108 words
A process for the preparation of a crystalline aluminum phosphate molecular sieve which includes an encapsulated multidentate metal chelate complex, the process comprising the steps of: a) preparing an aqueous acidic admixture of aluminate and phosphate anions in molar ratios appropriate for the formation of an aluminum phosphate molecular sieve; b) introducing a multidentate metal chelate complex larger than nominal pore size of the crystalline aluminophosphate molecular sieve into the admixture; c) reacting the admixture under conditions appropriate for the formation of an aluminum phosphate molecular sieve; and d) preparing from the reacted admixture the molecular sieve having the multidentate metal chelate complex encapsulated within the molecular sieve.
Claim 20
Dependent Claim
17 words
The process of claim 17, wherein the aluminate is introduced in the form of an aluminum alkoxide.
Claim 21
Dependent Claim
16 words
The process of claim 17, wherein the phosphorus is introduced in the form of phosphoric acid.
Claim 22
Dependent Claim
14 words
The process of claim 17, wherein the molecular sieve is at least 80% crystalline.
Claim 23
Dependent Claim
13 words
The process of claim 20, wherein the molecular sieve is about 100% crystalline.
Claim 24
Dependent Claim
17 words
The process of claim 17, further comprising incorporating a directing agent into the admixture prior to reacting.
Claim 25
Dependent Claim
18 words
The process of claim 22, wherein the directing agent comprises an alkyl ammonium salt or a neutral amine.
Claim 26
Dependent Claim
21 words
The process of claim 17, wherein the aqueous admixture comprises a molar ratio of aluminate/phosphorous in a range of about 1/1.
Claim 27
Dependent Claim
25 words
The process of claim 24, wherein the admixture is reacted at between about 125 and 200 degrees C., for between about 5 and 150 hours.
Claim 28
Dependent Claim
15 words
The process of claim 25, wherein the admixture is reacted until crystallization is essentially complete.
Claim 29
Dependent Claim
38 words
The process of claim 1 or 17, wherein the multidentate chelate ligand of the multidentate metal chelate complex comprises a polyazo, polyphosphoro, polysulfur, polyether macrocycle, or a heteronuclear chelate macrocycle comprising one or more of the foregoing groups.
Claim 30
Dependent Claim
14 words
The process of claim 27, wherein the multidentate chelate ligand comprises a polyazo macrocycle.
Claim 31
Dependent Claim
13 words
The process of claim 28, wherein the polyazo macrocycle comprises a tetraazo macrocycle.
Claim 32
Dependent Claim
55 words
The process of claim 27, wherein the multidentate metal chelate complex comprises one of the following compounds: ##STR5## wherein X is O, S, NR or PR; R is hydrogen, an alkyl, aryl, silyl, halogen, alkoxy, carboxylate, phosphate, or nitrogen containing moiety; and M is any transition metal, rare earth element, alkali or alkaline earth metal.
Claim 33
Dependent Claim
45 words
The process of claim 27, wherein the multidentate chelate of the multidentate metal chelate complex comprises one of the following compounds: ##STR6## wherein X is O, S, NR or PR; R is hydrogen, an alkyl, aryl, silyl, halogen, alkoxy, carboxylate, phosphate, or nitrogen containing moiety.
Claim 34
Dependent Claim
48 words
The process of claim 27, wherein the multidentate metal chelate complex comprises one of the following compounds: ##STR7## wherein R is hydrogen, an alkyl, aryl, silyl, halogen, alkoxy, carboxylate, phosphate, or nitrogen containing moiety; and M is any transition metal, rare earth element, alkali or alkaline earth metal.
Claim 35
Dependent Claim
55 words
The process of claim 27, wherein the multidentate metal chelate complex comprises one of the following compounds: ##STR8## wherein R is hydrogen, an alkyl, aryl, silyl, halogen, alkoxy, carboxylate, phosphate, or nitrogen containing moiety; R' is an alkyl or ether linkage; and M is any transition metal, rare earth element, alkali or alkaline earth metal.
Claim 36
Dependent Claim
70 words
The process of claim 27, wherein the multidentate metal chelate complex comprises one of the following compounds: ##STR9## wherein R is hydrogen, an alkyl, aryl, silyl, halogen, alkoxy, carboxylate, phosphate, or nitrogen containing moiety; a terminal X is OR, SR, NR 2 , or PR 2 ; a nonterminal X is O, S, NR or PR; and M is any transition metal, rare earth element, alkali or alkaline earth metal.
Claim 37
Dependent Claim
27 words
The process of claim 27, wherein the metal ion of the multidentate metal chelate complex comprises a transition metal, rare earth element, alkali or alkaline earth metal.
Claim 38
Dependent Claim
32 words
The process of claim 35, wherein the metal ion comprises a Co 2+ , Fe 2+ , Ni 2+ , Cu 2+ , Mn 2+ , Pd 2+ or Gd 3+ ion.
Claim 39
Dependent Claim
20 words
The process of claim 1 or 17, wherein step (d) comprises treating the admixture to remove impurities or unreacted materials.
Claim 40
Dependent Claim
17 words
The process of claim 37, wherein the reacted admixture is treated by washing with an aqueous wash.
Claim 41
Dependent Claim
15 words
The process of claim 37, wherein the reacted admixture is washed with a selected solvent.
Claim 42
Dependent Claim
10 words
The process of claim 39, wherein the solvent is pyridine.
Claim 43
Dependent Claim
13 words
The process of claim 37, wherein the reacted admixture is treated by sublimation.
Claim 44
Dependent Claim
15 words
The process of claim 17, wherein the prepared molecular sieve is at least 80% pure.
Claim 45
Dependent Claim
13 words
The process of claim 42, wherein the prepared molecular sieve is essentially pure.
Claim 46
Dependent Claim
10 words
A molecular sieve prepared by the process of claim 17.
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