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Manufacture of phillipsite-type zeolite with molecular sieve properties
ELSEVIER
PATENTREPORT As
in previous issues, a selection of the more interesting patents which have been published recently is given below under the headings synthesis, catalysis, separation processes, detergents, and miscellaneous applications. J.A. Barton
Manufacture of phillipsite-type sieve properties
SYNTHESIS Crystalline silicoaluminophosphates and SAPO-56 ST. Wilson UOP Inc. U.S. 5,370,851,
Dec.
6, 1994;
Appl.
A. Cichocki Uniwersytet Jagiellonski Polish 162,652; 162,653,
SAPO-36
May
27,
1993
The novel silicoaluminophosphate molecular sieves are represented by the empirical formula mR:(Si~l,P,)O, where R represents at least one organic templating agent present in the intracrystalline pore system; m is the molar amount of R/mol of (SiAl,,P,)O, and has -a value from zero to -0.3; x is the mol fraction of silicon and varies from -0.01 to -0.98: v is the mol fraction of aluminum and varies from -0.01 to -0.60, z is the mol fraction of phosphorus and varies from -0.01 to -0.52; and x+ y + z= 1. These molecular sieves have the structure of SAPO-36 or SAPO-56 and are useful as hydrocarbon conversion catalysts.
Manufacture
of modified
zeolite
V. Nair; D.F. Best; G.J. Gajda UOP Inc. U.S. 5.371,311, Dec. 6, 1994; Appl. Cont.-in-part of US. 5,230,790
omega Dec.
17, 1990
Manufacture of coarsely phate molecular sieves
crystalline
J. Kornatowski; M. Rozwadowski; Uniwersytet Mikolaja Kopernika Polish 160,436, Mar. 31, 1993;
aluminum
G. Finger Appl.
July
phos-
et al. 7, 1989
A phosphorus compound, a structure-controlling agent, and a strong inorganic acid are reacted in an aqueous medium at IO70°C; the resulting mixture with pH = 2-5 is mixed with a second aqueous mixture containing a reactive Al compound, followed by homogenizing and adding a strong inorganic acid to recover pH = 2-5. The gel-like blend is heated in a pressure container at 130-210°C to form aluminophosphate crystals, which are separated, dried, and calcined.
of synthetic
zeolites
J. Kornatowski; M. Rozwadowski; B. Woszek Uniwersytet Mikolaja Kopernika; Uniwersytet Warszawaki Polish 162,483, Dec. 13, 1993; Appl. Apr. 6, 1989 Y zeolites with a SiO,/AI,O, tured by reacting an alkali Zeolites 16:224-229, 0 Elsevier Science 655 Avenue of the
molecular ratio of 4-6 are manufacsilicate solution with an alkali alumi-
1996 Inc. 1996 Americas,
New
York,
NY
10010
Dec.
zeolite
31, 1993;
with
Appls.
molecular
July
18, 1988
An aqueous sodium aluminate solution containing NaOH and KOH is reacted with a concentrated silicic acid hydrosol or a wide pore silicic acid gel at the following molecular component ratios: Na,O/(Na,O + x,0) = 0.7-0.8; (Na,O + K,O)/SiO, = 0.30.5: H,O/(Na,O + K,O) = 3545. The starting components are mixedLand g;ound &d contacted with a borosilicate glass at a glass surface/mixture volume ratio of 110-130 m*/m”, followed by aging the resulting aluminosilicate gel at 280-305 K, hydrothermally crystallizing at 350-400 K, separating the crystals, and washing with water. A Si02/Al,03 molecular ratio in the reaction mixture is maintained at 2-4.6 before contacting with the glass.
Membrane-like T. Nanba Nok Corp. Jpn. Kokai 13, 1993
Forms of zeolite omega synthesized by hydrothermal crystallization from reaction systems containing alkali metal cations and an organic templating agent, modified by calcination in air, ion exchange, steam calcination, and treatment with a low pH aqueous ammonium ion solution, are significantly improved with respect to surface area, catalytic activity, and adsorption capacities for large molecular species. The zeolite compositions of the invention may be used in a variety of hydrocarbon conversion reactions.
Manufacture
nate solution to obtain in the resulting hydrogel the following reagent molecular ratios: SiO,/AI,O, = 7-40, Na,O/SiO, = 0.2-2, and H,O/Na,O = 12-90, followed by stabilizing the hydrogel at 283-313 K for l-10 days, and crystallization at 353-393 K for 1-15 days. The hydrogel is obtained by using the solutions with any given alkalinity.
Tokkyo
synthetic Koho
ZSM-35 94.321,530,
zeolites Nov.
22,
1994;
Appl.
May
Membrane-like ZSM-35 zeolite products are synthesized from solutions containing silica sources, alumina sources, alkali metal sources, tetramethylammonium salts as crystallization agents, and water by enclosing the mixtures in pressureresistant vessels and keeping at a hydrothermal synthesis temoerature of 150-200°C. The products are especially suitable for use as gas separation membranes, catalysts, adsorbents, etc. The use of ceramic supports is not needed in the manufacturing process.
Zeolite-type material with ultralarge of silicon and titanium oxides
pores
A. Corma Canos; M.T. Navarro Villalba; J. Perez Consejo Superior de lnvestigaciones Cientificas; Politecnica de Valencia PCT Int. Appl. 94,29,022, Dec. 22, 1994; Spanish 1993
and a lattice Pariente Universidad Appl.
June
15,
The invention relates to a zeolite-type material of silicotitanates having a crystalline structure similar to MCM-41 zeolites, characterized in that it contains in its lattice atoms oftitanium and channels in its porous structure of average size >I A. This makes possible its use in catalytic reactions involving large organic molecules, such as the oxidation of olefins to epoxides and gly~01s. alcohols to ketones, thioethers to sulfoxides and sulfones, and phenol to catechol and hydroquinone. If aluminum is introduced into the structure it is then possible to prepare bifunctional oxidation and acid/base catalysts. To obtain the material an aqueous solution is used which contains a tetraalkylammonium ion and another aqueous solution that contains tetramethylammonium hydroxide and a silica source. After homogenization the Ti source (e.g. Ti(C,H,O),) and more silica are added. The resultant gel is heated in an autoclave at 80-200°C and then activated by calcining between 350 and 800°C.
SSDI
0144.2449/96/$15.00 0144-2449(95)00126-3
PATENTREPORT As
in previous issues, a selection of the more interesting patents which have been published recently is given below under the headings synthesis, catalysis, separation processes, detergents, and miscellaneous applications. J.A. Barton
Manufacture of phillipsite-type sieve properties
SYNTHESIS Crystalline silicoaluminophosphates and SAPO-56 ST. Wilson UOP Inc. U.S. 5,370,851,
Dec.
6, 1994;
Appl.
A. Cichocki Uniwersytet Jagiellonski Polish 162,652; 162,653,
SAPO-36
May
27,
1993
The novel silicoaluminophosphate molecular sieves are represented by the empirical formula mR:(Si~l,P,)O, where R represents at least one organic templating agent present in the intracrystalline pore system; m is the molar amount of R/mol of (SiAl,,P,)O, and has -a value from zero to -0.3; x is the mol fraction of silicon and varies from -0.01 to -0.98: v is the mol fraction of aluminum and varies from -0.01 to -0.60, z is the mol fraction of phosphorus and varies from -0.01 to -0.52; and x+ y + z= 1. These molecular sieves have the structure of SAPO-36 or SAPO-56 and are useful as hydrocarbon conversion catalysts.
Manufacture
of modified
zeolite
V. Nair; D.F. Best; G.J. Gajda UOP Inc. U.S. 5.371,311, Dec. 6, 1994; Appl. Cont.-in-part of US. 5,230,790
omega Dec.
17, 1990
Manufacture of coarsely phate molecular sieves
crystalline
J. Kornatowski; M. Rozwadowski; Uniwersytet Mikolaja Kopernika Polish 160,436, Mar. 31, 1993;
aluminum
G. Finger Appl.
July
phos-
et al. 7, 1989
A phosphorus compound, a structure-controlling agent, and a strong inorganic acid are reacted in an aqueous medium at IO70°C; the resulting mixture with pH = 2-5 is mixed with a second aqueous mixture containing a reactive Al compound, followed by homogenizing and adding a strong inorganic acid to recover pH = 2-5. The gel-like blend is heated in a pressure container at 130-210°C to form aluminophosphate crystals, which are separated, dried, and calcined.
of synthetic
zeolites
J. Kornatowski; M. Rozwadowski; B. Woszek Uniwersytet Mikolaja Kopernika; Uniwersytet Warszawaki Polish 162,483, Dec. 13, 1993; Appl. Apr. 6, 1989 Y zeolites with a SiO,/AI,O, tured by reacting an alkali Zeolites 16:224-229, 0 Elsevier Science 655 Avenue of the
molecular ratio of 4-6 are manufacsilicate solution with an alkali alumi-
1996 Inc. 1996 Americas,
New
York,
NY
10010
Dec.
zeolite
31, 1993;
with
Appls.
molecular
July
18, 1988
An aqueous sodium aluminate solution containing NaOH and KOH is reacted with a concentrated silicic acid hydrosol or a wide pore silicic acid gel at the following molecular component ratios: Na,O/(Na,O + x,0) = 0.7-0.8; (Na,O + K,O)/SiO, = 0.30.5: H,O/(Na,O + K,O) = 3545. The starting components are mixedLand g;ound &d contacted with a borosilicate glass at a glass surface/mixture volume ratio of 110-130 m*/m”, followed by aging the resulting aluminosilicate gel at 280-305 K, hydrothermally crystallizing at 350-400 K, separating the crystals, and washing with water. A Si02/Al,03 molecular ratio in the reaction mixture is maintained at 2-4.6 before contacting with the glass.
Membrane-like T. Nanba Nok Corp. Jpn. Kokai 13, 1993
Forms of zeolite omega synthesized by hydrothermal crystallization from reaction systems containing alkali metal cations and an organic templating agent, modified by calcination in air, ion exchange, steam calcination, and treatment with a low pH aqueous ammonium ion solution, are significantly improved with respect to surface area, catalytic activity, and adsorption capacities for large molecular species. The zeolite compositions of the invention may be used in a variety of hydrocarbon conversion reactions.
Manufacture
nate solution to obtain in the resulting hydrogel the following reagent molecular ratios: SiO,/AI,O, = 7-40, Na,O/SiO, = 0.2-2, and H,O/Na,O = 12-90, followed by stabilizing the hydrogel at 283-313 K for l-10 days, and crystallization at 353-393 K for 1-15 days. The hydrogel is obtained by using the solutions with any given alkalinity.
Tokkyo
synthetic Koho
ZSM-35 94.321,530,
zeolites Nov.
22,
1994;
Appl.
May
Membrane-like ZSM-35 zeolite products are synthesized from solutions containing silica sources, alumina sources, alkali metal sources, tetramethylammonium salts as crystallization agents, and water by enclosing the mixtures in pressureresistant vessels and keeping at a hydrothermal synthesis temoerature of 150-200°C. The products are especially suitable for use as gas separation membranes, catalysts, adsorbents, etc. The use of ceramic supports is not needed in the manufacturing process.
Zeolite-type material with ultralarge of silicon and titanium oxides
pores
A. Corma Canos; M.T. Navarro Villalba; J. Perez Consejo Superior de lnvestigaciones Cientificas; Politecnica de Valencia PCT Int. Appl. 94,29,022, Dec. 22, 1994; Spanish 1993
and a lattice Pariente Universidad Appl.
June
15,
The invention relates to a zeolite-type material of silicotitanates having a crystalline structure similar to MCM-41 zeolites, characterized in that it contains in its lattice atoms oftitanium and channels in its porous structure of average size >I A. This makes possible its use in catalytic reactions involving large organic molecules, such as the oxidation of olefins to epoxides and gly~01s. alcohols to ketones, thioethers to sulfoxides and sulfones, and phenol to catechol and hydroquinone. If aluminum is introduced into the structure it is then possible to prepare bifunctional oxidation and acid/base catalysts. To obtain the material an aqueous solution is used which contains a tetraalkylammonium ion and another aqueous solution that contains tetramethylammonium hydroxide and a silica source. After homogenization the Ti source (e.g. Ti(C,H,O),) and more silica are added. The resultant gel is heated in an autoclave at 80-200°C and then activated by calcining between 350 and 800°C.
SSDI
0144.2449/96/$15.00 0144-2449(95)00126-3