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Growing sodium type X zeolite crystals
PATENTREPORT As in p r e v i o u s issues, a selection of t h e m o r e i n t e r e s t i n g patents t h a t have been p u b l i s h e d recently is g i v e n b e l o w u n d e r t h e h e a d i n g s : synthesis, catalysis, s e p a r a t i o n processes, d e t e r g e n t s , and m i s c e l l a n e o u s a p p l i c a t i o n s .
J.A. Barton
SYNTHESIS Zeolite manufacture from tempered sand
decompose pyrrolidine, exchanging cations in the ZSM-23 with NH4+, and calcining the NH4+-exchanged catalyst to decompose the NH4+.
Templating agent-free process for the manufacture of microporous, crystalline aluminophosphate molecular sieves Vereinigte Aluminium-Werke A.-G.; Akademie der Wissenschaften der DDR; Zentralinstitut fuer Physikalische Chimie; LeunaWerke A.-G.
Get Often 4,015,850, Nov. 21, 1991; Appl. May 17, 1990 In the manufacture of the aluminosilicates [MzO.AI203.xSiOz (M = K or Na; x = 1.8-12)], the SiO2 source is obtained by dissolving tempered sand at elevated temperatures in KOH or NaOH. The AI203 source may be K aluminate or Na aluminate.
Eur. Pat. Appl. 464,249, Jan. 8, 1992; Appl. July 5, 1990 The microporous molecular sieves, having pore entrances ~>0.8 nm, a structure formed from tetrahedral building blocks of AIOz- and PO2+, and manufacturd by crystallizing a gelled reaction mixture of an AI compound, P compound, water, and, optionally, seed crystals, are manufactured by using a P-O-P group-containing P compound, and hydrothermally reacting the gelled mixture. The molecular sieves are used in separation processes and catalytic reactions.
Manufacture of iron pentasil-type aluminosilicates
Manufacture of zeolitic gallosilicates
J.W. Hachgenei; H. Dolhaine; A. Heins et al.
Henkel K.-G.a.A.
W. Schwieger; K.H. Bergk; H. Fuertig et al.
Chernie A.-G. Bitterfeld-Wolfen E. Ger. 294,468, Oct. 2, 1991; Appl. Feb. 12, 1990 The process comprises hydrothermally crystallizing the aluminosilicates in a single step from organic templating agent-free, Si, AI, Na, Fe and OH ion-containing aqueous solutions with addition of nitrate and/or sulfate ion-containing compounds, These aluminosilicates are suitable for use as catalysts or catalyst components.
Purification of natural zeolites
Vereinigte A/uminium-Werke A.-G. Ger. Often. 4,021,118, Jan. 9, 1992; Appl. July 3, 1990 The gallosilicates, having Si/Ga atomic ratio /> 5:1 and obtained from aqueous alkali reaction mixtures con~taining SiO2, Ga203, or their hydrated derivatives, or alkali metal gallates and silicates, and, optionally, quarternary ammonium compounds, are manufactured using as crystallization promoter an aged, but still X-ray-amorphous, gallosilicate gel having Si/Ga atomic ratio ~> 5:1. These zeolites are used as catalysts for the aromatization of lower hydrocarbons.
N. Sakai; S. Noda; Y. Kawatani et al.
Manufacture of high-performance granular zeolites
Shirnane Prefecture
G. Prast; P. Lehmann; U. Haedicke et al.
Jpn Kokai Tokkyo Koho 91,252,310, Nov. 11, 1991 ; Appl. Feb. 28, 1990 Zeolitic minerals (e.g., tuff) containing clay minerals (e.g., montmorillonite) are pulverized without damaging zeolite crystals (e.g., clinoptilolite), dipped in water for disintegration, and classified to recover high-purity zeolites.
Manufacture of silicon-containing aluminophosphatetype molecular sieves
Chemie A.-G. Bitterfeld-Wolfen E. Ger. 295,609, Nov. 7, 1991; Appl. June 27, 1986 The zeolites, having predominant pore radius 200-800 A, are manufactured from granular starting zeolites, e.g., zeolites 5A, and 13X, by (a) calcination, (b) hydration, (c) treatment with Group IA hydroxides and (d) post-activation.
Growing sodium type X zeolite crystals I.L. Maclaine-Cross
S. Wohlrab; O. Rademacher; H. Scheler
Unisearch Ltd.
Technische Universitaet Dresden
PCT Int. Appl. 91,17,115, Nov. 14, 1991; Au. Appl. May 8, 1990 NaX zeolite crystals of particle size ~> 50 microns are grown from seed crystals at ca. 5 microns/d in a mother liquor containing Na20 0.94, AI203 0.011, and SiO2 0.200 moi/Kg by adding fine SiO2 powder, somewhat coarser AI203 powder, and NaOH at rates so that the mother liquor is kept at < 20% supersaturation with respect to AI203 to avoid the formation of a gel. Throughout growth, the mother liquor is stirred and kept at ca. 95°C.
E. Ger. 295,140, Oct. 24, 1991; Appl. June 13, 1990 The process comprises hydrothermally treating reaction mixtures that contain, in addition to Si-, AI-, and P-containing compounds, a template consisting of an asymmetrically substituted ammonium compound having general formula R1R2R3R4Ny[R1"4 = (substituted) alkyl /> 1 of which is different; Y = anion], and, as Si compound, a solution of an alkylammonium silicate having an asymmetrically substituted ammonium cation having general formula R1R2R3R4N+ (R1-4 as above), and heat-treating the resulting crystals to obtain the molecular sieves. The resulting molecular sieves of type ALPO-5 are suitable for use in catalyst sytems and as sorbents.
CATALYSIS
Z e o l i t e preparation using an alcohol directing agent G.W. Kirker; D.J. Klocke; J.C. Vartuli et al.
Z e o l i t e c a t a l y s t w i t h hexagonal structure and its application T. Des Courieres; J.L. Guth; J. Patarin et al.
Mobil Oil Corp.
Societe Nationale Elf Aquitaine (SNEA)
U.S. 5,063,038, Nov. 5, 1991; Appl. Oct. 21, 1985 Zeolites having ZSM-23 structure are obtained by preparing a mixture comprising a source of SiO2, a source of AI203, and a mixed organic directing agent comprising an amine, e.g., pyrrolidine, and a CI-s alcohol and/or diol, maintaining the reaction mixture at a sufficient temperature to crystallize the zeolite, and recovering the zeolite. The catalytic activity of ZSM-23 is enhanced by combining ZSM-23 with an AI203 binder, calcining the AI203-bound ZSM-23 to
PCT Int. Appl. 91,15,294, Oct. 17, 1991; FR. Appl. Apr. 9, 1990 The catalyst, suitable for acid catalysis reactions, especially fiuidized bed catalytic cracking, contains 1-99 wt.% of an inorganic binder, e.g., alumina, silica, alumina/silica clay, or magnesia, and 1-99 wt.% of a zeolite related to faujasite and having a hexagonally symmetrical structure and a Si:AI synthesis ratio of 3-30. The compensating cations of this zeolite consist partly or wholly of cations of ~> 1 of H, B, AI, Ga, In, rare earth metals, and transition metals. The catalyst
ZEOLITES, 1993, Vol 13, February
149
J.A. Barton
SYNTHESIS Zeolite manufacture from tempered sand
decompose pyrrolidine, exchanging cations in the ZSM-23 with NH4+, and calcining the NH4+-exchanged catalyst to decompose the NH4+.
Templating agent-free process for the manufacture of microporous, crystalline aluminophosphate molecular sieves Vereinigte Aluminium-Werke A.-G.; Akademie der Wissenschaften der DDR; Zentralinstitut fuer Physikalische Chimie; LeunaWerke A.-G.
Get Often 4,015,850, Nov. 21, 1991; Appl. May 17, 1990 In the manufacture of the aluminosilicates [MzO.AI203.xSiOz (M = K or Na; x = 1.8-12)], the SiO2 source is obtained by dissolving tempered sand at elevated temperatures in KOH or NaOH. The AI203 source may be K aluminate or Na aluminate.
Eur. Pat. Appl. 464,249, Jan. 8, 1992; Appl. July 5, 1990 The microporous molecular sieves, having pore entrances ~>0.8 nm, a structure formed from tetrahedral building blocks of AIOz- and PO2+, and manufacturd by crystallizing a gelled reaction mixture of an AI compound, P compound, water, and, optionally, seed crystals, are manufactured by using a P-O-P group-containing P compound, and hydrothermally reacting the gelled mixture. The molecular sieves are used in separation processes and catalytic reactions.
Manufacture of iron pentasil-type aluminosilicates
Manufacture of zeolitic gallosilicates
J.W. Hachgenei; H. Dolhaine; A. Heins et al.
Henkel K.-G.a.A.
W. Schwieger; K.H. Bergk; H. Fuertig et al.
Chernie A.-G. Bitterfeld-Wolfen E. Ger. 294,468, Oct. 2, 1991; Appl. Feb. 12, 1990 The process comprises hydrothermally crystallizing the aluminosilicates in a single step from organic templating agent-free, Si, AI, Na, Fe and OH ion-containing aqueous solutions with addition of nitrate and/or sulfate ion-containing compounds, These aluminosilicates are suitable for use as catalysts or catalyst components.
Purification of natural zeolites
Vereinigte A/uminium-Werke A.-G. Ger. Often. 4,021,118, Jan. 9, 1992; Appl. July 3, 1990 The gallosilicates, having Si/Ga atomic ratio /> 5:1 and obtained from aqueous alkali reaction mixtures con~taining SiO2, Ga203, or their hydrated derivatives, or alkali metal gallates and silicates, and, optionally, quarternary ammonium compounds, are manufactured using as crystallization promoter an aged, but still X-ray-amorphous, gallosilicate gel having Si/Ga atomic ratio ~> 5:1. These zeolites are used as catalysts for the aromatization of lower hydrocarbons.
N. Sakai; S. Noda; Y. Kawatani et al.
Manufacture of high-performance granular zeolites
Shirnane Prefecture
G. Prast; P. Lehmann; U. Haedicke et al.
Jpn Kokai Tokkyo Koho 91,252,310, Nov. 11, 1991 ; Appl. Feb. 28, 1990 Zeolitic minerals (e.g., tuff) containing clay minerals (e.g., montmorillonite) are pulverized without damaging zeolite crystals (e.g., clinoptilolite), dipped in water for disintegration, and classified to recover high-purity zeolites.
Manufacture of silicon-containing aluminophosphatetype molecular sieves
Chemie A.-G. Bitterfeld-Wolfen E. Ger. 295,609, Nov. 7, 1991; Appl. June 27, 1986 The zeolites, having predominant pore radius 200-800 A, are manufactured from granular starting zeolites, e.g., zeolites 5A, and 13X, by (a) calcination, (b) hydration, (c) treatment with Group IA hydroxides and (d) post-activation.
Growing sodium type X zeolite crystals I.L. Maclaine-Cross
S. Wohlrab; O. Rademacher; H. Scheler
Unisearch Ltd.
Technische Universitaet Dresden
PCT Int. Appl. 91,17,115, Nov. 14, 1991; Au. Appl. May 8, 1990 NaX zeolite crystals of particle size ~> 50 microns are grown from seed crystals at ca. 5 microns/d in a mother liquor containing Na20 0.94, AI203 0.011, and SiO2 0.200 moi/Kg by adding fine SiO2 powder, somewhat coarser AI203 powder, and NaOH at rates so that the mother liquor is kept at < 20% supersaturation with respect to AI203 to avoid the formation of a gel. Throughout growth, the mother liquor is stirred and kept at ca. 95°C.
E. Ger. 295,140, Oct. 24, 1991; Appl. June 13, 1990 The process comprises hydrothermally treating reaction mixtures that contain, in addition to Si-, AI-, and P-containing compounds, a template consisting of an asymmetrically substituted ammonium compound having general formula R1R2R3R4Ny[R1"4 = (substituted) alkyl /> 1 of which is different; Y = anion], and, as Si compound, a solution of an alkylammonium silicate having an asymmetrically substituted ammonium cation having general formula R1R2R3R4N+ (R1-4 as above), and heat-treating the resulting crystals to obtain the molecular sieves. The resulting molecular sieves of type ALPO-5 are suitable for use in catalyst sytems and as sorbents.
CATALYSIS
Z e o l i t e preparation using an alcohol directing agent G.W. Kirker; D.J. Klocke; J.C. Vartuli et al.
Z e o l i t e c a t a l y s t w i t h hexagonal structure and its application T. Des Courieres; J.L. Guth; J. Patarin et al.
Mobil Oil Corp.
Societe Nationale Elf Aquitaine (SNEA)
U.S. 5,063,038, Nov. 5, 1991; Appl. Oct. 21, 1985 Zeolites having ZSM-23 structure are obtained by preparing a mixture comprising a source of SiO2, a source of AI203, and a mixed organic directing agent comprising an amine, e.g., pyrrolidine, and a CI-s alcohol and/or diol, maintaining the reaction mixture at a sufficient temperature to crystallize the zeolite, and recovering the zeolite. The catalytic activity of ZSM-23 is enhanced by combining ZSM-23 with an AI203 binder, calcining the AI203-bound ZSM-23 to
PCT Int. Appl. 91,15,294, Oct. 17, 1991; FR. Appl. Apr. 9, 1990 The catalyst, suitable for acid catalysis reactions, especially fiuidized bed catalytic cracking, contains 1-99 wt.% of an inorganic binder, e.g., alumina, silica, alumina/silica clay, or magnesia, and 1-99 wt.% of a zeolite related to faujasite and having a hexagonally symmetrical structure and a Si:AI synthesis ratio of 3-30. The compensating cations of this zeolite consist partly or wholly of cations of ~> 1 of H, B, AI, Ga, In, rare earth metals, and transition metals. The catalyst
ZEOLITES, 1993, Vol 13, February
149