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Manufacture of porous crystalline silicates
PATENTREPORT As in previous patents which below under tion processes, tions.
issues, a selection of the more have been published recently the headings: synthesis, catalysis, detergents, and miscellaneous
Measurement
interesting is given separaapplica-
SYNTHESIS of porous
S.M. Kuznicki Engelhard Corp. U.S. 4,938,939, July
crystalline
3, 1990;
Appl.
titanium
Oct.
zeolites
Synthesis
of binderless
M. Tajima; H. Miyazaki Tosoh Corp. Jpn Kokai Tokkyo Koho 1988
7, 1986
faujasite
90,149,419,
June
zeolite
8, 1990;
bodies
Appl.
Nov.
30,
Binderless faujasite zeolites (SiOz/AlzOs mol ratio > 4.5) are activated, contacted with SiC14, and washed with strong acid for dealumination. Zeolites having high Si/AI ratio and excellent hydrothermal stability are prepared.
Manufacture
of submicron
gamma-type
zeolites
T. Yamamoto; M. Kamimura; K. lmura et al. Shinagawa Fuel Co. Ltd.; Shinanen New Ceramic Jpn Kokai Tokkyo Koho 90,116,614, May 1, 1990; 1988
K.K. Appl.
Oct.
24,
Slurries of Al compounds, Si compounds, and alkali metal compounds are kept at < 40°C for nucleation of zeolites, then kept at temperatures higher than or equal to the nucleation temperature for growth of submicron gamma-type zeolites with SiOz/AlzOz mol ratio 2 4.0 and particle size C 0.4 microns. The exchangeable metal ions can be replaced with antibacterial metal ions (Ag, Cu. Zn, Hg, Sn, Pb, Bi, Cd, Cr, and/or TI) and acid-treated to give antibacterial zeolites.
Manufacture
of porous
crystalline
H. Okaniwa; M. Kasahara Tosoh Corp. Jpn Kokai Tokkyo Koho 90,129,015, 1988
Butterworth-Heinemann
synthesis
Appl.
26, 1987
May
Cont.-in-part
July
ZSM-11
17, 1990;
Appl.
structure
Aug.
30, 1989
An improved method for preparing the crystalline ZSM-11 zeolite comprises using bis(butylpyrrolidinium) diquaternary ammonium compound as directing agent whereby synthesis is facilitated and reproducible and the product exhibits high purity and catalytic utility. The ZSM-11 zeolite is useful in hydrocarbon conversion, e.g., catalytic cracking reactions.
Manufacture
of high-silica
zeolites
T. Yokogawa; T. Maekawa; N. Yoshimi Nippon Steel Chemical Co. Ltd. Jpn Kokai Tokkyo Koho 90,141,415, May 30,199O; Appl. Nov. 24, 1988 High-silica zeolites (e.g., silicalite) are manufactured by adding water to a silicic acid tetraalkyl ester (e.g., tetra-Et silicate) in the presence of an organic template (e.g., tetra-Pr ammonium bromide) to form a sol, drying the sol to obtain a silica raw material, and subjecting to hydrothermal synthesis in the presence of alkali and water. The zeolites are useful as catalysts and adsorbents.
Crystalline
porous
borosilicate
G. Bellussi; A. Carati; R. Millini Eniricerche S.p.A. U.K. Pat. Appl. 2,226,307, June
27, 1990;
It. Appl.
Dec.
9, 1988
The borosilicate which is isostructural with levynite, containing Si and B oxides, has a composition: Mu,O.fl -x)Bz03.mM’z03.ySi0z where M is a metal cation of valency n or H+, M’ is Al, Fe, Ga, Cr. V, and/or Mn, 0 6 x < 0.3, and 5 < y < 40. Si can be partially replaced by Ge, Ti, and/or Zr. the borosilicate is prepared by subjecting the reaction mixture comprising a SiOz source (e.g., silica gel, colloidal SiOz), a B source (e.g., HsBOs), a cyclic amine (e.g., quinuclidine) as the template agent, and, optionally, an alkali metal or alkaline earth metal hydroxide to hydrothermal synthesis.
silicates CATALYSIS May
17,199O;
Appl.
Nov.
7,
Porous crystalline silicates having given powder X-ray diffraction pattern, similar to that of ZSM-48 zeolite, are manufactured from reaction mixtures containing NMe4+, a Si source, a OHsource, and water in molar ratio SiOz/AlzOz 2 50, OH-/SiOz 0.04-0.10, HzO/SiOz 15-60, and NMed+/SiOz 0.05-1.0. The silicates are used as catalysts, catalyst supports and adsorbents. A porous crystalline silicate, similar to ZSM-48, was manufactured from water glass, HzSOs, NMe&I, and water.
(Q 1991
of crystalline
E.W. Valyocsik Mobil Oil Corp U.S. 4,941,963,
The process comprises heating a reaction mixture containing a source of Ti, SiOz, alkali and water, and, optionally, an alkali metal fluoride, having composition (in mol ratios) SiOz/Ti (l-10):1, HzO/ SiOz (2-1OO):l and M,/SiOz (O.l-1O):l (M = cation of valance n derived from the source of alkali and KF) while controlling the pH at 10.45-(11.0 +/- 0.1). The crystalline Ti silicates have pore sizes 3-5 A0 and composition fin mol ratios): 1.0 +/- 0.25 M~,O:TiOz:ySiOz:yHzO (y = 1.0-100; z = O-100) and have X-ray diffraction pattern as presented and claimed. These zeolits are effective in the removal of Hg ions from aqueous solutions.
Dealumination
19, 1990;
of zeolite
A method is described for synthesizing a solid crystalline silicate product from a crystallization mixture containing a source of SiOz. A relationship is established between the dielectric constant of the crystallization mixture and the crystallinity of the solid product, and the silicate product is alllowed to crystallize. The dieletric constant of the mixture is measured and the crystallization is continued until the dielectric constant achieves a value which, from the relationship established earlier, is indicative of a selected crystallinity. When this value is achieved, the crystallization is terminated.
J.A. Barton
Preparation
and control
S. Krishnamurthy Mobil Oil Corp. US 4,935,215, June of U.S. 4,849,194.
Use of metal
tolerant
catalytic
cracking
catalyst
T.F. Degnan; B.K. Huh Mobil Oil Corp. U.S. 4,938,863, July 3, 1990; Appl. June 10, 1988 A catalytic cracking catalyst and process that tolerate high levels of V and coke precursors in the feed are described. A zeolite in an AlzOs-free binder or coating, preferably SiOz, is used as the cracking catalyst. Rare earth ultrastable Y in silica is especially preferred as it has a low affinity for V, low coking characteristics, and high stability.
ZEOLITES,
1991, Vol 11, September/October
751
issues, a selection of the more have been published recently the headings: synthesis, catalysis, detergents, and miscellaneous
Measurement
interesting is given separaapplica-
SYNTHESIS of porous
S.M. Kuznicki Engelhard Corp. U.S. 4,938,939, July
crystalline
3, 1990;
Appl.
titanium
Oct.
zeolites
Synthesis
of binderless
M. Tajima; H. Miyazaki Tosoh Corp. Jpn Kokai Tokkyo Koho 1988
7, 1986
faujasite
90,149,419,
June
zeolite
8, 1990;
bodies
Appl.
Nov.
30,
Binderless faujasite zeolites (SiOz/AlzOs mol ratio > 4.5) are activated, contacted with SiC14, and washed with strong acid for dealumination. Zeolites having high Si/AI ratio and excellent hydrothermal stability are prepared.
Manufacture
of submicron
gamma-type
zeolites
T. Yamamoto; M. Kamimura; K. lmura et al. Shinagawa Fuel Co. Ltd.; Shinanen New Ceramic Jpn Kokai Tokkyo Koho 90,116,614, May 1, 1990; 1988
K.K. Appl.
Oct.
24,
Slurries of Al compounds, Si compounds, and alkali metal compounds are kept at < 40°C for nucleation of zeolites, then kept at temperatures higher than or equal to the nucleation temperature for growth of submicron gamma-type zeolites with SiOz/AlzOz mol ratio 2 4.0 and particle size C 0.4 microns. The exchangeable metal ions can be replaced with antibacterial metal ions (Ag, Cu. Zn, Hg, Sn, Pb, Bi, Cd, Cr, and/or TI) and acid-treated to give antibacterial zeolites.
Manufacture
of porous
crystalline
H. Okaniwa; M. Kasahara Tosoh Corp. Jpn Kokai Tokkyo Koho 90,129,015, 1988
Butterworth-Heinemann
synthesis
Appl.
26, 1987
May
Cont.-in-part
July
ZSM-11
17, 1990;
Appl.
structure
Aug.
30, 1989
An improved method for preparing the crystalline ZSM-11 zeolite comprises using bis(butylpyrrolidinium) diquaternary ammonium compound as directing agent whereby synthesis is facilitated and reproducible and the product exhibits high purity and catalytic utility. The ZSM-11 zeolite is useful in hydrocarbon conversion, e.g., catalytic cracking reactions.
Manufacture
of high-silica
zeolites
T. Yokogawa; T. Maekawa; N. Yoshimi Nippon Steel Chemical Co. Ltd. Jpn Kokai Tokkyo Koho 90,141,415, May 30,199O; Appl. Nov. 24, 1988 High-silica zeolites (e.g., silicalite) are manufactured by adding water to a silicic acid tetraalkyl ester (e.g., tetra-Et silicate) in the presence of an organic template (e.g., tetra-Pr ammonium bromide) to form a sol, drying the sol to obtain a silica raw material, and subjecting to hydrothermal synthesis in the presence of alkali and water. The zeolites are useful as catalysts and adsorbents.
Crystalline
porous
borosilicate
G. Bellussi; A. Carati; R. Millini Eniricerche S.p.A. U.K. Pat. Appl. 2,226,307, June
27, 1990;
It. Appl.
Dec.
9, 1988
The borosilicate which is isostructural with levynite, containing Si and B oxides, has a composition: Mu,O.fl -x)Bz03.mM’z03.ySi0z where M is a metal cation of valency n or H+, M’ is Al, Fe, Ga, Cr. V, and/or Mn, 0 6 x < 0.3, and 5 < y < 40. Si can be partially replaced by Ge, Ti, and/or Zr. the borosilicate is prepared by subjecting the reaction mixture comprising a SiOz source (e.g., silica gel, colloidal SiOz), a B source (e.g., HsBOs), a cyclic amine (e.g., quinuclidine) as the template agent, and, optionally, an alkali metal or alkaline earth metal hydroxide to hydrothermal synthesis.
silicates CATALYSIS May
17,199O;
Appl.
Nov.
7,
Porous crystalline silicates having given powder X-ray diffraction pattern, similar to that of ZSM-48 zeolite, are manufactured from reaction mixtures containing NMe4+, a Si source, a OHsource, and water in molar ratio SiOz/AlzOz 2 50, OH-/SiOz 0.04-0.10, HzO/SiOz 15-60, and NMed+/SiOz 0.05-1.0. The silicates are used as catalysts, catalyst supports and adsorbents. A porous crystalline silicate, similar to ZSM-48, was manufactured from water glass, HzSOs, NMe&I, and water.
(Q 1991
of crystalline
E.W. Valyocsik Mobil Oil Corp U.S. 4,941,963,
The process comprises heating a reaction mixture containing a source of Ti, SiOz, alkali and water, and, optionally, an alkali metal fluoride, having composition (in mol ratios) SiOz/Ti (l-10):1, HzO/ SiOz (2-1OO):l and M,/SiOz (O.l-1O):l (M = cation of valance n derived from the source of alkali and KF) while controlling the pH at 10.45-(11.0 +/- 0.1). The crystalline Ti silicates have pore sizes 3-5 A0 and composition fin mol ratios): 1.0 +/- 0.25 M~,O:TiOz:ySiOz:yHzO (y = 1.0-100; z = O-100) and have X-ray diffraction pattern as presented and claimed. These zeolits are effective in the removal of Hg ions from aqueous solutions.
Dealumination
19, 1990;
of zeolite
A method is described for synthesizing a solid crystalline silicate product from a crystallization mixture containing a source of SiOz. A relationship is established between the dielectric constant of the crystallization mixture and the crystallinity of the solid product, and the silicate product is alllowed to crystallize. The dieletric constant of the mixture is measured and the crystallization is continued until the dielectric constant achieves a value which, from the relationship established earlier, is indicative of a selected crystallinity. When this value is achieved, the crystallization is terminated.
J.A. Barton
Preparation
and control
S. Krishnamurthy Mobil Oil Corp. US 4,935,215, June of U.S. 4,849,194.
Use of metal
tolerant
catalytic
cracking
catalyst
T.F. Degnan; B.K. Huh Mobil Oil Corp. U.S. 4,938,863, July 3, 1990; Appl. June 10, 1988 A catalytic cracking catalyst and process that tolerate high levels of V and coke precursors in the feed are described. A zeolite in an AlzOs-free binder or coating, preferably SiOz, is used as the cracking catalyst. Rare earth ultrastable Y in silica is especially preferred as it has a low affinity for V, low coking characteristics, and high stability.
ZEOLITES,
1991, Vol 11, September/October
751