- Email: [email protected]
Synthesis of β-zeolites
ELSEVIER
PATENTREPORT Synthesis source
As in previous issues, a selection of the more interesting patents that have been published recently is given below under the headings: synthesis, catalysis, separation processes, detergents, and miscellaneous applications. J.A. Barton
(IT-1
M.E. Davis; RF. Lobo PCT Int. Appl. 95,07,859,
Mar.
23, 1995;
U.S. Appl.
Sept.
15, 1993
A zeolite composition CIT-1 is provided which has a specific X-ray powder diffraction pattern and a mol ratio >20 of a first oxide selected from SiO, and/or GeO, to a second oxide comprising B,O,. The B,O, may be mixed with 21 of the oxides of Ga, Fe, Ti, and V. The preparation of the CIT-1 zeolite involves preparing an aqueous reaction mixture containing sources of a N,N,N-trimethyl-cis-myrtanyl ammonium ion and the two oxides as described. The mixture is maintained under crystallization conditions, preferably at a temperature of zlOo”C, in an autoclave under autogenous pressure until the crystals of the zeolite are formed.
Manufacture
of zeolite
G.W. Skeels; MB. UOP Inc. Australian 656,655,
LZ-277
Sears Feb.
9, 1995;
Appl.
Mar.
3, 1993
Aluminosilicate zeolite LZ-277 is synthesized hydrothermally from aqueous Na,O-Al,O,-SiO, gels in the absence of an organic templating agent. The as-synthesized LZ-277 has a chemical composition on an anhydrous basis expressed in terms of molar oxide ratios of (1.0 f O.l)Na,O:AI,O,:(3-16)SiO, and has a low adsorptive capacity for SF, compared with previously known zeolites.
Manufacture
of faujasite-type
S. Inui; T. Shioda; Mitsubishi Kagaku Jpn. Kokai Tokkyo 1993
zeolites
A. Nakanishi et al. K.K. Koho 95,101,718, Apr.
18, 1995;
Appl.
Oct.
4,
In the manufacture of faujasite-type zeolites by reaction of raw material mixtures of silica sources, alumina sources, and alkali sources, organic acid alkali metal salts are used as a part of the alkali sources. Zeolites containing alkali metals other than sodium can be manufactured by the method and are useful as absorbents. For example, Li-containing faujasite-type zeolites free from other phases were manufactured from a reaction mixture containing a silica sol, lithium citrate tetrahydrate, sodium hydroxide, aluminum sulfate, and sodium aluminate, and the zeolites showed high selective absorbability for 2,6-dimethylnaphthalene.
Heat-resistant
Zeolites placing
Apr.
11, 1995;
that are heat resistant to 2950°C are Al in the crystalline structure by SO.01
Zeolites 17:314-319, 0 Elsevier Science 655 Avenue of the
1996 Inc. 1996 Americas,
New
York,
Appl.
Sept.
29,
produced by rewt% P and/or V.
NY 10010
water
Appl.
glass as the silicon
Sept.
20, 1993
The p-zeolites are manufactured by adding an organic templating agent (tetraethylammonium hydroxide or tetraethylammonium halides), NaOH or H,SO,, and an Al source into water glass (mol ratio SiO,/Na,O = 2.0-3.7). The p-zeolites have a composition expressed in terms of oxide mol ratios: SiO,/AI,O, = IO-infinity, (tetra-Et NH,),O/SiO, = 0.03-0.85, Na,O/SiO, = O.lO0.80, and H,O/SiO, = 5.00-12.00. The Al source is selected from A12(S0&, AICI,, AhNO,),, and NaAIO,. The crystallization temperature and time are IlO-220°C and 4-48 h, respectively. It is claimed that the method of the invention uses less templating agent, involves shorter crystallization times, and reduces production costs.
Synthesis
of p-zeolites
Q. Zhou; W. Pang; China Petrochemical Chinese 1,086,792,
S. Qiu Corp. May 18, 1994;
Appl.
Sept.
20, 1993
p-Zeolites are synthesized by using a directing agent prepared by dissolving an Al salt (preferably NaAlO,) in an aqueous solution containing a tetraethylammonium hydroxide (TEAOH) template and NaOH and adding activated SiO,. The directing agent has a composition expressed in terms of oxide mol ratios: SiO,/AI,O, = 20-120, TEAOH/SiO, = 0.2-0.5, Na,O/SiO, = 0.040.10, and H,O/SiO, = 7.5-25; the directing agent is prepared at 15-70°C followed by aging at 50-150°C. In the manufacture of p-zeolites, the volume ratio of the directing agent to the raw material mixture is 0.5-10%.
High temperature hydrothermal mesoporosity in Y-type zeolites
treatment
D.A. Cooper; T.W. Hastings; E.P. Hertzenberg PO Corp. PCT Int. Appl. 95,07,236, Mar. 16, 1995; U.S.
for enhanced
Appl.
Sept.
7, 1993
Y-type zeolites with mesopore volume of -0.05 to 20.6 cm”/g (derived from pores of -2 to -60 nm diameter) are prepared by hydrothermal treatment of Y zeolites with an aqueous solution containing dissolved salts, acids, bases, or water-soluble organic compounds at a temperature greater than the atmospheric boiling point of the solution. The mesopore volume of the hydrothermally treated zeolites is 20.05 cm3/g for zeolite Y, ~0.18 cm3/g for USY, 20.23 cm3/g for very ultrastable Y (VUSY), and ~0.26 cm3/g for super dealuminated ultrastable Y (SDUSY) zeolites. The hydrothermal treatment is carried out at a pH
Synthesis
of crystalline
zeolite
A. Moini; K.D. Schmitt Mobil Oil Corp. U.S. 5,405,596, Apr. 11, 1995;
zeolites
T. Naka; T. Sugyama; Y. Fujisawa Honda Motor Co. Ltd. Jpn. Kokai Tokkyo Koho 95,97,209, 1993
using
Y. Sun; T. Song; W. Pang China Petrochemical Corp. Chinese 1,086,793, May 18, 1994;
SYNTHESIS Zeolite
of p-zeolites
Appl.
ZSM-23
June
29, 1993
This invention relates to a new form of crystalline material identified as having the structure of zeolite ZSM-23, to a new and useful method for synthesizing the crystalline material, and to use of the crystalline material as a catalyst for organic compound, for example, hydrocarbon compound, conversion.
SSDI
0144.2449/96/$15.00 0144-2449(95)00152-2
PATENTREPORT Synthesis source
As in previous issues, a selection of the more interesting patents that have been published recently is given below under the headings: synthesis, catalysis, separation processes, detergents, and miscellaneous applications. J.A. Barton
(IT-1
M.E. Davis; RF. Lobo PCT Int. Appl. 95,07,859,
Mar.
23, 1995;
U.S. Appl.
Sept.
15, 1993
A zeolite composition CIT-1 is provided which has a specific X-ray powder diffraction pattern and a mol ratio >20 of a first oxide selected from SiO, and/or GeO, to a second oxide comprising B,O,. The B,O, may be mixed with 21 of the oxides of Ga, Fe, Ti, and V. The preparation of the CIT-1 zeolite involves preparing an aqueous reaction mixture containing sources of a N,N,N-trimethyl-cis-myrtanyl ammonium ion and the two oxides as described. The mixture is maintained under crystallization conditions, preferably at a temperature of zlOo”C, in an autoclave under autogenous pressure until the crystals of the zeolite are formed.
Manufacture
of zeolite
G.W. Skeels; MB. UOP Inc. Australian 656,655,
LZ-277
Sears Feb.
9, 1995;
Appl.
Mar.
3, 1993
Aluminosilicate zeolite LZ-277 is synthesized hydrothermally from aqueous Na,O-Al,O,-SiO, gels in the absence of an organic templating agent. The as-synthesized LZ-277 has a chemical composition on an anhydrous basis expressed in terms of molar oxide ratios of (1.0 f O.l)Na,O:AI,O,:(3-16)SiO, and has a low adsorptive capacity for SF, compared with previously known zeolites.
Manufacture
of faujasite-type
S. Inui; T. Shioda; Mitsubishi Kagaku Jpn. Kokai Tokkyo 1993
zeolites
A. Nakanishi et al. K.K. Koho 95,101,718, Apr.
18, 1995;
Appl.
Oct.
4,
In the manufacture of faujasite-type zeolites by reaction of raw material mixtures of silica sources, alumina sources, and alkali sources, organic acid alkali metal salts are used as a part of the alkali sources. Zeolites containing alkali metals other than sodium can be manufactured by the method and are useful as absorbents. For example, Li-containing faujasite-type zeolites free from other phases were manufactured from a reaction mixture containing a silica sol, lithium citrate tetrahydrate, sodium hydroxide, aluminum sulfate, and sodium aluminate, and the zeolites showed high selective absorbability for 2,6-dimethylnaphthalene.
Heat-resistant
Zeolites placing
Apr.
11, 1995;
that are heat resistant to 2950°C are Al in the crystalline structure by SO.01
Zeolites 17:314-319, 0 Elsevier Science 655 Avenue of the
1996 Inc. 1996 Americas,
New
York,
Appl.
Sept.
29,
produced by rewt% P and/or V.
NY 10010
water
Appl.
glass as the silicon
Sept.
20, 1993
The p-zeolites are manufactured by adding an organic templating agent (tetraethylammonium hydroxide or tetraethylammonium halides), NaOH or H,SO,, and an Al source into water glass (mol ratio SiO,/Na,O = 2.0-3.7). The p-zeolites have a composition expressed in terms of oxide mol ratios: SiO,/AI,O, = IO-infinity, (tetra-Et NH,),O/SiO, = 0.03-0.85, Na,O/SiO, = O.lO0.80, and H,O/SiO, = 5.00-12.00. The Al source is selected from A12(S0&, AICI,, AhNO,),, and NaAIO,. The crystallization temperature and time are IlO-220°C and 4-48 h, respectively. It is claimed that the method of the invention uses less templating agent, involves shorter crystallization times, and reduces production costs.
Synthesis
of p-zeolites
Q. Zhou; W. Pang; China Petrochemical Chinese 1,086,792,
S. Qiu Corp. May 18, 1994;
Appl.
Sept.
20, 1993
p-Zeolites are synthesized by using a directing agent prepared by dissolving an Al salt (preferably NaAlO,) in an aqueous solution containing a tetraethylammonium hydroxide (TEAOH) template and NaOH and adding activated SiO,. The directing agent has a composition expressed in terms of oxide mol ratios: SiO,/AI,O, = 20-120, TEAOH/SiO, = 0.2-0.5, Na,O/SiO, = 0.040.10, and H,O/SiO, = 7.5-25; the directing agent is prepared at 15-70°C followed by aging at 50-150°C. In the manufacture of p-zeolites, the volume ratio of the directing agent to the raw material mixture is 0.5-10%.
High temperature hydrothermal mesoporosity in Y-type zeolites
treatment
D.A. Cooper; T.W. Hastings; E.P. Hertzenberg PO Corp. PCT Int. Appl. 95,07,236, Mar. 16, 1995; U.S.
for enhanced
Appl.
Sept.
7, 1993
Y-type zeolites with mesopore volume of -0.05 to 20.6 cm”/g (derived from pores of -2 to -60 nm diameter) are prepared by hydrothermal treatment of Y zeolites with an aqueous solution containing dissolved salts, acids, bases, or water-soluble organic compounds at a temperature greater than the atmospheric boiling point of the solution. The mesopore volume of the hydrothermally treated zeolites is 20.05 cm3/g for zeolite Y, ~0.18 cm3/g for USY, 20.23 cm3/g for very ultrastable Y (VUSY), and ~0.26 cm3/g for super dealuminated ultrastable Y (SDUSY) zeolites. The hydrothermal treatment is carried out at a pH
Synthesis
of crystalline
zeolite
A. Moini; K.D. Schmitt Mobil Oil Corp. U.S. 5,405,596, Apr. 11, 1995;
zeolites
T. Naka; T. Sugyama; Y. Fujisawa Honda Motor Co. Ltd. Jpn. Kokai Tokkyo Koho 95,97,209, 1993
using
Y. Sun; T. Song; W. Pang China Petrochemical Corp. Chinese 1,086,793, May 18, 1994;
SYNTHESIS Zeolite
of p-zeolites
Appl.
ZSM-23
June
29, 1993
This invention relates to a new form of crystalline material identified as having the structure of zeolite ZSM-23, to a new and useful method for synthesizing the crystalline material, and to use of the crystalline material as a catalyst for organic compound, for example, hydrocarbon compound, conversion.
SSDI
0144.2449/96/$15.00 0144-2449(95)00152-2