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Selective dealkylation of 1,4-dialkylbenzenes
Patent
Report
CATALYSIS Selective
dealkylation
Ti-containing silicalite zeolite microspheres having a diameter of 5-1000 microns are used as catalysts for aromatic hydrocarbon hydroxylation and olefin epoxidation (with HzOz used in both processes). The preparation of the zeolite is described.
of 1,Gdialkylbenzenes
l-l. Sato; N. Ishii; K. Hirose Sumitomo Chemical Co. ltd. U.S.4,642,409, Feb. 10, 1987; Appl.
Catalyst Feb. 10, 1986
An industrial method for selective dealkylation of 1,4dialkylbenzenes in a dialkylbenzene mixture is carried out in the presence of an ion-exchanged zeolite catalyst. The catalyst is prepared by treating Na+-ZSM-5 zeolite (NalAI = 0.95/l) (preparation given) with 8 wt.% Mg(OAc)z followed by drying and calcining to give MgO-Nat-ZSM-5 (MgO 20 wt.%.).
Catalyst
for the production
of aromatic
hydrocarbons
l-l. Katsuno; T. Murakawa; T. Yoneda Research Association for Utilisation of Light Oil Eur. Pat. Appl. 201,856, Nov. 20, 1986; Jap. Appl.
May
7, 1985
for gasoline
manufacture
from
methanol
H. Kudo; J. Kaita; R. Endo et al. Chiyoda Chemical Engineering and Construction Co. Ltd. Jpn Kokai Tokkyo Koho 87,15,288, Jan. 23, 1987; Appl. July 15, 1985 Catalysts for converting MeOH contain alkali cation-exchanged ably ZSM-5 zeolite, SiOz/AlzOs
Aromatic
or MezO to C,=e gasoline crystalline aluminosilicates mol ratio 25-500: 1).
fractions (prefer-
hydrocarbons
M. Ushio; T. Ishii; H. Okazaki et al. New Fuel Oil Development Technology Research Assoc. Jpn Kokai Tokkyo Koho 86,268,634, Nov. 28, 1986; Appl. 1985
May
24,
Aromatic hydrocarbons are prepared by contacting > 1 hydrocarbon selected from paraffins, olefins, acetylenes, cyclic paraffins and cyclic olefin hydrocarbons with L-type zeolite catalyst treated with a halogen-containing compound and containing deposited ft.
Aromatic hydrocarbons are prepared by heating aliphatic C,.,z hydrocarbons in the presence of zeolite ZSM-5 (SiOz/A1203 = 80) catalysts and > = 1 metal fluoride selected from Cu, Ag, Zn, Cd, Ga, Sn, Cr. MO, W, Se, Te, Re and Ni.
Hydrocarbon
SEPARATION
conversion
L. B. Young Mobil Oil Corp. Can. 1.215082, Dec. 9, 1986;
with
EM-22
U.S. Appl.
reolite
Apr. 30, 1982
ZSM-22 zeolites are catalysts for selective formation of pdisubstituted aromatic hydrocarbons, by such reactions as dispropottionation, alkylation (e.g., with MeOH or CzH& crackingdealkylation and transalkylation. The p-isomers are formed in larger amounts than those observed under equilibrium-control conditions.
Carboxylic
acids and esters
D. Feitlar Air Products U.S.4,612,387,
and Chemicals Inc. Sep. 16, 1986; Appl.
Jan. 4, 1982
Monocarboxylic acids and esters and C4.,c (gasoline-range) hydrocarbons are produced by conversion of C,.,-alcohols with CO in the presence of Rh-free ZSM-5 zeolite (SiOz/AlzOz ratio = > 6:lj at > 1 atmosphere in the absence of a halide promoter. The process is especially suitable for the production of HOAC and MeOAc from MeOH; in addition CzH4 can be co-produced to prepare a suitable feedback for vinyl acetate manufacture.
Preparation
of cyclohexanone
P. RoffTa; M. Padovan; Montedipe S.p.A. Eur. Pat. Appl. 208,311,
E. Moretti
oxime et a/.
Jan. 14, 1987; It. Appl.
Cyclohexanone oxime was prepared by reaction NHs and HzOz in the presence of a titanium-silicalite
July
10, 1985
of cyclohexanone, zeolite catalyst.
pDialkylbenzenes K. Kasano; S. Nakamura; M. lshii et a/. Technology Research Association for New Application Development for Light-Weight fractions Jpn Kokai Tokkyo Koho 86,221,135; 86,221,136, Oct. 1, 1986; Appls. Mar. 27, 1985 p-Dialkylbenzenes, useful as intermediates for p-cresol, hydroquinone and aromatic vinyl monomers (e.g., vinyltoluene, divinylbenzene), were prepared with high p-selectivity and high conversion rates by alkylation of monoalkylbenzenes with olefins in the presence of modified zeolites. The catalysts were prepared by treating proton-exchanged zeolites with heteropolyacids, e.g., 12tungstophosphoric acid, or their metal salts, drying and heating.
lsomeric bents
silicalite
catalyst
G. Belussi; M. Clerici; F. Buonomo et al. Enichem Sintesi S.p.A. Eur. Pat. Appl. 200,260, Dec. 10, 1986; It. Appl.
Apr. 23, 1985
toluenediamine
H. A. Zinnen UOP Inc. U.S.4,633,018,
separation
Dec. 30, 1986; Appl.
using zeolite
adsor-
Dec. 20, 1985
2,4-Toluenediamine, useful as diisocyanate precursor, is separated from 2,6-toluenediamine, and in some cases from other toluenediamines present in feed mixtures by contacting with a cationexchanged X-, Y-, or K-type zeolite adsorbent, and then desorbing the adsorbed diamine using a lower alcohol or amine.
Separation adsorption
of with
H. A. Zinnen; UOP Inc. U.S.4,642,397,
T. S. Franczyk
2,4-dinitrotoluene zeolite
Feb. 10, 1987; Appl.
from
isomers
by
Oct. 1, 1985
2.4-Dinitrotoluene is separated from a mixture with 2,6dinitrotoluene by selective adsorption with an L-type zeolite containing K ions, an X-type zeolite containing Na, Ca, Ba or K ions, or a Y-type zeolite containing Ca, Ba, K, Li or Mg ions and subsequent desorption of the 2,4-dinitrotoluene with a Cs.5 alcohol, a ketone, an ester or PhNOz.
Separation
of fructose
M. Negoro; K. Kanda; M. Minemoto Mitsubishi Heavy Industries Ltd. Jpn Kokai Tokkyo Koho 86.274,700,
et al. Dec. 4,1986;
Appl. May 30,1985
In separating fructose from its mixture with glucose in a solution containing Mg2+, on a Ca zeolite, the sugar solution was adjusted by adding CaC12 to Ca’+/Mg 2+ 40-4.5. The zeolite column could be used for a long period of time without degeneration of activity.
Recovery
of lower
alkenes
and alkynes
by adsorption
T. Nakamra; E. Nishikawa; T. Koyama Toa Nenryo Kogyo K.K. Jpn Kokai Tokkyo Koho 86,251,630, Nov. 8.1986;
Appl.
May
1,1985
Lower alkenes and alkynes, especially CzH4 and &Ha, are separated from gas with adsorbents prepared by treating X- or Y-type zeolite with aqueous Na2COa, washing and calcining.
Absorption Ti-containing
PROCESSES
separation
of dicholorobenzene
K. Miwa; M. Watanabe; K. Tada Toray industries Inc. Jpn Kokai Tokkyo Koho 86,268,636, 1985
ZEOLITES,
Nov.
28, 1986;
1988, Vol8,
isomers
Appl.
May
January
23,
87
Report
CATALYSIS Selective
dealkylation
Ti-containing silicalite zeolite microspheres having a diameter of 5-1000 microns are used as catalysts for aromatic hydrocarbon hydroxylation and olefin epoxidation (with HzOz used in both processes). The preparation of the zeolite is described.
of 1,Gdialkylbenzenes
l-l. Sato; N. Ishii; K. Hirose Sumitomo Chemical Co. ltd. U.S.4,642,409, Feb. 10, 1987; Appl.
Catalyst Feb. 10, 1986
An industrial method for selective dealkylation of 1,4dialkylbenzenes in a dialkylbenzene mixture is carried out in the presence of an ion-exchanged zeolite catalyst. The catalyst is prepared by treating Na+-ZSM-5 zeolite (NalAI = 0.95/l) (preparation given) with 8 wt.% Mg(OAc)z followed by drying and calcining to give MgO-Nat-ZSM-5 (MgO 20 wt.%.).
Catalyst
for the production
of aromatic
hydrocarbons
l-l. Katsuno; T. Murakawa; T. Yoneda Research Association for Utilisation of Light Oil Eur. Pat. Appl. 201,856, Nov. 20, 1986; Jap. Appl.
May
7, 1985
for gasoline
manufacture
from
methanol
H. Kudo; J. Kaita; R. Endo et al. Chiyoda Chemical Engineering and Construction Co. Ltd. Jpn Kokai Tokkyo Koho 87,15,288, Jan. 23, 1987; Appl. July 15, 1985 Catalysts for converting MeOH contain alkali cation-exchanged ably ZSM-5 zeolite, SiOz/AlzOs
Aromatic
or MezO to C,=e gasoline crystalline aluminosilicates mol ratio 25-500: 1).
fractions (prefer-
hydrocarbons
M. Ushio; T. Ishii; H. Okazaki et al. New Fuel Oil Development Technology Research Assoc. Jpn Kokai Tokkyo Koho 86,268,634, Nov. 28, 1986; Appl. 1985
May
24,
Aromatic hydrocarbons are prepared by contacting > 1 hydrocarbon selected from paraffins, olefins, acetylenes, cyclic paraffins and cyclic olefin hydrocarbons with L-type zeolite catalyst treated with a halogen-containing compound and containing deposited ft.
Aromatic hydrocarbons are prepared by heating aliphatic C,.,z hydrocarbons in the presence of zeolite ZSM-5 (SiOz/A1203 = 80) catalysts and > = 1 metal fluoride selected from Cu, Ag, Zn, Cd, Ga, Sn, Cr. MO, W, Se, Te, Re and Ni.
Hydrocarbon
SEPARATION
conversion
L. B. Young Mobil Oil Corp. Can. 1.215082, Dec. 9, 1986;
with
EM-22
U.S. Appl.
reolite
Apr. 30, 1982
ZSM-22 zeolites are catalysts for selective formation of pdisubstituted aromatic hydrocarbons, by such reactions as dispropottionation, alkylation (e.g., with MeOH or CzH& crackingdealkylation and transalkylation. The p-isomers are formed in larger amounts than those observed under equilibrium-control conditions.
Carboxylic
acids and esters
D. Feitlar Air Products U.S.4,612,387,
and Chemicals Inc. Sep. 16, 1986; Appl.
Jan. 4, 1982
Monocarboxylic acids and esters and C4.,c (gasoline-range) hydrocarbons are produced by conversion of C,.,-alcohols with CO in the presence of Rh-free ZSM-5 zeolite (SiOz/AlzOz ratio = > 6:lj at > 1 atmosphere in the absence of a halide promoter. The process is especially suitable for the production of HOAC and MeOAc from MeOH; in addition CzH4 can be co-produced to prepare a suitable feedback for vinyl acetate manufacture.
Preparation
of cyclohexanone
P. RoffTa; M. Padovan; Montedipe S.p.A. Eur. Pat. Appl. 208,311,
E. Moretti
oxime et a/.
Jan. 14, 1987; It. Appl.
Cyclohexanone oxime was prepared by reaction NHs and HzOz in the presence of a titanium-silicalite
July
10, 1985
of cyclohexanone, zeolite catalyst.
pDialkylbenzenes K. Kasano; S. Nakamura; M. lshii et a/. Technology Research Association for New Application Development for Light-Weight fractions Jpn Kokai Tokkyo Koho 86,221,135; 86,221,136, Oct. 1, 1986; Appls. Mar. 27, 1985 p-Dialkylbenzenes, useful as intermediates for p-cresol, hydroquinone and aromatic vinyl monomers (e.g., vinyltoluene, divinylbenzene), were prepared with high p-selectivity and high conversion rates by alkylation of monoalkylbenzenes with olefins in the presence of modified zeolites. The catalysts were prepared by treating proton-exchanged zeolites with heteropolyacids, e.g., 12tungstophosphoric acid, or their metal salts, drying and heating.
lsomeric bents
silicalite
catalyst
G. Belussi; M. Clerici; F. Buonomo et al. Enichem Sintesi S.p.A. Eur. Pat. Appl. 200,260, Dec. 10, 1986; It. Appl.
Apr. 23, 1985
toluenediamine
H. A. Zinnen UOP Inc. U.S.4,633,018,
separation
Dec. 30, 1986; Appl.
using zeolite
adsor-
Dec. 20, 1985
2,4-Toluenediamine, useful as diisocyanate precursor, is separated from 2,6-toluenediamine, and in some cases from other toluenediamines present in feed mixtures by contacting with a cationexchanged X-, Y-, or K-type zeolite adsorbent, and then desorbing the adsorbed diamine using a lower alcohol or amine.
Separation adsorption
of with
H. A. Zinnen; UOP Inc. U.S.4,642,397,
T. S. Franczyk
2,4-dinitrotoluene zeolite
Feb. 10, 1987; Appl.
from
isomers
by
Oct. 1, 1985
2.4-Dinitrotoluene is separated from a mixture with 2,6dinitrotoluene by selective adsorption with an L-type zeolite containing K ions, an X-type zeolite containing Na, Ca, Ba or K ions, or a Y-type zeolite containing Ca, Ba, K, Li or Mg ions and subsequent desorption of the 2,4-dinitrotoluene with a Cs.5 alcohol, a ketone, an ester or PhNOz.
Separation
of fructose
M. Negoro; K. Kanda; M. Minemoto Mitsubishi Heavy Industries Ltd. Jpn Kokai Tokkyo Koho 86.274,700,
et al. Dec. 4,1986;
Appl. May 30,1985
In separating fructose from its mixture with glucose in a solution containing Mg2+, on a Ca zeolite, the sugar solution was adjusted by adding CaC12 to Ca’+/Mg 2+ 40-4.5. The zeolite column could be used for a long period of time without degeneration of activity.
Recovery
of lower
alkenes
and alkynes
by adsorption
T. Nakamra; E. Nishikawa; T. Koyama Toa Nenryo Kogyo K.K. Jpn Kokai Tokkyo Koho 86,251,630, Nov. 8.1986;
Appl.
May
1,1985
Lower alkenes and alkynes, especially CzH4 and &Ha, are separated from gas with adsorbents prepared by treating X- or Y-type zeolite with aqueous Na2COa, washing and calcining.
Absorption Ti-containing
PROCESSES
separation
of dicholorobenzene
K. Miwa; M. Watanabe; K. Tada Toray industries Inc. Jpn Kokai Tokkyo Koho 86,268,636, 1985
ZEOLITES,
Nov.
28, 1986;
1988, Vol8,
isomers
Appl.
May
January
23,
87